Method for manufacturing pattern print and pattern print

Abstract

To provide a manufacturing method of a pattern printed matter capable of printing a pattern with a high aspect ratio.SOLUTION: A manufacturing method of a pattern printing material comprises the steps of: preparing a coating agent 10 containing a filler, a binder, and a solvent incompatible with the binder as a printing ink; adhering a substrate 40 to a back side 30b of a screen printing plate 30 provided with a hole pattern 32; injecting the coating agent 10 to the hole pattern 32 from a surface 30a side of the screen printing plate 30 using a pressure container 20 filled with the coating agent 10; sweep-eliminating, by a squeegee 50, a coating agent 14 protruding from the hole pattern 32 after the step of injection; and peeling the substrate 40 from the screen printing plate 30 after the step of sweep-elimination. In the step of sweep-elimination, the squeeze 50 applies pressure to a coating agent 12 in the hole pattern 32 from the surface 30a side of the screen printing plate 43.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a method for producing a pattern printed product, and a pattern printed product, and in particular to a method for producing a pattern printed product using a contact type pressure printing method including screen printing or metal mask printing, and a pattern printed product. [Background technology]

[0002] Patent Documents 1 and 2 disclose examples of screen printing methods. In the screen printing method disclosed in Patent Document 1, a preliminary squeegeeing operation is performed by moving the squeegee back and forth several times before screen printing, thereby stabilizing the viscosity of the coating agent and improving the printing quality. In the screen printing method disclosed in Patent Document 2, the coating agent is supplied to the outside of the squeegee mechanism and squeegeeed while being pressurized by the squeegee mechanism, thereby ensuring good filling of the pattern holes. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2001-246729 A [Patent Document 2] JP 2012-187739 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, a general coating agent 210 used in the screen printing methods disclosed in Patent Documents 1 and 2 passes through a mesh 234 of a screen plate and a mask 232, which is a resin film or a metal film with holes for a pattern, wiring pattern, circuit, etc. to be printed, as shown in FIG. 22(a), and is pushed out while receiving a certain shear S onto a substrate 240 overlapping therebelow. As a result, as shown in FIG. 22(b), cohesive failures 210a, 210b may occur between the mesh 234 or the wall surface of the mask 232 at the opening 232a and the coating agent 210 being pushed out. This is a so-called "sad separation" state, in which the coating agent remains on the wall surface of the mesh 234 or the opening 232a of the mask 232, and a state occurs in which not all of the coating agent can be transferred to the substrate 240 to be printed, resulting in a pattern print 210a having a semi-cylindrical shape or a cross-sectional shape with an arched upper surface. Therefore, there was a problem that a pattern with a high aspect ratio could not be printed.

[0005] The present invention has been made to solve the above-mentioned problems, and has an object to provide a method for manufacturing a pattern printed matter capable of performing pattern printing with a high aspect ratio, and a pattern printed matter. [Means for solving the problem]

[0006] One aspect of the present invention relates to a method for producing a pattern print. The method for producing a pattern print includes the steps of preparing a coating agent containing a filler, a binder, and a solvent incompatible with the binder as a printing ink, bonding a substrate to the back surface of a screen plate having a hole pattern, injecting the coating agent into the hole pattern from the front surface side of the screen plate using a pressurized container filled with the coating agent, sweeping and removing the coating agent that has overflowed from the hole pattern after the injecting step with a squeegee, and peeling the substrate from the screen plate after the sweeping and removing step. In the sweeping and removing step, pressure is applied to the coating agent in the hole pattern from the front surface side of the screen plate with the squeegee.

[0007] In this method for producing a pattern print, the coating agent used as the printing ink contains a solvent that is incompatible with the binder, and the coating agent is injected into the hole pattern, and then pressure is applied to the coating agent in the hole pattern by the squeegee. In this case, the solvent that is incompatible with the binder seeps out from the coating agent to which pressure is applied by the squeegee onto the surface of the coating agent as a lubricant, and covers the surface of the printed coating agent. As a result, a film is formed between the inner walls of the hole pattern of the screen plate and the printed coating agent, and when the substrate is peeled off from the screen plate, the coating agent is transferred onto the substrate without causing cohesive failure, making it possible to obtain a pattern print with a cross-sectional shape closer to a rectangle. As a result, according to the above-mentioned method for producing a pattern print, it is possible to perform pattern printing with a high aspect ratio.

[0008] In addition, according to the above-mentioned method for manufacturing a pattern print, for example, when a wiring pattern is printed with a coating agent that is a conductive material, the cross-sectional shape of the pattern can be made closer to a rectangle, and the cross-sectional area of ​​the wiring pattern can be calculated by a simple formula such as "base dimension x height dimension" in the case of a rectangle, and by a simple formula such as "(top dimension + base dimension) x height dimension ÷ 2" in the case of a trapezoid, and the wiring resistance value, etc. can be easily calculated from this cross-sectional area. In addition, according to this manufacturing method, a printed pattern having a cross-sectional shape with a high aspect ratio (narrow base and high height) can be obtained, and the dimensional width (base dimension) can be reduced even with the same wiring resistance value, so that dense wiring such as electronic circuits can be consolidated into a small area, and more current can be made to flow through the wiring. Furthermore, since the height of the wiring pattern can be increased, the side area of ​​the wiring (height x longitudinal direction of the wiring) becomes wider, and it is possible to increase the amount of current flow between, for example, two parallel electrodes and a resistor embedded in the gap between them.

[0009] Furthermore, since the above-mentioned method for producing a pattern print uses a screen printing method, it is possible to print complex and diverse patterns at high speed compared to a method of drawing a pattern by directly discharging a coating agent onto a substrate using a dispenser or the like. In other words, in a method of discharging a coating agent using a dispenser or the like, the patterns that can be formed are limited to stripe or line patterns, and there is a problem that the printing speed is slow and the cost is high, but according to this method, it is possible to deal with various patterns and reduce costs by increasing the printing speed. The screen plate used here may be configured by combining a resin mask and a metal mesh, or may be configured by combining a resin mask and a resin mesh, or may be configured by combining a metal mask and a metal mesh.

[0010] In addition, according to the above-mentioned method for manufacturing a pattern print, for example, a vertically steep printed pattern can be formed, so that it is possible to produce a wiring pattern with the wiring gap narrowed to the limit. Therefore, it is possible to produce wiring that passes more current and a wiring pattern with a large area per unit length of the vertically steep pattern side. For example, it is effective for heaters in which the larger the cross-sectional area between the electrodes, such as a circuit in which positive and negative electrodes are arranged in parallel, and a high-resistance heating element such as carbon is inserted between the positive and negative electrodes, and since electrodes that are high in the height direction and parallel to each other can be formed even with a narrow gap, it is possible to obtain particularly high efficiency in heat sinks that have a high heat dissipation effect as the surface area increases, and thermoelectric conversion materials such as Seebeck effect and Peltier effect.

[0011] In the above-mentioned method for producing a pattern print, the pressurized container is a dispenser having a nozzle, and in the injection step, it is preferable to inject the coating agent into the hole pattern by pressure injection or scraping injection from the nozzle of the dispenser. In this case, pressure is applied to the coating agent when the coating agent is injected into the hole pattern from the dispenser, and a solvent that is incompatible with the binder seeps out from the coating agent to which pressure is applied as a lubricant onto the surface of the coating agent, and covers the surface of the injected coating agent. Therefore, it is possible to further suppress the coating agent from causing cohesive failure when the substrate is peeled off from the screen plate, and it is possible to obtain a pattern print having a cross-sectional shape closer to a rectangle. As a result, it is possible to perform pattern printing with a high aspect ratio.

[0012] In the above method for producing a pattern print, at least one of the grooves, the front surface, and the back surface of the hole pattern of the screen plate may be coated with a hydrophilic coating or a water- and oil-repellent agent. When the solvent that is incompatible with the binder is water-soluble, coating with a hydrophilic coating results in a state in which the lubricant is held in advance in the grooves of the hole pattern of the screen plate, and the cohesive failure of the coating agent can be further suppressed. In this case, whether a photosensitive emulsion or a metal mask is used for the screen plate, the peelability is improved and the cohesive failure of the coating agent can be suppressed. In addition, if the water- and oil-repellent agent is coated on the screen plate, the peelability of the coating agent can be improved in the same manner as above, and the cohesive failure of the coating agent can be further suppressed. In addition, as the water- and oil-repellent agent, for example, a fluorine-based water- and oil-repellent agent can be used.

[0013] In the above-mentioned method for producing a pattern print, the hydrophilic coating coated on the screen preferably contains a polysaccharide whose main chain is composed of sugars containing at least one of galactose, arabinose, rhamnose, and glucuronic acid. Examples of materials containing such polysaccharides include gum arabic. Gum arabic has excellent emulsifying properties, and an emulsion dissolved in water has the property of preferentially adsorbing to the oil-water interface, so that the highly hydrophobic polypeptide chain can be easily adsorbed to the grooves of the hole pattern, which is a hydrophobic surface formed from a photosensitive resin or metal. On the other hand, the hydrophilic sugar chain portion of the gum arabic emulsion forms a film-like hydrophilic polysaccharide unit when completely dried on the screen surface. As a result, the lubricant is held in advance in the grooves of the hole pattern of the screen, and the cohesive failure of the coating agent can be further suppressed. Gum arabic is a polymeric polysaccharide obtained from plant sap, and is a material that has excellent emulsifying properties and film properties.

[0014] In the above method for producing a pattern print, the amount of the solvent mixed is preferably 0.1% by weight or more and 30% by weight or less, assuming that the mixture of the filler and binder is 100% by weight. It is more preferable that the amount of the solvent mixed is controlled to 5% by weight or more and 13% by weight or less, relative to the above mixture. In the case of the above formulation, a sufficient amount of solvent can be ensured to seep out from the coating agent that is injected into the screen and then subjected to pressure by sweeping and removing with a squeegee, making it possible to more reliably suppress cohesive failure of the coating agent by the seeped solvent.

[0015] In the above-mentioned method for producing a pattern print, it is preferable that the binder is water-insoluble and the solvent is water-soluble. In this case, the water-soluble solvent is temporarily impregnated and held in the gaps between the molecular bonds of the binder by constant stirring, resulting in a state in which the water-soluble solvent is contained in the sponge structure. When pressure is applied to the mixture, the balance is lost and the water-soluble solvent seeps out onto the binder surface. The seeped water-soluble solvent forms a fluid coating at the interface with the screen plate and becomes the direct shear target with the screen plate instead of the binder. This makes it possible to prevent the binder from undergoing cohesive failure due to shear and form a pattern that does not undergo cohesive failure.

[0016] In the above-mentioned method for producing a pattern printed matter, the binder may be water-soluble and the solvent may be water-insoluble. For example, in the electronic parts industry, when the filler of the mixture is a metal, ceramic, or other hydrophilic material from the viewpoint of environmentally friendly materials, a water-soluble binder is used, but in this case, the binder is water-soluble and the solvent is water-insoluble. This makes it possible to reduce the amount of water-insoluble solvent used in the entire mixture including the binder and filler, and contributes to environmentally friendly green procurement in material procurement.

[0017] In the above-mentioned method for producing a pattern print, the coating agents are different types of coating agents having different component compositions, and in the injection process, the different types of coating agents may be injected into the hole pattern of the screen plate by using the pressure containers filled with the different types of coating agents simultaneously or by switching between them. In this case, a pattern print having a more complicated configuration can be produced. In conventional screen printing, after printing one type of material, a different type of material is printed by overprinting using another screen plate after baking and drying once. The reason is that if one type of material is printed and then overprinted without baking and drying, the first pattern print will be crushed or will adhere to another screen plate during overprinting due to its half-dried state. In addition, even if drying is included, if overprinting is performed on a pattern with a high aspect ratio, the overprinted part will bleed or adhesion will be poor. However, in the above-mentioned method for producing a pattern print, it is possible to avoid the above-mentioned problems of conventional screen printing and at the same time, to complete the baking and drying process, for example, in one go.

[0018] In the above method for manufacturing a pattern print, the substrate has holes on the surface side of the substrate in which electronic components are arranged, and via holes extending from the surface of the substrate to the back side, and in the injecting step, a conductive coating agent is injected into the holes and the via holes, and the electronic components are mounted and connected by the conductive coating agent, and the conductive coating agent is filled into the via holes. In this case, the mounting of the electronic components and the filling of the via holes can be performed in a printing step using the same coating agent, and a product having stable conductivity can be manufactured. In addition, by mounting the electronic components and filling the via holes in the same printing step, the manufacturing time can be shortened, and the manufacturing cost can be reduced accordingly. In the above case, a back wiring may be provided in the area where the via holes are exposed on the back side of the substrate, and in the injecting step, the conductive filler may be connected to the back wiring when the conductive coating agent is injected into the via holes and the conductive coating agent is filled into the via holes.

[0019] In the above method for producing a pattern print, a recess may be formed on the surface of the pattern print at a position corresponding to the intersection of the screen mesh of the screen plate, and a protrusion may be formed on the surface of the pattern print at a position corresponding to the opening of the screen plate. In this case, the cross-sectional shape of the coating agent formed on the substrate can be made closer to a rectangle, and a pattern print with a high aspect ratio can be easily obtained. In the above case, the width of the recess may be 10 μm or more and 40 μm or less, and the top surface of the protrusion may be a square with a side length of 20 μm or more and 210 μm or less. The "square" here includes not only the case where the lengths of adjacent sides are completely the same, but also the case where the lengths of adjacent sides are shifted by ±10%. In addition, the mesh part of the screen plate may have a different shape, such as a line, and the marks of the part corresponding to the mesh may become recesses.

[0020] Another aspect of the present invention relates to a pattern print. This pattern print includes a substrate and a print pattern formed from a coating agent and printed on the substrate. In this pattern print, recesses are formed on the surface of the print pattern at positions corresponding to the intersections of the screen mesh of the screen plate used for printing, and protrusions are formed on the surface of the print pattern at positions corresponding to the openings of the screen plate. In this pattern print, the cross-sectional shape of each print may be trapezoidal or rectangular, and the ratio of the length of the upper surface to the lower surface on the substrate side may be 70% or more.

[0021] In the above-mentioned pattern printed matter, the coating agent used as the printing ink contains a solvent that is incompatible with the binder, and as described above, the cohesive failure of the coating agent is suppressed during the manufacturing process. Therefore, with this pattern printed matter, it is possible to have a cross-sectional shape that is closer to a rectangle and to increase the aspect ratio.

[0022] In the above pattern print, the width of the recesses may be 10 μm or more and 40 μm or less, and the top faces of the protrusions may be squares with a side length of 20 μm or more and 210 μm or less. In addition, the mesh part of the screen plate may have a different shape, such as parallel lines, and the marks of the parts corresponding to the mesh may become the recesses.

[0023] In the above-mentioned pattern printed matter, the substrate may be a stretchable substrate, the coating agent may be a conductive coating agent, and the printed pattern may be a stretchable conductive pattern wiring. In this case, a pattern printed matter having a stretchable wiring circuit can be obtained.

[0024] The pattern printed matter may further include an electronic component disposed on or within the substrate, and the electronic component may be mounted on the substrate with a conductive coating material. In this case, a module product with a high aspect ratio can be obtained. Effect of the Invention

[0025] According to the present invention, it is possible to provide a method for manufacturing a pattern printed matter capable of performing pattern printing with a high aspect ratio, and a printed matter. [Brief description of the drawings]

[0026] [Figure 1] FIG. 1 is a cross-sectional view for explaining a step of injecting a coating agent in a method for producing a pattern printed matter according to this embodiment. [Diagram 2] FIG. 2 is a cross-sectional view illustrating a step of sweeping and removing the coating agent with a squeegee in the method for producing a pattern-printed item according to this embodiment. [Diagram 3] FIG. 3 is a diagram showing various printing methods that can be applied to the method for producing a pattern printed matter according to this embodiment, and describes the effects of using each printing method. [Figure 4] FIG. 4 is a diagram showing the shear force generated between the opening of the mask and the coating material. [Diagram 5]FIG. 5 is a cross-sectional view for explaining in more detail the injection step in the method for producing a pattern-printed item according to this embodiment. [Figure 6] FIG. 6 is a cross-sectional view for explaining in more detail the injection step in the method for producing a pattern printed matter according to this embodiment. [Figure 7] FIG. 7 is a cross-sectional view for explaining in more detail the squeegee sweeping removal step in the method for producing a pattern-printed matter according to this embodiment. [Figure 8] FIG. 8 is a diagram showing the characteristics of a printed surface by a general printing method. [Figure 9] FIG. 9 is a diagram showing the characteristics of the printed surface by the printing method according to this embodiment. [Figure 10] FIG. 10 is a diagram showing an injection process when producing a pattern printed matter according to the first embodiment. [Figure 11] FIG. 11 is a diagram showing a squeegee sweeping removal step when producing a pattern printed matter according to the first embodiment. [Figure 12] FIG. 12 is an observation view showing the results of the manufacturing method of the pattern printed matter according to Example 1. [Figure 13] FIG. 13 is an observation view showing the results of the manufacturing method of the pattern printed matter according to Comparative Example 1. As shown in FIG. [Figure 14] FIG. 14 is an observation view showing a wiring pattern produced by the method for producing a pattern printed matter according to the second embodiment. [Figure 15] FIG. 15 is an observation view showing a wiring pattern produced by the method for producing a pattern printed matter according to Comparative Example 2. As shown in FIG. [Figure 16] FIG. 16 is a process outline diagram of a printing method in a method for producing a pattern printed matter according to the third embodiment. [Figure 17] FIG. 17 is a process outline diagram of a printing method in a method for producing a pattern printed matter according to the third embodiment. [Figure 18] FIG. 18 is a diagram showing a pattern print according to the third embodiment. [Figure 19] FIG. 19 is a diagram showing a pattern print according to the third embodiment. [Figure 20]FIG. 20 is a cross-sectional view for explaining a method for producing a pattern printed matter according to the fourth embodiment. [Figure 21] FIG. 21 is a cross-sectional view for explaining a method for producing a pattern print according to the fourth embodiment. [Figure 22] FIG. 22 is a cross-sectional view for explaining the occurrence of cohesive failure in a typical screen printing method. [Diagram 23] FIG. 23 is a cross-sectional view for explaining various printing methods in a general screen printing method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] Hereinafter, a method for producing a pattern printed matter and a pattern printed matter according to an embodiment of the present invention will be described in detail with reference to the drawings. In the description, the same reference numerals may be used for the same elements or elements having the same functions, and duplicated descriptions will be omitted.

[0028] FIG. 1 is a diagram showing a step of injecting a coating agent in the method for producing a pattern printed product according to this embodiment. FIG. 2 is a diagram showing a step of sweeping and removing the overflowing coating agent with a squeegee in the method for producing a pattern printed product according to this embodiment. The method for producing a pattern printed product according to this embodiment includes: (a) a step of preparing a coating agent containing a filler, a binder, and a solvent incompatible with the binder as a printing ink; (b) a step of bonding a substrate to the back surface of a screen plate having a hole pattern; (c) a step of injecting the coating agent into the hole pattern from the front surface side of the screen plate using a pressure vessel filled with the coating agent; (d) a step of sweeping and removing the coating agent overflowing from the hole pattern with a squeegee after the injecting step; and (e) a step of peeling the substrate from the screen plate after the sweeping and removing step. In the sweeping and removing step, pressure is applied to the coating agent in the hole pattern from the front surface side of the screen plate by the squeegee.

[0029] The method for producing a pattern print according to this embodiment includes a printing method generally called screen printing or metal mask printing, and will be described in detail later. First, a coating agent 10 containing a filler, a binder, and a solvent incompatible with the binder is prepared as a printing ink. In addition, a pressurized container 20 for pressurizing and applying the coating agent 10, a screen plate 30 for printing the coating agent 10 in a predetermined pattern, and a substrate 40 on which a printed pattern coated with the coating agent is formed are prepared. The pressurized container 20 has a slit 22 at its lower end that is horizontally long (in a direction perpendicular to the paper surface of FIG. 1, etc.) and matches the printing width. The coating agent 10 filled in the pressurized container 20 is applied onto the screen plate 30 through the slit 22. The screen plate 30 has a hole pattern 32. The hole pattern 32 corresponds to a pattern of a conductor or the like to be printed on the substrate 40, and penetrates between the front surface 30a and the back surface 30b of the screen plate 30.

[0030] Next, the base material 40 is attached to the rear surface 30b of the screen plate 30 on which the hole pattern 32 is provided.

[0031] Next, the coating agent 10 is injected into the hole pattern 32 from the surface 30a side of the screen plate 30 using the pressurized container 20 filled with the coating agent 10. At this time, the coating agent 10 filled in the pressurized container 20 is brought into close contact with the surface 30a of the screen plate 30 (see (a) of FIG. 1), and the internal pressure of the pressurized container 20 is increased to sweep the coating agent 10 while filling it into the hole pattern 32 of the screen plate 30 (see (b) of FIG. 1), and printing is performed on the substrate 40. For example, a syringe can be used as the pressurized container 20. During this injection, in addition to the coating agent 12 injected into the hole pattern 32, a part of the coating agent 10 that is not injected into the hole pattern 32 and protrudes remains on the surface 30a of the screen plate 30 (not shown in FIG. 1; see (a) of FIG. 2).

[0032] Next, when the injection of the coating agent is completed, the coating agent 14 that has overflowed from the hole pattern 32 is swept and removed by the squeegee 50, as shown in (a) of FIG. 2. At this time, after printing by the pressure filling method, the squeegee 50 sweeps the plate surface (surface 30a) of the screen plate 30 in the direction of the arrow. At this time, the squeegee 50 sweeps while tilting at a predetermined angle. Then, as shown in (b) of FIG. 2, the coating agent 14 that has leaked from the hole pattern 32 is removed and collected from the plate surface (surface 30a). The screen plate 30 may be composed of a screen plate, or may be composed of a plate in which a metal mask and a metal mesh are bonded together, or may be composed of a metal mask plate, and in this embodiment, these are collectively referred to as the screen plate. In this embodiment, the coating agent can be removed and collected regardless of whether the screen plate 30 has any of the above-mentioned configurations.

[0033] Next, when the sweeping and removal by the squeegee is completed, the substrate 40 is peeled off from the screen plate 30. As a result, a pattern print corresponding to the hole pattern 32 of the screen plate 30 is formed on the substrate 40.

[0034] In the printing method according to the present embodiment, for example, when the screen plate 30A shown in (a) of FIG. 3 is used, at the interface H between the filled coating agent 12 and the opening 32a and mesh 34A of the mask 32A, the pressure of the squeegee 50 and the pushing back pressure from the substrate 40 occur, causing a part of the additive (the above-mentioned solvent) in the coating agent 12 to seep out to the surface as a lubricant. This mechanism is because, as shown in FIG. 6, the filling pressure of the coating agent 10 causes a part of the additive 16 contained in the coating agent 10 to seep out to the surface as a lubricant, and the edge 32a of the hole pattern 32, the substrate 40, and the mesh 34 are covered with the lubricant. Therefore, the peeling of the coating agent 12 from the mask interface is promoted by the sweeping removal by the squeegee that applies the above-mentioned pressure, and the coating agent 12 is transferred onto the substrate 40 without causing cohesive failure. However, at the interface with the substrate 40, the inherent adhesive strength of the coating agent 12, the absorptivity of the lubricant at the interface with the substrate 40, the pressure due to the pressure of the squeegee 50, and the like contribute to adhesion to the substrate 40. The material of the substrate 40 can be selected from materials that improve adhesion to the coating agent 12, such as a porous material.

[0035] In addition, when a dispenser is used as the pressurized container 20 of the pressurized filling method, as shown in FIG. 3, the coating agent leaking from the contact point between the screen plate 30A, the screen plate 30B formed by bonding the metal mask 32B and the metal mesh 34B, the metal mask plate 30C, and the tip of the dispenser, and the coating agent leaking from the opening 32a of the mask can be removed from the plate surface by sweeping with the squeegee 50 and collected. When sweeping with the squeegee, a part of the additive in the coating agent 12 seeps out to the intersection with the screen mesh 34A as a lubricant, and this part becomes a recess 12a as shown in FIG. 3(a). A similar recess 12a is also formed in the metal mesh 34B shown in FIG. 3(b). According to the manufacturing method of the pattern printed matter of this embodiment, such a shape is generated. When cohesive failure occurs as shown in FIG. 22, the cross-sectional shape of the print is a kamaboko shape, but in contrast, in the method described in FIG. 3, cohesive failure does not occur, so the cross-sectional shape is not a kamaboko shape, but a rectangular shape with a recess 12a on the upper surface.

[0036] In addition, in a conventional general contact type pressure printing method (with injection as shown in FIG. 1 and without squeegee sweep as shown in FIG. 2), the coating agent filled in a pressure container with a slit corresponding to the horizontal printing width is brought into contact with the screen plate, the internal pressure of the pressure container is increased, and the coating agent is swept while filling the hole pattern of the screen plate, and printing is performed on the substrate. In this method, the screen plate 230A formed by bonding a metal mask 232A and a metal mesh 234A shown in FIG. 23(a), the plate 230B formed by bonding a metal mask 232B and a metal mesh 234B shown in FIG. 23(b), and the metal mask plate 230C shown in FIG. 23(c) each similarly remain in contact with the interface H4 between the filled coating agent 212 and the mesh of the opening 232a of the mask and the mask, which may cause cohesive failure as shown in FIG. 22. As a result, a large amount of the coating agent remains on the screen plate without being transferred to the substrate 240. However, according to the manufacturing method of this embodiment, such cohesive failure can be suppressed.

[0037] (Coating agent) Next, the coating agent used in the printing method according to this embodiment will be described in more detail, including its components and effects. The coating agent that can be used in this embodiment is a printing ink that contains a filler, a binder, and an additive (an incompatible solvent) that is incompatible with the binder. The binder contained in the coating agent contains at least a base material such as a resin, and may contain a solvent for dissolving the base material. Note that the binder may contain a solvent for dissolving the base material before becoming the coating agent used in this embodiment, and part or all of this solvent may be replaced with an incompatible additive.

[0038] Fillers used in the coating materials 10 and 12 include inorganic fillers and organic fillers.

[0039] Inorganic filler is a metal filler or a non-metal filler. Organic filler is a filler mainly made of a polymer composition. The metals constituting metal filler include precious metals and base metals, such as precious metals such as gold, silver, platinum, and palladium, and base metals such as iron, copper, nickel, aluminum, lead, zinc, tin, tungsten, molybdenum, tantalum, magnesium, cobalt, bismuth, cadmium, titanium, zirconium, antimony, manganese, beryllium, chromium, germanium, vanadium, gallium, hafnium, indium, niobium, rhenium, and thallium.

[0040] The nonmetals that make up nonmetallic fillers are elements other than the metals mentioned above. For example, when classified by reactivity, reactive nonmetals include hydrogen, carbon, nitrogen, oxygen, fluorine, phosphorus, sulfur, chlorine, bromine, selenium, iodine, and astatine; noble gases include helium, neon, argon, krypton, xenon, and radon; and semimetals that have chemical properties like nonmetals include boron, silicon, germanium, arsenic, antimony, and tellurium.

[0041] Furthermore, inorganic fillers include fillers made of a substance in which a plurality of elements are chemically bonded, such as calcium carbonate, silica, carbon black, graphite, carbon nanotubes, alumina, aluminum nitride, boron nitride, beryllia, barium titanate, lead zirconate titanate, ferrite, CMC, titanium oxide, glass beads, magnesium oxide, hydrotalcite, MOS, barium sulfate, titanium oxide, zinc oxide, iron oxide, calcium oxide, magnesium oxide, zeolite, calcium oxide, and magnesium oxide.

[0042] The polymer compound constituting the organic filler is a linear polymer compound formed by chemically bonding the above-mentioned inorganic fillers in a one-dimensional structure through chemical reactions such as addition polymerization, condensation polymerization, addition condensation, and covalent bonding to form a thread-like or chain-like structure, or a network-like polymer compound having a three-dimensional structure bonded by covalent bonds or the like.

[0043] The inorganic filler used in the coating materials 10 and 12 may be an inorganic compound in which copper, silver, silicon, etc. are chemically bonded with oxygen, hydrogen, carbon, etc., and may be a filler based on a metal atom having electrical conductivity or thermal conductivity, and is particularly preferably a filler having a siloxane bond, etc. The organic filler may be a polymer having a urethane bond such as polyurethane, which is usually produced by polyaddition of a compound having an isocyanate group and a hydroxyl group, and may be a urethane resin having a bond via urethane (-NH·CO·O-), or a synthetic resin made of a polymer of acrylic acid ester or methacrylic acid ester, such as urethane rubber acrylic resin, or a polymer compound having an amide bond (the same bond as protein).

[0044] Any of the fillers may be in any shape, such as spherical, flat, needle-like, or polygonal, and the particle size of the filler is preferably from 0.1 μm to several tens of μm.

[0045] The binder used in the coating materials 10 and 12 is, for example, a thermosetting resin, a photocurable resin, or a thermoplastic resin.

[0046] The thermosetting resins used in the binder are in a state before chemical reactions such as addition polymerization, condensation polymerization, covalent bonding of the organic fillers mentioned above. These resins are phenolic resins, amino resins, unsaturated polyester resins, epoxy resins, silicone rubbers, etc., in which relatively low molecular weight substances become three-dimensional cross-linked structures (network structures) of polymers when heated, and once hardened, they do not soften again even when heated. Thermosetting resins have a wide range of reaction temperatures from room temperature to high temperatures, and react by addition polymerization, condensation polymerization, addition condensation, covalent bonding, etc. For example, elastomers such as silicone rubber are mainly made of polyorganosiloxane (silicone polymer) with siloxane bonds (Si-O-) in which silicon atoms and oxygen atoms are arranged alternately as the polymer skeleton (main chain), but can be divided into HTV (High Temperature Vulcanizing rubber), LTV (Low Temperature Vulcanizing rubber), and RTV (Room Temperature Vulcanizing rubber). The curing temperature of HTV is 140℃ or higher, that of LTV is 40℃~140℃, and that of RTV is 0℃~40℃, but due to diversification, the boundary between HTV and LTV has disappeared, and they are often simply divided into heat curing and room temperature curing types. Also, depending on the properties before curing, they can be divided into solid millable type (HCR; High Consistency Rubber) and liquid type, and the liquid type includes LSR (Liquid Silicone Rubber) and RTV products. While HCR uses linear rubber with a degree of polymerization of about 5000~10000, liquid silicone rubber (LSR, RTV) mainly contains linear polymers with a degree of polymerization of about 100~2000. Furthermore, depending on the crosslinking mechanism, they can be classified into peroxide curing, addition reaction curing, and condensation reaction curing.

[0047] The photocurable resin used in the binder is a resin that polymerizes and hardens when exposed to light of a specific wavelength. In other words, the binder is a thermosetting resin, a photocurable resin, a hot air drying resin, or the like, before the above-mentioned chemical reaction or before fixing or bonding.

[0048] As the binder used in the coating agent, resins having rubber elasticity and porosity, such as polyurethane-based thermoplastic elastomers, which are block copolymers having urethane bonds, thermoplastic polyurethanes, thermosetting urethane elastomers, polyester-based, acrylic rubber and polypropylene, acrylic elastomers composed mainly of polyester, and thermoplastic elastomers having block copolymers of methyl methacrylate and butyl acrylate, can be used. More preferably, a material containing siloxane is used as the binder. Siloxane refers to a state in which silicon (Si) and oxygen (O) are alternately bonded to form a polymer, and is the main skeleton of silicone, called a siloxane bond. In particular, silicone elastomers with a siloxane compound as the skeleton can make the characteristics of the coating agent in this embodiment more effective.

[0049] The coating agents 10 and 12 used in this embodiment are defined based on a concept completely different from that of printing inks used in general printing applications. General printing inks are used by mixing a solvent with a small difference in solubility parameter (SP or SP value, hereinafter abbreviated as "SP value") with respect to the main agent of the binder contained in the printing ink. Two components with a small difference in SP value are easy to mix (high solubility), so that the handling during printing, the smoothness of the printed matter, and the adhesion to the printed matter can be ensured. However, in the pattern printing method according to this embodiment, unlike the concept of general printing inks, an additive with a large difference in SP value is used with respect to the inorganic filler or organic filler and / or binder contained in the coating agent, and in this embodiment, the additive can be made to ooze out as a lubricant by the filling pressure.

[0050] For example, as described above, when a silicone elastomer having a siloxane compound as a skeleton is used as the binder of the coating agents 10 and 12, since the binder is water-insoluble, it is preferable to use a water-soluble solvent as an additive. That is, the additive is a solvent that is incompatible with the binder. Furthermore, since the elastomer has rubber elasticity and porosity, the water-soluble solvent penetrates and is impregnated into the porous material. By using such a coating agent for printing, the impregnated additive seeps out of the coating agent 12 due to the pressure and shear applied to the coating agent, forms a coating at the interface between the screen plate 30 and the coating agent 12, and exhibits slipperiness as a lubricant. When the mixture of the filler and the binder is taken as 100% by weight, it is preferable that such an incompatible solvent is at least 0.1% by weight to 30% by weight, and it is more preferable if it can be controlled to be 5% by weight to 13% by weight.

[0051] The amount of the incompatible solvent (additive) to be mixed can be determined by an adjustment method in which, for example, when the existing solvent contained in the mixture containing the binder and filler to be mixed is a water-insoluble solvent and is 9% by weight, the content of the water-insoluble solvent is reduced to a content less than 9% by weight (including 0% by weight), and the reduced amount is replaced with a water-soluble solvent. In this case, the water-soluble solvent can be up to 9% by weight. Alternatively, in this case, for example, the water-insoluble solvent may be reduced to 4% by weight or less, and the remaining portion, which is 5% by weight or more and is greater than 4% by weight, may be replaced with an incompatible water-soluble solvent. Furthermore, depending on the molecular size of the mixture containing the binder and filler, the amount of the solvent to be added may be adjusted to 9% by weight or more of the entire mixture. The amount of the incompatible solvent to be added can be determined by, for example, measuring a mixture containing the target binder and filler using a heat-drying moisture meter or the like at a temperature rise of 160°C and determining the amount of evaporation when the solvent evaporation rate becomes 0.02% / min or less, as the total amount of existing solvent contained in the entire mixture, and adjusting the amounts of the filler, binder, and water-soluble solvent that is incompatible with the binder based on the weight percentage of the solvent.

[0052] Furthermore, in order to confirm the amount of solvent that can be impregnated into a mixture containing a target binder and filler according to the size of the molecule, an incompatible solvent is added in excess to the target mixture and kneaded, and the mixture after a certain deliquification process is measured using a heat-drying moisture meter or the like to determine the maximum amount of incompatible impregnating solvent that can impregnate the entire mixture. The range of the above-mentioned solvent mixture amount of 0.1% by weight to 30% by weight is a value determined from such a process. For example, when using the stretchable silver paste "DOTITE XA-9476" manufactured by Fujikura Kasei Co., Ltd., the existing solvent amount is 9% by weight and the maximum impregnating solvent amount is 13%, and when using ELASTOSIL LR 3162 manufactured by Asahi Kasei Wacker Co., Ltd., the existing solvent amount is 1% or less and the maximum impregnating solvent amount is 30%. Note that coating agents in a state exceeding the maximum impregnating solvent amount are not preferable because they may affect print transferability and drying time.

[0053] An example of the configuration of the coating agents 10 and 12 used in this embodiment is a configuration in which a conductive material such as silver or carbon is used as a filler, a silicone polymer dissolved in a solvent (e.g., a chain siloxane such as dimethylsiloxane or dodecamethylpentasiloxane, or a cyclic siloxane such as octadecamethylcyclononasiloxane) or normal undecane or other solvents mainly containing aliphatic hydrogen, etc., is used as a binder, and an additive is added to these. In this case, since the binder is water-insoluble, the additive is water-soluble.

[0054] The coating agent used in this embodiment will be described using a mixture of rubber (binder) and oil (additive) as an example. When rubber (binder) and oil (additive) are mixed, the rubber swells. This is a phenomenon in which oil gets between the molecules of rubber. If the oil (additive) is easily mixed with the rubber (binder), it swells, and if it is difficult to mix with the rubber (binder), it is difficult to swell. Even if it gets between the molecules of the rubber (binder), it will seep out onto the rubber surface under an environment such as compression. In other words, when the binder of the coating agent is non-water-soluble, by adding a water-soluble solvent additive, substances with different polarities and substances with a large difference in SP value are difficult to mix with each other, so a state is formed in which the additive, which is a water-soluble solvent, seeps out onto the coating agent surface. When the binder of the coating agent is water-soluble, a non-water-soluble solvent is used as the additive. Then, by the same mechanism as described above, the non-water-soluble solvent seeps out onto the coating agent surface and acts as a lubricant.

[0055] The solvent and additives used in the coating agent may be a water-insoluble or water-soluble solvent. The solvent generally used in the printing ink used in the filling agent and printing method may be a composition containing a compound represented by the following formula (1) (excluding monohydroxystearic acid). R 1 -CH2-R2(1) (In the formula, R 1 represents a monohydroxyalkyl group, and R 2 indicates a carboxyl group (C(=O)OH) or an amide group (C(=O)NH2)

[0056] Specific examples of the solvent include n-heptane (SP value: 7.3), 2-(2-ethoxyethoxy)ethyl acetate (SP value: 9.0), ethylene glycol monoethyl ether acetate (SP value: 8.8), n-propanol (SP value: 11.8), 1,2,5,6-tetrahydrobenzyl alcohol (SP value: 11.3), diethylene glycol ethyl ether (SP value: 10.9), 3-methoxybutanol (SP value: 10.9), triacetin (SP value: 10.2), propylene glycol monomethyl ether (SP value: 10.2), cyclohexane (SP value: 10.2), and cyclohexane (SP value: 10.2). Pentanone (SP value: 10.0), γ-butyrolactone (SP value: 9.9), cyclohexanone (SP value: 9.9), propylene glycol-n-propyl ether (SP value: 9.8), propylene glycol-n-butyl ether (SP value: 9.7), dipropylene glycol methyl ether (SP value: 9.7), 1,4-butanediol diacetate (SP value: 9.6), 3-methoxybutyl acetate (SP value: 8.7), propylene glycol diacetate (SP value: 9.6), ethyl lactate acetate (SP value: 9.6), ε-capric acid Lactone (SP value: 9.6), 1,3-butylene glycol diacetate (SP value: 9.5), dipropylene glycol-n-propyl ether (SP value: 9.5), 1,6-hexanediol diacetate (SP value: 9.5), dipropylene glycol-n-butyl ether (SP value: 9.4), tripropylene glycol methyl ether (SP value: 9.4), tripropylene glycol-n-butyl ether (SP value: 9.3), undecane (SP value: 15.8), decane (SP value: 15.8), dodecane (SP value: 16.0), cyclohexanone (SP value: 16.0), Chlorohexanol acetate (SP value: 9.2), diethylene glycol monoethyl ether acetate (SP value: 9.0), ethylene glycol methyl ether acetate (SP value: 9.0), diethylene glycol monobutyl ether acetate (SP value: 8.9), ethylene glycol monobutyl ether acetate (SP value: 8.9), methyl acetate (SP value: 8.8), ethyl acetate (SP value: 8.7), propylene glycol monomethyl ether acetate (SP value: 8.7), n-propyl acetate (SP value: 8.7), dipropylene glycol methyl ether acetate (SP value: 8.7), 3-methoxybutanol acetate (SP value: 8.7), butyl acetate (SP value: 8.7), isopropyl acetate (SP value: 8.5), tetrahydrofuran (SP value: 8.3), dipropylene glycol methyl-n-butyl ether (SP value: 8.0), dipropylene glycol methyl-n-propyl ether (SP value: 8.0), dipropylene glycol dimethyl ether (SP value: 7.9), propylene glycol methyl-n-butyl ether (SP value: 7.8), propylene glycol methyl-n-propyl ether (SP value: 7.8), dimethylsiloxane (SP value: 7.5), etc. can be mentioned.

[0057] In the coating agent of this embodiment, the SP value is positioned as a reference for selecting a solvent, and first, it is determined whether the binder is water-insoluble or water-soluble, and then a solvent that is the exact opposite of the main solvent of the binder is added.

[0058] In this embodiment, "water-insoluble" and "water-soluble" can be defined by utilizing the definition of water-soluble liquids of Class 4 hazardous materials. Class 4 hazardous materials are flammable liquids. They are further divided into (a) those that dissolve in water (water-soluble) and (b) those that do not dissolve in water (water-insoluble). These are defined as follows in the government ordinance. A water-soluble liquid is one that maintains a uniform appearance when mixed with the same volume of pure water at 1 atmosphere and 20°C, and a water-insoluble liquid is one other than a water-soluble liquid. A water-insoluble liquid separates into two layers when mixed with water. If the specific gravity of the liquid is smaller than that of water, a water-insoluble layer is formed above the water layer, and if the specific gravity is larger than that of water, a water-insoluble layer is formed below the water layer. In the case of a water-soluble liquid, when mixed, the layers do not separate and become uniform. Some liquids are slightly soluble in water, such as diethyl ether, a special flammable material, and ethyl acetate, a first petroleum product, but are classified as water-insoluble by definition.

[0059] Therefore, when classified based on the above definition, the water-soluble solvents are, for example, 2-(2-ethoxyethoxy)ethyl acetate (SP value: 9.0), ethylene glycol monoethyl ether acetate (SP value: 8.8), n-propanol (SP value: 11.8), 1,2,5,6-tetrahydrobenzyl alcohol (SP value: 11.3), diethylene glycol ethyl ether (SP value: 10.9), 3-methoxybutanol (SP value: 10.9), propylene glycol monomethyl ether (SP value: 10.2), γ-butyrolactone (SP value: 9.9), propylene glycol-n-propyl ether (SP value: 9.8), dipropylene glycol methyl ether (SP value: 9.7), lactate ethyl acetate (SP value: 9.6). ), ε-caprolactone (SP value: 9.6), tripropylene glycol methyl ether (SP value: 9.4), tripropylene glycol-n-butyl ether (SP value: 9.3), diethylene glycol monoethyl ether acetate (SP value: 9.0), ethylene glycol methyl ether acetate (SP value: 9.0), diethyl ether acetate (SP value: 9.0) tetrahydrofuran (SP value: 8.3), dipropylene glycol methyl-n-butyl ether (SP value: 8.0), dipropylene glycol methyl-n-propyl ether (SP value: 8.0), dipropylene glycol dimethyl ether (SP value: 7.9), propylene glycol methyl-n-propyl ether (SP value: 7.8).

[0060] In addition, the non-aqueous solvents are undecane (SP value: 15.8), decane (SP value: 15.8), dodecane (SP value: 16.0), triacetin (SP value: 10.2), cyclopentanone (SP value: 10.0), cyclohexanone (SP value: 9.9), propylene glycol-n-butyl ether (SP value: 9.7), 1,4-butanediol diacetate (SP value: 9.6), 3-methoxybutyl acetate (SP value: 8.7), propylene glycol diacetate (SP value: 9.6), 1,3-butylene glycol diacetate (SP value: 9.5), dipropylene glycol-n-propyl ether (SP value: 9.5), 1,6-hexanediol diacetate (SP value: 9.5), and dipropylene glycol-n-butyl ether (SP value: 9.4). , cyclohexanol acetate (SP value: 9.2), diethylene glycol monobutyl ether acetate (SP value: 8.9), ethylene glycol monobutyl ether acetate (SP value: 8.9), methyl acetate (SP value: 8.8), ethyl acetate (SP value: 8.7), propylene glycol monomethyl ether acetate (SP value: 8.7), n-propyl acetate (SP value: 8.7), dipropylene glycol methyl ether acetate (SP value: 8.7), 3-methoxybutanol acetate (SP value: 8.7), butyl acetate (SP value: 8.7), isopropyl acetate (SP value: 8.5), propylene glycol methyl-n-butyl ether (SP value: 7.8), and dimethylsiloxane (SP value: 7.5).

[0061] When the total weight of the coating agent used in this embodiment is 100 parts, the filler may be 50 parts or more and 99.9 parts or less. That is, the filler may be 50% by weight or more and 99.9% by weight or less with respect to the entire coating agent. Specifically, the coating agent may be mainly composed of a filler, a silver paste, a copper paste, an insulating paste, etc. used for printing purposes.

[0062] The coating agents 10 and 12 used in this embodiment may contain a solvent that is compatible with the binder in addition to a solvent that is incompatible with the binder. The presence of a compatible solvent makes it possible to ensure adhesion, electrical conductivity, and other properties between the inorganic filler or the mixture of the organic filler and the binder and the printed material (substrate 40). In this case, the above-mentioned slipperiness can be obtained while maintaining such properties. If the amount added is outside the above range, the chemical bonds of the main agent, such as the elastomer, are damaged and separated, becoming physically brittle, making printing difficult. Even if printing is possible, there is a possibility that elasticity will be lost, or electrical conductivity and thermal conductivity will be significantly lost.

[0063] As described above, the coating agents 10 and 12 used in this embodiment are configured to produce an effect of causing the lubricant in the coating agents 10 and 12 to seep out when pressure is applied to the coating agents 10 and 12. That is, as shown in Fig. 4, when the coating agent 12 is pushed out onto the substrate 40 through the mesh 34A of the screen plate 30 and the mask 32A having a hole pattern, the shear S between the wall surface of the mask 32A of the opening 32a and the extruded coating agent 12 is reduced by the lubricant in the coating agent seeping out, and an effect of preventing cohesive failure can be achieved.

[0064] (Screen version) Next, the screen plate 30 used in this embodiment will be described in more detail. The screen plate 30 may be a screen plate using polyester fiber (e.g., Tetron (registered trademark)) used in general screen printing as a mesh and used as a mask to which a photosensitive emulsion is applied, a screen plate using stainless steel used in fine line printing as a mesh and used as a screen mask using a photosensitive emulsion, a metal mask formed by electroforming a nickel film using photolithography technology and bonding this mask and a stainless steel mesh by plating technology, a nickel film mask and a mesh also formed by nickel electroforming technology and bonded by plating technology, or a screen plate without a mesh, such as a metal mask in which holes are simply opened in stainless steel or nickel by laser or etching, may be used. Note that fine and complicated circuit patterns, patterns with closed circuits such as circles and squares, etc., can be produced by selecting and using any of the above-mentioned plates in consideration of rigidity, etc.

[0065] In this embodiment, the screen plate 30 can preferably be a plate in which a mesh and a mask are bonded together. More preferably, the screen plate 30 can be a screen plate in which a metal mesh made of stainless steel, nickel, or the like is bonded together with a metal mask made of stainless steel, nickel, or the like. When using a combination of a Tetron mesh and a mask using a photosensitive emulsion, the screen plate 30 tends to be compatible with the coating agents 10 and 12 according to this embodiment, depending on the non-aqueous solvent and the aqueous solvent contained in the coating agents 10 and 12. This may reduce the effect of slipperiness that occurs at the interface between the screen plate 30 used in this embodiment and the coating agents 10 and 12. However, when using Tetron (registered trademark) mesh, the plate may be coated in advance with a fluorine-based water- and oil-repellent coating agent, a hydrophilic coating, or the like. It may also be used with a metal mask, as it is more effective when used. The hydrophilic coating is particularly effective when a water-soluble solvent is added as a slipping agent to the coating materials 10, 12, and the slipping agent is retained in advance in the mask pattern formed on the screen plate 30 regardless of whether the mask is a photosensitive emulsion mask or a metal mask, further improving the printability of the printing method according to this embodiment. Furthermore, it becomes easier to clean the mask surface during printing with a sponge, Molton roller, etc. impregnated with the slipping agent, improving continuous printability.

[0066] The hydrophilic coating used here may be a polysaccharide composed of sugars such as galactose, arabinose, rhamnose, or glucuronic acid, whose main chain is a galactose chain with β-1,3 bonds. Materials containing such polysaccharides include, but are not limited to, gum arabic. Gum arabic has excellent emulsifying properties, and when dissolved in water, the emulsion preferentially adsorbs to the oil-water interface. When applied to the plate surface, the highly hydrophobic polypeptide chains can be easily adsorbed to the grooves of the hole pattern, which is a hydrophobic surface formed of a photosensitive resin or metal. On the other hand, the hydrophilic sugar chain portion of the gum arabic emulsion forms a film-like hydrophilic polysaccharide unit when completely dried on the screen plate surface. Such a strong hydrophilic polysaccharide unit allows the formation of a strong coating on the plate surface, in the plate grooves, and on the screen mesh surface, and also allows the expression of a strong lubricant retention ability and the cleaning resistance of the mask surface to be obtained. In addition, the hydrophilic coating containing the above-mentioned polysaccharides has the property of being soluble in pure water, toluene, and xylene-based solvents, making it easy to remove the coating after continuous printing and to re-form the hydrophilic coating.

[0067] The screen plate 30, in which a metal mask and a metal mesh are bonded together, is made by forming a mask using a technique for electroforming a nickel film using photolithography, and bonding the mask to a stainless steel mesh using plating. There is no particular restriction on the metal mask, but a mask of a general standard can be used. For example, a mask of the standard HS325-16-CAL17, mesh bias angle 22.5°, metal mask thickness 100 μm (nickel), mesh plating thickness 2 to 3 μm (manufactured by Ceria Corporation) is used, and a stainless steel mesh with 325 wires, wire diameter φ16 μm, mesh thickness reduced to 17 μm by a calendaring process is made into a metal mask with a film thickness of 100 μm using nickel electroforming technology. There is a plate in which this metal mask and a stainless steel mesh are bonded together with a mesh plating thickness of 2 to 3 μm.

[0068] In addition, the nickel film mask and mesh are also formed by nickel electroforming technology and then bonded together using plating technology. For example, a mesh is formed by nickel electroforming with a bias of 45°, and a metal mask is formed by nickel electroforming with a mask thickness of 200 μm (nickel), and then bonded together using nickel plating technology to create a plate.

[0069] In particular, the latter nickel mask is considered by some manufacturers to have an advantage in that the mesh shape, number of lines, line width, and bias can be changed at any point on the plate. In the printing method of this embodiment, it is particularly preferable to use a plate with a metal mesh and metal mask specification that has a mesh line count of 80 lines / inch to 730 lines / inch, a line diameter of 10 μm to 40 μm, a mesh bias angle in the range of 22.5° to 45°, an opening of 20 μm to 210 μm, a metal mask thickness of 100 μm or more, and an electroplating thickness of 2 μm or more.

[0070] (Injection of coating agent and sweeping with a squeegee) Here, referring to Fig. 5, Fig. 6 and Fig. 7, the coating agent injection step and the sweeping removal step by the squeegee in the printing method according to the present embodiment will be described in more detail. Here, the above-mentioned coating agents 10 and 12 are used, and a filling method using a pressurized container 20 such as a dispenser is performed. In the process shown in Figs. 5 to 7, unlike the conventional techniques (e.g., the methods described in Patent Documents 1 and 2), the coating agents having the above-mentioned configurations are used as the coating agents 10 and 12, and the coating agent 10 is injected into the hole pattern 32 from the end 32a of the hole pattern 32 formed in the screen plate 30 (screen plate 30A, plate 30B in which a metal mask and a metal mesh are bonded together, or metal mask plate 30C) while moving the tip of the pressurized container 20 in the direction of the arrow A1.

[0071] As shown in (a) of FIG. 5, by filling the hole pattern 32 with the coating agent 10 using the pressurized container 20, the slipperiness of the coating agent 10 is effective, and the coating agent 10 injected from the end 32a of the hole pattern 32 flows smoothly in the direction of the arrow A2 without a large pressure loss in the hole pattern 32 formed on the substrate 40 and the printing plate (screen plate 30A, plate 30B in which a metal mask and a metal mesh are bonded together, or metal mask plate 30C) by utilizing the slipperiness in the lateral direction. Then, as shown in (b) and (c) of FIG. 5, the coating agent 12 that has lost its place in the hole pattern 32 moves in the direction of the arrow A3, and finally seeps out from the metal mesh on the upper surface of the hole pattern 32, forming a seeping portion 14 of the coating agent.

[0072] Here, referring to FIG. 6, the reason why the slipperiness of the coating agents 10 and 12 shown in the above-mentioned process is effective will be described. As shown in FIG. 6, the coating agent 10 according to this embodiment is in a state in which inorganic or organic filler, binder, and additive 16 incompatible with the binder are finely contained therein. Therefore, when the coating agent 10 passes through a narrow discharge path 26 such as a pressurized container 20 (dispenser) that uses a pressurized filling method, a large pressure is applied to the coating agent 10. The additive 16 incompatible with the mixture (main agent) of inorganic or organic filler and binder has been in a state of balance with the mixture (main agent) of inorganic or organic filler and binder up until now, but is squeezed out by pressure from inside the coating agent 10 and seeps out to the surface H2, covering the end 32a of the hole pattern 32, the substrate 40, and the mesh 34. This process produces the effect of the slipperiness of the coating agents 10 and 12.

[0073] 7(a)-(c), the coating material 14 oozing out from the mesh 34 on the upper surface of the hole pattern 32 is swept in the direction of the arrow with a squeegee 50 at an arbitrary pressure (post-squeegee process). The pressure during the squeegee sweep is calculated based on the stress generated when the tip of the squeegee is dropped onto the surface of the screen mask at an attack angle of 60 degrees to 80 degrees with respect to the screen mask, and the screen mask is pushed in from the height at which the tip of the squeegee hits the screen by, for example, 0.5 mm to 3 mm. When a Mino Group squeegee is used, the pressure during this squeegee sweep varies according to the specifications of a flat squeegee (yellow) with a rubber hardness of 80 to 85 degrees, a rubber thickness of 9 mm, and a height of 50 mm. The squeegee 50 used here may have a flat, square, or sword-shaped tip, a rubber hardness of 55 to 85 degrees, a rubber thickness of 6 to 9 mm, and a height of 30 to 50 mm. The coating agent 14a swept by the squeegee 50 of this configuration is brought to the edge of the printing plate. At this time, the squeegee 50 sweeps the oozing portion 14 of the coating agent 12, and the lubricant in the coating agent 10, 12 oozes out to the surface due to the pressure of the squeegee 50 and the pushback from the substrate 40 at the opening of the mask and the mesh of the hole pattern 32. Therefore, it is possible to promote peeling from the interface H3 of the mask, and the process of transferring to the substrate 40 without causing cohesive failure as described above is possible.

[0074] Here, the characteristics of a conductive wiring pattern printed by the printing method according to the present embodiment will be described as an example with reference to Figures 8 and 9. Figure 8 is a diagram showing the characteristics of a printed surface by a general printing method, and Figure 9 is a diagram showing the characteristics of a printed surface by the printing method according to the present embodiment.

[0075] First, when a general conventional coating agent and screen printing are used, as shown in the left diagram of Fig. 8, cohesive failure occurs in the coating agent on the surface of the printed pattern, forming an uneven structure due to screen mesh marks 261 and mesh openings 262. Screen mesh marks refer to traces of passing through a screen mesh that remain as uneven shapes on the surface at the intersections of the screen mesh in the printed pattern. When a conventional coating agent and conventional screen printing are used, the mesh marks 261 become convex parts and the mesh openings 262 become concave parts.

[0076] In contrast, when the coating agent and printing method according to this embodiment are used, as shown in the left diagram of Fig. 9, the uneven structure formed on the surface of the printed pattern has the screen mesh marks 61 as recesses and the mesh opening marks 62 as protrusions, resulting in a structure in which the recesses and protrusions are reversed from the case in which a conventional coating agent and screen printing are used as shown in Fig. 8. The reason why the mesh marks become recesses in this way is that, as shown in Fig. 5, the parts corresponding to the mesh marks do not undergo cohesive failure due to the action of the lubricant oozing out of the coating agent.

[0077] As a specific example, the uneven structure formed will be described in detail using a screen plate having a mesh wire diameter of 16±2 μm and a mesh opening with a side length of 60±2 μm.

[0078] In the case of conventional coating material and screen printing, as shown in the right diagram of Figure 8, the width D1 of the screen mesh mark formed on the pattern surface was 11.3 μm, which is 62.8% to 80.7% smaller than the mesh wire diameter. The length L1 of one side of the mesh opening mark was 75.5 μm, which is 121.8% to 130.2% larger than the length of one side of the mesh opening. In the unevenness around the screen mesh mark, a gap (height difference) G1 of 22.17 μm was generated with the mesh opening mark as the bottom.

[0079] In contrast, on the printed surface when the coating agent and printing method according to this embodiment are used, the width D2 of the screen mesh marks formed on the pattern surface is 15.8 μm, which is 87.8% to 113% of the mesh wire diameter, and the length L2 of one side of the mesh opening mark is 63 μm, which is 101.6% to 108.6% of the side length of the mesh opening of the screen plate, as shown in the right diagram of Fig. 9. It can be seen that the dimensional change is small in the printing method according to this embodiment, as compared with the conventional case shown in Fig. 8, as shown in Fig. 9.

[0080] In addition, the gap (height difference) G2 between the bottom of the screen mesh mark and the mesh opening mark at the top (top surface) was as small as 3.89 μm, showing a shape that was very close to flat. In other words, this shows that the coating agent and printing method according to this embodiment make the width and height difference of the uneven parts on the printed surface smaller than those of the conventional method.

[0081] This is because, after filling in a pressurized container 20 (dispenser), the mesh marks on the printed surface and the unevenness formed by the mesh openings are smoothed and flattened by the rubber squeegee biting into the mesh openings in the post-squeegeeing process shown in FIG. 7. However, even if the post-squeegeeing is performed with a metal squeegee instead of a rubber squeegee, the characteristic that the mesh openings become convex parts remains the same. Therefore, the characteristic of the mesh marks formed on the pattern surface obtained in this embodiment is that the screen mesh marks become concave parts, the screen openings become convex parts, and the fluctuation range is small with respect to the mesh line width and the mesh openings with respect to the screen mesh dimensions, and the uneven structure is generated with approximately the same size. Also, this characteristic is that the screen mesh marks become concave parts, and the mesh openings become convex parts. From these results, in the pattern printing method according to this embodiment, the concave parts may be formed with a mesh mark width of 10 μm or more and 40 μm or less, and the top surface of the convex parts may be formed with the opening mark having a side length of 20 μm or more and 210 μm or less, and may be a square with a side length of 20 μm or more and 210 μm or less. Here, "square" includes not only cases where the lengths of adjacent sides are perfectly equal, but also cases where the lengths of adjacent sides are off by ±10%. Also, the mesh part of the screen may have a different shape, such as lines, and in this case, the traces of the parts that correspond to the mesh will also become recesses.

[0082] (Use of different coating agents) The coating agent swept and scraped off by the squeegee 50 can be collected and reused. This process will be shown in the examples below, but different types of coating agents may be made using the configuration of the coating agents 10 and 12 according to this embodiment, and these may be filled into the same hole pattern 32 from each syringe (pressurized container) in a single printing run. In this case, a process that previously required at least two printing runs to use different types of coating agents can be completed in a single run. Different types of coating agents may also be made and filled into separate hole patterns in the same plate simultaneously from each syringe.

[0083] Therefore, the above process is not limited to the general dispenser method, but can also be applied to printing methods that use a screen plate, a plate made by bonding a metal mask and a metal mesh, or a metal mask plate, such as a pressure filling method and general screen printing.

[0084] According to the printing method of this embodiment, a vertically steep pattern can be formed on the base material 40, making it possible to create a wiring pattern with the narrowest possible wiring gaps. In addition, since wiring printing with a high aspect ratio is possible, the surface area in the vertical direction can be increased. For example, this method can be applied to electrodes in a stripe shape that require a large reaction area.

[0085] Here, the effects of the printing method according to this embodiment will be described in comparison with the screen printing methods described in Patent Document 1 and Patent Document 2. The screen printing method described in Patent Document 1 is frequently used in a printing method that utilizes thixotropy due to shear in conventional printing technology. The method of Patent Document 1 is a printing means that utilizes the leveling property (smoothness) of the printed pattern after printing and the substrate transferability (cohesiveness) of the ink by maximizing the fluidity and adhesion of the ink. However, the printing method according to this embodiment does not require the effect of the leveling property of the ink aimed at correcting the distorted shape due to cohesive failure, which is the tearful separation between the screen plate and the ink in the conventional technology, since it prevents the cohesive failure of the screen plate and the ink during printing, and therefore does not require a process such as a preliminary squeegee operation. In other words, according to the screen printing method according to this embodiment, it is possible to present a printing mechanism that is completely different from the existing printing concept. The thixotropy referred to here is a property exhibited by a substance that is intermediate between a plastic solid such as a gel and a non-Newtonian liquid such as a sol, and the viscosity changes over time. Specifically, if it continues to be subjected to shear stress, its viscosity will gradually decrease and it will become liquid. If it stops, its viscosity will gradually increase and it will eventually become solid.

[0086] In addition, as described in Patent Document 2, the method of supplying the coating agent to the outside of the squeegee mechanism and squeegeeing while applying pressure with the squeegee mechanism can ensure good filling of the pattern holes. However, since the method described in Patent Document 2 also follows the concept of the above-mentioned printing ink of the conventional technology as it is, cohesive failure during printing cannot be avoided. In addition, supplying the coating agent to the outside of the squeegee mechanism and supplying it to the squeegee mechanism causes changes in the ink properties due to compression, shear, etc. of the printing ink by the supply path. The method according to this embodiment is different from the method according to this embodiment in that the effect of the method according to this embodiment is achieved by the final compression and shear of the discharge process of the screen plate and the dispenser nozzle. Furthermore, the screen printing method according to this embodiment hardly causes cohesive failure during printing due to the ink characteristics to be filled, the follow-up squeegee process after filling, and the surface treatment method of the plate used. It is also possible to partially perform multiple different types of ink in one printing process.

[0087] As described above, according to the method for producing a pattern print according to the present embodiment, the coating agents 10 and 12 used as printing inks contain a solvent 16 that is incompatible with the binder, and such coating agents are injected into the hole pattern 32, and then the squeegee 50 applies pressure to the coating agent 12 in the hole pattern 32. In this case, the incompatible solvent seeps out from the coating agent 12 to which pressure is applied by the squeegee 50 onto the surface of the coating agent 12 as a lubricant, and covers the surface of the printed coating agent 12. As a result, a film is formed between the inner walls of the hole pattern 32 of the screen plate 30 and the printed coating agent 12, and when the substrate 40 is peeled off from the screen plate 30, the coating agent 12 is transferred onto the substrate 40 without causing cohesive failure, and a pattern print having a cross-sectional shape closer to a rectangle can be obtained. As described above, according to the method for producing a pattern print, it is possible to perform pattern printing with a high aspect ratio.

[0088] In addition, according to the manufacturing method of the pattern print according to the present embodiment, when a wiring pattern is printed with the coating material 10, 12, which is a conductive material, the cross-sectional shape of the pattern can be made closer to a rectangle. In the case of a rectangle, the cross-sectional area of ​​the wiring pattern can be calculated by a simple formula such as "base dimension x height dimension", and in the case of a trapezoid, the cross-sectional area of ​​the wiring pattern can be calculated by a simple formula such as "(top dimension + base dimension) x height dimension ÷ 2". From this cross-sectional area, it becomes possible to easily calculate the wiring resistance value, etc. In addition, the cross-sectional shape of this pattern has a trapezoidal or rectangular shape, and the ratio of the length of the upper surface to the lower surface on the substrate side may be 70% or more of the lower surface. In addition, according to this manufacturing method, a printed pattern having a cross-sectional shape with a high aspect ratio (narrow base and high height) can be obtained, and the dimensional width (base dimension) can be reduced even with the same wiring resistance value, so that dense wiring such as electronic circuits can be consolidated into a small area, and more current can be passed through the wiring. Furthermore, since the height of the wiring pattern can be increased, the side area of ​​the wiring (height x longitudinal direction of the wiring) becomes larger, making it possible to increase the amount of electricity flowing between, for example, two parallel electrodes and a resistor embedded in the gap between them.

[0089] In addition, since the method for producing a pattern print according to this embodiment uses a screen printing method, it is possible to print complex and diverse patterns at high speed compared to a method of drawing a pattern by directly discharging a coating agent onto a substrate using a dispenser or the like. In other words, in the method of discharging a coating agent using a dispenser or the like, the patterns that can be formed are limited to stripe or line patterns, and there is a problem that the printing speed is slow and the cost is high, but according to the method according to this embodiment, it is possible to easily deal with various patterns, and it is possible to reduce the manufacturing cost by increasing the printing speed. The screen plate used here may be configured by combining a resin mask and a metal mesh, or may be configured by combining a resin mask and a resin mesh, or may be configured by combining a metal mask and a metal mesh.

[0090] In addition, according to the method for producing a pattern print according to the present embodiment, for example, a vertically steep printed pattern can be formed, so that it is possible to produce a wiring pattern with the wiring gap narrowed to the limit. Therefore, it is possible to produce wiring that passes more current and a wiring pattern with a large area per unit length of the vertically steep pattern side. For example, it is effective for heaters in which the larger the cross-sectional area between the electrodes, such as a circuit in which positive and negative electrodes are arranged alternately in parallel and a high-resistance heating element such as carbon is inserted between the positive and negative electrodes, and since electrodes that are high in the height direction and parallel to each other can be formed even with a narrow gap, it is possible to obtain particularly high efficiency in heat sinks with a high heat dissipation effect as the surface area increases, and thermoelectric conversion materials such as the Seebeck effect and the Peltier effect.

[0091] In addition, in the manufacturing method of the pattern print according to the present embodiment, the pressurized container 20 is a dispenser having a nozzle, and in the injection step, it is preferable to inject the coating agent 10 into the hole pattern 32 by pressure injection or scraping injection from the nozzle of the dispenser. In this case, pressure is also applied to the coating agent when the coating agent 10 is injected into the hole pattern 32 from the dispenser, and the incompatible solvent 16 oozes out from the coating agents 10 and 12 to which pressure is applied as a lubricant onto the surface of the coating agents 10 and 12, and covers the surface of the injected coating agent 12. Therefore, it is possible to further suppress the coating agent 12 from causing cohesive failure when the substrate 40 is peeled off from the screen plate 30, and it is possible to obtain a pattern print having a cross-sectional shape closer to a rectangle. As a result, it is possible to perform pattern printing with a high aspect ratio.

[0092] In addition, in the manufacturing method of the pattern print according to the present embodiment, at least one of the grooves, the front surface, and the back surface of the hole pattern 32 of the screen plate 30 may be coated with a hydrophilic coating or a water- and oil-repellent agent. When the solvent that is incompatible with the binder is water-soluble, coating with a hydrophilic coating results in a state in which the lubricant is held in advance in the grooves of the hole pattern 32 of the screen plate 30, and the cohesive failure of the coating agent 12 can be further suppressed. In this case, whether a photosensitive emulsion or a metal mask is used for the screen plate, the peelability is improved and the cohesive failure of the coating agent can be suppressed. In addition, if the water- and oil-repellent agent is coated on the screen plate, the peelability of the coating agents 10 and 12 can be improved in the same manner as above, and the cohesive failure of the coating agent 12 can be further suppressed. In addition, as the water- and oil-repellent agent, for example, a fluorine-based water- and oil-repellent agent can be used.

[0093] In addition, in the method for producing a pattern print according to this embodiment, the hydrophilic coating coated on the screen 30 preferably contains a polysaccharide whose main chain is composed of sugars containing at least one of galactose, arabinose, rhamnose, and glucuronic acid. Examples of materials containing such polysaccharides include gum arabic. Gum arabic has excellent emulsifying properties, and an emulsion dissolved in water has the property of preferentially adsorbing to the oil-water interface, so that highly hydrophobic polypeptide chains can be easily adsorbed to the grooves of the hole pattern, which is a hydrophobic surface formed of a photosensitive resin or metal. On the other hand, the hydrophilic sugar chain portion of the gum arabic emulsion forms a film-like hydrophilic polysaccharide unit when it dries completely on the screen surface. As a result, the lubricant is held in advance in the grooves of the hole pattern of the screen, and cohesive failure of the coating agent can be further suppressed.

[0094] In addition, in the method for producing a pattern print according to the present embodiment, the amount of the solvent 16 mixed is preferably 0.1% by weight or more and 30% by weight or less, assuming that the mixture containing the filler and binder is 100% by weight. It is more preferable that the amount of the solvent mixed can be controlled to 5% by weight or more and 13% by weight or less, relative to the above mixture. In this case, a sufficient amount of the solvent 16 can be ensured to seep out from the coating agent 12 that has been injected into the screen 30 and then subjected to pressure by sweeping and removing with the squeegee 50, and the seeped solvent 16 can more reliably suppress cohesive failure of the coating agent 12.

[0095] In the method for producing a pattern print according to the present embodiment, the coating agents 10 and 12 are different types of coating agents having different component compositions, and in the injection step, the different types of coating agents may be injected into the hole pattern of the screen by simultaneously using or switching between pressure vessels filled with the different types of coating agents. In this case, a pattern print having a more complicated structure can be produced. EXAMPLES

[0096] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to these examples.

[0097] Example 1 In order to confirm the usefulness of the coating composition according to the present invention, a silicone-based silicone elastomer film (film thickness 200 μm) was used as a substrate, and a conductive ink (filler: silver, binder: siloxane elastomer) made of Fujikura Chemical Industries' stretchable silver paste "Dotite XA-9476" was used.

[0098] As an additive, 2-(2-ethoxyethoxy)ethyl acetate (also known as diethylene glycol monoethyl ether acetate), a water-soluble solvent that is incompatible with the above-mentioned siloxane elastomer, was prepared. The conductive ink (mixture) was taken as 100% by weight, and the existing non-water-soluble solvent contained in the entire conductive ink was quantified to be 9% by weight using a heat-drying moisture meter. Therefore, the amount was reduced to 1% by weight, and 10% by weight of 2-(2-ethoxyethoxy)ethyl acetate was mixed with the above-mentioned conductive ink to create a coating agent.

[0099] Here, explanation will be made with reference to Fig. 10. First, a screen plate 30D with holes for a printing pattern was prepared by attaching a nickel film with a thickness of 20 µm to a metal mesh such as nickel. Next, the base material of the silicone elastomer film (thickness 200 µm) was set on the printing stage, and the screen plate 30D with a nickel film thickness of 200 µm was placed on top of it so that the nickel film surface and the silicone elastomer film were in close contact with each other.

[0100] Next, an arbitrary tapered needle was attached to the lower end of the syringe 20A filled with the coating material according to the above-mentioned Example 1, and this tapered needle was pressed vertically against the upper surface of the screen plate 30D, that is, the metal mesh side of nickel or the like, with a certain pressure, so that the tip opening of the tapered needle and the screen plate 30D were closely attached without any gaps. In this state, the supply pressure to the syringe 20A filled with the coating material was set to 350 kPa.

[0101] At the same time, syringe 20A was moved in the Y-axis direction at a sweep speed of 10 mm / s over screen plate 30D on which the pattern to be printed was formed. After the pattern to be printed was shifted a certain distance, syringe 20A was shifted 1 mm in the X-axis direction, and then moved in the Y-axis direction again at a supply pressure of 350 kPa and a sweep speed of 10 mm / s. The supply pressure and sweep speed can be adjusted as desired.

[0102] By repeating the above-mentioned traveling shift, the coating material 10 was injected into the screen holes over the entire pattern to be printed. In this case, the supply pressure, sweep speed, shift length, etc. can be changed as desired depending on the printing conditions.

[0103] As a result, the printing method of the present invention does not require the use of a large amount of coating agent, as in the conventional screen printing method, which prints a wide area of ​​the entire screen plate at once using a squeegee or a contact pressure printing method. However, when the coating agent is simply injected into the inside of the pattern to be printed, as shown in Figure 5, the injection into the sealed space of the pattern holes of the substrate and screen plate is carried out along the pattern groove, and if the coating agent loses a place to go in the pattern groove, it escapes upward from the opening of the screen plate 30D that is not covered by the tapered needle, and the upper surface of the screen plate 30D becomes slightly contaminated with the coating agent.

[0104] Therefore, in this embodiment, when the filling of the scattered patterns to be filled by the squeegee 50A is completed in whole or in part, the coating material 10 contaminated on the screen plate 30D is cleaned by sweeping the empty squeegee 50A at a constant vertical pressure and at a constant speed at an inclination of about 60 degrees with respect to the plate surface, as shown in FIG. 11. In this cleaning process, the additive contained in the coating material, which is a feature of the coating material according to the present invention, seeps out to the interface with the wall surface and mesh formed on the mask due to the vertical distortion of the screen plate 30D and compression into the pattern grooves due to biting into the base material, and functions as a lubricant to produce a peeling effect. The coating material swept away by cleaning can be recovered and reused.

[0105] Due to this effect, it was confirmed that when the substrate was peeled off from the screen plate, it was possible to print a wiring pattern with a large aspect ratio and a wide vertically-steep side surface area, with a rectangular cross-sectional shape that directly transfers the groove shape formed in the mask, with a line width of approximately 100 μm and a height of approximately 200 μm. Since it has become possible to print this wiring pattern, the problem of pattern collapse caused by cohesive failure between the screen plate pattern grooves and the coating agent, which was a problem with general screen printing up to now, has been almost completely eliminated, and it was confirmed that it is now possible to form a wiring pattern with a large aspect ratio and a desired rectangular or trapezoidal cross-sectional shape by arbitrarily changing the film thickness of the screen plate and the film thickness of the metal mask, in other words, the depth and width of the pattern grooves.

[0106] The aspect ratio depends on the film thickness of the plate, the depth and width of the pattern groove, as described above, but when the aspect ratio of the wiring is in the range of 0.1 to 10, it is useful for forming wiring patterns that emphasize the flexibility of the wiring pattern, the ability to follow distortion such as stretchability, robustness, and reliability such as sensors with excellent sensitivity and precision. For example, when the aspect ratio is in the range of 0.1 to 5, it is useful as an electrode for a heater for precision heating. Also, when the aspect ratio is in the range of 5 to 10, it can be used as an electrode for a heater for rapid heating. When the aspect ratio is in the range of 5 to 30, it is useful for forming a heat sink with high heat dissipation effect and a thermoelectric conversion element such as a Seebeck effect or a Peltier effect. When the aspect ratio is in the range of 20 to 40, it is useful for forming various MEMS.

[0107] Comparative Example 1 Next, we decided to print using only the silver paste "Dotite XA-9476" as the coating agent of Comparative Example 1, and prepared a printing screen plate by bonding the same nickel film with a thickness of 200 μm to a metal mesh such as nickel, with holes for the printing pattern.

[0108] Next, a substrate with a silicone elastomer film thickness of 200 μm was set on the printing stage, and a screen plate with a nickel film thickness of 200 μm attached to a metal mesh such as nickel was placed on top of it so that the nickel film surface and the silicone elastomer film were in close contact with each other.Furthermore, a syringe filled with the coating agent of Comparative Example 1 and equipped with an arbitrary tapered needle was pressed vertically with a constant pressure against the metal mesh side such as nickel, which is the upper surface of the screen plate, so that the tip opening of the tapered needle was in close contact with the screen plate without any gaps.

[0109] In this state, the supply pressure to the syringe filled with the coating material of Comparative Example 1 was set to 350 kPa, and at the same time, the syringe was moved in the Y-axis direction on the screen plate on which the pattern to be printed was formed at a sweep speed of 10 mm / s. Next, the pattern to be printed was shifted by 1 mm in the X-axis direction at a certain distance away, turned around, and the syringe was moved in the Y-axis direction at a supply pressure of 350 kPa and a sweep speed of 10 mm / s. By repeating this traveling shift in the above manner, the coating material of Comparative Example 1 was injected into the screen holes of the entire pattern to be printed.

[0110] As a result, it was confirmed that there was a clear difference between the printing results using the coating material of Example 1 and the printing results using the coating material of Comparative Example 1.

[0111] Fig. 12 shows a pattern observation diagram of the printing result of Example 1, and Fig. 13 shows a pattern observation diagram of the printing result of Comparative Example 1. The printing patterns compared were comb patterns with a pattern width of 125 μm on the plate side and a film thickness of 200 μm. In Fig. 12, the printing pattern 15 of Example 1 was a continuous line pattern with a pattern width of 99 μm and a height of 149 μm, and a cross-sectional shape of a rectangle or trapezoid.

[0112] In contrast, in the printing pattern 215 of Comparative Example 1 in Figure 13, due to the effect of cohesive failure when the plate and the substrate were peeled off, the coating agent filled in the plate grooves was not completely transferred to the substrate, resulting in numerous collapses in the pattern.

[0113] From the above, it has been confirmed that the printing method of the present invention, which involves injecting into the pattern engraved on the screen plate 30D using a dispenser or the like and then sweeping with a squeegee 50A after injection, can further suppress cohesive failure in the grooves of the screen plate.

[0114] Example 2 It was also confirmed that the effect could be enhanced by coating the grooves of the holes of the pattern engraved on the screen with a coating such as a water- and oil-repellent agent for metals or a hydrophilic coating, in which the lubricant in the coating agent promotes peeling from the mask interface. As a hydrophilic coating, a 0.16% aqueous solution of gum arabic (manufactured by Wako Pure Chemical Industries) was first prepared, and the aqueous solution was applied to the pattern grooves of the screen and the entire screen surface. This was then dried at room temperature to prepare a coating formed of hydrophilic polysaccharide units on the mask surface, pattern grooves, and mesh parts of the screen. This coating improved the ability to retain the lubricant and had the property of strongly repelling lipophilic ink. The effect is shown by comparing Figures 14 and 15. Figure 14 shows a sample prepared under the same conditions as Example 1 described above (Example 2), and Figure 15 shows a sample prepared under the same conditions as Comparative Example 1 described above (Comparative Example 2). Both wiring patterns have terminal patterns with a width of 150 μm, a height of 150 μm, and a size of 2 mm square, but it can be seen that wiring pattern 18 in Fig. 14 has small protrusions due to cohesive failure at the edges of the wiring pattern, whereas wiring pattern 218 in Fig. 15 has large protrusions due to cohesive failure at the edges of the pattern. In this way, it was confirmed that there is a difference in the details of the printed patterns of Example 2 and Comparative Example 2. Therefore, it was found that the printing method of the present invention is an effective means.

[0115] Example 3 Next, an example of printing using different types of coating agents will be shown as Example 3. First, a 200 μm-thick nickel film was attached to a metal mesh such as nickel to prepare a printing screen with holes for the printing pattern.

[0116] Next, the following coating agent A and coating agent B were prepared as coating agents for Example 3. Coating agent A was prepared by mixing silver-based Dotite XA-9476 with 2-(2-ethoxyethoxy)ethyl acetate, a water-soluble solvent incompatible with Dotite. Coating agent B was prepared by mixing carbon-based Wacker Asahi Kasei ELASTOSIL LR 3162, a high-resistance conductive elastomer with a volume resistivity of 80 Ω·cm, with 2-ethyl acetate, a water-soluble solvent incompatible with this elastomer. Coating agents A and B, which have such components, had different electrical properties.

[0117] Next, the above-mentioned silicone elastomer film is set on the printing stage, and the screen plate with nickel film thickness of 200 μm is placed on it so that the nickel film surface and the silicone elastomer film are in close contact with each other.Furthermore, the syringe filled with the coating agent A of the above-mentioned two kinds of coating agents of Example 2 and the one with the taper needle attached thereto is pressed vertically with a constant pressure from the metal mesh side of the nickel or the like, which is the upper surface of the screen plate, and is in close contact with the tip opening of the taper needle without any gap.

[0118] Next, a dispenser drawing program was created in advance using software attached to the IMAGEMASTER350PC manufactured by Musashi Engineering, which is a dispenser robot. A printing attempt was made by tracing along the pattern on the screen on which the pattern to be printed was formed using this drawing program, while the supply pressure to the syringe filled with the coating material of Example 2 was set to 350 kPa, and the syringe was swept at a sweep speed of 10 mm / s.

[0119] Fig. 16 shows a schematic diagram of the printing process according to Example 3. Screen pattern 80 shown in Fig. 16(a) is composed of a straight line pattern with a line width of 125 μm, a film thickness of 200 μm, and a length of 120 mm, and terminal patterns with a square shape of 2 mm and a film thickness of 200 μm provided on both ends of the straight line pattern.

[0120] 16(b), a dispenser containing coating agent A was used to discharge coating agent A into an area including the terminal portions at both ends of the screen pattern 80 and 10 mm on both sides connected to the terminal portions, thereby coating dispenser drawing portion 81 and forming coating pattern 82. The dispenser drawing program described above was used for drawing with the dispenser.

[0121] Next, as shown in (c) of Figure 16, a squeegee 50B was swept from top to bottom over the coating pattern 82, filling the approximately 10 mm portions at both ends of the straight line pattern and the terminal pattern with coating material A, thereby forming a scraping print 83.

[0122] Furthermore, while keeping the screen plate and the substrate in close contact, the dispenser was switched to one containing coating agent B, and coating agent B was discharged from the dispenser using a dispenser drawing program to the portion of the straight line pattern 84 that was not filled with coating agent A in the above process, excluding end portions 85 of about 10 mm on both ends (see FIG. 17(a)), to form a discharged pattern 2003 (see FIG. 17(b)). Then, as shown in FIG. 17(c), coating agent B was printed by sweeping the squeegee 50B from above to below the discharged pattern 86 in the same manner as the previous time. At this time, the squeegee 50B was sucked and cleaned before sweeping the different coating agents.

[0123] Next, the printed matter was peeled off from the screen plate and baked at 90°C for 30 minutes and 160°C for 60 minutes. As a result, a wiring sheet was formed in which high-resistance wiring sandwiched between silver terminals with good conductivity was drawn at once (see FIG. 18(a)). As a result, a sensor was formed in which the fluctuation of the high-resistance wiring caused by fixing both terminals and pulling both terminals (see FIG. 18(b)) can be read as a large resistance fluctuation value. Furthermore, according to Example 3, since a wiring with a high aspect ratio can be formed with a thick film, a strain sensor can be fabricated in which the resistance value change due to strain from the top of the wiring can be read, as shown in FIG. 19. Note that FIG. 19(a) is a diagram showing a cross section of the wiring pattern, and the resistance value of the wiring changes depending on the pressure by applying pressure to the central part of the wiring pattern in the direction of the arrow as shown in FIG. 19(b) to strain it. This can be used to make a strain sensor.

[0124] Example 4 Next, a case where the method for manufacturing a pattern printed matter according to the present invention is applied to the manufacture of a structure in which electronic components are embedded in a molded body is shown as Example 4. Fig. 20 shows how a screen plate 30E is attached to a molded body 90 (substrate) in which holes 92 and grooves 94 are provided, and coating material 10 filled in a syringe 20E is discharged from above the screen plate 30E.

[0125] First, a screen plate 30E was prepared by attaching a nickel film having a thickness of 200 μm to a metal mesh such as nickel, and opening holes for a printing pattern. As a coating agent for Example 3, a coating agent 10 was prepared by mixing Dotite XA-9476, which is mainly composed of silver, and 2-(2-ethoxyethoxy)ethyl acetate, a water-soluble solvent that is incompatible with Dotite.

[0126] Next, a molded body 90 made of a silicone resin molded body (acrylonitrile-butadiene-styrene resin is also acceptable) was prepared with an electronic component 95 such as a capacitor embedded in its surface. The molded body 90 had a groove 94 provided around the terminal of the electronic component 95, a hole 92 penetrating from the top surface to the bottom surface of the molded body 90, and a conductor 96 that covers the hole 92 on the bottom surface of the molded body 90.

[0127] Next, the nickel film surface of the screen plate 30E was placed so as to be in close contact with the molded body 90. An arbitrary tapered needle (not shown) was connected to the lower end of the syringe 20E, and this was pressed vertically with a constant pressure against the metal mesh side of the nickel or the like, which is the upper surface of the screen plate 30E, so that the tip opening of the tapered needle was placed in close contact with the metal mesh side without any gaps.

[0128] The syringe 20E was filled with the coating material of Example 4, and the supply pressure to the syringe 20E was adjusted by the discharge pressure depending on the line width and depth of the pattern to be printed. For example, a pressure P1 of 100 kPa was applied to a shallow pattern, a pressure P2 of 450 kPa was applied when passing through a hole 92 penetrating from the top to the bottom of the molded body 90, and a pressure P3 of 300 kPa was applied when passing through a medium-deep groove around which an electronic component such as a capacitor was buried.

[0129] In this way, conditions such as adjusting the pressure and slowing or speeding up the running speed of each arbitrary part of the syringe are created as the dispenser drawing program. Then, by printing according to this drawing program, the process of mounting electronic components 95 on a member in which the molded body 90 is embedded and the process of conducting the front and back of the molded body 90 by filling vias can be printed in one go, making it possible to reduce process costs (see FIG. 21).

[0130] According to the manufacturing method of the pattern print according to the fourth embodiment, the molded body 90 has a hole (groove 94) on the front side of the molded body 90 in which the electronic component 95 is arranged, and a via hole (hole 92) extending from the front side to the back side of the molded body 90. In the process of injecting the coating agent, a conductive coating agent is injected into the hole (groove 94) and the via hole (hole 92), and the electronic component 95 is mounted and connected by the conductive coating agent, and the conductive coating agent is filled into the via hole. In this case, the mounting of the electronic component 95 and the filling of the via hole (hole 92) can be performed in a printing process using the same coating agent, and a product having stable conductivity can be manufactured. In addition, by performing the mounting of the electronic component 95 and the filling of the via hole (hole 92) in the same printing process, the manufacturing time can be shortened, and the manufacturing cost can be reduced accordingly. In this case, a conductive wire 96 (rear wiring) is provided in the region where the via hole is exposed on the rear surface of the molded body 90, and in the injection process, the conductive coating material is injected into the via hole (hole 92) to fill the via hole with the conductive coating material, and the conductive filler is connected to the conductive wire 96. In this case, the rear surface of the molded body 90 and the conductive wire 96 can also be connected by an anchor effect.

[0131] As described above, according to the various printing methods of the present invention, it is possible to print a stretchable wiring pattern with a high aspect ratio, so that it is possible to reduce the risk of non-conductivity due to expansion and contraction when the wiring resistance value fluctuates greatly due to expansion and contraction, which may cause malfunction or when the metal filler in the wiring pattern is in contact with the metal filler, and a stable current can be passed. In addition, since different materials, for example low resistance and high resistance materials, can be drawn and connected within the same wiring or on the same plane, it is possible to easily create a sensor that utilizes the change in resistance value. Furthermore, since the dispenser conditions can be changed arbitrarily on the program during printing, it is easy to change the parts that require high filling and the parts where low filling is sufficient, and it is possible to easily manufacture a molded body in which electronic components are mounted and vias are filled. [Industrial Applicability]

[0132] The present invention can easily and inexpensively produce high-quality pattern prints in fields that require three-dimensional structures such as high-definition line patterns and stripe patterns with uniform film thickness. For example, the present invention can be used to form high-definition wiring patterns in small electronic components such as resistors and capacitors, color filters for liquid crystal display elements (LCDs), fuel cells, lithium ion batteries, stretchable electrodes, sensors, surface heaters, and electrode wiring for thermoelectric conversion materials, although the present invention is not limited thereto. [Explanation of symbols]

[0133] 10, 12... coating agent, 14... exudation portion, 16... additive (solvent), 20... pressurized container, 20A... syringe (pressurized container), 30, 30A to 30E... screen plate, 30a... front surface, 30b... back surface, 32... hole pattern, 40... substrate, 50, 50A, 50B... squeegee.

Claims

1. preparing a coating agent containing a filler, a binder, and a solvent that is incompatible with the binder as a printing ink; A step of attaching a substrate to the rear surface of the screen plate having the hole pattern; injecting the coating material into the hole pattern from the front surface side of the screen plate using a pressurized container filled with the coating material; a step of sweeping and removing the coating material that has overflowed from the hole pattern after the step of injecting with a squeegee; peeling the substrate from the screen after the sweeping and removing step; Equipped with In the sweeping and removing step, pressure is applied to the coating material in the hole pattern from the front surface side of the screen plate by the squeegee; At least one of the grooves of the hole pattern of the screen plate, the front surface, and the back surface is coated with a hydrophilic coating; The hydrophilic coating contains a polysaccharide whose main chain is composed of a sugar containing at least one of galactose, arabinose, rhamnose, and glucuronic acid, A method for producing pattern prints.

2. the pressurized container is a dispenser having a nozzle; In the step of injecting, the coating material is pressure-injected or scraped into the hole pattern from the nozzle of the dispenser. A method for producing the pattern print according to claim 1.

3. The amount of the solvent mixed is 0.1% by weight or more and 30% by weight or less when the mixture of the filler and the binder is 100% by weight. A method for producing the pattern print according to claim 1 or 2.

4. The binder is water-insoluble and the solvent is water-soluble. A method for producing the pattern print according to any one of claims 1 to 3.

5. The binder is water-soluble and the solvent is water-insoluble. A method for producing the pattern print according to any one of claims 1 to 3.

6. The coating agents are different types of coating agents each having a different component composition, In the injecting step, the pressure containers filled with the different types of coating agents are used simultaneously or in a switching manner to inject the different types of coating agents into the hole pattern of the screen plate. A method for producing the pattern print according to any one of claims 1 to 5.

7. the substrate has a hole portion in which an electronic component is disposed on a front surface side of the substrate, and a via hole extending from the front surface to a back surface of the substrate, In the injecting step, the conductive coating material is injected into the hole and the via hole, and the electronic components are mounted and connected by the conductive coating material, and the conductive coating material is filled into the via hole. A method for producing the pattern print according to any one of claims 1 to 6.

8. a back surface wiring is provided in an area where the via hole is exposed on the back surface of the base material; In the injecting step, the conductive coating material is injected into the via hole to fill the via hole with the conductive coating material, thereby connecting the conductive filler to the back surface wiring. A method for producing the pattern print according to claim 7.

9. A recess is formed on the surface of the pattern print at a position corresponding to a screen mesh intersection of the screen plate, a projection is formed on the surface of the pattern print at a position corresponding to the opening of the screen plate; A method for producing the pattern print according to any one of claims 1 to 8.

10. The width of the recess is 10 μm or more and 40 μm or less, The top surface of the protrusion is a square with a side length of 20 μm or more and 210 μm or less. A method for producing the pattern print according to claim 9.

11. A method of preparing a coating agent as a printing ink, the coating agent including a filler, a binder, and a solvent that is incompatible with the binder; A step of attaching a substrate to the rear surface of the screen plate having the hole pattern; injecting the coating material into the hole pattern from the front surface side of the screen plate using a pressurized container filled with the coating material; a step of sweeping and removing the coating material that has overflowed from the hole pattern after the step of injecting with a squeegee; peeling the substrate from the screen after the sweeping and removing step; Equipped with In the sweeping and removing step, pressure is applied to the coating material in the hole pattern from the front surface side of the screen plate by the squeegee; The coating agents are different types of coating agents each having a different component composition, A method for manufacturing a semiconductor device, in which the injecting process injects the different types of coating agents into the hole pattern of the screen plate by simultaneously using or switching between pressure containers filled with the different types of coating agents.

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