JP2008149311A - Electronic component manufacturing apparatus, pattern wiring sheet, electronic device sheet and sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel electronic component fabrication apparatus for forming a pattern wiring or an electronic device on a substrate using paper or paper-based material with a simple principle and structure. <P>SOLUTION: The electronic component fabrication apparatus has another jet head having a shape which is different from that of a jet head and uses an electric function development material containing liquid or a liquid having the fluid physical property similar to that of the same. The desired shape of the droplets of the liquid is obtained by adjusting the drive signal to be applied to an electro-mechanical energy conversion element for another jet head while observing the flying shape of the liquid. The electric function development material containing liquid is jetted and imparted on a substrate by inputting the drive signal based on the adjusted result of the drive signal to the electro-mechanical energy conversion element for another jet head. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an apparatus for forming a pattern wiring sheet or an electronic device sheet by applying an electrical function-expressing material onto a substrate using an image forming means, and a pattern wiring sheet formed by the apparatus. Or, it relates to an electronic device sheet.

  In recent years, various devices such as a light emitting device / medium and an optical processing device / medium using fine particles / ultrafine particles have been studied (Patent Document 1). For the application of such fine particles to devices, high density integration obtained by depositing a film or layer of fine particle-containing material on a solid substrate is important. The thin film in which the fine particles are densely integrated is specifically reported to be applied to Non-Patent Document 1, Non-Patent Document 2, Non-Patent Document 3, Non-Patent Document 4, Non-Patent Document 5, Non-Patent Document 6, and the like. Has been.

  On the other hand, as a method of forming an inorganic compound thin film having excellent orientation, molecular beam epitaxy (MBE), cluster ion beam, ion beam irradiation vacuum deposition, chemical vapor deposition (CVD), physical vapor deposition ( PVD), liquid phase epitaxy (LPE) and the like are known. As a method for forming an organic compound thin film, a Langmuir-Blodgett method (LB method) or the like is known. What is generally called a quantum dot is manufactured using a process in which a raw material sublimated in a high vacuum using a vacuum apparatus such as the MBE method described above forms dots on a solid substrate in a self-organizing manner. Can do.

  However, in the above method, it is difficult to control the distance between dots and the size distribution, and there is a problem that it takes a lot of cost to control to a desired structure. Therefore, as a technique that can solve such a problem, it has been proposed to form a film of a material containing fine particles by an ink jet principle, that is, a liquid jet head. For example, in Patent Document 1, an emulsion containing nanoparticles is inkjet-coated on a solid substrate, and a photoluminescence intensity is increased or increased and stored as a function of irradiation time or irradiation amount of excitation light. There has been proposed a method of forming a thin film comprising an aggregate of fine particles (nanoparticles) on a solid substrate.

  In addition to such functional elements, studies have been made to apply the same principle to circuit board fabrication. For example, the following methods are conventionally known as circuit board manufacturing methods.

  (1) A method in which a copper-clad laminate is coated with a resist, and a copper line pattern is formed by exposure of a circuit pattern, dissolution and removal of an unexposed resist, and etching of a resist removal portion by a photolithography method.

  (2) A method of forming a conductive pattern by printing a conductive paste on a ceramic substrate by screen printing in a desired circuit pattern and then heat-treating it in a non-oxidizing atmosphere to sinter metal fine particles in the conductive paste.

  (3) A thin conductive layer is formed on the insulating substrate by vapor deposition of a conductive metal, and a resist is coated on the conductive layer, and exposure of the circuit pattern, dissolution and removal of the unexposed resist by the photolithography method, resist A method of forming a copper wire pattern by etching the removed portion.

  However, since these methods have a problem that they are not suitable for forming a fine pattern, for example, in Patent Document 2, a circuit pattern is directly drawn with a metal paste using an inkjet head on a substrate, There have been proposed a wiring pattern forming method and a circuit board manufacturing method that are easy to form a fine pattern, do not require waste liquid treatment, have a simple production process, and require less equipment and production costs.

  On the other hand, the present inventor has also proposed an invention for manufacturing an electron source substrate using the ink jet principle as Patent Document 3.

  Patent Document 4 also proposes an electric circuit forming apparatus that forms an electric circuit and visible information on a base using the same principle.

In this way, various proposals using the ink jet principle have begun to be made, but the idea of manufacturing various devices or patterns by such means is still new, and more specific methods are still unknown. The fact is that there are many parts and they are groping, and there are still many issues to consider.
JP 2000-126681 A JP 2002-134878 A JP 2001-319567 A JP 2005-183801 A Light emitting device (LED) (Alivisatos et al.) Photoelectric conversion element (Greenham, NC, et al., Phys. Rev. B, 54, 17628 (1996)) Ultra-high speed detector (Bhargava) Electroluminescent displays and panels (Bhargava, Alivisatos et al.) Nanostructured memory device (Chen et al.) Multicolor device consisting of nanoparticle arrays (Dushkin et al.)

  The present invention has been made in view of the above-described circumstances, and its object is to provide a novel electronic component manufacturing apparatus for manufacturing a patterned wiring substrate or an electronic device substrate based on a simple principle and structure. is there.

  In order to achieve the above object, according to the present invention, first, a liquid containing an electrical function-expressing material is jetted onto a paper or a paper-based base material by an ink jet principle jet head, In an electronic component manufacturing apparatus for forming a pattern wiring or an electronic device by forming solid patterns in a liquid to leave a solid content, the ejection head is configured to apply the liquid by an action force due to mechanical displacement of an electromechanical transducer. The liquid at the time of flight is a substantially round droplet shape just before adhering to the substrate surface, or a columnar shape extending in the flight direction and having a length within 3 times its diameter. It is a columnar shape that does not involve a plurality of minute droplets behind the flying liquid, and the shape is an ejection head that is different from the ejection head and exhibits the electrical function. A liquid obtained by adjusting the drive signal to the electromechanical conversion element of the another ejection head while observing the flying shape of the material-containing liquid or a liquid having the same fluid physical properties, and the drive signal By inputting a drive signal based on the adjustment result to the electromechanical conversion element of the ejection head, the electric function expressing material-containing liquid is ejected.

  Second, a liquid containing an electrical function-expressing material is jetted onto a paper or a paper-based base material by an ink jet principle jet head, and the solid content in the liquid remains on the base material. In the electronic component manufacturing apparatus for forming a pattern with dots and forming a pattern wiring or an electronic device, the jet head is a bubble growth action force generated instantaneously by heat generated by a heating element disposed in the liquid The liquid at the time of flight is an elongated columnar shape extending in the flight direction, and is a columnar shape having a length of 5 times or more of its diameter. Is a separate jet head that uses the liquid containing the electrical function-expressing material or a fluid having the same physical properties and observes the flying shape of the separate jet head. The liquid containing the electrical function-expressing material is obtained by inputting a drive signal based on the adjustment result of the drive signal to the heating element of the ejection head. The spray was given.

  Thirdly, in the first or second electronic component manufacturing apparatus, the apparatus includes a plurality of ejection heads, ejects different types of liquids, and stacks the patterns of the different types of liquids. Pattern wiring or electronic devices were formed.

  Fourthly, in the third electronic component manufacturing apparatus, the base material is held by a base material holding means, and the plurality of ejection heads are mounted on a carriage and move to face the base material to move the solution. In addition to spraying, after drying the previously sprayed pattern, the following different solutions were sprayed to form the laminated pattern.

  Fifthly, in the third electronic component manufacturing apparatus, the base material is transported by a base material transporting means, and the plurality of ejection heads are mounted on a carriage and move to face the base material to move the solution. When the next pattern is laminated after forming the pattern, the base material is returned to the position where the previous injection is started by the base material conveying means, and the next different solution is injected. The laminated pattern is formed.

  Sixthly, in any one of the first to fifth electronic component manufacturing apparatuses, the base material is transported by a base material transport unit, and after the pattern is formed on one surface, the transport unit performs the above-described process. The substrate was inverted and a pattern was formed on the other side.

  Seventhly, a pattern wiring sheet is formed in which a dot pattern of an electric function expressing material-containing liquid is formed on paper or a paper-based substrate, and the solid content in the liquid remains.

  Eighth, a dot pattern of a liquid containing an electrical function-expressing material is formed on the surface provided with a coating material that erases the unevenness of the paper fiber of the paper or paper base, and the solid content in the liquid The pattern wiring sheet was made to remain.

  Ninthly, in the seventh or eighth pattern wiring sheet, a plurality of the dot patterns are connected to form a belt-like pattern, and the belt-like pattern is a belt-like pattern formed by a combination of dots parallel to each of two orthogonal directions. The outer region of the region that is bent in the two directions of the pattern has a curved shape.

  Tenth, an electronic device sheet in which a dot pattern of a liquid containing an electrical function-expressing material is formed on paper or a paper-based substrate, and the solid content in the liquid remains is obtained.

  Eleventh, a dot pattern of a liquid containing an electrical function-expressing material is formed on a surface provided with a coating material that erases the irregularities of the paper fiber of paper or a paper-based substrate, and the solid content in the liquid The electronic device sheet was made to remain.

  Twelfth, in the tenth or eleventh electronic device sheet, a plurality of the dot patterns are connected to form a belt-like pattern, and the belt-like pattern is a belt-like pattern formed by combining dots in parallel directions in two orthogonal directions. The outer region of the region that is bent in the two directions of the pattern has a curved shape.

  Further, thirteenthly, a wiring pattern or an electronic device formed by forming a dot pattern of a liquid containing an electrical function-expressing material on the front and back of a paper or a paper-based substrate and leaving the solid content in the liquid remaining Or it was set as the sheet | seat which formed both of them.

  New electronic component manufacturing equipment capable of forming new paper or paper-based pattern wiring or electronic devices based on simple principles and structure, without using expensive and complicated methods such as conventional semiconductor manufacturing processes Can be realized.

  FIG. 1 shows an example in which a pattern is formed on paper or a paper-based substrate 10 by an ink jet principle (droplet ejection principle) which is one method of the image forming means of the present invention. FIG. 1A shows a state in which terminals 2 and 3 are formed on such a substrate 10, and a dotted line portion 1 'in the figure is a region where a wiring pattern 1 as described later is generated. FIG. 1B shows an example in which a wiring pattern 1 is formed by directly applying and drawing a liquid containing, for example, fine conductive fine particles as an electrical function-expressing material by the ink jet principle (droplet jet principle). It is.

  Here, in the present invention, for example, an inkjet technique is applied as means for applying a liquid containing an electrical function expressing material. The specific method will be described below.

  FIG. 2 is a view for explaining an embodiment of a manufacturing apparatus for forming a patterned wiring substrate or an electronic device of the present invention. In the figure, 11 is an ejection head unit (ejection head), 12 is a carriage, Is a substrate holder, 14 is a substrate such as a wiring substrate or an electronic device forming substrate, or a substrate forming an electronic device, 15 is a liquid supply tube containing an electrical function developing material, and 16 is a signal supply Cable, 17 is an ejection head control box (including a liquid tank), 18 is an X direction scan motor of the carriage 12, 19 is a Y direction scan motor of the carriage 12, 20 is a computer, 21 is a control box, 22 (22X1, 22Y1, 22X2) 22Y2) are substrate positioning / holding means. In this case, the ejection head 11 is moved by carriage scanning on the front surface of the substrate 14 placed on the substrate holder 13 and ejects a liquid containing an electrical function expressing material.

  FIG. 3 is a schematic view showing a configuration of a droplet applying apparatus applied to manufacture of a patterned wiring substrate or electronic device formation according to the present invention, and FIG. 4 is a main part of an ejection head unit of the droplet applying apparatus of FIG. It is a schematic block diagram.

  The configuration of FIG. 3 is different from the configuration of FIG. 2 in that the substrate 14 side is moved to form a wiring pattern or an electronic device on the substrate. 3 and 4, 31 is a head alignment control mechanism, 32 is a detection optical system, 33 is an ejection head, 34 is a head alignment fine movement mechanism, 36 is an image identification mechanism, 37 is an XY direction scanning mechanism, and 38 is a position detection mechanism. , 39 is a position correction control mechanism, 40 is an ejection head drive / control mechanism, 41 is an optical axis, 42 is an element electrode, 43 is a droplet, and 44 is a droplet landing position.

  The droplet applying device (ejecting head 33) of the ejecting head unit 11 may be any mechanism as long as it can discharge a given amount of droplets, and in particular, an ink jet principle capable of forming droplets of about 0.1 pl to several hundreds pl. The mechanism is desirable.

  Examples of the ink jet method include a method disclosed in US Pat. No. 3,683,212 (Zoltan method), a method disclosed in US Pat. No. 3,747,120 (Stemme method), and US Pat. No. 3,946,398. As in the disclosed method (Kyser method), an electrical signal is applied to the piezo-vibration element, this electrical signal is converted into mechanical vibration of the piezo-vibration element, and droplets are discharged from a fine nozzle according to the mechanical vibration. Is generally called a drop-on-demand system.

  As other methods, there are methods (Sweet method) disclosed in US Pat. No. 3,596,275, US Pat. No. 3,298,030, and the like. This generates a recording liquid droplet with a controlled charge amount by a continuous vibration generation method, and the generated charge amount controlled droplet flies between deflection electrodes to which a uniform electric field is applied. Thus, recording is performed on a recording member, which is usually called a continuous flow method or a charge control method.

  As another method, there is a method disclosed in Japanese Patent Publication No. 56-9429. This is a method in which bubbles are generated in a liquid, and droplets are ejected and ejected from fine nozzles by the action force of the bubbles, which is called a thermal ink jet method or a bubble jet (registered trademark) method.

  There are a drop-on-demand method, a continuous flow method, a thermal ink jet method, and the like as a method for ejecting droplets as described above, and the method may be appropriately selected as necessary.

  In the present invention, in the manufacturing apparatus (FIG. 2) for forming such a pattern wiring base material or electronic device, the base material 14 is determined by adjusting the holding position by the base material positioning / holding means 22 of this apparatus. Although simplified in FIG. 2, the base material positioning / holding means 22 is brought into contact with each side of the base material 14 and can be finely adjusted in the submicron order in the X direction and the Y direction perpendicular thereto. At the same time, it is connected to the ejection head control box 17, the computer 20, the control box 21 and the like, and its positioning information, fine adjustment displacement information, etc., and the position information, timing, etc. of droplet application can be constantly fed back. .

  Further, in the manufacturing apparatus for forming the patterned wiring substrate or the electronic device of the present invention, in addition to the position adjusting mechanism in the X and Y directions (not shown because it is located below the substrate 14), the rotational position adjustment It has a mechanism. In relation to this, the shape of the patterned wiring substrate or the electronic device forming substrate of the present invention and the arrangement of the electronic device group to be formed will be described.

  As the pattern wiring substrate or the electronic device forming substrate of the present invention, paper or a paper-based substrate is used. In addition, as will be described later, in the present invention, a liquid containing an electrical function-expressing material is applied to this base material to form a dot pattern, and various electrical functions are expressed. It can follow the deformation of the substrate. In other words, the pattern wiring sheet or the electronic device forming sheet of the present invention is not only reduced in weight but also flexible by using paper or a paper-based base material. Demand is expected.

  By the way, the pattern wiring sheet of the present invention, or an electronic device, an electronic device chip, an electronic device sheet, and an electronic device forming sheet are defined in advance.

  The pattern wiring sheet referred to in the present invention is an electric circuit pattern formed on paper or a paper-based substrate (sheet). Various types of transistors, resistors, capacitors, etc. are formed by a method described later. There may be a case of an electronic element, a display device element, etc. and a conductive wire pattern connecting them, or only the conductive wire pattern.

  The electronic device refers to various electronic elements such as the transistor, resistor, and capacitor, display device elements, and the like. Further, an integrated device such as an IC or LSI that is integrated into one chip is called an electronic device or an electronic device chip.

  The electronic device sheet and the electronic device forming sheet are sheets for forming a large number of so-called chips, which are formed by forming a plurality of the electronic devices and electronic device chips and later separated into chips. .

  Next, the base material for producing the patterned wiring sheet or the electronic device forming sheet of the present invention will be described.

  In the present invention, paper or a paper-based substrate is used as the substrate.

  In the definition of orthodox paper, “paper is the one in which plant fibers are suspended in water and then sprinkled with water and tangled thinly and flatly”, but the main points are represented by grass, wood, bamboo, etc. It is an aggregate of fibers obtained by decomposing plants. The raw material of paper, regardless of whether it is Western paper or Japanese paper, is a material having a characteristic property of cellulose fiber, and paper can be obtained by processing it with a unique technique called papermaking technology to make it thin.

  The cellulose fibers used here are wood fibers having a length of 1 to 3 mm, a width of 20 to 40 μm, and a thickness of 3 to 6 μm in the case of western paper. In general paper, about 10 to 100 are laminated in layers. By adopting such a configuration, the paper is extremely porous, and the property of a smooth material having high affinity of cellulose fibers can be obtained. Japanese paper is a paper using the same cellulose fiber, but unlike wood fiber, it is a relatively elongated fiber (width 5 to 20 μm, length 3 to 7 mm) than wood fiber called bast fiber. It has different characteristics and can be distinguished from hand-made or machine-made Japanese paper. FIG. 4 shows an image diagram of the surface of the paper. In FIG. 4, the lines indicate the cellulose fibers, and the paper is formed by overlapping the cellulose fibers in this way, and there is a gap formed by overlapping the fibers.

  The definition of paper is as described above, but paper with cellulose fibers simply overlapping is so-called base paper, and what is actually used is to increase opacity, whiteness, smoothness, air permeability, etc. Further, between these fibers, filler particles having a particle diameter of about 0.2 to 10 μm such as talc, clay, calcium carbonate and titanium dioxide are filled in the gaps between the fibers.

Depending on the application of the paper, the surface of the paper may further include kaolin (Al ₂ O ₃ .2SiO ₂ .2H ₂ O), calcium carbonate (CaCO ₃ ), satin white (3CaO.Al ₂ O ₃ .3CaSO ₄ .31 to 32H). There is a coated paper provided with a coating material by applying a coating liquid in which particles having a particle diameter of about 0.5 to 1 μm such as ₂ O) are dispersed together with a binder such as latex and starch.

  Other types of paper include newspaper rolls, non-coated printing paper (advanced, intermediate, lower grade, thin leaf printing paper), fine coated printing paper (fine coated fine paper, fine coated printing paper), and coating. Printing paper (art paper, coated paper, etc.), information paper (copying paper, photosensitive paper, foam paper, PPC paper, thermal paper, etc.), packaging paper (craft paper, imitation paper, etc.), sanitary paper (tissue paper, dust paper, Toilet paper, towel paper, etc.), hybrid paper (building paper, laminated paper, condenser paper, rice paper, glassine paper, etc.), corrugated paper (liner, medium paper, etc.) and so on.

  What is required for the paper or paper-based substrate suitably applied here is a certain mechanical strength. The electronic device sheet and the pattern wiring sheet of the present invention are manufactured by an apparatus as shown in FIG. At that time, even if the base material is large, it is held by the base material holding base 13, so that no trouble is caused by deformation or the like.

  However, when this sheet is actually used in various scenes as individual electronic device chips or pattern wiring units, there are many cases where it is difficult to deform. At least in the state where no external force is applied to the chip itself, the one that deforms cannot be used stably.

  More specifically, a chip that cannot support its own weight (is deformed by its own weight) is a problem in practice. For example, a non-rigid material that cannot maintain its own shape due to its own weight, such as a cloth such as tissue paper or a handkerchief, is not suitable as a base material used in the present invention.

  On the other hand, although some bending occurs due to its own weight, the bending is within an allowable range as long as the bending is within a range in which the electrical performance of the completed electronic device chip or pattern wiring unit can be maintained. Can be used for

  Here, it supplements about the bending within the range which can maintain electrical performance. For example, there is a sensor device known as a strain gauge (resistive strain gauge), and this is a strain detection that uses the principle that the electrical resistance changes due to the strain (which may be considered as a bend in the present invention). It is a sensor. In this case, the principle that the electric resistance changes due to distortion (which may be considered as bending according to the present invention) is well utilized. To the point where the electrical resistance changes is unacceptable. In other words, the base material that is not so rigid that it bends so far changes the electrical performance of the electronic device chip and pattern wiring unit made using it, so that the device function in the present invention can be maintained, Alternatively, it cannot be said that the pattern wiring function can be maintained.

  One standard for determining the rigidity required for the substrate of the present invention is, for example, the density of paper.

  Various papers with different densities are prepared in Table 1, and 10 electronic device chips having a size of 10 mm × 10 mm to 50 mm × 50 mm are randomly manufactured in a size within the range of each paper sample by the method described later. The result of examining the actual availability is shown.

  Sample No. Nos. 8 and 9 were weak in mechanical strength, easily bent, and lacked practical strength as an electronic device. On the other hand, the other samples had sufficient strength and were practical as electronic devices. No. Although No. 7 was deformed (bent), there was no problem in performance as an electronic device.

In other words, it is understood that the base material that can be used in the present invention must have a density of 0.40 g / cm ³ or more in order to obtain the minimum practical strength that can be handled normally. It was. The density mentioned here is a density generally applied in the papermaking industry, and is calculated by dividing the weight (weight per m ² (grams)) by the thickness ( It is not exactly the same density as in physics).

The above examination results show that in the case of an electronic device chip having a size of 10 mm × 10 mm to 50 mm × 50 mm, the density of the paper to be used must be 0.40 g / cm ³ or more. It is unclear whether this result can be applied when paper of × 1000 mm is used. In that case, however, the density and size of the paper should be selected as appropriate. Finally, whether the electronic device or pattern wiring unit or sheet can be evaluated while evaluating the electrical performance (whether the performance can be maintained even if it is bent). ).

  By the way, as described above, the rigidity required for the base material of the present invention can be maintained by the strength of the paper that is the base material. However, the electrical function expression material of the electronic device chip and the pattern wiring unit as described later is directly used. The intensity | strength can be made high also with the protection member provided in the provided surface or its back surface. That is, it is also a good method to increase the overall rigidity by the interaction between the base paper and the protective member. In this case, the protective member described later is very convenient because it not only protects the electronic device chip but also increases the mechanical strength.

  As will be described later, the formation of the protective member also responsible for the enhancement of the mechanical strength is achieved by applying the resin-containing solution to the substrate surface (device forming surface) or the entire substrate back surface according to the principle of liquid injection described in the present invention. It is only necessary to apply injection to only those portions that are selectively required. Such a resin material is very effective in improving the rigidity of the substrate by drying and solidifying after application.

  Next, it supplements a little about the paper which is a base material of this invention. As described above, the surface of the paper is formed by overlapping the cellulose fibers, and the thickness of the cellulose fibers, the gap formed by the overlapping of the fibers, and in the case of the coated paper as described above, the coating substance Depending on the particle size of the (coating material) and the like, the shape is uneven when viewed microscopically. Such a microscopic uneven shape forms a dot pattern by applying a liquid containing an electrical function-expressing material as in the present invention to produce a pattern wiring sheet or an electronic device forming sheet with good performance. It is one of the factors that hinders cases.

  However, by making good use of this coating material, it is possible to reduce or eliminate the unevenness of the paper fibers caused by the thickness of the cellulose fibers and the gap formed by the overlap, which will be described later.

  In the present invention, as will be described later, a pattern wiring sheet or an electronic device sheet is formed by directly applying an electrical function-expressing material on such paper or a paper-based substrate. Depending on the usage environment, the completed pattern wiring sheet and electronic device sheet may have moisture adhering to the back surface of the substrate (the surface on which the pattern is not formed). Electronic devices may be damaged.

  Therefore, in the present invention, the substrate is devised in order to prevent moisture from penetrating into the front pattern surface even if such moisture adheres to the back surface. For example, it is good to use the base material which laminated | stacked the resin film on the back surface side as a water-resistant member which does not permeate | transmit a water | moisture content.

  Such a resin laminate may be formed in various ways by a method as described later using such a laminated base material in advance, and a pattern wiring sheet or an electronic device sheet may be formed. Lamination may be performed on the back side after the pattern formation.

  As a material for the laminate resin, for example, vinyl chloride resin, polypropylene resin, and the like can be used as appropriate. Polyolefin-based polypropylene resin is known as an environmentally friendly polymer material resin and is one of preferable materials.

  Although the above explanation is an example of laminating the resin on the back surface in this way, in the process of manufacturing the paper as the base material, a composite paper in which one layer of such a resin film is inserted inside the paper is manufactured. It is also a good method to form the pattern wiring sheet or the electronic device sheet of the present invention by using it as a base material.

  As still another example, the resin-containing solution may be sprayed and applied to the entire back surface of the base material according to the principle of liquid jet described in the present invention, and the resin layer may be provided on the back surface side. Needless to say, the principle of liquid ejection is not necessarily required, and the resin layer may be formed by a technique such as roller coating.

  By adopting such a base material structure, the pattern wiring sheet and electronic device sheet formed according to the present invention are based on a simple principle and structure based on a new paper or paper, but are resistant to water, and the pattern wiring sheet and electronic device It can be a sheet.

  Next, the preferable shape of the base material used when manufacturing the pattern wiring sheet or electronic device formation sheet of this invention is demonstrated.

  The shape of the pattern wiring substrate of the present invention or the paper or paper-based substrate used for the electronic device forming substrate is economically produced, supplied, or finally produced. From the use of the electronic device forming substrate, it is rectangular. That is, the two vertical sides and the two horizontal sides constituting the rectangular shape are base materials in which the two vertical sides are parallel to each other, the two horizontal sides are parallel to each other, and the vertical and horizontal sides form a right angle.

  In the present invention with respect to such a substrate, the formed electronic device groups are arranged in a matrix, and the two directions perpendicular to each other of the matrix are the direction of the longitudinal side or the lateral side of the substrate. The electronic device groups are arranged so as to be parallel to each other. The reason why the electronic device groups are arranged in a matrix and the reason why the vertical and horizontal sides of the substrate are parallel to two orthogonal directions of the matrix will be described below.

  As shown in FIG. 2 or FIG. 3, in the present invention, after the positional relationship between the base material 14 and the liquid ejection port surface of the ejection head unit 11 is first determined, the position control is not particularly performed. That is, the ejection head unit 11 ejects the liquid while performing a relative movement in the X and Y directions parallel to the formation surface of the electronic device group while maintaining a certain distance from the base material 14. That is, the X direction and the Y direction are two directions orthogonal to each other. When positioning the base material, if the vertical side or the horizontal side of the base material is parallel to the Y direction or the X direction, Since the electronic device group to be formed is parallel to the two directions of the matrix arrangement, it is possible to form a highly accurate device group only by a mechanism that performs ejection while performing relative movement. In other words, if the substrate shape as in the present invention, the matrix arrangement of the electronic device group, and the relative movement device in two directions X and Y orthogonal to each other, the substrate before the droplet formation for device formation is performed. If positioning is performed accurately, a highly accurate matrix arrangement of electronic devices can be obtained.

Here, the description will be returned to the rotational position adjustment mechanism. As described above, in the present invention, the substrate is accurately positioned before droplet ejection for device formation is performed, only the relative movement in the X and Y directions is performed, and other controls are not performed. The goal is to obtain a matrix-like arrangement of groups. In this case, a problem is a shift in the rotation direction (the rotation direction with respect to the axis perpendicular to the plane determined by the two directions X and Y) when the substrate is initially positioned.
In order to correct the deviation in the rotational direction, the present invention includes a rotational position adjusting mechanism (not shown) that is not shown (not visible under the base material 14) as described above. Accordingly, when the shift in the rotation direction is also corrected and the side of the substrate is positioned, the apparatus of the present invention can obtain a highly accurate matrix arrangement of the electronic device group by the relative movement only in the X and Y directions.

  The rotation position adjustment mechanism has been described as a separate mechanism from 22 (22X1, 22Y1, 22X2, 22Y2) in the base material positioning / holding means in FIG. 2 (not visible under the base material 14). However, the substrate positioning / holding means 22 may have a rotational position adjusting mechanism. For example, the base material positioning / holding means 22 is brought into contact with the side of the base material 14, and the whole base material positioning / holding means 22 can be adjusted in the X direction or the Y direction. If the two screws provided at a distance are moved independently at the portion of the positioning / holding means 22 that is in contact with the side of the base material 14, the angle can be adjusted. This rotational position control information is also connected to the ejection head control box 17, the computer 20, the control box 21, etc. in the same manner as the positioning information and fine adjustment displacement information in the X and Y directions, and the droplet application position information, Timing, etc. can be constantly fed back.

  Next, other means and configuration of positioning according to the present invention will be described. In the above description, the base material positioning / holding means 22 is brought into contact with the side of the base material 14 so that the entire position of the base material positioning / holding means 22 can be adjusted in the X direction or the Y direction. Here, an example will be described in which strip-like patterns are provided in two directions orthogonal to each other on the substrate, not on the sides of the substrate 14. As described above, in the present invention, the electronic device groups are formed on the base material in a matrix form. Here, the two orthogonal band-like patterns as described above are formed in the two orthogonal directions of the matrix. It is formed so as to be in parallel with. Such a pattern can be easily formed on a substrate by printing or the like.

  The present invention is applied to a case where a wiring pattern as shown in FIG. 1 is formed in addition to the case where a large number of electronic device groups arranged in a matrix are formed. It forms in two orthogonal directions like this example, and it forms so that it may become parallel to the vertical and horizontal direction (X direction, Y direction) of a base material, respectively. This wiring pattern may be formed as a pattern for the purpose of such positioning at a position that does not hinder the original function of the base material of the present invention, and the element electrode 42 (FIG. 5), A wiring pattern such as an X-direction wiring or a Y-direction wiring of the device may be regarded as a two-direction belt-like pattern of the present invention. If such a belt-like pattern is provided, the pattern can be detected by a detection optical system 32 using a CCD camera and a lens as will be described later with reference to FIG.

  Next, in the Z direction, which is a direction perpendicular to the X and Y directions, in the present invention, after the positional relationship between the base material 14 and the liquid ejection port surface of the ejection head unit 11 is first determined, There is no position control. That is, the ejection head unit 11 ejects the liquid containing the electrical function-expressing material while performing relative movement in the X and Y directions while maintaining a certain distance (1 to 3 mm) with respect to the base material 14. During the ejection, the position control of the ejection head unit 11 in the Z direction is not particularly performed. The reason for this is that if the control is performed at the time of injection, not only the mechanism, the control system, etc. are complicated, but also the formation of an electronic device by applying droplets to the base material 14 is delayed, and the productivity is significantly reduced. is there.

  Instead, in the present invention, the flatness of the base material 14 and the flatness of the device that holds the base material 14 are improved, and the accuracy of a carriage mechanism that relatively moves the ejection head unit 11 in the X and Y directions is improved. By doing so, the Z direction control at the time of jetting is not performed, and the relative movement of the jet head unit 11 and the base material 14 in the X and Y directions is performed at high speed, thereby improving productivity. As an example, the variation in the distance between the base material 14 and the liquid ejection port surface of the ejection head unit 11 at the time of liquid application (ejection) of the present invention is suppressed to 2 mm or less (the size of the base material 14 is 100 mm × 100mm or more, 4000mm x 4000mm or less).

  In addition, although it is configured so that the plane determined by the two directions of X and Y directions is maintained horizontally (a plane perpendicular to the vertical direction), when the substrate 14 is small (for example, 500 mm × 500 mm or less) In this case, the plane determined by the two directions X and Y does not necessarily have to be horizontal, and it is sufficient that the positional relationship of the arrangement of the base materials 14 is most efficient for the apparatus.

  Next, the configuration of the ejection head unit 11 will be described with reference to FIG. In FIG. 5, reference numeral 32 denotes a detection optical system that captures image information on the substrate 14. The detection optical system 32 is close to the ejection head 33 that ejects the droplet 43, and the optical axis 41 and focal position of the detection optical system 32. It is arranged so that the landing position 44 of the droplet 43 by the same position coincides.

  In this case, the positional relationship between the detection optical system 32 and the ejection head 33 shown in FIG. 3 can be precisely adjusted by the head alignment fine movement mechanism 34 and the head alignment control mechanism 31. The detection optical system 32 uses a CCD camera and a lens.

  In FIG. 3, reference numeral 36 denotes an image identification mechanism for identifying image information captured by the previous detection optical system 32, and has a function of binarizing the contrast of the image and calculating the center of gravity position of the binarized specific contrast portion. I have it. Specifically, VX-4210, a high-precision image recognition device manufactured by Keyence Corporation can be used. A means for giving position information on the electronic device forming substrate 14 to the image information thus obtained is a position detection mechanism 38. For this purpose, a length measuring device such as a linear encoder provided in the XY direction scanning mechanism 37 can be used. The position correction control mechanism 39 corrects the position based on the image information and the position information on the electronic device forming substrate 14, and this mechanism corrects the movement of the XY direction scanning mechanism 37. Added. Further, the ejection head 33 is driven by the ejection head control / drive mechanism 40, and droplets are applied on the electronic device forming substrate 14. Each control mechanism described so far is centrally controlled by the control computer 35.

  By the way, FIG. 5 shows a diagram in which droplets are ejected obliquely onto the substrate surface. In order to illustrate the detection optical system 32 and the ejection head 33 together, the droplets fly obliquely in this way. However, in practice, spraying is applied so as to be substantially perpendicular to the substrate.

  In the above description, the ejection head unit 11 is fixed, and the electronic device forming substrate 14 is moved to an arbitrary position by the XY direction scanning mechanism 37 so that the ejection head unit 11 and the electronic device forming substrate 14 are relative to each other. Although the movement is realized, it is needless to say that the electronic device forming substrate 14 may be fixed and the ejection head unit 11 may scan in the XY directions as shown in FIG. In particular, when the present invention is applied to production of a medium-sized substrate of about 200 mm × 200 mm to a large substrate of 2000 mm × 2000 mm or more, the electronic device forming substrate 14 is fixed as in the latter, and the ejection head unit 11 is orthogonal. It is preferable that the scanning is performed in two directions of X and Y, and the liquid droplets are sequentially applied in such two orthogonal directions.

  When the substrate size is approximately 200 mm x 200 mm or less, the ejection head unit for applying droplets is a large array multi-nozzle type that can cover the range of 200 mm, and the relative movement between the ejection head unit and the substrate is orthogonal. It is also possible to perform the relative movement in only one direction (for example, only in the X direction) without performing in the two directions (X direction and Y direction), and the mass productivity can be increased. In the case of 200 mm × 200 mm or more, it is difficult to realize a large-array multi-nozzle type ejection head unit capable of covering such a range of 200 mm in terms of technology / cost. The unit 11 scans in two orthogonal X and Y directions, and liquid droplets are sequentially applied in such two orthogonal directions. It is better to have a configuration to do so.

  In particular, as a final base material, even when a product smaller than 200 mm × 200 mm is manufactured, when a plurality of large base materials are manufactured, the original base material is 400 mm × Since 400 mm to 2000 mm × 2000 mm or more is used, the ejection head unit 11 scans in two directions of X and Y orthogonal to each other, and the application of liquid droplets in such an orthogonal direction 2 is performed. It is better to have a configuration that sequentially performs in the direction.

  As the material of the droplet 43, for example, a liquid containing fine conductive fine particles is used as an electrical function expressing material. A liquid containing fine metal particles such as Au, Pt, Ag, Cu, Ni, Cr, Rh, Pd, Zn, Co, Mo, Ru, W, Os, Ir, Fe, Mn, Ge, Sn, Ga, and In. Preferably used. Alternatively, oxide fine particles of these metals are also preferably used.

  In particular, when fine metal particles such as Au, Ag, and Cu are used, it is possible to form a fine circuit pattern that has low electrical resistance and is resistant to corrosion.

  In the present invention, the liquid containing such fine conductive fine particles includes an aqueous liquid and an oily liquid.

  An aqueous liquid obtained by dispersing such fine conductive fine particles in a dispersion medium mainly composed of water can be prepared, for example, by the following method.

  That is, a water-soluble polymer is dissolved in a metal ion source aqueous liquid such as chloroauric acid or silver nitrate, and an alkanolamine such as dimethylaminoethanol is added with stirring. Metal ions are reduced in several tens of seconds to several minutes, and metal fine particles having an average particle size of 0.5 μm (500 nm) or less are deposited. After removing chlorine ions and nitrate ions by a method such as ultrafiltration, a concentrated liquid containing fine conductive particles can be obtained by concentration and drying. This conductive fine particle-containing liquid can be stably dissolved and mixed in water, an alcohol solvent, a sol-gel process binder such as tetraethoxysilane or triethoxysilane.

  The oil-based liquid obtained by dispersing fine conductive fine particles in a dispersion medium mainly composed of oil can be prepared by the following method, for example.

  That is, an oil-soluble polymer is dissolved in a water-miscible organic solvent such as acetone, and this liquid is mixed with a metal ion source water liquid. The mixture is heterogeneous, but when alkanolamine is added while stirring the mixture, the metal fine particles are precipitated on the oil phase side in a form dispersed in the polymer. When this is concentrated and dried, a concentrated conductive fine particle-containing liquid similar to the aqueous system is obtained. This conductive fine particle-containing liquid can be stably dissolved and mixed in an aromatic solvent, ketone solvent, ester solvent or the like, polyester, epoxy resin, acrylic resin, polyurethane resin, or the like.

  The concentration of the conductive fine particles in the dispersion medium of the conductive fine particle-containing liquid can be a maximum of 80% by weight, but it is appropriately diluted depending on the application.

  Usually, the content of conductive fine particles in the liquid containing fine conductive particles is 2 to 50% by weight, the content of surfactant and resin is 0.3 to 30% by weight, and the viscosity is suitably 3 to 30 centipoise.

  In any material, the present invention volatilizes the volatile components in the liquid and leaves the solid content on the substrate to form a dot pattern, which is electrically connected to the previously formed electrode pattern and the like. It is intended for patterning, pattern wiring or electronic device formation. This solid material generates the function of each pattern or device, and the solvent (volatile component) is a vehicle for ejecting droplets by the ink jet principle.

Other examples of the material of the droplet 43 include a group I-VII compound semiconductor such as CuCl, a group II-VI compound semiconductor such as CdS and CdSe, a group III-V compound semiconductor such as InAs, and a group IV semiconductor. Nano-particles such as a semiconductor crystal, a metal oxide such as TiO ₂ , SiO, SiO ₂ , a phosphor, a fullerene, an inorganic compound such as a dendrimer, an organic compound such as a phthalocyanine or an azo compound, or a composite material thereof. Examples of the liquid contained.

  In the present invention, the target fine particles and nanoparticles usually have a particle size of 0.0001 to 0.2 μm (0.1 to 200 nm), preferably 0.0001 to 0.05 μm (0.1 to 50 nm). Fine particles can be mentioned, but more strictly, it is determined in consideration of the dispersion stability of fine particles during liquid production, clogging during jetting, and the surface roughness of the substrate on which the pattern is formed.

  The surface of these nanoparticles may be chemically or physically modified within the range not impairing the object of the present invention, and additives such as surfactants, dispersion stabilizers and antioxidants may be added. good. Such nanoparticles can be obtained by colloidal chemical methods such as reverse micelle method (Lianos, P. et al., Chem. Phys. Lett., 125, 299 (1986)) and hot soap method (Peng. X. et al. , J. Am. Chem. Soc., 119, 7019 (1997)).

The nanoparticle-containing liquid that can be suitably used in the present invention is a dispersion in which the above nanoparticles are dispersed in an emulsion (O / W emulsion) in which the continuous phase is an aqueous phase and the dispersed phase is an oil phase.
The aqueous phase is mainly water, but a water-soluble organic solvent may be added to water. Examples of the water-soluble organic solvent include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (# 200, # 400), glycerin, alkyl ethers of the glycols, N-methylpyrrolidone, 1, 3- Examples thereof include dimethyl imidazolinone, thiodiglycol, 2-pyrrolidone, sulfolane, dimethyl sulfoxide, diethanolamine, triethanolamine, ethanol, isopropanol and the like. The amount of water-soluble organic solvent used in the aqueous dispersion medium is usually preferably 30% by weight or less, and more preferably 20% by weight.

  The content of the nanoparticles in the dispersion varies depending on the desired film (layer) structure or particle arrangement structure and film (layer) thickness, but is usually in the range of 0.01 to 15% by weight with respect to the total weight of the dispersion. Although it is used, it is more preferably in the range of 0.05 to 10% by weight. If the content of the nanoparticles is too small, there is a possibility that the device function cannot be expressed sufficiently. Conversely, if the content is too large, the ejection stability at the time of ejecting droplets by the ink jet principle is impaired.

  In addition, the nanoparticle-containing liquid that is preferably used in the present invention and ejected by the ink jet principle preferably contains a surfactant and a solvent for dispersing nanoparticles in the dispersion. Examples of the surfactant include an anionic surfactant (sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium laurate, ammonium salt of polyoxyethylene alkyl ether sulfate, etc.), nonionic surfactant (polyoxyethylene alkyl). Ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl amines, polyoxyethylene alkyl amides, etc.), and these may be used alone or in combination of two or more. be able to.

  The amount of the surfactant is usually used in the range of 0.1 to 30% by weight, more preferably in the range of 5 to 20% by weight, based on the total weight of the liquid. When the amount of the surfactant is less than this range, oil-water separation occurs in the aqueous dispersion, and there is a case where a uniform pattern cannot be coated by applying droplets. On the contrary, when the amount is more than this range, the viscosity of the aqueous dispersion medium tends to be too high.

  The solvent for dispersing the nanoparticles is usually a liquid such as toluene, hexane, pyridine, chloroform, and preferably volatile. The amount of the solvent for dispersion is usually used in the range of about 0.1 to 20% by weight, but more preferably in the range of 1 to 10% by weight. If the amount of the dispersing solvent is less than this range, the amount of ultrafine particles that can be contained in the aqueous medium decreases. On the other hand, if it is more than this range, oil-water separation may occur in the aqueous dispersion medium.

  Furthermore, the organic compound can be dissolved in the dispersion. Examples of such organic compounds include trioctylphosphine oxide (TOPO), thiophenol, photochromic compounds (spiropyran, fulgide, etc.), charge transfer complexes, electron-accepting compounds, and the like that are solid at room temperature are preferable. . In this case, the amount of the organic compound in the dispersion is at least 1/10000, preferably about 1/1000 to 10 times the weight of the nanoparticles.

  In addition, a surfactant, a dispersion stabilizer, an additive such as an antioxidant, or a binder such as a polymer or a material that gels in the coating / drying process may be added to the suspension as long as the object of the present invention is not impaired. good.

A droplet containing such a nanoparticle-containing liquid is applied onto a substrate by the ink jet principle and dried to form a pattern wiring or an electronic device. In the present invention, for example, it may be first air-dried at −20 to 120 ° C., preferably about 0 to 80 ° C. for 1 hour or more, preferably 3 hours or more, and then dried under reduced pressure as necessary. good. The degree of vacuum at this time may be 1 × 10 ⁵ Pa or less, preferably about 1 × 10 ⁴ Pa or less, and the temperature is usually −20 to 110 ° C., preferably 0 to 70 ° C. The decompression time is about 1 to 24 hours.

  Although the thickness of the nanoparticle thin film obtained by said method is not specifically limited, Usually, the diameter of a nanoparticle is 1 mm, Preferably it is the diameter of a nanoparticle-about 100 micrometers. In the nanoparticle thin film, the nanoparticles are preferably present at a density of a certain level or more. In this sense, the average interparticle distance between individual nanoparticles in the nanoparticle aggregate is usually within 10 times the particle diameter, and more preferably within 2 times the particle diameter. If this average interparticle distance is too large, the nanoparticles will not exhibit collective function.

  Other examples of the material of the droplet 43 include an organic semiconductor material-containing solution. For example, a π-conjugated material is used as the organic semiconductor material. For example, polypyrroles such as polypyrrole, poly (N-substituted pyrrole), poly (3-substituted pyrrole), poly (3,4-disubstituted pyrrole), polythiophene, Poly (3-substituted thiophene), poly (3,4-disubstituted thiophene), polythiophenes such as polybenzothiophene, polyisothianaphthenes such as polyisothianaphthene, and polychenylene vinylenes such as polychenylene vinylene , Poly (p-phenylene vinylene) such as poly (p-phenylene vinylene), polyaniline such as polyaniline, poly (N-substituted aniline), poly (3-substituted aniline), poly (2,3-substituted aniline) , Polyacetylenes such as polyacetylene, and polydiacetylenes such as polydiacetylene Polyazulenes such as polyazulene, polypyrenes such as polypyrene, polycarbazoles such as polycarbazole and poly (N-substituted carbazole), polyselenophenes such as polyselenophene, polyfurans such as polyfuran and polybenzofuran, poly (p -Phenylene), polyindoles such as polyindole, polypyridazines such as polypyridazine, naphthacene, pentacene, hexacene, heptacene, dibenzopentacene, tetrabenzopentacene, pyrene, dibenzopyrene, chrysene , Perylene, coronene, terylene, obalene, quaterrylene, circumcene anthracene, and other polyacenes and polyacenes in which part of the carbon is substituted with atoms such as N, S, and O, and functional groups such as carbonyl groups The polymer (triphenodioxazine, triphenodithiazine, hexacene-6,15-quinone, etc.), polyvinylcarbazole, polyphenylene sulfide, polyvinylene sulfide and the like can be used.

  In addition, α-sexual thiophene, α, ω-dihexyl-α-sexual thiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis, which are, for example, thiophene hexamers having the same repeating unit as these polymers Oligomers such as (3-butoxypropyl) -α-sexithiophene and styrylbenzene derivatives can also be suitably used.

  Furthermore, metal phthalocyanines such as copper phthalocyanine and fluorine-substituted copper phthalocyanine, naphthalene 1,4,5,8-tetracarboxylic acid diimide, N, N′-bis (4-trifluoromethylbenzyl) naphthalene 1,4,5,8 -N, N'-bis (1H, 1H-perfluorooctyl), N, N'-bis (1H, 1H-perfluorobutyl) and N, N'-dioctylnaphthalene 1,4,5 with tetracarboxylic acid diimide 8-tetracarboxylic acid diimide derivatives, naphthalene tetracarboxylic acid diimides such as naphthalene 2,3,6,7 tetracarboxylic acid diimide, and anthracene tetracarboxylic acid diimides such as anthracene 2,3,6,7-tetracarboxylic acid diimide Condensed ring tetracarboxylic acid diimides such as C60, C70, C76, C78 Fullerenes, such as C84, carbon nanotube such as SWNT, merocyanine dyes, such as dyes such as hemicyanine dyes, and the like.

  Among these π-conjugated materials, thiophene, vinylene, chelenylene vinylene, phenylene vinylene, p-phenylene, a substituent thereof, or two or more of these are used as a repeating unit, and the number n of the repeating units is 4 to 4 At least 1 selected from the group consisting of an oligomer of 10 or a polymer in which the number n of repeating units is 20 or more, a condensed polycyclic aromatic compound such as pentacene, fullerenes, condensed ring tetracarboxylic diimides, and metal phthalocyanine Species are preferred.

  Other organic semiconductor materials include tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTTF-iodine complex, TCNQ-iodine complex. Organic molecular complexes such as can also be used. Furthermore, σ conjugated polymers such as polysilane and polygermane can also be used.

  As an example that can be suitably used in the present invention, an organic semiconductor material mainly composed of a polymer having a repeating unit represented by the following general formula will be described in detail together with its synthesis method.

一般式（１）

General formula (1)

  For example, a carbonyl compound represented by the following general formula (2)

一般式（２）
［一般式（２）中、Ａ１、Ａ２はそれぞれ置換または無置換の単環または多環式のアリレン基またはヘテロアリレン基を表わす。Ｒ１は水素、置換または無置換のアルキル基、置換または無置換のアリール基を表わす。Ｖは−Ｏ−、−Ｓ−、−ＮＲ２−（Ｒ２は置換または無置換の単環または多環式のアリレン基、もしくは置換または無置換の単環または多環式のヘテロアリレン基を表わす）を表わし、ｎは≧０を表わす］、及び下記一般式（３）で表わされるリン化合物

General formula (2)
[In General Formula (2), A1 and A2 each represent a substituted or unsubstituted monocyclic or polycyclic arylene group or heteroarylene group. R1 represents hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. V represents —O—, —S—, —NR 2 — (R 2 represents a substituted or unsubstituted monocyclic or polycyclic arylene group, or a substituted or unsubstituted monocyclic or polycyclic heteroarylene group). And n represents ≧ 0], and a phosphorus compound represented by the following general formula (3)

一般式（３）
［一般式（３）中、Ａ３、Ａ４はそれぞれ置換または無置換の単環または多環式のアリレン基またはヘテロアリレン基を表わす。Ｒ３は水素、置換または無置換のアルキルまたはアリールまたはヘテロアリール基を表わす。Ｗは−Ｏ−、−Ｓ−、−ＮＲ４−（Ｒ４は置換または無置換の単環または多環式のアリレン基、もしくは置換または無置換の単環または多環式のヘテロアリレン基を表わす。ｍは≧０を表わす。ＸはＰＯ（ＯＲ５）２（Ｒ５は低級アルキル基）またはＰ（Ｒ６）３＋Ｙ―（Ｒ６は置換または無置換のアリール基、もしくは置換または無置換のアルキル基を表わし、Ｙはハロゲン原子を表わす）を表わす）を反応させ、炭素−炭素二重結合を含有する下記一般式（４）

General formula (3)
[In General Formula (3), A3 and A4 each represent a substituted or unsubstituted monocyclic or polycyclic arylene group or heteroarylene group. R3 represents hydrogen, a substituted or unsubstituted alkyl, aryl or heteroaryl group. W represents —O—, —S—, —NR 4 — (R 4 represents a substituted or unsubstituted monocyclic or polycyclic arylene group, or a substituted or unsubstituted monocyclic or polycyclic heteroarylene group, m. Represents ≧ 0, X represents PO (OR5) 2 (R5 is a lower alkyl group) or P (R6) 3 + Y— (R6 represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group; Represents a halogen atom), and the following general formula (4) containing a carbon-carbon double bond:

一般式（４）
の繰り返し単位をもつ重合体が製造される。

General formula (4)
A polymer having the following repeating unit is produced.

This will be described in more detail below.
Suitable basic compounds include all known basic compounds as long as they are uniformly dissolved in a non-aqueous solvent. However, in view of the ability to form phosphonate carbanions, the basicity point is considered. To metal alkoxides, metal hydrides, organolithium compounds, etc., such as potassium t-butoxide, sodium t-butoxide, lithium t-butoxide, potassium 2-methyl-2-butoxide, sodium 2-methyl-2-butoxide, sodium methoxy Sodium ethoxide, potassium ethoxide, potassium methoxide, sodium hydride, potassium hydride, methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, phenyl lithium, lithium Naphthylide, Richiu Amide, and lithium diisopropylamide.

  As the solvent for dissolving the base, a solvent that forms a stable solution with the base to be used must be selected, but as other factors, those having a high solubility of the base are preferable, and the high molecular weight product produced in the reaction system is also preferred. Those that do not impair the solubility in the reaction solvent are good. In addition, the solvent that dissolves the high molecular weight product is good. It can be arbitrarily selected from a system, an amine system, a hydrocarbon solvent and the like.

  Examples of a combination of a base and a solvent for uniformly dissolving the base include, for example, a methanol solution of sodium methoxide, an ethanol solution of sodium ethoxide, a 2-propanol solution of potassium t-butoxide, and 2-methyl-2-methyl ester of potassium t-butoxide. Propanol solution, potassium t-butoxide in tetrahydrofuran, potassium t-butoxide in dioxane, n-butyllithium in hexane, methyllithium in ether, lithium t-butoxide in tetrahydrofuran, lithium diisopropylamide in cyclohexane, potassium bis There are various combinations of solutions including a toluene solution of trimethylsilylamide and the like, and some solutions are easily available as commercial products. From the viewpoint of mild reaction conditions and ease of handling, a metal alkoxide-based solution is preferably used, such as solubility of the polymer to be produced, ease of handling, efficiency of the reaction, solubility of the polymer to be produced, etc. From the viewpoint, an ether system of metal t-butoxide is more preferably used, and a tetrahydrofuran solution of potassium t-butoxide is more preferably used.

  By mixing a solution in which the phosphorus compound and aldehyde compound are stoichiometrically equal to the above-mentioned base solution containing at least twice the molar amount of the base, the polymerization reaction proceeds easily and is preferably controlled to a narrow molecular weight distribution. The obtained high molecular weight polymer can be easily obtained. Usually, it is sufficient to use the same amount of the base with respect to the polymerization active site of the phosphorus compound, but even if an excessive amount is used, there is no problem.

  In the above polymerization reaction, a base solution may be added to the solution of the phosphorus compound and the aldehyde compound, a solution of the phosphorus compound and the aldehyde compound may be added to the base solution, and may be added to the reaction system in the same manner. There are no restrictions.

  The polymerization time in the above polymerization reaction may be appropriately set according to the reactivity of the monomers used or the molecular weight of the desired polymer, but is preferably 0.2 hours to 30 hours. Further, a sealing agent for sealing the end of the polymer can be added during or after the reaction, and can be added at the start of the reaction.

  The reaction temperature in the above polymerization reaction does not need to be controlled, and the polymerization reaction proceeds well at room temperature. However, it is possible to heat or cool to a milder condition in order to increase the reaction efficiency.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, organic semiconductor materials that can be suitably used in the present invention are not limited by these examples unless they exceed the gist.

  Various measurements were performed by the following methods. The number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the polymer are measured by gel permeation chromatography (GPC), using UV absorption and differential refractive index. The measurement was performed in terms of polystyrene using dispersed polystyrene as a standard.

(Example of material synthesis)
In a 100 ml four-necked flask, the following chemical formula (5) is shown:

化学式（５）
ジアルデヒドを０．８５２ｇ（２．７０ｍｍｏｌ）、及び以下の化学式（６）に示す

Chemical formula (5)
0.852 g (2.70 mmol) of dialdehyde and the following chemical formula (6)

化学式（６）
ジホスホネートを１．５２５ｇ（２．７０ｍｍｏｌ）を入れ、窒素置換してテトラヒドロフラン７５ｍｌを加えた。この溶液にカリウムｔ−ブトキシドの１．０ｍｏｌｄｍ−３テトラヒドロフラン溶液６．７５ｍｌ（６．７５ｍｍｏｌ）を滴下し、室温で２０時間撹拌した後、ベンジルホスホネート及びベンズアルデヒドを順次加え、さらに２時間３０分撹拌した。酢酸およそ１ｍｌを加えて反応を終了し、溶液を水洗した。溶媒を減圧留去し、残渣をテトラヒドロフラン１５ｍｌ及びメタノール８０ｍｌを用いて再沈澱による精製を行い、以下の化学式（７）に示す重合体を１．０７ｇ得た。

Chemical formula (6)
1.525 g (2.70 mmol) of diphosphonate was added, nitrogen substitution was performed, and 75 ml of tetrahydrofuran was added. To this solution, 6.75 ml (6.75 mmol) of a 1.0 moldm-3 tetrahydrofuran solution of potassium t-butoxide was added dropwise and stirred at room temperature for 20 hours. Then, benzylphosphonate and benzaldehyde were added successively, and the mixture was further stirred for 2 hours and 30 minutes. . About 1 ml of acetic acid was added to terminate the reaction, and the solution was washed with water. The solvent was distilled off under reduced pressure, and the residue was purified by reprecipitation using 15 ml of tetrahydrofuran and 80 ml of methanol to obtain 1.07 g of a polymer represented by the following chemical formula (7).

化学式（７）
得られた重合体の分子量及び分子量分布を測定したところ、収率：７３％、重量平均分子量（Ｍｗ）：１０４０００、数平均分子量（Ｍｎ）：３６０００、分子量分布（Ｍｗ／Ｍｎ）：２．８９、重合体：６３であった。

Chemical formula (7)
When the molecular weight and molecular weight distribution of the obtained polymer were measured, yield: 73%, weight average molecular weight (Mw): 104000, number average molecular weight (Mn): 36000, molecular weight distribution (Mw / Mn): 2.89 Polymer: 63.

  Using such an organic semiconductor material-containing solution, in the present invention, for example, an organic thin film transistor element as shown in FIGS. 6 and 7 can be formed. The organic thin film transistor element configuration includes a top gate type having a source electrode and a drain electrode in contact with an organic semiconductor layer on a paper-based substrate, and having a gate electrode on the gate insulating layer thereon, The material is roughly divided into a bottom gate type having a gate electrode on a material and having a source electrode and a drain electrode connected by an organic semiconductor layer through a gate insulating layer. The cross-sectional view of the element is as shown in FIGS.

  FIG. 6 shows an example of a top gate type layer structure, which has an organic semiconductor layer 8 on a paper-based substrate 10 and further a source electrode 4 as a first electrode electrically connected to the organic semiconductor layer 8. And a drain electrode 5 as a second electrode, provided between the pair of electrodes, and further between the electrodes and on the region where the organic semiconductor layer 8 is provided via the gate insulating layer 6 It has a gate electrode 7 as a third electrode. A voltage is applied between the source electrode 4 and the drain electrode 5, and a voltage is further applied and controlled to the gate electrode 7.

  FIG. 7 shows an example of a bottom gate type layer structure, in which an electrode layer as a gate electrode 7, a gate insulating layer 6, and an organic semiconductor layer 8 are formed in this order on a paper-based substrate 10. A pair of electrode layers composed of a source electrode 4 and a drain electrode 5 that are electrically conducted to the layer 8 are formed, and the region of the organic semiconductor layer 8 is made to have a sealing structure. A voltage is applied between the source electrode 4 and the drain electrode 5, and a voltage is further applied and controlled to the gate electrode 7.

Still another example of the droplet 43 includes a solution containing an organic EL light emitting material, for example. For example, the following solution composition examples are given for three colors of RGB (red, green, blue).
Solvent ... Dodecylbenzene / dichlorobenzene (1/1, volume ratio)
Red: Polyfluorene / perylene dye (98/2, weight ratio)
Green: Polyfluorene / coumarin dye (98.5 / 1.5, weight ratio)
Blue ... Polyfluorene

  In addition, for example, polyphenylene vinylene-based (polyparaphenylylene vinylene-based derivatives), polyphenylene-based derivatives, and other materials such as low-molecular organic EL materials soluble in benzene derivatives, high-molecular organic EL materials, and polyvinylcarbazole are used. be able to. Specific examples of the organic EL material include rubrene, perylene, 9,10-diphenylanthracene, tetraphenylbutadiene, Nile red, coumarin 6, quinacridone, polythiophene derivatives, and the like.

  In the present invention, the boiling point of the benzene derivative is preferably 150 ° C. or higher as the solution composition. Specific examples of such a solvent include O-dichlorobenzene, m-dichlorobenzene, 1,2,3-trichlorobenzene, O-chlorotoluene, p-chlorotoluene, 1-chloronaphthalene, bromobenzene, O-dibromo. Examples thereof include benzene and 1-dibromonaphthalene. Use of these solvents is preferable because volatilization of the solvent can be prevented. These solvents are preferable because of their high solubility in aromatic compounds. The solution composition of the present invention preferably contains dodecylbenzene. As dodecylbenzene, n-dodecylbenzene alone may be used, or a mixture of isomers may be used.

  This solvent has a boiling point of 300 ° C. or more and a viscosity of 6 cp or more (20 ° C.). Of course, this solvent alone may be used, but by adding it to other solvents, it is possible to effectively prevent the solvent from evaporating and is suitable. . Further, among the above solvents, those other than dodecylbenzene have a relatively low viscosity, which is very suitable because the viscosity can be adjusted by adding this solvent.

  According to the present invention, the solution composition as described above is supplied by droplet ejection onto a paper-based substrate by the electronic device manufacturing apparatus shown in FIGS. A functional film forming method is provided in which a film is formed by treatment at a temperature higher than the temperature. The temperature during discharge is room temperature, and it is preferable to heat the substrate after discharge. By performing such a treatment, the content deposited due to the volatilization of the solvent during discharge and the decrease in temperature is redissolved, and a uniform and homogeneous functional film can be obtained.

  In the method for producing the functional film described above, it is preferable to heat while applying pressure when the discharge composition is supplied onto the substrate by the electronic device manufacturing apparatus and then the substrate is processed at a temperature higher than the discharge temperature. By treating in this way, volatilization of the solvent during heating can be delayed, and the re-dissolution of the contents is further promoted. As a result, a uniform and homogeneous functional film can be obtained.

  In the method for producing a functional film described above, it is preferable to reduce the pressure immediately after the high temperature treatment to remove the solvent. By treating in this way, phase separation of the contents during the concentration of the solvent can be prevented.

  In any material, the present invention performs organic EL light emitting element formation by volatilizing a volatile component in a solution and leaving a solid content on a substrate. This solid matter generates a light emitting function, and the solvent (volatile component) is a vehicle for ejecting droplets by the ink jet principle.

  FIG. 8 shows a configuration in which the organic EL light emitting device of the present invention is used as a display device. A barrier member 24 made of an electrode 23 and an organic photosensitive material is formed on a paper-based substrate 10, and a solution containing the above organic EL light emitting material is sprayed and applied to a region surrounded by the barrier member 24. After that, the solvent is removed, the solid content is left to form the organic EL light emitting layer 25, and a transparent electrode 26 such as ITO and a transparent sheet 27 are further disposed thereon. The upper transparent electrode 26 and the transparent sheet 27 may be made of a transparent PET sheet having an ITO film formed on one side in advance.

  By adopting such a configuration, in the present invention, a flexible and lightweight display in which light from the organic EL light emitting layer 25 is extracted in the direction of the arrow in the figure is realized.

  As another material of the droplet 43 of the present invention, a silicon glass precursor of an interlayer insulating film frequently used for a semiconductor or the like, or a silica glass forming material can be mentioned. Examples of the precursor include polysilazane (for example, manufactured by Tonen), organic SOG material, and the like.

  Examples of the electrode material include known conductive polymers whose conductivity has been improved by doping and the like, such as conductive polyaniline, conductive polypyrrole, conductive polythiophene (polyethylenedioxythiophene and polystyrenesulfonic acid complex, etc.) , Platinum, gold, silver nanoparticles (size 1-50nm) dispersed solution, etc. can also be used suitably, also suitable for forming various wiring patterns and patterns such as antennas of RFID devices described later it can.

  In the present invention, the material of the droplet 43 is referred to as an electrical function-expressing material or a liquid containing an electrical function-expressing material, but refers to a material used for manufacturing an electronic device or the like. It goes without saying that a material having a mechanical insulation is also included in this.

  Next, a liquid jet head suitably applied to the present invention will be described with reference to FIGS. This example is an example of 7 nozzles.

  In this liquid ejecting head, a piezo element 46 is provided as an energy acting part in a flow path 45 into which a liquid 47 is introduced. When a pulsed signal voltage is applied to the piezo element 46 to mechanically distort the piezo element 46 as shown in FIG. 9A, the volume of the flow path 45 is reduced and a pressure wave is generated. The droplet 43 is ejected from the nozzle 48 by the wave. FIG. 9B shows a state in which the piezoelectric element 46 is no longer distorted and the volume of the flow path 45 is increased.

  When droplets are ejected by such an ejection head, the shapes shown in FIGS. 11 and 12 are obtained. That is, when the liquid is ejected by the action force due to the mechanical displacement of such an electromechanical conversion element (piezo element), the liquid at the time of flight has a substantially round droplet shape immediately before adhering to the substrate surface ( FIG. 11), or a columnar shape extending in the flight direction, or a column having a length within three times its diameter, even if the length is long (FIG. 12).

  In general, when liquid droplets are ejected by the principle of ejecting a liquid by the action force of a mechanical displacement of such an electromechanical transducer (piezo element), the characteristic of this principle is almost always such a shape. Droplets are obtained. The reason is described below.

  In general, when liquid droplets are ejected according to the principle of ejecting a liquid by the action force due to the mechanical displacement of such an electromechanical transducer (piezo element), the time-differentiated value of the impact force applied to the liquid by the electromechanical transducer However, in the case of an ejection head of this principle, the diameter when the liquid is ejected from the nozzle and the diameter of such a round droplet or elongated shape is at most 3 The conditions for jetting and flying in a columnar shape with a length within twice are almost the same.

  In other words, when droplets are ejected according to such a principle, the shape of the droplet at the time of flight is almost such a round droplet or an elongated shape, but the length is within 3 times the diameter at most. It is a columnar shape. The state at that time is a state where the flying droplets fly stably without being shaken by disturbance. The flight speed at that time is 5 m / s to 12 m / s.

  In the present invention, when using such an ejection head to eject an electrical function-expressing material-containing liquid to form a pattern wiring or an electronic device, this condition (the shape at the time of flight) is set. If the conditions are not met (usually rarely), the liquid containing the electrical function material or the liquid having the same physical properties (viscosity, surface tension) and the equivalent ejection head The jet signal is used to adjust the drive signal to the electromechanical transducer of the jet head while observing the flying shape under the microscope (the rising waveform is steep so that the shape is obtained), and the drive signal By inputting the drive signal based on the adjustment result to the electromechanical conversion element of the ejection head of the electronic component manufacturing apparatus of the present invention, a desired stable flight shape can be obtained. I have to so that.

  Another feature of the present invention is the filter configuration. The liquid 47 introduced into the flow path 45 immediately before the nozzle 48 has passed through the filter 49. In the present invention, the filter 49 is thus provided in the ejection head, and the filter removal function is provided in the vicinity of the nozzle 48. By doing so, foreign particles that are larger than those other than the conductive fine particles or nanoparticles in the liquid of the present invention are trapped, and the performance of the pattern or device formed on the substrate is not deteriorated. Yes. Such a filter 49 can be incorporated into the ejection head 11 as shown in FIG. The ejection head 11 itself can also be made compact.

  As such a filter 49, for example, a stainless mesh filter is preferably used. Alternatively, resin materials such as Teflon (registered trademark) (tetrafluoroethylene) and polypropylene are also preferably used. In short, a material that does not corrode or dissolve in the liquid of the present invention is appropriately selected. The pore size (filter mesh size) is selected so as to trap foreign matters having a size of 30 times or more the particle size in the liquid.

  More specifically, as described above, in the present invention, when a liquid containing, for example, fine conductive fine particles is used as the electrical function-expressing material, the particle size is usually 0.0001 to 0.2 μm (0 .1 to 200 nm), preferably 0.0001 to 0.05 μm (0.1 to 50 nm) containing a fine particle is used, so 0.003 to 0.6 μm, preferably 0.003 to 1.m. If the filter can trap foreign matter having a size of 5 μm or more, the problem that the foreign matter clogs the discharge port (nozzle) can be avoided. In addition, regarding the filter mesh size (the size of foreign matter that can be trapped), strictly speaking, there is a definition of whether the removal rate refers to the absolute removal rate or the average removal rate, but here the concept of the absolute removal rate In the above mesh size.

  Further, although the position of the filter 49 is shown in FIG. 10 as an example of being incorporated in the ejection head 11, it is not essential to be incorporated in the ejection head 11. Since the filter may be provided at a plurality of locations, in the present invention, the mesh size of the filter that is upstream of the discharge port (nozzle) 48 and closest to the discharge port (nozzle) 48 is within the above range. That is the point. The filter 49 is not only provided in the jet head having the above-described configuration, but is similarly applied to a thermal type (bubble type) liquid jet head, which will be described later, or another type of jet head.

  Next, another example of a liquid jet head suitably applied to the present invention will be described with reference to FIG. This example is an example of a thermal type (bubble type) liquid ejecting head, which does not eject droplets by the electro-mechanical conversion action by the above-described piezo element, but in addition to liquid in a short time (1 to 10 μs). The growth action force of the film boiling bubbles generated instantaneously at the high heat (300 to 500 ° C.) is used as the driving force for droplet ejection.

  The liquid ejecting head shown here is of a type in which droplets are ejected from a short channel portion through which a liquid flows, and is called an edge shooter type.

  Here, an example in which the number of nozzles of the liquid ejecting head is four is shown. This liquid ejecting head is formed by joining a heating element base 66 and a lid base 67. The heating element base 66 is formed on a silicon base 68 by an individual electrode 69 and a common electrode 70 by a wafer process. And a heating element 71 which is an energy action part.

  On the other hand, the lid base 67 is provided with a groove 74 for forming a channel into which a liquid containing a functional material is introduced, and a common liquid chamber for containing the liquid introduced into the channel. A recess region 75 is formed, and the heat generating body base 66 and the lid base 67 are joined as shown in FIG. 13 to form the flow path and the common liquid chamber. In the state where the heating element base 66 and the lid base 67 are joined, the heating element 71 is located on the bottom surface of the flow path, and is introduced into these flow paths at the end of the flow path. The nozzle 65 for discharging a part of the liquid as droplets is formed. Here, the nozzle shape is rectangular, but it may be round.

  Further, in consideration of jetting stability, a nozzle plate may be separately provided on the end face (the area of the nozzle 65) to have a desired nozzle diameter and nozzle shape (for example, a round shape). In this case, for example, Ni is used as the nozzle plate, and a highly accurate object can be formed by a technique such as electroforming. Alternatively, it is also a good method to use a resin film (base material) in which nozzle holes are drilled by excimer laser processing.

  The lid base 67 is formed with a liquid inlet 76 for supplying a liquid into the supply liquid chamber by a supply means (not shown).

  When the electric function expressing material-containing liquid used in the present invention is ejected by such an ejection head, the shape shown in FIG. 14 is obtained. That is, when the liquid is ejected by the bubble growth action force instantly generated by the heat generated by the heating element arranged in the liquid, the liquid at the time of flight is an elongated columnar shape extending in the flight direction. A columnar shape having a length of 5 times or more of the diameter can be obtained (FIG. 14).

  This is usually the case when the liquid is ejected by the growth action force of bubbles (film boiling bubbles) generated instantaneously by the heat generated by the heating element arranged in the liquid. Such a flying liquid shape is obtained. The reason is described below.

  In general, when the liquid is ejected according to the principle that the liquid is ejected by the growth action force of bubbles (film boiling bubbles) generated instantaneously by the heat generated by the heating element arranged in the liquid, The jet pressure is so high as to be incomparable with the jet head using the electromechanical conversion element, the liquid column as shown in FIG. 14 is elongated, and the flying form is such that a minute satellite droplet is dragged backward. Further, the flight speed at that time is very high such as 8 m / s to 18 m / s. Therefore, it is a flying form that drags a minute satellite drop in the back, and they also fly at high speed and land at almost the same position as the elongated columnar liquid preceding the substrate surface, so on the pattern formation There is no hindrance.

  In the present invention, when such an ejection head is used to eject a liquid containing an electrical function-expressing material to form a pattern wiring or an electronic device, this condition (the elongated columnar shape extending in the flight direction is If it is outside such conditions (usually rarely), the liquid containing the electrical function-expressing material or its equivalent is used. A liquid with fluid properties (viscosity, surface tension) and an equivalent jet head are used for jetting, and the flying signal is adjusted under the microscope to adjust the drive signal to the heating element of the jet head. The pulse voltage or the pulse width is slightly increased so that the drive energy is increased), and the drive signal based on the adjustment result of the drive signal is applied to the electronic component of the present invention. By inputting to the heating element of the ejection head of the granulator device, so that the desired stable flying shape can be obtained.

  In the present invention, a single electronic device is formed by a plurality of droplets, or a pattern for forming an electronic device or the like is formed by overlapping or contacting dots with a plurality of droplets. Therefore, when such a multi-nozzle type liquid jet head is used, an electronic device can be formed very efficiently. In this example, a four-nozzle liquid ejecting head is shown, but the present invention is not necessarily limited to four nozzles. Needless to say, the larger the number of nozzles, the more efficient the formation of electronic devices. However, this is not simply a matter of increasing the number, and if it increases, the liquid jet head becomes more expensive, and the probability of clogging of the jet nozzles increases. It is determined considering the balance of device production efficiency.

  FIG. 15 is a view of the multi-nozzle type liquid jet head manufactured as described above, as viewed from the nozzle side. In the present invention, such a multi-nozzle type liquid ejecting head is provided for each liquid to be ejected and mounted on a carriage as shown in FIG. FIG. 17 is a perspective view thereof.

  FIGS. 16 and 17 indicate the multi-nozzle type liquid jet heads as A, B, C, and D, respectively, but each of the liquid jet heads A, B, C, and D has a nozzle portion of each liquid jet head. It is possible to eject different types of liquids containing an electrical function-expressing material for each liquid ejecting head while being configured to be separated for each ejecting head.

  In the present invention, an electronic device or the like is manufactured by spraying a liquid containing an electrical function expressing material, etc., but not only a single liquid is sprayed, but as in this example, as described above. Various types of liquids can be ejected for each liquid ejecting head. Therefore, the device structure as shown in FIG. 6, FIG. 7 or the like can be easily formed by ejecting a plurality of different types of liquids to form patterns, and appropriately stacking or combining the patterns. Can do. At that time, if the pattern formed earlier and the pattern to be laminated later cannot form a good pattern due to the mixture of both liquids, the pattern formed earlier is dried and the volatile components are volatilized. A pattern formed from is formed.

  For this reason, in some cases, the next pattern (stacked thereon) cannot be formed immediately after the previous pattern is formed. That is, the previous pattern is not sufficiently dried, and when the next pattern is formed, the two solutions are mixed and a good pattern cannot be formed.

  In such a case, for example, a pattern previously formed is formed with a jet head mounted on a carriage, and after the volatile components are volatilized and dried, the carriage is returned to the original position again. Form a pattern.

  Alternatively, in the case of a manufacturing apparatus in which the carriage does not move in the two-dimensional direction of the vertical and horizontal directions (X and Y directions) orthogonal to each other, moves only in one direction (for example, the X direction), and the substrate moves in the direction perpendicular thereto. Once the pattern to be formed is formed once, after volatilization and drying of the volatile components, the substrate is returned to the original place (position where pattern formation by the previous jetting was started), and the next pattern is formed again. To. Such an apparatus configuration is not shown in the electronic component manufacturing apparatus of FIG. 2, but can be easily realized by means conventionally known as roller conveyance or belt conveyance as the substrate conveyance means. By doing so, it is possible to obtain a highly accurate pattern without pattern collapse and to obtain a highly reliable pattern wiring or electronic device.

  As an application example of this means, when the substrate is carried by roller conveyance or belt conveyance, after once forming an electronic device or pattern wiring on one side, the substrate is reversed and an electronic device or pattern wiring is formed on the back surface. It becomes possible. For the reversal of the substrate or its positioning, the double-sided printing technique performed by a so-called ink jet printer or the like can be applied as it is.

  By forming electronic devices or pattern wiring on both sides of the substrate in this way, in the case of electronic parts with more functions or memory functions, larger capacity memory parts and even more complicated electronic parts are manufactured. It becomes possible to do. Alternatively, the substrate (chip) size can be reduced by forming the front and back surfaces.

  In addition, it is possible to form an electronic device having different functions on the front and back sides to form a hybrid electronic component. For example, the RFID (Radio Frequency-Identification) device described below has a configuration in which a memory, a communication circuit, or a small antenna is combined. A memory is formed on the front surface and a communication circuit is formed on the back surface. A configuration in which a small antenna is formed is also possible.

  Next, as a preferable example to which the present invention can be preferably applied, an RFID device will be described. An RFID device is a combination of a memory, a communication circuit, and a small antenna, all of which are formed according to the present invention in which a device is formed by ejecting different types of liquids containing an electrically functioning material as described above. Printing can be formed.

  Conventional RFID chips are manufactured by a Si semiconductor process and integrated with separately formed antennas and electrode patterns. If the technology of the present invention is used, all are formed on a paper substrate by printing. Can be made at a very low cost. In this case, not only can the device be formed on the paper sheet as the base material, but also the cardboard used as the packaging material can be printed and formed by direct injection. New added value (product history, tracking information, etc. by the RFID method) can be easily given to the member. Note that the means for printing and forming an RFID device on such a packaging member is that the packaging member is a three-dimensional solid object, and the electrical function manifests by the ink jet principle rather than the Carlson process principle described later. Since the material-containing liquid can be sprayed directly and non-contactingly, the application range is wide.

  Next, still another feature of the present invention will be described. FIG. 18 is an example of pattern wiring of a pattern wiring substrate formed according to the principle of the present invention. This is an example in which a wiring pattern 92 is formed by later spraying a fine particle-containing liquid onto a terminal pattern (electrode pattern) 91 formed of a rectangle or a combination of rectangles previously formed on a substrate. In this example, the dot patterns of the wiring pattern 92 are arranged so that they are just in contact with each other in the adjacent oblique direction in order to avoid complication of the drawing. = Arrange so that there are many overlapping portions of the dot patterns), so that no uncovered portions occur in the wiring pattern portion.

  FIG. 19 is an example of one device of a device substrate formed according to the principles of the present invention. In this example, a device is formed by ejecting a liquid containing an electrical function-expressing material later onto a pair of element electrodes (electrode patterns) 93 formed by a rectangle or a combination of rectangles previously formed on a substrate. is there.

  However, there is one problem here. It is an abnormal discharge in the terminal pattern 91 and the element electrode (electrode pattern) 93 portion that occurs when the circuit pattern or various electronic devices are used after completion. This will be described with reference to FIGS.

  In the present invention, as shown in FIGS. 18 and 19, a wiring pattern 92 is formed by a liquid dot pattern containing a metal fine particle material between a plurality (two in this example) of terminal patterns (electrode patterns) 91, or opposed to each other. Various electronic devices are formed by the liquid dot pattern 94 containing the electrical function expressing material between the element electrodes 93 to be performed. Usually, the terminal patterns 91 and the element electrodes (electrode patterns) 93 are rectangular ( However, since the corner portions 91C and 93C of the electrode patterns 91 and 93 are pointed as shown in FIGS. 18 and 19, electric field concentration occurs in those portions. As a result, when applied between both electrodes, there is a problem in that abnormal electric discharge occurs in the electric field concentration portion, and a good electrical function cannot be obtained, or the portion is damaged.

  In view of this point, in the present invention, for example, the corner portions of the electrode patterns 91 and 93 are chamfered as shown in FIGS. In this example, c-shaped chamfering when displayed in a mechanical drawing is used, but it goes without saying that it may be r-shaped chamfering. Although the size of the chamfered portion is usually about 1/2 to 1/5 of the dot pattern diameter, that is, c2 μm to c5 μm, or r2 μm to r5 μm, a good electrode pattern in which electric field concentration does not occur is obtained. be able to.

  In the present invention, by eliminating the sharp part of the electrode pattern and eliminating the electric field concentration, there is no abnormal discharge when used as a circuit pattern or various devices, and it is stable even when used for a long time. The quality that you have come to get.

  Next, still another feature of the present invention will be described. 22 and 23 are equivalent to the wiring patterns or electronic devices described with reference to FIGS. 18 to 21 uses a paste-like liquid containing Al, Au, Cu or the like in advance on a substrate to form an electrode pattern (terminal pattern 91, element electrode 93), and screen printing. The electrode pattern 91, 93 is formed according to the liquid jet principle of the present invention, as shown in FIGS. 22 and 23.

  That is, a liquid containing fine particles of a conductive material such as Ag is used, and the electrode patterns 91 and 93 are formed as a combination of dots in the same manner as the pattern wiring or device pattern formation as described above. The merit of doing in this way is that the problem of abnormal discharge described above can be solved in addition to the fact that the manufacturing apparatus of the present invention described in FIGS. . As shown in FIGS. 22 and 23, if the electrode patterns 91 and 93 are formed by a dot pattern by liquid jetting in which metal fine particles of the present invention are dispersed, the outer shape of the dot pattern itself is a round shape. Since there is no pointed portion, it can be automatically chamfered.

  22 and 23, the dot diameters of the electrode pattern portions 91 and 93 are larger than the dot diameter of the wiring pattern 92 or the device pattern (dot pattern 94). The same ejection head having a dot pattern may be used so that the dot patterns have the same size.

  By the way, the wiring pattern 92 by the combination of dots shown in FIG. 18 is formed as a belt-like pattern extending in the longitudinal direction, or the dot pattern 94 is also formed as a belt-like pattern in the device of FIG. The direction in which such a belt-shaped pattern extends is the X direction or the Y direction described with reference to FIGS. 2, 3, and 5, that is, the relative movement direction of the base material 14 and the ejection head 11 (the carriage on which the ejection head is mounted). 12 in the direction of movement or the direction of movement of the base material 14), the pattern information for controlling the ejection of liquid and the control thereof can be simplified, and high-precision pattern formation can be realized at low cost.

  Similarly, these directions, that is, the direction in which the pattern is extended, can be positioned or parallelized by making the direction of each side of the rectangular base material to be used or the direction of the matrix arrangement of the device group to be formed. Formation can be performed with high accuracy.

  Next, another example for solving the above problem will be described.

  In view of this point, in the present invention, for example, as shown in FIGS. 24 and 25, the wiring pattern 92 or the dot pattern 94 forming the device pattern is covered so that the corner portions of the electrode patterns 91 and 93 are not exposed. . In the example of the wiring pattern 92 in FIG. 24, an example in which the dot pattern row is vertically arranged in four rows is shown, but it goes without saying that it may be one row as shown in FIG. The same applies to the device of FIG. 25, and only one dot may be used as shown in FIG.

  In short, if the sharp portions of the electrode patterns 91 and 93 are covered with a dot pattern and the portions are not exposed on the surface, abnormal discharge due to electric field concentration can be prevented, or damage can be prevented. Stable quality can be obtained even when used for a long time as an electronic device.

  Next, still another feature of the present invention will be described. FIG. 28 is an enlarged view of a part (corner portion) of the wiring pattern 1 of FIG. In the present invention, in relation to the above-described problem, the corner portion (outer region of the region where the pattern bends at a right angle) 1C of the wiring pattern 1 is prevented from being sharpened.

  This will be described more specifically with reference to FIGS. FIG. 29 shows an example of pattern wiring of a pattern wiring substrate formed according to the principle of the present invention. In this example, a dot pattern is combined to form a wiring pattern 92 that is bent 90 degrees in the middle. That is, such a wiring pattern 92 is formed into a strip-like pattern parallel to each of two orthogonal directions (arrows in the figure), and is arranged with its direction bent depending on the arrangement of the wiring pattern 92. In this case, as shown in part A in the figure, the outer region of the region where the wiring pattern 92 bends in two orthogonal directions is formed in a curved shape. In this way, the bent corners of the wiring pattern 92 can be prevented from being sharpened by forming a dot pattern, and electric field concentration can be avoided.

  FIG. 30 shows a case in which the wiring pattern 92 is formed by arranging the dot patterns in one row. In this case as well, the corner where the wiring pattern 92 is bent is not sharpened by the dot pattern as in the A part in the figure. And concentration of the electric field can be avoided.

  FIG. 31 is an example of a one-device electronic device substrate formed according to the principles of the present invention. An example of forming an electronic device by later ejecting a liquid containing an electrical function-expressing material onto a pair of element electrodes (electrode patterns) 93 formed by a rectangle or a combination of rectangles previously formed on a substrate It is. Also in this case, in order to obtain a desired electronic device shape, the pattern of the dot pattern 94 (electronic device pattern portion) is formed in a strip shape, and the strip pattern is a pattern that is bent 90 degrees in the middle. And, as shown in the B part in the figure, the outer area of the area where the dot pattern 94 bends in two orthogonal directions (in the direction of the arrow in the figure) has a curved shape. In this way, the pattern is bent. By forming a dot pattern, the corners can be prevented from being sharpened, and electric field concentration can be avoided.

  FIG. 32 shows a case where the electronic device pattern is formed by arranging the dot pattern 94 in one row. In this case as well, the corner where the pattern is bent is not sharpened by the dot pattern, as in the B portion in the figure. And concentration of the electric field can be avoided.

  By the way, the wiring pattern 92 by the combination of dots shown in FIGS. 18, 20, 24, 26, 29, and 30 is formed as a belt-like pattern extending in the longitudinal direction, or FIGS. In the electronic devices of FIGS. 25, 31, and 32, the dot pattern 94 is formed as a band pattern. The direction in which such a band pattern extends is described with reference to FIGS. The liquid is ejected in parallel with the X direction or the Y direction, that is, the relative movement direction of the base material 14 and the ejection head 11 (the movement direction of the carriage 12 on which the ejection head is mounted or the movement direction of the base material 14). Pattern information for control and control thereof can be simplified, and highly accurate pattern formation can be realized at low cost.

  Similarly, these directions, that is, the direction in which the pattern extends, are positioned by making them parallel to the direction of each side of the rectangular base material to be used or the direction of the matrix arrangement of the electronic device group to be formed. Pattern formation can be performed with high accuracy.

  As described above, the present invention is a technique for applying an electronic device or pattern wiring by directly applying an electrical function-expressing material on paper or a paper-based substrate. Here, the surface properties of the base material reflect the thickness of the cellulose fibers and the unevenness of the paper fibers caused by the gaps formed by the overlapping of the cellulose fibers. It is not necessarily a preferable shape for manufacturing a device forming sheet.

  In view of this point, the present invention examines the relationship between the surface properties of paper and the production of good wiring patterns. As described above, the cellulose fiber generally has a width (thickness) of about 5 to 20 μm although it depends on the type of paper. Paper is not usually made of fibers of such a size as it is, and in general, in the paper manufacturing process, a mechanical force is applied to the fibers called beating so that it becomes flexible. Because it is manufactured, the fiber size of the actually completed paper is smaller than this. Usually, the thickness or the thickness of the paper fiber manufactured through beating is about 4 to 10 μm.

  In the present invention, a dot pattern of an electrical function-expressing material is formed on the surface of the paper on which such fibers overlap, and the solid content in the liquid remains to form a wiring pattern or an electronic device. However, what is important in forming a good round dot pattern is the surface properties of the paper.

  In the present invention, in view of this point, the relationship between the surface roughness of paper and a good wiring pattern or electronic device is investigated. In addition to the irregularities formed by the cellulose fibers, the surface properties of the paper differ depending on the coating material of the coated paper as described above, which affects good pattern formation and device formation.

  An example of the results of studying these points will be shown. Here, papers having different surface properties are prepared according to the size of the fibers, the presence or absence of coating materials, and the like, and a wiring pattern as shown in FIG. 26 is formed. Evaluation of good pattern formation (sensory evaluation) and wiring pattern As a result, durability was evaluated.

  The application of the coating material to the paper includes a digital means such as applying / not applying dots as in the ink jet method. Here, as a means for applying more simply and quickly, roller coating is used. A method of giving the entire surface in an analog manner was adopted. As another analog whole surface applying means, there is spray coating or the like, but here, in order to apply more uniformly than the coating material, it was performed by roller coating.

  Further, dot formation for forming a wiring pattern is a liquid ejecting head using a piezo element as shown in FIGS. However, although the ejection heads shown in FIGS. 9 and 10 show the ones in which the tip of the flow path is the discharge port as it is, the one used in the experiment has the same arrangement as the arrangement density of the flow paths at the tip. A nozzle plate having nozzles formed with a density is provided. The nozzle plate was formed by Ni electroforming, and its thickness was 20 μm.

Also, the number of discharge ports (nozzles) shown in FIGS. 9 and 10 is only seven for ease of explanation, but the number of discharge ports actually used is Is 256, and the arrangement density is 180 dpi. The discharge port diameter is Φ20 μm (314 μm ^{2 in} terms of area).

  The solution used was an aqueous silver colloid solution and was produced as follows.

  First, 23.3 g of Dispervic 190 (manufactured by Big Chemie, solid content rate 40% by mass) and 420.5 g of ion-exchanged water were added to 2 liters of Kolben. The Kolben was placed in a water bath and stirred at 50 ° C. until Dispersic 190 was dissolved. To this, 100 g of silver nitrate dissolved in 420.5 g of ion-exchanged water was added with stirring, and the mixture was stirred at 70 ° C. for 10 minutes. Next, when 262 g of dimethylaminoethanol was added, the liquid turned black instantly and the liquid temperature rose to 76 ° C. When the liquid temperature dropped to 70 ° C. as it was, stirring was continued for 2 hours while maintaining this temperature, and an aqueous solution of silver colloid showing a dark yellow color was obtained.

  The obtained reaction solution was transferred to a 1 liter plastic bottle and allowed to stand in a thermostatic chamber at 60 ° C. for 18 hours. Next, ultrafiltration module AHP1010 (manufactured by Asahi Kasei Co., Ltd .; molecular weight cut off 50000, number of membranes used 400), magnet pump, 3 liter stainless steel cup with tube connection port at the bottom are connected by silicon tube, and ultrafiltration is performed. The device. The reaction solution that had been allowed to stand for 18 hours in a constant temperature room at 60 ° C. was placed in a stainless steel cup, 2 liters of ion exchange water was further added, and then the pump was operated to perform ultrafiltration. After about 40 minutes, when the filtrate from the module became 2 liters, 2 liters of ethanol was added to the stainless steel cup. Thereafter, the filtrate was confirmed to have a conductivity of 300 μS / cm or less, and concentrated until the amount of the mother liquor was 500 ml.

  Subsequently, an ultrafiltration apparatus including a 500 ml stainless steel cup containing mother liquor, an ultrafiltration module AHP0013 (manufactured by Asahi Kasei Corporation; molecular weight cut off 50000, number of membranes used 100), a tube pump, and an aspirator was assembled. The mother liquor obtained previously was put into this stainless steel cup and concentrated to increase the solid content concentration. When the mother liquor reached about 100 ml, the pump was stopped and the concentration was completed to obtain a silver colloid ethanol solution having a solid content of 10%. The average particle size of the silver colloid particles in this solution was 0.017 μm (17 nm). Moreover, when the content rate of the silver in solid content was measured using TG-DTA (made by Seiko Instruments Inc.), it was 90 mass% with respect to 87 mass% of preparation.

  The silver colloid aqueous solution thus produced is ejected by the liquid ejecting head as described above, so that about 1/3 dots overlap each other on a paper-based substrate whose surface properties are changed as shown in FIG. Then, a dot pattern was driven into a wiring pattern. The dot diameter varies depending on the surface properties of the substrate, but is φ40-50 μm. The electrode 91 has a thickness of 0.5 μm and was previously formed by Al sputtering. At this time, the piezoelectric element drive voltage of the droplet jet head was 30 V, and the drive frequency was 12 kHz.

Subsequently, the substrate after pattern formation was placed in an oven and dried at 100 ° C. for 10 minutes to obtain a dry film having a film thickness and a metallic luster of about 0.2 μm. As a result of measuring the surface resistance of the obtained dried film using a Lorester FP (manufactured by Mitsubishi Chemical Corporation) as a measuring instrument, it was impossible to measure (108Ω / □ or more). The dried film was irradiated with light of 5 J / cm ² using a low-pressure mercury lamp, and then heated at 100 ° C. for 40 minutes to obtain a metallic coating. As a result of measuring the surface resistance of the obtained metallic coating using Lorester FP (manufactured by Mitsubishi Chemical Corporation) as a measuring instrument, it was 3.76 × 100Ω / □.

  Next, the electrode 91 was repeatedly energized (pulse voltage 30 V, pulse width 50 ms, pulse interval 100 ms, 60 minutes), and the presence or absence of disconnection was evaluated as durability.

  The results are shown in Tables 2 and 3. Here, (○, x) in pattern shape determination is determined by sensory evaluation while viewing a 100 × microscope image (evaluated by picking up 20 pieces each), ○ is good, and x is bad. . Regarding durability, ○ indicates no disconnection and × indicates disconnection.

  From the results of Tables 2 and 3, the thickness of the cellulose fibers of the paper as the base material and the surface properties (unevenness) due to the gaps formed by overlapping them are smoothed by the coating material (here, calcium carbonate and starch are used) In other words, by making the surface roughness below the unevenness due to the thickness of the cellulose fibers and the gap formed by overlapping them (erasing the unevenness), it becomes a good pattern shape, and there is no disconnection of the wiring pattern and durability It can be seen that an excellent pattern is obtained.

In the present invention, in addition to such a coating material, porous polyimide fine particles (surface resistivity of 10 ¹⁴ Ω / surface) produced as insulating fine particles, for example, an acid anhydride and diisocyanate added with an amine catalyst and reacted. □ or more), AlN fine particles (size: 20 nm to 30 nm) obtained by injecting Al particles (20 μm) into arc plasma, SiO _X fine particles produced by gas evaporation method, and the like can also be suitably used.

  Further, the above experimental example was tested by using a relatively simple wiring pattern as shown in FIG. 26. However, the present invention is not limited to such a simple wiring pattern, and the above-described various materials are used to form a transistor. Even in the case of forming a functional electronic device such as the above, the technology for removing the unevenness of the base material in this way is effective for forming a good electronic device without failure.

  The present invention is a technique for forming a pattern wiring or an electronic device by directly applying an electrical function-expressing material on a paper or a paper-based substrate by an image forming means. The description has focused on image forming means based on the ink jet principle. As another image forming means that can be suitably used in the present invention, there is one based on the Carlson process principle known as so-called electrophotography. This will be described below.

  33 and 34 show an electrophotographic copying apparatus as a typical example for forming an image on paper suitably applied to the image forming means of the present invention. FIG. 33 shows the engine part (image forming part) of the electrophotographic principle (Carlson process principle). Here, a full-color image of a dry two-component development system in which photosensitive drums as a latent image carrier are arranged in tandem. 2 shows an image forming unit of the apparatus.

  FIG. 34 is a diagram showing the whole. In FIG. 34, an image forming unit 101 is disposed substantially at the center of a four-tandem type color image forming apparatus MFP (multifunction printer, multifunction peripheral), and a sheet feeding unit 102 is disposed immediately below the image forming unit 101. The paper feed unit 102 is provided with a paper feed tray 121 at each stage. A reading unit 103 that reads a document is disposed above the image forming unit 101. On the downstream side (left side in the figure) of the image forming unit 101 in the paper conveyance direction, a paper discharge storage unit, a so-called paper discharge tray 104, is provided, on which the discharged image-formed recording paper is stacked.

  In the image forming unit 101, as shown in FIG. 33, a plurality of yellow (Y), magenta (M), cyan (C), and black (K) prints are formed above the intermediate transfer belt 105 formed of an endless belt. An image unit 106 is juxtaposed. In each image forming unit 106, a charging device 162, an exposure unit 165, a developing device 163, a photoconductor cleaning device 164, and the like are arranged along the outer periphery of a drum-shaped photoconductor 161 provided for each color. The charging device 162 performs a charging process on the surface of the photoconductor 161, and the exposure unit 165 irradiates the laser light from the exposure device 107 that irradiates the surface of the photoconductor 161 with image information. The developing device 163 visualizes and develops (develops) the electrostatic latent image formed by exposing the surface of the photoconductor 161 by applying a toner that is a charged fine particle color material. The photoconductor cleaning device 164 The toner remaining on the surface of the photoreceptor 161 after the transfer is removed and collected.

  As an image forming process, an image for each color is formed on the intermediate transfer belt 105, and four colors are superimposed on the intermediate transfer belt 105 to form one color image. At that time, first, yellow (Y) toner is developed in the yellow (Y) image forming unit, and transferred to the intermediate transfer belt 5 by the primary transfer device 166. Next, the magenta (M) image forming unit develops the magenta toner and transfers it to the intermediate transfer belt 105. Next, cyan toner is developed in the cyan (C) image forming portion, transferred onto the intermediate transfer belt 105, and finally black (K) toner is developed, transferred onto the intermediate transfer belt 105, and transferred to four colors. A full-color toner image on which is superimposed is formed. The four-color toner images transferred onto the intermediate transfer belt 105 are transferred by the secondary transfer device 151 to the recording paper 120 fed from the paper feed unit 102, fixed by the fixing device 108, and then discharged. The paper is discharged onto the paper discharge tray 104 by the paper roller 141 or is conveyed to the double-sided device 109. During double-sided printing, the conveyance path is branched by the branching unit 191 and the recording paper 120 is reversed via the double-sided device 109. Then, the registration roller 123 corrects the skew of the sheet, and the image forming operation on the back surface is performed in the same manner as the image forming operation on the front surface. On the other hand, after the full-color toner image is transferred, the toner remaining on the surface of the intermediate transfer belt 105 is removed and collected by the intermediate transfer belt cleaning device 152. Reference numeral 192 denotes a reverse paper discharge path from the duplex device 109. In FIG. 33, Y, M, C, and K representing colors are added after the symbols of the respective parts to distinguish the image forming parts of the respective colors.

  In the paper feeding unit 102, unused recording paper 120 is stored in the paper feeding tray 121, and one end thereof swings to the bottom of the paper feeding tray 121 until the uppermost recording paper 120 contacts the pickup roller 125. The other end of the bottom plate 124 supported is raised. Then, by rotation of the paper feed roller 126, the uppermost recording paper 120 is pulled out from the paper feed tray 121 by the pickup roller 125, and conveyed to the registration roller 123 side by the paper feed roller 126 via the vertical conveyance path 127. . The registration roller 123 temporarily stops the conveyance of the recording paper 120, and sends out the recording paper 120 at a timing so that the positional relationship between the toner image on the intermediate transfer belt 105 and the leading edge of the recording paper 120 becomes a predetermined position. In addition to the recording paper 120 from the vertical conveyance path 127, the registration roller 123 functions similarly for the recording paper 120 conveyed from the manual feed tray 184. In FIG. 34, reference numeral 181 denotes a branching claw, and reference numeral 182 denotes a jam paper discharge tray. When a jam occurs on the downstream side of the vertical conveyance path 127, the branch claw 181 is activated and a sheet is fed to the discharge tray 182. Has the function of deriving.

  In the reading unit 103, first and second traveling bodies 132 and 133 mounted with a document illumination light source and a mirror reciprocate in order to perform scanning scanning of a document (not shown) placed on the contact glass 131. To do. The image information scanned by the traveling bodies 132 and 133 is condensed on the imaging surface of the CCD 135 installed behind by the lens 134 and read by the CCD 135 as an image signal. The read image signal is digitized and subjected to image processing.

  Here, the reading density is used. In the present invention, reading can be performed at a density of 300 dpi, 600 dpi, and 1200 dpi as necessary, and the reading density is selected. Further, after being filtered by the three primary color filters of red (R), green (G), and blue (B), it is read as an image signal by the CCD 135 and is taken in as color image data.

  Then, based on the image-processed signal, optical writing is performed on the surface of the photoreceptor 161 by light emission of a laser diode LD (not shown) in the exposure apparatus 107, and an electrostatic latent image is formed. The optical signal from the LD reaches the photosensitive member 161 (photosensitive members for yellow (Y), magenta (M), cyan (C), and black (K), respectively) through a known polygon mirror and lens. In addition, an automatic document feeder / reader (Auto Document Feeder ADF) 136 that automatically transports the document onto the contact glass is attached to the upper portion of the reading unit 103.

  The above is the description of the image forming means based on the principle of the Carlson process. In the present invention, instead of the above-described toner, an electrical function expressing material is used. In other words, instead of toner for image formation, a conductive material for forming an electrode pattern, a material that develops color by an electric signal, an insulating material, etc. are applied on paper or a paper-based substrate, as if Carlson. Depending on the process principle, various pattern wirings or electronic devices can be formed as if a full-color image is formed. As data for performing such pattern wiring or the like, data taken in by the reading unit 103 as described above may be used, or computer graphics data may be separately input to this apparatus. When such pattern wiring or device formation is performed, a pattern for each material is formed on the intermediate transfer belt 105 as in the case of image formation as described above, and each material is formed on the intermediate transfer belt 105. However, it is not explained as an image forming means based on the Carlson process principle, but it can be transferred to the paper for each material pattern. A laminated pattern may be formed by repeating.

  The toner used in the Carlson process principle is generally a styrene-based (styrene acrylic) or polyester-based (polyester in the case of polymerization method) resin having a size of about 1 to 10 μm, a colorant such as a pigment, and a charge control agent. , Mold release agents, and various external additives. Various colors are produced by this colorant, but the present invention is not intended to produce colors but to provide an electrical function. Therefore, in place of the colorant such as pigment, conductive fine particles, light emitting material, semiconductor material, insulating material, etc., as described for the solution jetted by the above-described ink jet principle, are added to the surface or inside of the resin, and the colorant By using the toner as the electrical function developing material instead of the toner as described above, various pattern wirings and / or electronic device formation can be realized instead of forming a color image.

  In general, image forming means based on the ink jet principle can form a high-speed pattern when nozzles are arranged so as to cover the entire width of the base material, but so-called serial as shown in FIGS. The printer type is slow in pattern formation. However, if the movable range of the ejection head is increased, a pattern can be formed even on a substrate having a large area such as a paper size of A0.

  On the other hand, the image forming means based on the Carlson process principle is capable of high-speed pattern formation (a large amount of high-speed output of 100 to 200 pattern forming sheets per minute is possible). Therefore, it is possible to combine both means to form a pattern of each specialty area. For example, when an insulating layer or a protective layer is formed on the front surface of the substrate, a combination of using an image forming means based on the Carlson process principle and applying a small amount of an electrical function developing material to each device based on the ink jet principle. You may go.

  In addition, the Carlson process, which is good at high-speed pattern formation on the entire surface, provides coating material to smooth the surface properties (unevenness) due to the thickness of the cellulose fibers of the paper as the base material and the gap formed by the overlap. It is also a good method performed by image forming means based on the principle. In this case, when fixing by the fixing device 108, fixing is often performed by a so-called heating and pressure roller, so that in addition to applying a coating material, there is also an advantage that unevenness of the substrate surface is smoothed by this roller.

  As mentioned above, although the example which forms various wiring patterns, an electronic device, etc. with various methods was demonstrated, the formed pattern surface is also protected by methods, such as resin lamination, like the back surface lamination of the above-mentioned base material. It is good.

  More preferably, the various wiring patterns, electronic devices, etc. of the present invention are used by being electrically connected to other electronic components, etc., so the connecting portion is excluded and a protective member such as a resin material is selectively formed. For this purpose, the solution jetting method based on the ink jet principle is a useful method because the selective pattern can be arbitrarily designated, and a protective member can be easily formed using a molten wax-based material.

  Of course, such a protective member made of a resin material may be formed by another printing technique, or may be formed by a technique such as roller coating. Alternatively, a coated / uncoated region may be selectively formed using a photosensitive resin such as a photoresist.

  Here, the term “protection” is intended to protect not only the above-described protection against water but also various wiring patterns, physical impacts, and the like from wiring patterns and electronic devices. Thereby, in the present invention, reliability (water resistance, shock resistance, light resistance, contamination resistance, insulation resistance, etc.) in various aspects of such a novel pattern wiring sheet and electronic device sheet can be ensured. Became.

  Next, other features of the present invention will be described.

  FIG. 35 is an electronic device sheet in which a plurality of electronic devices 200 are formed on paper or a paper-based substrate 10 according to the principle of the present invention. Here, the inside of the electronic device 200 is not described in detail. However, in accordance with the principle of the present invention, a plurality of types of liquids containing an electrical function-expressing material or an insulating material are applied to the base material to combine a number of transistors and the like. This is a so-called integrated circuit device composed of a circuit group. The plurality of electronic devices 200 are arranged via a device separation area 201.

  36, in order to make the device separation region 201 of the electronic device sheet of FIG. 35 more clear, a separation line pattern 202 is provided in that portion (dashed line in FIG. 36). The separation line pattern 202 is also applied in accordance with the principle of the present invention, that is, the same principle as that in which the electrical function developing material is directly applied to paper or a paper-based substrate by the image forming means. The material may be a liquid containing an electrical function-expressing material, or a simple coloring material for identification. Providing such a separation line pattern 202 makes it possible to easily identify the cut portion when the electronic device 200 is separated.

  FIG. 37 shows an example in which such a separation line pattern 202 is formed up to the end of the substrate 10. Thereby, when separating into each electronic device 200, the separation accuracy can be improved.

  The above description has shown an example in which the separation line pattern 202 is printed and formed on the base material 10. However, as another suitable example, the portion of the base material 10 corresponding to the separation line pattern 202 is shown. The intensity may be weaker than other areas. Specifically, a plurality of holes are drilled in a line so that they can be easily separated by hand like a stamp sheet, or so-called perforations are made so that the strength of the part is lower than that of other areas. It is also a good way to keep it. Further, as a weakening configuration, it is not always necessary to perforate the base material 10, and only the portion may be thinned in a line shape.

  As is clear from the above description, the present invention is a technique for manufacturing a pattern wiring substrate or a device substrate, but a very fine pattern of several tens of μm to several μm (more specifically, 50 μm to 1 μm). Instead of using conventional photolithographic technology, a simple device that directly jets liquid droplets containing a material that exhibits an electrical function to a substrate by a jet head having a micro discharge port, which is not conventional, or Carlson By applying image forming means based on the process principle, a pattern or a device is directly manufactured using a toner material containing such an electrical function expressing material. Therefore, an expensive manufacturing apparatus used in a so-called semiconductor manufacturing process is not required, and it can be manufactured stably at a low cost. As a typical example of such pattern formation, an example in which an image forming means based on an ink jet principle or a Carlson process principle is applied has been described. However, other printing means (thermal transfer, offset printing, letterpress printing, intaglio printing, screen printing) Needless to say, printing or the like may be used.

  Another object of the present invention is to propose an apparatus for manufacturing a pattern wiring substrate or an electronic device substrate having a more complicated structure by using such a new electronic component manufacturing apparatus.

  Furthermore, another object is to propose a more specific configuration of such a new electronic component manufacturing apparatus.

  Another object is to propose a more specific configuration of such a new electronic component manufacturing apparatus.

  Another object is to propose a more specific configuration of such a new electronic component manufacturing apparatus.

  Another object is to propose a more specific configuration of such a new electronic component manufacturing apparatus.

  Another object is to propose a new pattern wiring sheet.

  Another object is to enable such a new pattern wiring sheet to be formed with higher accuracy.

  Another object is to ensure the reliability of such a novel pattern wiring sheet.

  Another object is to propose a new electronic device sheet.

  Another object is to enable such a new electronic device sheet to be formed with higher accuracy.

  Another object is to ensure the reliability of such a new electronic device sheet.

  Another object is to propose a configuration capable of more effectively manufacturing such a novel pattern wiring or electronic device.

  According to the invention of claim 2, the liquid containing the electrical function-expressing material is jetted and applied to the paper or the base material based on the paper by the jet head based on the ink jet principle, and the solid content in the liquid is given to the base material. In an electronic component manufacturing apparatus that forms a pattern by dots by forming a pattern, and forms a pattern wiring or an electronic device, the ejection head is a bubble generated instantaneously by heat generated by a heating element disposed in the liquid The liquid at the time of flight is a slender columnar shape extending in the flight direction and having a columnar shape with a length of 5 times or more of its diameter. Using a liquid containing the electrical function expressing material or a liquid having the same physical properties as the jet head different from the jet head and observing the flight shape It is a shape obtained by adjusting a drive signal to a heating element of another ejection head, and the electrical function is expressed by inputting a drive signal based on the adjustment result of the drive signal to the heating element of the ejection head Since the material-containing liquid is sprayed and applied, a new paper or paper-based pattern wiring or electronic device based on a simple principle and structure can be used, regardless of the expensive and complicated construction method of the conventional semiconductor manufacturing process. A new electronic component manufacturing apparatus that can be formed has been realized.

  According to the invention of claim 3, in such an electronic component manufacturing apparatus, the apparatus includes a plurality of the ejection heads, ejects different types of liquids, and stacks the patterns of the different types of liquids. Since the pattern wiring or the electronic device is formed, in addition to the above effects, the pattern wiring or the electronic device having a more complicated structure can be formed.

  According to the invention of claim 4, in such an electronic component manufacturing apparatus, the base material is held by the base material holding means, and the plurality of ejection heads are mounted on a carriage and moved to face the base material. In addition to the above effects, the pattern is not destroyed, and the solution is sprayed, and after the pattern formed previously is sprayed, the next different solution is sprayed to form the laminated pattern. A highly reliable pattern wiring or electronic device can be formed.

  According to the invention of claim 5, in such an electronic component manufacturing apparatus, the base material is transported by the base material transporting means, and the plurality of ejection heads are mounted on a carriage and move to face the base material. When the solution is ejected and the next pattern is stacked after the pattern is formed first, the base material is returned to the position where the previous spraying is started by the base material conveying means, and the next different solution Since the laminated pattern is formed by spraying, in addition to the above effects, it is possible to form a pattern wiring or an electronic device having high accuracy, high reliability, and a complicated configuration without pattern collapse. It was.

  According to the invention of claim 6, in such an electronic component manufacturing apparatus, the base material is transported by the base material transporting means, and after forming the pattern on one surface, the base material is reversed by the transporting means. Since the pattern is formed on the other surface, in addition to the above effects, a higher-performance pattern wiring or electronic device, or a miniaturized pattern wiring or electronic device can be formed. It was.

  According to the invention of claim 7, a pattern wiring in which a dot pattern of a liquid containing an electrical function-expressing material is formed on paper or a paper-based substrate, and the solid content in the liquid remains. Since it is a sheet, a new paper or a paper-based pattern wiring sheet based on a simple principle and structure can be realized without using an expensive and complicated method as in the conventional semiconductor manufacturing process.

  According to the invention of claim 8, a dot pattern of a liquid containing an electrical function expressing material is formed on a surface provided with a coating material that erases irregularities of paper or paper fibers of a base material based on paper. Because it is a pattern wiring sheet in which the solid content remains, it is based on a new paper or paper based on a simple principle and structure, regardless of expensive and complicated construction methods like the conventional semiconductor manufacturing process In the pattern wiring sheet, a highly accurate and reliable pattern wiring sheet could be obtained.

  According to the invention of claim 9, in such a pattern wiring sheet, a plurality of the dot patterns are connected to form a belt-like pattern, and the belt-like pattern is a belt-like pattern formed by a combination of dots in parallel directions in two orthogonal directions. Since the outer region of the region bent in the two directions of the pattern has a curved shape, a highly reliable pattern wiring sheet can be obtained.

  According to the invention of claim 10, an electronic device in which a dot pattern of an electric function expressing material-containing liquid is formed on paper or a paper-based substrate, and the solid content in the liquid remains. Since it is a sheet, a new paper or a paper-based electronic device sheet with a simple principle and structure can be realized without using an expensive and complicated method as in the conventional semiconductor manufacturing process.

  According to the invention of claim 11, a dot pattern of a liquid containing an electrical function-expressing material is formed on a surface provided with a coating material that erases irregularities of paper or paper fibers of a base material based on paper. Because it is an electronic device sheet in which the solid content remains, it is based on a new paper or paper based on a simple principle and structure, regardless of an expensive and complicated construction method like the conventional semiconductor manufacturing process In the electronic device sheet, it was possible to obtain a highly accurate and highly reliable electronic device sheet.

  According to the invention of claim 12, in such an electronic device sheet, a plurality of the dot patterns are connected to form a belt-like pattern, and the belt-like pattern is a belt-like pattern formed by a combination of dots parallel to each of two orthogonal directions. In addition, since the outer region of the region bent in the two directions of the pattern has a curved shape, a highly reliable electronic device sheet can be obtained.

  According to the invention of claim 13, the wiring formed by forming the dot pattern of the liquid containing the electrical function material on the front and back of the paper or the paper-based substrate, and leaving the solid content in the liquid remaining Because it is a sheet on which patterns and / or electronic devices are formed, new paper or paper-based wiring based on a simple principle and structure, regardless of the expensive and complicated method of construction used in conventional semiconductor manufacturing processes Patterns or electronic devices could be made more sophisticated and miniaturized.

  Each of the above-described embodiments is a preferred embodiment of the present invention, and various modifications can be made without departing from the scope of the present invention.

It is a figure for demonstrating one Example of the pattern wiring formed with the electronic component manufacturing apparatus of this invention. It is a figure for demonstrating one Example of the electronic component manufacturing apparatus which manufactures the pattern wiring base material or device base material of this invention. It is a figure for demonstrating the other Example of the electronic component manufacturing apparatus which manufactures the pattern wiring base material or device base material of this invention. It is an image figure which shows the cellulose fiber of the paper used as the base material of this invention. It is a schematic block diagram which shows the droplet application apparatus applied to manufacture of the pattern wiring base material or device base material of this invention. It is a figure which shows the layer structural example (top gate type) of the organic transistor element formed using this invention. It is a figure which shows the other layer structural example (bottom gate type) of the organic transistor element formed using this invention. It is a block diagram of the organic electroluminescent element formed using this invention. It is a figure explaining the droplet ejection principle of the liquid jet head using a piezoelectric element used suitably for this invention. FIG. 3 is a diagram illustrating a structure of a liquid jet head using a piezoelectric element that is preferably used in the present invention. It is a shape of a droplet when ejected by a liquid ejecting head using a piezoelectric element that is preferably used in the present invention. This is a case where the shape of the droplet is ejected by a liquid ejecting head using a piezoelectric element that is preferably used in the present invention, and is slightly elongated. 2 is an example of a thermal type (bubble type) liquid jet head suitably applied to the present invention. It is a shape at the time of flight of a solution when ejected by a thermal (bubble) liquid ejecting head suitably used in the present invention. FIG. 5 is a diagram of a multi-nozzle type liquid jet head viewed from the nozzle side. FIG. 5 is a diagram illustrating a unit in which a multi-nozzle liquid ejecting head is stacked for each liquid to be ejected. It is a perspective view of the head unitized. It is a figure for demonstrating the example which forms a pattern wiring combining the dot of a droplet or a liquid by the principle of this invention. It is a figure for demonstrating the example which forms a device combining the dot of a droplet or a liquid by the principle of this invention. It is a figure for demonstrating the example which improved the abnormal discharge in a corner part in the example of FIG. It is a figure for demonstrating the example which improved the abnormal discharge in a corner part in the example of FIG. It is an example of the figure for demonstrating the other which improved the abnormal discharge in a corner part in the example of FIG. It is a figure for demonstrating the other example which improved the abnormal discharge in a corner part in the example of FIG. It is a figure for demonstrating the example which covered the corner part in the example of FIG. 18, and improved abnormal discharge. It is a figure for demonstrating the example which coat | covered the corner part and improved abnormal discharge in the example of FIG. It is a figure for demonstrating the other example which improved the abnormal discharge in a corner part. It is a figure for demonstrating the other example which improved the abnormal discharge in a corner part. It is the figure which expanded a part (corner part) of the wiring pattern of FIG.1 (B). It is a figure for demonstrating one example of the pattern wiring of the pattern wiring base material formed by the principle of this invention. It is a figure for demonstrating the other example of the pattern wiring of the pattern wiring base material formed by the principle of this invention. It is a figure for demonstrating the example of 1 device of the device base material formed by the principle of this invention. It is a figure for demonstrating the other example of the device of the device base material formed by the principle of this invention. FIG. 3 is a diagram illustrating an image forming unit of a full-color image forming apparatus of a dry two-component development system in which photosensitive drums are arranged in tandem as a latent image carrier of the Carlson process principle used in the electronic component manufacturing apparatus of the present invention. FIG. 2 is a diagram showing an entire full-color image forming apparatus of a dry two-component development system in which photosensitive drums are arranged in tandem as a latent image carrier of the Carlson process principle used in the electronic component manufacturing apparatus of the present invention. 1 is an electronic device sheet formed with a plurality of electronic devices manufactured according to the principle of the present invention. It is the example which provided the line pattern for device separation in the electronic device sheet | seat of this invention. It is another example of the device separation line pattern provided in the electronic device sheet of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Wiring pattern 2, 3 Terminal 4 Source electrode 5 Drain electrode 6 Gate insulating layer 7 Gate electrode 8 Organic-semiconductor layer 9 Element protective layer 10 Base material 23 Electrode 24 Barrier member 25 Organic EL light emitting layer 26 Transparent electrode 27 Transparent sheet 28 Power supply 29 Light 92 Wiring pattern (electrode pattern)
91, 93 Electrode pattern portion 94 Dot pattern 101 Image forming portion 102 Paper feed portion 103 Reading portion 104 Paper discharge tray 105 Intermediate transfer belt 106 Image forming portion 107 Exposure device 108 Fixing device 109 Double-sided device 120 Recording paper 121 Paper feed tray 123 Resist Roller 124 Bottom plate 125 Pickup roller 126 Paper feed roller 127 Vertical transport path 131 Contact glass 132 First traveling body 133 Second traveling body 134 Lens 135 CCD
136 Automatic Document Feeder and ADF (Auto Document Feeder ADF)
141 Paper discharge roller 1512 Next transfer device 152 Intermediate transfer belt cleaning device 161 Photoconductor 162 Charging device 163 Development device 164 Photoconductor cleaning device 165 Exposure unit 1661 Primary transfer device 181 Branch claw 182 Jam paper discharge tray 184 Manual feed tray 191 Branch 192 Reverse paper discharge path 200 Electronic device 201 Device separation area 202 Separation line pattern

Claims (13)

A liquid containing an electrical function-expressing material is jetted onto a paper or a paper-based base material by an ink jet principle jet head, and a solid pattern in the liquid is left on the base material to form a pattern by dots. In an electronic component manufacturing apparatus for forming and forming pattern wiring or electronic devices,
The ejection head is an ejection head that ejects the liquid with an action force due to mechanical displacement of an electromechanical conversion element, and the liquid at the time of flight has a substantially round droplet shape immediately before adhering to the substrate surface, or A columnar shape that extends in the flight direction and has a length that is less than three times the diameter of the column, and has a shape that does not involve a plurality of minute droplets behind the flying liquid. A drive signal to the electromechanical transducer element of the another jet head using the jet liquid containing the electrical function expressing material or a fluid having fluid properties equivalent to the same and observing the flight shape The liquid containing the electrical function-expressing material is ejected by applying a drive signal based on the adjustment result of the drive signal to the electromechanical conversion element of the ejection head. Electronic component manufacturing apparatus according to claim. A liquid containing an electrical function-expressing material is jetted onto a paper or a paper-based base material by an ink jet principle jet head, and a solid pattern in the liquid is left on the base material to form a pattern by dots. In an electronic component manufacturing apparatus for forming and forming pattern wiring or electronic devices,
The ejecting head is an ejecting head that ejects the liquid with a growth action force of bubbles generated instantaneously by heat generated by a heating element disposed in the liquid, and the liquid at the time of flight extends in the flight direction. It is a columnar shape that is an elongated column and has a length that is at least five times the diameter of the column. The shape is an ejection head that is different from the ejection head, and has the electrical function expressing material-containing liquid or a fluid property equivalent thereto. A shape obtained by adjusting a drive signal to the heating element of the another ejection head while observing the flying shape of the liquid, and a drive signal based on the adjustment result of the drive signal is transmitted to the ejection head The electronic component manufacturing apparatus is characterized in that the electric function expressing material-containing liquid is sprayed and applied by inputting to the heating element.   3. The pattern wiring or the electronic device is formed by having a plurality of the ejection heads, ejecting different types of liquids, and laminating the patterns of the different types of liquids. The electronic component manufacturing apparatus described.   The substrate is held by a substrate holding means, and the plurality of ejection heads are mounted on a carriage and move to face the substrate to eject the solution, and after drying the pattern formed earlier, The electronic component manufacturing apparatus according to claim 3, wherein the stacked pattern is formed by spraying different solutions.   The base material is transported by a base material transport means, and the plurality of ejection heads are mounted on a carriage and move to face the base material to eject the solution. 4. When forming a laminate, the substrate is returned to a position where the previous injection is started by the substrate conveying means, and the next different solution is injected to form the laminate pattern. The electronic component manufacturing apparatus described.   The substrate is conveyed by a substrate conveying means, and after forming the pattern on one surface, the substrate is reversed by the conveying means, and a pattern is also formed on the other surface. Item 6. The electronic component manufacturing apparatus according to any one of Items 1-5.   A pattern wiring sheet, wherein a dot pattern of an electric function expressing material-containing liquid is formed on paper or a paper-based substrate, and the solid content in the liquid is left.   A dot pattern of a liquid containing an electrical function-expressing material is formed on a surface provided with a coating material that erases the unevenness of the paper fiber of the paper or a paper-based substrate, and the solid content in the liquid remains. A pattern wiring sheet characterized by that. A plurality of the dot patterns are connected to form a belt-like pattern, and the belt-like pattern is a belt-like pattern formed by a combination of dots parallel to each of two orthogonal directions, and the outer region of the region that is bent in the two directions is curved. The pattern wiring sheet according to claim 7 or 8, wherein the pattern wiring sheet has a shape.   An electronic device sheet, wherein a dot pattern of a liquid containing an electrical function-expressing material is formed on paper or a paper-based substrate, and the solid content in the liquid is left.   A dot pattern of a liquid containing an electrical function-expressing material is formed on a surface provided with a coating material that erases the unevenness of the paper fiber of the paper or a paper-based substrate, and the solid content in the liquid remains. An electronic device sheet characterized by that. A plurality of the dot patterns are connected to form a belt-like pattern, and the belt-like pattern is a belt-like pattern formed by a combination of dots parallel to each of two orthogonal directions, and the outer region of the region that is bent in the two directions is curved. The electronic device sheet according to claim 10 or 11, wherein the electronic device sheet has a shape.   Form a dot pattern of liquid containing an electrical function material on the front and back of paper or a paper-based substrate, and form a wiring pattern and / or electronic device formed by leaving the solid content in the liquid. A sheet characterized by that.

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