JP2008168478A - Printing letterpress and manufacturing method of printing letterpress - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To attain a manufacturing method of printed matter being free from mixing of colors of ink and a printing fault such as a pattern slippage, in regard to the printed matter which requires patterning of a high-precision organic thin film such as an organic EL element, and to attain a plate enabling execution of this method and a manufacturing method of the plate. <P>SOLUTION: The printed matter is manufactured by using a printing letterpress which has a projecting metal pattern 103 on a base and has a resin layer 101 corresponding to a transfer area of a head top part of the projecting metal pattern 103 and an ink-repellent layer 102 covering a peripheral area of the surface of the projecting metal pattern 103. Moreover, the lateral side part of the projecting metal pattern 103 is covered with the ink-repellent layer 102. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a high-definition printing relief plate used in a relief printing method and a printed matter produced using the high-definition printing relief plate.

An organic electroluminescence element (hereinafter referred to as an organic EL element) is an element in which an organic light emitting layer made of an organic light emitting material is formed between two opposing electrodes, and light is emitted by passing a current through the organic light emitting layer. In order to emit light efficiently, the thickness of the light emitting layer is important, and it is necessary to form a thin film of about 100 nm. Furthermore, in order to make this a display capable of color display, it is necessary to pattern the organic EL element with high definition.

Organic light-emitting materials include low-molecular materials and high-molecular materials. In general, low-molecular materials are formed into thin films by resistance heating vapor deposition or the like, and then patterned using a fine pattern mask. There is a problem that the patterning accuracy is less likely to increase as the size increases.

Therefore, recently, a method of using a polymer material as an organic light emitting material, dissolving the organic light emitting material in a solvent to form a coating liquid, and forming a thin film by a wet coating method or a printing method has been tried. . The wet coating method for forming a thin film includes a spin coating method, a bar coating method, a discharge coating method, a dip coating method, and the like. It is difficult with the wet coating method. Therefore, it is effective to form a thin film by a printing method that is good at coating patterning.

Further, among various printing methods, in a display such as an organic EL element, a glass substrate is often used as a substrate, so a method using a hard plate such as a metal printing plate such as a gravure printing method is unsuitable, An offset printing method using an elastic rubber plate and a relief printing method using a photosensitive resin plate mainly composed of rubber or other resin are optimal. As attempts of these printing methods, a method by offset printing (Patent Document 1), a method by letterpress printing (Patent Document 2), and the like have been proposed.

JP 2001-93668 A JP 2001-155858 A

The pattern of the organic light emitting layer in the organic EL element has a line width of 100 μm and a pixel pitch of 500 μm in a wide display of 40 inches, for example, in a large display for television use. In the case of a small display such as a mobile phone, for example, in a mainstream QVGA (320 × 240 pixels) with a diagonal size of 2 inches, the pixel pitch is 120 μm, and the width of the sub-pixel of each color element is 40 μm. When such a high-definition display element is to be formed by the relief printing method, a very high printing pattern accuracy of 5 μm or less is required.

However, for example, in order to manufacture a display with a resolution of 200 ppi, lines and spaces with a pitch of about 40 μm are required per subpixel. Therefore, if the pattern accuracy is poor, the contact between the electrode layer and the hole transport layer or the electron transport layer A short circuit due to, and adjacent organic light emitting layers are mixed and color mixing occurs. Due to such a problem, a high-definition printing pattern with sufficient quality could not be formed with a conventional resin relief printing plate. Also, when inking into such a high-definition printing plate, ink oozes out into the concave portions of the plate, the ink of adjacent convex portions mixes, and this overflows and the mixed color ink is transferred to the printing medium. May end up. Furthermore, when the interval between the concave portions becomes narrow, it is difficult to form a print pattern because adjacent convex patterns are connected to each other.

From the technical background as described above, in the present invention, when a printing pattern that requires very high printing accuracy such as an organic functional layer in an organic EL element is formed by a relief printing method, color mixing due to outflow of ink is performed. It is an object of the present invention to provide a new relief printing plate for high-definition printing that does not cause printing defects such as the above and a method for producing the same, and to provide a high-quality printed matter using these.

The invention according to claim 1, which has been made to solve the above problems, includes a convex metal pattern on a substrate, an ink-repellent layer that covers a peripheral region of the top of the convex metal pattern, and the convex shape. And a resin layer that covers a transfer region at the top of the metal pattern. The transfer region consists of a portion other than the peripheral region at the top of the convex metal pattern.

The invention according to claim 2 is the printing relief plate according to claim 1, wherein a side surface portion of the convex portion is covered with an ink-repellent layer.

The invention according to claim 3 is a substrate having a metal surface, a convex metal pattern on the substrate, an ink-repellent layer covering a peripheral region of the top of the convex metal pattern, and the convex A printing relief plate comprising: a resin layer covering a transfer region at the top of a metal pattern; and an ink-repellent layer covering a side surface portion of the convex metal pattern and an exposed surface of the substrate surface. is there.

The invention according to claim 4 is the relief printing plate according to any one of claims 1 to 3, wherein the area of the surface region of the resin layer is larger than the area of the bottom surface region of the resin layer. .

The invention according to claim 5 is the relief printing plate according to any one of claims 1 to 4, wherein a step between the resin layer and the ink repellent layer is 5 μm or less.

The invention according to claim 6 is characterized in that the height of the ink-repellent layer from the substrate surface is 0.5 to 3 μm higher than the height of the resin layer from the substrate surface. The relief printing plate according to any one of 1 to 5

According to a seventh aspect of the present invention, there is provided a step of supplying ink from an ink supply body to the transfer region of the printing relief printing plate according to any one of the first to sixth aspects, and transferring the ink to a printing medium to obtain an ink pattern. Forming a printed material.

The invention according to claim 8 is the method for producing an organic electroluminescence device comprising at least a first electrode, one or more organic light emitting medium layers, and a second electrode, wherein at least one of the organic light emitting medium layers is according to claim 7. It is the manufacturing method of the organic electroluminescent element characterized by printing-forming using the manufacturing method of printed matter.

The invention according to claim 9 is a method for producing a relief plate having the convex pattern for transferring ink from a transfer region of the convex top portion of the convex pattern on the substrate to the printing material, Forming a convex metal pattern on the substrate; forming a resin layer in a transfer region of the top of the convex metal pattern; and forming an ink repellent layer in a peripheral region of the top of the convex metal pattern. And a step of forming at least a relief printing plate manufacturing method.

The invention according to claim 10 is the method for producing a relief printing plate according to claim 9, wherein the convex metal pattern is formed by electroforming.

The invention according to claim 11 is the method for producing a relief printing plate according to claim 9, wherein the convex pattern is formed by using an etching method.

The invention according to claim 12 is the method for producing a relief printing plate according to any one of claims 9 to 11, wherein the resin layer is formed by a photolithography method.

The invention according to claim 13 is the relief printing plate according to claim 12, wherein a negative photosensitive resin is used as a material of the resin layer.

The invention according to claim 14 is the method for producing a relief printing plate according to any one of claims 9 to 11, wherein the resin layer is formed by an electrodeposition method.

The invention according to claim 15 is the method for producing a relief printing plate according to any one of claims 9 to 14, wherein the ink repellent layer is formed by using an electrodeposition method.

According to the relief plate of the invention according to claim 1, since the convex portion of the relief plate is made of metal, deformation of the plate is suppressed, and the pattern is not crushed by pressure during printing, so that the resolution of the pattern is not lowered. It was. In addition, by covering the top of the convex portion with a resin layer, it can be printed without damaging even a hard substrate such as a glass substrate by showing flexibility at the time of printing similar to a resin plate, Further, since the ink repellent layer is provided on the peripheral edge of the top of the relief printing plate, ink is not connected between adjacent patterns during inking. As a result, printing with fewer printing defects due to misalignment of printing patterns or color mixing of inks can be performed.

By providing the ink-repellent layer on the exposed surface of the convex portion side surface in the invention according to the first aspect, the intaglio pattern of the invention according to the second aspect allows ink to be connected between adjacent patterns and ink to flow into the concave portion. Since it can be prevented more effectively, as a result, printing with fewer printing defects due to misalignment of printing patterns or color mixing of inks and the like has become possible.

By protecting the exposed metal surface with an ink repellent layer by the relief plate of the invention according to claim 3, damage to the plate due to metal corrosion or the like could be prevented. This made a durable plate.

According to the invention of claim 4, the area of the top of the convex pattern can be used efficiently, the deformation of the resin layer can be suppressed, and the flatness of the plate surface can be maintained. As a result, printing with less printing unevenness was made possible by a durable relief printing plate.

According to the invention of claim 5, the ink appropriately supplied to the resin layer can be transferred to the printing medium. Furthermore, the invention according to claim 6 makes it possible to fix the ink to the resin layer, and as a result, it is possible to perform high-definition printing with less printing defects due to misalignment of the printing pattern or color mixing of the inks.

According to the invention according to claim 7, by performing printing using a metal plate with little deformation, a resin layer on the top of the plate, and a plate having an ink repellent layer in the peripheral region, there is no deformation of the plate, and the ink Since the outflow is suppressed, it has become possible to produce high-definition printed matter with few printing defects due to misalignment of printing patterns and ink color mixing.

According to the invention according to claim 8, the deformation of the plate is prevented by forming the organic light emitting medium layer by using a metal plate with less deformation, a plate having a resin layer at the top thereof, and an ink repellent layer in the peripheral region. In addition, since the outflow of the ink is suppressed, it is possible to manufacture a high-quality organic EL element free from uneven light emission and short circuit.

According to the invention according to claim 9, since the convex portion of the invention according to claim 1 is made of a metal, the deformation of the plate is suppressed, and the pattern is not crushed by the pressure during printing. The top of the convex part is covered with a resin layer without lowering the resolution of the projection, showing flexibility at the time of printing similar to that of a resin plate, for a hard substrate such as a glass substrate Can be printed without damage, and there is an ink-repellent layer on the periphery of the top of the relief plate, making it possible to produce high-performance plates that do not connect ink between adjacent patterns during inking. It was.

According to the invention of claim 10, by forming the metal pattern of the plate using the electroforming method, it is possible to manufacture a high-definition plate with good pattern accuracy.

According to the eleventh aspect of the present invention, it is possible to manufacture a plate having excellent transfer surface flatness by forming a metal pattern using an etching method.

According to the invention of claim 12, by forming a resin layer using a photolithography method, a plate having a precise transfer region can be manufactured, and a high-definition printed matter can be manufactured.

According to the thirteenth aspect of the present invention, by using a negative photosensitive resin for the resin layer, a higher-definition resin layer pattern can be formed, and further, the resin layer can be easily formed into a reverse taper shape. It was. Since it can be formed in an inversely tapered shape, it is possible to efficiently use the region of the top of the plate, and furthermore, it is possible to produce a plate having flatness and less deformation of the resin layer.

According to the invention of claim 14, by forming an ink repellant layer by an electrodeposition method, it becomes possible to easily form an ink repellant layer on the metal surface, and there is no corrosion of the metal and durability. An excellent version can be manufactured.

<Letterpress>
FIG. 1 shows an example of a relief printing plate according to the present invention.

Fig.1 (a) is an example of the pattern shape of the relief printing plate surface of this invention. As a pattern of a plate used for manufacturing an organic functional element such as an organic EL element or a display element such as a color filter, a line pattern or a dot pattern is used. As shown in the drawing, the line width or pattern width of the plate surface convex portion is a, and the interval between adjacent convex patterns is b.

FIG. 1B is a cross-sectional view taken along the line P in FIG. Various materials can be used as the material of the substrate 100 as described in the description of the manufacturing method. In addition, when an electroforming method is used for plate production as described later, it is necessary to use a metal for the base material or to provide a metal film on the base material. When an etching method is used for producing a plate, the substrate 100 is formed by forming a resin layer on the substrate and etching portions other than the resin layer as described later in the section of the plate producing method. The metal convex part 103 can be formed.

Assuming that the plate depth from the top to the bottom of the convex pattern is d, conventionally, when printing a high-definition print pattern, the ink overflowing from the top during printing is leached into the concave portion, and the adjacent convex portion Ink mixed with the ink from No. 1 may be transferred to the printing medium, resulting in poor printing. Therefore, it is preferable that the aspect ratio a / d of the plate width and the plate depth is 1 or more because it is possible to prevent the ink leached into the recesses from overflowing. However, when such a convex pattern having a high aspect ratio is formed of resin, the strength is insufficient, so that the plate is deformed or damaged, resulting in printing failure.

Therefore, the above-described problems can be solved by forming the metal convex portion 103 as described above, forming a convex metal pattern, and covering the top of the metal pattern with a resin layer, and further, a glass substrate. Thus, the ink pattern can be transferred onto a hard and easily damaged substrate. This resin layer is preferably 1 μm or more so as not to damage the substrate to be printed during printing. Further, if the resin layer becomes too thick, the resin layer may be deformed or swelled during printing, and printing unevenness may occur.

Further, when the interval b between the adjacent convex patterns becomes narrow, the ink supplied to the top of the convex portion may come into contact with and connect with the adjacent convex portions. In this case, the ink transferred from the plate to the printing medium becomes a printing defect, and in the case of an organic EL element, a problem such as a short circuit or mixed color emission occurs.

Therefore, in the present invention, the area around the top of the convex portion of the convex pattern is an ink-repellent layer (ink-repellent layer), so that an area where ink can be reliably inhibited is formed, and the ink on the adjacent tops It became possible to prevent the connection. In addition, the ink-repellent layer covers the side surfaces of the convex portions of the convex pattern and the exposed substrate surface to prevent corrosion and influence of metal parts, and further suppresses ink entry into the concave portions. It is preferable because it can be done.

The resin layer at the top of the convex portion is desirably as flat as possible so as not to cause unevenness in the printed pattern to be transferred. Moreover, it is preferable that this resin layer has a large area of the resin layer on the top surface relative to the contact surface (bottom surface portion) with the metal convex surface, for example, a reverse taper shape (FIG. 1C). By having a shape like a reverse taper, the area of the crown located immediately above the metal convex portion can be used efficiently. This is important in the case of high-definition printing, because the convex pattern interval b becomes narrow and causes problems as listed in the problem, so that the transfer region is widened as much as possible and the interval b is not narrowed. . Further, as compared with the case of the forward taper shape, the deformation of the end of the resin layer sinks and is sunk under the ink repellent layer. Furthermore, when an ink repellent layer is formed by an electrodeposition method in the plate manufacturing process described later, since the material constituting the ink repellent layer is laminated on the metal surface, it is preferable that the area of the metal surface is wide. . For this reason, a shape such as a reverse taper shape in which the area of the surface region of the resin layer is larger than the area of the bottom surface of the resin layer is preferable.

The step between the resin layer and the ink repellent layer in the region around the top of the head is preferably at least 5 μm or less, more preferably 3 μm or less, particularly for high-definition printing such as organic EL. If the height of the ink-repellent layer is lower than this, the ink at the top of the head may flow out into the recesses. Conversely, if the height of the ink-repellent layer is high, the ink supplied to the resin layer is ink-repellent. This is because there is a case where the film cannot be completely transferred due to being blocked by the layer. Furthermore, the ink is fixed to the transfer area even at the time of transfer by using a relief printing plate in which the height of the ink repellent layer is higher than that of the resin layer as the transfer area in the range of 0.5 to 3 μm (FIG. 1 (c)). Therefore, it is possible to form a fine pattern. If the thickness is 3 μm or more, the ink repellent layer may be an obstacle as described above, and the ink in the transfer region may not be transferred well. If the thickness is 0.5 μm or less, the effect is insufficient.

In addition, it is more preferable that the other region of the top of the convex portion, that is, the transfer region is a layer (parent ink layer) having an affinity for ink in order to fix the supplied ink.

In order to print a fine organic thin film printing pattern such as an organic EL, the aspect ratio a / d of the plate width and plate depth is set to 1 or more as described above in order to prevent ink color mixing. However, it is preferable that the plate depth is 30 μm or more, more preferably 50 μm or more, with respect to the pattern width of the protrusions of 60 μm or less. When the convex pattern becomes as fine as 60 μm or less, the ink film thickness becomes higher than when it is applied on a flat surface due to surface tension when ink is applied to the surface of the convex part. This is because the ink may flow into the recesses, and if the plate depth is 30 μm or less, the inflowed ink may overflow and cause color mixing or misalignment of the printing pattern.

<Manufacture of letterpress>
Next, the manufacturing method of the relief printing plate of this invention is demonstrated based on FIG.2 and FIG.3.

As the relief printing base material 200 in the present invention, a plastic film such as glass, quartz, polypropylene, polyethersulfone, polycarbonate, cycloolefin polymer, polyacrylate, polyamide, polymethylmethacrylate, polyethylene terephthalate, polyethylene naphthalate, Sheets, silicon wafers, nickel iron alloys such as stainless steel and invar materials, and nickel cobalt iron alloy plates such as super invar can be used.

In addition, for example, in the case of using an electroforming method for forming the metal protrusions described later, a metal film such as chromium or aluminum may be formed on the formation portion. Alternatively, an insulating film such as a metal oxide, a metal nitride, a metal oxynitride film, or a polymer resin film may be formed on a non-formed portion on the metal substrate. Furthermore, a plastic film may be laminated on the back surface of the metal plate. Similarly, when an etching method is used, an insulating film such as a metal oxide, metal nitride, metal oxynitride film, or polymer resin film, a metal film, or a plastic film is used to protect a portion that is not desired to be removed. It may be formed.

In the above-mentioned base material, in order to form a high-definition pattern with high positional accuracy particularly on a large substrate, the base material having a thermal expansion coefficient of 50 × 10 −7 / ° C. or lower, more preferably 20 × 10 −7 / ° C. or lower. It is good to choose. Furthermore, it is more preferable to have flexibility that can be wound around a printing roll. As an example of such a base material 101, it is preferable to use a metal sheet having a low thermal expansion coefficient such as Invar material or Super Invar material. As the thickness of the metal sheet, it is sufficient that the metal sheet has sufficient flexibility to be wound around a printing plate copper and has a strength that does not deform due to heat or impact, and is preferably 0.5 mm or less, more preferably 0.8 mm. 3 mm or less can be used suitably.

First, as shown in FIGS. 2 (1d) and 2 (2d), a convex metal pattern 204 composed of metal convex portions is formed. As a method for forming a convex metal pattern, there are a method of depositing a metal film on a base material, or a method of forming a pattern by shaving the surface of the base material by etching.

As a method of forming the convex metal pattern 204 by depositing a metal film on a substrate, an electroforming method, a wet coating method, a CVD method, a sputtering method, a vapor deposition method, or an ion plating method is used as necessary. can do. For metal deposition, it is preferable to use an electroforming method that can be uniformly embedded in the recess without any gap. In other methods, it is possible to form a convex pattern by depositing metal in a pattern using a mask. However, in the production of a high-definition plate, which is the subject of the present invention, the pattern accuracy is high. This is because the characteristics of the electroforming method as described above are suitable. When the electroforming method is used, as described above, a metal substrate or a substrate on which a metal film is formed is used. There is no restriction | limiting in particular as a metal, For example, nickel, chromium, copper, gold | metal | money, aluminum, silver, iron etc. can be used.

First, a process of forming the convex metal pattern 204 by a method of depositing a metal film on a substrate will be described with reference to FIG. First, the photosensitive resin layer 201 is laminated on the substrate 200 (FIG. 2 (1a)). Next, by using a photolithography method, unnecessary portions are removed to form a plurality of convex patterns 202 (FIG. 2 (1b)). The convex pattern of the photosensitive resin formed at this time is a pattern that is inverted with respect to the convex pattern of the letterpress finally produced. Next, metal 203 is deposited in the gap recesses of the convex pattern 202 of the photosensitive resin (FIG. 2 (1c)). Finally, the convex metal pattern 204 can be formed by removing the convex pattern 202 of the photosensitive resin.

In the case of producing a plate by an etching method, the photosensitive resin layer 201 is similarly laminated on the substrate 200, and then unnecessary portions are removed by using a photolithography method to form a plurality of convex patterns 202 ( FIG. 3 (2b)). At this time, unlike the electroforming method, the convex pattern of the photosensitive resin to be formed is formed at the same location as the convex pattern of the relief plate to be finally produced. Next, using a wet etching method or a dry etching method, a portion of the substrate 200 where the convex pattern of the photosensitive resin is not formed is etched to form a concave portion 205 (FIG. 3 (2c)). Next, the convex metal pattern 204 can be formed by removing the convex pattern 202 of the photosensitive resin (FIG. 3 (2d)). According to the etching method, since the top of the convex metal pattern 204 hits the substrate surface, the height of the convex portion is excellent in uniformity and flatness.

The material of the photosensitive resin layer 201 is not particularly limited, but is preferably resistant to a plating solution and an etching solution. Furthermore, it is preferable to select one that can be easily removed with an organic solvent or an aqueous alkali solution. Resins such as acrylic, epoxy, nylon, polyester, urethane, silicone, polyvinyl alcohol, polyimide, and novolac can be used depending on the application. The thickness is not particularly limited, but when a metal plate is produced by electroforming, the pattern of the metal plate is determined by the photosensitive resin layer 201. Therefore, it is necessary at least as the plate depth of the relief printing plate. The thickness is preferably 30 μm or more, more preferably 50 μm or more. As a suitable means for forming such a thick resin on a large-area substrate, a negative acrylic or epoxy-based commercially available dry film resist can be used. On the other hand, when a metal plate is produced by an etching method, the thickness of the resist is not particularly limited, and resistance to an etching solution is required.

Next, a method of forming a resin layer and an ink repellent layer on the convex metal pattern produced by the process of FIG. 2 will be described with reference to FIG.

The resin layer 303 is not particularly limited in formation method, but can be formed by using, for example, a photolithography method or an electrodeposition method as in the step of FIG.

In the case of the photolithography method, a photosensitive resin is formed on the substrate 300 on which the convex pattern 301 is formed by a coating method such as a spin coating method, a slit coating method, a laminating method, a bar coating method, a roll coating method, or a knife coating method. A film 302 is formed (FIG. 3 (1b)), and a resin layer 303 is formed only on the convex pattern by photolithography (FIG. 3 (1c)). Since the resin layer 303 is formed in the central region of the convex metal pattern 301 and the upper part of the resin layer 303 affects the width and linearity of the print line, in order to obtain a normal print line pattern, The upper side of the resin layer 303 is preferably flat. In addition, it is more preferable that the width of the upper side of the resin layer 303 is narrower than the width of the upper side of the convex metal pattern 301 because an ink-repellent layer 304 described later can be formed with a film thickness substantially the same as that of the resin layer 303.

Further, as a method of obtaining the resin layer 303 by the electrodeposition method, for example, after forming the photosensitive resin film 302 as shown in FIG. 3B, the region where the resin layer 303 is formed is removed by a photolithography method ( 3 (2d), a resin layer 303 is formed by electrodeposition (FIG. 3 (2d)), and finally the photosensitive resin layer 302 is removed (FIG. 3 (2e)). That is, the region of the resin film 302 to be removed by the photolithographic method is preferably smaller than the width of the convex metal pattern convex portion because of the ink repellent layer formed in the peripheral region of the top of the final plate.

As a material of the resin layer used for the above resin layer formation, resins such as acrylic, epoxy, nylon, polyester, urethane, silicone, polyvinyl alcohol, polyimide, and novolac can be used, and the top side shape is made as flat as possible. In addition, it is preferable to use a negative photosensitive resin. By using a negative photosensitive resin, a high-definition resin layer pattern can be formed, and the resin layer can be easily formed into a reverse taper shape.

Finally, the ink-repellent layer 304 is formed on the peripheral region and the side surface of the top of the convex metal pattern 301 of FIGS. 3 (1c) and 3 (2e) and the exposed surface of the substrate 300 (FIGS. 3 (1d) and (2f). ). At this time, it is preferable that the film thickness of the peripheral part of the top of the head is approximately the same as the film thickness of the resin layer 303. Thereby, even if the print pattern is made high-definition, it is possible to prevent ink color mixing with adjacent lines, and the convex metal pattern 301 and the base material 300 are formed by an alcohol-containing acidic aqueous solution of a hole transport ink (PEDOT) described later. Has the effect of preventing corrosion. As a method for forming the ink repellent layer, an electrodeposition method, a coating method, a dry coating method, or the like can be used, but it is preferable to use an electrodeposition method capable of selectively forming a film only on a metal portion. When an ink repellent layer is formed by an electrodeposition method, the film thickness and density of the ink repellent layer can be determined by the electrodeposition time, the electric field strength, or the concentration of the solution used.

<Manufacture of printed matter>
Next, the manufacturing method of the printed matter which forms an ink pattern on the to-be-printed substrate surface by a relief printing method using the relief printing plate of this invention is shown. FIG. 5 shows a schematic diagram of a relief printing apparatus used for producing the printed matter of the present invention. A printing substrate 401 is fixed to the stage 400, a printing relief plate 402 is fixed to a plate cylinder 403, and the printing relief plate is in contact with an anilox roll 404 which is an ink supply body. And a doctor 406.

First, ink is replenished from the ink replenishing device 405 to the anilox roll 404, and excess ink out of the ink 407 supplied to the anilox roll is removed by the doctor 406. As the ink replenishing device, a dripping type ink replenishing device, a fountain roll, a slit coater, a die coater, a cap coater such as a cap coater, or a combination thereof may be used. As the doctor, a known object such as a doctor roll can be used in addition to the doctor blade. The anilox roll can be made of chromium or ceramics. Further, it is also possible to use a lithographic anilox plate instead of a cylindrical anilox roll as an ink supply to the printing relief plate. The lithographic anilox plate is disposed, for example, at the position of the substrate to be printed 401. After the ink is replenished to the entire surface of the anilox plate by an ink replenishing device, the plate cylinder is rotated to supply ink to the substrate to be printed. Can do.

The ink uniformly held by the doctor 406 on the surface of the anilox roll 404 which is an ink supply body to the printing relief plate is transferred and supplied to the convex pattern of the printing relief plate 402 attached to the plate cylinder 403. In the relief printing plate of the present invention, since the ink repellent layer is provided in the peripheral area of the convex part, the transfer area ink corresponding to the resin layer does not flow out, and further, it is connected to the ink of the adjacent convex pattern. There is nothing.

Next, in accordance with the rotation of the plate cylinder, the convex pattern of the printing relief plate and the substrate 401 to be printed move relatively while in contact with each other, and the ink 407 is transferred to a predetermined position on the substrate to be printed on the stage 400 to be covered. An ink pattern 408 is formed on the printed substrate. After the ink pattern is provided on the substrate to be printed, a drying step using an oven or the like can be provided as necessary.

When printing the ink on the printing relief plate 402 on the printing substrate 401, the stage 400 to which the printing substrate is fixed may be moved in accordance with the rotation of the plate cylinder 403. 5 may be a system in which a printing unit composed of an upper plate cylinder 405, a printing relief plate, an anilox roll 404, and an ink replenishing device 405 is moved in accordance with the rotation of the plate cylinder. The printing relief plate of the present invention may be formed by forming a resin layer on the plate cylinder 403 and directly making a plate to form a projection pattern.

Note that FIG. 5 shows a sheet-fed relief printing apparatus that forms an ink pattern on a substrate to be printed one by one. However, in the method for producing a printed material according to the present invention, the substrate to be printed can be wound in a web shape. In some cases, a roll-to-roll relief printing apparatus can be used. When a roll-to-roll type letterpress printing apparatus is used, it is possible to continuously form an ink pattern and to reduce the manufacturing cost.

According to the relief printing plate of the present invention, by providing a metal portion, the projection of the plate is not damaged or deformed at the time of formation, and the resin contact layer is provided on the ink contact surface. Even a hard substrate such as a glass substrate can be printed without being damaged. Since the convex peripheral area is ink-repellent, the ink does not flow out from the transfer area on the plate surface, and a fine print pattern can be formed.

<Manufacture of organic EL elements>
Next, a method for producing an organic EL element will be described as an example of a method for producing a printed material using a relief plate in the present invention.

FIG. 6 shows an example of the organic EL element. As a method for driving the organic EL element, there are a passive matrix type and an active matrix type. However, the manufacturing method of the present invention can be applied to both a passive matrix type organic EL element and an active matrix type organic EL element.

The passive matrix method is a method in which stripe-shaped electrodes are opposed to each other so as to be orthogonal to each other, and light is emitted at the intersection, whereas the active matrix method uses a so-called thin film transistor (TFT) substrate in which a transistor is formed for each pixel. Thus, the light is emitted independently for each pixel.

As shown in FIG. 4, the organic EL element of the present invention has a first electrode 502 in a stripe shape as an anode on a substrate 501. The partition wall 503 is provided between the first electrodes, and preferably covers the first electrode end for the purpose of preventing a short circuit due to burrs at the first electrode end.

The organic EL device of the present invention has an organic light emitting medium layer composed of an organic light emitting layer and a light emission auxiliary layer on the first electrode 502 and in a region partitioned by the partition walls 503. The organic light emitting medium layer sandwiched between the electrodes may be composed of an organic light emitting layer alone, or may be composed of a laminated structure of an organic light emitting layer and a light emission auxiliary layer. Examples of the light emission auxiliary layer include a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, and a charge generation layer. FIG. 6 shows a configuration having a laminated structure of a hole transport layer 604 that is a light emission auxiliary layer and an organic light emitting layer 605. When manufacturing a display, a hole transport layer 604 is provided on the first electrode, and a red (R) organic light emitting layer, a green (G) organic light emitting layer, and a blue (B) organic light emitting are formed on the hole transport layer. A layer may be provided for each pixel.

Next, the 2nd electrode 606 is arrange | positioned as a cathode so as to oppose the 1st electrode 602 which is an anode on an organic light emitting medium layer. In the case of the passive matrix method, the second electrode is provided in a stripe shape so as to be orthogonal to the first electrode having a stripe shape. In the case of the active matrix method, the second electrode is formed on the entire surface of the organic EL element. Further, although not shown, a sealing body such as a glass cap is provided on the entire effective pixel in order to prevent moisture and oxygen in the environment from entering the first electrode, the organic light emitting layer, the light emitting auxiliary layer, and the second electrode. It is provided and bonded to the substrate via an adhesive.

The organic EL device according to the production method of the present invention includes at least a substrate, a patterned first electrode supported by the substrate, an organic light emitting layer, and a second electrode. In contrast to FIG. 6, the organic EL element of the present invention may have a structure in which the first electrode is a cathode and the second electrode is an anode. In addition, in order to protect the organic light emitting medium layer and the electrode from the ingress of external oxygen and moisture in place of a sealing body such as a glass cap, a sealing layer having a function of a passivation layer and a protective layer for protecting from external stress, or both, is provided. You may provide a stop base material.

Next, a method for manufacturing the element will be described. As the substrate according to the present invention, any substrate can be used as long as it has an insulating property. In the case of a bottom emission type organic EL element that extracts light from the substrate side, it is necessary to use a transparent substrate. For example, a glass substrate or a quartz substrate can be used as the substrate. Further, it may be a plastic film or sheet such as polypropylene, polyethersulfone, polycarbonate, cycloolefin polymer, polyacrylate, polyamide, polymethyl methacrylate, polyethylene terephthalate, or polyethylene naphthalate. These plastic films or sheets are coated with metal oxide thin films, metal fluoride thin films, metal nitride thin films, metal oxynitride thin films, or polymer resin films for the purpose of preventing moisture from entering the organic light emitting medium layer. A laminate may be used as the substrate. In addition, it is more preferable to reduce the moisture adsorbed on the inside or the surface of the substrate as much as possible by performing a heat treatment on these substrates in advance. Further, in order to improve the adhesion depending on the material to be laminated on the substrate, it is preferable to use after performing surface treatment such as ultrasonic cleaning treatment, corona discharge treatment, plasma treatment, UV ozone treatment.

Further, a thin film transistor (TFT) can be formed on these to form a substrate for an active matrix organic EL element. In the case of the organic EL element substrate of the present invention, a planarization layer is formed on the TFT, and the lower electrode of the organic EL element is provided on the planarization layer, and the TFT and the lower electrode are provided. Are preferably electrically connected through a contact hole provided in the planarization layer. By comprising in this way, the outstanding electrical insulation can be obtained between TFT and an organic EL element. The TFT and the organic EL element formed above the TFT are supported by a support. The support is preferably excellent in mechanical strength and dimensional stability. Specifically, the materials described above as the substrate can be used.

  When the first electrode is used as an anode, the material is a metal composite such as ITO (indium tin composite oxide), IZO (indium zinc composite oxide), tin oxide, zinc oxide, indium oxide, zinc aluminum composite oxide. A single layer or a stacked layer of metal materials such as oxide, gold, platinum, and chromium can be used. As a method for forming the first electrode, a dry film forming method such as a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, or a sputtering method can be used. In addition, ITO is preferably used because of its low resistance, solvent resistance, and high transparency when the bottom mission method is adopted. ITO is formed on the glass substrate by sputtering, and is patterned by photolithography to form the first electrode 2.

After forming the first electrode 502, a partition wall 503 is formed so as to cover the edge of the first electrode. The partition wall 503 needs to have insulating properties, and a photosensitive material or the like can be used. The photosensitive material may be a positive type or a negative type, a photo-curing resin of a photo radical polymerization system, a photo cationic polymerization system, or a copolymer containing an acrylonitrile component, polyvinyl phenol, polyvinyl alcohol. , Novolac resin, polyimide resin, cyanoethyl pullulan, and the like can be used. Moreover, SiO2, TiO2, etc. can also be used as a partition wall forming material. When the partition wall forming material is a photosensitive material, the entire surface of the forming material solution is coated by a slit coating method or a spin coating method, and then patterning is performed by a photolithography method such as exposure and development. In the case of the spin coating method, the height of the partition wall can be controlled by conditions such as the number of rotations when spin coating, but there is a limit height in one coating, and if it is higher than that, multiple spin coatings are performed. Use an iterative approach. When the barrier rib is formed by a photolithography method using a photosensitive material, its shape can be controlled by exposure conditions and development conditions. For example, when a negative photosensitive resin is applied, exposed and developed, and then post-baked to obtain a partition wall, if the shape of the partition wall end portion is to have a forward tapered shape, development under this development condition The type, concentration, temperature, or development time of the liquid may be controlled. If the development conditions are mild, the partition wall ends have a forward taper shape, and if the development conditions are severe, the partition wall ends have a reverse taper shape. Further, when the partition wall forming material is SiO 2 or TiO 2, it can be formed by a dry film forming method such as a sputtering method or a CVD method. In this case, patterning of the partition walls can be performed by a mask or a photolithography method.

Next, an organic light emitting medium layer composed of an organic light emitting layer and a light emission auxiliary layer is formed. The organic light emitting medium layer sandwiched between the electrodes may be composed of an organic light emitting layer alone, or an organic light emitting layer and a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, a charge generation layer. Such a laminated structure with a light emission auxiliary layer for assisting light emission. The hole transport layer, hole injection layer, electron transport layer, electron injection layer, and charge generation layer are appropriately selected as necessary.

In the present invention, at least one of the organic light emitting medium layers composed of a light emitting auxiliary layer such as an organic light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, and a charge generation layer is used. It can be applied when forming by printing above the first electrode by a relief printing method using a relief printing plate of the present invention using an ink in which a layer material is dissolved or dispersed in a solvent. Hereinafter, in the present invention, a case where an organic light emitting ink in which an organic light emitting material is dissolved or dispersed in a solvent is used will be described.

The organic light emitting layer is a layer that emits light when an electric current is passed. Organic light-emitting materials formed by the organic light-emitting layer include 9,10-diarylanthracene derivatives, pyrene, coronene, perylene, rubrene, 1,1,4,4-tetraphenylbutadiene, tris (8-quinolato) aluminum complex, tris (4-methyl-8-quinolato) aluminum complex, bis (8-quinolato) zinc complex, tris (4-methyl-5-trifluoromethyl-8-quinolato) aluminum complex, tris (4-methyl-5-cyano-) 8-quinolate) aluminum complex, bis (2-methyl-5-trifluoromethyl-8-quinolinolate) [4- (4-cyanophenyl) phenolate] aluminum complex, bis (2-methyl-5-cyano-8-quinolinolate) ) [4- (4-cyanophenyl) phenolate] aluminum complex, Lis (8-quinolinolato) scandium complex, bis [8- (para-tosyl) aminoquinoline] zinc complex and cadmium complex, 1,2,3,4-tetraphenylcyclopentadiene, poly-2,5-diheptyloxy- A low molecular weight light emitting material such as para-phenylene vinylene can be used.

Further, coumarin phosphors, perylene phosphors, pyran phosphors, anthrone phosphors, polyphyrin phosphors, quinacridone phosphors, N, N′-dialkyl-substituted quinacridone phosphors, naphthalimide phosphors, A material obtained by dispersing a low molecular weight light emitting material such as an N, N′-diaryl-substituted pyrrolopyrrole fluorescent material or a phosphorescent light emitting material such as an Ir complex in a polymer can be used. As the polymer, polystyrene, polymethyl methacrylate, polyvinyl carbazole and the like can be used.

Further, poly (2-decyloxy-1,4-phenylene) (DO-PPP) and poly [2,5-bis- [2- (N, N, N-triethylammonium) ethoxy] -1,4-phenyl- PPP derivatives such as alto-1,4-phenylylene] dibromide, poly [2- (2′-ethylhexyloxy) -5-methoxy-1,4-phenylenevinylene] (MEH-PPV), poly [5-methoxy -(2-propanoxysulfonide) -1,4-phenylenevinylene] (MPS-PPV), poly [2,5-bis- (hexyloxy) -1,4-phenylene- (1-cyanovinylene)] ( CN-PPV), poly (9,9-dioctylfluorene) (PDAF), and polyspirofluorene may be used. Examples thereof include polymer precursors such as a PPV precursor and a PPP precursor. Other existing light emitting materials can also be used.

Examples of the hole transport material for forming the hole transport layer include metal phthalocyanines and metal-free phthalocyanines such as copper phthalocyanine and tetra (t-butyl) copper phthalocyanine, quinacridone compounds, 1,1-bis (4-di-p -Tolylaminophenyl) cyclohexane, N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine, N, N′-di (1- Naphthyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine and other aromatic amine-based low-molecular hole injection / transport materials, polyaniline, polythiophene, polyvinylcarbazole, poly (3,4 -Ethylenedioxythiophene) and polymer hole transport materials such as a mixture of polystyrene sulfonic acid, thiophene oligomer materials, and other existing positive It can be selected from among transport material.

Examples of the electron transport material for forming the electron transport layer include 2- (4-bifinylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, 2,5-bis (1 -Naphtyl) -1,3,4-oxadiazole, oxadiazole derivatives, bis (10-hydroxybenzo [h] quinolinolato) beryllium complexes, triazole compounds, and the like can be used.

Solvents that dissolve or disperse the organic light emitting material include toluene, xylene, acetone, hexane, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, butyl acetate, 2-methyl- (t-butyl) Benzene, 1,2,3,4-tetramethylbenzene, pentylbenzene, 1,3,5-triethylbenzene, cyclohexylbenzene, 1,3,5-tri-isopropylbenzene and the like can be used alone or in combination. . Moreover, surfactant, antioxidant, a viscosity modifier, a ultraviolet absorber, etc. may be added to organic luminescent ink as needed.

Examples of the solvent for dissolving or dispersing the hole transport material and the electron transport material include, for example, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, butyl acetate, water and the like Alternatively, a mixed solvent thereof can be used. In particular, water or alcohols are suitable when forming a hole transport material into an ink.

The organic light emitting medium layer is formed by a wet film forming method. Note that in the case where these layers have a laminated structure, it is not necessary to form all of the layers by a wet film formation method. As the wet film forming method, spin coating method, die coating method, dip coating method, discharge coating method, pre-coating method, roll coating method, bar coating method and the like, relief printing method, inkjet printing method, offset printing method, Examples of the printing method include a gravure printing method. In particular, when patterning organic light emitting layers of three colors of RGB, it can be selectively formed on the pixel portion by a printing method, and an organic EL element capable of color display can be manufactured. The film thickness of the organic light emitting medium layer is 1000 nm or less, preferably 50 nm to 150 nm, even when formed by a single layer or stacked layers.

Next, a second electrode is formed. When the second electrode is a cathode, a material having high electron injection efficiency is used as the material. Specifically, a single metal such as Mg, Al, or Yb is used, or a compound such as Li, oxidized Li, or LiF is sandwiched by about 1 nm at the interface in contact with the light emitting medium, and Al or Cu having high stability and conductivity is laminated. And use. Or, in order to achieve both electron injection efficiency and stability, one or more metals such as Li, Mg, Ca, Sr, La, Ce, Er, Eu, Sc, Y, Yb, etc., which have low work function, and stable Ag, Al An alloy system with a metal element such as Cu is used. Specifically, alloys such as MgAg, AlLi, and CuLi can be used. Further, in the case of a top emission type organic EL device, the cathode needs to have transparency, and for example, transparency can be achieved by a combination of these metals and a transparent conductive layer such as ITO.

As a method for forming the second electrode, a dry film formation method such as a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, or a sputtering method can be used. Moreover, when it is necessary to make a 2nd electrode into a pattern, it can pattern by a mask etc. The thickness of the second electrode is preferably 10 nm to 1000 nm. In the present invention, the first electrode can be a cathode and the second electrode can be an anode.

As an organic EL element, it is possible to emit light by sandwiching an organic light emitting layer between electrodes and passing an electric current. However, some of the organic light emitting material, the light emission auxiliary layer forming material, and the electrode forming material contain moisture in the atmosphere. Since it is easily deteriorated by oxygen, a sealing body is usually provided for shielding from the outside.

For example, the sealing body includes a first electrode, an organic light emitting layer, a light emitting auxiliary layer, and a substrate on which the second electrode is formed. Then, sealing is performed by adhering the cap and the substrate with an adhesive around the peripheral portion so that the concave portion hits the second electrode.

In addition, the sealing body is provided with a resin layer on a sealing material with respect to the substrate on which, for example, the first electrode, the organic light emitting layer, the light emission auxiliary layer, and the second electrode are formed. It is also possible to carry out by bonding the substrates.

At this time, the sealing material needs to be a base material having low moisture and oxygen permeability. Examples of the material include ceramics such as alumina, silicon nitride, and boron nitride, glass such as alkali-free glass and alkali glass, metal foil such as quartz, aluminum, and stainless steel, and moisture-resistant film. Examples of moisture-resistant films include films formed by CVD of SiOx on both sides of plastic substrates, films with low permeability and water-absorbing films, or polymer films coated with a water-absorbing agent. The water vapor transmission rate is preferably 10 −6 g / m 2 / day or less.

Examples of the resin layer include a photo-curing adhesive resin made of an epoxy resin, an acrylic resin, a silicone resin, a thermosetting adhesive resin, a two-component curable adhesive resin, and an ethylene ethyl acrylate (EEA) polymer. Examples thereof include acrylic resins, vinyl resins such as ethylene vinyl acetate (EVA), thermoplastic resins such as polyamide and synthetic rubber, and thermoplastic adhesive resins such as acid-modified products of polyethylene and polypropylene. Examples of methods for forming a resin layer on a sealing material include solvent solution method, extrusion lamination method, melting / hot melt method, calendar method, nozzle coating method, screen printing method, vacuum laminating method, hot roll laminating method, etc. Can be mentioned. A material having a hygroscopic property or an oxygen absorbing property may be contained as necessary. Although the thickness of the resin layer formed on a sealing material is arbitrarily determined by the magnitude | size and shape of the organic EL element to seal, about 5-500 micrometers is desirable.

The substrate on which the first electrode, the organic light emitting layer, the light emission auxiliary layer, and the second electrode are formed and the sealing body are bonded together in a sealing chamber. When the sealing body has a two-layer structure of a sealing material and a resin layer, and a thermoplastic resin is used for the resin layer, it is preferable to perform only the pressure bonding with a heated roll. When a thermosetting adhesive resin is used, it is preferable to perform heat curing at a curing temperature after pressure bonding with a heated roll. In the case where a photocurable adhesive resin is used, curing can be performed by further irradiating light after pressure bonding with a roll. Note that although the resin layer is formed over the sealing material here, the resin layer can be formed over the substrate and bonded to the sealing material.

Before or instead of sealing with a sealing body, for example, as a passivation film, it is also possible to form a sealing body with an inorganic thin film, such as a silicon nitride film having a thickness of 150 nm using a CVD method. It is also possible to combine these.

As described above, any organic light emitting medium layer can be formed using the relief printing plate of the present invention. Further, as the forming method, the steps described in the section of the printed material manufacturing method can be used. By using the relief printing plate of the present invention, ink overflows from the concave portion of the plate surface, ink supplied to the adjacent top portion is connected, etc., and the ink of each layer of the organic light emitting medium layer is mixed and short-circuited. In addition, there is no occurrence of unevenness of light emission, and it is possible to form a fine organic light emitting medium layer free from printing defects. As a result, a high-definition organic EL element can be manufactured.

Below, it shows about an example and a comparative example.

<Example 1>
(Preparation of printed substrate)
An ITO film was formed on a glass substrate by sputtering, and the ITO film was patterned in a stripe shape by photolithography and etching with an acid solution. The ITO line pattern as the anode was a pattern in which the line width was 25 μm, the space was 25 μm, and the line was formed with 192 lines. Next, a substrate to be printed was prepared by covering the end of the anode line with a photosensitive polyimide resin (thickness 2 μm).

(Preparation of printing letterpress)
An invar material having a thickness of 0.3 mm was used as a substrate, and an acrylic negative dry film was laminated on one surface as a photosensitive resin (FIG. 2 (1a)). Next, a stripe convex pattern, which becomes a negative pattern of the ITO line pattern of the substrate to be printed, was formed by using a photolithography method (FIG. 2 (1b)). Next, nickel was formed to a height of 50 μm by electroforming in the concave portion of the convex pattern of the photosensitive resin (FIG. 2 (1c)). Next, it was immersed in an aqueous solution of sodium hydroxide and the photosensitive resin pattern was peeled off to produce a convex metal pattern (FIG. 2 (1d)).

Next, as shown in FIG. 3 (b), the convex metal pattern concave portion and the convex top-periphery peripheral region are covered with a dry film resist, and the resin layer is formed on the convex top central portion, which is a transfer region, using an electrodeposition method. As shown in FIG. 3 (2d), the dry film resist was peeled off (FIG. 3 (2e)). Next, an acrylic resin in which PTFE particles are dispersed as an ink repellent layer is formed as an ink-repellent layer on the exposed portion of the metal on which the polyimide resin is not formed by using an electrodeposition method, thereby obtaining a relief printing plate for high-definition printing of the present invention ( FIG. 3 (2f)).

(Production of organic EL element)
The relief printing plate for high-definition printing was fixed to a cylinder of a sheet-fed printing press. As a material for the hole transport layer, an ink in which a mixture of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid is dispersed in an aqueous solvent is applied to the surface of the second photosensitive resin layer of the relief printing plate. The ink was inked, transferred to a substrate to be printed, and printed in a striped form in a lump of 192 lines. After printing, it was dried at 200 ° C. for 30 minutes. The film thickness after drying of the hole transport pattern formed at this time was 50 nm. A polyfluorene-based green light-emitting ink was applied onto the hole transport layer by spin coating, and then heated at 130 ° C. for 15 minutes in a nitrogen atmosphere. The thickness of the light emitting layer formed at this time was 80 nm. Next, a line was formed on the light emitting layer as a second electrode in a direction perpendicular to the first electrode. As for the cathode material, a laminated film of calcium (10 nm) and silver (150 nm) was formed by a vacuum deposition method. Finally, sealing was performed using a glass cap to produce the organic EL device of the present invention. When the light emission characteristics of this organic EL element were observed, uniform light emission of 1000 cd / m 2 was obtained at 5 V over the entire surface of the pattern portion. In addition, since the hole transport layer formed by the relief printing method did not contact the adjacent lines, no leakage between the lines occurred, and a good 192 × 192 dot matrix display could be produced.

<Example 2>
As Example 2, a relief printing plate was produced using an etching method.
An invar material having a thickness of 0.3 mm was used as a base material, and an acrylic negative dry film was laminated as a photosensitive resin on one surface (FIG. 2 (2a). Next, a substrate to be printed using a photolithographic method. A stripe convex pattern was formed to be a positive pattern of the ITO line pattern (FIG. 2 (2b)) Next, the invar material, which is a concave portion of the convex pattern of the photosensitive resin, was removed by using an etching method. 205 was formed (FIG. 2 (2c)) Next, it was immersed in a sodium hydroxide aqueous solution, and the photosensitive resin pattern was peeled off to produce a convex metal pattern (FIG. 2 (2d)).

Next, as shown in FIG. 3 (b), a polyimide resin is applied using a roll coating method so as to cover the convex metal pattern, and the top of the convex metal pattern is applied to the top of the convex metal pattern using a photolithography method. A pattern was formed (FIG. 3 (1c)). Finally, an acrylic resin in which PTFE particles were dispersed was formed as an ink-repellent layer using an electrodeposition method on the exposed portion of the metal on which no polyimide resin was formed (FIG. 3 (1d)).

An organic EL element similar to that of Example 1 was produced using this printing relief plate.
As a result of examining the light emission characteristics of the organic EL element, uniform light emission of 1000 cd / m 2 was obtained at 5 V over the entire surface in the pattern portion. In addition, since the hole transport layer formed by the relief printing method did not contact the adjacent lines, no leakage between the lines occurred, and a good 192 × 192 dot matrix display could be produced.

<Comparative Example 1>
As Comparative Example 1, a letterpress printing plate with L / S = 25/25 μm was formed using a commercially available flexographic plate (Asahi Kasei AWP plate) that can be used for water-based ink printing. As a result, the depth of the relief printing plate was about 5 μm. An organic EL element was produced in the same production process as in Example 1 except that this plate was used. As a result, most of the hole transport ink flowed into the intaglio, not on the printing relief plate, and this ink was transferred to the substrate to be printed, so that pattern formation was not possible, and in addition, a short-circuited portion occurred in all 192 lines. It was. Further, the film thickness uniformity of the hole transport layer was non-uniform as ± 30%. It was about 100 to 500 cd / m 2 at 5 V, light emission was nonuniform, and light emission unevenness was ± 30% or more.

<Comparative example 2>
As Comparative Example 2, a printing relief plate was prepared in the same manner as in Example 1 except that an acrylic negative photosensitive resin was applied on a substrate using a slit coating method to form a first photosensitive resin film. . As a result, a relief printing plate comprising a convex metal pattern and a resin layer at the top of the metal substrate, having a plate depth of 20 μm and a pattern width of 25 μm, could be produced.

An organic EL element was produced in the same process as in Example 1. As a result, the hole transporting ink flowed into the intaglio, and this ink was transferred to the substrate to be printed, resulting in printing pattern shifts and short-circuited parts in the lines. The voltage was about 300 to 600 cd / m 2 at 5 V, the light emission was nonuniform, and the light emission unevenness was ± 30% or more.

<Comparative Example 3>
As Comparative Example 3, an acrylic negative dry film (Hitachi Kasei HM4056: 56 μm thickness) was laminated as a first photosensitive resin on an invar material having a thickness of 0.3 mm. Using a photolithography method, a convex stripe pattern having the same pattern as the ITO line pattern of the substrate to be printed was formed, and a printing relief plate having a plate depth of 56 μm and a pattern width of 25 μm was produced. When an organic EL was produced by the same process as in Example 1, due to the remarkable deformation and damage of the plate, all lines were poorly printed, and most patterns could not be formed as organic EL elements.

These are sectional drawings of an example of the relief printing plate of this invention. These are explanatory sectional drawing of the manufacturing method of the relief printing plate of this invention. These are explanatory sectional drawing of the manufacturing method of the relief printing plate of this invention. These are the schematic diagrams of the relief printing apparatus used for manufacture of the printed matter of this invention. These are sectional drawings of an example of the organic EL element manufactured by this invention.

Explanation of symbols

100: base material 101: resin layer 102: ink repellent layer 103: metal protrusion 104: ink on plate 200: base material 201: photosensitive resin layer 202: photosensitive resin pattern 203: metal 204: metal pattern 205: metal Concave portion 300: base material 301: metal pattern 302: photosensitive resin film 303: resin layer 304: ink repellent layer 400: stage 401: substrate to be printed 402: relief printing plate 403: copper plate 404: anilox roll 405: ink replenishing device 406: Doctor 407: Ink 408: Ink pattern 501: Substrate 502: Partition 503: First electrode 504: Hole transport layer 505: Organic light emitting layer 506: Second electrode

Claims (15)

A convex metal pattern on the substrate;
An ink repellent layer covering a peripheral region of the top of the convex metal pattern;
A resin layer covering the transfer region at the top of the convex metal pattern;
A relief printing plate characterized by comprising: 2. The relief printing plate according to claim 1, wherein a side surface portion of the convex metal pattern is covered with an ink repellent layer. A substrate having a metal surface;
A convex metal pattern on the substrate;
An ink repellent layer covering a peripheral region of the top of the convex metal pattern;
A resin layer covering the transfer region at the top of the convex metal pattern;
An ink-repellent layer covering the side surface of the convex metal pattern and the exposed surface of the substrate surface;
A relief printing plate characterized by comprising: 4. The relief printing plate according to claim 1, wherein an area of the surface region of the resin layer is larger than an area of a bottom surface region of the resin layer. The relief printing plate according to any one of claims 1 to 4, wherein a step difference between the resin layer and the ink repellent layer is 5 µm or less. The height of the ink-repellent layer from the base material surface is 0.5 to 3 μm higher than the height of the resin layer from the base material surface. Letterpress for printing. The method includes at least a step of supplying ink from the ink supply body to the transfer region of the relief printing plate according to any one of claims 1 to 6, and a step of transferring the ink to a printing body to form an ink pattern. A method for producing a printed matter. In the method for producing an organic electroluminescence device comprising at least a first electrode, one or more organic light emitting medium layers, and a second electrode,
A method for producing an organic electroluminescent element, wherein at least one layer of the organic light emitting medium layer is printed and formed using the method for producing a printed matter according to claim 7. Forming a convex metal pattern on the substrate;
Forming a resin layer in the transfer region at the top of the convex metal pattern;
Forming an ink-repellent layer in the peripheral region of the top of the convex metal pattern;
A method for producing a relief printing plate, comprising: The method for producing a relief printing plate according to claim 9, wherein the convex metal pattern is formed using an electroforming method. The method for producing a relief printing plate according to claim 9, wherein the convex metal pattern is formed using an etching method. The method for producing a relief printing plate according to any one of claims 9 to 11, wherein the resin layer is formed by a photolithography method. The printing relief printing plate according to claim 12, wherein a negative photosensitive resin is used as a material of the resin layer. The method for producing a relief printing plate according to claim 9, wherein the resin layer is formed by an electrodeposition method. The method for producing a relief printing plate according to any one of claims 9 to 14, wherein the ink repellent layer is formed by using an electrodeposition method.