JP4797056B2 - Method for producing letterpress printing plate - Google Patents

Description

  The present invention relates to a method for producing a relief printing plate used for relief printing such as flexographic printing.

  Conventionally, a photolithographic method has been generally used to form a display panel or circuit pattern having a fine size. Compared to the photolithographic method, printing methods are expected to reduce costs, such as faster processing speed, less waste associated with the process, and higher material utilization efficiency. However, the printing method could not meet the demands in the following points.

  1A and 1B are diagrams showing a conventional relief printing plate used for relief printing and problems at the time of transfer. FIG. 1A is a sectional view showing the relief printing plate, and FIG. 1B shows a state where ink is pressed against a substrate. Sectional drawing (c) is a plan view of the substrate showing the ink transferred to the substrate. 2. Description of the Related Art Conventionally, a relief printing method in which an ink 2 is attached to the tip of a relief 1 and pressure-transferred to a printing substrate that is a printing medium has been widely used. A typical example of such a relief printing method is a flexographic printing method using a plate made of a resin material. The flexographic printing method is relatively easy to process because the plate is made of resin, and because the plate material is flexible, damage to the substrate and damage to the previously formed pattern during overprinting There is a feature that the ink is reduced and that the ink is not attached to the non-image portion because it is a letterpress. These features are advantageous when applied to electronic devices.

  However, letterpress and letterpress printing methods have hardly been used as means for printing and forming fine patterns. The main reason is that there is a problem peculiar to this method of generating a marginal and it is difficult to accurately form a fine pattern. In the relief printing method, printing pressure must be applied in the process of transferring the ink (FIG. 1B), but the ink 2 sandwiched between the relief 1 of the printing plate and the substrate 4 is transferred from the leading edge of the relief. It protrudes to the periphery and it becomes difficult to maintain a predetermined dimension. A portion in which the printed pattern is larger than the pattern on the printing plate is called a marginal (shown as marginal 3 in FIG. 1B), and as shown in FIG. The pattern 6 spread due to the above becomes larger than the pattern 5 without the marginal.

  Further, when the pattern becomes finer and the distance between the patterns becomes smaller, there arises a problem that the pattern is connected to the adjacent pattern by marginal. 2A and 2B are schematic diagrams showing the state of a printed pattern. FIG. 2A shows a state in which the patterns are connected because the margin is large in the prior art pattern, and FIG. 2B shows an improvement in the margin in the pattern of the present invention. The pattern is separated (the pattern (b) of the present invention will be described in detail later). In FIG. 2A, a state where the above-described problem of the related art that is connected to an adjacent pattern occurs is shown as a pattern 5 when there is no marginal and a pattern 6 spread by the marginal. In particular, when a conductive pattern such as a wiring or an electrode is formed, the connection of the patterns causes a short circuit, and there is a problem that the electronic device or the like cannot function normally.

  Until now, as a method for reducing the marginal, for example, a method has been proposed in which a depression is provided in the convex portion of the plate to improve marginal suppression and uniformity (see, for example, Patent Document 1).

JP 2006-240283 A

  However, Patent Document 1 does not specifically show the problem of reduction in printing durability (printing durability) caused by the relief thickness and the problem of line thickening in a thin line that is important in the field of electronic materials. In Patent Document 1, although a method for producing a relief printing plate by exposure and development is proposed, it is possible to easily and in large quantities produce a finely processed relief plate, and the desired relief plate A specific method for easily imparting characteristics (for example, printing durability, linearity at both ends of the printed matter) is not shown.

  The present invention is to produce a relief printing plate that is optimal for, for example, the formation of wiring in display panels, the formation of electrodes, and the formation of wiring for functional elements and electronic circuits using insulating materials and functional materials at low cost, easily and in large quantities. It is an object of the present invention to provide a method for producing a relief printing plate that can be used.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the method for producing a relief printing plate according to the present invention includes a relief printing plate for use in relief printing for use in relief printing that transfers the ink supplied to the top surface of the relief of the relief plate to a printing medium. A first step of pouring the resin-containing liquid into a mold incorporating the pattern (hereinafter also referred to as mold A), and a second step of preparing the resin printing plate by drying the resin-containing liquid poured in the first step And a third step of peeling the resin printing plate produced in the second step from the mold A to obtain the resin printing plate as a relief printing plate.

  In the method for producing a relief printing plate according to the present invention, it is preferable to use an aqueous resin dispersion as the resin-containing liquid. Since the aqueous resin dispersion is easy to handle and the plate can be produced without dissolving the mold A, the mold A can be used many times.

  In the method for producing a relief printing plate according to the present invention, by providing a plurality of fine protrusions at locations corresponding to the top surface of the relief of the mold A, the top surface of the relief of the resin printing plate corresponds to the fine protrusions. It is preferable to form a plurality of depressions. Thereby, it is possible to achieve both of the two factors of ensuring the film thickness of the transferred ink and ensuring the uniformity of the film thickness.

In the method for producing a relief printing plate according to the present invention, it is preferable that the depth of the recess is 1 μm or more and 30 μm or less. As a result, ink can easily enter and exit, and marginal occurrence hardly occurs, so that the pattern reproducibility is good.
In the method for producing a relief printing plate according to the present invention, the mold A is preferably formed of a silicone-based resin.

  In the method for producing a relief printing plate of the present invention, since a resin-containing liquid is used, for example, when a photosensitive resin (photopolymer) is used, an exposure step and a development step through a mask that are necessary are unnecessary. Is simple and easy, and stable production is possible. In addition, the degree of freedom in designing the resin used is high, and it is easy to control properties such as a balance between solvent resistance and hardness. Therefore, according to the present invention, a relief printing plate having desired characteristics (for example, printing durability) can be produced inexpensively and easily. In the present invention, since the mold can be used repeatedly, the relief printing plate can be mass-produced at a low cost. In particular, when the resin-containing liquid is water-based, handling of the resin-containing liquid is easy and the mold is less likely to be damaged when a plate is produced.

  Embodiments of the present invention will be described with reference to the accompanying drawings. The embodiment described below is an example of the configuration of the present invention, and the present invention is not limited to the following embodiment. Various modifications may be made as long as the effects of the present invention are achieved.

  Before describing “a method for producing a relief printing plate” according to the present invention, a relief printing plate obtained by the production method will be described. The relief printing plate obtained by the method for producing a relief printing plate according to the present invention is obtained by drying the resin-containing liquid.

  The relief printing plate produced according to the present invention is preferably provided with a plurality of depressions on the top surface of the relief. In this case, the flow of ink to the outside of the relief when the relief printing plate is pressed against the substrate during printing is prevented by the wall between the depression and the depression provided at the relief tip of the relief plate and the depression itself. Generation can be reduced. Thereby, it is possible to prevent the patterns from being connected to each other during pattern formation, and it is possible to improve in-film uniformity, printing durability, and linearity of both ends (edges) of the printed matter. For this reason, high-precision printing can be achieved when the line width (line (L)) is narrow and the line interval (space (S)) is narrow. For example, printing is possible even when the line width (L) is 5 μm or more and 400 μm or less and the line interval (S) is 3 μm or more and 500 μm or less. The high-definition printed matter as described above is suitable for use in electronic devices (formation of wiring, formation of electrodes, formation of functional elements and circuits using insulating materials and functional materials). In the relief end, it is preferable that the depression is arranged so that the relief does not hang over the relief end and the relief has an edge line portion along the original shape. In this case, the reproducibility of the pattern is also improved. Further, the film thickness of the transferred ink can be adjusted by the depression, and therefore the film thickness of the printed matter can be adjusted.

  3A and 3B are schematic views showing one embodiment in which a plurality of depressions are provided in the relief printing plate. FIG. 3A shows one embodiment of a relief cross section, and FIG. 3B shows one embodiment of a relief top surface. The relief printing plate 13 according to this embodiment has a plurality of depressions 9 formed on the top surface 8 of the relief 1 of relief relief (having a relief thickness H), and is arranged in a grid pattern. As shown in the sectional view of the relief 1 in FIG. 3A, a recess 9 is provided in the depth direction from the top surface 8 of the relief. Further, as shown by the surface on which the relief ink in FIG. 3B adheres, the depressions 9 are arranged in a grid pattern. Here, A represents the distance between the recesses defined by the shortest distance between the periphery of a recess and the periphery of the recess located next to the recess.

  4, 5 and 6 are schematic views showing examples of the formation mode of the recess in the present invention. FIG. 4 is a view showing that a plurality of depressions are formed on the relief, and the formed region extends over the entire area of the relief tip, and the depression is not formed on the relief end. When the depressions overlap, it is explained that the relief end portion side of the depression has a line portion along the relief end shape. 4, (a) is a plan view showing a case where the opening shape of the recess is circular and the arrangement direction thereof coincides with the direction of the relief end portion, and (b) is a square opening shape of the recess and the arrangement direction thereof. FIG. 4C is a plan view showing a case where the direction of the relief end coincides with the direction of the relief end, and FIG. 8C shows a depression shape along the relief end shape on the relief end side of the depression when the relief end overlaps with the depression. FIG. In the embodiment shown in FIG. 4 (c), the depression shape near the relief end is different from the depression shape of the other portions, so that no depression is applied to the relief end. 5A and 5B show a form in which the depressions are in a staggered arrangement, wherein FIG. 5A is a plan view showing a staggered arrangement when the opening shapes of the depressions are circular, and FIG. 5B is a staggered pattern when the opening shapes of the depressions are square. The top view which shows an arrangement | sequence, (c) is sectional drawing which shows the other form of the cross-sectional shape of a relief. FIG. 6 shows an example in which the size of the dent or the depth of the dent is adjusted in order to reduce the ink density around the relief, and FIG. 6A is a plan view showing a case where the size of the dent in the peripheral portion is reduced. (B) is sectional drawing which shows the case where the depth of the hollow of a peripheral part is made shallow.

  The shape of the recess is the shape shown in FIG. 3B, and is a quadrangular prism shape as in FIG. 3B, but has a different ratio of the opening area of the recess / the area of the top surface (see FIG. 4B). Not only the shown square column-shaped hole (non-through and bottomed) but also a cylindrical hole (non-through and bottomed) as shown in FIG. Here, as shown in FIG. 4, it is preferable that a region where a plurality of depressions are formed on the relief extends over the entire area of the tip of the relief, and further, the depression is not formed on the relief edge (relief end). It is preferable.

  The arrangement of the depressions is not limited to the grid-like arrangement as shown in FIG. 3B or 4B, but may be a staggered arrangement as shown in FIG. 5A or 5B. . The arrangement aims to more effectively suppress the flow of ink by devising the arrangement.

  As for the size of the depression, not only the depressions of the same size as shown in FIG. 3 (b) or FIG. 4 (b) are arranged, but also the size of the depression is different as shown in FIG. 6 (a). You may arrange at least. FIG. 6 shows an example in which a device is added to the size of the depression in order to further reduce the marginal. FIG. 6A shows an example in which the portion closer to the end of the relief is designed to reduce the amount of ink flowing out of the relief by reducing the size of the recess in order to reduce the amount of ink. 5 (c) and 6 (b), for the same purpose as in FIG. 6 (a), the portion closer to the end of the relief is made shallower to reduce the amount of ink, and the outside of the relief is removed. This is an example aiming to reduce the amount of ink flowing out to the water.

  In any of the above forms, the shape of the recess at the relief end is arranged so that the relief end shape is not interrupted, or when the recess overlaps the relief end for convenience of arrangement, It is preferable that the overlapping portion is closed by a side wall that matches the end shape.

  The thickness of the relief is preferably 10 μm or more from the viewpoint of the necessity of providing a dent and the ability to print accurately from the viewpoint of the amount of pressing, and from the viewpoint of preventing stains on the printed matter, from the viewpoint of resolution, printing durability and durability. 500 μm or less is preferable. The thickness of the relief is more preferably 400 μm or less. Further, when the line width is 400 μm or less, the relief thickness is preferably 200 μm or less. When the relief thickness exceeds 500 μm, the resolution tends to deteriorate, and in the case of a fine pattern, the uniformity and linearity of the line tend to deteriorate. Here, the thickness of the relief refers to the height of the convex portion whose top surface is the printing surface, for example, as shown as the relief thickness H in FIG.

  The depth of the recess formed on the relief is preferably 1 μm or more and 30 μm or less from the viewpoint of easy access of ink. More preferably, it is 3 μm or more and 20 μm or less. When the depth of the dent becomes deeper than 30 μm, it becomes difficult for the ink to enter and exit, and the pattern reproducibility tends to deteriorate. If the depth of the dent is less than 1 μm, marginal tends to occur.

  Further, in the relief printing plate according to the present invention, as shown in the partially enlarged view of FIG. 3 (b), the gap between the recesses defined by the shortest distance between the periphery of the recess and the periphery of the recess located next to the recess. The distance (A) is preferably 1 μm or more and 30 μm or less. By setting the distance (A) between the depressions in such a range, the leveling property of the ink is promoted and the uniformity is further increased. The distance (A) between the recesses is more preferably 3 μm or more and 20 μm or less.

  In particular, when the line width of the relief is 5 μm or more and 400 μm or less, it is preferable to set the depth of the depression provided on the top surface of the relief and the distance (A) between the depressions within the above range. When the depth of the dent is 1 μm or more and 30 μm or less, the reproducibility for a pattern having a line width of 5 μm or more and 400 μm or less is improved. Further, when the distance (A) between the recesses is 1 μm or more and 30 μm or less, it has a good ink film thickness uniformity and a marginal suppression effect in a line width pattern of 5 μm or more and 400 μm or less.

  Next, the shape of the depression will be described. The opening shape of the dent (planar shape), that is, the shape when the top surface of the relief is viewed from the front, is composed of, for example, a triangle, a quadrangle, a hexagon, a polygon more than that, a straight line and a curve. The shape can be used, but the volume of the recess for storing ink, moire and spots due to combination with an anilox roll for ink transfer, transferability of ink from an anilox roll, leveling status after printing, ink substrate It may be determined in consideration of the transfer efficiency. The amount of ink can also be adjusted by changing the configuration, the interval between the depressions, and the depth. Of course, these configurations may be changed within one pattern. As described above, regarding the arrangement, the form of FIG. 3 (b) and FIG. 4 (a) (b) showing a grid-like arrangement, or the form of FIG. 5 (a) (b) showing a staggered arrangement. It is also possible to adopt. For example, in FIGS. 5 (a) and 5 (b) showing a staggered arrangement, the leveling property is improved by making the distances between the depressions more uniform, and the adjacent depressions are displaced as compared with the grid arrangement of the grid, so in that direction This is considered to be effective in suppressing the ink flow.

  The size of the depressions can be designed as appropriate according to the pattern size to be formed. For example, the number of linear reliefs arranged in the width direction is preferably 2 or more in consideration of the uniformity of the edges and the inside of the pattern. More preferably, the number is 3 or more. For example, in the case of a line having a width of 60 μm, when three recesses are arranged in the width direction, the pitch is 20 μm, and the size (diameter) of the recesses is 10 μm if the size of the recesses is equal to the interval between the recesses. Similarly, in the case of a line having a width of 30 μm, when three recesses are arranged in the width direction, the pitch is 10 μm and the size (diameter) of the recesses is 5 μm. In addition, although the magnitude | size of the relief longitudinal direction of a hollow is fundamentally equivalent to the width direction, it does not necessarily need to be equivalent. The size of the recesses and the interval between the recesses may be adjusted in consideration of conditions such as the required pattern width and thickness, ink viscosity, ink leveling and density, amount of ink placed on the plate, marginal conditions, It is not limited to the above range. The plate making method may be selected depending on the required pattern size and the size of the recess.

  Next, a method for producing a relief printing plate will be described. The method for producing a relief printing plate according to the present invention is a method for producing a relief printing plate for use in relief printing in which the ink supplied to the top surface of the relief of the relief plate is transferred to a printing medium. The first step of pouring the resin-containing liquid into the assembled mold A, the second step of drying the resin-containing liquid poured in the first step to produce a resin printing plate, and the resin printing produced in the second step And removing the plate from the mold A to obtain a resin printing plate as a relief printing plate. Here, the mold A can be produced by (1) a process for producing an original plate from which a plate is formed, and (2) a process for producing a mold A from the original plate. The first to third steps are steps after the steps (1) and (2), and (3) a step of producing a duplicate resin printing plate that is the final object (ie, relief printing plate) from the mold A. is there. By the production method of the present invention, a large number of duplicate resin printing plates can be easily produced at low cost from the original plate produced in the step (1). FIG. 10 is an image diagram for explaining the process of producing a relief printing plate from the mold A, and shows an image diagram for explaining the process (3). 10, (a) is a step of pouring the aqueous resin dispersion 16 into the mold A17, (b) is a step of drying the aqueous resin dispersion to form a resin printing plate 18, and (c) is a resin printing from the mold A. A step of taking out the plate 18 to obtain a relief printing plate is shown.

(1) Preparation method of original plate used as original plate The original plate can be prepared, for example, by a method using an ordinary photosensitive resin. Typically, in accordance with the shape of the relief, a negative film is prepared that transmits light in a portion corresponding to a minute recess and does not transmit in other portions. When a liquid photosensitive resin is used before exposure, after laminating this negative film on the surface of the glass plate, a liquid photosensitive resin is applied thereon, a transparent base film is laminated on the surface, and the A glass plate is laminated on the surface. Note that the thickness of the photosensitive resin layer is set to a predetermined dimension. Next, using a lamp, the photosensitive resin is irradiated with ultraviolet rays through the upper glass plate and the base film, and the photosensitive resin is irradiated with ultraviolet rays through the lower glass plate and the negative film. A well-known irradiation light source for image exposure can be used. A portion where a predetermined amount of light entering from the entire upper surface of the layer made of the liquid photosensitive resin and light transmitted through the light transmitting portion of the negative film reaches a predetermined amount is cured. After curing, the upper and lower glass plates and the negative film are removed, the uncured portion is washed and removed, and the relief forming side is irradiated with ultraviolet rays to accelerate the curing to obtain a printing original plate.

  As another method, for the relief formation, a laser light source having a wavelength capable of curing the photosensitive resin may be used, and the amount of light necessary for curing may be scanned and exposed. In the case of using a photosensitive resin that is not a liquid type at room temperature but a solid solution at room temperature, after the photosensitive resin is heated to be molded to a predetermined thickness, operations after image exposure are similarly performed.

  Furthermore, although the manufacturing method of the original plate at the time of using negative type photosensitive resin was demonstrated above, it is also possible to use positive type photosensitive resin with a positive film.

  In addition, a method in which a mold is prepared in advance on a photomask and the depth of the depression is controlled more accurately can be employed. For example, a positive type photosensitive resin having a film thickness corresponding to the depth of the minute depression is deposited on the negative film, and the exposed portion is developed by irradiating ultraviolet rays from the negative film side. As a result, minute protrusions corresponding to the minute depressions are formed on the light shielding portion of the negative film. On the mold formed on the negative film, a negative photosensitive resin is further applied according to a desired relief thickness, and a base film is laminated on the surface. Next, ultraviolet rays are irradiated from the lower side (negative film side) through the negative film and mold, the negative film and the mold are removed, and the uncured portion is washed and removed, thereby accurately forming a relief having a minute depression on the base film. be able to. At this time, when a base film having a relatively high diffuse reflectance is used, the incident ultraviolet rays are diffusely reflected on the surface of the base film, and curing of the entire relief portion can be promoted. In order to securely attach the mold to the negative film, the surface of the negative film is coated with a commercially available adhesive (rubber, polyester, epoxy, acrylic, urethane, silane, etc.) having ultraviolet transparency. It is possible to perform a treatment, to provide various coating materials such as a hard coat (acrylic or the like) on the adhesive layer, and to perform a surface treatment with a coupling agent or the like.

(2) Method for producing mold A from original plate Using the original plate produced in the step (1) above, for example, the mold A can be produced by the following method. Specifically, a resin is applied to the original plate, a mold A made of the resin is produced, and the original plate is peeled off. As a result, a mold A in which a pattern opposite to the original plate is formed can be produced.

  The mold A is preferably provided with a plurality of fine protrusions at a location corresponding to the top surface of the relief of the relief printing plate produced according to the present invention. As a result, a plurality of depressions can be formed by the fine protrusions on the top surface of the relief of the resin printing plate (ie, relief printing plate) which is the final object.

(3) Method for producing a relief printing plate from mold A (first step to third step)
In the present invention, a resin-containing liquid is poured (or applied) into a mold A in which an uneven pattern corresponding to the relief of the relief printing plate is incorporated (first step), and the resin-containing liquid is dried to obtain a resin printing plate. Prepare (second step). Thereafter, the resin printing plate is peeled off from the mold A (third step). In addition, after applying the release agent to the mold A, the resin-containing liquid is poured (or applied) (first step), and the resin-containing liquid is dried to prepare a resin printing plate (second step). The resin printing plate may be peeled off (third step). As a result, a relief printing plate on which the same pattern as the original plate produced in the step (1) is formed can be produced.

  By using the production method of the present invention, the mold A can be used repeatedly, and a large number of resin relief printing plates can be easily produced from one plate. The type of the resin-containing liquid that is a material of the relief printing plate is not limited, and a solution in which various organic polymers are dissolved or a dispersion thereof can be used. Moreover, the same material as the material of the original plate mentioned above can also be used. Furthermore, when an aqueous resin dispersion is used as the resin-containing liquid, the mold A can be used a plurality of times because it is easy to handle and there is no risk of dissolving the mold A. Therefore, a large number of relief printing plates can be produced from one mold A. Therefore, according to the present invention, a large amount of finely processed relief printing plate can be produced in comparison with a method using exposure / development or laser processing, which has been used in the manufacture of conventional resin relief printing. be able to. Further, in the method of duplicating from one original plate, the material used for the relief printing plate as the duplication plate does not need to be a photosensitive material, and therefore, there is an advantage that the application range of the resin is wide (that is, the degree of freedom in design is high). It is done.

  In the present invention, as the original material for producing the mold A, a thermoplastic resin having a solid state at room temperature and a fluidity at high temperature as described above, a viscous resin at room temperature, or a solid solution, and a thermosetting resin. Resin can be used. There are no particular restrictions on the type of resin. In the case of using the production method of the present invention, it is not necessary to obtain printing appropriateness for the original plate. Further, a crosslinked rubber-based material can also be a material forming the original plate in the present invention.

  As the negative photosensitive resin, a radical polymerization system, a photocationic polymerization system, a photoanion polymerization system, a photodimerization reaction system, or the like is applicable. Hereinafter, a general-purpose radical polymerization system will be described as an example.

  Many of radically polymerizable resin compositions can be applied to the present invention, and among them, a composition containing a prepolymer, a monomer, an initiator, and a thermal polymerization inhibitor can be used as a representative one.

  The prepolymer has at least one polymerizable double bond in the molecule, such as unsaturated polyester, unsaturated polyurethane, unsaturated polyamide, unsaturated polyacrylate resin, unsaturated methacrylate resin, or various modified products thereof. And the like using at least one of them.

  The monomer is typically an ethylenically unsaturated monomer having a polymerizable double bond, such as styrene, chlorostyrene, vinyltoluene, diallyl phthalate, diallyl isophthalate, triallyl cyanurate, N, N ′. -Methylenebisacrylamide, methacrylamide, N-hydroxyethylacrylamide, N-hydroxymethacrylamide, α-acetamide, acrylamide, acrylic acid, methacrylic acid, α-chloroacrylic acid, paracarboxystyrene, 2,5-dihydroxystyrene, tri Ethylene glycol diacrylate, triethylene glycol dimethacrylate, and the like, and Photopolymer Social Society, “Photopolymer Handbook”, published by Kogyo Kenkyukai, June 26, 1989, p. The material described in 31-36 can be used.

  As the initiator, a known photopolymerization initiator or thermal polymerization initiator used for increasing the reaction efficiency when performing a three-dimensional crosslinking reaction using an ethylene addition polymerizable unsaturated group can be used. As radical photopolymerization initiator, benzoin, benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, Michler ketone, xanthone, thioxanthone, chloroxanthone, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, benzyl, 2,2-dimethyl- 2-hydroxyacetophenone, (2-acryloyloxyethyl) (4-benzoylbenzyl) dimethylammonium bromide, (4-benzoylbenzyl) trimethylammonium chloride, 2- (3-dimethylamino-2-hydroxypropoxy) -3-, 4-dimethyl-9H-thioxanthone-9-one-mesochloride, thiophenol, 2-benzothiazole thiol, 2-benzoxazole thiol, 2-benzimidazole , Diphenyl sulfide, decyl phenyl sulfide, di-n-butyl disulfide, dibenzyl sulfide, dibenzoyl disulfide, diacetyl disulfide, divinyl disulfide dimethoxyxanthogen disulfide, tetramethylthiuram monosulfide, tetramethylthiuram tetrasulfide, benzyldimethyldithiocarbamate Examples include quinoxaline, 1,3-dioxolane, N-laurylpyridinium and the like. On the other hand, as the thermal polymerization initiator, known ones such as peroxides such as benzoyl peroxide, 2,2-azobisisobutyronitrile, persulfate-sodium hydrogen sulfite, azo compounds, and redox initiators can be used. .

  As thermal polymerization inhibitors used in the present invention, hydroquinone, mono-tert-butylhydroquinone, benzoquinone, 2,5-diphenyl-p-benzoquinone, picric acid, di-p-fluorophenylamine, p-methoxyphenol, 2,6- And di-tert-butyl-p-cresol.

  Examples of the photosensitive resin composition include those described in JP-A-52-90804, JP-B-48-19125, JP-A-49-109104, JP-B-48-41708, and the like. In addition, Toray Research Center, Research and Research Division, “New Development of Photopolymer Technology” published by Toray Research Center, March 10, 1993, p. 35-37, supervised by Atsuo Yamaoka, “Basics and Applications of Photopolymers”, CMC Publishing, March 27, 2003, Chapter 4 Platemaking Materials and Photoresists, Supervised by Shinji Matsui et al., “Development and Application of Nanoimprints” , CMC Publishing, August 31, 2005, p. 50 and p. 151 can be used. P. 158 and p. The acrylate, methacrylate or fluorine-containing epoxy photosensitive resin having a fluorine-modified fluoroalkyl group described in 159 can also be used.

  Further, a photopolymerizable rubber composition comprising at least unvulcanized rubber, a monomer having a polymerizable double bond, and a polymerization initiator, so-called photosensitive elastomer (for example, JP-A-51-106501 and JP-A-47-37521) and a dialkyl silicone resin that requires a balance with ink-generating properties can be used.

  Thermoplastic resins include polymethyl methacrylate (PMMA), polycarbonate (PC), cyclic polyolefin resin (COP), polyamide (PA), polyacetal (POM), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), poly Methyl pentene (TPX), modified polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyether ether ketone (PEEK), polyether imide (PEI), polyarylate (PAR), polysulfone (PSF), polyether sulfone ( PES), polyamideimide (PAI), polyethylene (PE), polypropylene (PP), polystyrene (PSt), vinyl chloride (PVC), vinylidene chloride (PVDC), acrylonitrile Styrene (AS), acrylonitrile / butadiene / styrene (ABS), fluorinated polyolefins such as vinylidene fluoride (PVDF) and tetrafluoroethylene / norbornene copolymers as fluorine resins, fluorine-containing acrylic resins, fluorine-containing polyimide resins, Fluorine vinyl ether resins can be used as long as they can be processed by heat. For example, Tadahiro Miwa, “Science of Basic Synthetic Resins”, Gihodo Publishing Co., Ltd., June 15, 1987, p. . 113-397, discussions 1. Polymerization type resin The thermoplastic resin described in the condensation type resin may be used.

  Examples of the thermosetting resin include at least one resin of unsaturated polyester, unsaturated polyurethane, unsaturated polyamide, unsaturated polyacrylate, unsaturated methacrylate, or various modified products thereof, and an ethylenically unsaturated group having a polymerizable double bond. A radical polymerizable resin composition containing a saturated monomer and a thermal polymerization initiator, a resin composition obtained by adding a curing agent to epoxy, a silicon-based polydimethylsiloxane resin, or the like may be used. As the fluorine-based resin, a thermosetting resin using a crosslinking material, a fluorine monomer containing a polymerization initiator that generates radicals by heat, or a fluorine-containing oligomer may be used. Other than this, for example, Tadahiro Miwa, “Science of Basic Synthetic Resins”, Gihodo Publishing Co., Ltd., June 15, 1987, p. 240-397, each discussion You may use the thermosetting resin as described in condensation type | mold resin.

  As the rubber material, natural rubber, butadiene, isoprene, chloroprene, butyl, ethylene propylene, styrene butadiene, polyisobutylene, styrene butadiene, nitrile, acrylic, epichlorohydrin, urethane, silicon, and fluorine rubber may be used.

  By using the materials described above, the original plate of the relief printing plate of the present invention can be made.

  Next, the material of the mold A will be described. As the material of the mold A, the same material as the original plate material can be used. The condition of the material of the mold A includes not dissolving the plate (original plate). In view of ease of peeling, a silicone-based resin is preferably suitable. The silicone-based resin in the present invention is a compound having a siloxane bond. Specifically, polydimethylsiloxane (PDMS) resin is preferable.

  Next, the material of the resin printing plate (replicated plate) which is a relief printing plate will be described. As the material of the duplicate plate, for example, the same material as the above-mentioned original plate material can be used, but it can be selected according to the desired characteristics of the relief printing plate. The present invention has an advantage that the degree of freedom in designing the resin is higher than that of a conventional relief printing plate made of, for example, a photosensitive resin (the resin used in this case is limited to a photopolymer). A material obtained by dissolving or dispersing an original plate material in water or an organic solvent may be used as a material for a relief printing plate. Among these, an aqueous resin dispersion is preferable because it is easy to handle and does not damage the base. As the aqueous resin dispersion, acrylic latex, vinylidene chloride latex, styrene butadiene latex and the like can be used.

  Materials for the aqueous resin dispersion (latex) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxy. Propylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane , Cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, tertiary butylcyclohexyl (meth) acrylate, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, Inic acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate, 4-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, caprolactone modified (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (Meth) acrylate, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, octamethylcyclotetrasiloxane, octaphenylcyclosiloxane, Hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyl Ethoxysilane, diphenyldiethoxysilane, methylphenylsilane, triphenylethoxysilane, trimethylmethoxysilane, methylchlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenylchlorosilane, (meth) acrylic acid ester, styrene , Aromatic monomers such as vinyl toluene, vinyl esters such as vinyl acetate, vinyl propionate and vinyl persuccinate, vinyl cyanides such as (meth) acrylonitrile, vinyl halides such as vinyl chloride and vinylidene chloride, Butadiene and the like, and various functional monomers such as (meth) acrylamide, diacetone acrylamide, vinyl pyrrolidone, glycidyl (meth) acrylate, N-methylol Copolymers such as acrylamide, N-butoxymethylacrylamide, divinylbenzene, and methyl vinyl ketone are included.

  Specific examples of (meth) acrylic acid esters include (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms in the alkyl moiety, and (poly) oxyethylene mono (meth) having 1 to 100 ethylene oxide groups. Acrylate, (poly) oxypropylene mono (meth) acrylate, (meth) acrylic acid hydroxyalkyl ester having 1 to 18 carbon atoms in the alkyl portion, and (poly) oxyethylene di (1) having 1 to 100 ethylene oxide groups And (meth) acrylate. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic acid t-. Examples include butyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, and the like.

  As a method for producing the aqueous resin dispersion of the present invention, an ordinary multistage emulsion polymerization method can be employed. As a typical example, an unsaturated monomer is emulsion-polymerized in water in the presence of an emulsifier, a polymerization initiator, etc., usually under heating at 40 ° C. to 90 ° C., and this step is repeated a plurality of times. A method is mentioned.

  The emulsifier is not particularly limited, and for example, an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, an amphoteric emulsifier, a polymer emulsifier, and the like can be used. For example, fatty acid salts such as sodium lauryl sulfate, higher alcohol sulfates, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether sulfates, polyoxyethylene polycyclic phenyl ether sulfates, polyoxynonyls Anionic surface activity such as so-called reactive emulsifier having phenyl ether sulfonate, polyoxyethylene-polyoxypropylene glycol ether sulfate, sulfonic acid group or sulfate ester group and polymerizable unsaturated double bond in the molecule Agent; polyoxyethylene alkyl ether, polyoxyethylene nonylphenyl ether, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block copolymer, or Nonionic surfactants such as reactive nonionic surfactants having a skeleton and a polymerizable unsaturated double bond in the molecule; Cationic surfactants such as alkylamine salts and quaternary ammonium salts; Modification) Polyvinyl alcohol and the like.

  Although the usage-amount of the said emulsifier is not specifically limited, For example, Preferably it is 1.0-5.0 mass% with respect to the total usage-amount of all the polymerizable monomer components. Increasing the amount of emulsifier used relative to the total amount of all polymerizable monomer components (for example, 1.0% by mass or more) improves the polymerization stability and decreases it (for example, 5.0% by mass or less). ) And water resistance can be improved.

  As a polymerization method when the aqueous resin dispersion used in the present invention is subjected to emulsion polymerization, a monomer batch charging method in which monomers are charged in a batch, a monomer dropping method in which monomers are continuously dropped, Examples include a pre-emulsion method in which a monomer, water and an emulsifier are mixed and emulsified in advance, and these are added dropwise, or a combination thereof. At this time, the method of using the polymerization initiator is not particularly limited. Further, the use method of the Si-containing compound may include the condensation reaction of hydrolyzable silane and the radical polymerization of unsaturated monomer at the same time and / or after the condensation reaction of hydrolyzable silane is preceded. For example, an emulsion polymerization method in which radical polymerization of the body proceeds or a method in which the condensation reaction of hydrolyzable silane proceeds after the radical polymerization of the unsaturated monomer proceeds.

  Examples of the polymerization initiator used in emulsion polymerization of the aqueous resin dispersion used in the present invention include generally used radical polymerization initiators. Radical polymerization initiators are those that generate radicals by heat or reducing substances to cause addition polymerization of polymerizable monomers, and include water-soluble or oil-soluble persulfates, peroxides, and azobis compounds. It is done. Specifically, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis ( 2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like are mentioned, and water-soluble ones are preferred. When acceleration of the polymerization rate or a low temperature reaction is desired, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbic acid, formaldehyde sulfooxylate salt or the like can be used in combination with the radical polymerization initiator.

  In the emulsion polymerization, a molecular weight modifier can be used as necessary. Specific examples include dodecyl mercaptan and butyl mercaptan. The method of use is not particularly limited, but it is preferably used in the shell part, and the amount is preferably 2% by mass or less of the total amount of monomers.

  In addition, a film forming aid can be arbitrarily blended in the aqueous resin dispersion used in the present invention. Specific examples of film forming aids include diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol mono 2-ethylhexyl ether, 2,2,4-trimethyl-1,3-butanediol iso Examples include butyrate, diisopropyl glutarate, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol methyl ether, and tripropylene glycol methyl ether. These film forming aids can be arbitrarily blended alone or in combination.

  Next, a printing machine that can be used for printing using the relief printing plate obtained by the production method of the present invention will be described. FIG. 7 is a diagram showing an example of a printing machine that can be used for printing using the relief printing plate according to the present invention. For example, a commercially available printer shown in FIG. 7 can be used. This is an example and is not limited to this method. Printing is performed as follows. Using the printing machine of the system shown in FIG. 7, the ink 2 is placed on the anilox roll 11 and the doctor blade 12 provided with projections and depressions, and the anilox roll 11 rotates to measure the ink. Next, when the anilox roll 11 and the plate 13 wound around the plate cylinder 14 come into contact with each other, ink adheres to the top surface which is the tip of the relief. In this state, the plate 13 is pressed against the substrate 4 to transfer the ink. Thereafter, the ink leveling proceeds and becomes uniform. FIG. 8 is a cross-sectional view illustrating a printing method using the relief printing plate according to the present invention, and shows a plate portion at the time of printing as an enlarged cross-sectional view. In FIG. 8, (a) shows a state in which the plate is pressed on the anilox plate on which the ink has been developed, (b) shows a state in which pattern forming ink is supplied to the relief tip, and (c) shows a state in which the plate is pressed against the substrate. (D) shows a state where the transfer is completed by separating the plate from the substrate, and (e) shows a state where the ink is leveled. The ink 2 spread on the anilox roll 11 of the printing press comes into contact with the top surface which is the front end surface of the relief 1 of the plate 13 and the anilox roll 11 as shown in FIG. ), The ink 2 is transferred to the top surface of the relief 1 of the plate 13, and then the pattern 15 is transferred to the substrate 4 as shown in FIGS. 8C, 8D and 8E.

  In the relief printing plate according to the present invention, the plate configuration may be a multilayer configuration in order to further suppress the marginal. FIG. 9 is a cross-sectional view showing the relief cross-sectional shape of the relief printing plate according to the present invention, showing a single layer configuration and a multilayer configuration. In FIG. 9, (a) shows a single layer plate. (B) shows a multilayer plate having a two-layer structure (low hardness layer 1a and high hardness layer 1b) provided with a hardness difference. (C) is a two-layer structure (low hardness layer 1a and high hardness layer 1b) provided with a hardness difference as in (b), but the angle formed by the top surface of the relief and the side surface of the low hardness layer 1a is A multi-layer plate having a two-layer structure in which the angle is more acute than the angle formed by the top surface of the relief and the side surface of the high-hardness layer 1b (that is, a shoulder difference is provided) is shown. Note that (c) shows a plate in which the angle of the relief tip (the angle formed between the top surface of the relief and the relief side surface) is set to an acute angle as compared with the form of (b). (D) shows a single-layer plate in which a shoulder angle 10 (an angle formed by the base portion 7 (that is, the base layer) and the relief side surface) is set. (E) shows a multilayer plate having a three-layer structure of a relief layer 1 (low hardness layer 1a and high hardness layer 1b) and a base layer. That is, as an aspect in which the plate structure is a multilayer structure, the relief relief of the relief printing is multilayered (for example, FIGS. 9B and 9C), the relief layer 1 and the base layer (base part 7). (Fig. 9 (e)), and these may be used in combination. In order to improve the uniformity of the ink film transferred from the plate, as shown in FIGS. 9 (b) and 9 (c), it is preferable that the relief upper portion on which the ink is deposited is a low hardness (low compression modulus) layer. .

  However, when the hardness is low, the dot gain at the time of printing tends to increase, so it is preferable to optimize the thickness of the low hardness layer by a printing experiment. On the contrary, if the ink coverage is sufficient but the dot gain is large, the hardness of the relief upper layer is set higher than that of the lower layer in order to suppress the marginal more, and the stress due to the printing pressure is increased more in the relief lower layer. There are cases where it can be dealt with by absorption. If the hardness is too low, the printing pressure absorption effect may act excessively and the ink transfer may decrease, so it is preferable to optimize the hardness difference.

  As a method for further suppressing the marginal, as shown in FIG. 9C, a technique of making the shoulder of the relief upper layer (the angle of the relief tip) more acute can be applied. As a method of forming a relief having such a shape, there is a method of processing the relief shape of the original mold in multiple stages in the process of producing a plate by pouring uncured resin into the mold. As the marginal suppression means, for example, there is a means for providing a flexible layer under the support, but the printing pressure absorption effect tends to be lower than that of the above method. As shown in FIG. 9 (d), the cross-sectional shape of the relief can prevent tilting. As shown in FIG. 9D, the relief shape close to the base layer (base portion 7) is expanded like Mt. Fuji, that is, the shoulder angle 10 is small. It is considered that a single layer plate or a multilayer relief structure in which the shoulder angle of the lower layer portion is small as shown in FIG. 9C is preferable.

  In the above description, the flexographic method using a resin plate is described as an example of the printing method. However, the present invention applies not only to typical flexographic printing but also to other relief printing methods, such as relief printing using a relief offset printing method. It can be implemented.

  By suppressing marginal by the method described above, a closer pattern can be independently formed. As described above, the schematic diagram of FIG. 2 shows a comparison of pattern reproducibility between the pattern (a) of the prior art and the pattern (b) of the present invention. Conventionally, there is a case where patterns are connected to each other when the patterns are brought close to each other by marginal (FIG. 2A), but in the present invention, the connection between patterns can be suppressed by reducing the marginal (FIG. 2B). Therefore, the pattern interval can be further reduced as compared with the conventional case. That is, as is apparent from the above-described aspect of the present invention, according to the present invention, the protrusion of ink around the relief is suppressed, and the marginal is suppressed. Therefore, it is possible to further narrow the interval between patterns.

  In addition, when the ink viscosity is 5 Pa · S or less, it has been difficult to form a uniform thick film by the conventional relief printing, but by using the relief printing plate according to the present invention, the ink enters the relief depression. As a result, the amount of ink transferred can be secured. Therefore, it is possible to form a thick film that is more uniform than a conventional relief. As a method for adjusting the surface free energy of the relief printing plate, a method of adjusting with an emulsifier when polymerizing the resin-containing liquid can be used.

  Next, a printed matter formed using the relief printing plate according to the present invention will be described. Examples of the printed material include an organic EL element, an organic thin film solar cell, a transistor, an electrode, and a wiring.

  A method for printing the printed matter using the relief printing plate obtained from the production method of the relief printing plate according to the present invention will be specifically described. In the relief printing method including the step of printing by pressing the relief printing plate against the printing material, the relief printing plate is disposed on the outer peripheral surface of the cylindrical printing cylinder, and the printing drum is rolled to the printing material. In the transfer process for transferring the image, it is preferable to print at a printing pressure at which the pressing amount between the relief and the printing material at the time of transfer is 100 μm or less. In the case of a printing pressure at which the pushing amount is higher than 100 μm, the relief is crushed, the effect of the depression is lost, and a problem may occur in marginal and pattern uniformity.

  A transistor will be described as an example of a printed material. First, a conductive pattern corresponding to a gate electrode and wiring is printed on a substrate by using a relief printing plate. As the ink for forming the conductive pattern, an ink in which metal fine particles are dispersed, a conductive polymer, or the like can be used. Next, a pattern corresponding to the gate insulating film of the transistor is printed in alignment with a predetermined position on the formed pattern. The relief printing plate is replaced with one corresponding to the pattern of the insulating film. Thereafter, the version is changed each time the pattern is changed. As the ink for forming the gate insulating film, an organic material dissolved in a solvent or an inorganic coating material such as a polysilazane material can be used. Next, a source electrode and a drain electrode and wirings connected to these are formed at predetermined positions. Next, a semiconductor pattern is formed so as to straddle the source electrode and the drain electrode. As the ink for forming a semiconductor pattern, organic semiconductors such as polythiophene derivatives and polyacenes that are soluble in a solvent can be used. Next, in order to protect the element, a protective film pattern is formed so as to cover these patterns. As the material for the protective film, a polymer resin material or the like dissolved in a solvent can be used.

  Moreover, an organic EL element is demonstrated as another example of printed matter. Organic EL elements are used in displays and lighting applications. The organic EL element has a structure in which an organic substance is sandwiched between an anode and a cathode. Among them, as the process using the relief printing plate according to the present invention, a process of applying an organic substance, specifically a hole injection material or a light emitting material sandwiched between the electrodes at the time of electrode formation is suitable. As an electrode forming method, a transparent electrode such as indium tin oxide (ITO) is printed in a desired pattern on a glass substrate or a plastic substrate. When producing this transparent electrode, a pattern can be produced using the printing method using the relief printing plate according to the present invention. Moreover, also in the case of forming the hole injection material and / or hole transport material on the ITO electrode and further the light emitting material thereon, the printing method using the relief printing plate according to the present invention can be used.

  Examples of the hole injection material, the hole transport material, or the hole injection / transport material having the functions of both materials include aromatic amine materials, phthalocyanine complexes such as copper phthalocyanine (CuPc) and zinc phthalocyanine (ZnPc), and aniline-based materials. Examples thereof include polymers, porphyrin compounds, imidazole derivatives, triazole derivatives, pyrazoline derivatives, oxazole derivatives, oxadiazole derivatives, stilbene derivatives, polyarylalkane derivatives, and acene compounds such as anthracene, tetracene, pentacene, and hexacene. Also, derivatives of these acene compounds, that is, the above acene compounds are alkyl groups, alkoxy groups, halogen groups, ketone groups, ester groups, ether groups, amino groups, hydroxy groups, benzyl groups, benzoyl groups, phenyl groups, Derivatives into which a substituent such as a naphthyl group is introduced, quinone derivatives of the above acene compounds, and the like are also included.

  Also, polyaniline, polyvinylanthracene, polycarbazole, poly (N-vinylcarbazole) (PVK), polyfluorene, poly (ethylenedioxy) thiophene / poly (styrenesulfonic acid) (PEDOT / PSS), thiophene-fluorene copolymer , Phenylene ethynylene-thiophene copolymer, polyalkylthiophene, poly (p-phenylene vinylene), and other polymer hole injection materials such as thiophene compounds or polymer hole transport materials.

Examples of the light emitting material include polymer light emitting materials such as poly (para-phenylene vinylene), poly (thiophene), poly (fluorene), and derivatives thereof. Also, tris (8-hydroxyquinolinolato) aluminum complex (Alq ₃ ), bis (2-methyl-8-quinolinolato) (p-phenylphenolate) aluminum (III) (BAlq), bis (benzoquinolinolato) Beryllium complex (BeBq ₂ ), phenanthroline-based europium complex (Eu (TTA) ₃ (phn)), perylene, coumarin derivatives, quinacridone, iridium complex (Ir (ppy) ₃ , Irpic, Ir (ppy) ₂ (acac)) Examples thereof include fluorescent materials and phosphorescent materials.

  These may be used by doping a small amount into a host material having holes or electron transporting properties or both. Such host materials include 4,4′-bis (9-carbazole) biphenyl (CBP), 2,7-di-9-carbazolyl-9,9′-spirobiflurane (spiro-CBP), bis (2-methyl). -8-quinolinolato) (p-phenylphenolato) aluminum (III) (BAlq), poly (N-vinylcarbazole) (PVK), and the like.

  When the printing method of the present invention is used, the above various materials (for example, a hole injection material, a hole transport material, a light emitting material, an organic semiconductor material, etc.) are used by being dispersed or dissolved in various solvents. As the solvent at that time, water, methanol, ethanol, propanol, butanol, hexanol and other alcohols, ethylene glycol, propylene glycol and other glycols, acetone, methyl ethyl ketone and other ketones, ethyl acetate, butyl acetate and other esters, Ethers such as dioxane and tetrahydrofuran, amides such as N, N-dimethylformamide, benzene, toluene, xylene, trimethylbenzene, hexane, heptane, octane, nonane, decane, cyclohexane, decahydronaphthalene (decalin), tetralin and the like And hydrocarbons.

  Hereinafter, the method for producing a relief printing plate of the present invention will be described in detail with reference to examples. In addition, this invention is not restrict | limited by an Example.

[Example 1]
1) Preparation method of original plate In line / space (L / S 200μm / 400μm, length 20mm) shape, a 2.3mm-thick quartz chrome mask with a light-shielding part corresponding to a minute recess in the light transmission part is prepared. did. After the surface of the quartz chrome mask is treated with a UV cleaning apparatus, HMDS (1,1,1,3,3,3-Hexamethyldisilazane) (1,1,1,3,3,3-hexamethyldibenzene) is obtained in a nitrogen atmosphere. Silazane) was treated for 20 minutes. A positive photosensitive resin was applied to the quartz chrome mask surface with a spin coater so that the thickness after drying was 10 μm, air-dried, and then heat-treated at 110 ° C. for 7 minutes. As the positive photosensitive resin, PMER (P-LA300PM) manufactured by Tokyo Ohka Co., Ltd. was used. Next, exposure and dip development (developing solution P-7G) were performed from the quartz chromium mask side using a parallel light exposure apparatus manufactured by Oak, and air-dried, followed by heat treatment at 110 ° C. for 10 minutes. On a resin mold formed on this quartz chrome mask, a 4 wt% solution of CYTOP (CTL-809AP2) manufactured by Asahi Glass Co., Ltd. as a release agent was applied by a spin coater so as to have a thickness of 0.1 μm. Dry at 15 ° C. for 15 minutes. After applying the negative liquid photosensitive resin APR-G31 (polyester resin) manufactured by Asahi Kasei Chemicals Co., Ltd. to a thickness of 100 μm using a knife coater on the obtained resin mold treated with the release agent, A stainless sheet (SUS304) having a thickness of 150 μm was laminated as a base film on the upper surface. The stainless sheet used was a surface treated with a silane coupling agent (KBM-503) manufactured by Shin-Etsu Chemical Co., Ltd. The exposure was performed from the quartz chrome mask side with an exposure amount of 500 mj / cm ² using a parallel light exposure apparatus manufactured by Oak. The base film was peeled off from the resin mold, washed with a 0.1 wt% sodium carbonate solution and a surfactant, and post-exposure was performed to obtain an original L / S pattern having a predetermined micro-dent at the tip on the relief.

2) Method for producing mold A A material to be mold A was applied to the original produced in 1). Specifically, a mold was prepared using SILPOT184 W / C manufactured by Toray Dow Corning, which is a silicone resin. 10.0 g of SILPOT184 was weighed and 1.0 g of CATALYST SILPOT184 was added thereto and stirred. After stirring, the liquid was applied so as to cover the entire original plate prepared in 1). Thereafter, vacuum defoaming was performed for 30 minutes, and then the mixture was placed on an 80 ° hot plate and cured. After leaving at room temperature, the mold A was peeled off from the original.

3) Method for Producing Letterpress Printing Plate Into mold A produced in 2), SB latex L-1571 manufactured by Asahi Kasei Chemicals Corporation, which is an aqueous resin dispersion, was poured as a resin-containing liquid. After carrying out vacuum defoaming for 30 minutes, it was placed on a hot plate at 80 degrees and dried to prepare a resin plate. After leaving at room temperature, the resin plate was peeled from the mold A to obtain a relief printing plate.

  By using this method, a plurality of relief printing plates (resin plates) can be produced from one mold A, so that the production becomes easy. FIG. 11 is a drawing-substituting photograph showing the observation results of an original plate, a mold A, and a relief printing plate (resin plate), which is a duplicate plate, with an optical microscope. The upper row is the original plate, the middle row is the mold A, and the lower row is the duplicate plate. . FIG. 12 is a perspective view showing the observation results of the original plate and the relief printing plate with a laser microscope, where (a) shows the top surface of the relief of the original plate, and (b) shows the relief printing plate as a duplicate plate. It is a figure which shows the top surface of a relief. The original plate had a recess width of 27 μm and a depth of 12 μm in the relief upper portion, and the relief printing plate as a duplicate plate had a recess width of 26 μm and a depth of 11 μm.

  According to the present invention, it is possible to easily produce a relief printing plate suitable for producing a fine pattern related to electronics or the like by the relief printing method.

It is a figure showing the conventional relief printing plate used for relief printing and the subject at the time of transfer, (a) is a sectional view showing a relief printing plate, (b) is a sectional view showing the state where ink was pressed against a substrate, ( c) is a plan view of the substrate showing the ink transferred to the substrate. It is the schematic which shows the state of the printed pattern, (a) shows the state in which the pattern was connected because the marginal was large in the pattern of the prior art, and (b) shows the marginal improved and the pattern separated in the pattern of the present invention Indicates the state that has been performed. It is the schematic which shows one form which provides a some depression in a relief printing plate, (a) shows one form of a relief cross section, (b) shows one form of a relief top face. It is the schematic which shows the example of the formation aspect of the hollow in this invention, and when the relief edge part and a depression overlap, it has demonstrated that the relief edge part side of a depression has a line part along the relief edge part shape, ( a) is a plan view showing the case where the opening shape of the dent is circular and the arrangement direction and the direction of the relief end coincide with each other, and FIG. The top view which shows the case where a direction corresponds, (c) is a top view which shows the hollow shape along the relief edge part shape in the relief edge part side of a hollow, when a relief edge part and a hollow overlap. . It is the schematic which shows the example of the formation aspect of the dent in this invention, The dent shows the form which is a staggered arrangement | sequence, (a) is a top view which shows the zigzag arrangement | sequence when the opening shape of a dent is circular, (b ) Is a plan view showing a staggered arrangement in the case where the opening shape of the dent is a quadrangle, and (c) is a cross-sectional view showing another form of the cross-sectional shape of the relief. It is the schematic which shows the example of the formation aspect of the dent in this invention, and has shown the example which adjusted the magnitude | size of the dent or the depth of the dent in order to reduce the ink density of a relief periphery, (a) is a peripheral part. The top view which shows the case where the magnitude | size of a hollow is made small, (b) is sectional drawing which shows the case where the depth of the hollow of a peripheral part is made shallow. It is a figure which shows the example of the printing machine which can be used for the printing using the relief printing plate which concerns on this invention. It is sectional drawing explaining the printing method using the relief printing plate which concerns on this invention, (a) is the state by which the plate was pressed on the anilox plate by which the ink was expand | deployed, (b) is for pattern formation to the relief front-end | tip. The state where ink is supplied, (c) shows the state where the plate is pressed against the substrate, (d) shows the state where the transfer is completed by separating the plate from the substrate, and (e) shows the state where the ink is leveled. It is sectional drawing which shows the relief cross-sectional shape of the relief printing plate which concerns on this invention, (a) is a single layer plate, (b) is the multilayered plate of the 2 layer structure which provided the hardness difference, (c) provided the shoulder difference (D) a single-layer plate having a shoulder angle of 10 and (e) a three-layer plate having a relief layer and a base layer. It is an image figure for demonstrating the process of producing a relief printing plate from the type | mold A, (a) is the process of pouring an aqueous resin dispersion into the mold A, (b) is drying the aqueous resin dispersion, The forming step (c) shows a step of taking out the resin printing plate from the mold A. It is a drawing substitute photograph which shows the observation result of the original plate, the type | mold A, and a relief printing plate with the optical microscope. It is a perspective view which shows the observation result of the original plate and a relief printing plate of the laser microscope, (a) is a figure which shows the top surface of the relief of an original plate, (b) is a figure which shows the top surface of the relief of a relief printing plate.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Relief 1a Low hardness layer 1b High hardness layer 2 Ink 3 Marginal 4 Substrate 5 Pattern without marginal 6 Pattern spread by marginal 7 Base part 8 Top surface 9 Depression 10 Shoulder angle 11 Anilox roll 12 Doctor blade 13 Version 14 version Body 15 Pattern 16 Aqueous resin dispersion 17 Type A
18 Resin printing plate

Claims (4)

In the method for producing a relief printing plate used for relief printing that transfers the ink supplied to the top surface of the relief of the relief plate to the printing medium,
A first step of pouring the resin-containing liquid into a mold in which an uneven pattern corresponding to the relief is incorporated;
A second step of producing a resin printing plate by drying the resin-containing liquid poured in the first step;
A third step of removing the resin printing plate produced in the second step from the mold to obtain the resin printing plate as a relief printing plate;
I have a,
A plurality of recesses corresponding to the fine protrusions are formed on the top surface of the relief of the resin printing plate by providing a plurality of fine protrusions at locations corresponding to the top surface of the relief of the mold. A method for producing a relief printing plate.   The method for producing a relief printing plate according to claim 1, wherein an aqueous resin dispersion is used as the resin-containing liquid. 3. The method for producing a relief printing plate according to claim 1, wherein the depth of the depression is 1 μm or more and 30 μm or less. 4. The method for producing a relief printing plate according to any one of claims 1 to 3 , wherein the mold is formed of a silicone-based resin.