JP2012051359A - Method of manufacturing printed article, printing plate, and paste - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a new printed article, by which a printed article, in which a plurality of rectangular printing parts are arrayed with a narrow lattice-like non-printing area formed across on a surface of a printed material, is manufactured continuously with high accuracy, and to provide a printing plate and paste suitable to be used in the same method.SOLUTION: The printing plate 6 is formed of silicone rubber, includes a projected part 4 corresponding to the printing area 2 and a lattice-like recessed groove 5 corresponding to the non-printing area 1, and has a width Wof 3-80 μm, a difference in height Dof 3-20 μm, and a length Lof 15 μm or more. The paste is coated on an approximately entire surface of the printing plate 6, and is semi-dried. Then, by press-contacting a substrate, only the paste on the projected part 4 is transferred on a surface of the substrate. The paste, of which viscosity ηis 18.6-374 Pa s, and of which a thixo index value TI=η/ηis 1.8-8.6, is used.

Description

  The present invention is used in a manufacturing method for manufacturing a printed article in which a plurality of image line parts are arranged on a surface of a printing medium with a non-image line part having a narrow width and a constant width, and the manufacturing method. The present invention relates to a printing plate and paste.

For example, an image line portion having a very fine planar shape as compared with the area of the substrate as the substrate to be printed, such as a conductive pattern for a flat display panel or a color pattern for a color filter, is formed on almost the entire surface of the substrate. In order to form with high accuracy, a forming method using a so-called photolithographic method has been conventionally employed.
However, recently, it is becoming popular to use a printing method instead of the photolithographic method. According to the printing method, the number of steps can be reduced as much as possible, the energy consumption can be reduced, the waste of the material used can be reduced, and the pattern can be formed with high productivity in a short time as compared with the photolithography method. Further, according to printing, it is possible to form a pattern having a thickness of 0.5 μm or more, which was not easy to form by the photolithography method.

As a printing method, for example, an intaglio offset printing method, a reverse printing method, a peeling printing method, and the like have been put into practical use.
Among these, in the intaglio offset printing method, an intaglio having a concave portion corresponding to the image line portion is prepared, and the concave portion is selectively filled with a paste (in the conductive pattern, a conductive paste such as silver paste), The printing blanket is transferred to the surface of the printing blanket by bringing the surface of the printing blanket formed of silicone rubber or the like into contact with the surface of the intaglio plate and then peeling off, thereby transferring the paste in the depression to the surface of the printing blanket. A paste pattern corresponding to the recess is formed on the surface of the substrate.

Next, the printing blanket is brought into contact with the substrate, the pattern-formed paste is retransferred to the surface of the substrate, dried, and then fired as necessary, whereby the concave portion is formed on the surface of the substrate. An image line portion corresponding to the shape is formed.
In such an intaglio offset printing method, when the paste is selectively filled in the concave portions of the intaglio, the paste supplied onto the intaglio is generally doctored using a doctor blade. By the doctoring, the paste can be selectively filled only in the concave portion while removing the paste on the convex portion between the concave portions on the surface of the intaglio.

  In the reverse printing method, the surface of the printing blanket has a concave portion corresponding to the pattern of the image line portion and a convex portion corresponding to the non-image area portion in a state where the paste is applied to substantially the entire surface of the printing blanket. A pattern of a paste corresponding to the concave portion is formed on the surface of the printing blanket by selectively removing the paste in the region in contact with the convex portion from the surface of the printing blanket by peeling after contacting the plate. Form.

Next, the printing blanket is brought into contact with the substrate, the pattern-formed paste is retransferred to the surface of the substrate, dried, and then fired as necessary, whereby the concave portion is formed on the surface of the substrate. An image line portion corresponding to the shape is formed (Patent Document 1).
In the peeling printing method, a planar plate in which a resin-repellent region corresponding to an image area and a resin-resinous region corresponding to a non-image area are formed on the same plane is prepared. The paste of the resin-repellent region is selected as the surface of the printing blanket by peeling off the printing blanket in contact with the surface in a state where the paste is applied to almost the entire surface where the both regions are formed. Thus, a paste pattern corresponding to the region is formed on the surface of the printing blanket.

Next, the printing blanket is brought into contact with the substrate, the pattern-formed paste is retransferred to the surface of the substrate, dried, and then fired as necessary, whereby the surface of the substrate is repelled. An image portion corresponding to the shape of the resinous region is formed (Patent Document 2).
However, in the various printing methods described above, for example, a plurality of image line portions are arranged on the surface of a printing medium such as a substrate with a non-image line portion having a narrow width of about 100 μm or less, and a width of about It is difficult to continuously produce a printed article having a thickness of the image line portion having a thickness of, for example, 0.5 μm or more with high accuracy.

  For example, in the intaglio offset printing method, the narrower the non-image area, the easier the paste forming the image area protrudes to the non-image area. When the protrusion occurs, the paste is adjacent to the non-image area. It is easy for the image line parts to contact each other (when each image line part is a conductive part made of a conductive paste, a short circuit). In addition, the width of the non-image portion that should be constant is likely to vary irregularly, and the edge of the image portion is likely to be disturbed.

These phenomena occur particularly in the convex portion corresponding to the non-image portion extending in a direction substantially perpendicular to the moving direction of the doctor blade during doctoring in the printing process of the intaglio offset printing method described above. As the width of the portion, that is, the width of the non-image portion is narrower, the paste on the convex portion is not sufficiently removed by the doctor blade.
Therefore, it is conceivable to increase the pressure of the doctor blade that is brought into pressure contact with the surface of the intaglio during doctoring.

However, in that case, a part of the doctor blade is deformed by the pressure contact force and enters into the concave portion corresponding to the image portion, and scrapes out the paste in the concave portion, so that the amount of paste in the concave portion ( Variation in the surface direction tends to occur in the thickness of the paste.
As a result, the thickness of the image area formed by transferring the paste to the surface of the substrate varies in the surface direction, or the thickness becomes too small and the image area is blurred or chipped. Arise.

  Further, since the intaglio is generally formed of a hard material such as metal or glass, the smaller the width of the non-imaged portion, that is, the width of the convex portion of the plate, the smaller the convex portion becomes the silicone rubber or the like. It tends to bite into the surface of the printing blanket made of and damage the surface. For this reason, the number of times that the same printing blanket can be used for continuous good printing is limited, and there is a problem that the printing blanket must be frequently replaced.

Since the reverse printing method does not require a doctoring step unlike the intaglio offset printing method, various problems occurring in the doctoring step can be solved.
However, since the same plate as the intaglio used in the intaglio offset printing method is used, the problem that the convex portions of the plate tend to bite into the surface of the printing blanket and easily damage the surface cannot be solved.

  Furthermore, in the peeling printing method, since a flat plate is used, the problem of scratches on the printing blanket can be solved. However, since the resin-resinous region of the plate has a high adhesive energy to the base, the paste remaining in the resin-resinous region must be cleaned with a solvent each time it is printed. In addition, there is a problem that a great deal of labor is required for the management of the solvent, the treatment of the waste liquid after washing, consideration for the environment, and the like.

Japanese Patent No. 3689536 Japanese Patent No. 4364534 JP 2009-28947 A

  An object of the present invention is to provide a printed article in which a plurality of image line parts are arranged on the surface of a printing medium with a non-image line part having a narrow width of about 100 μm or less and a fixed width. It is an object of the present invention to provide a method for producing a novel printed article that can be produced continuously with high accuracy, and a printing plate and paste suitable for use in the production method.

A microcontact printing method is known as a printing method for forming, for example, a nano-level very thin pattern on a substrate using a liquid having a viscosity lower than that of a paste (for example, Patent Document 3).
In such a microprint contact method, a plate having a convex portion corresponding to an image line portion and a concave portion corresponding to a non-image line portion is prepared on the surface, and the liquid is applied to substantially the entire surface of the plate. After that, the substrate is brought into contact with the surface of the plate. Then, the liquid on the convex portion of the plate is selectively transferred to the surface of the substrate, and a pattern is formed on the surface of the substrate.

The inventor uses the microprint contact method to print a printed article, particularly a grid-like non-image, in which a plurality of image areas are arranged on a surface of a printing medium with a non-image area having a narrow width. The application to the manufacture of a printed article in which a plurality of rectangular image line portions are arranged with a line portion therebetween was studied.
However, since the viscosity of the paste and liquid to be printed is too different between the production of printed products and the microprint contact method, and the thickness of the image area formed on the surface of the substrate is also too different, the microprint contact method can be simply transferred. Was technically impossible.

Accordingly, as a result of further examination of the plate mainly used for printing, the present invention has been completed.
That is, the present invention is a manufacturing method for manufacturing a printed article in which a plurality of image line portions are arranged on a surface of a substrate to be printed with a non-image line portion having a certain width therebetween.
A plurality of convex portions corresponding to the image line portion, and a concave groove having a constant width corresponding to the non-image line portion between the convex portions, and at least the surface of the convex portion is made of silicone rubber, and adjacent convex portions The width of the concave groove, which is the interval between the parts, is 3 μm or more and 80 μm or less, the height difference between the surface of the convex part and the bottom surface of the concave groove is 3 μm or more and 20 μm or less, and the convexity is the distance between adjacent concave grooves Applying a paste over substantially the entire surface of the printing plate having a width of 15 μm or more;
Semi-drying the paste;
A step of selectively transferring only the paste on the convex portion of the surface of the printing plate to the surface of the printing body by pressing the printing body on the surface of the printing plate coated with the paste. When,
It is characterized by including.

  Further, the present invention is a printing plate used in the manufacturing method, wherein a plurality of convex portions corresponding to the image line portion, and a concave groove having a constant width corresponding to the non-image line portion between the convex portions. And at least the surface of the convex portion is made of silicone rubber, and the width of the concave groove, which is an interval between adjacent convex portions, is 3 μm or more and 80 μm or less, and there is a difference in height between the surface of the convex portion and the bottom surface of the concave groove. The width of the convex portion, which is 3 μm or more and 20 μm or less, and is an interval between adjacent concave grooves is 15 μm or more.

  According to the present invention, as described above, by using a printing plate having at least the surface of the convex portion corresponding to the image line portion made of silicone rubber, the paste applied on the convex portion is printed. It is possible to prevent so-called separation that separates the portion transferred onto the surface of the body and the portion remaining on the convex portion. Then, the entire amount of paste on the convex portion is transferred to the surface of the printing medium, and the surface of the printing medium has a sufficient thickness and the thickness is constant, and the shape of the edge is not disturbed. A good image area can be formed.

  Further, by setting the width of the concave groove, which is an interval between adjacent convex portions of the printing plate, to 3 μm or more, the paste applied on the convex portion and the paste applied in the concave groove, In the half-drying step, the separation can be satisfactorily performed based on the level difference between the surface of the convex portion and the bottom surface of the groove. For this reason, it is possible to prevent contact between adjacent image line parts across the non-image line part (short circuit when each image line part is a conductive part made of a conductive paste). Further, it is possible to prevent the irregular width of the non-image portion that should be constant and the edges of the image portion from being disturbed, thereby improving the accuracy of the printed shape.

  Further, by setting the width of the concave groove to 80 μm or less, the paste on the bottom surface of the concave groove comes into contact with the surface of the printing medium due to deformation of the printing plate or the like at the time of press contact with the printing medium. It is possible to prevent the matching image line parts from contacting each other. Further, it is possible to prevent the irregular width of the non-image portion that should be constant and the edges of the image portion from being disturbed, thereby improving the accuracy of the printed shape.

  Further, by making the height difference between the surface of the convex portion and the bottom surface of the concave groove of the printing plate 3 μm or more, the paste applied on the convex portion and the paste applied in the concave groove, While being semi-dried in the semi-drying step, it is well separated based on the level difference between the surface of the convex part and the bottom surface of the concave groove, and due to deformation of the printing plate during pressure contact with the printing medium It is also possible to prevent so-called bottoming, in which the paste on the bottom surface of the concave groove contacts the surface of the printing medium. Therefore, it is possible to prevent the adjacent image line parts from contacting each other across the non-image line part. Further, it is possible to prevent the irregular width of the non-image portion that should be constant and the edges of the image portion from being disturbed, thereby improving the accuracy of the printed shape.

Moreover, the paste in the said ditch | groove can be easily removed without using a solvent by making the said height difference into 20 micrometers or less.
For example, the concave groove is formed by pressing a resin film or sheet on the surface of a printing plate after transferring the paste on the surface of the convex portion to the printing body with a higher pressure than the printing body and then peeling it. The paste remaining inside can be removed by transferring it to the surface of the resin film or sheet.

Further, the adhesive sheet is pressed against the surface of the printing plate after transfer and then peeled off, whereby the paste remaining in the concave groove can be transferred to the surface of the adhesive sheet and removed.
Therefore, by using the solvent, the labor required for the management of the solvent, the treatment of the waste liquid after washing, consideration for the environment, etc. can be greatly reduced.

Further, by setting the width of the convex portion, which is an interval between adjacent concave grooves of the printing plate, to 15 μm or more, the deformation of the convex portion when the printing medium is pressed against the surface of the printing plate. And the accuracy of the printed shape can be improved.
In the case of manufacturing a printed article in which non-image line parts are arranged in a grid pattern and the image line part is formed in a rectangular shape with the grid-like non-line image part therebetween, the printing plate As a plurality of convex portions corresponding to the image line portion, and a lattice-shaped concave groove corresponding to the non-image line portion between the convex portions, and a concave groove that is an interval between adjacent convex portions. The width is 3 μm or more and 80 μm or less, the height difference between the surface of the convex part and the bottom surface of the concave groove is 3 μm or more and 20 μm or less, and the length of one side of the rectangle as the width of the convex part is 15 μm or more. Use it.

The printing plate is preferably integrally formed of silicone rubber having a JIS A hardness of 15 or more and 80 or less as a whole. Thereby, the structure of the printing plate can be simplified.
Further, by setting the JIS A hardness to 15 or more, it is possible to suppress the excessive deformation of the convex portion when the printing medium is pressed against the surface of the printing plate and to improve the accuracy of the printed shape.
Further, by setting the JIS A hardness to 80 or less, the paste on the convex portion is applied to the surface of the printing medium while the convex portion is elastically deformed and closely adhered to the surface of the printing body at the time of the press contact. The accuracy of the printed shape can be improved. It is also possible to prevent the surface of the printing medium from being damaged.

Further, as a result of examining the paste used in the method for producing the printed matter, the inventors have completed the present invention.
That is, the present invention includes a plurality of convex portions corresponding to a plurality of image line portions, and a groove having a constant width corresponding to a non-image line portion having a constant width between the convex portions, and at least a surface of the convex portion is provided. Using a printing plate made of silicone rubber,
After applying the paste to substantially the entire surface of the printing plate, semi-drying, and then selectively pressing only the paste on the convex portion of the surface of the printing plate by pressing the printed material to the surface, By transferring to the surface of the substrate,
The paste used in a manufacturing method for manufacturing a printed article formed by arranging the plurality of image line portions on the surface of the substrate to be printed with the non-image line portions separated from each other,
Using an E-type viscometer, the viscosity η ₁ measured under the conditions of a temperature of 25 ° C. and a shear rate of 1 (1 / s) is 18.6 Pa · s or more and 374 Pa · s or less, a temperature of 25 ° C., and a shear rate of 10 viscosity eta ₁₀ as measured under the conditions of (1 / s), from the viscosity eta ₁ Tokyo, equation (1):
_{TI = η 1 / η 10 (} 1)
The thixo index value TI obtained in (1) is 1.8 or more and 8.6 or less.

When the paste is applied to almost the entire surface of the printing plate, a part of the paste applied to the convex portion is recessed due to its own fluidity between application and transfer to the surface of the printing plate. It flows into the groove.
However, in the paste of the present invention in which the viscosity η ₁ and the thixo index value TI are adjusted within the above ranges, the fluidity is appropriately controlled, and the inflow is suppressed. Can be maintained until the transfer.
Accordingly, it is possible to prevent contact between adjacent image line parts with a non-image line part interposed therebetween (short circuit when each image line part is a conductive part made of a conductive paste).

On the other hand, the paste having a viscosity η ₁ of less than 18.6 Pa · s or the paste having a thixo index value TI of less than 1.8 has too high fluidity after application, and the groove is formed on the convex portion. Since a large amount flows into the surface, the height difference between the surface of the paste on the convex portion and the surface of the paste in the concave groove cannot be sufficiently secured, and the adjacent image portions sandwiching the non-image portion They come into contact with each other (in the case where each image portion is a conductive portion made of a conductive paste).

In addition, a paste having a viscosity η ₁ exceeding 374 Pa · s, or a paste having a thixo index value TI exceeding 8.6 is too low in fluidity at the time of application, and the coating film thickness increases. The height difference between the surface of the paste and the surface of the paste in the groove cannot be sufficiently secured, and the adjacent image portions are in contact with each other across the non-image area (each image area is electrically conductive). In the case of a conductive part made of a conductive paste).

  According to the present invention, a printed article in which a plurality of image line portions are arranged on a surface of a printing medium with a non-image line portion having a narrow width of about 100 μm or less and a constant width therebetween. It is possible to provide a method for producing a novel printed article that can be continuously produced with high accuracy, and a printing plate and paste suitable for use in the production method.

In an example of the printed article manufactured by the manufacturing method of this invention, it is a top view which expands and shows a part of grid-like non-image part formed on the surface of a to-be-printed body, and a rectangular image line part. is there. It is a perspective view which expands and shows a part of example of embodiment of the printing plate of this invention used for manufacture of the printed article of the example of FIG. FIGS. (A) to (d) are enlarged sectional views for explaining the respective steps of the production method of the present invention. FIGS. 3A and 3B are enlarged cross-sectional views for explaining the subsequent steps of FIGS. 3A to 3D. In another example of the printed article manufactured by the manufacturing method of this invention, it is a top view which expands and shows a part of striped non-image part and image part formed in the surface of a to-be-printed body. It is a perspective view which expands and shows a part of other example of embodiment of the printing plate of this invention used for manufacture of the printed article of the example of FIG.

<Method for producing printed article and printing plate>
FIG. 1 is an enlarged view of a grid-like non-image portion and a rectangular image portion formed on the surface of a printing medium in an example of a printed article produced by the production method of the present invention. FIG. FIG. 2 is an enlarged perspective view showing a part of an embodiment of the printing plate of the present invention used for manufacturing the printed article of the example of FIG.
Referring to FIG. 1, according to the manufacturing method of the present invention, a plurality of rectangular image line portions 2 are arranged on a surface of a printing medium such as a substrate with a grid-like non-image line portion 1 therebetween. The printed article 3 can be manufactured. In the drawing, the image line portion 2 is formed in a square shape out of rectangles, but the image line portion 2 may be rectangular.

Referring to FIG. 2, in order to manufacture the printed article 3 of FIG. 1, a plurality of convex portions 4 corresponding to the image line portion 2 and the non-image line portion 1 between the convex portions 4 are supported. A printing plate 6 having concave grooves 5 connected in a lattice shape is used.
In the printing plate 6, at least the surface of the convex portion 4 is formed of silicone rubber. As a result, it is possible to prevent so-called separation, in which the paste applied onto the convex portion 4 is separated into a portion transferred onto the surface of the printing medium and a portion remaining on the convex portion 4. Then, the entire amount of the paste on the convex portion 4 is transferred to the surface of the printing body, and the surface of the printing body has a sufficient thickness and the thickness is constant, and the shape of the edge is also disturbed. It is possible to form a good image area 2 having no image.

In the present invention, the entire printing plate 6 having the plurality of convex portions 4 and the concave grooves 5 is integrally formed of silicone rubber having a JIS A hardness (23 ± 1 ° C.) of 15 or more and 80 or less. It is preferable to simplify the structure.
Further, by setting the JIS A hardness to 15 or more, it is possible to suppress the excessive deformation of the convex portion when the printing medium is pressed against the surface of the printing plate and to improve the accuracy of the printed shape.

Further, by setting the JIS A hardness to 80 or less, the paste on the convex portion is applied to the surface of the printing medium while the convex portion is elastically deformed and closely adhered to the surface of the printing body at the time of the press contact. The accuracy of the printed shape can be improved. It is also possible to prevent the surface of the printing medium from being damaged.
In consideration of further improving these effects, the silicone rubber JIS
It is preferable that A hardness is 28 or more also in the said range.

Note that a film or sheet of resin or metal, for example, may be bonded to the back surface (not shown) of the printing plate 6 integrally formed of the silicone rubber as a support layer. As a result, it is possible to suppress the deformation of the printing plate 6 particularly in the surface direction and further improve the printing accuracy.
The width W ₁ of the groove 5 that is the distance between the adjacent convex portions 4 of the printing plate 6 needs to be 3 μm or more and 80 μm or less in any of the vertical and horizontal directions of the lattice.

By setting the width W ₁ to 3 μm or more, the paste applied on the convex portion 4 and the paste applied to the concave groove 5 are semi-dried in a semi-drying process until the convex portion is formed. Good separation can be achieved based on the level difference between the surface of the portion 4 and the bottom surface of the groove 5. For this reason, it is possible to prevent the adjacent image line parts 2 from contacting or short-circuiting each other with the non-image line part 1 interposed therebetween. You can also vary irregularly width W ₂ of the non-image portion 1 which should be constant, thereby preventing the or disturbed edge of the image area 2, the accuracy of the printing form can be improved.

By the width W ₁ and 80μm or less Further, the paste of the bottom surface of the groove 5 contacts the surface of the printing material by the deformation of the printing plate 6 during pressing of the printing material, the conditioned called bottom It is possible to prevent the adjacent image line portions 2 from coming into contact with each other. You can also vary irregularly width W ₂ of the non-image portion 1 which should be constant, thereby preventing the or disturbed edge of the image area 2, the accuracy of the printing form can be improved.

In consideration of further improving these effects, the width W ₁ is preferably 5 μm or more, and preferably 67 μm or less, even within the above range.
The height difference D ₁ between the depth of the concave groove 5, that is, the surface of the convex portion 4 that is the surface of the printing plate 6 and the bottom surface of the concave groove 5 needs to be 3 μm or more and 20 μm or less.
With the height difference D ₁ to 3μm or more, a paste is applied on the convex portion 4, and a paste applied to the groove 5, until to semi-dry semi-dry process, the Based on the level difference between the surface of the convex portion 4 and the bottom surface of the groove 5, the paste on the bottom surface of the groove 5 is covered by deformation of the printing plate 6 or the like when pressed against the printing medium. It is also possible to prevent bottoming in contact with the surface of the printed body. Therefore, it is possible to prevent the adjacent image line parts 2 from contacting each other across the non-image line part 1. You can also vary irregularly width W ₂ of the non-image portion 1 which should be constant, thereby preventing the or disturbed edge of the image area 2, the accuracy of the printing form can be improved.

Also by less 20μm the height difference D _1, the paste in the concave groove 5, in the removal step described below, can be easily removed without the use of solvents.
In consideration of further improving these effects, the height difference D ₁ is preferably 4 μm or more, more preferably 15 μm or less, even within the above range.
The cross-sectional shape of the concave groove 5 is preferably a substantially rectangular shape having the same width from the opening to the bottom surface of the printing plate 6 as shown in the drawing. As a result, the surface of the convex portion 4 and the bottom surface of the concave groove 5 until the paste applied to the convex portion 4 and the paste applied to the concave groove 5 are semi-dried in the semi-drying step. Can be satisfactorily separated based on the level difference between them.

The width of the convex portion 4, which is the distance between the adjacent concave grooves 5, that is, the length L1 of _one side of the rectangle needs to be 15 μm or more in both the vertical and horizontal directions of the lattice.
By setting the length to 15 μm or more, it is possible to suppress the deformation of the convex portion 4 when the printing medium is pressed against the surface of the printing plate 6 and to improve the accuracy of the printing shape.
Note the upper limit of the length is in the printed article of manufacture, it can be arbitrarily set according to the length L ₂ of one side of the image area 2.

The printing plate 6 can be manufactured by any method, but the manufacturing method using the following master and stamper is particularly preferable.
In such a manufacturing method, for example, a lattice-like groove corresponding to the concave groove 5 is formed on the surface of a metal plate such as a nickel plate or a plate material such as a glass plate by etching using patterning by a photolithographic method or the like. A master that is the basis of the printing plate 6 is produced, and the master is electroformed to produce a stamper with the concavities and convexities reversed.

Next, on the uneven surface of the stamper, a liquid silicone rubber that is the basis of the printing plate 6 is applied and cured using, for example, a bar coater or the like, and then peeled off from the stamper to correspond to the shape of the master. A printing plate 6 can be manufactured.
The stamper can be used to manufacture a plurality of printing plates 6. The master can also be used to manufacture multiple stampers. Therefore, according to the manufacturing method, a large number of printing plates having the same shape and the same accuracy can be manufactured.

Examples of the metal plate among the plate materials that serve as the master are, for example, a plate material made of nickel, copper or an alloy thereof, aluminum or an alloy thereof, iron or an alloy thereof, and the like. Moreover, as a glass plate, the board | plate material which consists of quartz glass etc. is mentioned, for example. Furthermore, a plate material made of an inorganic material such as silicon oxide (SiO ₂ , quartz, etc.), silicon (Si), or a plate material made of an organic material such as polymethyl methacrylate (PMMA) can be used.

Further, by applying a liquid silicone rubber on a horizontal stamper and then curing it, the thickness of the printing plate can be made uniform by the self-leveling effect of the liquid during curing.
Before the surface of the applied silicone rubber is cured, the film or sheet such as resin or metal described above is overlaid, and then the silicone rubber is cured, so that the film or sheet can be bonded as a reinforcing layer. it can.

The liquid silicone rubber is preferably a two-component addition reaction type comprising two components, a main agent and a curing agent, and curing the both by an addition reaction.
The two-component addition reaction type silicone rubber improves the dimensional accuracy of the printing plate because it does not produce a by-product (water or the like by dehydration condensation reaction) during the curing reaction, and includes bubbles or the like based on the by-product. A uniform printing plate can be formed.

  Examples of the room temperature curing type two-component addition type liquid silicone rubber include, for example, product numbers KE1600, KE1603, KE1606, KE1310ST, KE1300T, KE1314, KE1241, KE106, KE103, Momentive Performance, manufactured by Shin-Etsu Chemical Co., Ltd. Examples include one or more of TSE3062, TSE3402, TSE3450, TSE3453, TSE3455T, TSE3457, TSE3466, and RTV662 manufactured by Materials Japan GK.

3 (a) to 3 (d) and FIGS. 4 (a) and 4 (b) are enlarged cross-sectional views for explaining each step of the manufacturing method of the present invention.
With reference to these drawings, in the manufacturing method of the present invention, first, a predetermined amount of paste 7 is supplied to the surface of the printing plate 6 on which the convex portions 4 and the concave grooves 5 are formed. For example, the doctor blade 8 is used for doctoring, that is, the doctor blade 8 is brought into pressure contact with the surface of the printing plate 6 with a predetermined pressing force, and is constant on the surface in the direction indicated by the solid arrow in the figure. It is applied to almost the entire surface by moving it at a speed [FIG. 3 (a)].

Next, the paste 7 is left to stand to be semi-dried [FIG. 3 (b)]. Then, the surface of the convex portion 4 and the concave groove are formed until the paste 7a applied on the convex portion 4 of the printing plate 6 and the paste 7b applied in the concave groove 5 are semi-dried. 5 can be satisfactorily separated based on the level difference between the bottom surface and the bottom surface.
The semi-dry state as used in the present invention is a state before the paste 7 is completely dried and loses transferability to the printing material, and more than 10% of the total amount of solvent contained in the paste 7 is in the atmosphere. The state in which it is evaporated and diffused in the printing plate 6 is pointed out.

Next, the surface of the printing plate 6 is peeled off after the substrate 9 such as a resin film or sheet as a printing medium or a glass plate is brought into pressure contact with a predetermined pressure and then peeled off. Among them, only the paste 7a on the convex portion 4 is selectively transferred to the surface of the substrate 9 [FIGS. 3 (c) (d)].
Thereafter, the paste 7a is dried, and further fired as necessary. As shown in FIG. 1, a plurality of rectangular image areas are formed on the surface of the substrate 9 with the grid-shaped non-image areas 1 being separated. A printed article 3 formed by arranging 2 can be manufactured.

Further, as shown in FIGS. 4A and 4B, a cleaning film or sheet 10 is pressed against the surface of the printing plate 6 after the paste 7a is transferred to the surface of the substrate 9 with a predetermined pressing force. Then, the paste 7b remaining in the concave groove 5 in the surface of the printing plate 6 is transferred to the surface of the film or sheet 10 and removed.
As the film or sheet 10, for example, a resin film or sheet similar to that of the substrate 9 is used, and the film or sheet 10 is pressed against the surface of the printing plate 6 with a higher pressing force than the substrate 9 and then peeled off. Or a pressure-sensitive adhesive sheet having a tackiness applied to the surface that contacts the surface of the printing plate 6 is used.

As a result, the paste 7b can be removed from the groove 5 without being washed with a solvent. Therefore, the labor required for the management of the solvent, the treatment of the waste liquid after washing, consideration for the environment, and the like by using the solvent can be greatly reduced.
In the former case, there is no particular limitation on how much the cleaning film or sheet 10 is brought into pressure-contact with the substrate 9. For example, the printing plate 6 and the substrate 9 or the printing plate 6 The latter is preferably set to about 2 to 5 times the former, expressed in terms of the amount of pressing (μm) from the contact position of the film or sheet 10 in the thickness direction of the printing plate.

The printing plate 6 from which the paste 7b has been removed can be used repeatedly for the production of a new printed article 3.
Examples of the printed article produced by the production method of the present invention include an electronic paper electrode substrate.
In addition, the structure of this invention is not limited to embodiment described above, A various change can be given in the range which does not change the summary of this invention.
For example, the printed article manufactured by the manufacturing method of the present invention is not limited to the above-described one in which a plurality of rectangular image line portions are arranged with a lattice-shaped non-image line portion therebetween.

FIG. 5 is an enlarged plan view showing a stripe-shaped non-image portion and a part of the image portion formed on the surface of the printing medium in another example of the printed article manufactured by the manufacturing method of the present invention. FIG. FIG. 6 is an enlarged perspective view showing a part of another example of the embodiment of the printing plate of the present invention used for manufacturing the printed article of the example of FIG.
Referring to FIG. 5, according to the manufacturing method of the present invention, a plurality of image line portions 2 are arranged in stripes on the surface of a printing medium such as a substrate with linear non-image line portions 1 being separated from each other. It is also possible to manufacture the printed article 3 formed as described above.

With reference to FIG. 6, in order to manufacture the printed article 3 of FIG. 5, a plurality of convex portions 4 corresponding to the image line portion 2 and the non-image line portion 1 between the convex portions 4 are supported. The printing plate 6 of the present invention having the linear concave groove 5 is used.
The printing plate 6 is formed of at least the surface of the convex portion 4, preferably the entire surface thereof with silicone rubber, particularly silicone rubber having a JIS A hardness (23 ± 1 ° C.) of 15 or more, 80 or less, especially 28 or more. It is preferable to do this.

Further, the width W ₁ of the concave groove 5 which is an interval between the adjacent convex portions 4 of the printing plate 6 needs to be 3 μm or more and 80 μm or less, and particularly preferably 67 μm or less.
Further, the depth difference D ₁ between the depth of the groove 5, that is, the surface of the convex portion 4 that is the surface of the printing plate 6 and the bottom surface of the groove 5 must be 3 μm or more and 20 μm or less, and 4 μm or more, It is preferably 15 μm or less.

Furthermore, the width L ₁ of the convex portion 4 is the distance between the grooves 5 of adjacent should be 15μm or more.
All of these reasons are as described above.
By using the printing plate 6 and passing through the steps shown in FIGS. 3 (a) to 3 (d) and FIGS. 4 (a) and 4 (b), the surface of the printed material such as a substrate is linearly non-coated. A printed article 3 in which a plurality of image line portions 2 are arranged in a stripe shape with the image line portion 1 therebetween can be manufactured continuously with high accuracy.

<paste>
As the paste, a viscosity η ₁ measured using an E-type viscometer under the conditions of a temperature of 25 ° C. and a shear rate of 1 (1 / s) is 18.6 Pa · s or more and 374 Pa · s or less, and a temperature of 25 ° C. From the viscosity η ₁₀ measured at a shear rate of 10 (1 / s) and the viscosity η ₁ , the formula (1):
_{TI = η 1 / η 10 (} 1)
The paste of the present invention having a thixo index value TI determined in (1) of 1.8 or more and 8.6 or less is used.

When the paste is applied to almost the entire surface of the printing plate, a part of the paste applied to the convex portion is recessed due to its own fluidity between application and transfer to the surface of the printing plate. It flows into the groove.
However, in the paste of the present invention in which the viscosity η ₁ and the thixo index value TI are adjusted within the above ranges, the fluidity is appropriately controlled, and the inflow is suppressed. Can be maintained until the transfer.
Accordingly, it is possible to prevent contact between adjacent image line parts with a non-image line part interposed therebetween (short circuit when each image line part is a conductive part made of a conductive paste).

On the other hand, the paste having a viscosity η ₁ of less than 18.6 Pa · s or the paste having a thixo index value TI of less than 1.8 has too high fluidity after application, and the groove is formed on the convex portion. Since a large amount flows into the surface, the height difference between the surface of the paste on the convex portion and the surface of the paste in the concave groove cannot be sufficiently secured, and the adjacent image portions sandwiching the non-image portion They come into contact with each other (in the case where each image portion is a conductive portion made of a conductive paste).

In addition, a paste having a viscosity η ₁ exceeding 374 Pa · s, or a paste having a thixo index value TI exceeding 8.6 is too low in fluidity at the time of application, and the coating film thickness increases. The height difference between the surface of the paste and the surface of the paste in the groove cannot be sufficiently secured, and the adjacent image portions are in contact with each other across the non-image area (each image area is electrically conductive). In the case of a conductive part made of a conductive paste).
For example, when the image area 2 is a conductive part, a conductive paste in which conductive powder is blended with a binder resin, a solvent, or the like is used as the paste.

In order to adjust the viscosity η ₁ and the thixo index value TI of the conductive paste within the above ranges, for example, the particle size and shape of the conductive powder, the type and molecular weight of the binder resin, the conductive powder, and the binder resin The mixing ratio of the solvent and the like may be adjusted as appropriate.
Among the above, as the conductive powder, for example, a metal powder such as gold, silver, copper, platinum, nickel, aluminum, iron, palladium, chromium, molybdenum, tungsten, manganese, cobalt, or an alloy of two or more of the above metals. One type or two or more types of powders, powders of plating composites such as silver-plated copper, and powders of metal oxides such as silver oxide, cobalt oxide, iron oxide, and ruthenium oxide can be used. Among them, silver powder that can form a conductive pattern with excellent conductivity is preferable because it has high conductivity and is excellent in oxidation resistance that hardly generates a highly insulating oxide.

In order to adjust the viscosity η ₁ and the thixo index value TI of the conductive paste within the above ranges, a conductive powder having an arbitrary particle size and shape can be appropriately selected and used. Further, for example, two or more kinds of conductive powders made of the same or different metals and having different shapes and / or particle sizes may be used in combination.
Examples of the binder resin include polyester resins, acrylic resins, ethyl cellulose, polyvinyl butyral, polyester-melamine resins, melamine resins, epoxy-melamine resins, phenol resins, polyimide resins, and epoxy resins. Two or more types can be mentioned.

A binder resin having an arbitrary molecular weight can be appropriately selected and used in order to adjust the viscosity η ₁ and the thixo index value TI of the conductive paste within the above ranges. Further, for example, two or more binder resins having different types and molecular weights may be used in combination.
As the solvent, various solvents that can dissolve the binder resin and disperse the conductive powder can be used.

  Examples of the solvent include alcohols such as hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, stearyl alcohol, seryl alcohol, cyclohexanol, α-terpineol; ethylene glycol monobutyl ether ( Butyl cellosolve), ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monobutyl ether (butyl carbitol), ethylene glycol monoethyl ether acetate (cellosolve acetate), ethylene glycol monobutyl ether acetate (butyl cellosolve acetate), diethylene glycol monoethyl ether acetate (carbitol acetate) ), Jie Alkyl ethers such as glycol monobutyl ether acetate (butyl carbitol acetate) and the like.

As the solvent, in order to adjust the viscosity η ₁ and the thixo index value TI of the conductive paste within the above ranges, any solvent may be used alone, or two or more kinds may be used in combination.
In addition to the above-mentioned components, various additives such as a leveling agent, a dispersant, a thixotropic viscosity imparting agent, an antifoaming agent, a filler, and a curing catalyst are added to the conductive paste in an arbitrary ratio. You can also.
The conductive paste is prepared by blending the above components at a predetermined ratio and mixing them using a three roll, ball mill, attritor, sand mill or the like. The treatment conditions are not particularly limited, and may be treated according to a conventional method.

Production of printing plates, preparation of silver paste, production of printed articles, and evaluation in the following examples and comparative examples were performed in an environment of a temperature of 23 ± 1 ° C. and a relative humidity of 55 ± 1%, unless otherwise specified. .
<Example 1>
(Preparation of printing plate)
A pattern of a resist layer is formed on the surface of the nickel flat plate by photolithography and then etched, and a plurality of square-shaped convex portions corresponding to the image-line portions are formed on the surface, and the non-image-line portions between the convex portions. A master for forming a printing plate was prepared by forming a grid-like concave groove corresponding to the above, and a stamper with the concavities and convexities reversed by electroforming the master.

Referring to FIG. 2, in the master, the width W ₁ of the groove 5 that is the distance between the adjacent protrusions 4 is 9 μm in any of the vertical and horizontal directions of the lattice, and the depth of the groove 5, that is, the protrusion The height difference D ₁ between the surface of the portion 4 and the bottom surface of the groove 5 was 3 μm, and the length L ₁ of one side of the convex portion 4 was 141 μm in both the vertical and horizontal directions of the lattice.
Also, after mixing 100 parts by mass of the main agent and 10 parts by mass of the curing agent of room temperature curing type and two-component addition reaction type liquid dimethyl silicone rubber (TSE3455T manufactured by Momentive Performance Materials Japan GK), defoaming is performed. Thus, a coating solution that becomes the basis of the printing plate was prepared.

Then, the coating solution was applied to the uneven surface of the stamper using a bar coater, allowed to stand at room temperature for 24 hours to undergo a curing reaction, and then demolded to prepare a printing plate.
The dimensions of each part of the printing plate coincide with the dimensions of each part of the master, and the width W _{1 of the} groove 5 is 9 μm in both the vertical and horizontal directions of the lattice, and the surface of the convex part 4 and the groove 5 The height difference D _{1 from the} bottom surface was 3 μm, and the length L ₁ of one side of the convex portion 4 was 141 μm in both the vertical and horizontal directions of the lattice.

The printing plate had a JIS A hardness (JIS K-6253) of 37.
(Preparation of silver paste)
Butyl carbitol acetate was added to a commercially available silver paste (AGES-102X manufactured by Sumitomo Electric Industries, Ltd.) to adjust the viscosity η ₁ to 32.6 Pa · s. The viscosity η ₁ is a value measured using an E-type viscometer at a temperature of 25 ° C. and a shear rate of 1 (1 / s).
The viscosity η ₁₀ of the silver paste measured at a temperature of 25 ° C. and a shear rate of 10 (1 / s) using the E-type viscometer is 14.2 Pa · s, and the above formulas are obtained from the above two viscosities η ₁ and η _10. The thixo index value TI obtained by (1) was 2.3.

(Manufacture of printed products)
A silver paste is applied to substantially the entire surface of the printing plate and allowed to stand for 10 seconds. Then, a PET film as a printing medium is brought into contact with the surface, and further, 50 μm in the thickness direction of the printing plate from the contact position. After pressing and pressing, the silver paste on the convex part of the surface of the printing plate is selectively transferred to the surface of the PET film, followed by drying and baking processes. A printed article was produced.

In addition, a cleaning PET film is brought into contact with the surface of the printing plate after the transfer, and further pressed into the thickness direction of the printing plate from the contact position so as to be pressed by 300 μm, and then peeled off, thereby remaining in the groove. The paste to be removed.
<Examples 2 to 16, Comparative Examples 1 to 6>
By changing the shape of the master, the width W ₁ of the concave groove 5 (the same in both the vertical and horizontal directions of the lattice), the height difference D ₁ between the surface of the convex portion 4 and the bottom surface of the concave groove 5, and the one side of the convex portion 4 Printing plates were prepared in the same manner as in Example 1 except that the length L ₁ (same in both the vertical and horizontal directions of the lattice) was the values shown in Tables 1 to 3, respectively, and the printing plate was used. The article was manufactured and the printing plate after transfer was cleaned. The JIS A hardness (JIS K-6253) of the printing plate was 37.

<Measurement of thickness>
The thickness of the paste before drying and baking was measured after transferring to a PET film in Examples and Comparative Examples.
<Evaluation of printability>
The shapes of the image area and the non-image area of the printed articles produced in Examples and Comparative Examples were observed, and the printability was evaluated according to the following criteria.

X: A short circuit occurred between adjacent image areas, or the pattern could not be reproduced. Printability is poor.
○: Although there was a slight disturbance in shape, no short circuit was observed between adjacent image areas. Good printability.
A: No disorder in shape or short circuit was observed. Very good printability.

<Cleanability evaluation>
The printing plate after cleaning was observed and the cleaning property was evaluated according to the following criteria.
X: Only less than 40% of the paste in the groove was removed. Poor cleaning performance.
○: Paste of 40% or more and less than 80% in the groove was removed. Good cleaning performance.
A: More than 80% of the paste in the groove was removed. Excellent cleaning performance.

  The results are shown in Tables 1 to 3.

From Tables 1 to 3, the width W ₁ of the concave groove between adjacent convex portions of the printing plate is 3 μm or more and 80 μm or less, and the height difference D ₁ between the surface of the convex portion and the bottom surface of the concave groove is 3 μm or more. When the length L1 of _one side of the rectangular shape of the convex portion is within a range of 15 μm or more, the accuracy of the printed shape and the cleaning property are improved while preventing adjacent image line portions from being short-circuited. Thus, it has been found that a printed article in which a plurality of rectangular image line portions are arranged with a grid-like non-image line portion therebetween can be manufactured continuously with high accuracy.

<Examples 17 to 21>
By using the following coating liquid (liquid silicone rubber) as the basis for the printing plate, the printing plate having the JIS A hardness (JIS K-6253) as shown in Table 4 was prepared. A printed article was produced in the same manner as in Example 4 except that the printing plate was used, and the transferred printing plate was cleaned.

Example 17: Mixture of 50 parts by mass of TSE3450 main ingredient and 5 parts by mass of hardener made by Momentive Performance Materials Japan GK, and 50 parts by mass of main ingredient of TSE3062 made by the same company and 5 parts by mass of hardener A mixture with the mixture at a mass ratio of 1: 1 (JIS A hardness after curing: 15).
Example 18: A mixture of 50 parts by mass of a main agent and 50 parts by mass of a curing agent of KE1603 manufactured by Shin-Etsu Chemical Co., Ltd. (JIS A hardness after curing: 28).

Example 19: A mixture of 100 parts by mass of a main agent of TSE3450 and 10 parts by mass of a curing agent manufactured by Momentive Performance Materials Japan GK (JIS A hardness after curing: 34).
Example 20: Mixture of 100 parts by mass of the main agent of TSE3466 manufactured by Momentive Performance Materials Japan GK and 10 parts by mass of the curing agent (JIS A hardness after curing: 56).

Example 21: Mixture of 100 parts by mass of RTV662 main ingredient and 10 parts by mass of curing agent manufactured by Momentive Performance Materials Japan GK (JIS A hardness after curing: 66).
The dimensions of each part of the printing plate are the same as in Example 4. That is, the width W _{1 of the} groove 5 is 17 μm in both the vertical and horizontal directions of the lattice, and the height difference D between the surface of the protrusion 4 and the bottom surface of the groove 5 ₁ was 6 μm, and the length L ₁ of one side of the convex portion 4 was 132 μm in both the vertical and horizontal directions of the lattice.

  About the said Example, each evaluation demonstrated previously was implemented. The results are shown in Table 4 together with the results of Example 4.

  From Table 4, when the JIS A hardness of the printing plate is 15 or more, the accuracy of the printed shape and the cleaning property are improved while preventing the adjacent image line portions from being short-circuited. It has been found that a printed article in which a plurality of rectangular image line portions are arranged with an image line portion therebetween can be manufactured continuously with high accuracy.

<Examples 22 to 26, Comparative Examples 7 to 10>
(Silver powder)
As the silver powder, one or two of the following three types were used.
(a) TC-38S manufactured by Tokuru Honten Co., Ltd. [Shape: flake, specific surface area: 2.27 m ² / g, tap density: 4.00 g / cm ³ , 50% average particle diameter D ₅₀ : 1.02 μm ]
(b) SPQ03R manufactured by Mitsui Mining & Smelting Co., Ltd. [shape: spherical or granular, wet reaction process, tap density: 4.35 g / cm ³ , specific surface area: 1.51 m ² / g, particle size distribution: D ₁₀ = 0 .35 μm, D ₅₀ = 0.6 μm, D ₉₀ = 1.2 μm]

(c) Isolated from Mitsuboshi Belting Co., Ltd. highly conductive silver nanoparticle paste MDot (registered trademark) [particle diameter: several tens of nm, metal content: 80 to 90% by mass, viscosity: several tens Pa · s] Silver nanoparticles (binder resin)
As the binder resin, one or two of the following three types were used.
(i) jER (registered trademark) 1001 manufactured by Mitsubishi Chemical Corporation [epoxy resin, solid type, epoxy equivalent: 450 to 500, softening point (ring and ball method): 64 ° C., specific gravity (25 ° C.): 1.19, Molecular weight: about 900]

(ii) EMR470 manufactured by Mitsubishi Rayon Co., Ltd. (prototype grade)
(iii) V1.5 (polyester / melamine resin) manufactured by Sumitomo Rubber Industries, Ltd.
As a curing agent for the epoxy resin, an amine adduct-based latent curing agent / curing accelerator [Amicure (registered trademark) PN-40 manufactured by Ajinomoto Fine Techno Co., Ltd.] was used.

While blending the above components at the ratios shown in Tables 5 and 6, blending an appropriate amount of butyl carbitol acetate as a solvent and mixing using three rolls, Examples 21 to 26, Comparative Examples 7 to 10 A silver paste was prepared.
<Viscosity measurement>
Of the silver paste, the temperature 25 ° C., a shear rate 1 (1 / s) viscosity eta ₁ [Pa · s] at, and temperature 25 ° C., the viscosity at a shear rate of ₁₀ (1 / s) η 10 [Pa · s Was measured using an E-type viscometer.

Further, the thixo index value TI was obtained from the measurement results of the both viscosities η ₁ and η ₁₀ according to the equation (1).
<Evaluation of printability>
(Preparation of printing plate)
A pattern of a resist layer is formed on the surface of the nickel flat plate by photolithography and then etched, and a plurality of square-shaped convex portions corresponding to the image-line portions are formed on the surface, and the non-image-line portions between the convex portions. A master for forming a printing plate was prepared by forming a grid-like concave groove corresponding to the above, and a stamper with the concavities and convexities reversed by electroforming the master.

Referring to FIG. 2, in the master, the width W ₁ of the groove 5 that is the distance between the adjacent protrusions 4 is 10 μm in any of the vertical and horizontal directions of the lattice, that is, the depth of the groove 5, that is, the protrusion The height difference D ₁ between the surface of the portion 4 and the bottom surface of the groove 5 was 8 μm, and the length L ₁ of one side of the convex portion 4 was 140 μm in both the vertical and horizontal directions of the lattice.
Also, after mixing 100 parts by mass of the main agent and 10 parts by mass of the curing agent of room temperature curing type and two-component addition reaction type liquid dimethyl silicone rubber (TSE3455T manufactured by Momentive Performance Materials Japan GK), defoaming is performed. Thus, a coating solution that becomes the basis of the printing plate was prepared.

Then, the coating solution was applied to the uneven surface of the stamper using a bar coater, allowed to stand at room temperature for 24 hours to undergo a curing reaction, and then demolded to prepare a printing plate.
The dimensions of each part of the printing plate are the same as the dimensions of each part of the master, and the width W _{1 of the} concave groove 5 is 10 μm in both the vertical and horizontal directions of the lattice, and the surface of the convex part 4 and the concave groove 5 The height difference D _{1 from the} bottom surface was 8 μm, and the length L ₁ of one side of the convex portion 4 was 140 μm in both the vertical and horizontal directions of the lattice.

The printing plate had a JIS A hardness (JIS K-6253) of 37.
(Manufacture of printed products)
The silver paste prepared in Examples 22 to 26 and Comparative Examples 7 to 10 was applied to substantially the entire surface of the printing plate and allowed to stand for 10 seconds, and then a PET film as a printing medium on the surface. The contact is made so that the silver paste on the convex portion of the surface of the printing plate is selectively removed by press-contacting so that it is further pressed by 50 μm in the thickness direction of the printing plate from the contact position. After being transferred to the surface of the film, a printed article was produced through drying and baking processes.

In addition, a cleaning PET film is brought into contact with the surface of the printing plate after the transfer, and further pressed into the thickness direction of the printing plate from the contact position so as to be pressed by 300 μm, and then peeled off, thereby remaining in the groove. The paste to be removed.
(Evaluation)
The shape of the image line part and the non-image line part of the manufactured printed article was observed, and the printability was evaluated according to the following criteria.

X: A short circuit occurred between adjacent image portions. Printability is poor.
○: No short circuit was observed between adjacent image areas. Good printability.
The above results are shown in Tables 5 and 6.

表５、表６より、温度２５℃、せん断速度１（１／ｓ）の条件で測定した粘度η_１が１８．６Ｐａ・ｓ以上、３７４Ｐａ・ｓ以下で、かつ温度２５℃、せん断速度１０（１／ｓ）の条件で測定した粘度η_１０と、前記粘度η_１とから、前記式(1)で求められるチキソインデックス値ＴＩが１．８以上、８．６以下である銀ペーストを使用することで、隣り合う画線部同士が短絡するのを防止できることが判った。

From Tables 5 and 6, the viscosity η ₁ measured under the conditions of a temperature of 25 ° C. and a shear rate of 1 (1 / s) is 18.6 Pa · s to 374 Pa · s, a temperature of 25 ° C., and a shear rate of 10 ( A silver paste having a thixo index value TI determined by the above formula (1) of 1.8 or more and 8.6 or less from the viscosity η ₁₀ measured under the condition of 1 / s) and the viscosity η ₁ is used. Thus, it has been found that the adjacent image line portions can be prevented from being short-circuited.

1 non-image portion 2 printing area 3 printed article 4 protrusions 5 groove 6 printing plate 7, 7a, 7b paste 8 doctor blade 9 substrate 10 sheet _W 1, _{W 2} width _{D 1} height difference _L 1, _{L 2} length

For example, an image line portion having a very fine planar shape as compared with the area of the substrate as the substrate to be printed, such as a conductive pattern for a flat display panel or a color pattern for a color filter, is formed on almost the entire surface of the substrate. In order to form with high accuracy, a forming method using a so-called photolithographic method has been conventionally employed.
However, recently, it is becoming popular to use a printing method instead of the photolithographic method. According to the printing method, the number of steps can be reduced as much as possible, the energy consumption can be reduced, the waste of the material used can be reduced, and the pattern can be formed with high productivity in a short time as compared with the photolithography method. Also, according to the printing method , it is possible to form a pattern having a thickness of 0.5 μm or more, which was not easy to form by the photolithography method.

Furthermore, in the peeling printing method, since a flat plate is used, the problem of scratches on the printing blanket can be solved. However, since the parent resin of the region of the plate has a high adhesion energy of the paste, to remove the remaining parent resinous regions paste must be solvent washed with each time of printing In addition, there is a problem that a great deal of labor is required for the management of the solvent, the treatment of the waste liquid after washing, consideration for the environment, and the like.

A microcontact printing method is known as a printing method for forming, for example, a nano-level very thin pattern on a substrate using a liquid having a viscosity lower than that of a paste (for example, Patent Document 3).
In such a microcontact printing method, a plate having a convex portion corresponding to an image line portion and a concave portion corresponding to a non-image line portion is prepared on the surface, and the liquid is applied to substantially the entire surface of the plate. After that, the substrate is brought into contact with the surface of the plate. Then, the liquid on the convex portion of the plate is selectively transferred to the surface of the substrate, and a pattern is formed on the surface of the substrate.

The inventor uses the microcontact printing method to print a printed article, particularly a grid-like non-image, in which a plurality of image areas are arranged on a surface of a printing medium with a non-image area having a narrow width. The application to the manufacture of a printed article in which a plurality of rectangular image line portions are arranged with a line portion therebetween was studied.
However, since the viscosity of paste and liquid to be printed is too different between the production of printed goods and the micro contact printing method, and the thickness of the image area formed on the surface of the substrate is also too different, the micro contact printing method can be simply transferred. Was technically impossible.

The solvent, for example hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, stearyl alcohol, ceryl alcohol, cyclohexanol, alcohols such as α- terpineol, ethylene glycol monobutyl ether ( Butyl cellosolve), ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monobutyl ether (butyl carbitol), ethylene glycol monoethyl ether acetate (cellosolve acetate), ethylene glycol monobutyl ether acetate (butyl cellosolve acetate), diethylene glycol monoethyl ether acetate (carbitol acetate) ), Jie Alkyl ethers such as glycol monobutyl ether acetate (butyl carbitol acetate) and the like.

Claims (8)

A manufacturing method for manufacturing a printed article in which a plurality of image line portions are arranged on a surface of a substrate to be printed with a non-image line portion having a constant width therebetween,
A plurality of convex portions corresponding to the image line portion, and a concave groove having a constant width corresponding to the non-image line portion between the convex portions, and at least the surface of the convex portion is made of silicone rubber, and adjacent convex portions The width of the concave groove, which is the interval between the parts, is 3 μm or more and 80 μm or less, the height difference between the surface of the convex part and the bottom surface of the concave groove is 3 μm or more and 20 μm or less, and the convexity is the distance between adjacent concave grooves Applying a paste over substantially the entire surface of the printing plate having a width of 15 μm or more;
Semi-drying the paste;
A step of selectively transferring only the paste on the convex portion of the surface of the printing plate to the surface of the printing body by pressing the printing body on the surface of the printing plate coated with the paste. When,
A method for producing a printed article comprising:   The printed article is formed by arranging a plurality of rectangular image-line portions across a grid-like non-image area, and the printing plate has a plurality of rectangular shapes corresponding to the image-line portions. A convex groove and a lattice-shaped concave groove corresponding to the non-image portion is provided between the convex parts, and the width of the concave groove, which is an interval between adjacent convex parts, is 3 μm or more and 80 μm or less. The method for producing a printed article according to claim 1, wherein the height difference between the surface and the bottom surface of the groove is 3 μm or more and 20 μm or less, and the length of one side of the rectangle as the width of the convex portion is 15 μm or more.   The resin film or sheet is pressed onto the surface of the printing plate after the transfer with a pressure contact force higher than that of the printing material and then peeled off, whereby the paste remaining in the concave groove is removed from the resin film. Alternatively, the method of the printed article according to claim 1, further comprising a step of transferring and removing the sheet on the surface of the sheet.   The method further comprises a step of transferring the paste remaining in the groove to the surface of the pressure-sensitive adhesive sheet and removing the pressure-sensitive adhesive sheet by peeling the pressure-sensitive adhesive sheet onto the surface of the printing plate after the transfer. The method for producing a printed article according to any one of 1 to 3.   A printing plate for use in a manufacturing method for manufacturing a printed article in which a plurality of image line portions are arranged on a surface of a substrate to be printed with a non-image line portion having a certain width therebetween. A plurality of convex portions corresponding to the line portion, and a concave groove having a constant width corresponding to the non-image portion between the convex portions, and at least the surface of the convex portion is made of silicone rubber, and between adjacent convex portions The width of the concave groove, which is an interval of the convex portion, is 3 μm or more and 80 μm or less, and the height difference between the surface of the convex portion and the bottom surface of the concave groove is 3 μm or more and 20 μm or less, and A printing plate having a width of 15 μm or more.   A plurality of rectangular convex portions corresponding to the image line portions, and the convex portions, which are used in the manufacture of a printed article in which a plurality of rectangular image line portions are arranged across a grid-like non-image line portion In addition to having a grid-like concave groove corresponding to the non-imaged portion in between, the width of the concave groove, which is an interval between adjacent convex parts, is 3 μm or more and 80 μm or less, and the surface of the convex part and the bottom surface of the concave groove The printing plate according to claim 5, wherein the height difference is 3 μm or more and 20 μm or less, and the length of one side of the rectangle which is the width of the convex portion is 15 μm or more.   The printing plate according to claim 5 or 6, wherein the whole is integrally formed of silicone rubber having a JIS A hardness of 15 or more and 80 or less. Printing having a plurality of convex portions corresponding to a plurality of image line portions, and a groove having a constant width corresponding to a non-image line portion having a constant width between the convex portions, and at least the surface of the convex portion is made of silicone rubber Use the plate
After applying the paste to substantially the entire surface of the printing plate, semi-drying, and then selectively pressing only the paste on the convex portion of the surface of the printing plate by pressing the printed material to the surface, By transferring to the surface of the substrate,
The paste used in a manufacturing method for manufacturing a printed article formed by arranging the plurality of image line portions on the surface of the substrate to be printed with the non-image line portions separated from each other,
Using an E-type viscometer, the viscosity η ₁ measured under the conditions of a temperature of 25 ° C. and a shear rate of 1 (1 / s) is 18.6 Pa · s or more and 374 Pa · s or less, a temperature of 25 ° C., and a shear rate of 10 viscosity eta ₁₀ as measured under the conditions of (1 / s), from the viscosity eta ₁ Tokyo, equation (1):
_{TI = η 1 / η 10 (} 1)
The thixo index value TI calculated | required by is 1.8 or more and 8.6 or less, The paste characterized by the above-mentioned.

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