JP2017030229A - Printing plate and method for forming printing pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing plate that can suppress disruption of a printing pattern in a low density area of printing pattern without forming any unnecessary printing pattern and to provide a method for forming a high-accuracy printing pattern using the printing plate.SOLUTION: A printing plate 1 has a first pattern 11 and a second pattern 12 each for filling an ink composition and in the printing plate, the average value of a depth Dof the second pattern 12 is smaller than the average value of a depth Dof the first pattern 11; and the first pattern 11 and the second pattern 12 are present near each other. The method for forming a printing pattern has: a step of filling an ink composition in the first pattern 11 and the second pattern 12 of the printing plate 1; a step of transferring the ink composition filled in the first pattern 11 to an object to be printed without transferring the ink composition filled in the second pattern 12 to the object to be printed; and a step of forming a printing pattern on the object to be printed with the ink composition transferred from the first pattern 11.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a printing plate for forming a printing pattern using an ink composition, and a method for forming a printing pattern using the printing plate.

  A laminate in which a printed pattern is formed on a substrate is widely used in various applications as well as an application for merely visually recognizing a printed pattern. For example, a conductive printed pattern is useful as a wiring for constituting a circuit, and a laminate in which such a wiring is formed on a base material can be used as a circuit board. In recent years, in the field of electronic devices such as various display elements and communication devices, various techniques for forming a conductive print pattern have been reported by a printing technique using a conductive ink composition.

  As a method for forming a conductive pattern, a photolithography method has been mainly used. However, the photolithography method requires the use of a resist composition, has many incidental processes such as development and cleaning, and has a problem that the process is complicated and cost reduction is difficult. On the other hand, the process for forming a conductive pattern by a printing technique is simplified, and is particularly advantageous for forming a pattern with a large area, and there is a large room for cost reduction. And, for example, it has become possible to form a fine conductive pattern by an offset printing method. As described above, pattern formation by printing technology has become highly useful in various fields.

  Under such circumstances, a peculiar problem has been pointed out in the pattern forming method by the printing technique. For example, in the offset printing method, as is well known, a printing plate having a patterned recess for filling the ink composition is used, and after the ink composition is supplied onto the printing plate, the recess is formed by a doctor blade. Is filled with an ink composition, the filled ink composition is transferred onto a blanket, and the transferred ink composition is further transferred onto a printing object to form a printing pattern. At this time, the formed print pattern is often deformed, rubbed, or missing in an area close to the edge (edge) on the print object, and the desired shape can be obtained with high accuracy. There was a problem that there was not. Such a phenomenon is likely to occur particularly when the print surface has a large area and the print pattern is fine.

  The above-described disorder of the printing pattern is caused by the fact that in the printing plate filled with the ink composition, the volatilization amount of the solvent in the ink composition is relatively smaller in the vicinity of the outer periphery than in the center. I guess that. In a printing plate, generally, the closer to the outer peripheral portion, the smaller the number of concave portions for forming a print pattern that are present in the vicinity of each other. Accordingly, the vapor pressure of the volatilized solvent is relatively lower in the vicinity of the outer peripheral portion of the printing plate than in the central portion. proceed. As a result, in the vicinity of the outer peripheral portion, the filled ink composition is more solidified than the central portion, and therefore, it is difficult to transfer to the blanket or the print object. This is presumed to be the cause of the disturbance of the printing pattern.

  As a method for solving such a problem, a predetermined pattern has an actual pattern corresponding to a concave portion for forming a target print pattern, and a concave portion for forming a non-target print pattern. A method of forming a printing pattern by an offset printing method using a printing plate having a dummy pattern in the vicinity of the outer peripheral portion is disclosed (see Patent Document 1). In this method, the ink composition filled in the dummy pattern increases the vapor pressure of the volatilized solvent in the vicinity of the outer peripheral portion of the printing plate from the beginning of filling, as in the central portion. Drying (solidification) is suppressed. Therefore, in the vicinity of the outer peripheral portion of the printing plate, as in the central portion, the filled ink composition is maintained in a state that is easily transferred to a blanket or a printing object, and the disorder of the printing pattern is suppressed. Guessed. Further, in this method, an unintended print pattern is formed on the object to be printed by the dummy pattern. However, the print pattern is further overlapped on the unintended print pattern and finally formed. As a whole, a target print pattern is formed on a print object.

JP 2001-353974 A

  However, in the method disclosed in Patent Literature 1, even if the apparent trace is erased by forming the print pattern in an overlapping manner, an unintended print pattern is formed on the print object. There was a problem that it was accompanied by formation of an unnecessary print pattern. Further, such an unnecessary print pattern has a problem that the arrangement position is limited. Further, the method disclosed in Patent Document 1 suppresses the disturbance of the print pattern in a region close to the edge (edge) on the print object corresponding to the vicinity of the outer peripheral portion of the printing plate. The disorder of the printing pattern is a region on the printing object corresponding to a portion where the density of the recess for filling the ink composition in the printing plate is low and the filled ink composition is easy to dry, in other words, the printing object. As long as the density of the printed pattern on the object is low, it may occur in areas other than the area close to the edge.

  The present invention has been made in view of the above circumstances, and includes a printing plate capable of suppressing disturbance of a printing pattern in a region where the density of the printing pattern is low without accompanying formation of an unnecessary printing pattern, and the printing plate. It is an object of the present invention to provide a method for forming a high-precision printed pattern.

  In order to solve the above-described problem, the present invention has a first pattern and a second pattern for filling an ink composition, and an average value of the depth of the second pattern is the depth of the first pattern. A printing plate is provided in which the first pattern and the second pattern are in the vicinity of each other, which is smaller than the average value.

In the printing plate of this invention, it is preferable that the average value of the depth of the said 2nd pattern is a value 0.5 times or less of the average value of the depth of the said 1st pattern.
In the printing plate of this invention, it is preferable that the distance between the said 1st pattern and the said 2nd pattern which are adjacent is 200 micrometers or less.
In the printing plate of the present invention, the width of the first pattern is preferably 20 μm or less.
Further, the present invention is a method of forming a printing pattern using the printing plate, the step of filling the first pattern and the second pattern of the printing plate with an ink composition, and filling the second pattern. The step of transferring the ink composition filled in the first pattern to the printing object without transferring the ink composition to the printing object, and the printing from the ink composition transferred from the first pattern And a step of forming a print pattern on an object.

  According to the present invention, a printing plate that can suppress the disturbance of the printing pattern in a region where the density of the printing pattern is low without accompanying formation of an unnecessary printing pattern, and a high-precision printing pattern using the printing plate. A forming method is provided.

1 is a plan view schematically showing an embodiment of a printing plate according to the present invention. It is sectional drawing in the II line of the printing plate shown in FIG. It is a figure which expands and shows typically the cross-sectional shape of the 1st pattern or 2nd pattern different from what is shown in FIG. It is a top view which expands and shows typically other embodiments of a printing plate concerning the present invention. It is a top view which expands and shows typically other embodiment of a printing plate concerning the present invention typically. It is sectional drawing for demonstrating one Embodiment of the formation method of the printing pattern which concerns on this invention. It is sectional drawing for demonstrating the state where the vapor pressure of a solvent is high when the printing plate which concerns on this invention is used. It is sectional drawing for demonstrating other embodiment of the formation method of the printing pattern which concerns on this invention. It is sectional drawing for demonstrating other embodiment of the formation method of the printing pattern which concerns on this invention. It is sectional drawing which shows typically the state of a blanket when forming a printing pattern using the conventional printing plate. It is sectional drawing which shows typically the state of a blanket when forming a printing pattern using the printing plate shown to FIG.

<< Print version >>
The printing plate according to the present invention has a first pattern and a second pattern for filling the ink composition, and the average depth of the second pattern is greater than the average depth of the first pattern. The first pattern and the second pattern are in the vicinity of each other.
In the printing plate, since the first pattern and the second pattern are in the specific relationship as described above, the printing pattern can be printed even in an area where the density of the printing pattern is low, without forming an unnecessary printing pattern. Disturbance can be suppressed and a target print pattern can be formed with high accuracy.
The printing plate is suitable for use in a printing method including a step of transferring a filled ink composition to a printing object, such as an offset printing method and a gravure offset printing method.

FIG. 1 is a plan view schematically showing an embodiment of a printing plate according to the present invention. FIG. 2 is a cross-sectional view taken along line II of the printing plate shown in FIG.
The printing plate 1 shown here has a first pattern 11 and a second pattern 12 on one surface 1a which is the printing surface.

  The first pattern 11 is for filling the ink composition and forming a target print pattern on the print object from the ink composition, and corresponds to an actual pattern.

As shown in FIG. 1, the first pattern 11 is a groove having a linear shape when viewed from above the surface 1 a of the printing plate 1, and has a width W _X1 and a depth as shown in FIG. 2. It is composed of a recess of the _{D X1.}
And in the cross section of the direction orthogonal to the longitudinal direction (line length direction), the 1st pattern 11 has a shape from which one side of the rectangle was removed as shown in FIG.

The first pattern 11 has the same width W _X1 and depth D _X1 in all the portions in the longitudinal direction (line length direction). However, the present invention is not limited to this, and the first pattern 11 may have one or both of the width W _X1 and the depth D _X1 in a part or all of the longitudinal direction (line length direction). May be different.

  Similar to the first pattern 11, the second pattern 12 is an object to be filled with the ink composition. However, when the second pattern 12 forms a target print pattern on the print object from the ink composition filled in the first pattern 11, the second pattern 12 is free from disturbances such as deformation, rubbing, and loss of the print pattern. It is for suppressing. And the ink composition with which the 2nd pattern 12 was filled does not form the unintended printing pattern on a printing target object, but the 2nd pattern 12 is corresponded to a dummy pattern.

  In the printing plate 1, one first pattern 11 and two second patterns 12 are alternately formed substantially or completely in parallel so that their longitudinal directions coincide. That is, one second pattern 12 is formed on each side of the first pattern 11 along the first pattern 11 in the width direction of the first pattern 11. The two second patterns 12 have the same shape.

As shown in FIG. 1, the second pattern 12 is a groove having a linear shape when viewed from above the surface 1 a of the printing plate 1, as in the case of the first pattern 11. Thus, it consists of a recess having a width W _Y1 and a depth _DY1 .
The second pattern 12 has a shape in which one side of the quadrangle is removed as shown in FIG. 2 in a cross section in a direction orthogonal to the longitudinal direction (line length direction). That is, the second pattern 12 has the same shape as the first pattern 11.

Similar to the first pattern 11, the second pattern 12, in all parts of the longitudinal direction (line length direction), and has a both width W _Y1 and the depth D _Y1 same. However, the present invention is not limited to this, and the second pattern 12 may have one or both of the width W _X1 and the depth D _X1 in a part or all of the longitudinal direction (line length direction). May be different.

In the printing plate 1, the average value of the depth D _Y1 of the second pattern 12 is smaller than the average value of the depth D _X1 of the first pattern 11 ([average value of _DY1 ] <[D _X1 Average value]). In this specification, the “average value of the depth of the first pattern” means that, as shown here, when the first pattern is in a line shape, “the length direction of the first pattern” Means the average value of the depth of the first pattern. Similarly, “the average value of the depth of the second pattern” means that, as shown here, when the second pattern is a line (line), “the second pattern in the line length direction of the second pattern”. Means the average value of the depth.

In the printing plate 1, the average value of the depth _DY1 of the second pattern 12 is 0.5 times or less of the average value of the depth D _X1 of the first pattern 11 ([average value of _DY1 ] ≦ 0. 5 × [average value of D _X1 ]), which is not more than 0.3 times the average value of the depth D _X1 of the first pattern 11 ([average value of _DY1 ] ≦ 0.3 × [ The average value of D _X1 ] is more preferable, and a value equal to or less than 0.1 times the average value of the depth D _X1 of the first pattern 11 (the average value of [D _Y1 ] ≦ 0.1 × [D _X1 still more preferably of the average value), the average of the mean value] ≦ 0.08 × _{[D X1} depth 0.08 times the value of the average value of _{D X1 ([D Y1} of the first pattern 11 Value]) is particularly preferred. Since the depth D _Y1 of the second pattern 12 is in such a relationship with the depth D _X1 of the first pattern 11, the printing plate 1 suppresses the disturbance of the printing pattern, and the intended printing is performed. The pattern can be formed with higher accuracy.

It depth _{D X1} of the first pattern 11 is not particularly limited as long as conditions are satisfied the above between the depth _{D Y1} of the second pattern 12 is preferably 5 to 20 [mu] m, is 6~17μm Is more preferable, and it is especially preferable that it is 7-14 micrometers. The printing plate 1 is particularly suitable for forming a fine linear pattern as a printing pattern.

The width W _X1 of the first pattern 11 may be appropriately set according to the purpose in consideration of, for example, the depth D _X1 of the first pattern 11, but is preferably 20 μm or less, It is more preferably 20 μm, further preferably 0.5 to 15 μm, and particularly preferably 1 to 10 μm.

Since the printing plate 1 is more effective in suppressing the disturbance of the printing pattern, the depth D _X1 of the first pattern 11 and the width W _X1 of the first pattern 11 are both within the above numerical range. It is particularly preferred.

The depth _{D Y1} of the second pattern 12 is not particularly limited as long as conditions are satisfied the above between the depth _{D X1} of the first pattern 11 is preferably 0.05～4Myuemu, 0.05 to More preferably, it is 2 micrometers, and it is especially preferable that it is 0.1-1 micrometer.

The width W _Y1 of the second pattern 12 may be appropriately set according to the purpose in consideration of, for example, the depth _DY1 of the second pattern 12, the number of the first patterns 11 existing in the vicinity, It is preferably 1 to 1000 μm, more preferably 1 to 500 μm, and particularly preferably 1 to 100 μm.

Since the printing plate 1 has a higher effect of suppressing the disturbance of the printing pattern, the depth _DY1 of the second pattern 12 and the width _WY1 of the second pattern 12 are both within the above numerical range. It is particularly preferred.

  In the printing plate 1, the first pattern 11 and the second pattern 12 exist in the vicinity of each other. In this specification, “the first pattern and the second pattern exist in the vicinity of each other” means that the ink composition filled in the first pattern is present due to the presence of the ink composition filled in the second pattern. It means that the first pattern and the second pattern are formed close to each other to such an extent that drying with time is clearly suppressed.

In the printing plate 1, one distance L ₁ between the adjacent first pattern 11 and second pattern 12 is not particularly limited as long as the arrangement relationship between the first pattern 11 and the second pattern 12 described above is satisfied. However, the distance L ₁ is preferably 200 μm or less, for example, 150 μm or less, 100 μm or less, 50 μm or less, etc. from the viewpoint that the effect of suppressing the disturbance of the printing pattern of the printing plate 1 becomes higher. it can.
The lower limit value of the distance L ₁ is not particularly limited, but is preferably 10 μm. By the lower limit of the distance L ₁ is such values, the formation of the first pattern 11 or the second pattern 12 becomes easier.

  In the present specification, the “distance between the first pattern and the second pattern” refers to the formation surface of the first pattern and the second pattern of the printing plate (the surface 1a of the printing plate 1 in FIGS. 1 and 2). Means the distance between the opening (edge) of the first pattern and the opening (edge) of the second pattern.

In the printing plate 1, also the other distance L ₂ between the first pattern 11 adjacent to the second pattern 12, the distance L ₁ is not particularly limited in the same manner as is the same numerical range as the distance L ₁ Preferably, it may be the same value as the distance L ₁ or a different value.

Since the printing plate 1 has a higher effect of suppressing the disturbance of the printing pattern, the depth D _X1 of the first pattern 11, the width W _X1 of the first pattern 11, and the depth D _Y1 of the second pattern 12 are increased. When a width W _Y1 of the second pattern 12, and the distance L _1, and the distance L ₂ is particularly preferably all within the numerical range described above.

  Although the thickness of the area | region in which the 1st pattern 11 and the 2nd pattern 12 of the printing plate 1 are not formed is not specifically limited, It is preferable that it is 0.1-0.5 mm, 0.2-0.4 mm It is more preferable that

  The material of the printing plate 1 may be the same as that of a known printing plate, and examples thereof include metals such as iron and nickel, and glass. The printing plate 1 can be manufactured by forming the first pattern 11 and the second pattern 12 having a desired shape on the plate made of such a material, for example, by a technique such as etching or electroforming. .

1 and 2 show only one first pattern, the printing plate according to the present invention may have two or more first patterns.
Thus, when the printing plate according to the present invention has two or more first patterns, it is preferable that these first patterns do not exist in the vicinity of each other, and the distance between the adjacent first patterns is 200 μm or more, more preferably 500 μm or more, still more preferably 800 μm or more, and particularly preferably 1000 μm or more.
The printing plate in which the number of the first patterns is only 1 or the number of the first patterns is 2 or more and the distance between the adjacent first patterns is 200 μm or more has a particularly high density of the first patterns. Although it is low, in such a printing plate, the effect of the present invention that suppresses the disturbance of the printing pattern in the region where the density of the printing pattern is low can be obtained more remarkably.

  In addition, as described above, the number of the first patterns is only 1 or the number of the first patterns is 2 or more, and the distance between the adjacent first patterns is far away. The case where the first patterns are not in the vicinity has been described. However, in the printing plate according to the present invention, the number of the first patterns is 2 or more, the adjacent first patterns are extremely close to each other, the first patterns are finer, and the filling amount of the ink composition is larger. There may be few things. In such a printing plate, two or more first patterns existing in the very vicinity can be collectively considered as one first pattern, and if these first patterns are finer, It can be said that the pseudo one first pattern (first pattern group) also has a particularly low density on the printing plate. And such a printing plate can also obtain the effect of this invention more remarkably that suppresses the disorder of the printing pattern in the region where the density of the printing pattern is low.

Thus, the distance between the adjacent first patterns existing in the very vicinity is preferably 10 μm or less, more preferably 6 μm or less, and particularly preferably 3 μm or less. The effect of this invention is acquired more notably because the said distance is below the said upper limit. On the other hand, the lower limit value of the distance is not particularly limited, but is preferably 1 μm in view of the point that these first patterns can be formed.
Further, the depth D _X1 of the first pattern at this time is preferably 7 to 10 μm, and the width W _X1 is preferably 1 to 5 μm.

  In the present invention, when the printing plate has three or more patterns corresponding to the first pattern or the second pattern and having different average depth values, the average depth value is the maximum. The pattern is a first pattern, and all other patterns are second patterns.

The printing plate according to the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention.
For example, in FIGS. 1 and 2, as the first pattern and the second pattern, the shape in the cross section is a shape in which one side of a square is removed, that is, the side surface 2 and the bottom surface 1 are all flat. A printing plate having However, in the printing plate according to the present invention, in either one or both of the first pattern and the second pattern, at least one of the side surface and the bottom surface is a curved surface, an uneven surface, and a flat surface, a curved surface, or an uneven surface. May have any one of non-standard surfaces. Further, in the printing plate according to the present invention, either one or both of the first pattern and the second pattern may have a face that is difficult to distinguish between the side face and the bottom face, The entire surface may be configured in a surface that is difficult to distinguish. In the printing plate according to the present invention, either one or both of the first pattern and the second pattern may not have a planar bottom.

FIG. 3 is a diagram schematically showing an enlarged shape of the first pattern or the second pattern different from that shown in FIGS. 1 and 2 in the cross section.
FIG. 3A shows the first pattern or the second pattern in which the two side surfaces and the one bottom surface are all flat. This pattern is different from FIGS. 1 and 2 in that the two side surfaces are not parallel. It is different from the first pattern or the second pattern shown.
FIG. 3B shows a first pattern or a second pattern in which the side surface and the bottom surface are connected via a non-planar surface (curved surface), and the boundary between the side surface and the bottom surface is unclear, although the side surface and the bottom surface have planar portions. Is shown.
FIG. 3C shows the first pattern or the second pattern in which the entire surface is configured by a curved surface that is difficult to distinguish between the side surface and the bottom surface. The curved surface is composed of a curved surface portion that is convex toward the opening side (upper side) of the pattern and a curved surface portion that is convex toward the bottom side (lower side) of the pattern.
FIG. 3D shows the first pattern or the second pattern formed of curved surfaces whose side surfaces and bottom surfaces are difficult to distinguish, as in FIG. 3C. It is different from c). Here, the curved surface is constituted only by a curved surface that is convex toward the bottom side (lower side) of the pattern.
FIG. 3E shows a first pattern or a second pattern having a flat side surface and no planar bottom.
FIG. 3F shows a first pattern or a second pattern in which the side surface is a curved surface convex toward the opening side (upper side) of the pattern and does not have a planar bottom.

In FIGS. 1 to 3, as the first pattern and the second pattern, the shape in the cross section is shown to be symmetrical in the width direction (direction perpendicular to the longitudinal direction) of these patterns. The shape of the first pattern and the second pattern in the cross section may be asymmetric in the width direction.
Moreover, the 1st pattern and 2nd pattern which are shown in FIGS. 1-3 are only examples in this invention, for example, in the 1st pattern and 2nd pattern which are shown in FIGS. A non-smooth surface having an irregular shape instead of a smooth surface is also suitable as the first pattern and the second pattern in the present invention.

  For example, as shown in FIGS. 3C to 3F, when the depth of the first pattern or the second pattern changes in the width direction of these patterns (direction orthogonal to the longitudinal direction). As the pattern depth, the maximum value is adopted (the depth of the deepest part is adopted as the depth of these patterns).

In FIGS. 1 and 2, the first pattern and the second pattern are shown as having a linear groove when viewed from above the printing plate, but the first pattern and the second pattern The overall shape is not limited to this, and can be appropriately set according to the shape of the target print pattern.
The first pattern and the second pattern may be curved grooves as viewed in plan from above the printing plate, for example, as shown in FIG. In the printing plate 2 shown here, both the first pattern 21 and the second pattern 22 are grooves having a curved shape when viewed in plan.
Further, the first pattern and the second pattern may be non-linear concave portions as shown in FIG. 5, for example, when viewed from above the printing plate. In the printing plate 3 shown here, the first pattern 31 and the second pattern 32 are both concave portions having an elliptical shape when viewed in plan.
The printing plates 2 and 3 can have the same configuration as the printing plate 1 shown in FIGS.

<< Print Pattern Formation Method >>
A printing pattern forming method according to the present invention is a printing pattern forming method using the printing plate, and a step of filling an ink composition into the first pattern and the second pattern of the printing plate (hereinafter, “ The ink composition filled in the first pattern is transferred to the printing object without transferring the ink composition filled in the second pattern to the printing object. And a step of forming a print pattern on the printing object from the ink composition transferred from the first pattern (hereinafter referred to as “print pattern formation”). It may be abbreviated as “process”).
The printing pattern forming method according to the present invention includes a step of transferring a filled ink composition to a printing object, such as an offset printing method, except that the printing plate according to the present invention is used. It can be the same as the law.

  FIG. 6 is a cross-sectional view for explaining an embodiment of a method for forming a print pattern according to the present invention. Here, a method for forming a printing pattern when the printing plate 1 shown in FIGS. 1 and 2 is used will be described. However, if the printing plate according to the present invention is used, a printing plate other than the printing plate 1 shown in FIGS. Even if it uses, a printing pattern can be formed similarly. In the following drawings, the same elements as those shown in FIGS. 1 and 2 are denoted by the same reference numerals as those used in FIGS. 1 and 2, and detailed description thereof is omitted.

<Filling process>
In the forming method, first, as shown in FIG. 6A, a filling process is performed in which the first pattern 11 and the second pattern 12 of the printing plate 1 are filled with the ink composition 9 respectively.
The ink composition 9 may be filled by a known method. For example, after supplying the ink composition 9 to a predetermined location on the surface 1a of the printing plate 1 using a means for supplying a liquid such as a dispenser, a means for spreading the liquid such as a doctor blade is used. The ink composition 9 can be filled into the first pattern 11 and the second pattern 12 by spreading the supplied ink composition 9 on the surface 1a of the printing plate 1.
The ink composition used in this step will be described in detail later.

<Transfer process>
In the forming method, after the filling step, the ink composition filled in the second pattern is transferred to the printing object without transferring the ink composition filled in the second pattern to the printing object. I do. Here, the step of transferring the ink composition filled in the first pattern onto the blanket and then further transferring the ink composition on the blanket to the printing object will be described as the transfer step.

  A blanket may be a well-known thing in the said field | area, for example, as the material, rubber-type materials, such as a silicone resin, are mentioned.

  In this step, first, as shown in FIG. 6B, the ink composition 9 filled in the first pattern 11 and the ink composition 9 filled in the second pattern 12 are both transferred onto the blanket 8. . In the present invention, at this time, at least the ink composition 9 filled in the first pattern 11 is transferred onto the blanket 8 without any abnormality such as deformation, rubbing, or loss. The reason is presumed as follows.

That is, in the printing plate 1, since the first pattern 11 and the second pattern 12 exist in the vicinity of each other, the region where these patterns exist in the state where the ink composition 9 is filled is filled with these patterns. The vapor pressure of the solvent volatilized from the ink composition 9 is relatively high, and drying of the ink composition 9 filled in the first pattern 11 with time is suppressed. FIG. 7 is a cross-sectional view for explaining a state where the vapor pressure of the solvent is high in the region where the first pattern 11 and the second pattern 12 exist at this time. In FIG. 7, what is indicated by reference numeral 90 is a volatilized solvent.
As described above, the ink composition 9 filled in the first pattern 11 is prevented from solidifying, has a high solvent content, and maintains a state suitable for transfer. Therefore, as described above, the ink composition 9 is deformed and rubbed. It is estimated that the image is transferred onto the blanket 8 without any abnormality such as a defect.
In the present specification, an ink composition whose composition has changed after filling in the printing plate, such as a solvent in which a part of the solvent is volatilized, is also referred to as an ink composition before the printing pattern is formed.

  Here, the ink composition 9 filled in the second pattern 12 is also shown as being transferred onto the blanket 8 without any abnormality such as deformation, rubbing, or loss. In the invention, the ink composition 9 filled in the second pattern 12 may not be transferred onto the blanket 8 at all. For example, as is clear from FIG. 5, the vapor pressure of the solvent volatilized from the ink composition 9 is lower immediately above the second pattern 12 than immediately above the first pattern 11. This is because the filled ink composition 9 is less effective in suppressing drying over time than the ink composition 9 filled in the first pattern 11. Whether or not the ink composition 9 filled in the second pattern 12 is transferred to the blanket 8 is determined depending on the state of the second pattern 12.

  In this step, the ink composition 9 on the transferred blanket 8 is further transferred to the printing object 7 as shown in FIG. In the present invention, at this time, the ink composition 9 transferred from the first pattern 11 is transferred to the print object 7, while the ink composition 9 transferred from the second pattern 12 is transferred to the print object 7. It remains on the blanket 8 without being transferred. The reason is presumed as follows.

That is, as described above, the ink composition 9 transferred from the first pattern 11 onto the blanket 8 is prevented from drying due to the high vapor pressure of the solvent, and as a result, the content of the solvent is large. Furthermore, drying may be suppressed by the fact that the ink composition 9 forms a thick layer (film) itself. This is because the thick layer (film) of the ink composition 9 is dried from the exposed surface, and the composition of the layer (film) changes between the exposed surface where the drying has progressed and the vicinity thereof. This is because the passage of the solvent inside can be suppressed more than this, and a state where the content of the solvent is high can be maintained. In this case, the drying of the ink composition 9 as a whole (film) is further suppressed.
Depending on the material of the blanket 8, the solvent in the ink composition 9 is absorbed by the blanket 8, but the effect of suppressing the drying of the ink composition 9 as described above is much greater.

  As described above, the ink composition 9 transferred from the first pattern 11 onto the blanket 8 has a high solvent content, and thus drying, that is, solidification is suppressed, and a state suitable for transfer is maintained. There are no factors that inhibit transcription. Accordingly, the ink composition 9 transferred onto the blanket 8 can be printed from above the blanket 8 without any abnormality such as deformation, rubbing, or loss as in the transfer from the first pattern 11 onto the blanket 8. Presumed to be transferred to the object 7.

  On the other hand, the ink composition 9 transferred from the second pattern 12 is thinner than the ink composition 9 transferred from the first pattern 11, as is apparent from FIG. 6B. As described above, the solvent contained in the ink composition 9 is easily volatilized from the thin layer (film) of the ink composition 9. Further, depending on the material of the blanket 8, the solvent in the ink composition 9 is absorbed by the blanket 8. Therefore, the ink composition 9 is easily solidified on the blanket 8. As described above, the ink composition 9 transferred from the second pattern 12 is easily solidified on the blanket 8, thereby increasing the adhesive strength with the blanket 8, and is not transferred to the printing object 7. 8 is expected to remain.

  In this step, the ink composition 9 remaining on the blanket 8 can be removed from the blanket 8 by a known method such as a method of removing the ink composition 9 by sticking to an adhesive tape.

<Print pattern formation process>
In the forming method, after the transferring step, as shown in FIG. 6D, a printing pattern 9 ′ is formed on the printing object 7 from the ink composition 9 transferred from the first pattern 11. A pattern formation process is performed. The printing pattern 9 ′ can be formed, for example, by drying the ink composition 9, and the drying conditions can be arbitrarily adjusted as appropriate. The formed printed pattern 9 ′ is prevented from being disturbed such as deformation, rubbing, and loss, and realizes a target pattern with high accuracy. In addition, according to the present embodiment, as described above, the ink composition 9 transferred from the second pattern 12 remains on the blanket 8 without being transferred to the print object 7. Unnecessary unnecessary print patterns are not formed.

  FIG. 6 shows a method for forming a print pattern when the ink composition 9 filled in the second pattern 12 is also transferred onto the blanket 8 in the transfer step. The ink composition 9 filled in the second pattern 12 may not be transferred onto the blanket 8 at all. FIG. 8 is a cross-sectional view for explaining the method for forming a print pattern according to the present invention in such a case. FIG. 8B shows that the ink composition 9 filled in the second pattern 12 is not transferred onto the blanket 8 at all.

The printing pattern forming method shown in FIG. 8 is the same as the printing pattern forming method shown in FIG. 6 except that the ink composition 9 filled in the second pattern 12 is not transferred onto the blanket 8. In order to prevent the ink composition 9 filled in the second pattern 12 from being transferred onto the blanket 8, for example, the ink composition 9 filled in the second pattern 12 has a low solvent content. Those that contain a solvent with a low boiling point, those that contain a thickener or the like and have a high viscosity, or the like that suppresses transfer when the thickness is thin may be used.
Also in the present embodiment, the formed printed pattern 9 ′ is prevented from being disturbed such as deformation, rubbing, and loss, and realizes a target pattern with high accuracy. Further, as described above, the ink composition 9 filled in the second pattern 12 is not transferred onto the blanket 8 and remains in the second pattern 12. A print pattern is not formed.

  In the printing pattern forming method shown in FIG. 8, in the transfer step, after the ink composition filled in the first pattern is transferred onto the blanket, the ink composition on the blanket is further transferred onto the printing object. It is a process. In such a method for forming a print pattern according to the present invention, the transfer step may be a step of directly transferring the ink composition filled in the first pattern to a print object. FIG. 9 is a cross-sectional view for explaining still another embodiment of the method for forming a print pattern according to the present invention. FIG. 9B shows a state in which the ink composition filled in the first pattern is directly transferred to the printing object in the transfer step.

In the printing pattern forming method shown in FIG. 9, after the ink composition 9 filled in the first pattern 11 is transferred onto the blanket 8, the ink composition 9 on the blanket 8 is further transferred onto the printing object 7. Instead of performing a series of steps, the printing pattern forming method shown in FIG. 8 is the same as that shown in FIG. 8 except that the ink composition 9 filled in the first pattern 11 is directly transferred to the printing object 7. is there.
Also in the present embodiment, the formed printed pattern 9 ′ is prevented from being disturbed such as deformation, rubbing, and loss, and realizes a target pattern with high accuracy. In addition, as described above, the ink composition 9 filled in the second pattern 12 is not transferred to the print object 7 and remains in the second pattern 12. A simple print pattern is not formed.

  In the method for forming a printing pattern according to the present invention, as described above, by using a specific printing plate, the printing pattern can be printed even in an area where the density of the printing pattern is low without accompanying the formation of an unnecessary printing pattern. Disturbance can be suppressed and a target print pattern can be formed with high accuracy. For example, in the method described in “JP-A 2001-353973” (Patent Document 1) described above, printing is performed in an area close to the edge (edge) on the printing object corresponding to the vicinity of the outer peripheral portion of the printing plate. Although pattern disturbance can be suppressed, in other areas where the density of the print pattern is low, it is not certain whether the print pattern disturbance can be suppressed. As described above, the method for forming a print pattern according to the present invention has an advantage that the disturbance of the print pattern can be surely suppressed in the entire region having a low print pattern density.

  In the method for forming a printed pattern according to the present invention, when a blanket is used, there is an advantage that durability during repeated use of the blanket can be improved. This point will be described in detail below.

FIG. 10 schematically shows a blanket state when a printing pattern is formed using a conventional printing plate having a plurality of concave portions (patterns) having the same depth as concave portions (patterns) for filling the ink composition. FIG. Here, the case where a printing plate that is the same as that shown in FIGS. 1 and 2 is used except that the depths of the patterns are all the same is shown.
The ink composition 9 filled in the recesses of such a conventional printing plate forms a layer (film) of the same thickness on the blanket 8 as shown in FIG.

  Next, the ink composition 9 on the blanket 8 is further transferred to a printing object (not shown), and the ink composition 9 disappears from the blanket 8 as shown in FIG. However, a part of the solvent in the ink composition 9 is absorbed by the blanket 8, and this absorbing portion of the blanket 8 is swollen by the solvent. In FIG.10 (b), the absorption site | part of the solvent of the blanket 8 is attached | subjected and highlighted with the code | symbol 8a. The three solvent absorption parts 8a in the blanket 8 have almost the same thickness, reflecting the thickness of the ink composition 9 that has been transferred. In addition, this swelling accompanying absorption of a solvent degrades the blanket 8 and becomes a factor which reduces durability.

  Next, consider a case where the ink composition 9 is transferred to a printing object (not shown) using the blanket 8 again. At this time, for example, as shown in FIG. 10C, the transfer position of the ink composition 9 from the printing plate on the blanket 8 overlaps the previous transfer position (that is, the solvent absorption portion 8a of the blanket 8). In this case, the solvent is absorbed again at the same portion of the blanket 8 and further swells. As described above, when the solvent is repeatedly absorbed and swells at the same portion of the blanket 8, the durability of the blanket 8 is significantly reduced. In addition, as shown in FIG. 10C, when the transfer position of the ink composition 9 from the printing plate in the blanket 8 overlaps with the previous transfer position, for example, the plurality of concave portions of the printing plate are all the same. If the patterns are arranged in the same direction, the transfer of the ink composition 9 from the printing plate to the blanket 8 is performed under the same conditions as before, so that all the transfer positions of the ink composition 9 are the previous transfer positions. When the transfer of the ink composition 9 from the printing plate to the blanket 8 is shifted along the surface of the blanket 8 so as to overlap the previous transfer position, a partial transfer position And the case of overlapping the previous transfer position.

  For example, as shown in FIG. 10D, the ink composition 9 is transferred from the printing plate to the blanket 8 as a method for suppressing such a decrease in the durability of the blanket 8 when a conventional printing plate is used. In the case where the transfer is repeatedly performed, there is a method in which the transfer is performed by shifting the position along the surface of the blanket 8 so as not to overlap the transfer position (that is, the solvent absorption portion 8a of the blanket 8) at all. It is done. However, in this method, as is clear from FIG. 10 (d), the distance by which the transfer position is shifted in the blanket 8 is large corresponding to the three solvent absorbing portions 8a. There is a problem that it will decrease.

On the other hand, when the printing plate according to the present invention is used, such problems can be solved. This point will be described below by taking the case where the printing plate 1 shown in FIGS. 1 and 2 is used as an example. FIG. 11 is a cross-sectional view schematically showing a blanket state when a printing pattern is formed using the printing plate 1 shown in FIGS. 1 and 2.
As shown in FIG. 11A, the ink composition 9 filled in the first pattern 11 and the second pattern 12 of the printing plate 1 has layers (films) having different thicknesses depending on the depth of these patterns. ) On the blanket 8. This is as shown in FIG.

  Next, these ink compositions 9 on the blanket 8 are further transferred to an object to be printed (not shown), and the ink composition 9 disappears from the blanket 8 as shown in FIG. However, a part of the solvent in the ink composition 9 is absorbed by the blanket 8, and this absorbing portion of the blanket 8 is swollen by the solvent. Also in FIG.11 (b), the absorption site | part of the solvent of the blanket 8 is attached | subjected and highlighted with the code | symbol 8a. The three solvent absorbing portions 8a in the blanket 8 are different in thickness from each other, reflecting the thickness of the ink composition 9 that has been transferred. Specifically, the solvent absorption site 8a derived from the ink composition 9 transferred from the second pattern 12 (hereinafter sometimes referred to as “solvent absorption site 82a”) is transferred from the first pattern 11. Further, the thickness is thinner than the solvent absorption portion 8a derived from the ink composition 9 (hereinafter, sometimes referred to as “solvent absorption portion 81a” separately). That is, the degree of swelling of the solvent absorption part 82a is lower than that of the solvent absorption part 81a.

  Next, consider a case where the ink composition 9 is transferred to a printing object (not shown) using the blanket 8 again. At this time, for example, as shown in FIG. 11 (c), the transfer of the ink composition 9 from the printing plate 1 to the blanket 8 is shifted along the surface of the blanket 8 by one solvent absorbing portion 8 a. As a result, a part of the transfer position overlaps with the previous transfer position, and the solvent is absorbed again at the same portion of the blanket 8 as in the case shown in FIG. However, in this case, as shown in FIG. 11C, the ink composition transferred from the second pattern 12 having a low solvent content overlaps with the solvent absorption portion 81a corresponding to the transfer position having a high degree of swelling. Even if the solvent is absorbed again at this site, unlike the case shown in FIG. 10 (c), the total absorbed amount of the solvent is small and the degree of swelling is still low. On the other hand, it is the ink composition 9 having a high solvent content transferred from the first pattern 11 that overlaps with the solvent absorption part 82a corresponding to the transfer position having a low degree of swelling, but the solvent is absorbed again at this part. However, unlike the case shown in FIG. 10C, the total absorbed amount of the solvent is small and the degree of swelling is still low. Of course, the portion where the transfer positions do not overlap has a low degree of swelling. In this way, by transferring the ink composition 9 along the surface of the blanket 8 by shifting it by one of the solvent absorption sites 8a, a low degree of swelling can be maintained in the blanket 8, and the durability of the blanket 8 can be maintained. Reduction can be suppressed. Moreover, since the distance for shifting the transfer position is only one solvent absorption portion 8a, the number of times the blanket 8 is used can be increased as compared with the case shown in FIG. As described above, the printing pattern forming method using the printing plate according to the present invention has a remarkably excellent effect.

The print pattern to which the present invention is applied can be arbitrarily selected according to the purpose and is not particularly limited.
Preferred examples of the printing pattern include a pattern for visual recognition containing a colorant such as a pigment or a dye, a pattern containing a conductive component and intended for use as a conductor, and the like. It is done.
As described above, the method for forming a print pattern according to the present invention has a high effect of suppressing disturbance of the print pattern in a region where the density of the print pattern is low, and is particularly suitable for forming a fine linear pattern as the print pattern. It is. From such a viewpoint, the method for forming a printed pattern according to the present invention is particularly suitable for forming a conductor pattern (conductive pattern).

The conductive pattern formed according to the present invention preferably has a volume resistivity of 20 μΩ · cm or less, more preferably 15 μΩ · cm or less, further preferably 10 μΩ · cm or less, more preferably 7 μΩ · cm or less. It is especially preferable that it is cm or less. The volume resistivity of the conductive pattern can be adjusted by the material and thickness of the conductive pattern.
Here, the volume resistivity of the conductive pattern is, for example, the line resistance value R (Ω) of the conductive pattern, the cross-sectional area A (cm ² ) of the conductive pattern, and the line length L (cm) of the conductive pattern. It can be measured and calculated as a volume resistivity ρ (Ω · cm) by the formula “ρ = R × A / L”.
The volume resistivity of the conductive pattern can also be calculated by, for example, measuring the surface resistivity and thickness of the conductive pattern and multiplying these values. In addition, the thickness of a conductive pattern can be calculated | required by well-known methods, such as the method of using a laser microscope, for example.

  A laminate formed by using a variety of base materials as print objects and forming a conductive pattern on the base material as the print pattern is, for example, an electronic device such as a data transmitter / receiver, a communication device, or a transparent conductive film. Is available. Such an electronic device can maintain high performance over a long period because the conductive pattern is formed with high accuracy.

  For example, the laminated body provided with the conductive pattern as an antenna can be a data receiving / transmitting body by adopting the same configuration as a known data receiving / transmitting body except for this point. For example, in such a laminate, a non-contact type data transmitter / receiver can be configured by providing an IC chip electrically connected to the conductive pattern on the substrate to form an antenna portion.

  In addition, the laminated body that forms at least a part of the casing (exterior material) with the base material and serves as an antenna portion adopts the same configuration as that of a known communication device except for this point. can do. For example, a flat or curved surface portion of an exterior material in a communication device such as a mobile phone is used as the base material, and a thin line made of the conductive pattern is formed directly on the exterior material (base material), and the thin line is used as a circuit. Thus, the laminate can be used as a circuit board. For example, a cellular phone can be configured by combining a voice input unit, a voice output unit, an operation switch, a display unit, and the like in addition to the laminate.

  Moreover, the said laminated body provided with the said electroconductive pattern as an ultrafine wiring or an ultrathin wiring can be made into a transparent conductive film by employ | adopting the structure similar to a well-known data transparent conductive film except this point. . For example, a touch panel or an optical display can be configured by combining the laminate with a transparent substrate or the like. The presence of the conductive pattern having an appropriate line width or thickness is difficult to recognize visually.

In each laminate such as a data transmitter / receiver, communication device, transparent conductive film, etc., for example, it is necessary to electrically connect the conductive patterns constituting the antenna, circuit, transparent conductive film, etc. However, unlike the conductive patterns in other regions, the conductive pattern constituting such a connection portion tends to have a low density on the substrate. The present invention is particularly suitable for forming a conductive pattern in a region where the density of such a conductive pattern is low.
Moreover, in the transparent conductive film used for the touch panel, for example, in order to improve the light transmittance, it is conceivable to increase the interval between the conductive patterns. It is also particularly suitable for forming a conductive pattern in a low region.

  In the laminate, the thickness of the base material is preferably 12 to 5000 μm, and more preferably 12 to 2000 μm.

The material of the base material in the laminate is not particularly limited. Preferred examples include polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and polymethylpentene. Acrylic resin such as (PMP), polycycloolefin, polystyrene (PS), polyvinyl acetate (PVAc), polymethyl methacrylate (PMMA), AS resin, ABS resin, polyamide (PA), polyimide, polyamideimide (PAI) , Polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyphenylene sulfide (PPS) , Polysulfone (PSF), polyethersulfone (PES), polyetherketone (PEK), polyetheretherketone (PEEK), polycarbonate (PC), polyurethane, polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), Examples thereof include synthetic resins such as polyarylate, epoxy resin, melamine resin, phenol resin, and urea resin.
In addition to the above, the material of the substrate can be exemplified by ceramics such as glass and silicon, and paper.
The base material may be a combination of two or more materials such as glass epoxy resin and polymer alloy.

The substrate may be composed of a single layer, or may be composed of two or more layers. When a base material consists of multiple layers, these multiple layers may be the same as or different from each other. That is, all the layers may be the same, all the layers may be different, or only some of the layers may be different. And when several layers differ from each other, the combination of these several layers is not specifically limited. Here, the plurality of layers being different from each other means that at least one of the material and the thickness of each layer is different from each other.
In addition, when a base material consists of multiple layers, it is good to make it the total thickness of each layer be the thickness of said preferable base material.

<Ink composition>
The ink composition used in the method for forming a print pattern according to the present invention is not particularly limited as long as it contains a component for forming a target print pattern and a solvent.

  The solvent contained in the ink composition is not particularly limited as long as it is liquid at normal temperature and pressure. In the present specification, “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and includes a temperature of 15 to 25 ° C., for example. In addition, “normal pressure” means a pressure when neither depressurizing nor pressurizing, and is usually a pressure equal to the atmospheric pressure and is about 1 atm.

  Examples of the solvent include aromatic hydrocarbons such as toluene, o-xylene, m-xylene, and p-xylene; pentane, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, and pentadecane. Aliphatic hydrocarbons such as ethanol and 2-propanol; unsaturated alcohols; halogenated hydrocarbons such as dichloromethane and chloroform; esters such as ethyl acetate, monomethyl glutarate, and dimethyl glutarate; diethyl ether; Ethers such as tetrahydrofuran (THF) and 1,2-dimethoxyethane (dimethylcellosolve); ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; nitriles such as acetonitrile; N, N-dimethylformua De (DMF), N, N-but amides of dimethylacetamide, and the like, without limitation.

  The aliphatic hydrocarbon preferably has 15 or less carbon atoms.

  Examples of the unsaturated alcohol include acetylene alcohols represented by the following general formula (2) (hereinafter sometimes abbreviated as “acetylene alcohol (2)”).

（式中、Ｒ’及びＲ’’は、それぞれ独立に炭素数１〜２０のアルキル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基である。）

(In the formula, R ′ and R ″ are each independently an alkyl group having 1 to 20 carbon atoms or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.)

  In the formula, the alkyl group having 1 to 20 carbon atoms in R ′ and R ″ may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic. The alkyl group for R ′ and R ″ preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.

  Examples of the substituent in which the hydrogen atom of the phenyl group in R ′ and R ″ may be substituted include, for example, a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, A monovalent group formed by bonding an aromatic hydrocarbon group to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a cyano group, a phenoxy group, and the like. And the number and position of a substituent are not specifically limited, When there are two or more substituents, these several substituents may mutually be same or different.

  R ′ and R ″ are preferably an alkyl group having 1 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 10 carbon atoms.

  Examples of preferable acetylene alcohol (2) include 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, and 3-methyl-1-pentyn-3-ol.

  The said solvent which the said ink composition contains may be only 1 type, may be 2 or more types, and when they are 2 or more types, those combinations and ratios can be adjusted arbitrarily.

  The boiling point of the solvent is preferably 180 ° C. or lower. For example, various solvents having a boiling point of 160 ° C. or lower, 130 ° C. or lower, 110 ° C. or lower, or 80 ° C. or lower can be used. By using a solvent having such a boiling point, the effect of suppressing the disturbance of the printing pattern becomes higher.

  The content of the solvent in the ink composition is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, and particularly preferably 35 to 55% by mass. When the content of the solvent in the ink composition is equal to or higher than the lower limit value, the effect of suppressing the disturbance of the printing pattern is further increased. In addition, when the content of the solvent in the ink composition is equal to or less than the upper limit value, it becomes easier to form a target print pattern.

  When a conductive pattern is formed as the print pattern, a conductive composition formed by blending a conductor forming component may be used as the ink composition. Only 1 type may be sufficient as the formation component of the said conductor mix | blended, and when it is 2 or more types, when it is 2 or more types, the combination and ratio can be adjusted arbitrarily.

  The conductive composition may be appropriately selected according to the material of the conductive pattern to be formed, but may be a metal ink composition in which a metal or a metal forming material is blended as a component for forming the conductor. preferable. By using such a metal ink composition, a conductive pattern having a low resistance value can be easily formed.

The metal to be blended may be either a single metal or an alloy. Preferred examples of the metal include silver and copper as long as it is a single metal.
The metal (single metal or alloy) to be blended is preferably in the form of particles or fibers (tube shape, wire shape, etc.), more preferably nanoparticles or nanowires, silver nanoparticles, silver nanoparticles Particularly preferred are wires, copper nanoparticles or copper nanowires.
In the present specification, “nanoparticle” means a particle having a particle size of 1 nm or more and less than 1000 nm, preferably 1 to 100 nm, and “nanowire” means a width of 1 nm or more and less than 1000 nm, preferably It means the wire which is 1-100 nm.

The metal forming material to be blended may be any material that has a corresponding metal atom (element) and generates a metal by structural change such as decomposition, such as a metal salt, a metal complex, an organometallic compound (metal-carbon bond). And the like. The metal salt and the metal complex may be any of a metal compound having an organic group and a metal compound having no organic group. Among these, the metal forming material is preferably a metal salt, and more preferably a silver salt or a copper salt.
By using a metal forming material, a metal is generated from the material, and a conductive pattern including the metal is formed. In this case, the conductive pattern is mainly composed of the metal, and the ratio of the metal is sufficiently high so that it can be regarded as consisting of only the metal, and the ratio of the metal in the conductive pattern is preferably Is 99% by mass or more. The upper limit value of the metal ratio in the conductive pattern is, for example, 99.9% by mass, 99.8% by mass, 99.7% by mass, 99.6% by mass, 99.5% by mass, 99.4% by mass. , 99.3% by mass, 99.2% by mass, and 99.1% by mass.

  The metal and the metal forming material to be blended may be either one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio can be arbitrarily adjusted.

  The conductive pattern is formed, for example, by attaching the metal ink composition onto a printing object such as the base material and appropriately performing post-processing such as drying or heating (firing). It is preferable to do.

  The metal ink composition is preferably in a liquid form, and preferably a metal or a metal-forming material dispersed uniformly.

  The metal species in the metal ink composition is particularly preferably silver (metal silver). That is, the metal ink composition is preferably a silver ink composition in which metal silver or a metal silver forming material is blended, and is a silver ink composition in which a metal silver forming material is blended. More preferred.

[Silver carboxylate]
Examples of the metal silver forming material include silver carboxylate having a group represented by the formula “—COOAg”.
In this invention, silver carboxylate may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.
The silver carboxylate is not particularly limited as long as it has a group represented by the formula “—COOAg”. For example, the number of groups represented by the formula “—COOAg” may be only one, or two or more. Further, the position of the group represented by the formula “—COOAg” in the silver carboxylate is not particularly limited.

The silver carboxylate is represented by the following general formula (1) β-ketocarboxylate silver (hereinafter sometimes abbreviated as “β-ketocarboxylate (1)”) and the following general formula (4). One or more selected from the group consisting of silver carboxylate (hereinafter sometimes abbreviated as “silver carboxylate (4)”) is preferable.
In the present specification, the simple description of “silver carboxylate” is not limited to “silver β-ketocarboxylate (1)” and “silver carboxylate (4)”, unless otherwise specified. It is intended to mean “silver carboxylate having a group represented by the formula“ —COOAg ””.

（式中、Ｒは１個以上の水素原子が置換基で置換されていてもよい炭素数１〜２０の脂肪族炭化水素基若しくはフェニル基、水酸基、アミノ基、又は一般式「Ｒ^１−ＣＹ^１ _２−」、「ＣＹ^１ _３−」、「Ｒ^１−ＣＨＹ^１−」、「Ｒ^２Ｏ−」、「Ｒ^５Ｒ^４Ｎ−」、「（Ｒ^３Ｏ）_２ＣＹ^１−」若しくは「Ｒ^６−Ｃ（＝Ｏ）−ＣＹ^１ _２−」で表される基であり；
Ｙ^１はそれぞれ独立にフッ素原子、塩素原子、臭素原子又は水素原子であり；Ｒ^１は炭素数１〜１９の脂肪族炭化水素基又はフェニル基であり；Ｒ^２は炭素数１〜２０の脂肪族炭化水素基であり；Ｒ^３は炭素数１〜１６の脂肪族炭化水素基であり；Ｒ^４及びＲ^５はそれぞれ独立に炭素数１〜１８の脂肪族炭化水素基であり；Ｒ^６は炭素数１〜１９の脂肪族炭化水素基、水酸基又は式「ＡｇＯ−」で表される基であり；
Ｘ^１はそれぞれ独立に水素原子、炭素数１〜２０の脂肪族炭化水素基、ハロゲン原子、１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはベンジル基、シアノ基、Ｎ−フタロイル−３−アミノプロピル基、２−エトキシビニル基、又は一般式「Ｒ^７Ｏ−」、「Ｒ^７Ｓ−」、「Ｒ^７−Ｃ（＝Ｏ）−」若しくは「Ｒ^７−Ｃ（＝Ｏ）−Ｏ−」で表される基であり；
Ｒ^７は、炭素数１〜１０の脂肪族炭化水素基、チエニル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはジフェニル基である。）

(In the formula, R represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, a hydroxyl group, an amino group, or a general formula “R ¹ -CY” in which one or more hydrogen atoms may be substituted with a substituent. ¹ ₂ − ”,“ CY ¹ ₃ − ”,“ R ¹ —CHY ¹ — ”,“ R ² O— ”,“ R ⁵ R ⁴ N— ”,“ (R ³ O) ₂ CY ¹ — ”or“ R ⁶ —C (═O) —CY ¹ ₂ — ”;
Y ¹ is each independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom; R ¹ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms or a phenyl group; R ² is an aliphatic having 1 to 20 carbon atoms R ³ is an aliphatic hydrocarbon group having 1 to 16 carbon atoms; R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms; R ⁶ is An aliphatic hydrocarbon group having 1 to 19 carbon atoms, a hydroxyl group or a group represented by the formula "AgO-";
X ¹ is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a phenyl group or benzyl group in which one or more hydrogen atoms may be substituted with a substituent, a cyano group, N - phthaloyl-3-aminopropyl group, 2-ethoxyethyl vinyl group, or the general formula ^{"R 7} O -", ^{"R 7} S -", ^"R 7 -C (= O) -" or ^"R 7 -C ( ═O) —O— ”;
R ⁷ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group, or a phenyl group or diphenyl group in which one or more hydrogen atoms may be substituted with a substituent. )

（式中、Ｒ^８は炭素数１〜１９の脂肪族炭化水素基、カルボキシ基又は式「−Ｃ（＝Ｏ）−ＯＡｇ」で表される基であり、前記脂肪族炭化水素基がメチレン基を有する場合、１個以上の該メチレン基はカルボニル基で置換されていてもよい。）

(In the formula, R ⁸ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a carboxy group or a group represented by the formula “—C (═O) —OAg”, and the aliphatic hydrocarbon group is a methylene group. And one or more of the methylene groups may be substituted with a carbonyl group.)

(Silver β-ketocarboxylate (1))
The aliphatic hydrocarbon group having 1 to 20 carbon atoms in R may be any of linear, branched and cyclic (aliphatic cyclic group), and when it is cyclic, it may be monocyclic or polycyclic. . Further, the aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Preferred examples of the aliphatic hydrocarbon group for R include an alkyl group, an alkenyl group, and an alkynyl group.

  In the aliphatic hydrocarbon group having 1 to 20 carbon atoms in R, one or more hydrogen atoms may be substituted with a substituent, and preferred examples of the substituent include a fluorine atom, a chlorine atom, and a bromine atom. . Moreover, the number and position of substituents are not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other. That is, all the substituents may be the same, all the substituents may be different, or only some of the substituents may be different.

The phenyl group in R may have one or more hydrogen atoms substituted with a substituent, and the preferred substituent is a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms. , A monovalent group formed by bonding the aliphatic hydrocarbon group to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group (—OH), a cyano group (—C≡N), a phenoxy group (—O— C ₆ H ₅ ) and the like can be exemplified, and the number and position of substituents are not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other.
Examples of the aliphatic hydrocarbon group that is a substituent include the same aliphatic hydrocarbon groups as those described above for R except that the number of carbon atoms is 1 to 16.

In the phenyl group and benzyl group in X ¹ , one or more hydrogen atoms may be substituted with a substituent. Preferred examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), nitro group (-NO ₂₎ or the like can be exemplified, the number and position of the substituent is not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other.

In the general formula (1), two X ^{1 s} may be bonded as one group through a double bond with a carbon atom sandwiched between two carbonyl groups. A group represented by the formula “═CH—C ₆ H ₄ —NO ₂ ” can be exemplified.

β-ketocarboxylate silver (1) is silver 2-methylacetoacetate (CH ₃ —C (═O) —CH (CH ₃ ) —C (═O) —OAg), silver acetoacetate (CH ₃ —C (= O) —CH ₂ —C (═O) —OAg), silver 2-ethylacetoacetate (CH ₃ —C (═O) —CH (CH ₂ CH ₃ ) —C (═O) —OAg), silver propionyl acetate _{(CH 3 CH 2 -C (=} O) -CH 2 -C (= O) -OAg), isobutyryl silver acetate _{((CH 3) 2 CH-} C (= O) -CH 2 -C (= O) - OAg), silver pivaloyl acetate ((CH ₃ ) ₃ C—C (═O) —CH ₂ —C (═O) —OAg), silver caproyl acetate (CH ₃ (CH ₂ ) ₃ CH ₂ —C (═O) _{) -CH 2 -C (= O)} -OAg), 2-n- Buchiruaseto silver acetate _{(CH 3 -C (= O)} -CH (C _{H 2 CH 2 CH 2 CH 3} ) -C (= O) -OAg), 2- benzyl acetoacetate silver _{(CH 3 -C (= O)} -CH (CH 2 C 6 H 5) -C (= O) -OAg), silver benzoylacetate _{(C 6 H 5 -C (=} O) -CH 2 -C (= O) -OAg), Pibaroiruaseto silver acetate _{((CH 3) 3 C-} C (= O) -CH 2 _{-C (= O) -CH 2 -C} (= O) -OAg), isobutyryl acetoacetate silver _{((CH 3) 2 CH-} C (= O) -CH 2 -C (= O) -CH 2 -C (= O) -OAg), 2- acetyl pivaloyl silver acetate _{((CH 3) 3 C-} C (= O) -CH (-C (= O) -CH 3) -C (= O) -OAg), 2- acetyl isobutyryl silver acetate _{((CH 3) 2 CH-} C (= O) -CH (-C (= O) -CH 3) -C (= O) - Ag), or is preferably acetone dicarboxylic silver _{(AgO-C (= O)} -CH 2 -C (= O) -CH 2 -C (= O) -OAg).

  The β-ketocarboxylate (1) can further reduce the concentration of remaining raw materials and impurities in a conductor (metal silver) formed by a solidification process such as a drying process or a heating (baking) process. The smaller the raw materials and impurities, for example, the better the contact between the formed metal silvers, the easier the conduction, and the lower the resistivity.

  The β-ketocarboxylate (1) decomposes at a low temperature of, for example, preferably 60 to 210 ° C., more preferably 60 to 200 ° C., without using a reducing agent or the like known in the art. It is possible to form. And by using together with a reducing agent, it decomposes at a lower temperature to form metallic silver. The reducing agent will be described later.

  In the present invention, the β-ketocarboxylate (1) may be used alone or in combination of two or more. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

(Silver carboxylate (4))
In the formula, the aliphatic hydrocarbon group for R ⁸ is the same as the aliphatic hydrocarbon group for R except that it has 1 to 19 carbon atoms. However, the aliphatic hydrocarbon group for R ⁸ preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.

When the aliphatic hydrocarbon group for R ⁸ has a methylene group (—CH ₂ —), one or more of the methylene groups may be substituted with a carbonyl group. The number and position of the methylene groups that may be substituted with a carbonyl group are not particularly limited, and all methylene groups may be substituted with a carbonyl group. Here, the “methylene group” is not only a single group represented by the formula “—CH ₂ —” but also one alkylene group in which a plurality of groups represented by the formula “—CH ₂ —” are linked. And a group represented by the formula “—CH ₂ —”.

Silver carboxylate (4) is silver pyruvate (CH ₃ —C (═O) —C (═O) —OAg), silver acetate (CH ₃ —C (═O) —OAg), silver butyrate (CH _{3 - (CH 2) 2 -C (} = O) -OAg), isobutyric acid silver _{((CH 3) 2 CH-} C (= O) -OAg), hexane silver 2-ethylhexyl _(CH 3 - _{(CH 2} ) ₃ —CH (CH ₂ CH ₃ ) —C (═O) —OAg), silver neodecanoate (CH ₃ — (CH ₂ ) ₅ —C (CH ₃ ) ₂ —C (═O) —OAg), Shu It is preferably silver oxide (AgO—C (═O) —C (═O) —OAg) or silver malonate (AgO—C (═O) —CH ₂ —C (═O) —OAg). Also, 2 of the silver oxalate (AgO-C (= O) -C (= O) -OAg) and malonic silver _{(AgO-C (= O)} -CH 2 -C (= O) -OAg) Of the groups represented by the formula “—COOAg”, one is a group represented by the formula “—COOH” (HO—C (═O) —C (═O) —OAg, HO) _{-C (= O) -CH 2 -C} (= O) -OAg) it is also preferred.

  As in the case of silver β-ketocarboxylate (1), silver carboxylate (4) is also used in the conductor (metal silver) formed by solidification treatment such as drying treatment or heating (firing) treatment. The concentration can be further reduced. And by using together with a reducing agent, it decomposes at a lower temperature to form metallic silver.

  In this invention, carboxylate silver (4) may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

The silver carboxylate is silver 2-methylacetoacetate, silver acetoacetate, silver 2-ethylacetoacetate, silver propionylacetate, silver isobutyrylacetate, silver pivaloylacetate, silver caproylacetate, silver 2-n-butylacetoacetate, 2-benzylacetoacetate Silver acetate, silver benzoyl acetate, silver pivaloyl acetoacetate, silver isobutyryl acetoacetate, silver acetone dicarboxylate, silver pyruvate, silver acetate, silver butyrate, silver isobutyrate, silver 2-ethylhexanoate, silver neodecanoate, silver One or more selected from the group consisting of silver oxide and silver malonate are preferred.
Among these silver carboxylates, silver 2-methylacetoacetate and silver acetoacetate are excellent in compatibility with the nitrogen-containing compounds (among others amine compounds) described later, and are particularly suitable for increasing the concentration of silver ink compositions. It is mentioned as a thing.

[Nitrogen-containing compounds]
The silver ink composition is preferably one in which a nitrogen-containing compound is further blended in addition to the metal silver forming material, particularly when the metal silver forming material is the silver carboxylate.
The nitrogen-containing compound is an amine compound having 25 or less carbon atoms (hereinafter sometimes abbreviated as “amine compound”), a quaternary ammonium salt having 25 or less carbon atoms (hereinafter abbreviated as “quaternary ammonium salt”). Ammonia, an ammonium salt formed by reacting an amine compound having 25 or less carbon atoms with an acid (hereinafter sometimes abbreviated as “ammonium salt derived from an amine compound”), and ammonia reacting with an acid. One or more selected from the group consisting of ammonium salts (hereinafter sometimes abbreviated as “ammonium salts derived from ammonia”). That is, the nitrogen-containing compound to be blended may be only one type, or two or more types, and when two or more types are used in combination, the combination and ratio can be arbitrarily adjusted.

(Amine compound, quaternary ammonium salt)
The amine compound has 1 to 25 carbon atoms, and may be any of primary amine, secondary amine, and tertiary amine. The quaternary ammonium salt has 4 to 25 carbon atoms. The amine compound and the quaternary ammonium salt may be either chain or cyclic. Further, the number of nitrogen atoms constituting the amine moiety or ammonium salt moiety (for example, the nitrogen atom constituting the amino group (—NH ₂ ) of the primary amine) may be one, or two or more.

  Examples of the primary amine include monoalkylamines, monoarylamines, mono (heteroaryl) amines, and diamines in which one or more hydrogen atoms may be substituted with a substituent.

  Examples of the secondary amine include dialkylamine, diarylamine, di (heteroaryl) amine and the like in which one or more hydrogen atoms may be substituted with a substituent.

  Examples of the tertiary amine include trialkylamine and dialkylmonoarylamine in which one or more hydrogen atoms may be substituted with a substituent.

In the present invention, examples of the quaternary ammonium salt include halogenated tetraalkylammonium, in which one or more hydrogen atoms may be substituted with a substituent.
Examples of the halogen constituting the halogenated tetraalkylammonium include fluorine, chlorine, bromine and iodine.
Specific examples of the preferred tetraalkylammonium halide include dodecyltrimethylammonium bromide.

So far, the chain amine compound and the quaternary organic ammonium salt have been mainly described. However, in the amine compound and the quaternary ammonium salt, the nitrogen atom constituting the amine moiety or the ammonium salt moiety is a ring skeleton structure ( A heterocyclic compound which is a part of a heterocyclic skeleton structure) may be used. That is, the amine compound may be a cyclic amine, and the quaternary ammonium salt may be a cyclic ammonium salt. At this time, the ring (ring containing the nitrogen atom constituting the amine moiety or ammonium salt moiety) structure may be either monocyclic or polycyclic, and the number of ring members (number of atoms constituting the ring skeleton) is also particularly limited. Any of an aliphatic ring and an aromatic ring may be sufficient.
If it is a cyclic amine, a pyridine can be illustrated as a preferable thing.

  In the primary amine, secondary amine, tertiary amine and quaternary ammonium salt, the “hydrogen atom optionally substituted with a substituent” means a nitrogen atom constituting an amine moiety or an ammonium salt moiety. A hydrogen atom other than a hydrogen atom bonded to. The number of substituents at this time is not particularly limited, and may be one or two or more, and all of the hydrogen atoms may be substituted with a substituent. When the number of substituents is plural, the plural substituents may be the same as or different from each other. That is, the plurality of substituents may all be the same, may all be different, or only some may be different. Further, the position of the substituent is not particularly limited.

Examples of the substituent in the amine compound and the quaternary ammonium salt include an alkyl group, an aryl group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, and a trifluoromethyl group (—CF ₃ ). Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The amine compound is n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, sec-butylamine, tert-butylamine, 3-aminopentane, 3-methyl. Butylamine, 2-heptylamine, 2-aminooctane, 2-ethylhexylamine, 2-phenylethylamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, N-methyl-n-hexylamine, diisobutylamine, N-methylbenzylamine, di (2-ethylhexyl) amine, 1,2-dimethyl-n-propylamine, N, N-dimethyl-n-octadecylamine or N, N-dimethylcyclohexylamine is preferred. .
Among these amine compounds, 2-ethylhexylamine is excellent in compatibility with the above-mentioned silver carboxylate, particularly suitable for increasing the concentration of the silver ink composition, and particularly for reducing the surface roughness of metallic silver. Listed as suitable.

(Ammonium salts derived from amine compounds)
In the present invention, the ammonium salt derived from the amine compound is an ammonium salt obtained by reacting the amine compound with an acid, and the acid may be an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic acid such as acetic acid. However, the type of acid is not particularly limited.
Examples of the ammonium salt derived from the amine compound include, but are not limited to, n-propylamine hydrochloride, N-methyl-n-hexylamine hydrochloride, N, N-dimethyl-n-octadecylamine hydrochloride and the like. .

(Ammonium salt derived from ammonia)
In the present invention, the ammonium salt derived from ammonia is an ammonium salt formed by reacting ammonia with an acid, and examples of the acid include the same ones as in the case of the ammonium salt derived from the amine compound.
Examples of the ammonium salt derived from ammonia include ammonium chloride, but are not limited thereto.

In the present invention, the amine compound, the quaternary ammonium salt, the ammonium salt derived from the amine compound and the ammonium salt derived from ammonia may be used alone or in combination of two or more. Good. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.
And as said nitrogen-containing compound, you may use individually 1 type selected from the group which consists of said amine compound, quaternary ammonium salt, ammonium salt derived from amine compound, and ammonium salt derived from ammonia, Two or more kinds may be used in combination. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

  In the silver ink composition, the compounding amount of the nitrogen-containing compound is preferably 0.3 to 15 mol, more preferably 0.3 to 5 mol, per mol of the metal silver forming material. preferable. When the blending amount of the nitrogen-containing compound is within such a range, the silver ink composition is further improved in stability and the quality of the conductor (metal silver) is further improved. Furthermore, the conductor can be formed more stably without performing heat treatment at a high temperature.

[Reducing agent]
The silver ink composition preferably contains a reducing agent in addition to the metal silver forming material. By blending a reducing agent, the silver ink composition can more easily form metallic silver. For example, a conductor (metal silver) having sufficient conductivity can be formed even by heat treatment at a low temperature.

The reducing agent is one or more reducing agents selected from the group consisting of oxalic acid, hydrazine and a compound represented by the following general formula (5) (hereinafter sometimes abbreviated as “compound (5)”). It is preferably a compound (hereinafter sometimes simply referred to as “reducing compound”).
HC (= O) -R ²¹ (5)
(In the formula, R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group, an N, N-dialkylamino group, a hydroxyl group, or an amino group.)

(Reducing compounds)
The alkyl group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms, and may be linear, branched or cyclic, and is the same as the alkyl group in R of the general formula (1) Is.

The alkoxy group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms, and examples thereof include monovalent groups in which the alkyl group in R ²¹ is bonded to an oxygen atom.

The N, N-dialkylamino group having 20 or less carbon atoms in R ²¹ has 2 to 20 carbon atoms, and the two alkyl groups bonded to the nitrogen atom may be the same as or different from each other, Each alkyl group has 1 to 19 carbon atoms. However, the total value of the carbon number of these two alkyl groups is 2-20.
The alkyl group bonded to the nitrogen atom may be linear, branched or cyclic, respectively, and the alkyl in R of the general formula (1) except that it has 1 to 19 carbon atoms. It is the same as the group.

As the reducing compound, hydrazine may be a monohydrate (H ₂ N—NH ₂ .H ₂ O).

  The said reducing compound may be used individually by 1 type, and may use 2 or more types together. When two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.

Preferred examples of the reducing compound include formic acid (HC (═O) —OH); methyl formate (HC (═O) —OCH ₃ ), ethyl formate (HC (═O) —OCH). Formic acid esters such as ₂ CH ₃ ) and butyl formate (HC (═O) —O (CH ₂ ) ₃ CH ₃ ); propanal (HC (═O) —CH ₂ CH ₃ ), butanal (H Aldehydes such as —C (═O) — (CH ₂ ) ₂ CH ₃ ) and hexanal (HC— (O) — (CH ₂ ) ₄ CH ₃ ); formamide (HC— (O) —NH ₂ ), N, N-dimethylformamide (HC (═O) —N (CH ₃ ) ₂ ) and other formamides (groups represented by the formula “HC (═O) —N (—) —”) And oxalic acid.

  In the silver ink composition, the compounding amount of the reducing agent is preferably 0.04 to 3.5 mol, and preferably 0.06 to 2.5 mol per 1 mol of the metal silver forming material. Is more preferable. When the blending amount of the reducing agent is within such a range, the silver ink composition can form a conductor (metal silver) more easily and more stably.

[alcohol]
The silver ink composition is preferably one in which alcohol is further blended in addition to the metal silver forming material.

  The said alcohol may be used individually by 1 type, and may use 2 or more types together. When two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.

  The alcohol is preferably the acetylene alcohol (2) described above.

  In the silver ink composition, the blending amount of acetylene alcohol (2) is preferably 0.03 to 0.7 moles per mole of blending material of the metallic silver, and 0.04 to 0.3 moles. It is more preferable that When the blending amount of acetylene alcohol (2) is within such a range, the stability of the silver ink composition is further improved.

[Other ingredients]
The silver ink composition may contain other components other than the metallic silver forming material, nitrogen-containing compound, reducing agent, and alcohol.
The other components in the silver ink composition can be arbitrarily selected depending on the purpose, and are not particularly limited. Preferred examples thereof include liquid saturated aliphatic hydrocarbons under normal temperature and pressure conditions.

  The saturated aliphatic hydrocarbon may be linear, branched or cyclic, and can be arbitrarily selected according to the type and amount of the compounding components. The saturated aliphatic hydrocarbon preferably has 15 or less carbon atoms, and more preferable examples include pentane, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane and the like. It can be illustrated.

  The other components in the silver ink composition may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.

What is necessary is just to select suitably the compounding quantity of the said other component in a silver ink composition according to the kind of said other component.
For example, when the other component is a saturated aliphatic hydrocarbon, its blending amount may be selected according to the purpose, such as the viscosity of the silver ink composition. The ratio of the amount of the saturated aliphatic hydrocarbon to the total amount is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
When the other component is a component other than the saturated aliphatic hydrocarbon, the ratio of the blended amount of the other component to the total amount of the blended components in the silver ink composition is 10% by mass or less. Preferably, it is 5 mass% or less.
The ratio of the blended amount of the other components with respect to the total amount of the blended components is 0 mass, that is, even if the other components are not blended, the silver ink composition exhibits its effect sufficiently.

  In the silver ink composition, all the compounding components may be dissolved, or some or all of the components may be dispersed without dissolving, but it is preferable that all the compounding components are dissolved. The undissolved component is preferably dispersed uniformly.

  In the silver ink composition, any of the components other than the metal silver forming material, such as nitrogen-containing compounds, reducing agents, alcohols and saturated aliphatic hydrocarbons exemplified above, and liquids at normal temperature and pressure, In the silver ink composition after blending, those that react with other components to produce a reaction product that does not function as a solvent component can be identified as a solvent. .

<Method for producing ink composition>
The said ink composition is obtained by mix | blending the component for comprising the target printing pattern, a solvent, and components other than these as needed. After the blending of the respective components, the obtained product may be used as it is, or the ink composition obtained by performing a known refining operation as necessary may be used as the ink composition. Among the ink compositions, in particular, in the case of a silver ink composition using silver β-ketocarboxylate (1) as the metal silver forming material, impurities that inhibit conductivity are not generated when the above components are blended. Alternatively, since the amount of such impurities generated can be suppressed to a very small amount, a conductor (metal silver) having sufficient conductivity can be obtained even when a silver ink composition that has not been subjected to a purification operation is used.

At the time of blending each component, all the components may be added and then mixed, or some components may be mixed while being added sequentially, or all components may be mixed while being added sequentially. Good. However, in the silver ink composition, the reducing agent is preferably added dropwise, and the surface roughness of the metallic silver tends to be further reduced by suppressing fluctuations in the dropping speed.
The mixing method is not particularly limited, a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer, a three-roller, a kneader, a bead mill or the like; a method of mixing by adding ultrasonic waves, etc. What is necessary is just to select suitably from a well-known method.
In the silver ink composition, when the undissolved component is uniformly dispersed, for example, a method of dispersing using the above-described three rolls, kneader, bead mill or the like is preferably applied.

The temperature at the time of compounding is not particularly limited as long as each compounding component does not deteriorate. For example, in the silver ink composition, the temperature at the time of blending is preferably −5 to 60 ° C. And the temperature at the time of mixing | blending is good to adjust suitably so that the mixture obtained by mix | blending may become the viscosity which is easy to stir according to the kind and quantity of a mixing | blending component.
Further, the blending time is not particularly limited as long as each blending component does not deteriorate. In the silver ink composition, the blending time is preferably 10 minutes to 36 hours.

[carbon dioxide]
Among the ink compositions, the silver ink composition may be further supplied with carbon dioxide. Such a silver ink composition has a high viscosity and is suitable when it is necessary to thicken the ink composition during printing.

Carbon dioxide may be supplied at any time during the production of the silver ink composition.
In the present invention, for example, carbon dioxide is supplied to the first mixture in which the metal silver forming material and the nitrogen-containing compound are blended to form a second mixture, and if necessary, the second mixture It is preferable that a silver ink composition is produced by further blending the reducing agent with the mixture. Moreover, when mix | blending the said alcohol or another component, these can be mix | blended at the time of manufacture of any one or both of a 1st mixture and a 2nd mixture, and can be arbitrarily selected according to the objective.

  Carbon dioxide gas may be supplied by various known methods of blowing gas into the liquid, and a suitable supply method may be selected as appropriate. For example, a method in which one end of a pipe is immersed in the first mixture, the other end is connected to a carbon dioxide gas supply source, and the carbon dioxide gas is supplied to the first mixture through the pipe. At this time, the carbon dioxide gas may be supplied directly from the end of the pipe. For example, a plurality of voids that can serve as gas flow paths, such as a porous one, are provided to diffuse the introduced gas. A gas diffusion member that can be discharged as minute bubbles may be connected to the end of the pipe, and the carbon dioxide gas may be supplied through the gas diffusion member. Moreover, you may supply a carbon dioxide gas, stirring the 1st mixture by the method similar to the time of manufacture of a 1st mixture. By doing in this way, carbon dioxide can be supplied efficiently.

  The supply of dry ice (solid carbon dioxide) may be performed by adding dry ice to the first mixture. The total amount of dry ice may be added all at once, or may be added stepwise (continuously across a time zone during which no addition is performed).

  The silver ink composition supplied with carbon dioxide preferably has a viscosity at 20 to 25 ° C. of 1 Pa · s or more, for example. In the present specification, the value of viscosity means a value measured by an ultrasonic viscometer unless otherwise specified.

  In the present invention, it is also preferable to produce a silver ink composition by supplying carbon dioxide to a mixture containing the metallic silver forming material, alcohol and nitrogen-containing compound. In this case, a method similar to the above can be adopted as a method for supplying carbon dioxide.

  When the silver ink composition is used, the drying treatment of the silver ink composition in the pattern forming step may be performed under normal pressure, reduced pressure, or air blowing conditions. Either may be used. Also, the drying temperature is not particularly limited, and may be either heat drying or room temperature drying. As a preferable drying method when the heat treatment is unnecessary, a method of drying in the atmosphere at 18 to 30 ° C. can be exemplified.

  When the silver ink composition is heated (baked), the conditions may be adjusted as appropriate according to the type of compounding component of the silver ink composition. Usually, it is preferable that heating temperature is 60-370 degreeC, and it is more preferable that it is 70-280 degreeC. The heating time may be adjusted according to the heating temperature, but is usually preferably 1 minute to 24 hours, and more preferably 1 minute to 12 hours. Among the silver metal forming materials, the silver carboxylate, particularly β-ketocarboxylate silver (1) is different from metal silver forming materials such as silver oxide, for example, using a reducing agent known in the art. Even if not, it decomposes at low temperature. Reflecting such decomposition temperature, the silver ink composition can form metallic silver at an extremely lower temperature than the conventional one as described above.

  When the silver ink composition is attached to a substrate having low heat resistance and is heated (baked), the heating temperature is preferably less than 130 ° C, more preferably 125 ° C or less, and 120 ° C or less. It is particularly preferred that

  The method for heat treatment of the silver ink composition is not particularly limited, and for example, heating by an electric furnace, heating by a thermal head, heating by far infrared irradiation, heating by blowing a hot gas, or the like can be performed. Further, the heat treatment of the silver ink composition may be performed in the air, in an inert gas atmosphere, or may be performed under humidified conditions. And you may carry out under any of normal pressure, pressure reduction, and pressurization.

  In the present specification, “humidification” means that the humidity is artificially increased unless otherwise specified, and preferably the relative humidity is 5% or more. At the time of heat treatment, since the humidity in the treatment environment becomes extremely low due to the high treatment temperature, it can be said that the relative humidity of 5% is clearly artificially increased.

  The relative humidity when the heat treatment of the silver ink composition is performed under humidified conditions is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, and 70%. It is particularly preferable that it be 90% or more, or 100%. And you may perform the heat processing under humidification conditions by spraying the high pressure steam heated to 100 degreeC or more. Thus, by heat-processing under humidification conditions, highly pure metallic silver can be formed in a short time.

The heat treatment of the silver ink composition may be performed in two stages. For example, in the first stage heat treatment, there is exemplified a method in which the silver ink composition is mainly dried rather than the formation of metal silver, and the formation of metal silver is completed in the second stage heat treatment.
In the first-stage heat treatment, the heating temperature may be appropriately adjusted according to the type of compounding component of the silver ink composition, but is preferably 60 to 110 ° C, more preferably 70 to 90 ° C. preferable. Moreover, what is necessary is just to adjust a heating time according to heating temperature, Usually, it is preferable that it is 5 second-12 hours, and it is more preferable that it is 30 second-2 hours.
In the second stage heat treatment, the heating temperature may be appropriately adjusted according to the type of compounding component of the silver ink composition so that metallic silver is satisfactorily formed, but it should be 60 to 280 ° C. Preferably, it is 70-260 degreeC. Moreover, what is necessary is just to adjust a heating time according to heating temperature, Usually, it is preferable that it is 1 minute-12 hours, and it is more preferable that it is 1 minute-10 hours.
As will be described later, when the silver ink composition is attached to a substrate having low heat resistance and is heated (baked), the heating temperature in the first and second stages is less than 130 ° C. It is preferably 125 ° C. or lower, more preferably 120 ° C. or lower.

When heat treatment under humidified conditions is employed, the heat treatment of the silver ink composition is not the formation of metallic silver as described above under non-humidified conditions in the first stage heat treatment. It is particularly preferable to perform drying in a two-stage method in which the formation of metallic silver is performed to the end as described above under humidified conditions in the second-stage heat treatment.
In the present specification, “non-humidification” means that the above “humidification” is not performed, that is, the humidity is not artificially increased, and preferably the relative humidity is less than 5%. .

When performing the above-mentioned heat treatment by a two-stage method, the heating temperature during the heat treatment under non-humidifying conditions in the first stage is preferably 60 to 110 ° C, more preferably 70 to 90 ° C. preferable. The heating time is preferably 5 seconds to 3 hours, more preferably 30 seconds to 2 hours, and particularly preferably 30 seconds to 1 hour.
When performing the above-mentioned heat treatment by a two-stage method, the heating temperature during the heat treatment under the second-stage humidification condition is preferably 60 to 230 ° C, more preferably 70 to 210 ° C. . The heating time is preferably 1 minute to 2 hours, more preferably 1 minute to 1 hour, and particularly preferably 1 minute to 30 minutes.
As will be described later, when the silver ink composition is attached to a substrate having low heat resistance and heated (baked), the heat treatment under the first non-humidifying condition and the second humidifying condition are performed. The heating temperature in the heat treatment at is preferably less than 130 ° C, more preferably 125 ° C or less, and particularly preferably 120 ° C or less.

  When the silver ink composition is used as the ink composition, the conductive pattern can be formed at a low temperature in the laminate, and a wide selection of materials such as the base material can be selected. The degree of freedom is greatly improved, and the data receiving / transmitting body, communication device, transparent conductive film, and other electronic devices can be made more rational.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

[Example 1]
<Formation of printed pattern (production of laminate)>
(Manufacture of silver ink composition)
In a beaker, 2-ethylhexylamine (1.3-fold mol amount relative to 2-methylacetoacetate silver described later) and isobutylamine (0.2-fold mol amount based on 2-methylacetoacetate silver described later). Mix and stir for 1 minute using a mechanical stirrer. Here, 52.9 g of silver 2-methylacetoacetate, formic acid (0.4 times molar amount with respect to silver 2-methylacetoacetate), 3,5-dimethyl-1 so that the liquid temperature becomes 25 ° C. or less. -Hexin-3-ol ("Surfinol 61" manufactured by Air Products Japan, hereinafter abbreviated as "DMHO") (0.04-fold molar amount with respect to silver 2-methylacetoacetate) in this order And mixed, and stirred for 2 hours using a mechanical stirrer. Thus, a silver ink composition was obtained. Table 1 shows the types and blending ratios of each blending component. In Table 1, “nitrogen-containing compound (molar ratio)” means the compounding amount (number of moles) of nitrogen-containing compound per mol of compounding material of the metallic silver ([number of moles of nitrogen-containing compound] / [metal The number of moles of silver forming material]). Similarly, the “reducing agent (molar ratio)” is the amount (mole number) of the reducing agent per mole of the metal silver forming material ([mole number of reducing agent] / [mole of metal silver forming material). Number]). Similarly, in the case of “alcohol (molar ratio)”, the blending amount (number of moles) of alcohol per mole of forming material of metallic silver ([number of moles of alcohol] / [number of moles of forming material of metallic silver]) Means.

(Formation of print pattern)
Using the silver ink composition obtained above and the printing plate shown in FIGS. 1 and 2, a conductive pattern mainly composed of metallic silver was formed as a printing pattern by a gravure offset printing method. More specifically, it is as follows.
As a printing plate, the material is nickel, the first pattern depth (D _X1 ) is 10 μm, the width (W _X1 ) is 5 μm, and the second pattern depth (D _Y1 ) is 0.2 μm. The width (W _Y1 ) is 5 μm, and the distances (L ₁ , L ₂ ) between the adjacent first and second patterns are both 200 μm. In the printing plate, the first pattern and the second pattern were linear, and the length was 25 mm. Table 2 shows the sizes of these printing plates.

  Using this printing plate, printing is performed on one main surface (surface) of a glass substrate (thickness 1.5 mm), and the substrate after printing is performed in an oven at 200 ° C. for 10 minutes. By making it dry, the electroconductive pattern which has metal silver as a main component was formed in the base-material surface. In addition, the electroconductive pattern corresponding to the 2nd pattern of a printing plate was not formed on the base material.

<Evaluation of printing pattern>
(Observation of printed pattern shape)
About the formed conductive pattern, the shape was observed using the laser microscope ("VK-X100" by Keyence Corporation). The results are shown in Table 3.

(Calculation of volume resistivity)
About the formed conductive pattern, the line resistance value R (Ω), the cross-sectional area A (cm ² ), and the line length L (cm) are measured, and the expression “ρ = R × A / L” Volume resistivity ρ (μΩ · cm) was calculated. The line resistance R was measured by a two-terminal method using a digital multimeter (“7352” manufactured by ADC), and the cross-sectional area A was measured using a laser microscope (“VK-X100” manufactured by Keyence). . Moreover, the thickness was calculated | required at the time of the measurement of the cross-sectional area A about an electroconductive pattern. The results are shown in Table 3.

<Formation of printed pattern (production of laminate) and evaluation>
[Comparative Example 1]
A conductive pattern was formed and evaluated in the same manner as in Example 1 except that the printing plate used was that on which the second pattern was not formed. The results are shown in Table 3.

As shown in the above results, the conductive pattern of Example 1 was suppressed in deformation, rubbing and chipping over the entire length, had high uniformity in width and thickness, and low volume resistivity.
On the other hand, in the conductive pattern of Comparative Example 1, deformation, rubbing and chipping were all remarkable, the uniformity of width and thickness was low, and disconnection was observed, so the volume resistivity could not be measured. . The thickness of the conductive pattern in Comparative Example 1 was almost the same as that in Example 1 at the measurable site.

1, 2, 3 ... printing plate, 11, 21, 31 ... first pattern, 12, 22, 32 ... second pattern, 7 ... printing object, 8 ... blanket, 9 ... Ink composition, 9 '... Print pattern, D _X1 ... Depth of first pattern, _DY1 ... Depth of second pattern, L ₁ , L ₂ ... Adjacent first Distance between 1 pattern 11 and 2nd pattern 12

Claims (5)

Having a first pattern and a second pattern for filling the ink composition;
The average depth of the second pattern is smaller than the average depth of the first pattern,
A printing plate in which the first pattern and the second pattern exist in the vicinity of each other.   2. The printing plate according to claim 1, wherein an average value of the depth of the second pattern is a value equal to or less than 0.5 times an average value of the depth of the first pattern.   The printing plate according to claim 1 or 2, wherein a distance between the adjacent first pattern and the second pattern is 200 µm or less.   The printing plate as described in any one of Claims 1-3 whose width | variety of a said 1st pattern is 20 micrometers or less. A method for forming a printing pattern using the printing plate according to any one of claims 1 to 4,
Filling the first pattern and the second pattern of the printing plate with an ink composition;
Transferring the ink composition filled in the first pattern to the print object without transferring the ink composition filled in the second pattern to the print object;
Forming a print pattern on the print object from the ink composition transferred from the first pattern.

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