JP6552095B2 - Method of forming print pattern - Google Patents

Description

  The present invention relates to a printing plate for forming a printing pattern using an ink composition, and a method of 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. And, 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 of forming the conductive pattern, the photolithographic method has been mainstream in the past. However, in the photolithography method, it is necessary to use a resist composition, there are many incidental steps such as development and washing, and there is 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, formation of a fine conductive pattern by offset printing is also becoming possible. 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 an ink composition is used, and after the ink composition is supplied onto the printing plate, the recess is applied by a doctor blade. The printed ink pattern is formed by transferring the filled ink composition onto a blanket and then transferring the transferred ink composition onto a print target. At this time, the formed printing pattern is frequently deformed, rubbed, or chipped off in a region near the edge on the object to be printed, and the target shape is accurately obtained. There was a problem that there was nothing that did not occur. Such a phenomenon is likely to occur particularly when the print surface has a large area and the print pattern is fine.

  The above-mentioned disorder of the printing pattern is caused in the printing plate filled with the ink composition at the beginning of filling, because the volatilization amount of the solvent in the ink composition is relatively smaller in the vicinity of the outer peripheral portion than in the central portion. 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. Therefore, in the vicinity of the outer periphery of the printing plate, the vapor pressure of the volatilized solvent is relatively lower than that of the central portion, so that with the passage of time, the filled ink composition dries faster than the central portion in the vicinity of the outer periphery. proceed. As a result, since the filled ink composition is in a more solidified state in the vicinity of the outer peripheral portion than in the central portion, transfer to a blanket or a print target is difficult, which is the above-mentioned. It is presumed to be the cause of print pattern disorder.

  As a method of solving such a problem, it has an actual pattern corresponding to a recess for forming a target print pattern in a predetermined area, and corresponds to a recess for forming an unintended 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 vapor pressure of the volatilized solvent is increased by the ink composition filled in the dummy pattern as in the central part even in the vicinity of the outer peripheral part of the printing plate from the beginning of the filling. Drying (solidification) is suppressed. Therefore, in the vicinity of the outer peripheral portion of the printing plate as well as in the central portion, the filled ink composition is maintained in an easily transferred state with respect to the blanket and the printing object, and the disturbance of the printing pattern is suppressed. It is guessed. Also, in this method, an unexpected print pattern is formed on the print target by the dummy pattern, but a print pattern is further superimposed and formed on the print pattern other than this purpose, and finally, As a whole, a target print pattern is formed on a print object.

JP 2001-353974 A

  However, according to the method disclosed in Patent Document 1, by forming the print pattern in an overlapping manner, even if the trace is apparently erased, an unintended print pattern is formed on the print target, There is a problem in that it involves the formation of unnecessary print patterns. And such an unnecessary printing pattern also had the problem that an arrangement position was limited. Furthermore, the method disclosed in Patent Document 1 suppresses the disturbance of the print pattern in the area near the edge on the print object corresponding to the vicinity of the outer peripheral portion of the printing plate, but the same applies. The disturbance of the printing pattern is the area on the printing object corresponding to the portion where the density of the concave portion for filling the ink composition in the printing plate is low and the filled ink composition tends to dry, in other words, the printing object As long as the density of the print pattern on the object is low, it may occur outside the area close to the edge.

  The present invention has been made in view of the above-mentioned circumstances, and it is possible to suppress the disturbance of the printing pattern in the area where the density of the printing pattern is low without involving the formation of the unnecessary printing pattern, and the printing plate It is an object of the present invention to provide a method of forming a print pattern with high accuracy.

In order to solve the above problems, the present invention has a first pattern and a second pattern for filling an ink composition, and the average value of the depths of the second pattern is the depth of the first pattern. A method of forming a printing pattern using a printing plate, wherein the first pattern and the second pattern are smaller than an average value, and the first pattern and the second pattern are in the vicinity of each other, wherein the first pattern and the second pattern of the printing plate Filling the composition, transferring the ink composition filled in the first pattern to the printing object without transferring the ink composition filled in the second pattern to the printing object; Forming a print pattern on the print target from the ink composition transferred from the first pattern .

In the method for forming a printed pattern of the present invention, it is preferable that an average value of the depth of the second pattern is a value not more than 0.5 times an average value of the depth of the first pattern.
In the method for forming a print pattern of the present invention, it is preferable that the distance between the adjacent first pattern and the second pattern is 200 μm or less.
In the method of forming a print pattern according to the present invention, the width of the first pattern is preferably 20 μm or less .

  According to the present invention, there is provided a printing plate capable of suppressing the disturbance of the printing pattern in the area where the density of the printing pattern is low without accompanied formation of unnecessary printing pattern, and a highly accurate 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 a different embodiment of a printing plate concerning the present invention typically, and is shown. It is a top view which expands and shows typically other embodiment of the printing plate which concerns on this invention. 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 the further another 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. 1 and 2. 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 value of the depths of the second pattern is based on the average value of the depths of the first pattern. Also, the first pattern and the second pattern are close to each other.
In the printing plate, the first pattern and the second pattern are in the specific relationship as described above, so that the printing pattern is formed even in the area where the density of the printing pattern is low without the formation of unnecessary printing patterns. It is possible to form the target print pattern with high accuracy by suppressing the disturbance.
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 a printing plate according to an embodiment of the present invention in an enlarged manner. Moreover, FIG. 2 is sectional drawing in the II line 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 1 a which is the printing surface.

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

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

The width W _X1 and the depth D _{X1 of} the first pattern 11 are the same at all portions in the longitudinal direction (line length direction). However, the present invention is not limited to this, and one or both of the width W _X1 and the depth D _X1 of the first pattern 11 may be in 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 target print pattern is formed on the print target from the ink composition in which the second pattern 12 is filled in the first pattern 11, the distortion such as deformation, rubbing, and loss of the print pattern is caused. It is for suppressing. Then, the ink composition filled in the second pattern 12 does not form an unintended print pattern on the print target, and the second pattern 12 corresponds 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 the longitudinal directions thereof coincide with each other. That is, one second pattern 12 is formed on both sides 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 of width W _Y1 and depth D _Y1 .
The second pattern 12 has a shape in which one side of a square 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 width W _Y1 and the depth D _{Y1 of} the second pattern 12 are the same at all portions in the longitudinal direction (line length direction). 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 D _Y1 ] <[D _X1 Average value]). In the present specification, the “average value of the depth of the first pattern” means the “line length direction of the first pattern” when the first pattern is in the form of a line as shown here. Mean the average value of the depth of the first pattern in Similarly, the “average value of the depth of the second pattern” means, as shown here, “the second pattern in the line length direction of the second pattern, when the second pattern is in the shape of a line (line)”. Means the average value of the depth.

In the printing plate 1, the average value of the depth D _Y1 of the second pattern 12 is not more than 0.5 times the average value of the depth D _X1 of the first pattern 11 ([average value of D _Y1 ] ≦ 0. 5 × [average value of D _X1 ]) is preferable, and a value of 0.3 times or less of the average value of depth D _X1 of the first pattern 11 ([average value of D _Y1 ] ≦ 0.3 × [ The average value of D _X1 ] is more preferable, and a value of not more than 0.1 times the average value of the depth D _X1 of the first pattern 11 ([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 has such a relationship with respect to the depth D _X1 of the first pattern 11, the printing plate 1 suppresses the disturbance of the printing pattern to achieve the target printing The pattern can be formed with higher accuracy.

The depth D _X1 of the first pattern 11 is not particularly limited as long as the above condition is satisfied with the depth D _Y1 of the second pattern 12, but it is preferably 5 to 20 μm, and is 6 to 17 μm. Is more preferable, and 7 to 14 μm is particularly preferable. The printing plate 1 is particularly suitable for the formation of 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, The thickness is more preferably 20 μm, still more 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 The thickness is more preferably 2 μm, and particularly preferably 0.1 to 1 μm.

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

In the printing plate 1, the depth D _Y1 of the second pattern 12 and the width W _Y1 of the second pattern 12 are both within the above-described numerical range, from the viewpoint that the effect of suppressing the disturbance of the printing pattern is further _enhanced. 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 the present specification, “the first pattern and the second pattern are present in the vicinity of each other” means the ink composition filled in the first pattern by 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 above-described arrangement relationship between the first pattern 11 and the second pattern 12 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, because the effect of suppressing the disturbance of the printing pattern of the printing plate 1 is further enhanced. it can.
The lower limit of the distance L ₁ is not particularly limited, is preferably 10 [mu] m. 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” means the surface on which the first pattern and the second pattern of the printing plate are formed (the surface 1 a of the printing plate 1 in FIGS. 1 and 2). Means the distance between the opening of the first pattern (edge) and the opening of the second pattern (edge).

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.

  The thickness of the area of the printing plate 1 where the first pattern 11 and the second pattern 12 are not formed is not particularly limited, but is preferably 0.1 to 0.5 mm, and 0.2 to 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. And the printing plate 1 can be manufactured by forming the 1st pattern 11 and the 2nd pattern 12 of the target shape by methods, such as an etching and electroforming, with respect to the plate of such a material, for example. .

Although only one first pattern is shown in FIGS. 1 and 2, 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 adjacent first patterns is The thickness is preferably 200 μm or more, more preferably 500 μm or more, still more preferably 800 μm or more, and particularly preferably 1000 μm or more.
In a printing plate in which the number of first patterns is only 1 or the number of first patterns is 2 or more and the distance between adjacent first patterns is 200 μm or more, the density of the first patterns is particularly large. 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.

  Also, up to this point, as described above, the number of first patterns is only one, or the number of first patterns is two or more, and the distance between adjacent first patterns is far, The case where the first patterns are not close to each other has been described. However, in the printing plate according to the present invention, the number of first patterns is two or more, adjacent first patterns are extremely close to each other, these first patterns are finer, and the filling amount of the ink composition is more There may be few things. In such a printing plate, two or more first patterns existing extremely close to each other can be collectively regarded as one first pattern in a pseudo manner, and such a first pattern may be finer if such first patterns are finer. One pseudo first pattern (first pattern group) can also be said to have a particularly low density in 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. By the distance being equal to or less than the upper limit value, the effects of the present invention can be more remarkably obtained. On the other hand, the lower limit value of the distance is not particularly limited, but is preferably 1 μm in view of the fact that these first patterns can be formed.
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, in the case where the printing plate has three or more patterns having different average depth values corresponding to the first pattern or the second pattern, the average depth 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 has a shape in which one side of a square is removed, that is, two side surfaces and one bottom surface 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. It may also have any of the non-regular surfaces that do not apply. 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 to be difficult to distinguish. In the printing plate according to the present invention, either or both of the first pattern and the second pattern may not have a planar bottom.

FIG. 3 is a schematic enlarged view of the cross-sectional shape of the first pattern or the second pattern different from that shown in FIGS. 1 and 2.
FIG. 3 (a) shows a first pattern or a second pattern in which two side surfaces and one bottom surface are all flat, but this pattern is not shown in 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.
Although FIG.3 (b) has a plane part as a side surface and a bottom surface, the side surface and the bottom surface are connected via a non-plane (curved surface), and the 1st pattern or 2nd pattern of a shape where the boundary of a side surface and a bottom surface is unknown. Is shown.
FIG. 3C shows a first pattern or a second pattern in which the entire surface is constituted by a curved surface in which it 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.
Similarly to FIG. 3 (c), FIG. 3 (d) shows the first pattern or the second pattern which is formed of a curved surface in which it is difficult to distinguish between the side surface and the bottom surface. It is different from c). The curved surface here is composed of only 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 in which the side surface is flat and does not have a 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.

Although FIGS. 1 to 3 show the first pattern and the second pattern in which the shapes in the cross section are symmetrical in the width direction (direction orthogonal to the longitudinal direction) of these patterns, in the present invention, The shape in the cross section of the first pattern and the second pattern may be asymmetric in the width direction.
Further, the first pattern and the second pattern shown in FIGS. 1 to 3 are merely examples in the present invention, and for example, in the first pattern and the second pattern shown in FIGS. It is preferable that the first pattern and the second pattern in the present invention are not smooth surfaces but irregular surfaces having irregular shapes.

  In addition, for example, as shown in FIGS. 3C to 3F, in the case where the depth of the first pattern or the second pattern changes in the width direction (direction orthogonal to the longitudinal direction) of these patterns. As the pattern depth, the largest value is adopted (the depth of the deepest part is adopted as the depth of these patterns).

Moreover, in FIG. 1 and 2, although the shape which planarly viewed from the upper direction of a printing plate is a linear groove is shown as a 1st pattern and a 2nd pattern, the 1st pattern and a 2nd pattern are shown. The entire shape is not limited to this, and can be appropriately set in accordance with the shape of the target print pattern.
The first pattern and the second pattern may have, for example, curved grooves as shown in FIG. 4 when viewed in plan from above the printing plate. In the printing plate 2 shown here, each of the first pattern 21 and the second pattern 22 has 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, each of the first pattern 31 and the second pattern 32 is a recess having an elliptical shape in plan view.
The printing plates 2 and 3 can be configured in the same manner as the printing plate 1 shown in FIGS. 1 and 2 except for the points described above.

<< Print Pattern Formation Method >>
The method for forming a printing pattern according to the present invention is a method for forming a printing pattern using the printing plate, and the step of filling the first pattern and the second pattern of the printing plate with an ink composition (hereinafter referred to as “ Filling process) and transferring the ink composition filled in the first pattern to the printing object without transferring the ink composition filled in the second pattern to the printing object Forming a print pattern on the print object from the ink composition transferred from the first pattern (hereinafter referred to as “print pattern formation” (hereinafter, may be abbreviated as “transfer process”) And 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 of forming a print pattern according to the present invention. Here, a method of forming a print pattern when using the printing plate 1 shown in FIGS. 1 and 2 will be described, but in the case of the printing plate according to the present invention, the 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 step of filling the first pattern 11 and the second pattern 12 of the printing plate 1 with the ink composition 9 is performed.
The filling of the ink composition 9 may be performed by a known method. For example, after the ink composition 9 is supplied to a predetermined place on the surface 1 a 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 in the first pattern 11 and the second pattern 12 by spreading the supplied ink composition 9 on the surface 1 a 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, as the transfer step, after transferring the ink composition filled in the first pattern onto a blanket, the step of further transferring the ink composition on the blanket to a print target will be described.

  The blanket may be one known in the art, and examples of the material include rubber-based materials such as silicone resin.

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

That is, in the printing plate 1, when the first pattern 11 and the second pattern 12 exist in the vicinity of each other, in the state where the ink composition 9 is filled, the area where the patterns are present is filled in these patterns. The vapor pressure of the solvent volatilized from the ink composition 9 is relatively high, and the drying with the passage of time of the ink composition 9 filled in the first pattern 11 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, a solvent indicated by reference numeral 90 is a solvent which has volatilized.
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 presumed that the image is transferred onto the blanket 8 without any defects such as defects.
In the present specification, an ink composition whose composition has changed after filling the printing plate, such as one in which a part of the solvent is volatilized, is also referred to as an ink composition before the formation of the printing pattern.

  Here, the case where the ink composition 9 filled in the second pattern 12 is similarly transferred onto the blanket 8 without any abnormality such as deformation, rubbing, or loss is shown. In the invention, the ink composition 9 filled in the second pattern 12 may not be transferred at all on the blanket 8. This is because, for example, as is apparent 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, but the ink composition 9 transferred from the second pattern 12 is the print object 7. Remain on the blanket 8 without being transferred to the The reason is presumed as follows.

That is, as described above, the ink composition 9 transferred from the first pattern 11 to the blanket 8 is prevented from drying because the vapor pressure of the solvent is high, 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. The reason is that the passage of the solvent inside is suppressed by this, and the state in which the content of the solvent is high may be maintained. In this case, the drying of the entire layer (film) of the ink composition 9 is further suppressed.
Although the solvent in the ink composition 9 is absorbed by the blanket 8 depending on the material of the blanket 8, the effect of suppressing the drying of the ink composition 9 as described above is much larger.

  As described above, the ink composition 9 transferred from the first pattern 11 to the blanket 8 has a large content of solvent, and drying, that is, solidification is suppressed, and thus a state suitable for transfer is maintained. There are no factors that inhibit transcription. Therefore, the ink composition 9 transferred onto the blanket 8 is printed from above the blanket 8 without any abnormality such as deformation, rubbing, and defects as in the case of transfer from the first pattern 11 onto the blanket 8. It is 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 clear from FIG. 6 (b). As described above, the solvent contained in the thin layer (film) of the ink composition 9 is easily volatilized, and the solvent in the ink composition 9 is absorbed by the blanket 8 depending on the material of 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 to increase the adhesive strength with the blanket 8, so that the ink composition 9 is not transferred to the printing object 7 and thus the blanket It is presumed to remain on 8th.

  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, for example, a method of attaching to the adhesive tape and removing it.

<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 print pattern 9 ′ can be formed, for example, by drying the ink composition 9, and the drying conditions can be arbitrarily adjusted. Disturbance such as deformation, rubbing, and defects is suppressed in the formed print pattern 9 ′, and the target pattern is realized with high accuracy. Further, 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, and so on. Unintended unnecessary printing patterns are not formed.

  Although FIG. 6 shows a method of 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, as described above, The ink composition 9 filled in the second pattern 12 may not be transferred onto the blanket 8 at all. A cross-sectional view for explaining the method of forming a print pattern according to the present invention in such a case is shown in FIG. FIG. 8B shows that the ink composition 9 filled in the second pattern 12 is not transferred onto the blanket 8 at all.

The method of forming the printing pattern shown in FIG. 8 is the same as the method of forming the printing pattern 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 A solvent containing a solvent having a lower boiling point, one containing a thickener or the like to increase the viscosity, or the like that can suppress the transfer when the thickness is thin may be used.
Also in the present embodiment, the formed printed pattern 9 'is suppressed from being distorted, rubbed, or otherwise disturbed, and the target pattern is realized 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 method for forming a print pattern shown in FIG. 8, the transfer step further transfers the ink composition on the blanket after transferring the ink composition filled in the first pattern onto the blanket. It is a process. In the 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 target. 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 how the ink composition filled in the first pattern is directly transferred to the print target 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 suppressed from being distorted, rubbed, or otherwise disturbed, and the target pattern is realized with high accuracy. In addition, as described above, the ink composition 9 filled in the second pattern 12 is not transferred to the print target 7 and remains in the second pattern 12. A simple print pattern is not formed.

  In the method of forming a printing pattern according to the present invention, as described above, by using a specific printing plate, the printing pattern can be formed even in a region where the density of the printing pattern is low without the formation of unnecessary printing patterns. It is possible to form the target print pattern with high accuracy by suppressing the disturbance. For example, in the method described in “Japanese Patent Application Laid-Open No. 2001-353973” (Patent Document 1) described above, printing in a region close to the edge (edge) on the printing object corresponding to the vicinity of the outer periphery 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 reliably suppressed in the entire region where the density of the print pattern is low.

  The method for forming a print pattern according to the present invention has the advantage that when using a blanket, the durability of the blanket during repeated use 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 of using a printing plate which is the same as that shown in FIGS. 1 and 2 is shown except that the depths of the patterns are all the same.
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 print target (not shown), and the ink composition 9 disappears from above the blanket 8 as shown in FIG. 10B. 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 sites 8a in the blanket 8 have substantially 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 in the blanket 8 overlaps with the previous transfer position (that is, the absorption site 8a of the solvent of the blanket 8). In this case, the solvent is absorbed again at the same site 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.10 (c), when the transfer position of the ink composition 9 from the printing plate in the blanket 8 overlaps with the transfer position of the last time, for example, all the recessed parts of a printing plate are the same. If the ink composition 9 is transferred from the printing plate to the blanket 8 under the same conditions as the previous time, all the transfer positions of the ink composition 9 are the previous transfer position if they are arranged in the same direction in the pattern. And 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 with the previous transfer position, so that a part of the transfer position is performed. May overlap with the previous transfer position.

  When a conventional printing plate is used, as a method for suppressing such a decrease in durability of the blanket 8, for example, as shown in FIG. When the transfer is repeated, there is a method of performing transfer along the surface of the blanket 8 while shifting the position so as not to overlap with the transfer position up to the previous time (that is, the solvent absorption site 8a of the blanket 8). Be However, in this method, as apparent from FIG. 10 (d), since the distance for shifting the transfer position in the blanket 8 is as large as three solvent absorption sites 8a, the number of times the blanket 8 is used is 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 of using the printing plate 1 shown in FIGS. 1 and 2 as an example. FIG. 11 is a cross-sectional view schematically showing the state of a blanket 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. 6 (b).

  Next, the ink composition 9 on the blanket 8 is further transferred to a print target (not shown), and the ink composition 9 disappears from above 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, may be separately described 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. 11C, 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 absorption site 8a. 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 having a small solvent content transferred from the second pattern 12 overlaps the solvent absorbing 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 the solvent absorbing portion 82a corresponding to the transfer position having a low degree of swelling, but the solvent is absorbed again at this portion 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. And, naturally, the degree of swelling is also low in the portions where the transfer positions do not overlap. As described above, by transferring the ink composition 9 by shifting the ink composition 9 by one solvent absorbing portion 8 a along the surface of the blanket 8, a low degree of swelling can be maintained in the blanket 8, and the durability of the blanket 8 is improved. It is possible to suppress the decline. Moreover, since the distance for shifting the transfer position is only one solvent absorption site 8a, the number of times of use of the blanket 8 can be increased more than in 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 printing 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 of forming a printing pattern according to the present invention is highly effective in suppressing the disturbance of the printing pattern in the area where the density of the printing pattern is low, and is particularly suitable for forming a fine linear pattern as the printing pattern. It is. From such a point of view, the method of forming a printed pattern according to the present invention is particularly suitable for forming a pattern of a conductor (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, still more preferably 10 μΩ · cm or less, and 7 μΩ · cm. 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 measures and it can calculate as volume resistivity rho (ohm * cm) by a formula "rho = RxA / L."
Also, the volume resistivity of the conductive pattern can be calculated, for example, by measuring the surface resistivity and thickness of the conductive pattern and multiplying them by these values. The thickness of the conductive pattern can be determined by a known method such as a method using a laser microscope.

  A laminate formed by using various substrates as print objects and forming a conductive pattern as the print pattern on this substrate is, for example, an electronic device such as a data transmitter / receiver, communication device, transparent conductive film, etc. It 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 transmission / reception body by adopting the same configuration as a known data transmission / reception body except this point. For example, in such a laminate, a noncontact data transmitter / receiver can be configured by providing an IC chip electrically connected to the conductive pattern on a substrate to form an antenna portion.

  In addition, the laminated body, which constitutes at least a part of the casing (exterior material) with the base material and is the antenna unit, adopts a configuration similar to 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 directly formed on the exterior material (base material). 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 equipped with the said electroconductive pattern as ultra-fine wiring or ultra-thin wiring can be made into a transparent conductive film by employ | adopting the structure similar to a data transparent conductive film well-known 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 such a low density region of the conductive pattern.
Moreover, in the transparent conductive film used for the touch panel, for example, when improving the light transmittance, it is conceivable to widen the interval between the conductive patterns, but in the present invention, the density of such conductive patterns is It is also particularly suitable for the formation of conductive patterns in low areas.

  In the laminate, the thickness of the base 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, but preferred examples thereof 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, polyamide imide (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 include synthetic resins such as polyarylate, epoxy resin, melamine resin, phenol resin, urea resin and the like.
Moreover, as a material of the said base material, ceramics, such as glass and a silicon | silicone other than the above, and paper can be illustrated.
The substrate 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 the substrate comprises a plurality of layers, the plurality of layers may be identical to or different from one another. That is, all layers may be the same, all layers may be different, or only some layers may be different. And when several layers mutually differ, the combination of these several layers is not specifically limited. Here, that the plurality of layers are different from each other means that at least one of the material and 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 thickness of the sum total of each layer be the thickness of said preferable base material.

<Ink composition>
The ink composition used in the method of forming a printing pattern according to the present invention is not particularly limited as long as it contains a component for forming a target printing 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 addition, in this specification, "normal temperature" means the temperature which does not cool or heat especially, ie, the normal temperature, for example, the temperature of 15-25 degreeC etc. are mentioned. 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: saturated aliphatic alcohols such as ethanol and 2-propanol; unsaturated alcohols; halogenated hydrocarbons such as dichloromethane and chloroform; esters such as ethyl acetate, monomethyl glutarate, dimethyl glutarate; diethyl ether, Ethers such as tetrahydrofuran (THF) and 1,2-dimethoxyethane (dimethyl cellosolve); ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; nitriles such as acetonitrile; N, N-dimethylforma 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。）

(Wherein R ′ and R ′ ′ each independently represent 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 which may be substituted on the hydrogen atom of the phenyl group in R ′ and R ′ ′ include, for example, a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, the fat 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 solvent contained in the ink composition may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily adjusted.

  The boiling point of the solvent is preferably 180 ° C. or less, and for example, various solvents having a boiling point of 160 ° C. or less, 130 ° C. or less, 110 ° C. or less, or 80 ° C. or less can be used. By using such a solvent having a boiling point, the effect of suppressing the disorder of the printing pattern is further enhanced.

  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 of the ink composition is equal to or more than the lower limit value, the effect of suppressing the disturbance of the print pattern is further enhanced. In addition, when the content of the solvent of the ink composition is equal to or less than the upper limit value, formation of a target print pattern becomes easier.

  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 one type, or two or more types may be sufficient as the formation component of the said conductor mix | blended, When it is two 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 it is a metal ink composition in which a metal or a forming material of a metal is blended as a forming component of 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, and preferred examples thereof include silver, copper and the like in the case of a single metal.
The metal (single metal or alloy) to be compounded is preferably in the form of particles or fibers (tubes, wires, etc.), more preferably nanoparticles or nanowires, silver nanoparticles, silver nanoparticles Particular preference is given to wires, copper nanoparticles or copper nanowires.
In the present specification, “nanoparticles” means particles having a particle size of 1 nm to less than 1000 nm, preferably 1 to 100 nm, and “nanowires” has a width of 1 nm to less than 1000 nm, preferably It means a wire that is 1 to 100 nm.

The forming material of the metal to be compounded may have any corresponding metal atom (element) and may generate a metal by structural change such as decomposition, metal salt, metal complex, organic metal compound (metal-carbon bond (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 them, 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. The conductive pattern in this case contains the metal as a main component, and the ratio of the metal is high enough to be regarded as apparently consisting only of 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 ratio of the metal 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 weight, 99.2% by weight and 99.1% by weight.

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

  The conductive pattern is formed, for example, by depositing the metal ink composition on a print target such as the substrate and appropriately selecting and performing post treatments such as drying treatment and heating (baking) treatment. 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 a forming material of metal silver or metal silver is blended, and a silver ink composition in which a forming material of metal silver is blended. More preferable.

[Silver carboxylate]
As a forming material of the said metal silver, silver carboxylate which has group represented by a formula "-COOAg" can be illustrated.
In the present invention, one kind of silver carboxylate may be used alone, or two or more kinds may be used in combination. 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 silver carboxylate is not particularly limited.

The silver carboxylate is represented by silver β-ketocarboxylate represented by the following general formula (1) (hereinafter sometimes abbreviated as “β-ketocarboxylate silver (1)”) and the following general formula (4) Or more selected from the group consisting of silver carboxylates (hereinafter sometimes abbreviated as "silver carboxylate (4)").
In the present specification, the description “simple silver carboxylate” is not limited to “silver β-ketocarboxylate (1)” and “silver carboxylate (4)” unless specifically stated otherwise. 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 — ”a group represented by
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 Group hydrocarbon group; 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 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a phenyl group or a 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 ( A group represented by = O) -O- ";
R ⁷ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group, or a phenyl or diphenyl group in which one or more hydrogen atoms may be substituted by 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 linear, branched or cyclic (aliphatic cyclic group), and when it is cyclic, it may be either monocyclic or polycyclic. . 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. As preferable said aliphatic hydrocarbon group in R, an alkyl group, an alkenyl group, and an alkynyl group can be illustrated.

  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 preferable examples of the substituent include a fluorine atom, a chlorine atom, and a bromine atom . Also, 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. And a monovalent group in which the aliphatic hydrocarbon group is bonded 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. And when the number of substituents is plural, these plural substituents may be same or different.
As said aliphatic hydrocarbon group which is a substituent, the thing similar to the said aliphatic hydrocarbon group in R can be illustrated except a point which carbon number is 1-16.

In the phenyl group and the benzyl group in X ¹ , one or more hydrogen atoms may be substituted with a substituent, and 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. And when the number of substituents is plural, these plural substituents may be same or different.

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. groups represented by the formula _{"= CH-C 6 H 4 -NO} 2 " may 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 (OO) —OAg), caproyl acetate silver (CH ₃ (CH ₂ ) ₃ CH ₂ —C (= O) ) -CH ₂ -C (= O) -OAg), silver 2-n-butylacetoacetate (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).

  Silver (beta) -ketocarboxylic acid (1) can reduce more the density | concentration of the raw material and impurity which remain | survive in the conductor (metallic silver) formed by solidification process, such as a drying process and 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.

  Silver β-ketocarboxylate (1) decomposes, for example, at a low temperature of 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 the carbon number is 1 to 19. 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, "methylene group" is not only a group represented by the single formula "-CH _2- " but also one of an alkylene group in which a plurality of groups represented by the formula "-CH _2- " are connected. The group represented by the formula “—CH ₂ —” of

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), silver isobutyrate ((CH ₃ ) ₂ CH-C (= O) -OAg), silver 2-ethylhexanoate (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), oxalic acid 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.

  Similarly to silver β-ketocarboxylate (1), silver carboxylate (4) is a raw material or impurity remaining in a conductor (metallic silver) formed by solidification treatment such as drying treatment or heating (baking) 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 the present invention, one kind of silver carboxylate (4) may be used alone, or two or more kinds thereof may be used in combination. 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 propionyl acetate, silver isobutyryl acetate, silver pivaloyl acetate, silver caproyl acetate, silver 2-n-butylacetoacetate, 2-benzylacetoate 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 It is preferable that it is 1 or more types selected from the group which consists of silver acid and silver malonate.
And, among these silver carboxylates, silver 2-methylacetoacetate and silver acetoacetate are excellent in compatibility with nitrogen-containing compounds (particularly, 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 forming material of the metal silver, particularly when the forming material of the metal silver 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 the reaction of an amine compound having 25 or less carbon atoms with an acid (hereinafter sometimes abbreviated as “an ammonium salt derived from an amine compound”), and ammonia reacts with an acid And at least one selected from the group consisting of ammonium salts (hereinafter sometimes abbreviated as "ammonium salts derived from ammonia"). That is, only one type, or two or more types of nitrogen-containing compounds may be blended, and in the case of using two or more types in combination, the combination and ratio thereof can be arbitrarily adjusted.

(Amine compound, quaternary ammonium salt)
The amine compound has 1 to 25 carbon atoms, and may be any of a primary amine, a secondary amine and a tertiary amine. The quaternary ammonium salt has 4 to 25 carbon atoms. The amine compound and the quaternary ammonium salt may be either linear or cyclic. Further, the number of nitrogen atoms constituting an amine site or an ammonium salt site (for example, nitrogen atoms constituting an amino group (-NH ₂ ) of a 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 dialkylamines, diarylamines, di (heteroaryl) amines and the like in which one or more hydrogen atoms may be substituted by 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.
As preferable said tetraalkyl ammonium halide, dodecyl trimethyl ammonium bromide can be illustrated specifically.

So far, the chain amine compound and quaternary organic ammonium salt have been mainly described, but in the amine compound and quaternary ammonium salt, the nitrogen atom constituting the amine site or the ammonium salt site has a ring skeleton structure ( The heterocyclic compound may be a part of the heterocyclic skeleton structure). That is, the amine compound may be a cyclic amine, and the quaternary ammonium salt may be a cyclic ammonium salt. The ring (a ring containing a nitrogen atom constituting an amine moiety or an ammonium salt moiety) structure at this time may be either monocyclic or polycyclic, and the number of ring members (number of atoms constituting a 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 above-mentioned primary amine, secondary amine, tertiary amine and quaternary ammonium salt, "a hydrogen atom which may be substituted by a substituent" means a nitrogen atom constituting an amine site or an ammonium salt site Is 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. Also, the position of the substituent is not particularly limited.

Examples of the substituent in the amine compound and quaternary ammonium salt, an alkyl group, an aryl group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, trifluoromethyl group (-CF ₃₎ or the like can be exemplified. Here, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be exemplified.

The above-mentioned amine compounds are 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 silver carboxylate, is particularly suitable for increasing the concentration of the silver ink composition, and is particularly suitable 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 n-propylamine hydrochloride, N-methyl-n-hexylamine hydrochloride, N, N-dimethyl-n-octadecylamine hydrochloride and the like, but are not limited thereto. .

(Ammonium salt derived from ammonia)
In the present invention, the ammonium salt derived from ammonia is an ammonium salt formed by the reaction of ammonia with an acid, and as the acid, the same salts as in the case of the ammonium salt derived from the amine compound can be exemplified.
Although ammonium chloride etc. can be illustrated as said ammonium salt derived from ammonia, It is not limited to this.

In the present invention, one of each of the amine compound, the quaternary ammonium salt, the ammonium salt derived from the amine compound and the ammonium salt derived from the ammonia may be used alone, or two or more types may be used in combination. Good. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.
And, as the nitrogen-containing compound, one selected from the group consisting of 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, 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 compounding amount of the nitrogen-containing compound is in such a range, the stability of the silver ink composition is further improved, and the quality of the conductor (metallic 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 is preferably one in which a reducing agent is further blended in addition to the forming material of the metallic silver. 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 preferable that it is a compound (Hereinafter, it may only be abbreviated as "reducing compound").
H-C (= O) -R ²¹ (5)
(Wherein, R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group or 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 a monovalent group formed by bonding the above-mentioned alkyl group in R ^{21 to} an oxygen atom can be exemplified.

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 identical to or different from each other. Each alkyl group has 1 to 19 carbon atoms. However, the total value of carbon number of these two alkyl groups is 2-20.
The alkyl group bonded to the nitrogen atom may be linear, branched or cyclic, 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.

Hydrazine (H ₂ N—NH ₂ · H ₂ O) may be used as the reducing compound.

  The said reducing compound 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.

Preferred examples of the reducing compound include: formic acid (H-C (= O) -OH); methyl formate (H-C (= O) -OCH ₃ ), ethyl formate (H-C (= O) -OCH) Formic acid esters such as ₂ CH ₃ ), butyl formate (H—C (= O) —O (CH ₂ ) ₃ CH ₃ ), etc .; propanal (H—C (= O) —CH ₂ CH ₃ ), butanal (H Aldehydes such as —C (CO) — (CH ₂ ) ₂ CH ₃ ), hexanal (H—C (= O) — (CH ₂ ) ₄ CH ₃ ), etc .; formamide (H—C (= O) —NH ₂ Formamides (groups represented by the formula “HC (= O)-N (-)-”) such as N, N-dimethylformamide (HC (= O)-N (CH ₃ ) ₂ ) 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 preferred. 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 an alcohol is further blended in addition to the forming material of the metallic silver.

  The alcohols 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.

  The alcohol is preferably the above-mentioned acetylene alcohol (2).

  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 be one in which other components other than the forming material of the metallic silver, the nitrogen-containing compound, the reducing agent and the alcohol are blended.
The other components in the silver ink composition can be optionally selected according to the purpose, and are not particularly limited. Preferred examples thereof include saturated aliphatic hydrocarbons which are liquid 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 blending components. The saturated aliphatic hydrocarbon preferably has a carbon number of 15 or less, more preferably 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 using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

The compounding amount of the other components in the silver ink composition may be appropriately selected according to the type of the other components.
For example, when the other component is a saturated aliphatic hydrocarbon, the compounding amount may be selected according to the purpose such as the viscosity of the silver ink composition, but generally, in the silver ink composition, the compounding components The content of the saturated aliphatic hydrocarbon 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.
Even if the ratio of the blending amount of the other components to the total amount of the blending components is 0 mass, that is, the other components are not blended, the silver ink composition sufficiently exhibits its effect.

  In the silver ink composition, all of the compounding components may be dissolved, or some or all of the components may be dispersed without being dissolved, but it is preferable that all of the compounding components be dissolved. The components which are not dissolved are preferably uniformly dispersed.

  In the silver ink composition, any components other than the forming material of metallic silver, such as nitrogen-containing compounds, reducing agents, alcohols, and saturated aliphatic hydrocarbons exemplified above, which are liquid at normal temperature and normal pressure, can be used. Although it can be a solvent, in the above-mentioned silver ink composition after compounding, one that can react with other components to form a structurally identifiable reactant that does not function as a solvent component shall not be treated as a solvent. .

<Method for producing ink composition>
The ink composition can be obtained by blending a component for constituting a target print pattern, a solvent, and other components as necessary. After blending of each component, the obtained composition may be used as it is as an ink composition, or, if necessary, it may be obtained as a result of performing a known purification operation, as an 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 blended by dropping, and by suppressing the fluctuation of the dropping speed, the surface roughness of the metallic silver tends to be further reduced.
The mixing method is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer, a triple roll, a kneader, a bead mill, etc .; a method of adding ultrasonic waves and mixing, etc. What is necessary is just to select suitably from a well-known method.
In the case of uniformly dispersing undissolved components in the silver ink composition, it is preferable to apply the method of dispersing using, for example, the above-mentioned triple roll, kneader or bead mill.

The temperature at the time of compounding is not particularly limited as long as each compounded component is not deteriorated. 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.
Also, 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 further be 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 at the time of printing.

Carbon dioxide may be supplied at any time during production of the silver ink composition.
And, in the present invention, carbon dioxide is supplied to the first mixture obtained by blending the forming material of the metallic silver and the nitrogen-containing compound, for example, to form a second mixture, and the second mixture may be formed if necessary. The mixture is preferably further blended with the reducing agent to produce a silver ink composition. 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 selected arbitrarily 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, the method of immersing one end of piping in the first mixture, connecting the other end to the carbon dioxide gas supply source, and supplying carbon dioxide gas to the first mixture through the piping can be exemplified. At this time, carbon dioxide gas may be supplied directly from the end of the pipe, but for example, a large number of void portions that can be gas flow paths, such as porous ones, are provided to diffuse the introduced gas. A gas diffusion member that can be released as a minute air bubble may be connected to the end of the pipe, and carbon dioxide gas may be supplied through the gas diffusion member. Alternatively, carbon dioxide gas may be supplied while stirring the first mixture in the same manner as in the preparation of the first mixture. By doing this, carbon dioxide can be efficiently supplied.

  The supply of dry ice (solid carbon dioxide) may be performed by adding dry ice to the first mixture. Dry ice may be added all at once, or may be divided and added stepwise (continuously across a time zone in which addition is not 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.

  Further, in the present invention, it is also preferable to supply carbon dioxide to a mixture containing the metal silver-forming material, an alcohol and a nitrogen-containing compound to produce a silver ink composition. 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 process of the silver ink composition in the pattern forming step may be performed under normal pressure, reduced pressure, or air blowing conditions, under the atmosphere and under an inert gas atmosphere. 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 subjected to a heating (baking) treatment, the conditions may be appropriately adjusted in accordance with the types of the components of the silver ink composition. In general, the heating temperature is preferably 60 to 370 ° C., and more preferably 70 to 280 ° C. The heating time may be adjusted according to the heating temperature, but usually, it is preferably 1 minute to 24 hours, and more preferably 1 minute to 12 hours. Among the forming materials of the metal silver, the silver carboxylate, particularly the silver β-ketocarboxylate (1), for example, is different from the forming material of metal silver such as silver oxide, and a reducing agent known in the relevant field is used Even if not, it decomposes at low temperature. And, reflecting such decomposition temperature, the silver ink composition can form metallic silver at a much lower temperature than that of the conventional one, as described above.

  When the silver ink composition is attached to a substrate having low heat resistance and subjected to heating (baking) treatment, 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 of heat treatment of the silver ink composition is not particularly limited, and may be, for example, heating by an electric furnace, heating by a thermal head of a thermal type, heating by far infrared irradiation, heating by spraying a high heat gas, or the like. The heat treatment of the silver ink composition may be performed under the atmosphere, may be performed under an inert gas atmosphere, or may be performed under humidified conditions. And, it may be performed under normal pressure, under reduced pressure or under pressure.

  In the present specification, “humidification” means that the humidity is artificially increased unless otherwise specified, and preferably the relative humidity is 5% or more. During the heat treatment, the relative humidity of 5% is apparently artificially increased because the treatment temperature is so high that the humidity in the treatment environment is extremely low.

  The relative humidity in the case where the heat treatment of the silver ink composition is performed under humidified conditions is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more, 70% The above is particularly preferable, and it may be 90% or more or 100%. And the heat processing under humidification conditions may be performed by spraying of the high pressure steam heated to 100 ° C 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 steps. For example, in the heat treatment in the first stage, the silver ink composition is mainly dried instead of the formation of metallic silver, and in the second heat treatment, the formation of metallic silver can be exemplified to the end.
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. The heating time may be adjusted according to the heating temperature, but generally, it is preferably 5 seconds to 12 hours, and more preferably 30 seconds to 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. The heating time may be adjusted according to the heating temperature, but usually, it is preferably 1 minute to 12 hours, and more preferably 1 minute to 10 hours.
As described later, when the silver ink composition is attached to a substrate having low heat resistance and subjected to heating (baking) treatment, the heating temperature in the first and second steps of heat treatment is less than 130 ° C. Preferably it is 125 degrees C or less, It is especially preferable that it is 120 degrees C or less.

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-humidifying" means not performing the above-mentioned "humidifying", that is, not to artificially increase the humidity, preferably to make the relative humidity less than 5%. .

When the above-mentioned heat treatment is performed by a two-step method, the heating temperature at the time of heat treatment under the first step of non-humidifying conditions is preferably 60 to 110 ° C., and 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 described later, when the silver ink composition is attached to a substrate having low heat resistance and subjected to heating (baking) treatment, the heat treatment under the first stage non-humidifying condition and the second stage humidifying condition The heating temperature in the heat treatment in 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, in the laminate, the conductive pattern can be formed at a low temperature, and a wide range of materials such as the substrate 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 by way of 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-fold molar amount with respect to silver 2-methylacetoacetate), 3,5-dimethyl-1, so that the liquid temperature is 25 ° C. or less. -Hexyne-3-ol ("Serphynol 61" manufactured by Air Products Japan, hereinafter sometimes abbreviated as "DMHO") (0.04 molar amount relative to silver 2-methylacetoacetate) in this order And mixed 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 the nitrogen-containing compound per mole of the compounding amount of the forming material of metal silver ([mole number of nitrogen-containing compound] / [metal The number of moles of silver forming material]). Similarly, in the case of "reducing agent (molar ratio)", the compounding amount (number of moles) of reducing agent per mole of compounding amount of metal silver forming material ([mole number of reducing agent] / [mol of metal silver forming material] Number]). Similarly, in the case of "alcohol (molar ratio)", the blending amount of alcohol (mole number) per mole of the blending amount of the metallic silver forming material ([mole number of alcohol] / [mole number of metallic silver forming material]) 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 depth (D _X1 ) of the first pattern is 10 μm, the width (W _X1 ) is 5 μm, and the depth (D _Y1 ) of the second pattern is 0.2 μm. The width (W _Y1 ) was 5 μm, and the distance (L ₁ , L ₂ ) between the adjacent first pattern and second pattern was 200 μm. In the printing plate, the first pattern and the second pattern were linear, and their lengths were both 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 subjected to conditions of 200 ° C. and 10 minutes in an oven. By drying, a conductive pattern mainly composed of metallic silver was formed on the surface of the substrate. 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)
The shape of the formed conductive pattern was observed using a laser microscope ("VK-X100" manufactured by Keyence Corporation). The results are shown in Table 3.

(Calculation of volume resistivity)
The line resistance value R (Ω), the cross-sectional area A (cm ² ), and the line length L (cm) were measured for the formed conductive pattern, and the conductive pattern was measured according to the formula “ρ = R × A / L”. The volume resistivity ρ (μΩ · cm) was calculated. The wire resistance value R was measured by a two-terminal method using a digital multimeter ("7352" manufactured by ADCC), and the cross-sectional area A was measured using a laser microscope ("VK-X100" manufactured by Keyence Corporation). . Moreover, thickness was calculated | required at the time of the measurement of the cross-sectional area A about a conductive 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 one in 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 equal to that in Example 1 at the measurable portion.

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 (4)

Having a first pattern and a second pattern for filling the ink composition,
The average value of the depths of the second pattern is smaller than the average value of the depths of the first pattern,
A method of forming a print pattern using a printing plate, wherein the first pattern and the second pattern are present in the vicinity of each other ,
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 a 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. The method for forming a print pattern according to claim 1, wherein the average value of the depths of the second pattern is 0.5 or less times the average value of the depths of the first pattern. The method for forming a printed pattern according to claim 1, wherein a distance between the adjacent first pattern and the second pattern is 200 μm or less. The method for forming a print pattern according to claim 1, wherein the width of the first pattern is 20 μm or less.

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