JP4798439B2 - Manufacturing method of base material with conductor layer pattern, base material with conductor layer pattern, and electromagnetic wave shielding member using the same - Google Patents

Description

  The present invention relates to a conductive substrate for plating, a method for producing the same, a method for producing a substrate with a conductor layer pattern patterned so as to have excellent electrical properties and light transmittance, a substrate with a conductor layer pattern, and a method using the same The present invention relates to an electromagnetic wave shielding member.

  Various methods have been proposed for shielding electromagnetic waves on the walls of public facilities, halls, hospitals, schools, corporate buildings, houses, etc., glass windows, resin panels, display surfaces of displays that generate electromagnetic waves, and the like. For example, a method of applying an electromagnetic shielding coating over the surface to be shielded, a method of bonding a metal foil on the surface to be shielded, an electromagnetic shielding sheet formed by thermally laminating a metal-plated fiber mesh on a resin plate, In general, a method of bonding to a surface, a method of bonding conductive fibers knitted in a mesh shape to a surface to be shielded, and the like are performed.

  Among these, when shielding the electromagnetic wave on the transparent glass surface, the transparent resin panel surface, the display surface of a display such as a cathode ray tube (CRT) or a plasma display panel (PDP), the electromagnetic shielding member is required to be as thin as possible. In addition, an electromagnetic wave shielding member having a metal mesh as an electromagnetic wave shielding layer has become mainstream as a light balance (transparency) and an electromagnetic wave shielding property opposite to this in a balanced manner. .

  As a method for producing an electromagnetic wave shielding member having a metal mesh as an electromagnetic wave shielding layer, Patent Document 1 discloses that a metal electrolyte is used for electrodeposition on an electrodeposition substrate capable of metal electrodeposition in a mesh shape, and then bonded. A method for producing an electromagnetic wave shielding plate by adhesion and transfer to an electromagnetic wave shielding substrate through an agent (hereinafter referred to as a transfer method) is described. The above electrodeposition substrate is formed on a conductive substrate such as a metal plate with a pattern opposite to the mesh pattern made of an insulating film that inhibits electrodeposition. As a result, metal electrodeposition in a mesh shape is possible. It is produced so that a simple electrodeposition portion is exposed. Patent Document 2 also describes a method using an electrodeposition substrate in which a convex conductive mesh layer is formed on an insulating layer support.

  Patent Document 2 discloses a metal layer transfer base sheet for producing a circuit pattern of an electronic component or an electrode pattern of a ceramic capacitor. The metal layer transfer base sheet includes a base metal layer and an electrical insulating layer, and a convex pattern for forming the transfer metal layer by electrolytic plating is formed on the surface of the base metal layer. The layer is formed on the surface of the base metal layer where the convex pattern is not formed. As a method of making a base sheet for transferring a metal layer, an etching resist is first formed on the surface of the base metal layer using a dry film resist or the like in the same pattern as the convex pattern, and is not covered with the etching resist and exposed. The surface of the base metal layer is etched to form a groove, and then the etching resist is removed, and an electrically insulating layer is formed on the entire surface of the etched base metal layer, and then the convex pattern is exposed. A method for polishing an electrically insulating layer is disclosed. At this time, the surface of the electrical insulating layer and the surface of the convex pattern of the base metal layer are arranged on the same plane and are flush with each other. As another example of the manufacturing method, an electrical insulating layer made of a plating resist is formed on the surface of the base metal layer in a reverse pattern (inverted pattern) using a dry film resist or the like to electrically insulate. The electrolytic plating metal layer is formed in a convex pattern on the surface of the base metal layer exposed from between the layers. At this time, a method of making the thickness of the electrolytic plating metal layer thicker than the electrical insulating layer is described. By forming the surface of the electroplated metal layer higher than the surface of the electrical insulation layer, the electrical insulation layer is transferred to the adhesive sheet when the transfer metal layer formed by electroplating on the convex pattern is transferred to the adhesive sheet. It is described that the adhesive sheet can be prevented from being damaged.

JP-A-11-26980 JP 2004-186416 A

The transfer method described in Patent Document 1 can be expected as a method capable of reducing the cost in producing the electromagnetic wave shielding member. The electrodeposition substrate is formed on a conductive substrate such as a metal plate with a mesh pattern made of an insulating film that inhibits electrodeposition. As a result, the electrodeposited portion that can be electrodeposited in a mesh shape is exposed. It is made to make it. When this electrodeposition substrate is used, it can be used repeatedly several times to several tens of times, but there is a problem that it cannot be used several hundred times to several thousand times and does not reach a mass production level. This is because the insulating film forming the mesh pattern on the electrodeposition substrate is subjected to peeling stress by adhesion transfer, and the insulating film is peeled off from the conductive base material after a few repeated uses.
Patent Document 1 describes a method of using an electrodeposition substrate in which a convex conductive mesh layer is formed on an insulating layer support. However, according to this method, the side surface of the conductive mesh is actually used. In addition, metal is electrodeposited, and this becomes resistance to the adhesion transfer of the mesh electrodeposited metal layer, and the mesh pattern cannot be peeled or even if it can be peeled off, the mesh pattern will be broken and the electromagnetic shielding properties will be reduced. The present inventors have confirmed that there is a problem that defects occur.

In Patent Document 2, the surface of the electrically insulating layer and the surface of the convex pattern of the base metal layer are arranged on the same plane and formed on the convex pattern using the metal layer transfer base sheet. When the transfer metal layer is transferred to the pressure-sensitive adhesive sheet, the electrical insulating film on the electrodeposition substrate is subjected to peeling stress by adhesion transfer, and from a conductive base material after a few repeated uses, as in the above description of Patent Document 1. There is a problem that the insulating film is peeled off.
In addition, in Patent Document 2, a transfer metal layer formed on a convex pattern using a metal layer transfer base sheet in which the surface of the convex pattern made of an electroplated metal layer is formed higher than the surface of the electrical insulating layer. When transferring to an adhesive sheet, the transfer metal layer is also plated on the side surface of the convex pattern in the same manner as described above with respect to Patent Document 1, which provides resistance to adhesive transfer of the transfer metal layer, and makes the transfer metal layer convex. There is a problem that the mesh pattern is broken even if it cannot be peeled off from the shaped pattern, or even if it can be peeled off, and the electromagnetic shielding properties are deteriorated. Further, when transferring the metal deposited on the convex conductive mesh layer, if the difference in height between the surface of the electrical insulating layer and the convex pattern is about several μm at the maximum, the adhesive for transfer As in the above description of Patent Document 1, due to the pressure at the time of transfer to the film, the deflection of the base material, etc., the electrical insulating film on the electrodeposition substrate is subjected to peeling stress by adhesive transfer, and can be used repeatedly for a few times. There exists a problem that an insulating film will peel from an electroconductive base material.
In addition, conventionally, a resin or an adhesive is applied or laminated for the purpose of protecting the surface on which the metal mesh of the electromagnetic wave shielding member having the metal mesh as an electromagnetic wave shielding layer exists. Since the metal mesh protrudes in a convex shape on the surface where the metal mesh exists, there is a problem that bubbles are likely to remain.
In addition, it is important to prevent adhesion of foreign matters in the post-transfer process.

In view of such problems, the present invention provides a conductive substrate for plating for producing a substrate with a conductor layer pattern patterned so as to have conductivity or electromagnetic shielding properties with high productivity using a transfer method. And a method for producing the same, a method for producing a substrate with a conductor layer pattern using such a conductive substrate, a substrate with a conductor layer pattern, and an electromagnetic wave shielding member using the same. It is intended.
In addition, the second object of the present invention is to make it easy to prevent foreign matters from adhering in the method for producing a substrate with a conductor layer pattern.
Furthermore, the present invention provides a method for producing a substrate with a conductor layer pattern in which air bubbles hardly remain when a resin, an adhesive, a film, glass, a plastic plate or the like is laminated on the conductor layer pattern of the substrate with a conductor layer pattern. Is the third purpose.

The present invention relates to the following.
1. An insulating layer is formed on the surface of the concave portion at a position lower than the position 0.5 to 5 μm lower than the upper end of the convex portion on the conductive substrate for plating having the convex pattern and the concave portion of the geometrical drawing shape drawn thereby. A step of depositing a metal by electroplating or electroless plating on the convex tip portion of the conductive substrate, and a radiation curable adhesive layer for the metal deposited on the convex tip portion of the conductive substrate. A substrate having a conductor layer pattern, characterized by comprising a step of transferring to another substrate and a step of curing and reacting a radiation curable resin after the time when the metal is bonded to another substrate via an adhesive layer Method.
2. Item 2. The conductor according to Item 1, wherein the position of the uppermost end of the metal transferred through the adhesive layer is 3.5 μm or less in the vertical direction with respect to the position of the uppermost end of the adhesive layer in the vicinity of the metal. The manufacturing method of a base material with a layer pattern.
3. Item 3. The method for producing a substrate with a conductor layer pattern according to any one of Items 1 and 2, wherein the radiation-curable adhesive layer has a thickness of 3 to 50 µm.
4). Item 1 to 3 characterized in that a tack value at 50 ° C. before curing or at the time of transfer of the radiation curable adhesive layer is 20 to 100 gf, and a tack value after curing by irradiation with radiation is 10 gf or less. The manufacturing method of the base material with a conductor layer pattern in any one of.
5. The manufacturing method of the base material with a conductor layer pattern in any one of claim | item 1 -4 whose space | interval of the convex part of the said electroconductive base material is 100 micrometers-1000 micrometers.
6). Item 1 in which the metal is deposited so that the metal thickness is 0.5 to 50 μm at the convex portion of the conductive substrate in the step of depositing the metal on the conductive substrate by electroplating or electroless plating. 6. A process for producing a substrate with a conductor layer pattern according to any one of 5 above.
7). The manufacturing method of the base material with a conductor layer pattern in any one of claim | item 1 -6 whose electroconductive base material is a rotary body (roll).
8). The manufacturing method of the base material with a conductor layer pattern in any one of claim | item 1 -6 whose electroconductive base material is hoop shape.
9. Item 9. The conductor according to any one of Items 1 to 8, which includes a step of blackening the metal pattern deposited on the convex portion of the conductive base material before the step of transferring the metal deposited on the convex portion to the base material. The manufacturing method of a base material with a layer pattern.
10. The manufacturing method of the base material with a conductor layer pattern characterized by including the process of blackening the metal pattern transcribe | transferred to the base material after performing the manufacturing method in any one of claim | item 1 -9.
11. After manufacturing the manufacturing method in any one of claim | item 1 -10, the conductor layer pattern of the base material with a conductor layer pattern is further coat | covered with resin, The manufacturing method of the base material with a conductor layer pattern characterized by the above-mentioned.
12 The base material with a conductor layer pattern manufactured by the method in any one of claim | item 1 -11.
13. A conductive layer pattern made of metal is bonded to the substrate via an adhesive layer, and the position of the uppermost end of the metal is 3 μm or less in the vertical direction with respect to the position of the uppermost end of the adhesive layer in the vicinity of the metal. Item 13. The substrate with a conductor layer pattern according to Item 12, which is located in the position.
14 Item 14. A translucent electromagnetic wave shielding member obtained by bonding a surface having a conductor layer pattern of a substrate with a conductor layer pattern according to Item 12 or 13, to a transparent substrate.
15. Item 14. A translucent electromagnetic wave shielding member obtained by coating the conductor layer pattern of the substrate with a conductor layer pattern according to Item 12 or 13 with a resin.

  According to the present invention, since the surface of the adhesive layer has an appropriate tackiness by using a radiation-curing adhesive for transferring the conductive layer pattern produced on the conductive substrate for plating, the conductor The layer pattern can be transferred to the adhesive layer, and by applying radiation to the adhesive layer, the adhesive layer is cured and the surface of the adhesive layer can be made tack-free. As a result, it is possible to obtain a product with extremely high productivity that also serves to prevent adhesion of foreign matter to the surface of the adhesive layer.

In the present invention, on the surface of the adhesive layer after transferring the conductor layer pattern to the adhesive layer, the conductor layer pattern is buried in the adhesive layer by 50% or more of the thickness of the conductor layer pattern, and transferred to the adhesive layer. moderate unevenness due conductor layer pattern of the conductor layer position of the uppermost adhesive surface after the transfer of the conductor layer pattern by Oh Rukoto at 3.5μm or less with respect to the uppermost of the adhesive layer surface of the conductive layer near of Become flat or flat. Therefore, from the top of the conductor layer pattern, or laminating another layer, when applying a resin or glue, or eliminate entrainment of air bubbles, or to reduce, also, into the opening of the conductive layer pattern Bubbles can be easily defoamed, and as a result, a decrease in light transmittance can be prevented. In addition, it is possible to increase the speed of lamination or coating, thereby improving productivity.

The conductive substrate for plating used in the present invention has an insulating layer in the concave portion, the insulating layer is provided lower than a specific height from the upper end of the convex portion, and the height from the lowermost portion of the insulating layer is a certain level or more. As a result, the problem of peeling off of the insulating layer when repeatedly transferred can be solved, and the lifetime of the conductive substrate for plating can be extended in the production method of the present invention.
Moreover, the said electroconductive base material for metal plating can make the said lifetime especially longer by making an insulating layer into an insulating layer which consists of DLC. The adhesion between the conductive substrate and the insulating layer can be improved by the intermediate layer, whereby the life of the conductive substrate for plating can be further reliably extended.

  According to the production of the substrate with a conductor layer pattern of the present invention, a substrate with a conductor layer pattern excellent in light transmittance can be easily produced, and the substrate with a conductor layer pattern excellent in electromagnetic wave shielding property or conductivity. Can be easily manufactured. Furthermore, such a base material with a conductor layer pattern can be produced with high production efficiency.

  The electromagnetic wave shielding member in the present invention is excellent in light transmittance and electromagnetic wave shielding properties by using a specific conductor layer pattern, and can be produced with high production efficiency.

  The conductive material used for the conductive substrate for plating according to the present invention has sufficient conductivity for depositing a metal on its surface by electroplating, and is particularly preferably a metal. Moreover, it is preferable that the base material is such that the metal layer formed thereon is easily peeled off so that the metal layer formed by electroplating on the surface can be transferred to the adhesive support. . Such a conductive base material is particularly preferably made of stainless steel, chrome-plated cast iron, chrome-plated steel, titanium, a titanium-lined material, or a material having good plating peelability such as nickel.

  Examples of the shape of the conductive base material on which the convex portions are formed include a sheet shape, a plate shape, a roll shape, and a hoop shape. In the case of a roll, a sheet or plate attached to a rotating body (roll) may be used. In the case of a hoop shape, a configuration in which rolls are installed at two to several locations inside the hoop and a hoop-shaped conductive base material is passed through the roll can be considered. Since it is possible to continuously produce a metal foil in both a roll shape and a hoop shape, the production efficiency is higher than that in a sheet shape or a plate shape, which is preferable.

  The convex portion of the conductive substrate corresponds to the conductor layer pattern in the substrate with a conductor layer pattern, and the conductor layer pattern is a pattern so as to have conductivity or electromagnetic shielding properties, more preferably Although it has a light-transmitting pattern, it becomes an electromagnetic wave shielding layer when an electromagnetic wave shielding member is finally produced. The geometric figure of the concave part with respect to this convex part (the geometric figure of the concave part as a planar shape drawn by the convex part) is a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, and a parallelogram. , Squares such as trapezoids, (positive) hexagons, (positive) octagons, (positive) dodecagons, (positive) n-decagons such as dodecagons (n is an integer greater than or equal to 3), circles, etc. The pattern is a combination of a circle, a star, and the like, and these units can be repeated alone or in combination of two or more.

  From the viewpoint of electromagnetic wave shielding, the triangle is most effective. From the viewpoint of visible light transmission, if the number of (positive) n-gons is larger, the aperture ratio of the conductor layer pattern increases with the same line width. The aperture ratio is required to be 50% or more from the viewpoint of visible light transmission, and the aperture ratio of the conductor layer pattern is more preferably 50% or more. The aperture ratio of the conductor layer pattern is determined from the effective area of the electromagnetic shielding material to the conductive layer from the effective area with respect to the effective area of the electromagnetic shielding material (for example, the area that functions effectively for electromagnetic shielding such as the area in which the geometric figure is drawn). It is the percentage of the area ratio minus the area covered.

As a method of forming a geometric figure of a concave portion with respect to a convex portion on a conductive base material, a conductive base material having a smooth surface, for example, a flat conductive base material, from the above geometric figure The method of processing so as to form a concave portion is the simplest.
FIG. 1 is a perspective view showing an example of a conductive base material on which a geometric figure of a concave portion with respect to a convex portion is formed. The example illustrated in FIG. 1 is a square as a geometrical figure of the concave part 2, and the convex part 3 is formed in a lattice shape on the conductive substrate 1 so that the geometrical figure of the concave part 2 becomes a square. .
2 and 3 show the AA cross section of FIG. 1, FIG. 2 shows four types (a) to (d), and FIG. 3 shows one type (e). The cross-sectional shapes of the concave portion 2 and the convex portion 3 are appropriately determined, and the side surface 5 of the convex portion 3 is a slope (in the case of (a), (b)), a curved surface (in the case of (c)), a stepped slope ((d ))) Etc. are arbitrary. Also, the bottom surface of the recess 2 has various shapes. In all of these, the side surface of the convex portion has an inclination angle at least at the tip portion. This inclination angle is α in the figure, and preferably corresponds to 30 ° to 80 °, more preferably 50 ° or more.
The upper surface 4 of the convex portion 3 does not necessarily have to be a flat surface, and the entire upper surface or a part of the upper surface may be deformed from the flat surface. In this case, it is preferable that the upper surface 4 is curved as smoothly as possible. Here, the tip portion of the convex portion means the surface of the convex portion from the most advanced portion of the convex portion to a position 0.5 to 5 μm lower.
The reference surface of the angle α is the upper surface of the convex portion, the horizontal surface or the vertical surface. When an original conductive substrate having a (substantially) uniform thickness is used and a convex pattern is applied to this one surface, the other surface can be used as a reference surface.
It is also possible to place or fix a sample for cross-sectional observation on a horizontal plane or a vertical plane and observe it. The horizontal plane or the vertical plane can be set using an appropriate table or the like.
Further, a flat plate that does not bend can be placed on the conductive base material having the convex portion, and the surface of the flat plate can be used as a reference plane. If the conductive base material is a cylinder, prepare a cylinder (reference cylinder) whose cross section is larger than that of the cylinder, place the reference cylinder sideways, and pass these through the conductive base material into the reference cylinder. It is also possible to overlap the cylinders so that the vertices of the cross-sectional circles of the reference cylinder are horizontal, and the tangent surface in contact with the vertices of the cylinder can be used as the reference surface.
Specifically, the observation of the cross-section of the conductive substrate can be performed with an appropriate magnification of the microscope so that the upper surface of the convex portion can be observed, the other surface (surface) of the conductive substrate can be observed, or , By checking the reference plane so that the reference object can be observed, appropriately increasing the magnification after photography, observing a detailed cross section (cross section with a lower magnification in some cases), and taking a photograph, Measurements regarding the angle α can be made. When checking the reference plane, it is recommended to copy the ruler and other standards at the same time.
The reference plane described above can also be used as a reference plane for measuring thickness, height and width. Further, in many cases, the surface of another base material is not deformed and is easily adopted as a reference surface.
On the other hand, as shown in FIG. 3E, the side surface 5 of the convex portion may be a vertical surface.

The width of the tip portion of the convex portion formed on the conductive base material and the interval between the tip portion of the convex portion are 1 μm to 40 μm in order to make the opening ratio of the conductor layer pattern 50% or more. It is preferable that the center interval (line pitch) of the portions is 100 μm to 1000 μm.
In the present invention, when the center interval (line pitch) of the tip portion of the convex portion cannot be easily determined because the pattern is a complicated figure or a combination of a plurality of figures, the repeating unit of the pattern is used. As a reference, the area is converted into a square area and defined as the length of one side.

  The height of the convex portion 3 formed on the conductive substrate is defined as the height from the most depressed portion of the concave portion 2 to the tip of the convex portion 3. As for the height of the convex part 3, 11 micrometers or more are preferable. This is because the recess has a sufficient depth even if an insulating layer is formed in the recess. Further, the upper limit of the height of the convex portion 3 is preferably 110 μm. As the height of the convex portion is increased, the aspect ratio increases, so that the processing becomes difficult and the processing cost increases. Therefore, the height of the convex portion is particularly preferably 60 μm or less.

Examples of the method for forming the convex portion on the conductive substrate include the following methods.
(1) A portion of the conductive base material where the concave portion should be formed (a portion corresponding to the opening of the conductive layer pattern of the base material with the conductive layer pattern) is directly irradiated with laser light to form a concave portion, and the conductive layer pattern A method of forming a convex portion corresponding to
(2) After conducting a step of forming a geometrical pattern (resist pattern) with a photo-curable resin or a thermosetting resin on a conductive substrate by a photolithographic method or a printing method, Etching method,
(3) There is a method of excavating a portion (a portion corresponding to the opening portion of the conductor layer pattern of the substrate with the conductor layer pattern) where the concave portion of the conductive substrate is to be formed by engraving.
When the material of the conductive substrate is hard, it is preferable to use the method (1) (laser processing method) or the method (2) (etching method) or the like for direct processing. When an excellent material is used, it can be easily processed by the method (3) (engraving method). At this time, after processing, a hard plating such as chrome is applied to the surface to increase the strength. it can.

In the method (2), when a printing method is used, various methods can be used as a resist pattern printing method. For example, screen printing, letterpress printing, letterpress offset printing, letterpress reversal offset printing, intaglio printing, letterpress printing, ink jet printing, flexographic printing, and the like can be used. As the resist, a photocurable or thermosetting resin can be used.
In addition, when using the photolithographic method, a dry film resist or the like is laminated, a mask is attached, exposed, developed, and then a resist film etching process can be performed. After drying or pre-curing, the resist film can be subjected to an etching process after a mask is attached, exposed and developed. If the patterning can be performed by irradiating the photocurable resin with active energy rays through a mask, the mode is not limited. From the viewpoint of productivity, the method of laminating a dry film resist and exposing it through a mask when the size of the plate is large or when it is produced by roll-to-roll (Roll-to-Roll) Preferably, when processing directly on a plating drum or the like, a method of directly exposing with a laser or the like without passing through a mask after pasting a dry film resist or applying a liquid resist is preferable.
Moreover, the etching of the conductive substrate in the method (2) can be performed using an etching solution. There are various types of etching liquids depending on the material of the conductive metal, and since etching liquids are commercially available for the respective metals, they can be used. For example, if the conductive metal is stainless steel, it is common to use ferric chloride, and if it is titanium, a hydrofluoric acid-based etching solution is often used. Regarding the etching of stainless steel, a liquid having a specific gravity of ferric chloride in the range of 40 ° Be (Baume) to 60 ° Be (Baume) is preferably used. If the specific gravity is low, the etching speed is fast, but the side etching becomes large, so the concave portion tends to become shallow. Conversely, if the specific gravity is high, the etching speed is slow, but the side etching is small, and the concave portion tends to be deep. . Therefore, the specific gravity of the etching solution is more preferably 45 ° Be (Baume) to 50 ° Be (Baume). Moreover, since etching speed will fall and productivity will fall when etching temperature is low, it is preferable that it is 40 degreeC or more. Furthermore, if the etching temperature exceeds 60 ° C., the corrosiveness of the etching solution increases, so that the equipment investment such as making the etching tank made of titanium increases. Therefore, the etching temperature is preferably 60 ° C. or less.
The remaining resist can be stripped using a stripping solution or the like after the conductive substrate is etched.

The conductive base material for plating in the present invention is covered with an insulating layer with its concave portion remaining partly.
When the conductive substrate for plating is plated, the plating grows isotropically, and therefore deposits so as to cover the insulating layer in the vicinity of the exposed portion of the convex portion. Plating that covers the insulating layer causes stress to be applied to the insulating layer every time it is peeled and transferred. Therefore, when an insulating layer is formed on the entire surface of the concave portion, the stress applied to the insulating layer during transfer is greatest in the vicinity of the exposed portion of the convex portion. The stress applied to the layer can be reduced, and as a result, the lifetime of the electroconductive substrate for plating in which the concave portion is covered with the insulating layer can be improved. If the tip of the convex part is exposed too little, the effect of improving the life is small. The distance from the leading edge of the convex portion to the position 0.5 to 5 μm lower is preferable, and the position to the position 0.5 to 3 μm lower is still more preferable.

  In addition, in order to extend the life of the convex pattern, when transferring the metal deposited on the exposed portion of the convex part to another base material, the adhesive surface of the other base material and the concave part of the conductive base material are transferred. It is preferable to reduce contact of the formed insulating layer. Therefore, it is preferable that the height of the convex portion after applying the insulating layer is sufficient. The thickness of the insulating layer is preferably in the range of 1 μm to 10 μm. When the insulating layer is too thick, the time for forming the insulating layer becomes long, so that the working efficiency is lowered. In addition, if the insulating layer is too thin, the adhesion between the insulating layer and the conductive substrate is reduced, and pinholes are likely to be generated. Become.

The structure of the conductive substrate for plating having an insulating layer will be described with reference to the drawings. FIG. 4 is a cross-sectional view showing an example of a conductive substrate having a pattern of convex portions and a concave portion having a geometric diagram shape drawn thereby according to the present invention. However, the shape of the recess will be described with reference to FIG. In FIG. 4, three forms of (a), (b), and (c) are shown. In any case, the conductive substrate 1 has a concave portion 2 with respect to the convex portion 3. An insulating layer 6 is formed in the concave portion 2, and the insulating layer 6 is formed along the side surface 5 of the convex portion, but is not formed at the tip portion of the convex portion 3, and therefore, the convex portion The tip is exposed.
In the figure, h ′ is the height of the convex portion described above. h is the height of the convex portion after applying the insulating layer to the concave portion (hereinafter referred to as “insulating height”). t indicates the thickness of the insulating layer. The height h ′ of the convex part is preferably 11 μm to 110 μm, and more preferably 60 μm or less. The insulation height h is preferably 10 to 100 μm, and t is determined such that h ′ is smaller than h, but is preferably 10 μm or less. It is preferable that the thickness is 1 to 10 μm at the end portion. Further, the tip portion of the convex portion is exposed. As for the degree of exposure of the tip portion of the convex portion, the width d is preferably 1 to 40 μm, and the distance (height direction) s from the tip of the convex portion is preferably 0.5 to 5 μm, More preferably, it is 0.5-3 micrometers. Because of this distance s, the stress applied to the insulating layer at the time of peeling can be reduced.
The insulating layer is preferably a thin film insulating layer, and preferably has a uniform thickness in order to eliminate non-uniformity in strength.
FIG. 5 is a cross-sectional view showing an example of a conductive substrate having a pattern of convex portions and a concave portion of a geometric diagram drawn by the pattern in the present invention.
As shown in FIG. 5, when the side surface of the convex portion is a vertical surface, the insulating layer is applied to the concave portion in the above-described manner, and the tip portion of the convex portion is exposed. .
If the insulation height h is too low, the transfer substrate contacts the conductive substrate during transfer and damages the transfer substrate, or the transfer substrate is provided with an adhesive surface on the conductive substrate. Since it becomes easy to come into contact with the layer and a peeling stress is applied to the insulating layer, the insulating layer may peel off when repeatedly used.

であることが好ましく、ｄ_１０は０．８３９×ｈ_１０以上であることがより好ましい。
図６（ａ）では、導電性基材の凸部３として、断面が台形上のものとして模式的に図示したが、（ｂ）に示すように凸部３の表面が凸凹であってもよい。また、絶縁層の表面は、（ａ）では平面の組み合わせとして模式的に図示されているが、これも（ｂ）に示すように凹凸のある面の組み合わせであってもよい。なお、図６では、上下方向を強調して引き延ばし気味に図示してある。
また、図６中、前記第２の位置は、先端部分の側面に位置するように図示されているが、場合により、第２の位置が凸部の上面に位置していてもよい。 FIG. 6 is a cross-sectional view showing an example of the vicinity of the tip portion of the convex portion of the conductive substrate in the present invention. In FIG. 6, the tip portion of the convex portion 3 is exposed, and the side surface 5 is covered with an insulating layer 6. It is preferable that at least the exposed portion of the convex portion 3 does not increase in width as it advances in the tip direction, and as a whole, the width is smaller at the upper portion than at the lower portion of the convex portion. The exposed portion of the convex portion is near the end of the insulating layer, for example, the end of the insulating layer on the side surface of the convex portion (first position) and the inner side in the width direction by an amount corresponding to 10% of the exposed width of the convex portion. The relationship between the distance d _{10 in} the width direction between the first position and the second position with respect to h ₁₀ in the height direction distance from the position of the convex surface (second position) in FIG. _{relationship)} d _{10 / h} 10 width _{d 10} to the height _{h 10} is preferably equivalent to 30 ° to 80 ° at an angle, and more preferably 50 ° or more.
D ₁₀ is

It is preferable that d ₁₀ is 0.839 × h ₁₀ or more.
In FIG. 6A, the convex portion 3 of the conductive base material is schematically illustrated as having a trapezoidal cross section, but the surface of the convex portion 3 may be uneven as shown in FIG. 6B. . Moreover, although the surface of the insulating layer is schematically illustrated as a combination of planes in (a), it may be a combination of uneven surfaces as shown in (b). In FIG. 6, the vertical direction is emphasized and is shown to be stretched.
In FIG. 6, the second position is illustrated so as to be positioned on the side surface of the tip portion. However, the second position may be positioned on the upper surface of the convex portion depending on circumstances.

When the side surface of the convex portion has an inclination as described above, the plating (metal) deposited by electroplating on the exposed portion of the convex portion of the conductive base material for plating is easier than when it is not, It can be peeled off and transfer can be performed smoothly.
In addition, when plating is applied to the conductive substrate, the plating grows isotropically, so if the convex side surface of the conductive substrate is also exposed, plating is deposited there, but during the transfer, When the transfer substrate is peeled after bringing the adhesive surface of the transfer substrate into contact with the plating, if the stress is applied to the plating layer in an oblique direction, the peel will occur if the angle of the convex portion exceeds 80 °. During (transfer), the resistance becomes too large, and transfer failure may occur. From this, the angle of the convex portion is preferably in the range of 30 ° to 80 °, more preferably 50 ° to 80 °.

As the insulating material for the insulating layer used in the present invention, a material having high adhesion to metal and strong chemical resistance is preferably used. In the step of electroplating or electroless plating, a material strong against both acid resistance and alkali resistance is particularly preferable because it is immersed in a pretreatment solution or a plating solution. Examples of such resins include aniline formaldehyde resin, urea formaldehyde resin, phenol formaldehyde resin, ligrin resin, xylene formaldehyde resin, xylene formaldehyde resin, melamine formaldehyde resin, epoxy resin, urea resin, aniline. Resins, melamine resins, phenol resins, formalin resins, metal oxides, metal chlorides, oximes, alkylphenol resins and the like are used, and these are self-curing (a curing catalyst may be used).
As the thermosetting resin, one using a curing agent can be used. Examples of such a resin include a resin having a functional group such as a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an unsaturated hydrocarbon group, and a functional group such as an epoxy group, a hydroxyl group, an amino group, an amide group, a carboxyl group, and a thiol group. Some are used in combination with a curing agent having a group or a curing agent such as a metal chloride, isocyanate, acid anhydride, metal oxide, or peroxide. In addition, for the purpose of increasing the curing reaction rate, additives such as general-purpose catalysts can be used. Specific examples include curable acrylic resin compositions, unsaturated polyester resin compositions, diallyl phthalate resins, epoxy resin compositions, polyurethane resin compositions, and the like. Examples of the method for forming the insulating layer include brush coating, spray coating, and dipping, and then scraping off the resin with a squeegee or blade, followed by drying.

Furthermore, as the insulating material, an electrodeposition paint may be used because of the uniformity of the film, the ease of formation, and the low environmental burden.
The electrodeposition paint can be used in any known cationic type or anionic type, and here, an example of the electrodeposition paint that can be used is shown.
Cationic electrodeposition coatings include cathodic deposition type thermosetting electrodeposition coatings prepared by preparing pastes of resins with basic amino groups, neutralizing them with acids, and then making them water-soluble (dispersed in water). Is done. The cationic electrodeposition coating is applied using the conductive substrate (object to be coated) as a cathode.
Resins having basic amino groups include epoxy groups such as bisphenol type epoxy resins, epoxy group (or glycidyl group) -containing acrylic resins, glycidyl ethers of alkylene glycols, epoxidized polybutadiene, and epoxidized products of novolak phenol resins. Polymers obtained by adding an amine compound to the epoxy group (oxirane ring) of the resin or an unsaturated compound having a basic amino group (for example, dimethylaminoethyl methacrylate, N-vinylpyrazole, N-diethylaminoethyl acrylate, etc.) A reaction product of a glycol component containing a tertiary amino group-containing glycol (for example, N-methyldiethanolamine) as a component of a glycol with a polyisocyanate compound, and further a reaction between an acid anhydride and a diamine compound. There By producing include those obtained by introducing an amino group to the resin. Here, the above-described amine compound is a basic amine compound, which is an aliphatic, alicyclic or araliphatic primary or secondary amine, alkanolamine, tertiary amine, quaternary. Examples include amine compounds such as ammonium salts.
Moreover, a crosslinking agent can be mix | blended with a cationic electrodeposition coating material. As the crosslinking agent, a blocked polyisocyanate compound is well known. However, when the coating film is heated (about 140 ° C. or higher), the blocking agent is dissociated and the isocyanate group is regenerated, and in the cationic resin as described above, It is cured by crosslinking reaction with a reactive group with an isocyanate group such as a hydroxyl group.
In addition, for cationic electrodeposition paints, pigments (colored pigments, extender pigments, rust preventive pigments, etc. The amount of pigment is preferably 40 parts by weight or less per 100 parts by weight of resin solids), hydrophilic solvent, water, added An agent or the like can be blended as necessary.
The cationic electrodeposition paint is preferably diluted with deionized water or the like so that the solid content concentration is about 5 to 40% by weight, and the pH is preferably adjusted within the range of 5.5 to 8.0. Cationic electrodeposition paints using the cation type electrodeposition paint thus prepared can usually be carried out using the substrate as a cathode under conditions of a bath temperature of 15 to 35 ° C. and a load voltage of 100 to 400V. In general, the baking temperature of the coating film is suitably in the range of 100 to 200 ° C.

The anionic electrodeposition paint is preferably an anodic deposition electrodeposition paint based on a resin having a carboxyl group, neutralized with a basic compound, and water-solubilized (water-dispersed). Painted with the (coating object) as the anode.
As resins having carboxyl groups, maleated oil resins obtained by adding maleic anhydride to drying oils (such as linseed oil, dehydrated castor oil, tung oil), and anhydrous in polybutadiene (1,2-type, 1,4-type, etc.) Maleated polybutadiene added with maleic acid, resin obtained by adding maleic anhydride to unsaturated fatty acid ester of epoxy resin, high molecular weight polyhydric alcohol (molecular weight of about 1000 or more, epoxy resin partial ester and styrene-allyl alcohol copolymer) And the like), resins obtained by adding polybasic acids (trimellitic anhydride, maleated fatty acids, maleated oils, etc.), carboxyl group-containing polyester resins (including those modified with fatty acids), carboxyl group-containing acrylic resins , Polymerizable unsaturated monomers containing glycidyl groups or hydroxyl groups and unsaturated fats Examples thereof include resins obtained by adding maleic anhydride or the like to a polymer or copolymer formed using a reaction product with an acid, and the carboxyl group content is generally about 30 to 200 in terms of acid value. A range is suitable.

  Moreover, a crosslinking agent can be mix | blended with an anion type electrodeposition coating material. As a crosslinking agent, low molecular weight melamine resins, such as hexakis methoxymethyl melamine, butoxylated methyl melamine, and ethoxylated methyl melamine, can be used as needed. Furthermore, anionic electrodeposition paints include pigments (colored pigments, extender pigments, rust preventive pigments, etc. The amount of pigment is preferably 40 parts by weight or less per 100 parts by weight of resin solids), hydrophilic solvents, water Additives can be blended as necessary.

  For the anionic electrodeposition coating, it is preferable to adjust the solid content concentration to about 5 to 40% by weight with deionized water or the like, and maintain the pH in the range of 7 to 9 for use in anion electrodeposition coating. Anionic electrodeposition coating can be carried out according to a conventional method, and for example, it can be carried out with the object to be coated as an anode under conditions of a bath temperature of 15 to 35 ° C. and a load voltage of 100 to 350 V. The anion electrodeposition coating film can be cured by heating in the range of 100 to 200 ° C., preferably 140 to 200 ° C. in principle. However, when an air-dried unsaturated fatty acid-modified resin is used, it is dried at room temperature. It can also be made.

  Furthermore, as the insulating layer used in the present invention, the insulating layer has an insulating property among materials mainly composed of carbon, for example, a carbon thin film similar to diamond, so-called diamond-like carbon (hereinafter referred to as a DLC thin film). It can also be made of a material. The DLC thin film is particularly preferable because it can be etched with oxygen plasma and has excellent chemical resistance.

As a method for forming the DLC thin film, a dry coating method such as a physical vapor deposition method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method such as a plasma CVD method can be adopted. A plasma CVD method using a high frequency capable of controlling the film temperature from room temperature is particularly preferable.
In order to form the DLC thin film by the plasma CVD method, a hydrocarbon-based gas is preferably used as a carbon source as a raw material. For example, alkane gases such as methane, ethane, propane, butane, pentane, hexane, alkene gases such as ethylene, propylene, butene, pentene, alkadiene gases such as pentadiene, butadiene, acetylene, methylacetylene, etc. Alkyne gases, aromatic hydrocarbon gases such as benzene, toluene, xylene, indene, naphthalene and phenanthrene, cycloalkane gases such as cyclopropane and cyclohexane, cycloalkene gases such as cyclopentene and cyclohexene, methanol And alcohol gases such as ethanol, ketone gases such as acetone and methyl ethyl ketone, and aldehyde gases such as methanal and ethanal. The said gas may be used independently and may use 2 or more types together. Also, a mixture of the above-mentioned carbon source and hydrogen gas as a raw material gas containing carbon and hydrogen as elements, and a mixture of the above-described carbon source and a compound gas consisting of only carbon and oxygen, such as carbon monoxide gas and dioxide gas. , A mixture of a compound gas composed of only carbon and oxygen, such as carbon monoxide gas and carbon dioxide gas, and a hydrogen gas, a compound gas composed of only carbon and oxygen, such as carbon monoxide gas and carbon dioxide gas, and oxygen Examples thereof include a mixture with gas or water vapor. Further, these source gases may contain a rare gas. The rare gas is a gas composed of an element belonging to Group 0 of the periodic table, and examples thereof include helium, argon, neon, and xenon. These rare gases may be used alone or in combination of two or more.

The insulating layer may be formed entirely by the above-described insulating DLC thin film, but it improves the adhesion of the DLC thin film to a conductive substrate such as a metal plate, thereby improving the durability of the insulating layer. In order to further improve, it is preferable to insert an intermediate layer composed of one or more components selected from Ti, Cr, W, Si, nitrides or carbides thereof, or the like, between the two.
The Si or SiC thin film has excellent adhesion to, for example, a metal such as stainless steel, and also forms SiC at the interface with the insulating DLC thin film laminated thereon to improve the adhesion of the DLC thin film. Has the effect of improving.
The intermediate layer can be formed by the dry coating method as described above.
The thickness of the intermediate layer is preferably 1 μm or less, and more preferably 0.5 μm or less in consideration of productivity. A coating of 1 μm or more is not suitable because the coating time becomes long and the internal stress of the coating film increases.

The manufacturing method of the electroconductive base material for plating in this invention is demonstrated using drawing.
FIG. 7 to FIG. 9 are cross-sectional views showing an example of a process showing a method for producing a conductive substrate for plating. In these, it illustrates using the electroconductive base material which has the cross-sectional shape shown in FIG.2 (c).
First, the photocurable resin layer 7 is formed on both surfaces of the conductive substrate 1 (FIG. 7A). The photocurable resin layer 7 on one surface of the conductive substrate 1 is patterned using a photolithographic method (FIG. 7B). By etching the conductive substrate using the patterned photocurable resin layer 7 as an etching resist, the etched conductive substrate shown in the figure is obtained (FIG. 7C). At this time, the inclination angle of the side surface 5 of the convex portion 2 can be adjusted (at least at the tip portion of the convex portion). The inclination angle can be adjusted by optimizing the specific gravity of the ferric chloride solution, which is an etching solution, and the etching temperature. Next, the etching resist is removed by dipping in an alkaline aqueous solution such as sodium hydroxide or sodium carbonate (FIG. 7D).

Next, an adhesive film 9 capable of peeling off one surface of the conductive substrate 1 is bonded and protected, and the insulating layer 8 is covered on the entire etched surface (FIG. 8E). Thereafter, a mask layer 10 for plasma etching is formed on the insulating layer (FIG. 8F).
Since the insulating layer is not etched at the portion where the mask layer is formed, the mask layer 10 on the insulating layer 8 formed at the tip of the convex portion 3 of the conductive substrate 1 is removed (FIG. 8G )).
This partial removal of the mask layer 10 is removed in consideration of the width of the tip portion exposed by the protrusion 3. When the convex portion has a planar or substantially planar upper surface, it is preferable that the width of the exposed insulating layer is larger than the width of the upper surface (FIG. 8G). Thereby, in the next partial removal of the insulating layer 8, it becomes easy to remove the insulating layer on the side surface portion near the upper surface of the convex portion 3. In particular, when the mask layer 10 is removed by polishing, the result is as shown in FIG.

Next, by performing dry etching on the insulating layer, the insulating layer 8 formed at the tip portion of the convex portion 3 can be removed, thereby exposing the tip portion of the convex portion 3 ((FIG. 9). (H)).
In particular, when plasma etching is performed with oxygen gas, the conductive base material becomes a stopper layer. When the convex portion has a planar or substantially planar upper surface, if the insulating layer in a portion exceeding the width of the upper surface of the convex portion 3 is exposed (FIG. 8G), the insulating layer is dry-etched. The removal extends to the side surface portion of the convex portion, and as a result, it can be exposed to the side surface of the convex portion ((FIG. 9 (h)). Can be done by output.
Next, the mask layer 9 formed on the insulating layer 8 in the recess 3 is removed by chemical immersion or the like. Thus, an example of the electroconductive base material for plating which concerns on this invention can be produced (FIG. 9 (i)).
Further, when an intermediate layer is provided between the insulating layer made of DLC and the conductive base material, when the intermediate layer is made of an organic material, for example, following the removal of the insulating layer made of DLC with the oxygen plasma described above. The intermediate layer can be removed, and a conductive substrate for plating having a structure similar to that shown in FIG. When the intermediate layer is not a material mainly composed of carbon, it is difficult to etch the intermediate layer by oxygen plasma. In this case, the gas is changed according to the material of the insulating layer and the intermediate layer, or If the thickness of the intermediate layer is about 0.5 μm or less, the intermediate layer formed at the tip of the convex portion is removed without increasing the exposed width of the tip of the convex portion by mechanical polishing with a weak force. Is possible.
When the intermediate layer is not etched by oxygen plasma when the DLC thin film is dry etched, the intermediate layer can be dry etched by changing the gas or removed by mechanical polishing. Since the intermediate layer is a thin film, it can be removed by light polishing without thickening the line. In addition, when the intermediate layer is conductive, if the plating deposited by energization can be easily peeled off from the intermediate layer, it is not always necessary to remove the intermediate layer. As such, it can be part of a conductive substrate.

The mask layer in this invention can be divided roughly into an inorganic type and an organic type mask layer.
As the inorganic mask layer, metals such as aluminum (Al), chromium (Cr), nickel (Ni), cobalt (Co), gold (Au), and titanium (Ti) are particularly preferable because of their high resistance to oxygen plasma. Used. These films are formed by thin film forming methods such as sputtering, vacuum deposition, ion beam deposition, CVD, ion plating, electrodeposition, and electroless plating. Among these materials, aluminum (Al) is preferred because it is highly resistant to oxygen plasma, inexpensive, easy to deposit, and soluble in both acidic and basic substances. Used. Since aluminum is conductive, if it is left after dry etching, plating will be deposited on the entire surface of the conductive substrate, so it must be removed. Etching agents for aluminum include sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, dipotassium phosphate, etc. as basic substances, and sulfuric acid, persulfuric acid as acidic substances , Phosphoric acid, hydrochloric acid and salts thereof, etc., which are appropriately selected in consideration of the resistance of the insulating layer.

Further, as an inorganic material having resistance to oxygen plasma, when a wet coating method is used, a metal oxide polymer composed of alkali metal, organopolymetal, organoalkoxy metal, alkoxy metal, modified acetylacetonate metal, etc., inorganic A paint containing a filler and a paint made of silicon compound frit called a ceramic coating can be applied by spraying, dispenser, dipping, roll, spin coating or the like with a solvent such as alcohol or water added. Alternatively, a metal fluoride complex can be used as a mask layer on the insulating layer by a liquid layer deposition method (LPD method) or the like. It is also possible to form oxides of various metals by a dry coating method. As a coating method, it can be produced using a PVD method such as vapor deposition, sputtering, or ion plating, a CVD method such as plasma CVD or thermal CVD, or a method such as thermal spraying. Specifically, Al ₂ O ₃ , Cr ₂ O ₃ , Fe ₂ O ₃ , MgO, SiO, SiO ₂ , SnO ₂ , TaO ₅ , TiO ₂ , WO ₃ , Y ₂ O ₃ , ZnO, ZnO ₂ , ZrO A film such as ₂ is preferably used.

  In addition, the organic mask layer is resistant to dry etching, and a known one can be used. In particular, when oxygen plasma is used, a resist film containing silicon is generally resistant to oxygen plasma. Therefore, it is used favorably. The resist film containing silicon may or may not be photosensitive. As a method of removing the mask layer on the upper surface of the convex portion, when the mask layer on the upper surface of the convex portion is developed and removed and then the developed portion is dry-etched, the resist film has photosensitivity. However, when the mask layer on the upper surface of the convex portion is removed by mechanical polishing, the photosensitivity is not necessarily required. The resist film to be used may be negative or positive, and may be liquid or film. In the case of a liquid, it can be applied by spraying, dispenser, dipping, roll, spin coating or the like, and in the case of a film, it can be heated and laminated so that the resist is embedded in the recess.

  The resist film containing silicon described above will be described. As the silicon-containing photosensitive composition used for the resist film containing silicon, known ones can be used, but as a typical example of a suitable silicon-containing photosensitive composition, the main chain has silicon atoms, A chemically amplified silicon-containing photosensitive composition using a siloxane polymer containing an acid-decomposable group such as an acetal structure, a tertiary ester structure, or a t-butyloxycarbonyl structure, and a resist composition comprising a novolak resin and naphthoquinone diazide And a silicon-containing photosensitive composition for ultraviolet exposure in which an alkali-soluble ladder type polysiloxane having a silicon atom in the main chain and a silanol structure in the molecule is blended. Vinyl polymers and photoacids having a silicon atom in the side chain and an acid-decomposable group such as an acetal structure, tertiary ester structure, t-butyloxycarbonyl structure, or β-silylethyl ester structure in the side chain A chemically amplified silicon-containing photosensitive composition for far-ultraviolet light exposure comprising a generator, a structure formed by polymerization of a monomer containing a silicon derivative of methyl methacrylate, and silicon in the ester part of an acrylate polymer. And a resist composition having a polymer comprising an acrylic monomer having two trimethylsilyl groups, a silicon-containing monomer, maleic anhydride, and a polymer comprising t-butyl acrylate.

  The method of partially removing the mask layer includes (a) a method of developing and removing the mask layer formed on the upper surface of the convex portion by a photolithographic process using a photosensitive mask layer, and (b) a mask layer. For example, there is a method of mechanically polishing the removed portion. In the method (a), the photosensitive mask layer may be a positive type or a negative type, and the developer may be the same liquid as the mask layer peeling liquid described later. . Moreover, as a method of polishing and removing the mask layer (b), for example, there is a method of polishing while rotating the buffalo. As the buff, a commercially available non-woven fabric, ceramic buff, diamond buff or the like can be used.

  The dry etching used in the present invention is a method of introducing a gas into a vacuum vessel, exciting the gas with a high frequency, microwave, etc., generating plasma, generating radicals, ions, radicals generated by plasma, This is etching performed by reacting ions with an object to be etched (insulating layer, intermediate layer), converting the reaction product into a volatile gas, and exhausting the reaction product to the outside through a vacuum exhaust system. In dry etching, reactive ion etching and etching are performed in which high-frequency power is applied to the electrode on which the object is to be etched, and the ions generated from the plasma are accelerated by the negative self-bias voltage to impact the object to be etched. In general, plasma etching is used to etch an object to be etched by radicals generated from plasma without applying a bias. Reactive ion etching includes parallel plate type, magnetron type, dual frequency type, ECR type, helicon type, ICP type, etc., and the etching shape that is often obtained at a low pressure is isotropic. Plasma etching apparatuses include a barrel type, a parallel plate type, and a down flow type, and the pressure used is often high, and the etching shape obtained is isotropic. In the present invention, any of the above methods may be used.

In addition, as a gas composition in dry etching, a gas that can etch the formed insulating layer and is difficult to etch the conductive substrate is appropriately selected. As a typical gas composition, an F atom-containing plasma is generated. , F ₂ , CF ₄ -O ₂ , C ₂ F ₆ -O ₂ , C ₃ F ₈ -O ₂ , SF ₆ -O ₂ , SiF ₄ -O ₂ , NF ₃ , ClF ₃ , and unsaturated species Generate plasma, CF ₄ , C ₂ F ₆ , CHF ₃ , CF ₄ -H ₂ , CH ₄ , and further generate plasma containing Cl · Br atoms, Cl ₂ , CCl ₄ , CF ₃ Cl, Cl _2- CCl ₄ , Br ₂ , O ₂ , O ₂ —Ar, etc. that generate oxygen plasma are used. Since it does not have a global warming action and is not corrosive, a gas composition that generates oxygen plasma is preferable, and it is preferable to select a carbon-based material that can etch an insulating layer with oxygen plasma.

  The mask layer for dry etching of the insulating layer is preferably one having an etching rate in dry etching that is similar to or lower than that of the insulating layer. When the etching rate of the mask layer is higher than the etching rate of the insulating layer in the dry etching, the mask layer must be thickened when the insulating layer is thick, and the thickness varies. In some cases, the insulating layer under the mask layer may be etched. Therefore, it is particularly preferable that the etching rate of the mask layer is 1/2 or less of the etching rate of the insulating layer.

A conventionally known alkaline aqueous solution can be used as the stripping solution for the organic mask layer. For example, sodium silicate, potassium, tribasic sodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, Examples include inorganic alkali salts such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium.
Monoethanolamine, diethanolamine, triethanolamine, 2- (2-aminoethoxy) ethanol, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N-methylethanol Alkanolamines such as amine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine; diethylenetriamine, triethylenetetramine, propylenediamine, N, N-diethyl Polyethylene, 1,4-butanediamine, N-ethyl-ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,6-hexanediamine, etc. Alkylene polyamines; aliphatic amines such as 2-ethyl-hexylamine, dioctylamine, tributylamine, tripropylamine, triallylamine, heptylamine and cyclohexylamine; aromatic amines such as benzylamine and diphenylamine; piperazine, N- Water-soluble amines such as cyclic amines such as methyl-piperazine, methyl-piper-methyl-piperazine, methyl-piperazine, and hydroxyethylpiperazine are also preferably used.

  A quaternary ammonium hydroxide is also preferably used as the mask layer stripping solution. Specifically, tetramethylammonium hydroxide [= TMAH], tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, trimethylethylammonium hydroxide (2-hydroxyethyl) trimethylammonium hydroxide [= choline], (2-hydroxyethyl) triethylammonium hydroxide, (2-hydroxyethyl) tripropylammonium hydroxide, (1-hydroxypropyl) trimethylammonium hydroxide, etc. Is exemplified. Of these, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, methyltributylammonium hydroxide, methyltripropylammonium hydroxide, choline and the like are preferable. One or more quaternary ammonium hydroxides can be used.

  When an organic alkali agent or a quaternary ammonium hydroxide is used as a mask layer stripping solution, it is usually used in a mixture with a water-soluble organic solvent in order to improve the stripping property of the resist film. . Examples of the water-soluble organic solvent include sulfoxides such as dimethylsulfoxide; sulfones such as dimethylsulfone, diethylsulfone, bis (2-hydroxyethyl) sulfone, tetramethylenesulfone [= sulfolane]; N, N-dimethylformamide, N- Amides such as methylformamide, N, N-dimethylacetamide, N-methylacetamide, N, N-diethylacetamide; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, Lactams such as N-hydroxymethyl-2-pyrrolidone and N-hydroxyethyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3- Imidazolidinones such as diisopropyl-2-imidazolidinone; Tylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl And polyhydric alcohols such as ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and derivatives thereof. Among them, dimethyl sulfoxide, dimethyl imidazolidinone, N-methyl-2-pyrrolidone, diethylene glycol monobutyl ether, sulfolane, N, N-dimethylacetamide, N, N-dimethylformamide and the like are preferably used. One or two or more water-soluble organic solvents can be used.

In FIG. 7C, the conductive base material 1 is etched in the case where the width of the upper surface 4 of the projection 3 is the same as the width of the resist pattern, but as shown in FIG. In addition, overetching may be performed so that the width of the upper surface 4 of the protrusion 3 is smaller than the width of the resist pattern. In this case, sufficient over-etching is performed to continuously form an insulating layer, as shown in FIG. 10B, and then the resist pattern is peeled to have an insulating layer as shown in FIG. 10C. A conductive substrate may be produced. This can be used as a conductive substrate for plating. In the above, the resist pattern forming method, etching method, insulating layer forming method, residual resist peeling method and the like are the same as described above.
Thereafter, except for the fact that there is no insulating layer on the upper surface of the convex portion, the target conductive substrate for plating as shown in FIG. 9 (i) can be produced in the same manner as in FIG. it can.

  The above-described conductive substrate for plating does not necessarily have an insulating layer. It is sufficient if the metal deposited on the tip portion of the convex portion can be selectively transferred. As such, by reducing the surface roughness of the tip of the convex part and increasing the surface roughness of the other part (corresponding to the part where the insulating layer described above is formed), the plating conductive The metal deposited on the tip portion of the conductive substrate can be selectively transferred. If the surface roughness of the tip of the convex part is low and the surface roughness of the other part is rough, the metal appearing in the part other than the tip part (in the recess) becomes granular and tends to deposit discontinuously. Therefore, it is possible to selectively transfer only the metal layer formed on the tip portion of the convex portion by another base material. Specifically, the surface roughness of the tip portion of the convex part is preferably 2.0 μm or less in terms of ten-point average roughness Rz (measured in accordance with JIS B 0601-1994), and Rz is 1. More preferably, it is 0 μm or less. Moreover, as for the surface roughness in a recessed part, it is preferable that Rz exceeds 2.0 micrometers, and it is more preferable that Rz is 3.0 micrometers or more.

The conductive substrate for plating having the convex pattern described in detail above and the concave portion of the geometric drawing drawn by the convex pattern and having the insulating layer in the concave portion has the convex pattern and the geometric drawn thereby. The concave portion having the illustrated insulating layer is formed with an appropriate width. If the region is defined as region A, the conductive support for plating according to the present invention can be provided with a region (referred to as region B) corresponding to the ground portion of the electromagnetic wave shielding member. At this time, the region A and the region B may have the same pattern. Moreover, it is preferable to make the area ratio of the recessed part in the area | region A the same or larger than the area ratio of the recessed part in the area | region B, and it is still more preferable to enlarge 10% or more. The area ratio of the recesses refers to the ratio of the area of the part excluding the exposed part in the convex part of each area to the total area of each area when viewed in a plan view. In addition, in this case, a solid metal film is formed around the conductive support for plating by plating. Since the solid metal film is easily broken during transfer, the area ratio of the recesses in the region B is preferably 40% or more, and preferably less than 97%.
In the region B, the above-described geometric diagram shape drawn by the pattern of the convex portion can be used.
(1) Mesh-like geometric pattern (2) Square geometric pattern regularly arranged at predetermined intervals (3) Parallelogram pattern regularly arranged at predetermined intervals (4) Circular pattern or ellipse Pattern (5) Triangular pattern (6) Polygonal pattern of pentagon or more (7) Star pattern etc.
In addition, the formation of the protrusions in the region B, the formation of the insulating layer, and the like can be performed at the same time as in the region A described above. Further, the height of the exposed portion of the convex portion, the width does not increase as the exposed portion proceeds in the tip direction, and the width is made smaller at the upper portion than at the lower portion as a whole, and the relationship d ₁₀ / h ₁₀ Etc. are preferably the same as those in the region A.

  The conductive substrate for plating according to the present invention is a durable plating that can be repeatedly used as a patterned plating plate for repeated plating, peeling, and use even with a fine pattern. It is possible to easily produce a conductive substrate having excellent properties.

A known method can be employed as the plating method for the conductive substrate for plating in the present invention. As the plating method, an electroplating method, an electroless plating method, or other plating methods can be applied.
The electroplating will be further described. For example, in the case of electrolytic copper plating, a copper sulfate bath, a copper borofluoride bath, a copper pyrophosphate bath, a copper cyanide bath, or the like can be used as an electrolytic bath for plating. At this time, it is known that the dispersion of electrodeposition stress can be further reduced by adding a stress relieving agent (also having an effect as a brightener) due to organic matter or the like to the plating bath. In the case of electro nickel plating, a Watt bath, a sulfamic acid bath, or the like can be used. In order to adjust the flexibility of the nickel foil in these baths, additives such as saccharin, paratoluenesulfonamide, sodium benzenesulfonate, sodium naphthalene trisulfonate, and commercial additions that are preparations as necessary An agent may be added. Furthermore, in the case of electrogold plating, alloy plating using potassium gold cyanide, pure gold plating using an ammonium citrate bath or a potassium citrate bath, or the like is used. In the case of alloy plating, a gold-copper, gold-silver, gold-cobalt binary alloy or a gold-copper-silver ternary alloy is used. Similarly, other known methods can be used for other metals. For example, Non-Patent Document 1, pages 87 to 504 can be referred to as the electroplating method.
Next, the electroless plating will be further described. Typical examples of the electroless plating method include copper plating, nickel plating, tin plating, gold plating, silver plating, cobalt plating, iron plating, chromium plating, and the like. In the process of electroless plating used industrially, a reducing agent is added to a plating solution, and electrons generated by the oxidation reaction are used for metal precipitation reaction. , Reducing agent, pH adjusting agent, pH buffering material, stabilizer and the like. In the case of electroless copper plating, copper sulfate is preferably used as the metal salt, formalin as the reducing agent, and Rossel salt or ethylenediaminetetraacetic acid (EDTA) as the complexing agent. Moreover, although pH is mainly adjusted with sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. can be used, carbonate and phosphate are used as a buffer, and monovalent as a stabilizer. Cyanide, thiourea, bipyridyl, O-phenanthroline, neocuproine, etc. that complex preferentially with copper are used. In the case of electroless nickel plating, nickel sulfate is preferably used as the metal salt, and sodium hypophosphite, hydrazine, a borohydride compound, or the like is preferably used as the reducing agent. When sodium hypophosphite is used, phosphorus is contained in the plating film, and the corrosion resistance and wear resistance are excellent. Moreover, as a buffering agent, a monocarboxylic acid or its alkali metal salt is often used. As the complexing agent, one that forms a stable soluble complex with nickel ions in the plating solution is used, and acetic acid, lactic acid, tartaric acid, malic acid, citric acid, glycine, alanine, EDTA, etc. are used. In this case, sulfur compounds and lead ions are added. As for the electroless plating method, reference can be made to pages 505 to 545 of “Practical Plating for On-Site Engineers”, edited by Japan Plating Association (published by Sakai Shoten in 1986).
Furthermore, in order to obtain the reducing action of the reducing agent, it may be necessary to activate the catalyst on the metal surface. When the substrate is a metal such as iron, steel, nickel, etc., these metals have catalytic activity, so they are deposited just by immersing them in the electroless plating solution, but copper, silver or their alloys, and stainless steel In this case, in order to impart catalyst activation, a method is used in which the object to be plated is immersed in an acidic hydrochloric acid solution of palladium chloride and palladium is deposited on the surface by ion substitution.
The electroless plating that can be used in the present invention includes, for example, a palladium catalyst on the convex portion of the conductive substrate having the convex pattern having the upper surface described above and the concave portion of the geometric drawing drawn thereby, as necessary. After making it adhere, there is a method of immersing in an electroless copper plating solution having a temperature of about 60 to 90 ° C. to perform copper plating.
In electroless plating, the substrate is not necessarily conductive. However, as described above, when the insulating layer is formed by electrodeposition in the concave portion of the base material, the base material needs to be conductive, and is deposited on the base material in preparation for electroless plating. As a treatment for easily peeling the metal, when the portion to be electrolessly plated is subjected to anodization treatment, the substrate needs to be conductive.
In particular, when the material of the conductive base material is Ni, for electroless plating, after anodizing the conductive base material having a convex pattern having an upper surface and a concave portion having a geometric diagram shape drawn thereby, There is a method of depositing copper by dipping in an electroless copper plating solution.

As a metal that appears or precipitates by plating, conductive metals such as silver, copper, gold, aluminum, tungsten, nickel, iron, and chromium are used, but the volume resistivity (specific resistance) at 20 ° C. is used. It is desirable to include at least one kind of metal of 20 μΩ / cm or less. This is because when the structure obtained according to the present invention is used as an electromagnetic wave shielding sheet, the metal constituting it is grounded as an electromagnetic wave as a current, and the higher the conductivity, the better the electromagnetic wave shielding property. Such metals include silver (1.62 μΩ / cm), copper (1.72 μΩ / cm), gold (2.4 μΩ / cm), aluminum (2.75 μΩ / cm), tungsten (5.5 μΩ / cm). ), Nickel (7.24 [mu] [Omega] / cm), iron (9.0 [mu] [Omega] / cm), chromium (17 [mu] [Omega] / cm, all values at 20 [deg.] C.), etc., but are not particularly limited thereto. If possible, the volume resistivity is more preferably 10 μΩ / cm, and further preferably 5 μΩ / cm. In view of the price of metal and availability, copper is most preferably used. These metals may be used alone, or may be an alloy with another metal or a metal oxide for imparting functionality. However, it is preferable from the viewpoint of conductivity that a metal having a volume resistivity of 20 μΩ / cm is contained in the largest amount as a component.
The thickness (plating thickness) of the metal layer formed by plating on the exposed portion of the convex portion of the conductive substrate for plating described above exhibits sufficient conductivity (at this time, the electromagnetic wave shielding property is sufficiently developed). Therefore, the thickness is preferably 0.5 μm or more, and the thickness is 3 μm or more in order to reduce the possibility that pinholes are formed in the conductor layer (in this case, the electromagnetic wave shielding property is reduced). More preferably. In addition, if the plating thickness is too large, the formed metal layer also spreads in the width direction, so the width of the transferred line is widened, the aperture ratio of the pattern base material with the conductor layer is lowered, transparency, non-visible Sex is reduced. Therefore, in order to ensure transparency and invisibility, the thickness of the formed metal is preferably 20 μm or less. Further, in order to shorten the plating time and increase the production efficiency, the thickness of the plating is preferred. Is more preferably 10 μm or less.
The thickness of the plating or conductor layer pattern is measured at the center of the width of the conductor layer pattern produced by plating.

Examples of another substrate (substrate on which the conductor layer pattern is transferred) in the present invention include a plate made of glass, plastic, etc., a plastic film, and a plastic sheet. As the glass, glass such as soda glass, non-alkali glass, and tempered glass can be used.
Plastics include polystyrene resin, acrylic resin, polymethyl methacrylate resin, polycarbonate resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene resin, polypropylene resin, polyamide resin, polyamideimide resin, polyetherimide resin, polyetheretherketone Resin, polyarylate resin, polyacetal resin, polybutylene terephthalate resin, thermoplastic polyester resin such as polyethylene terephthalate resin, cellulose acetate resin, fluororesin, polysulfone resin, polyethersulfone resin, polymethylpentene resin, polyurethane resin, diallyl phthalate Examples thereof include thermoplastic resins such as resins and thermosetting resins. Among plastics, polystyrene resin, acrylic resin, polymethyl methacrylate resin, polycarbonate resin, and polyvinyl chloride resin, which are excellent in transparency, are preferably used. The thickness of another substrate is preferably 0.5 mm to 5 mm from the viewpoint of protection of the display, strength, and handleability.

Another substrate in the present invention is preferably a plastic film. The plastic film includes polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyolefins such as polyethylene, polypropylene, polystyrene, and EVA, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, polysulfone, and polyethersulfone. A film made of plastic such as phon, polycarbonate, polyamide, polyimide, acrylic resin, etc., having a total visible light transmittance of 70% or more is preferable. These can be used as a single layer, but may be used as a multilayer film in which two or more layers are combined. Among the plastic films, a polyethylene terephthalate film or a polycarbonate film is particularly preferable from the viewpoints of transparency, heat resistance, ease of handling, and cost.
Although there is no restriction | limiting in particular in the thickness of the said plastic film, The thing of 1 mm or less is preferable, and when it is too thick, there exists a tendency for visible light transmittance | permeability to fall easily. In consideration of the fact that if the film is too thin, the handleability deteriorates, the thickness of the plastic film is more preferably 5 to 500 μm, and further preferably 50 to 200 μm.
These substrates such as plastic films are preferably transparent (that is, transparent substrates) in order to be used as an electromagnetic wave shielding film for preventing leakage of electromagnetic waves from the front surface of the display.

  The surface on which the conductor layer pattern of the other substrate is transferred needs to have adhesiveness when transferred. For this purpose, the substrate itself may have the necessary adhesiveness, but it is preferable to laminate an adhesive layer on the transfer surface. Further, an adhesive layer may be formed on the surface of the conductor layer pattern to be transferred.

  The radiation curable adhesive for transferring the conductor pattern layer in the present invention includes (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond, and (C) light. What contains a polymerizable initiator is preferable and it is preferable to be comprised from said (A), (B) and (C).

The weight average molecular weight of the (A) binder polymer in the present invention is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000. When the weight average molecular weight is less than 5,000 or exceeds 1,000,000, the transferability of the conductor layer pattern to the adhesive layer tends to be remarkably lowered. However, the weight average molecular weight and the number average molecular weight in the present invention are measured by gel permeation chromatography using a standard polystyrene calibration curve.
The photopolymerization initiator is activated by absorption of radiation to initiate polymerization, and preferably generates radicals by absorption of radiation.

  Examples of the binder polymer include those that can be produced by radical polymerization of a monomer having one polymerizable double bond such as an acrylic resin or a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, an alkyd resin, A phenol resin etc. are mentioned. From the viewpoint of transferability of the conductor layer pattern, an acrylic resin is preferable. These can be used alone or in combination of two or more.

  In the above binder polymer, the monomer having one polymerizable double bond may be a polymerizable styrene derivative or acrylonitrile substituted at the α-position or aromatic ring such as styrene, vinyltoluene, or α-methylstyrene. , Acrylamide such as diacetone acrylamide, ester compounds of vinyl alcohol such as vinyl-n-butyl ether, acrylic acid, alkyl acrylate ester, glycidyl acrylate ester, 2,2,2-trifluoroethyl acrylate, 2,2,3 , 3-tetrafluoropropyl acrylate, α-bromoacrylic acid, α-chloroacrylic acid, β-furylacrylic acid, β-styrylacrylic acid and other acrylic acids or derivatives thereof, methacrylic acid, methacrylic acid alkyl ester, glycidyl methacrylate Beauty treatment 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, α-bromomethacrylic acid, α-chloromethacrylic acid, β-furylmethacrylic acid, β-styrylmethacrylic acid, etc. Methacrylic acid or its derivatives, maleic acid, maleic anhydride, maleic acid monoester such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, croton An acid, propiolic acid, etc. are mentioned.

（式中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２は炭素数１〜１２のアルキル基を示す）で表される化合物、これらの化合物のアルキル基に水酸基、エポキシ基、ハロゲン等が置換した化合物などが挙げられる。 As the alkyl acrylate ester or the alkyl methacrylate ester, the general formula (I)

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 12 carbon atoms), and the alkyl group of these compounds has a hydroxyl group, an epoxy group, a halogen or the like. Examples include substituted compounds.

  Examples of the alkyl group having 1 to 12 carbon atoms represented by R2 in the general formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Group, decyl group, undecyl group, dodecyl group and structural isomers thereof. Examples of the monomer represented by the general formula (I) include acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, acrylic acid butyl ester, acrylic acid pentyl ester, acrylic acid hexyl ester, and acrylic acid. Heptyl ester, acrylic acid octyl ester, acrylic acid 2-ethylhexyl ester, acrylic acid nonyl ester, acrylic acid decyl ester, acrylic acid undecyl ester, acrylic acid dodecyl ester, methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester , Butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, methacrylic acid 2- Ethylhexyl ester, methacrylic acid nonyl ester, decyl methacrylate esters, methacrylic acid undecyl ester, and methacrylic acid dodecyl ester. These can be used alone or in combination of two or more.

  In addition, the binder polymer as component (A) in the present invention preferably contains a carboxyl group, a hydroxyl group, a glycidyl group, etc. from the viewpoint of transferability to the adhesive layer of the conductive pattern layer. It can manufacture by radical-polymerizing the polymerizable monomer which has this, and another polymerizable monomer. As the polymerizable monomer having a carboxyl group, methacrylic acid, acrylic acid, maleic acid and the like are preferable. As the polymerizable monomer having a hydroxyl group, 2-hydroxyethyl methacrylate and the like are preferable, and polymerization having a glycidyl group is performed. As the functional monomer, glycidyl methacrylate and the like are preferable.

  These (A) binder polymers are used alone or in combination of two or more. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binder polymers having different degrees of dispersion are used. Examples thereof include a binder polymer. The degree of dispersion here means a value of weight average molecular weight ÷ number average molecular weight.

  The binder polymer as component (A) in the present invention includes phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, maleic anhydride, maleic acid, fumaric acid, trimellitic anhydride adipic acid , Divalent or higher carboxylic acids such as pyromellitic anhydride and ethylene glycol, propylene glycol, 1,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, neopentyl glycol, hydrogenated bisphenol A, glycerin, trimethylol A polyester resin obtained by an esterification reaction with a divalent or higher alcohol such as propane can also be used. Examples of the epoxy resin include a bisphenol epoxy resin and a novolac epoxy resin, and those added with a monovalent carboxylic acid such as acetic acid, oxalic acid, acrylic acid, and methacrylic acid.

In the adhesive of the present invention, a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in the molecule is used. Of these, at least one polymerizable ethylenically unsaturated group is used in the molecule. Examples of the photopolymerizable compound having a saturated bond include bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, and polyethylene. Glycol diacrylate (number of oxyethylene groups is 2 to 14), polypropylene glycol diacrylate (number of oxypropylene groups is 2 to 14), tetraethylene glycol diacrylate, trimethylolpropane triacrylate, Pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate,
Bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate (the number of oxyethylene groups is 2 to 2) 14), polypropylene glycol dimethacrylate (having 2 to 14 oxypropylene groups), tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, tris (methacryloxyethyl) isocyanurate, penta Erythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol Le hexa-methacrylate, dipentaerythritol penta methacrylate,
Trimethylolpropane triglycidyl ether triacrylate, 2,2-bis (4-acryloxy-2-hydroxy-propyloxy) phenyltrimethylolpropane triglycidyl ether trimethacrylate, 2,2-bis (4-methacryloxy-2-hydroxy-) A compound obtained by reacting a glycidyl group-containing compound such as propyloxy) phenyl with an α, β-unsaturated carboxylic acid,
Examples of the above include γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β- Acrylic acid derivatives or methacrylic acid derivatives having an OH group at the β-position such as hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate and isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, Addition reaction products with 1,6-hexamethylene diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, etc. And the like, and the like. Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups.
Etc.

（ただし、式中、Ｒはエチレン基又はプロピレン基を示し、ｍ及びｎはそれぞれ独立に、１〜２０の整数を示す）で示されるビスフェノールＡのアルキレンオキシド付加物のジアクリレート又はこの化合物のアクリロイル基をメタクリロイル基に変えた化合物（これらは、２，２−ビス（４−（アクリロキシポリアルコキシ）フェニル）プロパン又は２，２−ビス（４−（メタクリロキシポリアルコキシ）フェニル）プロパンとも称される、具体的には、２，２−ビス（４−（アクリロキシジエトキシ）フェニル）プロパン、２，２−ビス（４−（アクリロキシトリエトキシ）フェニル）プロパン、２，２−ビス（４−（アクリロキシペンタエトキシ）フェニル）プロパン、２，２−ビス（４−（アクリロキシデカエトキシ）フェニル）２，２−ビス（４−（メタクリロキシジエトキシ）フェニル）プロパン、２，２−ビス（４−（メタクリロキシトリエトキシ）フェニル）プロパン、２，２−ビス（４−（メタクリロキシペンタエトキシ）フェニル）プロパン、２，２−ビス（４−（メタクリロキシデカエトキシ）フェニル）等が挙げられ、２，２−ビス（４−（メタクリロキシペンタエトキシ）フェニル）プロパンは、ＢＰＥ−５００（新中村化学工業（株）商品名）として商業的に入手可能である）、
一般式（ｂ） Examples of the monomer having two or more polymerizable unsaturated bonds in the molecule further include the general formula (a)

(Wherein, R represents an ethylene group or a propylene group, and m and n each independently represents an integer of 1 to 20) diacrylate of an alkylene oxide adduct of bisphenol A or acryloyl of this compound Compounds in which the group is changed to a methacryloyl group (these are also referred to as 2,2-bis (4- (acryloxypolyalkoxy) phenyl) propane or 2,2-bis (4- (methacryloxypolyalkoxy) phenyl) propane. Specifically, 2,2-bis (4- (acryloxydiethoxy) phenyl) propane, 2,2-bis (4- (acryloxytriethoxy) phenyl) propane, 2,2-bis (4 -(Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4- (acryloxydecaethoxy) phenyl) 2, -Bis (4- (methacryloxydiethoxy) phenyl) propane, 2,2-bis (4- (methacryloxytriethoxy) phenyl) propane, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane 2,2-bis (4- (methacryloxydecaethoxy) phenyl) and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE-500 (Shin Nakamura Chemical ( (Commercially available as product name)),
General formula (b)

（ただし、式中、ｍ及びｎはそれぞれ独立に、１〜１０の整数を示す）で示されるビスフェノールＡのエピクロルヒドリン変性物とアクリル酸の付加エステル化物又はこの化合物のアクリロイル基をメタクリロイル基に変えた化合物、
一般式（ｃ）

(In the formula, m and n each independently represents an integer of 1 to 10) An epichlorohydrin modified product of bisphenol A and an addition ester product of acrylic acid or an acryloyl group of this compound was changed to a methacryloyl group. Compound,
Formula (c)

（ただし、式中、Ｒはエチレン基又はプロピレン基を示し、ｍ及びｎはそれぞれ独立に、１〜２０の整数を示す）で示されるリン酸のアルキレンオキシド付加物のジアクリレート又はこの化合物のアクリロイル基をメタクリロイル基に変えた化合物、一般式（ｄ）

(Wherein, R represents an ethylene group or a propylene group, and m and n each independently represents an integer of 1 to 20) diacrylate of an alkylene oxide adduct of phosphoric acid or acryloyl of this compound Compounds in which the group is changed to a methacryloyl group, general formula (d)

（ただし、式中、ｍ及びｎはそれぞれ独立に、１〜１０の整数を示す）で示されるフタル酸のエピクロリン変性物とアクリル酸の付加エステル化物又はこの化合物のアクリロイル基をメタクリロイル基に変えた化合物、一般式（ｅ）

(In the formula, m and n each independently represents an integer of 1 to 10) The epichlorine-modified product of phthalic acid and the addition esterified product of acrylic acid or the acryloyl group of this compound was changed to a methacryloyl group. Compound, general formula (e)

（ただし、式中、ｍ及びｎはそれぞれ独立に、１〜２０の整数を示す）で示される１，６−ヘキサンジオールのエピクロリン変性物とアクリル酸の付加エステル化物（アクイリル基を一分子中に２個有するもの）、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、一般式（ｆ）

(Wherein m and n each independently represents an integer of 1 to 20) 1,6-hexanediol epichlorine modified product and acrylic acid addition esterified product (acylyl group in one molecule) 2), trimethylolpropane triacrylate, pentaerythritol triacrylate, general formula (f)

（ただし、式中、Ｒはエチレン基又はプロピレン基を示し、３個のｍはそれぞれ独立に、１〜２０の整数を示す）で示されるリン酸のアルキンオキシド付加物のトリアクリレート又はこの化合物のアクリロイル基をメタクリロイル基に変えた化合物、一般式（ｇ）

(Wherein, R represents an ethylene group or a propylene group, and three m's each independently represents an integer of 1 to 20), a triacrylate of an alkyne oxide adduct of phosphoric acid represented by Compound in which acryloyl group is changed to methacryloyl group, general formula (g)

（ただし、式中、Ｒはエチレン基又はプロピレン基を示し、ｍ、ｍ′及びｍ″はそれぞれ独立に、１〜２０の整数を示す）で示されるトリメチロールプロパンのアルキレンオキシド付加物のトリアクリレート又はこの化合物のアクリロイル基をメタクリロイル基に変えた化合物などが挙げられる。
これらのモノマーは、単独で又は２種以上を組み合わせて用いることができる。

(Wherein R represents an ethylene group or a propylene group, and m, m ′, and m ″ each independently represents an integer of 1 to 20), a triacrylate of an alkylene oxide adduct of trimethylolpropane. Or the compound etc. which changed the acryloyl group of this compound into the methacryloyl group are mentioned.
These monomers can be used alone or in combination of two or more.

  The photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond can include a monomer having one polymerizable double bond in the molecule. As such a compound, those exemplified in the description of the binder polymer can be used.

  Examples of the photopolymerization initiator of the component (C) in the present invention include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-. Diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] Aromatic ketones such as 2-morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenyl Anthraquinone, 2,3-diphenylanthraquinone 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, quinones such as 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl Benzoin ether compounds such as ether and benzoin phenyl ether, benzoin compounds such as benzoin and methylbenzoin / ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2 -(O-chlorophenyl) -4,5-diphenylimidazole dimer, N-phenylglycine, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone It is used in combination Roh α- hydroxy ketone. Note that 1-hydroxy-cyclohexyl-phenyl-ketone is preferable from the viewpoint of transparency and sensitivity of the substrate and transferability of the conductive pattern layer to the adhesive layer. These can be used alone or in combination of two or more.

  The blending amount of the (A) binder polymer is preferably 30 to 80 parts by weight and more preferably 40 to 70 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). preferable. If this blending amount is less than 30 parts by weight, the photocured product tends to be brittle, and when used as an ultraviolet curable resin, the coating property tends to be inferior, and if it exceeds 80 parts by weight, the photosensitivity tends to be insufficient. is there.

The blending amount of the (B) photopolymerizable compound is preferably 20 to 70 parts by weight, and preferably 30 to 60 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). Is more preferable. If the amount is less than 20 parts by weight, the photosensitivity tends to be insufficient, and if it exceeds 70 parts by weight, the photocured product tends to be brittle.
(B) As the photopolymerizable compound, 100% of the photopolymerizable compound (bifunctional or higher monomer) having at least two polymerizable ethylenically unsaturated bonds in the molecule may be used. The blending ratio of the monomer and the photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule (monofunctional or higher monomer) is from 67 to 98% by weight of bifunctional or higher monomer, and monofunctional monomer 33 to It is preferably 2% by weight, more preferably 78 to 92% by weight of bifunctional or higher monomer, and more preferably 22 to 8% by weight of monofunctional monomer.

  The blending amount of the photopolymerization initiator (C) is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B), and is 0.2 to 10 parts by weight. More preferably, it is a part. If the blending amount is less than 0.1 parts by weight, the photosensitivity tends to be insufficient, and if it exceeds 20 parts by weight, the absorption on the surface of the composition increases during exposure and the internal photocuring is insufficient. Tend to be.

  In addition, the photocurable resin composition of the present invention includes, if necessary, a thermochromic inhibitor, a plasticizer such as p-toluenesulfonamide, a filler, a stabilizer, an adhesion imparting agent, a leveling agent, an antioxidant. An agent, a fragrance | flavor, etc. can be contained at 20 weight part or less each with respect to 100 weight part of total amounts of (A) component and (B) component. These are used alone or in combination of two or more. For expression of each effect, 0.01 parts by weight or more is preferable.

In the present invention, by using a radiation curable adhesive for the adhesive layer for transferring the conductor layer pattern formed on the conductive substrate for plating, the transferability of the conductor layer pattern to the adhesive layer can be improved. I can plan.
Moreover, it is preferable that the uppermost position of the conductor layer pattern transferred to the adhesive layer does not protrude above 3 μm with respect to the adhesive layer, and the conductor layer pattern may be embedded in the adhesive layer. .
At this time, the measurement of the protruding height is obtained as a vertical difference between the position of the uppermost end of the conductor layer pattern and the position of the uppermost end of the adhesive layer in the vicinity of the conductor layer pattern with reference to the reference plane. be able to. Obtained from the uppermost end of the adhesive layer as a base point, when the value is positive, the conductor layer pattern protrudes, and when the value is negative, it is buried. The height of this protrusion is preferably +3 or less. At the time of transfer, the conductor layer pattern on the convex portion of the conductive substrate for plating is pressed against the adhesive layer. However, since the adhesive of the present invention has fluidity, the conductor layer pattern is bonded. Since at least some of the adhesive layer becomes buried, it is common for the surrounding adhesive layer to swell. In this case, the uppermost end of the adhesive layer in the vicinity of the conductor layer pattern can be easily confirmed by a cross-sectional photograph. When the adhesive layer does not rise, the surface of the adhesive layer is the uppermost end.
Thereby, when the conductor layer pattern is coated with a resin, entrainment of bubbles is reduced, which is preferable in terms of transparency.
In consideration of adhesive strength, it is preferable that 50% or more of the height of the conductor layer pattern is buried in the adhesive layer in the conductor layer pattern transferred to the adhesive layer. The height of the conductor layer pattern refers to a vertical difference between the uppermost end and the lowermost end of the conductor layer pattern with reference to the reference plane.

When the protrusion height of the conductor layer exceeds +3.5 μm, productivity is improved especially when coating a transparent resin on the conductor layer pattern of another substrate to which the conductor layer pattern is transferred via the adhesive layer. Therefore, when the coating speed is increased, the resin around the location where the conductive layer pattern is separated from the adhesive layer to which the transparent resin has transferred the conductive layer pattern deteriorates or the transparent resin that enters the opening It is difficult to defoam air bubbles entrained in the film, which may cause a decrease in light transmittance.
The cross-sectional shape of the conductor layer pattern used in the present invention is not particularly limited, and can be transferred to the adhesive layer in a wide range of shapes such as a rectangular shape, a curved shape, and a trapezoidal shape.

The tack value at 50 ° C. on the surface of the radiation curable adhesive layer in the present invention is preferably 20 to 100 gf. When the tack value on the surface of the adhesive layer at 50 ° C. is 20 gf or less, the transferability of the conductor layer pattern to the adhesive layer is poor, and when the tack value on the surface of the adhesive layer at 50 ° C. is 100 gf or more, adhesion The adhesiveness with the cover film affixed for the purpose of protection on the agent layer is increased, resulting in a problem that the cover film is difficult to peel off, resulting in a decrease in productivity.
Moreover, it is preferable that the tack value in the surface of an adhesive bond layer is 10 gf or less after irradiation of the radiation after transferring a conductor layer pattern to an adhesive bond layer. After irradiation of the radiation after transferring the conductor layer pattern to the adhesive layer, if the tack value on the surface of the adhesive layer is 10 gf or more, foreign matter adheres to the surface of the adhesive layer, and productivity decreases. Tend.
In the radiation curable adhesive layer, as long as the above-mentioned properties regarding adhesiveness are satisfied, the curing reaction may partially proceed before the transfer step.
The radiation refers to α rays, β rays, γ rays, ultraviolet rays, electron beams, and the like.
The tack value is measured according to JIS Z 0237. As a measuring device, a tack tester (TAC-II, manufactured by Reska Co., Ltd.) can be used. : 600 mm / min, temperature: room temperature. In the examples, the measurement was performed with this apparatus and conditions.

If the thickness of the adhesive layer is too thin, sufficient adhesive strength cannot be obtained. Therefore, when transferring the metal deposited by plating, the metal does not adhere to the adhesive layer, and transfer failure may occur. . Therefore, the thickness of the adhesive layer is preferably 1 μm or more, and more preferably 3 μm or more in order to ensure transfer reliability during mass production. In addition, if the thickness of the adhesive layer is large, the manufacturing cost of the adhesive layer increases, and when the laminate is laminated, the amount of deformation of the adhesive layer increases, and the conductive substrate for plating has an insulating layer. In order to increase the chance of contact with it, the thickness of the adhesive layer is preferably 50 μm or less, more preferably 15 μm or less,
In particular, from the viewpoint of reducing the chance that the insulating layer and the adhesive layer are in contact with each other, it is preferably 15 μm or less.

An example of a method for producing a substrate with a conductive layer pattern using the conductive substrate for plating produced according to the present invention is obtained by forming a convex portion 3 (FIG. 2) on a conductive substrate so that the concave portion has a curved shape in cross-sectional shape. The case where (c) is formed will be described as an example with reference to FIG.
First, FIG. 11A is a cross-sectional view showing an example of a conductive substrate for plating in the present invention. The tip portion including the insulating layer 8 and the side surface 3 'of the convex portion 3 in the concave portion 2 of the surface having the convex portion 3 of the conductive substrate 1 having the concave portion 2 of the geometrical drawing shape drawn by the pattern of the convex portion 3 4 'is formed to be exposed.
Next, plating is performed on the conductive base material 1 where the tip portion 4 ′ of the convex portion 3 (ie, the exposed portion of the convex portion 3) is exposed, and the metal 11 is deposited on the tip portion 4 ′ of the convex portion 3. Let FIG. 11B shows a cross-sectional view of this state.
Next, the adhesive film 12 (film obtained by applying the adhesive layer 14 to the film 13 as another base material) is bonded to the surface of the conductive base material 1 on which the metal 11 is deposited. FIG. 11C shows a cross-sectional view of this state. When the adhesive layer 14 of the adhesive film 12 is bonded to the surface on which the metal 11 is deposited, it is heated if necessary according to the characteristics of the pressure-sensitive adhesive.
Then, by peeling off the adhesive film 12, the metal 11 is adhered to the adhesive layer 14 and peeled off from the conductive substrate 1, that is, transferred to the film 13 via the adhesive 14 (that is, the adhesive film). 12). The obtained transfer product is subjected to a curing reaction by irradiating the adhesive layer with radiation to form a substrate 15 with a conductor layer pattern. A sectional view of this state is shown in FIG.
The time when the adhesive layer is irradiated with radiation to cause a curing reaction is the same as or later than when the adhesive film 12 is bonded to the surface of the conductive substrate 1 on which the metal 11 is deposited.
In the above description, another substrate may be other than a film.

The conductor layer pattern (metal 11) of the substrate 15 with a conductor layer pattern obtained above is blackened to obtain a substrate with a conductor layer pattern having a conductor layer pattern that has been blackened. FIG. 12 schematically shows a cross-sectional view of the substrate with a conductor layer pattern. In FIG. 12, a conductor layer pattern (metal 11) whose surface has been blackened to become a black layer 16 is bonded to another base material 13 via an adhesive layer 14.
Further, in the state of FIG. 11B, the metal 11 (plating layer) deposited on the tip portion 4 ′ of the convex portion 3 of the conductive base material 1 is subjected to blackening treatment, and then the subsequent transfer process is performed. FIG. 13 schematically shows a cross-sectional view of the substrate with a conductor layer pattern obtained by performing the process. In FIG. 13, a conductor layer pattern made of metal 11 having a black layer 17 is bonded to another base material 13 with an adhesive layer 14. The black layer 17 is formed on the transfer surface side and side surfaces of the conductor layer pattern. Is formed.
When a substrate with a conductor layer pattern having the above-described blackened conductor layer pattern is used on the front surface of a display as an electromagnetic wave shielding member, generally, the surface on which the black layer is provided faces the viewer side of the display. It is used in this way.
It is also possible to perform both of the above two blackening processes so that the black layer can be seen from either side.
One of the blackening treatment methods described above is a method of forming a black layer on a metal pattern. For this purpose, various methods such as plating, oxidation treatment, and printing can be used on the metal layer.
12 and 13, the conductor layer pattern is not embedded in the adhesive layer.

  When the base material with a conductor layer pattern in the present invention is used as an electromagnetic wave shielding body, it can be used as it is by being attached to a display screen with or without another adhesive as appropriate. You may apply to a display after sticking to. Other substrates need to be transparent for use to block electromagnetic waves from the front of the display.

FIG. 14 shows a cross-sectional view of an electromagnetic wave shielding member obtained by attaching a base material with a conductor layer pattern to another base material. In FIG. 14, the conductor layer pattern which consists of the metal 18 is affixed on the adhesive bond layer 14 laminated | stacked on the base material (other base material) 13, and the other base material 19 is laminated | stacked on this, The metal 18 is embedded in the adhesive layer 14. This can be produced by pressurizing the conductor layer pattern side of the substrate with the conductor layer pattern to another substrate 19 and then irradiating the adhesive layer with radiation to cure. In this case, the conductor layer pattern is embedded in the adhesive layer 14 by applying an appropriate pressure while the adhesive layer 14 before curing has sufficient fluidity or has sufficient fluidity. As the base material (another base material) 13 and the base material (another base material) 19, an electromagnetic wave shielding member having high transparency can be obtained by using a material having transparency and excellent surface smoothness. Obtainable.
FIG. 15 is a cross-sectional view of an electromagnetic wave shielding member in which a base material with a conductor layer pattern is covered with a protective resin. A conductor layer pattern made of a metal 18 is affixed on an adhesive layer 14 laminated on a base material (another base material) 13, and these are covered with a transparent protective resin 20.

FIG. 16 is a cross-sectional view of another aspect of the electromagnetic shielding member. In this electromagnetic wave shielding body, the electromagnetic wave shielding member in FIG. 15 is a surface opposite to the surface on which the conductor layer pattern of the base material 13 is provided, and another base material 22 is bonded through an adhesive layer 21. .
FIG. 17 further shows a cross-sectional view of an electromagnetic wave shielding body according to another aspect. In FIG. 17, a conductor layer pattern made of a metal 18 is bonded to a base material (another base material) 13 via an adhesive layer 14, and is coated with an adhesive or an adhesive 23 made of a transparent resin. Further, a protective film 24 is laminated thereon. Another substrate 22 such as a glass plate is attached to the other surface of the substrate 13 via an adhesive layer 21. In this electromagnetic wave shielding member, a surface on which a conductor layer pattern of a substrate with a conductor layer pattern having a conductor layer pattern bonded to a base material (another base material) 13 via an adhesive layer 14 exists is a transparent resin. 23, and a protective film 24 is further laminated. Then, an adhesive is applied to the other surface (the surface on which nothing is laminated) of the base material 13 of the obtained laminate to form an adhesive layer 21. It can be manufactured by forming and pressing it against another substrate 22 for adhesion. As the transparent protective resin 20 and the transparent resin 23, a radiation curable curable resin may be used in addition to the thermoplastic resin and the thermosetting resin. The use of a radiation curable curable resin is preferable because it cures instantaneously or in a short period of time, thereby increasing productivity. As the radiation curable curable resin, a resin composition having the same composition as the radiation curable adhesive described above can be used.
The thickness of the protective resin or transparent resin (excluding the metal portion) is preferably 3 to 100 μm, and the thickness is selected so that the conductor layer is covered.

  In addition, as described above, a rotating body (roll) can be used as the conductive base material for plating used in the present invention. The rotating body (roll) is preferably made of metal. Furthermore, it is preferable to use a drum electrode or the like used in the drum-type electrolytic deposition method as the rotating body. As described above, the material that forms the surface of the drum electrode may be a material with relatively low plating adhesion, such as stainless steel, chrome-plated cast iron, chrome-plated steel, titanium, or titanium-lined material. preferable. By using a rotating body as the conductive base material, it is possible to obtain a base material with a conductor layer pattern as a roll, and in this case, productivity is greatly increased.

  A process of obtaining a structure as a scroll while continuously peeling a pattern formed by electroplating using a rotating body will be described with reference to FIG. FIG. 18 shows the concept of an apparatus for continuously depositing metal by electroplating and continuously peeling the deposited metal when the drum electrode is used as the conductive base material while rotating the drum electrode. It is sectional drawing (partial front view) shown.

  That is, the electrolytic solution 101 in the electrolytic bath 100 is supplied to the space between the anode 102 and the rotating body 103 such as a drum electrode by the pipe 104 and the pump 105. When a voltage is applied between the anode 102 and the rotator 103 and the rotator 103 is rotated at a constant speed, a metal is electrolytically deposited on the surface of the rotator 103, and a convex portion on the surface of the rotator 103 outside the electrolyte 101 The adhesive layer of the film 107 on which the adhesive layer is formed is pressure-bonded to the metal 106 deposited on the upper surface of the film 106 with the pressure roll 108, and the adhesive layer is formed on the film 107 with the metal 106 being continuously peeled from the rotating body 103. The metal 106 is transferred to form a base material 109 with a conductor layer pattern. This can be wound up on a roll (not shown). Thus, the base material 108 with a conductor layer pattern can be manufactured. In addition, the convex part and the recessed part of the geometrical drawing shape drawn by it are formed in the surface of said rotary body 103. As shown in FIG. Further, after the metal 106 deposited on the upper surface of the convex portion is peeled off from the rotating rotor 103 that is rotating, the surface of the rotating body 103 is etched and washed (not shown) before being immersed in the electrolytic solution 101. May be. Although not shown, a draining roll may be installed at the upper end of the anode 102 in order to prevent the electrolyte circulating at high speed from being ejected upward. The electrolyte stopped by the draining roll is the anode 102. Return to the bottom electrolyte bath from outside and circulated by the pump. Further, although not shown, it is preferable to add a mode in which a copper ion source and additives consumed during the circulation are added as necessary.

Furthermore, as described above, a hoop-like conductive base material can be used as the conductive base material used in the present invention.
The hoop-like conductive base material can be produced by forming convex portions on the surface of the belt-like conductive base material and then joining the end portions. As described above, the material forming the surface of the conductive substrate is made of a material having relatively low plating adhesion, such as stainless steel, chrome-plated cast iron, chrome-plated steel, titanium, or titanium-lined material. It is preferable. When a hoop-like conductive base material is used, the process of blackening treatment, rust prevention treatment, transfer, etc. can be processed in one continuous process, so the productivity of the base material with a conductive pattern is high. Moreover, the base material with an electroconductive pattern can be produced continuously, and it can be set as a product as a scroll. The thickness of the hoop-like conductive substrate may be determined as appropriate, but is preferably 100 to 1000 μm.

  A process of obtaining a structure as a scroll while continuously peeling a conductor layer pattern formed by electroplating using a hoop-like conductive substrate will be described with reference to FIG. FIG. 19 is a conceptual diagram of an apparatus that peels while continuously depositing a conductor layer pattern by electroplating when a hoop-like conductive substrate is used as the conductive substrate.

  The hoop-shaped conductive substrate 110 is pre-treated tank 129, plating tank 130, washing tank 131, blackening tank 132, washing tank 133, rust prevention tank 134, washing tank 135 using transport rolls 111 to 128. Set up to move around in order. In the pretreatment tank 129, pretreatment such as degreasing or acid treatment of the conductive substrate 110 is performed. Thereafter, a metal is deposited on the conductive substrate 110 in the plating tank 130. Thereafter, the water washing tank 131, the blackening treatment tank 132, the water washing tank 133, the rust prevention treatment tank 134, and the water washing tank 135 are sequentially passed through, and the surface of the metal deposited on the conductive substrate 110 is blackened. Further rust prevention treatment. Although only one tank is shown in the figure after each treatment process, a plurality of tanks may be used as needed, or other pretreatment tanks may be provided before each treatment process. Next, the plastic film substrate 136 on which the adhesive layer is laminated is transferred between the conductive substrate 110 and the pressure roll 137 on the transport roll 128 so that the metal deposited on the upper surface of the convex portion of the conductive substrate 110 is transferred. Then, the metal can be transferred to the plastic film substrate 136 to continuously manufacture the substrate 138 with a conductive layer pattern. The obtained base material 138 with a conductive layer pattern can be wound into a roll. If necessary, the pressure-bonding roll 137 can be heated. Although not shown, the plastic film substrate 136 may be preheated through a preheating tank before passing through the pressure-bonding roll. In addition, release PET or the like may be inserted as needed for winding the transferred film. Furthermore, after the metal is transferred, the hoop-like conductive base material repeats the above steps. Thus, the base material with a conductor layer pattern can be manufactured continuously with high productivity.

  Further, the present invention is not limited to the plating method as described above, and can be manufactured by a single wafer. When performed in a single wafer, it is easy to handle when preparing a conductive substrate for plating, and even when the same insulating layer is peeled off after repeated use of the same conductive substrate for plating, it is drum-shaped. In the case of a hoop-shaped substrate, it is difficult to extract or replace only a specific portion. However, if it is a sheet, it is possible to extract or replace only the conductive substrate for plating in which a defect has occurred. In this way, by making a single wafer, it is easy to handle when a problem occurs in the conductive substrate for plating. The thickness of the sheet-like conductive base material may be determined as appropriate, but the thickness is preferably 20 μm or more in consideration of giving sufficient strength not depending on the stirring of the liquid in the plating tank. If it is too thick, the weight increases and it is difficult to handle, so a thickness of 10 μm or less is preferable.

  The line width of the conductor layer pattern of the base material with the conductor layer pattern finally obtained (meaning the conductor layer pattern that has been blackened when the metal pattern is blackened) is 40 μm or less, and the line spacing is 100 μm or more. It is preferable to set it as the range. Further, the line width is more preferably 25 μm or less from the viewpoint of invisibility of the conductor layer pattern (geometrical figure), and the line interval is more preferably 120 μm or more from the viewpoint of visible light transmittance. If the line width is too small and thin, the surface resistance becomes too large and the shielding effect is inferior, so 1 μm or more is preferable. The larger the line spacing, the better the aperture ratio and the visible light transmittance. When the conductor layer pattern obtained by the present invention is used on the front surface of the display, the aperture ratio needs to be 50% or more, more preferably 60% or more. If the line interval becomes too large, the electromagnetic wave shielding property is deteriorated. Therefore, the line interval is preferably set to 1000 μm (1 mm) or less. When the line interval is complicated by a combination of geometric figures or the like, the area is converted into a square area with the repetition unit as a reference, and the length of one side is set as the line interval.

  Further, the thickness of the conductor layer pattern line is preferably 50 μm or less. When applied as an electromagnetic wave shielding sheet on the front surface of the display, the thinner the thickness, the wider the viewing angle of the display and the more preferable as an electromagnetic wave shielding material. Therefore, the time required for the reduction is preferably 20 μm or less, and more preferably 10 μm or less. If the thickness is too thin, the surface resistance becomes too high and the electromagnetic wave shielding effect becomes inferior. Also, the strength of the conductor layer pattern is inferior, and peeling from the conductive substrate during transfer becomes difficult. And more preferably 1 μm or more.

  In the base material with a conductor layer pattern in the present invention, the aperture ratio of the conductor layer pattern can be increased, thereby making it possible to improve the translucency. When a metal such as copper, silver or nickel is used as the conductor layer, the conductivity is particularly excellent. The base material with a conductor layer pattern in the present invention can be used as a translucent electromagnetic wave shielding member.

  When using the base material with a conductor layer pattern in the present invention as an electromagnetic wave shielding member, it is preferable to use the outer side of the translucent electromagnetic wave shield part as an earth part (corresponding to the region B). This earth part may have the same pattern as the translucent electromagnetic wave shield part (corresponding to the region A), or may have a different pattern. Further, the ground portion may be a pattern as described above or a completely solid film. It is preferable that the ground part is electrically connected to the inner translucent electromagnetic wave shield part.

  When the substrate with a conductor layer pattern obtained as described above is used as an electromagnetic wave shielding member, an antireflection layer, a near infrared shielding layer, or the like may be further laminated. The base material itself that transfers the metal deposited on the conductive base material may also serve as a functional layer such as an antireflection layer or a near infrared shielding layer. Furthermore, a cover film (for example, the protective film 24 in FIG. 17) used when forming a protective layer on the conductor layer pattern may also serve as functional layers such as an antireflection layer and a near infrared shielding layer.

  In addition, when the substrate with a conductor layer pattern in the present invention is used as an electromagnetic wave shielding member on the front surface of a display or the like, the conductive layer pattern is blackened in order to ensure visibility including antireflection and the like. Preferably there is. In the electromagnetic wave shielding member, the conductive layer pattern is preferably black on the front side because it satisfies requirements such as high contrast and a black screen when the display is turned off.

The protruding height of the above-described conductor layer pattern will be described with reference to the drawings.
FIG. 20 is a partial cross-sectional view (schematic diagram) showing a state in which a conductor layer pattern made of metal 11 is transferred to another base material 13 via an adhesive layer 14. The conductor layer pattern is shown on top. In FIG. 20, the height u is the height of the conductor layer, and v is the protruding height of the conductor layer from the adhesive layer. In this case, since the uppermost end of the conductor layer is higher than the uppermost end of the adhesive layer, v is a positive value. v is the vertical difference between the uppermost end of the conductor layer and the uppermost end of the adhesive layer in the vicinity of the conductor layer, and the adhesive layer is often raised in the vicinity of the conductor layer. Here, the reference surface is the surface of another substrate.

(Preparation of a conductive substrate having a convex pattern and a geometrical figure-shaped concave portion drawn thereby)
A resist film (Photec H-Y920, 20 μm thickness, manufactured by Hitachi Chemical Co., Ltd.) was bonded to both sides of a 10 cm square stainless steel (SUS304, finish 3 / 4H, thickness 100 μm, manufactured by Nisshin Steel Co., Ltd.). . The bonding conditions were a roll temperature of 105 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Next, the line width of the light transmission part is 40 μm, the line pitch is 300 μm, and the bias angle is 45 ° (in the regular square, the line is arranged at an angle of 45 degrees with respect to the side of the regular square). Then, the negative film formed in a lattice shape was allowed to stand on one surface of the stainless steel plate to which the resist film was bonded. Using an ultraviolet irradiation device, ultraviolet rays were irradiated at 120 mJ / cm ² from above and below the stainless plate on which the negative film was placed under a vacuum of 600 mmHg or less. Subsequently, a resist mask having a line width of 40 μm, a line pitch of 300 μm, and a bias angle of 45 ° was formed on the SUS plate by developing with a 1% sodium carbonate aqueous solution. In addition, since the entire surface opposite to the surface on which the pattern is formed is exposed, it is not developed and a resist film is formed on the entire surface.
Next, the SUS plate was etched using an aqueous ferric chloride solution (45 ° Be ′, manufactured by Tsurumi Soda Co., Ltd.) heated to 40 ° C. Etching is performed until the line width of the SUS plate reaches about 7 μm, and the resist mask remains on the conductive substrate having the convex pattern having the upper surface and the concave portion having the geometrical shape drawn thereby. A conductive substrate (intermediate product) was produced. When observed with a microscope from above the resist mask, the width of the line (the width of the upper surface of the convex portion) was 5 to 8 μm. Note that the surface opposite to the surface on which the pattern was formed was not etched because a resist film was formed on the entire surface.
Next, after washing with water and drying at 100 ° C. for 10 minutes, the resist mask was peeled off with a 2% aqueous sodium hydroxide solution.

(Preparation of a conductive substrate having an insulating film)
Next, with the conductive base material (intermediate product) as a cathode, the anode as a stainless steel (SUS304) plate, in a cationic electrodeposition paint (Insulated 3020, manufactured by Nippon Paint Co., Ltd.), under the condition of 15V10 seconds, Electrodeposition coating was applied to a stainless steel plate etched into a lattice pattern. Next, the electrodeposition coating film was baked at 230 ° C. for 40 minutes under a nitrogen stream. The oxygen concentration in the furnace was 1%. The coating thickness of the electrodeposition paint was 2.5 μm. The conductive substrate for plating in which the recesses thus obtained were covered with an insulating film was such that the insulating film was selectively formed in the recesses as shown in FIG. .

(Copper plating)
Next, an adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface (back surface) where the uneven pattern of the conductive base material for plating obtained above was not formed. Electrolytic copper plating was performed using the conductive substrate for plating with the adhesive film attached as a cathode. In the electrolytic copper plating bath (copper sulfate (pentahydrate) 230 g / L, sulfuric acid 55 g / L, cube light # 1 AHH (Sugawara Eugene Corporation, additive) 4 ml / L aqueous solution, 25 ° C.) for the above plating The conductive substrate was immersed in the cathode and the phosphorous copper was immersed in the anode. Voltage was applied to both electrodes, the current density was set to 5 A / dm ² , and plating was performed until the thickness of the metal deposited on the upper surface of the convex portion of the conductive base material for plating became approximately 4 μm.

(Preparation of adhesive film for transfer)
The following ultraviolet curable resin composition 1 was used as an adhesive. This ultraviolet curable resin composition was applied to a thickness of 15 μm on a 125 μm thick polyethylene terephthalate (PET) film (A-7300, manufactured by Toyobo Co., Ltd.) to prepare an adhesive film for transfer. Next, the surface tack value was measured and found to be 30 gf.
<Composition of UV curable resin composition 1>
Polymer (Methyl methacrylate 50% by weight, methacrylic acid 25% by weight and styrene 25% by weight copolymer, weight average molecular weight 51200, dispersity 1.96): 55 parts by weight monomer FA321M (manufactured by Hitachi Chemical Co., Ltd., EO modified) Dimethacrylate): 16 parts by weight UA1137 (manufactured by Shin-Nakamura Chemical Co., Ltd., urethane dimethacrylate): 10 parts by weight UA21 (manufactured by Shin-Nakamura Chemical Co., Ltd., tris isocyanurate): 5 parts by weight FA-023M (Shin-Nakamura Chemical) Industrial Co., Ltd., EO / PO modified dimethacrylate): 5 parts by weight TMPT21 (manufactured by Hitachi Chemical Co., Ltd., trimethylolpropane EO modified trimethacrylate): 4 parts by weight M114 (manufactured by Kyoeisha Chemical Co., Ltd., nonylphenyl EO modified acrylate) ): 5 parts by weight photopolymerization initiator Irgac 184 (supplied by Ciba Specialty Chemicals, 1-hydroxy - cyclohexyl - phenyl ketone): 3 parts by weight

(Transcription)
The surface of the adhesive layer of the transfer adhesive film and the copper-plated surface of the conductive substrate for plating were bonded together using a roll laminator. Lamination conditions were a roll temperature of 50 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Subsequently, when the adhesive film bonded to the plating transfer plate was peeled off, copper deposited on the upper surface of the convex portion of the conductive substrate for plating was transferred to the adhesive film. As a result of observing the surface of the conductive substrate for plating after the transfer, there was no place where the insulating film was peeled off.

(Curing the adhesive layer)
Next, a cover film (OPP) (E-200C, manufactured by Oji Paper Co., Ltd.) was bonded to the adhesive film to which the conductor layer pattern was transferred from above the conductor layer pattern using a roll laminator. Lamination conditions were a roll temperature of 50 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Next, the adhesive layer was cured by irradiating UV light at 350 mJ / cm ² with an exposure machine (HMW-6N manufactured by Oak Co., Ltd.) from the transparent substrate side of the adhesive film to which the conductor layer pattern bonded with the cover film was transferred. . Next, the cover film was peeled off, and the surface tack value of the cured adhesive layer was measured and found to be 4 gf.
As a result, the line width is 11 to 18 μm, the line pitch is 300 ± 2 μm, the thickness (center part) of the conductor layer is 3 to 5 μm, the height of the conductor layer is 4 to 7, and the protruding height of the conductor layer is 0.6 to 1.0. The base material with a conductor layer pattern which consists of a grid | lattice-like metal pattern was obtained.

(Formation of protective film)
The cover film on the surface where the conductor layer pattern of the base material with the conductor layer pattern obtained above is removed, and then UV curable resin Hitaroid 7983AA3 (manufactured by Hitachi Chemical Co., Ltd.) is applied at a coating speed of 10 m / min. And a cover film (OPP) (E-200C, manufactured by Oji Paper Co., Ltd.) was laminated thereon. Subsequently, the ultraviolet curable resin was cured by irradiating ultraviolet rays of 1 J / cm ² using an ultraviolet lamp to obtain a substrate with a conductor layer pattern having a protective film. As a result of peeling the cover film and observing the appearance from both sides of the protective film layer side and the base material PET side with a magnifying microscope, no generation of bubbles was observed, and the haze value of the base material with the conductor layer pattern was 2.5. Met.

(Repeated use)
Next, as a result of repeating the copper plating-transfer process 500 times in the same manner as described above using the above conductive base material for plating, there is no change in the transfer property of the copper plating, and the peeled portion of the insulating film is also observed. There wasn't.

  In the same manner as in Example 1, a conductive base material having an insulating film was prepared. Further, in the same manner as in Example 1, the thickness of the metal deposited on the upper surface of the convex portion of the conductive base material for plating was 10 μm. Plated as a guide.

(Transcription)
The surface of the adhesive layer of the same adhesive film for transfer as prepared in Example 1 and the surface of the conductive substrate for plating subjected to copper plating were bonded together using a roll laminator. Lamination conditions were a roll temperature of 50 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Subsequently, when the adhesive film bonded to the plating transfer plate was peeled off, copper deposited on the upper surface of the convex portion of the conductive substrate for plating was transferred to the adhesive film. As a result of observing the surface of the conductive substrate for plating after the transfer, there was no place where the insulating film was peeled off.

Next, a cover film (OPP) film was bonded to the adhesive layer to which the conductive layer pattern was transferred in the same manner as in Example 1, and the adhesive was cured. As a result, the surface tack value of the cured adhesive layer was measured and found to be 5 gf.
Accordingly, the line width is 13 to 18 μm, the line pitch is 300 ± 2 μm, the conductor layer thickness (center part) is 10 to 13 μm, the conductor layer height is 12 to 14, and the conductor layer protruding height is 2.8 to 3.2. The base material with a conductor layer pattern which consists of a grid | lattice-like metal pattern was obtained.
Further, a protective film was formed in the same manner as in Example 1. As a result of observing the appearance of the obtained base material with a conductor layer pattern with a protective film from both sides of the protective film layer side and the base material PET side with a magnifying microscope, no bubbles were observed and the haze value was 2.8. Met.

  A conductive base material having an insulating film was prepared in the same manner as in Example 1, and the thickness of the metal deposited on the upper surface of the convex portion of the conductive base material for plating was 5 μm as in Example 1. Plated as a guide.

(Preparation of adhesive film for transfer)
The following ultraviolet curable resin composition 2 was used as an adhesive. This ultraviolet curable resin composition 2 was applied to a polyethylene terephthalate (PET) film (A-7300, manufactured by Toyobo Co., Ltd.) having a thickness of 125 μm so as to have a thickness of 15 μm, thereby preparing a transfer adhesive film. Next, the surface tack value was measured and found to be 35 gf.
<Composition of UV curable resin composition 2>
Polymer (Methyl methacrylate 50% by weight, methacrylic acid 25% by weight and styrene 25% by weight copolymer, weight average molecular weight 51200, dispersity 1.96): 55 parts by weight monomer FA321M (manufactured by Hitachi Chemical Co., Ltd., EO modified) Dimethacrylate): 16 parts by weight UA1137 (manufactured by Shin-Nakamura Chemical Co., Ltd., urethane dimethacrylate): 10 parts by weight UA21 (manufactured by Shin-Nakamura Chemical Co., Ltd., tris isocyanurate): 5 parts by weight FA-023M (Shin-Nakamura Chemical) Industrial Co., Ltd., EO / PO modified dimethacrylate): 5 parts by weight TMPT21 (manufactured by Hitachi Chemical Co., Ltd., trimethylolpropane EO modified trimethacrylate): 4 parts by weight M114 (manufactured by Kyoeisha Chemical Co., Ltd., nonylphenyl EO modified acrylate) ): 5 parts by weight photopolymerization initiator Irgac 184 (supplied by Ciba Specialty Chemicals, 1-hydroxy - cyclohexyl - phenyl ketone): 3 parts by weight

(Transcription)
The surface of the adhesive layer of the transfer adhesive film and the copper-plated surface of the conductive substrate for plating were bonded together using a roll laminator. Lamination conditions were a roll temperature of 50 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Subsequently, when the adhesive film bonded to the plating transfer plate was peeled off, copper deposited on the upper surface of the convex portion of the conductive substrate for plating was transferred to the adhesive film. As a result of observing the surface of the conductive substrate for plating after the transfer, there was no place where the insulating film was peeled off.

Next, a cover film (OPP) film was bonded to the adhesive layer to which the conductive layer pattern was transferred in the same manner as in Example 1, and the adhesive was cured. As a result, the surface tack value of the cured adhesive layer was measured and found to be 4 gf.
Thus, a grid having a line width of 15 to 19 μm, a line pitch of 300 ± 2 μm, a conductor thickness (center portion) of 3 to 6 μm, a conductor layer height of 5 to 7 μm, and a conductor layer protrusion height of 1.0 to 1.3 The base material with a conductor layer pattern which consists of a metal-like pattern was obtained.

  Further, a protective film was formed in the same manner as in Example 1. As a result of observing the appearance of the obtained base material with a conductor layer pattern with a protective film from both sides of the protective film layer side and the base material PET side with a magnifying microscope, no bubbles were observed and the haze value was 2.9. Met.

  In the same manner as in Example 1, a conductive base material having an insulating film was prepared. Further, in the same manner as in Example 1, the thickness of the metal deposited on the upper surface of the convex portion of the conductive base material for plating was 1 μm. Standard plating.

(Transcription)
The surface of the adhesive layer of the same adhesive film for transfer as prepared in Example 1 and the surface of the conductive substrate for plating subjected to copper plating were bonded together using a roll laminator. Lamination conditions were a roll temperature of 50 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Subsequently, when the adhesive film bonded to the plating transfer plate was peeled off, copper deposited on the upper surface of the convex portion of the conductive substrate for plating was transferred to the adhesive film. As a result of observing the surface of the conductive substrate for plating after the transfer, there was no place where the insulating film was peeled off.

Next, a cover film (OPP) film was bonded to the adhesive layer to which the conductive layer pattern was transferred in the same manner as in Example 1, and the adhesive was cured. As a result, the surface tack value of the cured adhesive layer was measured and found to be 5 gf.
As a result, the line width is 11 to 18 μm, the line pitch is 300 ± 2 μm, the thickness (center portion) of the conductor layer is 1 to 2 μm, the height of the conductor layer is 3 to 4 A substrate with a conductor layer pattern composed of a −3.3 μm grid-like metal pattern was obtained.
Further, a protective film was formed in the same manner as in Example 1. As a result of observing the appearance of the obtained substrate with a protective film-coated conductor layer pattern from both sides of the protective film layer side and the substrate PET side with a magnifying microscope, no generation of bubbles was observed, and the haze value was 2.1. Met.

(Comparative Example 1)
In the same manner as in Example 1, a conductive base material having an insulating film was prepared. Further, in the same manner as in Example 1, the thickness of the metal deposited on the upper surface of the convex portion of the conductive base material for plating was 10 μm. It plated until it became.

(Transcription)
The surface of the adhesive layer of the same adhesive film for transfer as prepared in Example 1 and the surface of the conductive substrate for plating subjected to copper plating were bonded together using a roll laminator. Lamination conditions were a roll temperature of 50 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Subsequently, when the adhesive film bonded to the plating transfer plate was peeled off, copper deposited on the upper surface of the convex portion of the conductive substrate for plating was transferred to the adhesive film. As a result, the line width is 16 to 19 μm, the line pitch is 300 μm, the conductor thickness is 10 μm, the conductor layer pattern is embedded in the adhesive layer by 3.0 μm, and protrudes 7.0 μm from the adhesive layer surface. The base material with a conductor layer pattern which consists of a metal-like pattern was obtained. As a result of observing the surface of the conductive substrate for plating after the transfer, there was no place where the insulating film was peeled off.

  Next, a cover film (OPP) film was bonded to the adhesive layer to which the conductive layer pattern was transferred in the same manner as in Example 1, and the adhesive was cured. As a result, the surface tack value of the cured adhesive layer was measured and found to be 4 gf.

  Further, a protective film was formed in the same manner as in Example 1. As a result of observing the appearance of the obtained base material with a conductor layer pattern with a protective film from both sides of the protective film layer side and the base material PET side with a magnifying microscope, it was confirmed that many fine bubbles were generated. The haze value was 4.8.

(Preparation of a conductive substrate having a convex pattern and a geometrical figure-shaped concave portion drawn thereby)
Resist film (Photech H-Y920, 20 μm thickness, 680 mm width, manufactured by Hitachi Chemical Co., Ltd.) 700 × 1100 mm stainless steel plate (SUS304, finish 3 / 4H, thickness 100 μm, manufactured by Nisshin Steel Co., Ltd.) (Corresponding to FIG. 7A). The bonding conditions were a roll temperature of 105 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Next, the line width of the light transmission part is 40 μm, the line pitch is 300 μm, and the bias angle is 45 ° (in the regular square, the line is arranged at an angle of 45 degrees with respect to the side of the regular square). Then, the negative film formed in a lattice shape having the same pattern size as the substrate size was allowed to stand on the surface on which the stainless steel resist film was bonded. Using an ultraviolet irradiation device, ultraviolet rays were irradiated at 120 mJ / cm 2 from above and below the stainless plate on which the negative film was placed under a vacuum of 600 mmHg or less. Further, by developing with a 1% aqueous sodium carbonate solution, a resist mask having a line width of 40 μm, a line pitch of 300 μm, and a bias angle of 45 ° was formed on the SUS plate. Furthermore, the SUS plate on which the resist was formed was heat-treated at 150 ° C. for 30 minutes to improve the adhesion between the resist and the SUS plate. Since the entire surface opposite to the surface on which the pattern is formed is exposed, it is not developed and a resist film is formed on the entire surface (corresponding to FIG. 7B).
Next, 1.5 t of an aqueous ferric chloride solution (47 ° Be ′, manufactured by Rasa Kogyo Co., Ltd.) was added to a rotary etching machine having a width of 800 mm (made by Ishii Corporation). The temperature of the etching solution was 40 ° C., and the SUS plate was etched for 300 seconds at a spray thickness of 3 kg / cm 2. An electroconductive substrate for plating in which a resist mask remained on an electroconductive substrate having a pattern of convex portions having an upper surface and a concave portion having a geometric diagram shape drawn thereby was produced. The width of the upper surface of the convex portion was 5 to 8 μm, the interval (pitch) between the upper surfaces of the convex portions was 300 ± 2 μm, and the height of the convex portion was 35 to 38 μm.
The surface opposite to the surface on which the convex pattern was formed was not etched because the resist film was formed on the entire surface (corresponding to FIG. 7C). Next, when the conductive substrate for plating was immersed in a 5% aqueous sodium hydroxide solution at a liquid temperature of 30 ° C., the surface on which the convex pattern was formed and the resist film formed on the opposite surface were removed (FIG. 7). Corresponding to (d)).

(Preparation of a conductive substrate having an insulating film)
A DLC film was formed by an RF plasma CVD apparatus (HTC 1500, manufactured by Hauzer Technology Coating BV). The RF plasma CVD apparatus includes an upper electrode, a vacuum chamber having a lower electrode on which a substrate is placed, and a gas inlet, an RF power source for generating plasma, a switch / matching box, a matching box, a vacuum pump, and the like. The vacuum chamber is depressurized to a vacuum degree of 10-3 torr by a vacuum pump. First, the substrate is cleaned by exciting plasma with Ar gas, and then using the chromium as a target material, both sides of the conductive substrate having the convex pattern produced above and the concave portion of the geometrical shape drawn thereby. As a result, a chromium layer of about 1 μm was formed. In addition, the masking tape was bonded to the outer periphery 10mm of 4 sides before sputtering, in order to take the conduction | electrical_connection at the time of plating on the back surface. Next, acetylene gas is introduced at a flow rate of 15 sccm, and a pattern of convex portions and a pattern are drawn on the chromium layer as an intermediate layer so that the film thickness is 2.5 to 3.5 μm at an RF output of 500 W. DLC layers were formed on both sides of the conductive substrate having a geometrically shaped recess (corresponding to FIG. 8 (e)). Finally, the masking tape bonded to the back surface was peeled off to expose the SUS surface. I let you.

(Dry etching with oxygen plasma)
In a conductive substrate for plating in which an insulating layer is formed on the entire surface, a silicon-based resist DLR-501 (manufactured by NTT Advantes Technology Co., Ltd.) is applied to the surface on which the convex pattern is formed by a die coater (Tatsumo Co., Ltd.). The film thickness was 1 to 3 μm. Subsequently, it was heated and dried for 90 seconds on a hot plate heated to 90 ° C. The thickness of the silicon resist in the TOP portion of the insulating layer was 1 μm (corresponding to FIG. 8F). Further, the entire surface was lightly manually polished with # 4000 polishing paper, and the silicon resist layer on the insulating layer on the upper surface of the convex portion was removed (corresponding to FIG. 8G).
Next, using a plasma CVD apparatus (HTC1500, manufactured by Hauzer Technology Coating BV), the insulating layer on the upper surface of the convex portion was dry-etched using oxygen plasma (corresponding to FIG. 9H).
The gas composition was a mixed gas of oxygen 16 sccm and argon 2 sccm, and the gas pressure was 4 Pa. Further, dry etching was performed at an RF output of 300 W for 40 minutes. Next, the conductive substrate for plating is immersed in a solution of dipropylene glycol monomethyl ether: monoisopropanolamine = 75: 25 heated to 50 ° C. for 3 minutes, and the silicon resist formed on the insulating film is peeled off. did. As described above, the stainless steel at the tip of the convex portion was exposed, and the exposed width was 5.9 to 10.0 μm and the insulation height was 32 to 36.5 μm. The insulating layer was removed from the upper end of the convex part to 1.5 to 2.5 μm in the height direction. That is, the height of the exposed portion of the convex portion was 1.5 to 2.5 μm. Further, the width of the upper surface of the convex portion of the conductive substrate for plating after etching was not different from 5 to 8 μm. As described above, a conductive substrate for plating for transfer was obtained (corresponding to FIG. 9 (i)).
Electron micrograph of the cross section showing that the exposed portion of the convex portion of the conductive substrate for plating does not increase in width as it advances in the tip direction, and as a whole the width is smaller than the lower portion of the convex portion. I confirmed. Further, the difference in the width direction between the first position and the second position with respect to the height difference between the end (first position) of the insulating layer on the side surface of the convex portion and the position higher than that (second position). As shown in FIG. 6, the relationship with (reduction width) is the relationship of the width d10 with respect to the height h10, that is, d10 / h10 is 0.306 to 0.404 (corresponding to 68 to 73 °). there were.

(Copper plating)
After immersing the conductive substrate for plating prepared above in the following copper pyrophosphate electrolyte, plating is performed at a current density of 15 A / dm2 for 55 seconds, and the exposed portion of the convex portion of the conductive substrate for plating is exposed. Copper was deposited. Next, plating was carried out for 5 seconds at a current density of 30 A / dm 2, and the surface of the previously deposited copper was blackened. As a result, the thickness was 3 to 5 μm on the upper surface of the metal convex portion deposited on the exposed portion of the convex portion. The conductive substrate having copper plating (conductor pattern) whose surface was blackened on the exposed portion of the convex portion was subsequently washed with water and dried.
(Electrolyte composition, etc.)
Copper pyrophosphate 100g / L
Potassium pyrophosphate 200g / L
Ammonia water (30%) 5mL / L
pH 8-9
Current density 20A / dm2
Bath temperature 30 ° C
Anode Copper plate Rotation speed 0.55m / min

(Transcription, etc.)
Using the same transfer adhesive film as in Example 1, transfer was performed in the same manner as in Example 1, and the adhesive layer was cured in the same manner as in Example 1.
In this way, the line width is 11 to 15 μm, the line pitch is 300 ± 2 μm, the thickness (center portion) of the conductor layer is 3 to 5 μm, the height of the conductor layer is 6 to 8, and the protruding height of the conductor layer is 0.5 to 0. A substrate with a conductor layer pattern in which a grid-like metal pattern of .8 was transferred onto an adhesive film was obtained.

(Formation of protective film)
In the same manner as in Example 1, a protective film was formed on the surface of the substrate with the conductor layer pattern on which the conductor layer pattern was present. As a result of observing the appearance of the obtained base material with a conductor layer pattern with a protective film from both sides of the protective film layer side and the base material PET side with a magnifying microscope, no bubbles were observed and the haze value was 2.3. Met.

(Repeated use)
As a result of repeating the copper plating-transfer process 5000 times in the same manner as described above using the above-described conductive substrate for plating transfer, there was no change in the transferability of copper plating, and no peeling of the insulating film was observed. It was.

(Preparation of a conductive substrate having a convex pattern and a geometrical figure-shaped concave portion drawn thereby)
700 × 1100 mm stainless steel (SUS316L, finish 3 / 4H, thickness 100 μm, manufactured by Nisshin Steel Co., Ltd.) 400 screen polyester screen plate with line width 40 μm, line pitch 225 μm, bias angle 45 ° Then, an alkali-removable etching resist ink (226 Black, manufactured by Nazdar Company) was applied using a plate on which a lattice pattern was formed, and then excess resist ink was scraped off at a speed of 50 mm / min with a squeegee. In the formation of the pattern, only a geometric figure was formed in the range of 650 × 1050 mm in the center of the SUS substrate. The resist ink was applied to the entire other surface. Dry at 120 ° C. for 5 minutes using a drying furnace, and on one side of the SUS plate, a resist mask with a line width of 40 μm, a line pitch of 225 μm, and a bias angle of 45 ° is provided in the center of the SUS substrate in the range of 650 × 1050 mm. Then, a resist film was formed on the entire other surface (corresponding to FIG. 7B).
Next, 1.5 t of an aqueous ferric chloride solution (47 ° Be ′, manufactured by Rasa Kogyo Co., Ltd.) was added to a rotary etching machine having a width of 800 mm (made by Ishii Corporation). The temperature of the etching solution was 50 ° C., and the SUS plate was etched for 180 seconds with a spray thickness of 3 kg / cm 2.
The actual width of the upper surface of the convex portion after etching was 18 to 23 μm, the interval (pitch) of the upper surface of the convex portion was 225 ± 2 μm, and the height of the convex portion was 12 to 17 μm. The surface opposite to the surface on which the pattern was formed was not etched because the resist film was formed on the entire surface (corresponding to FIG. 7C). Furthermore, the entire surface was etched in a range of 50 mm on each of the four sides from the outer periphery of the pattern. Next, when the conductive substrate for plating was immersed in a 5% aqueous sodium hydroxide solution at a liquid temperature of 30 ° C., the surface on which the convex pattern was formed and the resist film formed on the opposite surface were removed (FIG. 7). Corresponding to (d)).

(Preparation of a conductive substrate having an insulating film)
Next, a protective adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) is bonded to the surface opposite to the surface on which the convex pattern of the conductive substrate is present, and a cationic electrodeposition paint (power As a result of electrodeposition coating of Knicks 110F (manufactured by Nippon Paint Co., Ltd.) at Shuei Sangyo Co., Ltd., an insulating layer having a thickness of 5 to 7 μm was formed on the SUS pattern forming surface. After washing with water, the electrodeposition coating film was baked under conditions of 180 ° C. for 30 minutes to form an insulating layer. Thus, the electroconductive base material by which the insulating film was given to the convex part pattern surface whole surface was obtained (corresponding to FIG.8 (e)).

(Dry etching with oxygen plasma)
In a conductive substrate for plating in which an insulating layer is formed on the entire surface, a silicon-based resist DLR-501 (manufactured by NTT Advantes Technology Co., Ltd.) is applied to the surface on which the convex pattern is formed by a die coater (Tatsumo Co., Ltd.). The film thickness was 1 to 3 μm. Subsequently, it was heated and dried for 90 seconds on a hot plate heated to 90 ° C. The thickness of the silicon resist in the TOP portion of the insulating layer was 1 μm (corresponding to FIG. 8F). Further, the entire surface was lightly manually polished with # 4000 polishing paper, and the silicon resist layer on the insulating layer on the upper surface of the convex portion was removed (corresponding to FIG. 8G).
Next, using a plasma CVD apparatus (HTC1500, manufactured by Hauzer Technology Coating BV), the insulating layer on the upper surface of the convex portion was dry-etched using oxygen plasma (corresponding to FIG. 9H).
The gas composition was a mixed gas of oxygen 16 sccm and argon 2 sccm, and the gas pressure was 4 Pa. Further, dry etching was performed at an RF output of 300 W for 10 minutes. Next, the conductive substrate for plating is immersed in a solution of dipropylene glycol monomethyl ether: monoisopropanolamine = 75: 25 heated to 50 ° C. for 3 minutes, and the silicon resist formed on the insulating film is peeled off. did.
As a result, the stainless steel at the tip of the convex portion was exposed, and the exposed width was 29.9 to 35.0 μm and the insulation height was 8.5 to 14.1 μm. The insulating layer was removed from the upper end of the convex part to 0.5 to 1.5 μm in the height direction. That is, the height of the exposed portion of the convex portion was 0.5 to 1.5 μm. Further, the width 29-32 μm of the upper surface of the convex portion of the conductive substrate for plating after etching was not changed.
As described above, a conductive substrate for plating with a protective adhesive film attached thereto was obtained (corresponding to FIG. 9 (i)).
Electron micrograph of the cross section showing that the exposed portion of the convex portion of the conductive substrate for plating does not increase in width as it advances in the tip direction, and as a whole the width is smaller than the lower portion of the convex portion. I confirmed. Further, the difference in the width direction between the first position and the second position with respect to the height difference between the end (first position) of the insulating layer on the side surface of the convex portion and the position higher than that (second position). As shown in FIG. 6, the relationship with (reduction width) is the relationship of the width d10 with respect to the height h10, that is, d10 / h10 is 0.870 to 1.000 (corresponding to 45 to 49 °). there were.

(Copper plating)
In the same manner as in Example 6, by plating on the conductive substrate for plating, a copper plating (conductor pattern) whose surface was blackened was formed on the exposed portion of the convex portion, washed with water, and dried.
(Transcription, etc.)
Using the same transfer adhesive film as in Example 1, transfer was performed in the same manner as in Example 1, and the adhesive layer was cured in the same manner as in Example 1.
Thus, the line width is 34 to 38 μm, the line pitch is 225 ± 2 μm, the thickness of the conductor layer (central part) is 2.5 to 3.5 μm, the height of the conductor layer is 4 to 7 μm, and the protruding height of the conductor layer is − A base material with a conductor layer pattern in which a grid-like metal pattern of 0.6 to −2.3 μm was transferred onto the adhesive film was obtained.
(Formation of protective film)
In the obtained base material with a conductor layer pattern, a protective film was formed in the same manner as in Example 1 on the surface on which the conductor layer pattern of each pattern was formed. The material was obtained. As a result of observing the appearance of the obtained substrate with a conductor layer pattern with a protective film from both sides of the protective film layer side and the substrate PET side with a magnifying microscope, no generation of bubbles was observed, and the haze value was 2.0. Met.

(Repeated use)
As a result of repeating the copper plating-transfer process 500 times in the same manner as described above using the above-described conductive substrate for plating transfer, there was no change in the transferability of copper plating, and no peeling of the insulating film was observed. It was.

The evaluation results of the above examples and comparative examples are shown in Table 1.

In the present invention, measurement of width, thickness, height, etc. can be performed as follows. Applicable in the examples are as follows. In the examples, 5 points were arbitrarily selected and measured.
The width of the upper surface of the convex portion is obtained by cutting a part of the conductive base material and casting it with a resin, and observing the cross section with a microscope (Digital Microscope VHX-500, manufactured by Keyence Corporation) at a magnification of 1000 times. To measure. Since the upper surface of the convex portion is not roughened by the etching solution, it has a glossy appearance under microscopic observation. This glossy portion is defined as the upper surface of the convex portion.
The interval (pitch) between the upper surfaces of the convex portions is measured by observing at a magnification of 200 times using a microscope (Digital Microscope VHX-500, manufactured by Keyence Corporation).
Further, the height of the convex portion, the thickness of the insulating layer, and the protruding amount are measured by cutting a part of the conductive base material and casting it with a resin, and observing the cross section by SEM at a magnification of 3000 times. .
The height h10 and the width d10 of the exposed part of the tip of the convex part at the first position and the second position are cut out of a part of the conductive base material and cast with resin, and the magnification is 10000 times. Is measured by SEM observation.
The line width and the conductor thickness are measured by cutting a part of the obtained substrate with a conductor layer pattern and casting it with a resin, and observing the cross section with a magnification of 3000 times by SEM. The line pitch is measured by observing at a magnification of 200 times using a microscope (digital microscope VHX-500, manufactured by Keyence Corporation).

The perspective view which shows an example of the electroconductive base material in which the geometric figure of the recessed part with respect to a convex part is formed. A part of AA sectional drawing of FIG. FIG. 3 is a part of a cross-sectional view taken along the line AA in FIG. Sectional drawing of the electroconductive base material of the state which formed the insulating layer on the surface in the electroconductive base material which has the pattern of a convex part and the geometrical drawing shape recessed part drawn by it. Sectional drawing which shows the other example of the electroconductive base material of the state which formed the insulating layer in the surface in the electroconductive base material which has the recessed part of the pattern of a convex part and the geometric drawing shape drawn by it. Sectional drawing which shows an example of the structure of the pattern of the convex part of the electroconductive base material in this invention, and the insulating layer of a convex part side surface. Sectional drawing which shows an example of the production method of the electroconductive base material which has the pattern of a convex part and the recessed part of the geometric diagram shape drawn by it. Sectional drawing which shows an example of the process (first half) of forming an insulating layer in the electroconductive base material which has the recessed part of the pattern of a convex part, and the geometrical drawing shape drawn by it. Sectional drawing which shows an example of the process (latter half) of forming an insulating layer in the electroconductive base material which has the pattern of a convex part and the concave part of the geometric diagram shape drawn by it. Sectional drawing which shows the other example of the process of forming an insulating layer in the conductive base material which has the pattern of a convex part, and the recessed part of the geometrical drawing shape drawn by it. Sectional drawing which shows an example of the preparation methods of the base material with a conductor layer pattern using the produced plate for plating transcription | transfer. Sectional drawing of the base material with a conductor layer pattern which consists of a metal pattern by which the conductor layer pattern was blackened. Sectional drawing of the base material with a conductor layer pattern which consists of a metal pattern by which the conductor layer pattern was blackened. Sectional drawing which shows an example of the electromagnetic wave shielding member by which the base material with a conductor layer pattern was affixed on the other base material. Sectional drawing which shows an example of the electromagnetic wave shielding member by which the base material with a conductor layer pattern was affixed on the other base material. Sectional drawing which shows an example of the electromagnetic wave shielding member by which the base material with a conductor layer pattern was affixed on the other base material. Sectional drawing which shows an example of the electromagnetic wave shielding member by which the base material with a conductor layer pattern was affixed on the other base material. The conceptual sectional drawing of the apparatus for producing continuously the base material with a conductor layer pattern using a rotary body. The conceptual sectional drawing of the apparatus for producing continuously the base material with a conductor layer pattern using the hoop-shaped electroconductive base material for plating. The partial cross section figure (schematic diagram) which shows the state where the conductor layer pattern which consists of metal 11 was transcribe | transferred to another base material through the adhesive bond layer.

Explanation of symbols

1: conductive substrate for plating 2: concave portion 3: convex portion 4: upper surface of convex portion 4 ': exposed portion of convex portion 5: side surface of convex portion 6: insulating layer 7: resist film 8: insulating film 9: adhesive Film 10: Mask layer 11: Metal 12: Adhesive film 13: Another substrate 14: Adhesive layer 15: Substrate with conductor layer pattern 16, 17: Black layer 18: Metal 19: Other substrate 20: Protective resin 21 : Adhesive 22: Other base material 23: Adhesive or adhesive 24: Protective film 100: Electrolytic bath 101: Electrolytic solution 102: Anode 103: Rotating body 104: Piping 105: Pump 106: Metal 107: Film 108: Pressure bonding Roll 109: Substrate with conductor layer pattern 110: Hoop-like conductive substrate 111-128: Transport roll 129: Pretreatment tank 130: Plating tank (electrolytic bath)
131: Washing tank 132: Blackening treatment tank 133: Washing tank 134: Rust prevention tank 135: Washing tank 136: Plastic film substrate (adhesive film)
137: Crimp roll 138: Substrate with conductive layer pattern

Claims (15)

  An insulating layer is formed on the surface of the concave portion at a position lower than a position 0.5 to 5 μm lower than the upper end of the convex portion on the conductive substrate for plating having the convex portion pattern and the concave portion of the geometrical diagram shape drawn thereby. A step of depositing metal by electroplating or electroless plating on the tip of the convex portion of the conductive substrate, a radiation curable adhesive layer of the metal deposited on the tip of the convex portion of the conductive substrate A substrate having a conductor layer pattern, the method comprising: a step of transferring to a different substrate having an adhesive layer; and a step of curing and reacting a radiation curable resin after the time when the metal is bonded to the other substrate through the adhesive layer Production method.   The position of the uppermost end of the metal transferred through the adhesive layer is at a position of 3.5 μm or less in the vertical direction with respect to the position of the uppermost end of the adhesive layer in the vicinity of the metal. The manufacturing method of a base material with a conductor layer pattern.   3. The method for producing a substrate with a conductor layer pattern according to claim 1, wherein the radiation curable adhesive layer has a thickness of 3 to 50 μm.   The tack value at 50 ° C before curing or at the time of transfer of the radiation-curable adhesive layer is 20 to 100 gf, and the tack value after curing by irradiation with radiation is 10 gf or less. 4. A method for producing a substrate with a conductor layer pattern according to any one of 3 above.   The manufacturing method of the base material with a conductor layer pattern in any one of Claims 1-4 whose space | interval of the convex part of the said electroconductive base material is 100 micrometers-1000 micrometers.   2. The metal is deposited so that the metal thickness is 0.5 to 50 μm at the convex portion of the conductive substrate in the step of depositing the metal on the conductive substrate by electroplating or electroless plating. The manufacturing method of the base material with a conductor layer pattern in any one of -5.   An electroconductive base material is a rotary body (roll), The manufacturing method of the base material with a conductor layer pattern in any one of Claims 1-6.   The method for producing a base material with a conductor layer pattern according to any one of claims 1 to 6, wherein the conductive base material has a hoop shape.   The method according to any one of claims 1 to 8, comprising a step of blackening the metal pattern deposited on the convex portion of the conductive base material before the step of transferring the metal deposited on the convex portion to the base material. The manufacturing method of a base material with a conductor layer pattern.   A method for producing a substrate with a conductor layer pattern, comprising the step of blackening the metal pattern transferred to the substrate after performing the production method according to claim 1.   A method for producing a substrate with a conductor layer pattern, wherein the conductor layer pattern of the substrate with a conductor layer pattern is further coated with a resin after the production method according to claim 1 is performed.   The base material with a conductor layer pattern manufactured by the method in any one of Claims 1-11. A conductive layer pattern made of metal is bonded to the substrate via an adhesive layer, and the position of the uppermost end of the metal is 3 μm or less in the vertical direction with respect to the position of the uppermost end of the adhesive layer in the vicinity of the metal. The base material with a conductor layer pattern according to claim 12 in the position of   The translucent electromagnetic wave shielding member formed by bonding the surface which has the conductor layer pattern of the base material with a conductor layer pattern of Claim 12 or Claim 13 on a transparent substrate.   The translucent electromagnetic wave shielding member formed by coat | covering the conductor layer pattern of the base material with a conductor layer pattern of Claim 12 or Claim 13 with resin.

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