JP5370752B2 - SUBSTRATE WITH CONDUCTIVE LAYER PATTERN, ITS MANUFACTURING METHOD, AND ELECTROMAGNETIC SHIELDING MEMBER USING THE SAME - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a base with a conductor layer pattern which has high adhesiveness of the conductor layer pattern and is highly reliable. <P>SOLUTION: The base with the conductor layer pattern has the conductor layer pattern laminated on a base including a resin layer, and the whole or an upper portion of the conductor layer pattern is sectioned in a trapezoidal shape, wherein at least an upper surface or a portion of the trapezoidal shape is exposed from the resin layer and at least a portion below a portion of maximum width is embedded in the resin layer of the base. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a substrate with a conductor layer pattern, a method for producing the same, and an electromagnetic wave shielding member using the same.

A base material having a conductor layer pattern such as a metal mesh (base material with a conductor layer pattern) can be used for various applications by changing the conductor layer pattern and by selecting various base materials.
A base material having a conductor layer pattern having a conductor layer pattern made of a metal mesh is useful as an electromagnetic wave shielding member.
A base material with a conductive layer pattern having a conductive pattern such as a metal mesh having a specific slot has high light transmittance and high antenna gain, and is used as a film antenna that is attached to a windshield of an automobile. be able to.
In a solar cell, a transparent conductive film is laminated on the photoelectric conversion layer to collect electrons generated in the photoelectric conversion layer. In order to make this current collection more efficient, a conductor layer to the transparent conductive film. Although a pattern (wiring with a metal wiring layer or silver paste) is applied, a base material with a conductor layer pattern can be used for the facility of this metal wiring layer.
Moreover, a base material with a conductor layer pattern can be used as a transparent electrode of a touch panel.

The substrate with a conductor layer pattern is formed as follows, for example.
The most common method for producing a substrate having a conductor layer pattern such as a metal mesh is a photolithography method. The process of bonding the metal foil and the substrate through an adhesive, the process of forming a photosensitive resist on the metal foil, the process of exposing in a pattern using a mask, the developing process, and the liquid that corrodes the metal foil It consists of an etching process and a process of removing the photosensitive resist (see Patent Document 1).

There is also a method in which a pattern is formed directly on a base material by a printing method such as screen printing, offset printing, and gravure printing. Furthermore, a catalyst for electroless plating such as a palladium compound is dispersed in a resin, and a pattern is formed on the substrate by the above printing method, and then electroless plating is performed to obtain a substrate having a conductor layer pattern. Can do.
In these methods, if necessary, electrolytic plating can be further performed to improve conductivity.

Patent Document 2 describes that a silver metal pattern can be obtained by chemically developing silver halide grains by silver salt photography. The developed silver is obtained by chemical development and is an aggregate of filamentous metallic silver or an aggregate of metallic silver in which filamentous metallic silver is bonded and fused together.
As a method for obtaining developed silver, generally well-known principles and methods of silver salt photography can be used, and the method described in the above publication can be used.
Since developed silver can be made sufficiently conductive to be used as a cathode for electrolytic plating, it is possible to improve the conductivity by forming electrolytic silver after forming developed silver.

  Furthermore, as a method for producing a substrate with a conductor layer pattern, Patent Document 3 discloses that a metal electrolyte is used for electrodeposition on an electrodeposition substrate capable of metal electrodeposition in a mesh shape, and an adhesive is used. A method for producing an electromagnetic wave shielding plate by adhesion and transfer to an electromagnetic wave shielding substrate (hereinafter referred to as a transfer method) is described. The above electrodeposition substrate has an electrodeposited portion on which a metal pattern can be deposited in a mesh pattern by forming a reverse pattern to the mesh pattern with an insulating film that inhibits electrodeposition on a conductive substrate such as a metal plate. It is produced so as to be exposed. Patent Document 1 describes a method using an electrodeposition substrate in which a convex conductive mesh layer is formed on an insulating layer support.

  Patent Document 3 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 base sheet for metal layer transfer 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 surface of the base metal layer is formed on the portion where the convex pattern is not formed. As a method of manufacturing a base sheet for transferring a metal layer, an etching resist is formed in the same pattern as a convex pattern on the surface of the base metal layer using a dry film resist or the like, and is exposed without being covered with the etching resist. The surface of the layer is etched to form a recess, after which the etching resist is removed, an electrical insulation layer is formed on the entire surface of the etched base metal layer, and then the electrical insulation layer until the convex pattern is exposed A method of polishing the surface 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. An electroplated 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 is described in which the thickness of the electroplated metal layer is made thicker than the electrical insulating layer. . 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.

Japanese Patent Laid-Open No. 10-41682 JP 2004-221564 A JP-A-11-26980 JP 2004-186416 A

In a base material with a conductor layer pattern, in many cases, a conductor layer is laminated on a specific base material via a resin such as an adhesive layer.
In the conventional base material with a conductor layer pattern, since the contact area between the adhesive layer and the pattern surface is small, the adhesion between the resin and the pattern is low, and the pattern is easy to peel off. Moreover, since the cross section of the line protrudes from the pressure-sensitive adhesive layer, the adhesion is particularly low with respect to the shearing force in the lateral direction. For example, in electromagnetic wave shielding applications, the surface to be visually recognized is generally coated with a resin layer, so there is no particular problem. However, since the conductor must be exposed at the ground connection portion, high adhesion is achieved. Required. In the ground connection part, a gasket is used for ground connection with the chassis. However, when the chassis is transported, the gasket and the ground connection part are rubbed by vibration and a shear force is applied in the lateral direction, which causes the pattern to collapse. In some cases, ground connection failure may occur.
In addition, when applying a substrate with a conductor layer pattern for applications in harsh environments such as film antennas, solar cells, touch panels, etc., high adhesion of the conductor layer pattern is required, which is the reliability of the product. Will be improved.

  However, in any of the above-described methods for producing a substrate with a conductor layer pattern or a conductor layer, it is not possible to produce a substrate with a conductor layer pattern or a conductor layer that sufficiently satisfies such requirements. Such a thing was not able to be manufactured with high productivity for reasons such as a large number.

  In view of such problems, the present invention provides a substrate with a conductor layer pattern having high adhesion and excellent reliability, a method for producing the same, and an electromagnetic wave shielding member using the same.

The present invention relates to the following.
1. A substrate with a conductor layer pattern in which a pattern of a conductor layer is laminated on a substrate including a resin layer, and the cross-sectional shape of the conductor layer is continuous with a trapezoidal portion (trapezoidal shape portion) and this portion. A pattern of a conductor layer comprising a portion wider than this portion (maximum width portion) , wherein at least the trapezoidal upper surface or part of the trapezoidal shape is exposed from the resin layer. A base material with a conductor layer pattern, wherein at least a lower part from a part ( maximum width part ) wider than a trapezoidal part continuous to a trapezoidal part is embedded in the resin layer of the base material.
2. Item 2. The substrate with a conductor layer pattern according to Item 1, wherein the conductor layer is partially exposed in a trapezoidal shape having a cross-sectional shape.
3. Item 2. The substrate with a conductor layer pattern according to Item 1, wherein the conductor layer is coated with the resin layer on all of the side surfaces and part of the upper surface of the trapezoidal shape section having a cross-sectional shape.
4). Item 4. The substrate with a conductor layer pattern according to any one of Items 1 to 3, wherein an angle of a side surface of the trapezoidal shape portion having a cross-sectional shape of the conductor layer is in a range of 30 ° to 80 °.
5. Item 5. The substrate with a conductor layer pattern according to any one of Items 1 to 4, wherein the conductor layer has a thickness in the range of 0.1 to 30 μm.
6). Item 6. The substrate with a conductor layer pattern according to any one of Items 1 to 5, wherein the width of the upper side of the trapezoidal shape of the conductor layer pattern is in the range of 0.1 to 40 μm.
7). Item 7. The substrate with a conductor layer pattern according to any one of Items 1 to 6, wherein the substrate including the resin layer is formed by laminating a resin layer on a heat-resistant transparent substrate.
8). Item 8. The substrate with a conductor layer pattern according to Item 7, wherein the heat-resistant transparent substrate is a glass plate.
9. Item 7. The substrate with a conductor layer pattern according to any one of Items 1 to 6, wherein the substrate including the resin layer is formed by laminating a resin layer on a transparent plastic film.
10. Item 10. A substrate with a surface-protected conductor layer pattern obtained by laminating a surface-protecting substrate or a resin on a surface of the substrate with a conductor layer pattern according to any one of Items 1 to 9, wherein the conductor layer is exposed.
11. (A) An insulating layer is formed on the surface of the conductive base material, and a conductive pattern for plating in which a concave pattern for forming plating is formed on the insulating layer and becomes wider in the opening direction. the substrate, by plating so as to extend to the outside of the concave portion of that is continuous to the portion and the portion of the cross-sectional shape trapezoidal, the conductor layer comprising a portion of the width greater than the portion (portion of the maximum width) pattern And (B) a transfer step of transferring the pattern of the conductor layer deposited on the concave portion of the conductive base material to a base material having a resin layer on the surface. After the step, at least the cross- sectional shape of the conductor layer is continuous to at least the trapezoidal portion of the conductor layer while exposing a part of the trapezoidal upper surface or a part of the trapezoidal shape of the cross-sectional shape from the resin layer. Wider than trapezoidal part Portions preparation of conductive layers patterned substrate, wherein the portion of the bottom (the largest part of the width) be embedded in the resin layer of the substrate.
12 Resin of the resin layer is a curable resin, the conductive layer pattern, after transferring the substrate having a resin layer on the surface, the conductor layer on the resin layer of the substrate having a resin layer on the surface of at least a cross-sectional shape base Item 12. The method for producing a substrate with a conductor layer pattern according to Item 11, wherein at least the surface of the resin layer is cured in a state where a part of the shape is embedded.
13. (A) An insulating layer is formed on the surface of the conductive base material, and a conductive pattern for plating in which a concave pattern for forming plating is formed on the insulating layer and becomes wider in the opening direction. the substrate, by plating so as to extend to the outside of the concave portion of that is continuous to the portion and the portion of the cross-sectional shape trapezoidal, conductive layer fabrication process for forming a conductor layer pattern composed of a part of the width wider than the portion ,
(B) a step of transferring the conductor layer pattern deposited on the concave portion of the conductive substrate to the substrate (I) having an adhesive resin layer on the surface, and (C) the conductor layer of the obtained substrate with the conductor layer pattern Laminating the substrate (II) on the exposed surface,
In the above transfer step or after the transfer step, at least the cross-sectional shape of the conductor layer pattern is part of the trapezoidal top surface or part of the cross-sectional shape trapezoidal shape is exposed from the adhesive resin layer. A lower portion from a portion ( maximum width portion ) having a width wider than a trapezoidal portion continuous to at least the trapezoidal portion of the conductor layer pattern is embedded in the adhesive resin layer of the substrate (I). A method for producing a surface-protected substrate with a conductor layer pattern.
14 After carrying out all the steps of the method for producing the surface-protected conductor layer-patterned substrate according to Item 13, the substrate (I) of the obtained surface-protected conductor layer-patterned substrate is peeled or peeled off Then, the manufacturing method of the base material with a surface-protected conductor layer pattern including the process of laminating | stacking base material (III) on the exposed adhesive resin layer.
15. Item 15. The method for producing a substrate with a conductor layer pattern according to Item 14, wherein the substrate (III) is a heat-resistant transparent substrate.
16. Item 16. The method for producing a substrate with a conductor layer pattern according to Item 15, wherein the heat-resistant transparent substrate is a glass plate.
17. Item 11. An electromagnetic wave shielding member comprising a substrate with a conductor layer pattern according to any one of Items 1 to 10.
18. Item 18. An electromagnetic wave shielding plate obtained by bonding the electromagnetic wave shielding member according to Item 17 to a transparent substrate.

  In the base material with a conductor layer pattern in the present invention, since the portion which becomes the maximum width of the pattern is buried in the resin layer formed on the base material, the contact area between the resin and the pattern is increased, and the adhesion is improved. Furthermore, since the pattern is buried in the resin layer, the shear adhesive strength in the lateral direction of the pattern is improved. Therefore, for example, there is no pattern abnormality after vibration impact such as a vibration test of the connection portion between the conductor layer pattern and other electrical wiring, and there is no deterioration in characteristics after transportation of the structure to which the conductor layer pattern is connected. In addition, there is no decrease in adhesion after a reliability test such as a heat humidification test or a water resistance test, which is good.

  In particular, in the base material with a conductor layer pattern in the present invention, since the smoothness of the surface where the conductor layer is exposed is high, particularly when the conductor layer exposes only the upper surface or almost the upper surface from the resin layer. ) When the resin is coated or the adhesive film is pasted together, the generation of bubbles is suppressed, and particularly the adhesion of the conductor layer to the conductive member can be satisfactorily prevented, and the bubbles can be prevented from being involved. Excellent reliability in applications using a substrate with a conductor layer pattern.

  In the base material with a conductor layer pattern in the present invention, a part or all of the side part of the trapezoidal shape part which is the upper layer (the upper surface of the upper layer is exposed), or in some cases, a part of the upper surface becomes the resin layer. By coating, the above-described effects are further improved.

  According to the method for producing a substrate with a conductor layer pattern of the present invention, since the conductor layer pattern obtained by plating is easy to peel off, the substrate with a conductor layer pattern can be easily produced, and also has an electromagnetic shielding property or conductivity. A substrate with a conductor layer pattern having excellent properties can be easily produced. Furthermore, such a substrate with a conductor layer pattern can be produced with high production efficiency. Moreover, the base material with a conductor layer pattern excellent in transparency can be produced easily.

  According to the method for producing a substrate with a conductor layer pattern in the present invention, a step of bonding the substrate onto the plating deposited on the conductive substrate for plating or a cover film, a peelable film, etc. after transferring the plating to the substrate. By applying heat and pressure as needed in the bonding process, the conductor layer can be adjusted and embedded in the resin, and the conductor layer patterned substrate is excellent in the adhesion of the conductor layer and excellent in reliability. Can be easily obtained. At the same time, in particular, by setting the turbidity of the cover film to be bonded to the surface on which the conductor layer exists after transfer to 2.0 or less, a highly transparent substrate with a conductor layer pattern can be obtained.

  By using a specific conductor layer pattern, the electromagnetic wave shielding member and the electromagnetic wave shielding plate in the present invention are excellent in conductivity, adhesion of the conductor layer, and reliability, and can be produced with high production efficiency. Excellent light transmittance can also be imparted.

The partial cutaway perspective view which shows an example of the base material with a conductor layer pattern which concerns on this invention. The perspective view which cut off some conductor layers. Sectional drawing of the width direction of the conductor layer shown in FIG.2 (b). Sectional drawing of the other example of the width direction of the conductor layer shown in FIG.2 (b) The cross-sectional view of a conductor layer. The cross-sectional view of a conductor layer. The fragmentary sectional view which shows the state by which the conductor layer is embed | buried under the resin layer. The fragmentary sectional view which shows the state by which the conductor layer is embed | buried under the resin layer. The perspective view which shows an example of the electroconductive base material for plating of this invention. AA sectional drawing of FIG. Sectional drawing which shows an example of the process which shows the manufacturing method of the electroconductive base material for plating. Sectional drawing of the electroconductive base material for plating which has an intermediate | middle layer, and its precursor is shown. Sectional drawing which shows the first half of the example of preparation of the base material with a conductor layer pattern. Sectional drawing which shows the second half of the preparation examples of the base material with a conductor layer pattern. Sectional drawing which shows the state which formed the conductor layer pattern by plating in the recessed part of the electroconductive base material for plating. Sectional drawing of the base material with a conductor layer pattern obtained by transferring the conductor layer pattern in the recessed part shown in FIG. Sectional drawing which shows the example of the base material with a conductor layer pattern in which the conductor layer is protected. Sectional drawing which shows an example of a base material with a conductor layer pattern. Sectional drawing which shows the example of the resin layer with a conductor layer. Sectional drawing which shows the example of the base material with a conductor layer pattern which has a transparent conductive film. Sectional drawing which shows an example of the exchange process of a support base material Sectional drawing of the base material with a conductor layer pattern obtained using what has an adhesive layer as a new support base material. Sectional drawing of the laminated body using the base material with a conductor layer pattern in this invention. Sectional drawing of the laminated body which shows another aspect. Sectional drawing which shows the structure of the solar cell using the base material with a conductor layer pattern which concerns on this invention. Sectional drawing which shows another structure of the solar cell using the base material with a conductor layer pattern which concerns on this invention. Sectional drawing of a solar cell element. Sectional drawing of another solar cell element. Sectional drawing of another solar cell element. Sectional drawing of another solar cell element. Sectional drawing which shows an example of a solar cell. Sectional drawing which shows the other example of a solar cell. Sectional drawing which shows the other example of a solar cell. Sectional drawing which shows the other example of a solar cell. 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 base material with a conductor layer pattern according to the present invention includes a base material including a resin layer and a conductor layer, and the conductor layers are arranged in a pattern on the surface of the base material.
FIG. 1 is a partially cutaway perspective view (schematic diagram) showing an example of a substrate with a conductor layer pattern according to the present invention. In the substrate 1 with a conductor layer pattern, a conductor layer 5 is embedded on the surface of a substrate 4 having a resin layer 3 on a support substrate 2.

Therefore, the resin layer and the support base material which comprise the base material 4 can be selected with a use. In consideration of the application of the substrate with the conductor layer pattern to a display electromagnetic wave shielding material, a film antenna, a liquid crystal panel, a touch panel, a planar light source using inorganic EL, a solar cell (application to the surface side), and the like are preferable. . At this time, the base material with a conductor layer pattern according to the present invention preferably has light transmittance particularly in the visible region, and generally has a total light transmittance of 90% or more.
The base material has a resin layer for embedding the conductor layer on the side of the surface where the conductor layer is embedded.
The resin layer may be a thermoplastic resin or a curable resin. The curable resin may or may not be cured, and the resin may be cured after the substrate with the conductor layer pattern is used.
Moreover, it is preferable that this resin layer is laminated | stacked on the support base material, However, You may comprise the base material only with the resin layer.

Examples of the supporting substrate include a plate made of glass, plastic, and the like, 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.

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.
Substrates such as plastic films are more flexible than glass plates and plastic plates, and can be used for electromagnetic wave shielding films and film antennas to prevent leakage of electromagnetic waves from the front of the display. Is preferred.

As the resin for forming the resin layer, a thermoplastic resin or a curable resin is used as described above.
Typical examples of the thermoplastic resin include the following. For example, natural rubber, polyisoprene, poly-1,2-butadiene, polyisobutene, polybutene, poly-2-heptyl-1,3-butadiene, poly-2-t-butyl-1,3-butadiene, poly-1,3 -Dienes such as butadiene), polyethers such as polyoxyethylene, polyoxypropylene, polyvinyl ethyl ether, polyvinyl hexyl ether and polyvinyl butyl ether, polyesters such as polyvinyl acetate and polyvinyl propionate, polyurethane, ethyl cellulose , Polyvinyl chloride, polyacrylonitrile, polymethacrylonitrile, polysulfone, polysulfide, phenoxy resin, polyethyl acrylate, polybutyl acrylate, poly-2-ethylhexyl acrylate, poly-t-butyl Acrylate, poly-3-ethoxypropyl acrylate), polyoxycarbonyl tetramethacrylate, polymethyl acrylate, polyisopropyl methacrylate, polydodecyl methacrylate, polytetradecyl methacrylate, poly-n-propyl methacrylate, poly-3,3,5-trimethyl Poly (meth) acrylates such as cyclohexyl methacrylate, polyethyl methacrylate, poly-2-nitro-2-methylpropyl methacrylate, poly-1,1-diethylpropyl methacrylate, polymethyl methacrylate, thermoplastic polyester resins, thermoplastic polyamides Resin etc. can be used. The monomers constituting these polymers may be used as a copolymer obtained by copolymerization of two or more, if necessary, or may be used by blending two or more of the above polymers or copolymers. .

Among the curable resins, as a resin curable by active energy rays, a material in which an acrylic resin, an epoxy resin, a polyester resin, a urethane resin, or the like is used as a base polymer and a radically polymerizable or cationically polymerizable functional group is added to each of them is used. Can be illustrated. As the radical polymerizable functional group, there are carbon-carbon double bonds such as an acrylic group (acryloyl group), a methacryl group (methacryloyl group), a vinyl group, and an allyl group, and a highly reactive acrylic group (acryloyl group) is preferable. Used for. As the cationically polymerizable functional group, an epoxy group (glycidyl ether group, glycidylamine group) is representative, and a highly reactive alicyclic epoxy group is preferably used. Specific materials include acrylic urethane, epoxy (meth) acrylate, epoxy-modified polybutadiene, epoxy-modified polyester, polybutadiene (meth) acrylate, and acrylic-modified polyester. As the active energy rays, ultraviolet rays, electron beams and the like are used.
When the active energy ray is ultraviolet light, the photosensitizer or photoinitiator added at the time of ultraviolet curing includes known materials such as benzophenone, anthraquinone, benzoin, sulfonium salt, diazonium salt, onium salt, and halonium salt. Can be used. In addition to the above materials, a general-purpose thermoplastic resin may be blended.

Among the curable resins, thermosetting resins include natural rubber, isoprene rubber, chloroprene rubber, polyisobutylene, butyl rubber, halogenated butyl, acrylonitrile-butadiene rubber, styrene-butadiene rubber, polyisobutene, carboxy rubber, and neoprene. Sulfur, 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 resin, melamine resin , Phenol resins, formalin resins, metal oxides, metal chlorides, oximes, alkylphenol resins, and the like. In addition, for these purposes, additives such as general-purpose vulcanization accelerators can be used for the purpose of increasing the crosslinking reaction rate.

  As a thermosetting resin, those using a curing agent include a resin having a functional group such as a carboxyl group, a hydroxyl group, an epoxy group, an amino group, an unsaturated hydrocarbon group, an epoxy group, a hydroxyl group, an amino group, an amide group, Some are used in combination with a curing agent having a functional group such as a carboxyl group or a thiol 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.

Furthermore, as a thermosetting resin or a resin curable with an active energy ray, an adduct of acrylic acid or methacrylic acid can be exemplified as a preferable one.
As an adduct of acrylic acid or methacrylic acid, epoxy acrylate (n = 1.48 to 1.60), urethane acrylate (n = 1.5 to 1.6), polyether acrylate (n = 1.48 to 1) .49), polyester acrylate (n = 1.48 to 1.54), and the like can also be used. In particular, urethane acrylate, epoxy acrylate, and polyether acrylate are excellent from the viewpoint of adhesiveness. Examples of epoxy acrylate include 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, and resorcinol. (Meth) acrylic such as diglycidyl ether, diglycidyl adipate, diglycidyl phthalate, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether An acid adduct is mentioned. A polymer having a hydroxyl group in the molecule, such as epoxy acrylate, is effective in improving adhesion. These copolymer resins can be used in combination of two or more as required.

Note that a general-purpose thermoplastic resin may be blended with the thermosetting resin or the resin curable with active energy rays.
Moreover, additives, such as a plasticizer, antioxidant, a filler, a coloring agent, and an ultraviolet absorber, may be mix | blended with the resin layer.
The thickness of the resin layer needs to be at least thicker than the thickness for embedding the conductor layer. In order to more reliably embed the conductor layer in the resin, the thickness of the resin layer is more preferably 1.5 times or more the thickness of the conductor layer embedded. The thickness of the resin layer is preferably 100 μm or less. Even if it is thicker than necessary, the cost increases.

The conductor layer in the present invention comprises a trapezoidal cross section or an upper part having a trapezoidal cross section and a lower part continuous thereto.
This will be described with reference to the drawings. FIG. 2 is a perspective view in which a part of the pattern of the conductor layer 5 is cut off. FIG. 2A shows a conductor layer pattern having a trapezoidal cross section, and FIG. 2B shows a pattern of the conductor layer 5 having a trapezoidal upper section and a lower width wider than the upper part. FIG. 3 is a cross-sectional view in the width direction of the conductor layer 5 shown in FIG. 2 (b). The cross section is continuous with the trapezoidal upper portion 6 and the upper portion, and the ellipse-shaped lower portion 7 is wider than the upper portion. The upper base 6 has a trapezoidal base and the lower part 7 has an oval string part. In FIG. 2B and FIG. 3, the lower part has an oval cross-sectional shape, but this is not restrictive. In the case shown in FIGS. 2B and 3, the shoulder portion 8 protruding from the upper base of the lower portion 7 can be a feature. The above elliptical shape is not necessarily limited to a shape obtained by cutting a perfect circle, but includes a shape obtained by cutting an ellipse or a shape obtained by deforming an ellipse or a perfect circle. For example, the shape as shown in (a), (b), or (c) of FIG. 4 (another example of the cross-sectional view in the width direction of the conductor layer shown in FIG. 2B) may be used.
2 and 3, the maximum width of the lower portion (and hence the maximum width of the conductor layer pattern) is along the plane portion, but may have a shape in which the maximum width exists below the shoulder portion.
Furthermore, the conductor layer pattern may have a maximum width narrower than the maximum width of the upper portion of the conductor layer pattern. The lower cross-sectional shape may be rectangular.

As a dimension of the conductor layer, the thickness of the entire conductor layer is preferably 0.1 to 30 μm. If the thickness is less than 0.1 μm, it tends to be difficult to obtain a sufficiently low resistance. If the thickness exceeds 30 μm, the resistance hardly changes. Therefore, material costs and process time increase, which is disadvantageous in terms of cost. In consideration of the above, the thickness is more preferably 0.5 to 20 μm, and further preferably 3 to 15 μm.
Moreover, although the maximum width of a conductor layer is determined suitably, in order to improve light transmittance, it is preferable that it is 1-50 micrometers. If the width of the conductor layer is too narrow, the electromagnetic shielding property tends to be lowered, and if it is too wide, the visible light transmittance is lowered. In consideration of the above, the width is more preferably 5 to 30 μm. If light transmission does not matter, the width may be increased.

The dimensions of the conductor layer will be further described with reference to the drawings.
FIG. 5 shows a cross-sectional view of the conductor layer. FIG. 5A shows a trapezoidal shape, and FIG. 5B shows an integrated trapezoidal upper part and an ellipse-shaped lower part wider than the upper part. In both cases, the upper surface width (length of the upper side of the trapezoidal shape) L1 and the maximum width L in the cross-sectional shape of the conductor layer are preferably as follows.

As described above, the thickness T of the conductor layer is preferably 0.1 to 30 μm, more preferably 0.5 to 20 μm, and still more preferably 3 to 15 μm.
In the case of the shape in FIG. 5B, if the total thickness T of the trapezoidal upper part thickness T1 and the lower part thickness T2 is in the range of 0.1 to 30 μm, the value of T1 and T2 is obtained. Although there is no restriction, in order to further improve the adhesion between the resin layer and the conductor layer pattern, T2 is preferably 0.5 μm or more, and more preferably 1 μm or more.

  Moreover, as described above, the maximum width L of the conductor layer is preferably 1 to 50 μm, and more preferably 5 to 30 μm.

  In the case of the shape shown in FIG. 5B, the upper trapezoidal shape upper base width L1 and lower base width L2 have a desired maximum width L. As will be described later, the angle of the side of the trapezoidal shape is If the conditions described later are satisfied, the width is not particularly limited. When the lower part is completely buried and the resin layer covers the shoulder and part of the upper part, the adhesion between the conductor layer and the resin layer is improved. From this point of view, the maximum width L and the upper part are improved. The difference in the width L2 of the lower base of the trapezoidal shape is preferably 1.0 μm or more. There is no particular limitation on the maximum width (T) of the conductor layer and the width L1 of the upper base of the upper trapezoidal shape, and the size may be, for example, 5 mm.

  In the case of the shape shown in (a) or (b) of FIG. 5, when importance is attached to light transmittance, L1 is preferably 1 to 40 μm in view of the manufacturing method described later.

  In FIGS. 6A and 6B, the trapezoidal shape means that the side edge has an inward inclination as a condition, but the inclination of the trapezoidal side edge is in each of the left and right sides. The inner angle α is preferably 30 ° or more and less than 90 °, more preferably 30 ° or more and 80 ° or less, further preferably 30 ° or more and 60 ° or less, and particularly preferably 40 ° or more and 60 ° or less. If the angle of the trapezoidal shape is small, the width becomes wider with respect to the height of the trapezoidal shape, so that transparency is easily hindered. In addition, as the angle increases, the side surface is less likely to be covered by the transparent conductive film due to the manufacturing method, and is more likely to be corroded by the electrolyte solution. As for the inclination of the trapezoidal side, the inner angles of the left and right sides do not have to be equal.

  Moreover, the width | variety of the part whose cross-sectional shape of a conductor layer is trapezoid should just narrow as a whole toward an upper surface. It does not necessarily have to be narrowed at a constant gradient α as in the above-mentioned drawing, and it is sufficient that it does not spread toward the upper surface but narrows as a whole. In particular, it is preferable that there are no portions whose side surfaces are perpendicular to the top surface.

・・・・・（１）
によってαを決定する。
αは、角度で３０度以上９０度未満が好ましく、３０度以上８０度以下がより好ましく、３０度以上６０度以下がさらに好ましく、４０度以上６０度以下が特に好ましい。 The side surface corresponding to the trapezoidal section of the conductor layer is not necessarily a flat surface. In this case, as shown in the cross-sectional view of the conductor layer in FIG. 6, the gradient α has the trapezoidal height h and the trapezoid side width s (horizontal direction of the trapezoidal side width direction). ) And formula (1)

(1)
Determines α.
α is preferably from 30 ° to less than 90 °, more preferably from 30 ° to 80 °, even more preferably from 30 ° to 60 °, and particularly preferably from 40 ° to 60 °.

の関係にあることが好ましい。また、

の関係にあることがより好ましい。
これにより、導体層は、幅方向へのめっきの広がりよりも、厚み方向への広がりが大きく、厚み方向に異方的にめっきが生長するので、表面抵抗を上昇させることなく、ライン幅を微細化することができ、このような導体層を有する導体層パターン付き基材は、透明性と低抵抗の両立を高いレベルで実現可能である。特に、ライン幅が３０μｍ以下の微細パターンにおいて、上記効果は顕著である。めっきが厚み方向に異方的に生長すると、等方的に生長した場合に比較して、断面形状が円形状に近づく。したがって、このような導体層を有する導体層付きパターン基材は、ラインを転写する際の応力によるラインの折れが改善され、抵抗の低下や外観の異常をより良く抑制することができる。特に、めっき厚が薄くなるほど、この効果は、顕著となってくる。 In FIG. 5, L3 and T1 are

It is preferable that the relationship is Also,

It is more preferable that the relationship is
As a result, the conductor layer has a larger spread in the thickness direction than the spread in the width direction, and the plating grows anisotropically in the thickness direction, so that the line width is reduced without increasing the surface resistance. The base material with a conductor layer pattern having such a conductor layer can realize both transparency and low resistance at a high level. In particular, the effect is remarkable in a fine pattern having a line width of 30 μm or less. When the plating grows anisotropically in the thickness direction, the cross-sectional shape approaches a circular shape as compared with the case where the plating grows isotropically. Therefore, the pattern base material with a conductor layer having such a conductor layer can improve the folding of the line due to the stress when transferring the line, and can more effectively suppress the decrease in resistance and the appearance abnormality. In particular, this effect becomes more remarkable as the plating thickness is reduced.

The line spacing of the conductor layer is preferably in the range of 50 μm or more. The larger the line spacing, the better the aperture ratio and the visible light transmittance. The aperture ratio of the conductor layer pattern in the present invention is preferably 50% or more, more preferably 60% or more, and particularly preferably 80% or more. If the line spacing is too large, the effect of lowering the front surface resistance decreases, the line spacing is preferably a 2000 .mu.m (2 mm) or less, particularly preferably 100 to 1000 [mu] m. When the line interval is complicated by a combination of geometric figures surrounded by the conductor layer pattern, 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. .

In the present invention, the conductor layer is preferably entirely or partially embedded in the resin layer with at least the upper surface exposed. Thereby, since the anchor effect appears, the adhesiveness to the base material of a conductor layer pattern improves. It is important for improving the adhesion that the conductor layer has at least a portion having the maximum width in the cross-sectional shape embedded in the resin layer.
7 and 8 are partial cross-sectional views showing a state in which the conductor layer is embedded in the resin layer.
7A shows a state in which the conductor layer 5 having a trapezoidal cross-sectional shape is partially embedded in the resin layer 3, and FIG. 7B shows the conductor layer while the upper surface is exposed from the resin layer 3. 5 shows a state where the entirety of 5 is embedded in the resin layer 3. FIG. 8A shows a conductor layer in which a trapezoidal upper section 6 and a lower section 7 wider than the upper section are integrated at a trapezoidal base of the upper section 6 and an oval string portion of the lower section 7. A state in which the entire lower part 7 (in the depth direction) is embedded in the resin layer 3 (the shoulder 8 is exposed) is shown. FIG. 8B shows a state in which a similar conductor layer including the upper surface of the upper portion 6 is embedded in the resin layer 3 with a part thereof exposed from the resin layer 3. FIG. 8C shows a state in which a similar conductor layer is embedded in the resin layer 3 with only the upper surface of the upper part 6 exposed from the resin layer 3. 7 and 8, the maximum width portion of the conductor layer is embedded in the resin layer 12.
Further, in the state of FIG. 7B or FIG. 8C, the resin layer 3 may be further covered so as to cover a part of the upper surface of the conductor layer 5 or the upper portion 6.

Various patterns can be used for the conductor layer, but the pattern is appropriately selected depending on the application.
As a pattern of the conductor layer, the conductor layer itself has a linear or planar shape, and the conductor layer itself has a planar shape such as a triangle such as an equilateral triangle, an isosceles triangle, a right triangle, a square, a rectangle, Rectangles such as rhombuses, parallelograms, trapezoids, (positive) hexagons, (positive) octagons, (positive) dodecagons, (positive) dodecagons, etc. (positive) n-gons (n is an integer greater than or equal to 3) ), Geometric shapes such as circles, ellipses, stars, etc., and with conductor layers, in particular with linear or other shape conductor layers, equilateral triangles, isosceles triangles, right triangles, etc. Triangles, squares, rectangles, rhombuses, parallelograms, trapezoids, and other quadrangles, (positive) hexagons, (positive) octagons, (positive) dodecagons, (positive) n-gons ( n is an integer greater than or equal to 3), geometric figures such as circles, ellipses, and stars, or any combination of these It may be set to draw a pattern was (e.g., may be shaped as a hole of these shapes to the conductor layer on the plane). These units can be repeated alone or in combination of two or more.

Light transmissive electromagnetic wave shielding member used in front of the display, housing or in applications of the film antenna or the like used for a window of an automobile, the conductive layer pattern having a sufficiently large aperture ratio so as not to interfere with visibility preferred. In particular, the mesh pattern is preferable in terms of production and performance.
Moreover, as a solar cell electrode base material, a mesh pattern, a stripe pattern, and a comb pattern are preferable.
The wiring (heat sink or the like) of the semiconductor device mounting substrate is preferably a wiring pattern that is suitable for necessary wiring such as a straight line. In these applications, the conductor layer is preferably conductive.

The manufacturing method of the base material with a conductor layer pattern which concerns on this invention is demonstrated.
The substrate with a conductor layer pattern according to the present invention is
(I) First, a conductor layer preparation step is performed in which a conductor layer pattern is formed on a conductive substrate for plating by plating.
(II) Thereafter, a transfer step of transferring the conductor layer formed on the conductive substrate for plating to an appropriate substrate including a resin layer,
And (III) When said base material contains a support base material, it is produced by the method further including the process of replacing | exchanging this support base material to another support base material by the case. The step of embedding the conductor layer in the resin layer is performed in the transfer step or after the transfer step.

  The conductive substrate for plating according to the present invention is a conductive substrate having a patterned plating forming portion, and an insulating layer is formed on the surface of the conductive substrate, and the insulating layer faces the opening direction. And a concave portion (plating forming portion) for forming a wide plating. The conductive material is exposed on the bottom surface of the recess.

  In the present invention, the conductive material used for the conductive substrate has sufficient conductivity for depositing metal on the exposed surface by electrolytic plating, and is particularly preferably a metal. In addition, the base material has a low adhesion to the metal layer formed on it so that the metal layer formed by electrolytic plating on the surface can be transferred to the adhesive support, and can be easily peeled off. It is preferable that As such a conductive base material, stainless steel, chrome-plated cast iron, chrome-plated steel, titanium, titanium-lined material, nickel and the like are particularly preferable.

  Examples of the shape of the conductive substrate 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. When the conductive substrate is used by being wound around a roll, a conductive roll is preferably used so that the roll and the conductive substrate are easily conducted.

  The thickness of the insulating layer corresponds to the depth of the recess. Since the depth of the recess is related to the thickness of the plating to be deposited, it is appropriately determined according to the purpose. The thickness of the insulating layer is preferably in the range of 0.10 μm to 100 μm, and more preferably in the range of 0.5 μm to 10 μm. If the insulating layer is too thin, pinholes are likely to be generated in the insulating layer, so that when the plating is performed, the metal is likely to be deposited on the portion where the insulating layer is applied. The thickness of the insulating layer is particularly preferably 1 to 5 μm.

The insulating layer can be formed of a carbon thin film similar to diamond, a so-called diamond-like carbon (hereinafter referred to as DLC) thin film having an insulating property. The DLC thin film is particularly preferable because it is excellent in durability and chemical resistance.
Furthermore, the insulating layer can be formed of an inorganic material such as Al ₂ O ₃ or SiO ₂ .

  The shape of the recess or the insulating layer is appropriately determined according to the pattern of the conductor layer described above. Since the conductor layer is formed in the recess, the pattern shape of the conductor layer is substantially determined by this shape. In one conductive substrate for plating, the shape of the concave portion and the shape of the insulating layer are shapes corresponding to each other. As for the shape of the recess or the insulating layer, the planar shape is a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid, or a quadrangle, (positive) hexagon, (positive) eight There are geometric shapes such as squares, (positive) dodecagons, (positive) n-gons such as (positive) dodecagons (n is an integer of 3 or more), circles, ellipses, stars, straight lines, etc. These units, which may be combined as appropriate, can be repeated alone or in combination of two or more.

An example of the present invention will be described with reference to the drawings.
FIG. 9 is a partial perspective view showing an example of the conductive substrate for plating according to the present invention. FIG. 10 is a cross-sectional view taken along the line AA in FIG. FIG. 10A shows a case where the side surface of the recess is planar, while FIG. 10B shows a case where the side surface of the recess has gentle irregularities. In the conductive base material 11 for plating, the insulating layer 13 is laminated on the conductive base material 12, the concave portion 14 is formed in the insulating layer 13, and the conductive base material 12 is formed at the bottom of the concave portion 14. Exposed. The bottom of the recess 14 may be a conductor layer that is electrically connected to the conductive substrate.
In this example, the insulating layer 13 has a square shape as a geometric figure, and a recess 14 is formed in a groove shape around the square.
A conductive or insulating intermediate layer (not shown) may be laminated between the conductive substrate 12 and the insulating layer 13 for the purpose of improving the adhesiveness of the insulating layer 13 or the like. Or the recessed part 14 is wide as a whole toward the opening direction. It is not always necessary that the width is constant and wide at the gradient α as shown in the drawing. If there is no problem in peeling off the conductor layer pattern formed by plating, the recess may have a portion whose width becomes narrower in the opening direction, but it is better not to have such a portion, It is preferable that it is not narrowed toward the opening direction but spreads as a whole. In particular, it is preferable that one side surface of the concave portion together with the opposite surface thereof has no portion that is perpendicular to the bottom surface and continues in the height direction by 1 μm or more. If it is such a conductive substrate for plating, after plating using it, when peeling the deposited metal layer from the conductive substrate for plating, friction between the metal layer and the insulating layer or The resistance can be reduced, and the peeling becomes easier.

によってαを決定する。
αは、角度で３０度以上９０度未満が好ましく、３０度以上８０度以下がより好ましく、４０度以上６０度以下が特に好ましい。この角度が小さいと作製が困難となる傾向があり、大きいと凹部にめっきにより形成し得た金属層（導体層パターン）を剥離する際、又は、別の基材に転写する際の抵抗が大きくなる傾向がある。 The side surface of the recess is not necessarily a flat surface. In this case, as shown in FIG. 10 (b), the gradient α is such that the height h of the concave portion (that is, the thickness of the insulating layer) and the width s of the side surface of the concave portion (in the horizontal direction). The width direction of the side surface of the recess)

Determines α.
α is preferably 30 degrees or more and less than 90 degrees, more preferably 30 degrees or more and 80 degrees or less, and particularly preferably 40 degrees or more and 60 degrees or less. If this angle is small, the production tends to be difficult, and if it is large, the resistance when peeling the metal layer (conductor layer pattern) that can be formed by plating in the recess or transferring to another substrate is large. Tend to be.

The planar shape of the insulating layer and the thickness of the insulating layer or the depth of the recess in the conductive substrate for plating of the present invention are appropriately determined according to the use of the patterned metal obtained using the conductive substrate for plating of the present invention. Is done.
The concave portion of the conductive base material for plating corresponds to the shape of the patterned metal generated by plating, but also corresponds to the conductive layer pattern in the base material with a conductive layer pattern, and the conductive layer pattern is This corresponds to the electromagnetic wave shielding layer when the electromagnetic wave shielding member is finally produced.

  In addition, the thickness of the insulating layer is the same as described above. In order to correspond to this, the depth of the recess 4 in the conductive substrate for plating of the present invention is preferably 0.1 to 100 μm. 0.1 to 20 μm is more preferable, 0.5 to 10 μm is further preferable, and 1 to 5 μm is particularly preferable.

When the conductive substrate for plating of the present invention is used to produce a member or product that requires light transmission, such as a light transmissive electromagnetic wave shielding member, by a transfer method, the recess 14 as shown in FIG. The width d of the opening is preferably 2 to 60 μm and the width d ′ of the bottom is 1 to 40 μm. The width d of the opening of the recess 14 is particularly preferably 4 to 15 μm, and the width d ′ of the bottom is particularly preferably 3 to 10 μm. The center interval (line pitch) of the recesses 14 is preferably 50 to 2000 μm, and particularly preferably 100 to 1000 μm. The width of the groove and the interval between the grooves are determined considering that the opening ratio of the conductor layer pattern is preferably 50% or more, more preferably 60% or more, and particularly preferably 80% or more.
The width and other dimensions of the recess are determined in accordance with the shape of the conductor layer described above.
In the present invention, the center interval (line pitch) of the recesses cannot be easily determined because the figure pattern of the insulating layer formed by the recesses is a complicated figure or a combination of a plurality of figures. Is defined as the length of one side of the pattern by converting the area into a square area based on the repeating unit of the pattern.

From the viewpoint of visible light transmittance in the electromagnetic wave shielding material for display, the conductive layer pattern aperture ratio for drawing the geometric figure as described above in the electromagnetic wave shielding material is required to be 50% or more. The aperture ratio is more preferably 80% 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.

  According to the conductive base material for plating described above, since the concave portion in which the metal layer is formed by plating is wide in the opening direction, the conductor layer pattern obtained by plating can be easily peeled off. Moreover, since an insulating layer consists of DLC or an inorganic material, the adhesiveness to an electroconductive base material is excellent, and the peeling resistance is excellent. The insulating layer can improve the adhesion between the conductive base material and the insulating layer by the intermediate layer, thereby further extending the life of the conductive base material for plating. The conductive substrate for plating having a wide concave portion toward the opening direction of the present invention is a convex shape in which a convex pattern is formed on the conductive substrate and the insulating layer is adhered after the insulating layer is formed. Since the concave portion can be produced by removing the pattern, the manufacture is easy and the productivity is high.

The method for producing a conductive substrate for plating according to the present invention includes a step of forming an insulating layer on the surface of the conductive substrate so that a geometric figure is drawn by the recesses exposing the conductive substrate. .
This step includes (A) a step of forming a removable convex pattern on the surface of the conductive substrate, (B) a surface of the conductive substrate on which the removable convex pattern is formed, A step of forming an insulating layer; and (C) a step of removing the convex pattern to which the insulating layer is attached.

For the step (A) of forming a removable convex pattern on the surface of the conductive substrate, a method of forming a resist pattern using a photolithographic method can be used.
This method (Method a)
(A-1) forming a photosensitive resist layer on the conductive substrate;
(A-2) a step of exposing the photosensitive resist layer through a mask corresponding to the conductor layer pattern, and (a-3) a step of developing the exposed photosensitive resist layer.

In addition, a method using laser light can be applied to the step (A) of forming a removable convex pattern on the surface of the conductive substrate. This method (method b)
(B-1) a step of forming a photosensitive resist layer on the conductive substrate;
(B-2) including a step of irradiating the photosensitive resist layer with a laser beam without masking a portion corresponding to the conductor layer pattern; and (b-3) a step of developing the photosensitive resist layer after the laser beam irradiation. .

  As the photosensitive resist, a well-known negative resist (a portion irradiated with light is cured) can be used. At this time, a negative mask (light passes through a portion corresponding to the concave portion) is also used as the mask. Further, a positive resist can be used as the photosensitive resist. Corresponding to these methods, the light irradiation part in the method a and method b is appropriately determined.

  As a specific method, by laminating a dry film resist (photosensitive resin layer) on a conductive substrate, and wearing a mask to expose it, the part that remains as a convex pattern can be cured and the unnecessary part can be developed. It can be formed by developing and removing unnecessary portions. In addition, the convex pattern is a state in which the portion that remains as the convex pattern is cured by applying a liquid resist to the conductive substrate and then drying or temporarily curing the solvent, and then exposing the mask with a mask. Alternatively, the unnecessary portion can be developed, and the unnecessary portion can be developed and removed. The liquid resist can be applied by spraying, dispenser, dipping, roll, spin coating or the like.

In the above, after laminating a dry film resist or applying a liquid resist, it is also possible to employ a method of directly exposing without using a mask with a laser beam or the like instead of exposing through a mask. If the patterning can be performed by irradiating the photocurable resin with active energy rays with or without a mask, the mode is not limited.
When the size of the conductive substrate is large, a method using a dry film resist is preferable from the viewpoint of productivity. When the conductive substrate is a plating drum, the dry film resist is laminated or a liquid resist is applied. Then, a method of directly exposing with a laser beam or the like without using a mask is preferable.

  In the above, it can carry out also by the method of using a thermosetting resin instead of a photosensitive resist, and removing the unnecessary part of a thermosetting resin by irradiation of a laser beam.

  Although a resist pattern (convex pattern) can be formed by using a printing method, in this case, 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. After printing, the resist is cured by light irradiation or heat.

An example of the manufacturing method of the electroconductive base material for plating in this invention is demonstrated using drawing.
FIG. 11 is a cross-sectional view showing an example of a process showing a method for producing a conductive substrate for plating.

  A photosensitive resist layer (photosensitive resin layer) 15 is formed on the conductive substrate 12 (FIG. 11A). The photosensitive resist layer 15 is patterned by applying a photolithographic method to the photosensitive resist layer (photosensitive resin layer) 15 of the laminate (FIG. 11B). Patterning is performed by placing a photomask on which a pattern is formed on the photosensitive resist layer 15, exposing it, developing it, removing unnecessary portions of the photosensitive resist layer 15, and leaving protrusions 16. Done. The shape of the protrusion 16 and the convex pattern formed therefrom are considered to correspond to the recess 14 and the pattern on the conductive substrate 12.

At this time, in the cross-sectional shape of the protrusion 16, the side surface is perpendicular to the conductive base material, or the end of the protrusion 16 is in contact with the end where the protrusion 16 contacts the conductive base material 12. It is preferable to be in a position where at least a part of the upper side surface covers the end portion. In terms of the width of the protrusion 16, the maximum value d ₁ of the convex pattern width is preferably equal to or larger than the width d ₀ in contact with the convex pattern and the conductive substrate 12. This is because the concave width of the insulating layer having good adhesion is determined by d ₁ . Here, as a method of increasing the width d ₀ of the protrusion 16 in contact with the conductive group 12 in the sectional shape of the protrusion 16, the maximum width d ₁ of the protrusion 16 is equal to or larger than the width d ₀ when the protrusion 16 is developed. A resist having a characteristic of over-developing or having an undercut shape may be used. d ₁ is preferably is realized at the top of the convex portion.
The shape of the protrusion 16 that forms the pattern of the removable convex portion is associated with the shape of the concave portion. From the ease of production, the maximum width is 1 μm or more, the interval is 1 μm or more, and the height is 1 to 50 μm Preferably there is. When the conductive substrate for plating is used for producing a conductor layer pattern for a light-transmitting electromagnetic wave shielding member, the protrusion 16 has a maximum width of 1 to 40 μm, a distance of 50 to 1000 μm, and a height of 1 to 1. Each of 30 μm is preferable. In particular, it is preferable that the maximum width is 3 to 10 μm and the interval is 100 to 400 μm. Further, when the conductive substrate for plating is used for producing a perforated metal foil, the planar shape is a circular or rectangular shape having an appropriate size so that the insulating layer 13 as described above is formed. Are arranged at appropriate intervals.

The step (B) of forming an insulating layer on the surface of the conductive substrate on which the removable convex pattern is formed will be described.
An insulating layer 17 is formed on the surface of the conductive substrate 12 having a convex pattern composed of the protrusions 16 (FIG. 11C).

  As a method for forming a DLC thin film as an insulating layer, a vacuum deposition method, a sputtering method, an ion plating method, an arc discharge method, a physical vapor deposition method such as an ionization deposition method, a chemical vapor deposition method such as a plasma CVD method, etc. However, the plasma CVD method using a high frequency or pulse discharge in which the film forming temperature can be controlled 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. Further, a mixture of the above-described carbon source and hydrogen gas as a raw material gas containing carbon and hydrogen as elements, and the above-described carbon source and a gas of a compound composed only of carbon and oxygen such as carbon monoxide gas and carbon dioxide gas. A mixture of a compound gas composed of only carbon and oxygen, such as a mixture, carbon monoxide gas, carbon dioxide gas, and hydrogen gas; a compound gas composed of only carbon and oxygen, such as carbon monoxide gas, carbon dioxide gas; Examples thereof include a mixture with oxygen 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.

Even when the insulating layer is formed of an inorganic material such as Al ₂ O ₃ or SiO ₂ , a physical vapor deposition method such as a sputtering method or an ion plating method or a chemical vapor deposition method such as plasma CVD can be used. . For example, in the case of forming by sputtering, an oxide or nitride such as SiO ₂ or Si ₃ N ₄ can be formed by introducing Si or Al as a target and introducing oxygen, nitrogen or the like as a reactive gas. it can. In the case of using the ion plating method, Si or Al can be used as a raw material, and an electron beam can be irradiated to evaporate to form a film on the substrate. At that time, an oxide, nitride, or carbide film can be formed by introducing a reactive gas such as oxygen, nitrogen, or acetylene.
In the case of forming a film by the CVD method, the film can be formed by using a chemical gas such as a metal chloride, a metal hydride, an organometallic compound, etc. as a raw material. The CVD of silicon oxide can be performed by plasma CVD using, for example, TEOS or ozone. The CVD of silicon nitride can be performed by plasma CVD using ammonia and silane, for example.

Next, the step (C) of removing the convex pattern to which the insulating layer is attached will be described. In the state where the insulating layer 17 is attached (see FIG. 11C), the convex pattern formed of the protrusions 16 is removed (see FIG. 11D).
A commercially available resist stripping solution, inorganic, organic alkali, organic solvent, or the like can be used to remove the resist to which the insulating layer is attached. In addition, if there is a dedicated stripping solution corresponding to the resist used to form the pattern, it can be used.
As a peeling method, for example, it is possible to remove the resist after it has been swelled, broken or dissolved by immersion in a chemical solution. In order to sufficiently impregnate the resist with the solution, techniques such as ultrasonic waves, heating, and stirring may be used in combination. In addition, the liquid can be applied with a shower, a jet or the like in order to promote peeling, and can be rubbed with a soft cloth or cotton swab.
In addition, when the heat resistance of the insulating layer is sufficiently high, a method of baking at a high temperature to carbonize the resist and removing it, or irradiating with a laser to burn off can be used.
As the stripping solution, for example, a 3% NaOH solution is used, and showering or dipping can be applied as the stripping method.

The insulating layer formed on the conductive substrate 12 and the insulating layer formed on the side surface of the protruding portion 16 are made to have different properties or characteristics. That is, the hardness of the former is greater than the latter. This is the case when the DLC film is formed by plasma CVD. In general, when an insulating film is formed, when the moving speed of the insulating material is different by, for example, an angle of 90 degrees, the properties or characteristics of the film formed as described above are different.
When the protrusion 16 is removed, the insulating layer is separated at this boundary, and as a result, the side surface of the recess has an inclination angle α. The angle of inclination α is preferably 30 degrees or more and less than 90 degrees, more preferably 30 degrees or more and 80 degrees or less, more preferably 30 degrees or more and 60 degrees or less, and particularly preferably 40 degrees or more and 60 degrees or less, and the DLC film is formed by plasma CVD. In the case of manufacturing by, it becomes easy to control to approximately 40 to 60 degrees. That is, the concave portion 14 is formed so as to become wider toward the opening direction. As a method of controlling the inclination angle α, a method of adjusting the height of the protrusion 16 is preferable. As the height of the protrusion 16 is increased, the inclination angle α is easily controlled.

  In the formation of the insulating layer, the conductive base material does not become a shadow of the resist, and therefore the insulating layer on the conductive base material has uniform properties. On the other hand, the insulating layer is formed on the side surface of the convex pattern because the side surface of the convex pattern has an angle with respect to the film thickness direction on the conductive substrate. As for the film, an insulating layer having the same characteristics (for example, the same hardness) as the insulating layer on the conductive substrate cannot be obtained. In such a heterogeneous insulating layer contact surface, a boundary surface of the insulating layer is formed as the insulating layer grows, and the boundary surface is a growth surface of the insulating layer, and is smooth. For this reason, when the convex pattern consisting of the protrusions is removed, the insulating layer (particularly the DLC film) is easily separated at this boundary. Furthermore, the inclination angle α that becomes the boundary surface, that is, the side surface of the concave portion is that the growth of the insulating layer is delayed on the side surface of the protruding portion with respect to the film thickness direction on the conductive substrate. , Controlled as described above.

In the present invention, the hardness of the insulating layer formed on the conductive substrate is preferably 10 to 40 GPa. The insulating layer having a hardness of less than 10 GPa is soft, and when the conductive substrate is used as a plating plate, durability in repeated use is reduced. When the hardness is 40 GPa or more, it becomes impossible to follow the deformation of the base material when the conductive base material is processed such as bending, and the insulating layer is likely to be cracked or cracked. The hardness of the insulating layer formed on the conductive substrate is more preferably 12 to 30 GPa.
On the other hand, the hardness of the insulating layer formed on the side surface of the convex portion is preferably 1 to 15 GPa. The insulating layer formed on the side surface of the convex portion must be formed so as to be at least lower than the hardness of the insulating layer formed on the conductive substrate. By doing so, a boundary surface is formed between the two, and a wide concave portion is formed after a step of peeling the convex pattern composed of the protruding portion to which the insulating layer adheres later. The hardness of the insulating layer formed on the side surface of the protrusion is more preferably 1 to 10 GPa.

The hardness of the insulating layer can be measured using a nanoindentation method. In the nanoindentation method, a regular triangular pyramid (Berkovic) indenter with a diamond tip is pressed into the surface of a thin film or material, and the hardness is obtained from the load applied to the indenter and the projected area under the indenter. As a measurement by the nanoindentation method, a device called a nanoindenter is commercially available. The hardness of the film formed on the conductive substrate can be measured by pressing an indenter from the conductive substrate as it is. In addition, in order to measure the hardness of the film formed on the side surface of the convex part, a part of the conductive substrate is cut out and cast with resin, and the indenter is pushed into the insulating layer formed on the side surface of the convex part from the cross section. Can be measured. Normally, in the nanoindentation method, the hardness is measured by applying a minute load of 1 to 100 mN to the indenter, but in the present invention, the value measured by applying a load of 3 mN for 10 seconds is described as the hardness value.
Thus, the electroconductive base material 11 for plating can be produced.

FIG. 12 shows a cross-sectional view of a conductive substrate for plating having an intermediate layer and its precursor.
Before forming the insulating layer 17 on the surface of the conductive base material 12 on which the convex pattern composed of the protrusions 16 is formed, it is preferable to form the intermediate layer 18 (FIG. 12 (c ′)). As the intermediate layer, those described above can be used, and the formation method is also as described above. When the intermediate layer 18 is formed, the conductive base material for plating obtained is such that the conductive base material 12 is exposed at the bottom of the recess 14, and otherwise, the insulating layer 17 is formed on the intermediate layer 18. (FIG. 12 (d ′)). The intermediate layer may be formed on the surface of the conductive substrate 12 before the convex pattern 16 is formed. Then, you may perform the process of forming an insulating layer on the surface so that a geometric figure may be drawn by the recessed part which has exposed the electroconductive base material as mentioned above. In this case, if an intermediate layer is used that is sufficiently conductive to allow electroplating, the bottom of the recess may remain the intermediate layer, but if the intermediate layer does not have sufficient conductivity, dry The intermediate layer at the bottom of the recess is removed by a method such as etching to expose the conductive substrate 12.

A well-known method can be employ | adopted for the plating method in this invention. As the plating method, an electrolytic plating method, an electroless plating method, or other plating methods can be applied.
The electrolytic plating 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. For electrolytic 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 electrolytic gold 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. As the electroplating method, for example, “Practical plating for field engineers” (edited by the Japan Plating Association, published by Sakai Shoten in 1986), pages 87 to 504 can be referred to.

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, 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. Regarding the electroless plating method, the above-mentioned Non-Patent Document 1 No. 505-505.
See page 545.
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 is, for example, immersed in an electroless copper plating solution at a temperature of about 60 to 90 ° C. after a palladium catalyst is attached to the recesses of the conductive base material for plating, if necessary. This is a method of performing copper plating.
In electroless plating, the substrate is not necessarily conductive. However, when anodizing the substrate, the substrate needs to be conductive.
In particular, when the material of the conductive substrate is Ni, electroless plating includes a method in which the recesses are anodized and then immersed in an electroless copper plating solution to deposit copper.

  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 in the concave portion of the conductive substrate is appropriately determined according to the purpose. The plating thickness is preferably 0.5 μm or more in order to exhibit sufficient conductivity (at this time, sufficient electromagnetic shielding properties are exhibited), and pinholes are formed in the conductor layer (at this time, For example, the thickness is more preferably 3 μm or more in order to reduce the possibility that the electromagnetic wave shielding property is reduced). If the plating thickness is too large, the formed metal layer also spreads in the width direction. This is also adjusted appropriately according to the purpose. Thus, when the plating thickness is too large, the line width becomes wide, and when the resulting metal layer is used for the electromagnetic wave shielding layer, the aperture ratio is lowered, and the transparency and invisibility of the electromagnetic wave shielding member are lowered. There is a tendency to make it. Therefore, in order to ensure sufficient transparency and invisibility as an electromagnetic wave shielding member, the thickness of the formed metal layer is preferably 20 μm or less, and further, the plating time is shortened and the production efficiency is improved. In order to increase the thickness, the thickness of the plating is more preferably 10 μm or less.

  The line width of the conductor layer pattern of the finally obtained base material with a conductor layer pattern (meaning the conductor layer pattern that has been blackened when the metal pattern is blackened) is 40 μm or less, and the line interval is 50 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.

  In addition, when the substrate with a conductor layer pattern obtained by the present invention is used for a display front application, the aperture ratio of the portion that bears the electromagnetic wave shielding function is required to be 50% or more from the viewpoint of visible light transmittance. 60% or more is preferable, and 80% or more is particularly preferable. If the aperture ratio is too large, the line width becomes too small. Therefore, the aperture ratio is preferably 97% or less. From the viewpoint of the line interval, the line interval is preferably 1000 μm (1 mm) or less. If the line spacing becomes too large, the electromagnetic wave shielding property tends to decrease. 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. From the viewpoint of visible light transmittance, the line interval is preferably 50 μm or more, more preferably 100 μm or more, and particularly preferably 120 μm or more. The larger the line spacing, the better the aperture ratio and the visible light transmittance.

  Further, the thickness of the conductor layer pattern is preferably 100 μm or less, and 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, it is more preferably 40 μm or less, and further preferably 18 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.

The thickness of the metal foil formed by plating is reduced from the viewpoint that the metal layer to be deposited can be more shaped by making the recess deeper relative to the thickness of the deposited metal layer. The height of the insulating layer is preferably 2 times or less, particularly preferably 1.5 times or less, and further preferably 1.2 times or less, but is not limited thereto.
The degree of plating can be such that the deposited metal layer is present in the recess. Even in such a case, since the concave shape is wide in the opening direction, and further, the surface of the concave side surface formed by the insulating layer can be smoothed, so that the anchor effect at the time of peeling of the metal foil pattern is reduced. it can. Moreover, it becomes possible to make high the ratio of the height with respect to the width | variety of the metal layer to deposit, and to improve the transmittance | permeability more.

  The conductor layer in the present invention has a shape corresponding to the surface shape of the conductive substrate for plating described above. The shape and dimensions are as described above.

  In order to make the relationship between L3 and T1 of the above-described conductor layer the relationship of the formula (2) [more preferably, the formula (3)], for example, when using a copper sulfate bath as the plating solution, What consists of these is preferable.

Copper sulfate (pentahydrate) 50-400 g / L (12-100 g / L as copper content)
Sulfuric acid 50-200 g / L
Including, if necessary,
Chlorine ion (hydrochloric acid or sodium chloride) 20-100 mg / L
Brightener (3-mercapto-1-propanesulfonate, etc.) Appropriate amount Surfactant (polyethylene glycol, etc.) An aqueous solution in which an appropriate amount is dissolved and blended is used.
It is also possible to use high molecular weight polysaccharides and low molecular weight glue as an alternative to brighteners and surfactants.

  Next, the next step in the manufacturing process of the substrate with the conductor layer pattern, that is, (II) a conductor layer formed on the conductive substrate for plating (metal deposited in the concave portion of the conductive substrate for plating) A transfer process for transferring the film to a suitable base material including a resin layer will be described.

  The above-mentioned appropriate base material (including the resin layer or the supporting base material and the resin layer thereon) is as described above, but in the transfer step, the resin layer has adhesiveness or It consists of what shows adhesiveness (these are called "adhesive" or "adhesive resin"). This pressure-sensitive adhesive may contain additives such as a crosslinking agent, a curing agent, a diluent, a plasticizer, an antioxidant, a filler, a colorant, an ultraviolet absorber and a tackifier, as necessary. Good. The “adhesiveness” includes “adhesiveness”.

If the thickness of the pressure-sensitive adhesive layer (resin layer) is too thin, sufficient strength cannot be obtained. Therefore, when transferring a conductive layer formed by plating, the conductive layer does not adhere to the pressure-sensitive adhesive layer, resulting in poor transfer. May occur. Therefore, the thickness of the pressure-sensitive adhesive layer is preferably 1 μm or more, and more preferably 3 μm or more in order to ensure transfer reliability during mass production. Further, if the thickness of the pressure-sensitive adhesive layer is too thick, the production cost of the pressure-sensitive adhesive layer increases, and the amount of deformation of the pressure-sensitive adhesive layer increases when laminated, so the thickness of the pressure-sensitive adhesive layer is preferably 100 μm or less. 50 μm or less is more preferable.
When the substrate is bonded to the surface of the conductive substrate for plating, on which the conductor layer is formed, the adhesive layer exhibits appropriate fluidity or adhesiveness, depending on the properties of the adhesive layer. In order to do so, it is heated if necessary. When the substrate has a supporting substrate that holds the pressure-sensitive adhesive layer, it is preferable that the supporting substrate has sufficient heat resistance to maintain the shape even during such heating.

The example which produces a base material with a conductor layer pattern through said transfer process is shown next.
FIG. 13: is sectional drawing which shows the first half of the preparation examples of the base material with a conductor layer pattern. FIG. 14 is a cross-sectional view showing the latter half.
On the conductive base material 11 for plating, plating is performed in the recesses 14 by the above-described plating step, thereby forming a pattern of the conductor layer 19 (FIG. 13E). Next, the transfer substrate 20 prepared separately, which is a support substrate (transparent substrate) 21, is laminated with an adhesive layer 22. Preparation is made to pressure-bond the transfer base material 20 with the adhesive layer 22 facing the conductive base material 11 for plating on which the pattern of the conductor layer 19 is formed (FIG. 13F). At this time, the support substrate 21 may have an adhesive different from the adhesive layer 22 on the surface. Accordingly, for example, the support base material 21 can be easily peeled from the pressure-sensitive adhesive layer 22 later.

  Next, the transfer substrate 20 is pressure-bonded to the plating conductive substrate 11 on which the conductor layer pattern is formed with the adhesive layer 22 facing (FIG. 14G). At this time, the pressure-sensitive adhesive layer 22 may contact the insulating layer 17. The thickness of the conductor layer embedded in the pressure-sensitive adhesive layer 22 can be adjusted by the degree of pressure bonding. At this time, the pressure-sensitive adhesive layer 22 preferably exhibits fluidity with respect to pressure, and in some cases, is heated to flow the pressure-sensitive adhesive layer 22.

  The same state as the case where the transfer base material 20 is pressure-bonded with the adhesive layer 22 facing the conductive base material 11 for plating on which the conductor layer pattern is formed (FIG. 14 (g)) is as follows. Can be realized. That is, on the conductive substrate 11 for plating on which the conductor layer pattern is formed, a liquid pressure-sensitive adhesive is applied to a certain thickness or a sheet-like pressure-sensitive adhesive is placed, and a support base is further formed thereon. The material 21 is placed and bonded with appropriate pressure. At this time, as a pressure-sensitive adhesive, when using a photocurable resin or a thermosetting resin that is cured by irradiation with active energy rays, curing is performed by appropriately irradiating with active energy rays or heating. The degree of curing is appropriately determined depending on the degree of adhesion remaining in the adhesive. When a thermoplastic resin is used as the adhesive, it is preferable to relatively cool and solidify after placing the support base material. In the above, a peelable substrate may be used as the support substrate (or instead of the support substrate), and the pressure-sensitive adhesive layer may be peeled off after being cured or solidified. At this time, the base material including the resin layer does not include the support base material.

Next, when the transfer substrate 20 is peeled off, the pattern of the conductor layer 19 is adhered to the adhesive layer 22 and peeled off from the conductive substrate 12 for plating. As a result, a substrate 23 with a conductor layer pattern is obtained. (FIG. 14 (h)). Adjusting the thickness of the conductor layer embedded in the pressure-sensitive adhesive layer 22 by pressing with a pressing roll or the like through a film (preferably a peelable film) from above the obtained substrate 23 with a conductor layer pattern Can do. At this time, the pressure-sensitive adhesive layer 22 preferably exhibits fluidity with respect to pressure, and in some cases, is heated to flow the pressure-sensitive adhesive layer 22.

FIG. 15 is a cross-sectional view showing a state in which a conductor layer pattern is formed by plating in a concave portion of a conductive base material for plating, and FIG. 16 shows a conductor layer pattern obtained by transferring the conductor layer pattern in the concave portion. A cross-sectional view of the substrate 23 is shown.
Since plating grows isotropically when plating on a conductive substrate for plating, the deposition of plating that started from the exposed portion of the conductive substrate overflows from the recess and covers the insulating layer as it progresses. To protrude and precipitate. From the viewpoint of sticking to the transfer substrate, it is preferable to deposit the plating so as to protrude. However, at this time, the plating may be deposited so as to be contained in the recess 14. This state is shown in FIG. Even in this case, as shown in FIG. 16, the pattern of the conductor layer 19 is transferred to the pressure-sensitive adhesive layer 22 by pressing the transfer substrate, and the pattern of the conductor layer 19 from the conductive substrate 11 for plating. Can be peeled off to produce a substrate 23 with a conductor layer pattern. In this case, since the conductor layer is not completely embedded in the pressure-sensitive adhesive layer 22, it is applied with a pressure roll or the like through a film (preferably a peelable film) from above the obtained substrate 23 with a conductor layer pattern. The conductor layer is embedded in the pressure-sensitive adhesive layer 22 by an appropriate thickness by pressure bonding. At this time, the pressure-sensitive adhesive layer 22 preferably exhibits fluidity with respect to pressure, and in some cases, is heated to flow the pressure-sensitive adhesive layer 22. Even in the transfer step in this case, as described above, a liquid adhesive is applied to the plating conductive substrate 11 having the pattern of the conductor layer 19 to a certain thickness or a sheet-like shape. It is possible to employ a method in which an adhesive is placed, and the support base material 21 is placed thereon, and an appropriate pressure is applied thereto for adhesion.

In the transfer step, when an adhesive containing a curable resin such as a thermosetting resin or a photocurable resin is used for the adhesive layer 22 of the transfer substrate 20, the curing is performed by plating the transfer substrate 20. It may be performed before peeling from the conductive base material 11 or after peeling, may be semi-cured before peeling, and may be completely cured after peeling.
In particular, when curing or complete curing of the pressure-sensitive adhesive containing the curable resin is performed after the transfer substrate 20 is peeled off from the plating conductive substrate 11, the coverlay film and the peelable support are laminated and adhered. You may carry out simultaneously with bonding to an agent layer. Thereby, it can be set as the base material with a conductor layer pattern which protected the conductor layer.
Generally, the conductor layer pattern side of the substrate with the conductor layer pattern is bonded to the cover film, peelable support, etc., optionally via a resin layer, and the resin layer is applied. By coating, it can be set as the base material with a conductor layer pattern which protected the conductor layer. Such a base material with a conductor layer pattern can be used for an electromagnetic wave shielding member, a film antenna, or the like.

  The base material 23 with the conductor layer pattern (FIG. 14 (h) or FIG. 16) can be used after adjusting the thickness of the conductor layer 19 embedded in the adhesive layer 22 as appropriate. At this time, it is particularly preferable that the pressure-sensitive adhesive layer 22 and the upper surface of the conductor layer 19 embedded therein are flush with each other. Note that. When a base material with a conductor layer pattern contains a support base material, this support base material may be called base material (I). The support base material 21 of the base material 23 with the conductor layer pattern corresponds to the base material (I).

FIG. 17 is a cross-sectional view showing an example of a base material with a conductor layer pattern in which the conductor layer is protected by the protective base material. This protective substrate is sometimes referred to as substrate (II).
FIG. 17 shows a substrate 25 with a conductor layer pattern in which a protective substrate [substrate (II)] is laminated on the conductor layer side of the substrate 23 with a conductor layer pattern, that is, the surface is protected. That is, the conductor layer 19 is embedded in the resin layer 22 on the support substrate 21, and the protective substrate 24 is laminated thereon. As a method, a protective base material 24 [base material (II)] such as a film (preferably a peelable film) is applied to the base material 23 with the conductor layer pattern from above the conductor layer 19 by using a press roll or the like. The conductor layer is embedded in the pressure-sensitive adhesive layer 22 by an appropriate thickness, but in FIG. 17, the pressure-sensitive adhesive layer 22 and the upper surface of the conductor layer 19 embedded in the same are flush with each other. At this time, the pressure-sensitive adhesive layer 22 preferably exhibits fluidity with respect to pressure, and in some cases, is heated to flow the pressure-sensitive adhesive layer 22. In the protective substrate 24, a pressure-sensitive adhesive may be laminated on the adhesive surface to the resin layer 22 and the conductor layer 19. In addition, if the base material (II) has the function to protect a conductor layer, it may have another function simultaneously. The substrate (II) can be appropriately selected from those similar to the above-mentioned support substrate.
The substrate 25 with a conductor layer pattern whose surface is protected can be used as an electromagnetic wave shielding member, a film antenna, or the like.

18 is a cross-sectional view showing an example of a substrate with a conductor layer pattern, and the substrate 26 with a conductor layer pattern shown in FIG. 18 is a protective substrate 24 from the substrate 25 with a conductor layer pattern of FIG. The conductor layer 19 is embedded in the resin layer 22 on the support base material 21 so that the surface of the resin layer 22 (the portion without the conductor layer 19) and the upper surface of the conductor layer 19 are flush with each other. Yes.
Although the base material 26 with a conductor layer pattern can be used as an electromagnetic wave shielding member, a film antenna, etc., it can also be used as an electrode base material for solar cells. In order to use the substrate 26 with a conductor layer pattern also as an electrode substrate for a solar cell, the exposed surface of the conductor layer 19 of the resin layer (adhesive layer) 22 is brought into contact with the solar cell element. To use. Use as such a solar cell substrate includes use as a back electrode substrate or an interconnector substrate.

  The base material 23 with a conductor layer pattern is manufactured by adjusting the thickness of the conductor layer 19 embedded in the pressure-sensitive adhesive layer 22 without adjusting the thickness of the conductor layer 19 on the surface having the conductor layer 19 by vapor deposition or the like. It can be used as a solar cell substrate. This solar cell substrate can be made into a crystalline silicon solar cell, a silicon thin film solar cell, a CIGS thin film solar cell, and a dye-sensitized solar cell by producing a solar cell element on a transparent conductive film.

  The substrate 23 with a conductor layer pattern ((FIG. 14 (h) or FIG. 16)) or the substrate 26 with a conductor layer pattern (FIG. 18) is also peeled off from the support substrate 21 to form a resin layer (adhesive layer). ) A conductor layer-attached resin layer (adhesive layer) 27 in which the conductor layer 19 is embedded in 22 can be prepared and used. FIG. 19 shows this cross-sectional view. At this time, the embedded thickness of the conductor layer 19 is preferably adjusted in advance as described above, and the pressure-sensitive adhesive layer 22 may no longer remain adhesive.

  FIG. 20 is a cross-sectional view showing an example of a base material with a conductor layer pattern having a transparent conductive film. The substrate 29 with a conductor layer pattern having the transparent conductive film of FIG. 20 is manufactured by forming a transparent electrode 28 such as ITO on the surface where the conductor layer 19 of the substrate 26 with the conductor layer pattern of FIG. It is a film.

Third step in the production process of the base material with a conductor layer pattern, that is, (III) When the base material includes a support base material, the support base material [base material (I)] Will be described with respect to a process for exchanging the substrate with another support substrate (this is also referred to as a substrate (III)). This step is appropriately performed and may not be performed depending on circumstances.
In connection with this process, various laminated structures can be derived.

In the transfer step (II) described above, a substrate with a conductor layer pattern is obtained by transferring the plating formed on the conductive substrate for plating to a substrate including a resin layer. Therefore, if the substrate with a conductor layer pattern obtained in this way is used thereafter, the method for producing a substrate with a conductor layer pattern is preferable because the number of steps is small, but considering mass productivity, If a flexible resin film is used as the material, it is good, but if a hard material such as a glass plate is used as the base material, a continuous production method such as a roll-to-roll method cannot be selected. There are restrictions.
Therefore, after the plating formed on the conductive substrate for plating is transferred to an appropriate substrate including a resin layer by a roll-to-roll method to obtain a roll-shaped conductive layer-supporting substrate, By bonding a conductive layer to a hard substrate and forming the conductive layer on a hard substrate, a hard substrate with a conductive layer pattern can be produced without losing mass productivity, and a hard substrate such as a glass substrate can be easily produced. A conductive layer can be formed on the material.
The above step (III) is convenient in such a case, and is convenient because the support base material can be appropriately replaced.

When performing the step (III), the appropriate base material in the step (II) includes a support base material and a resin layer thereon, and is the same as the base material already described above. As the substrate, a plastic film is preferable. The resin layer is preferably a pressure-sensitive adhesive layer.
Moreover, as a new support base material to be replaced, a rigid material such as a glass plate or a plastic plate is particularly suitable for the above method, but is not limited thereto.
During or after the above steps, the conductor layer is embedded in the resin layer at least from the maximum width portion. Adjustment of the embedded thickness of the conductor layer at the time of transfer or after transfer can be performed in the same manner as described above.

In the step (II), the conductor layer is covered by laminating a cover lay film, a peelable support or the like via a resin layer, or by coating a resin or the like. (II) can be laminated to form a surface-protected substrate with a conductor layer pattern, which is preferably subjected to the next support substrate replacement step.
The lamination can be performed using a laminator, a press, a hot press, a vacuum pressure laminator, or the like.

In the step (III), as the new support base material [base material (III)] to be replaced, the above-mentioned support base material can be used, but the surface thereof may have an adhesive layer.
As an exchange method between the old support base [base (I)] and the new support base [III (III)], the former is peeled off or after the release (the new support base) There is a method of laminating.

The step (III) (exchange step) will be described with reference to the drawings.
During this process, various intermediate laminates are obtained, which can also be used for specific applications as appropriate.
FIG. 21 is a cross-sectional view showing an example of a support substrate replacement step.
FIG. 21A is a cross-sectional view showing a state where the support base material 21 [base material (I)] of the surface-protected base material 25 with conductor layer pattern shown in FIG. 17 is peeled off.

  FIG. 21B is a cross-sectional view of the base material 30 with a conductor layer pattern from which the support base material 21 of the base material 25 with a conductor layer pattern whose surface is protected is completely peeled off. In this state, the base material 30 with a conductor layer pattern can be used for electromagnetic wave shielding films, film antennas, and other applications. When adhesiveness remains in the resin layer 22, the adhesiveness is utilized, and when the resin layer 22 does not have adhesiveness, an adhesive is separately applied or laminated and adhered to the object. be able to.

  A new support substrate is adhered to the surface-protected substrate 30 with the conductor layer pattern from which the support substrate 21 has been peeled off. FIG. 21C is a cross-sectional view of a base material with a conductor layer pattern in which a new support base material is attached and the surface is protected. FIG. 21C shows the resin layer 22 on the new support base 31 [base (III)], and the conductor layer 19 that is embedded in the resin layer 22 but is exposed from the resin layer 22 and protects it. The base material 32 with a conductor layer pattern which consists of the protective base material 24 [base material (II)] laminated | stacked in order to do is shown.

As shown in FIG. 21A, in order to peel off the support base material 21 [base material (I)], the resin layer 22 and the protective base material 24 are used rather than the adhesive force between the resin layer 22 and the support base material 21. The adhesive strength with [Substrate (II)] must be higher. However, in the step (II), as shown in FIG. 14 (h), the transfer base material 23 must peel the conductor layer 19 from the plating conductive base material 12. Therefore, the adhesive force between the conductor layer 19 and the resin layer 22 must be higher than the adhesive force between the conductor layer 19 and the conductive substrate 12 for plating. In addition, the adhesive force between the resin layer 22 and the support substrate 21 must be higher than the adhesive force between the resin layer 22 and the plating conductive substrate 12. This relationship of adhesive strength is
The adhesive force between the resin layer 22 and the conductive substrate 12 for plating;
The adhesive strength between the resin layer 22 and the supporting base material 21 and the adhesive strength between the resin layer 22 and the protective base material 24 increase in the order (hereinafter referred to as “Relationship 1”).
Also,
The adhesive strength between the conductor layer 19 and the electroconductive substrate 12 for plating and the adhesive strength between the conductor layer 19 and the resin layer 22 increase in this order (hereinafter referred to as “Relationship 2”).
Specifically, since the adhesive force between the resin layer 22 and the electroconductive substrate 12 for plating is low, for example, an intermediate release separator or a heavy release separator is used for the support base 21 and polyethylene terephthalate is used for the protective base 24. Thus, “Relationship 1” can be satisfied. Further, “Relationship 2” can be satisfied by lowering the adhesive force between the conductor layer 19 and the conductive substrate 12 for plating depending on the plating conditions and the like.

  Although the new base material 32 with a conductor layer pattern having the protective base material of FIG. 21 (c) may be used as it is for an electromagnetic wave shielding film, a film antenna, and other uses, the protective base material 24 [ Substrate (II)] may be peeled off and used for the use of an electrode substrate for solar cells or the like. FIG. 21D is a cross-sectional view of the substrate with a conductor layer pattern in which the protective substrate is peeled off and the upper surface of the conductor layer is exposed. FIG. 21D shows a substrate 33 with a conductor layer pattern in which a resin layer 22 is embedded on a new support substrate 31 and the conductor layer 19 exposed from the resin layer 22 is laminated on the upper surface. Show. When the adhesive property remains, the resin layer 22 utilizes the adhesive property. When the resin layer 22 does not have adhesive property, the adhesive is applied or laminated separately and adhered to the object. can do.

As shown in FIG. 21 (d), in order to peel off the protective base material 24 [base material (II)], the resin layer 22 and the new support base material are used rather than the adhesive force between the resin layer 22 and the protective base material 24. The adhesive strength with 31 [base (III)] must be higher. This relationship of adhesive strength is
The adhesive force between the resin layer 22 and the conductive substrate 12 for plating;
The adhesive force between the resin layer 22 and the support substrate 21;
The relationship is such that the adhesive strength between the resin layer 22 and the protective base material 24 and the adhesive strength between the resin layer 22 and the new support base material 31 are larger in order (hereinafter referred to as “Relationship 3”).
Since the adhesive force between the resin layer 22 and the electroconductive substrate 12 for plating is low, for example, an intermediate release separator or a heavy release separator is used for the support base material 21 and polyethylene terephthalate is used for the protective base material 24. By using glass for 31, “Relation 3” can be satisfied. Further, the relationship 3 can be satisfied by improving the adhesion between the resin layer 22 and the new support base 31 by improving the adhesion to the adherend by heat treatment or the like. Alternatively, it is possible to satisfy “Relationship 3” by generating a functional group or the like in the resin layer 22 by heat treatment or irradiation with actinic rays to improve the adhesive force between the resin layer 22 and the new support substrate 31. it can.

  When using the base material 33 with a conductor layer pattern as a base material for solar cells, the surface of the resin layer 22 and the conductor layer 19 is laminated | stacked on a solar cell element. For example, when an ethylene-vinyl acetate copolymer is used for the new support substrate 31, the process of laminating the substrate 33 with the conductive layer pattern and the solar cell element and the sealing of the solar cell element with the ethylene-vinyl acetate copolymer are performed. The stopping process can be the same.

FIG. 22 is the same as the base material 33 with the conductor layer pattern of FIG. 21 (d), but the base material with the conductor layer pattern obtained using a new support base material having an adhesive layer. FIG. That is, FIG. 22 shows a conductor in which a resin layer 22 is embedded on a new support base 31 via an adhesive layer 34, and a conductor layer 19 is embedded in the upper surface but exposed from the resin layer 22. The base material 35 with a layer pattern is shown. Thereby, even if the adhesive force between the resin layer 22 and the new support base material 31 is low and “Relationship 3” is not established, this can be realized. In this case, the relationship of adhesive strength is
The adhesive force between the resin layer 22 and the conductive substrate 12 for plating;
The adhesive force between the resin layer 22 and the support substrate 21;
The adhesive strength between the resin layer 22 and the protective substrate 24 and the adhesive strength between the resin layer 22 and the pressure-sensitive adhesive layer 34 are increased in this order (hereinafter referred to as “Relationship 4”).
Also,
The adhesive strength between the resin layer 22 and the protective base material 24 and the adhesive strength between the pressure-sensitive adhesive layer 34 and the new support base material 31 become larger in order (hereinafter referred to as “Relationship 5”). Specifically, if a pressure-sensitive adhesive with high adhesive strength is used for the pressure-sensitive adhesive layer 34, “Relationship 4” and “Relationship 5” can be satisfied.

The method for embedding the conductor layer in the resin layer in the present invention will be further described, but is not limited thereto.
Immediately after transferring the plating deposited in the recesses of the conductive base material for plating to the base material including the resin layer, at least the portion of the conductor layer that is the maximum width may be already embedded in the resin layer, You don't have to. In order to embed at least the portion having the maximum width of the conductor layer immediately after the transfer, it is necessary to increase the fluidity of the resin layer of the base material at the time of transfer. For example, there are a method of increasing the laminating temperature, a method of adding a reactive low molecular weight material as the composition of the resin layer, and a method of using a liquid resin as the resin layer. In this case, it is preferable to peel the transparent substrate after the resin layer is cured or solidified while the substrate is in contact with the plating conductive substrate. The curing reaction is due to heating, irradiation with active energy rays such as ultraviolet rays, etc., but since the productivity is improved by instantaneous curing, curing by irradiation with active energy rays such as ultraviolet rays is preferable.
In addition, immediately after the conductor layer is transferred to the base material, if the portion having the maximum width of the conductor layer is not yet buried in the resin layer (including the case where it is not buried at all or almost), the conductor is formed in a separate process. It is necessary to embed at least the portion of the resin layer in which the maximum width of the conductor layer is embedded in the resin layer. For this purpose, after transferring the conductor layer to the base material, the base material with the conductor layer is pressed with a roll laminator or a press, while applying heat or irradiating active energy rays as necessary, at least of the conductor layer. At least the portion of the maximum width is buried in the resin. At this time, if necessary, the curing reaction may be performed simultaneously by heating or irradiation with energy rays, and the heating may be performed in order to enhance fluidity. Also, in this case, a separate film or other removable substrate is used for the substrate with the conductor layer for the purpose of protecting the surface or blocking oxygen when the resin is UV-cured in the pressurizing step or in the subsequent step. You may laminate | stack from a conductor layer. When a curable resin is used for the resin layer, in the case where the resin layer is not cured simultaneously with the pressurization, it is preferable to cure the resin layer by heating or irradiating active energy rays after the pressurization.
In addition, when a curable resin is used for the resin layer, it is partially cured before the substrate is subjected to the above transfer and before the embedding process after the transfer, in order to adjust the fluidity of the resin layer. The reaction may be performed, but when it is performed before transfer, it is performed to such an extent that the adhesiveness required for transfer is not impaired.

Since the resin layer of the base material contacts the insulating layer of the conductive base material for plating during transfer, the adhesiveness increases as the resin thickness increases, making it difficult to peel off or causing hunting during peeling. Since plating breakage may occur, the thickness is preferably 100 μm or less, and more preferably 50 μm or less. If the resin layer is a curable resin, it may be partially cured in order to adjust adhesion or fluidity before subjecting the substrate to transfer.
7A, 7B, 8B, and 8C, the entire trapezoidal shape (excluding the upper surface) of the upper part of the metal wiring layer or a part thereof is covered with the resin layer. ing. This can be done by applying pressure (and heating as necessary) to flow the resin during or after the transfer. For this purpose, it is necessary for the resin to flow around the shape of the metal wiring layer. Therefore, the thickness T when the metal wiring layer has a shape as shown in FIG. 5A, and the upper thickness when the metal wiring layer has a shape as shown in FIG. 5B. If T1 is thick, the flow rate of the resin becomes large, so that it is difficult to completely coat, or the time of the heating and pressurizing process becomes long and the productivity may be reduced, but this is avoided. Therefore, T or T1 is preferably 10 μm or less, and more preferably 5 μm or less. In addition, when the metal wiring layer has a shape as shown in FIG. 5B, if T1 is thin, the thickness of the resin existing above the lower portion is reduced, and the effect of improving the adhesion is reduced. Is preferably 1.0 μm or more.

The conductor layer of the substrate with a conductor layer pattern obtained by the present invention can be blackened to obtain a substrate with a conductor layer pattern having a conductor layer pattern that has been blackened. For this purpose, the base 23 with a conductor layer pattern as shown in FIG. 14 (h) or FIG. 16 or the conductor layer 19 of these bases with a conductor layer pattern, the conductor layer 19 having a buried thickness adjusted, is blackened. There are a method of performing a blackening treatment, a method of blackening the conductor layer 19 formed in the concave portion 14 of the conductive base material 11 for plating before it is peeled and transferred, and a method of performing both blackening treatments. .
When a substrate with a conductor layer pattern having a conductor layer pattern thus blackened is used as an electromagnetic wave shielding member on the front surface of the display, generally, the surface on which the black layer is provided is on the viewer side of the display. Used to face.

  The above blackening treatment method 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 for the metal layer.

FIG. 23 shows a cross-sectional view of a laminate using the substrate with a conductor layer pattern in the present invention. For example, the surface-protected base material 25 with the conductor layer pattern shown in FIG. The base material 37 is bonded. Other base materials 37 include functional films such as near-infrared films and polarizing films, and support base materials such as glass plates and plastic plates. This laminate can be used for electromagnetic shielding materials and other applications.
FIG. 24 further shows a cross-sectional view of a laminate according to another embodiment. This laminate is a laminate in which the protective substrate 24 is peeled off and the substrate 39 is laminated via an adhesive 38 instead of the laminate in FIG. Further, the base material 39 is laminated on the surface where the conductor layer 19 of the base material 26 with the conductor layer pattern shown in FIG. 18 exists via an adhesive 38, and the other surface is connected to another surface via an adhesive 36. The base material 37 is bonded together. As the base material 39, it can select from the thing similar to what can be used as another base material 37, and can be used. This laminate can also be used for electromagnetic shielding materials and other applications.
The transparent pressure-sensitive adhesives 36 and 38 can be applied by laminating coatings or films, and a pressure-sensitive adhesive mainly composed of a resin curable with active energy rays in addition to a thermoplastic resin and a thermosetting resin. It can also be used. It is preferable to use a resin that cures with an active energy ray because it cures instantaneously or in a short period of time, resulting in an increase in productivity.

  When the substrate 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 sticking it to the display screen as appropriate with or without another adhesive. 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.

The utilization to the solar cell of the base material with a conductor layer pattern which concerns on this invention is demonstrated.
FIG. 25 is a cross-sectional view showing a configuration of a solar cell using a substrate with a conductor layer pattern according to the present invention. A solar cell element 40 is sandwiched and laminated between two base materials with a conductor layer pattern composed of a resin layer 22 that embeds and carries a pattern of the conductor layer 19 having an exposed surface [FIG. ]]]. Moreover, the support base material 21 may be laminated | stacked on the surface on the opposite side to the surface where the conductor layer of the base material with a conductor layer pattern is exposed (FIG.25 (b)). Then, the conductive layer 19 is laminated so that the exposed pattern of the conductive layer 19 of the substrate with the conductive layer pattern comes into contact therewith.

  The solar cell of the above structure can be made into a solar cell module by carrying a plurality by a transparent ethylene-vinyl acetate copolymer between a glass plate and a back sheet. In that case, a conductive layer pattern plays the role of the wiring which connects a solar cell element. For example, when a part of the conductive layer pattern on one side of the solar cell element protrudes from the end of the solar cell element, the conductive layer pattern of the protruding part is formed on the opposite surface of the adjacent solar cell. The connection between the solar cell elements can be formed by connecting to the wiring. The conductor layer pattern and the back surface wiring may be connected by any method, such as a connection using a conductive adhesive, a connection through conductive particles, or a back surface wiring due to the adhesiveness of the resin layer 22. Bonded connection may be used.

FIG. 26 is a cross-sectional view showing another configuration of a solar cell using the substrate with a conductor layer pattern according to the present invention. The solar cell element 40 is formed on a base material with a conductor layer pattern formed of a resin layer 22 that embeds and carries the pattern of the conductor layer 19 having an exposed surface [FIG. 26 (b)]. Moreover, the support base material 21 may be laminated | stacked on the surface opposite to the surface where the conductor layer of the base material with a conductor layer pattern is exposed ([FIG.26 (b)]. Then, the conductive layer 19 is laminated so that the exposed pattern of the conductive layer 19 of the substrate with the conductive layer pattern comes into contact therewith.

The solar cell element 40 shown in FIG. 25 will be described.
As such a solar cell element 40, there is one shown in FIG. FIG. 27 is a cross-sectional view of a solar cell element. The i-type amorphous silicon 42 is laminated on both surfaces of the single crystal n-type silicon 41 by the CVD method or the like, one surface thereof is the p-type amorphous silicon 43 by the CVD method or the like, and the other surface is formed by the CVD method or the like. The n-type amorphous silicon 44 has a structure in which a transparent conductive film 45 such as ITO is laminated thereon by sputtering or the like. The above-mentioned base material with a conductor layer pattern is adhered to both of the transparent conductive films 45 by the resin layer 22 so that the conductor layer 19 is in contact therewith.
The solar cell of the above structure can be made into a solar cell module by carrying a plurality by a transparent ethylene-vinyl acetate copolymer between a glass plate and a back sheet.

The solar cell element 40 shown in FIG. 26 will be described.
An example of such a solar cell element 40 is shown in FIG. FIG. 28 is a cross-sectional view of another solar cell element. The i-type amorphous silicon 42 is laminated on both surfaces of the single crystal n-type silicon 41 by the CVD method or the like, and the p-type amorphous silicon 43 and the transparent conductive film 45 are sequentially formed on the one surface by the CVD method or the like. The solar cell element 48 has a structure in which an n-type amorphous silicon 44 and a metal film 47 such as Al or Ag are sequentially laminated on the other surface by a CVD method or the like by a sputtering method or a printing method. The above-mentioned base material with a conductor layer pattern is adhered to the transparent conductive film 45 by the resin layer 22 so that the conductor layer 19 is in contact therewith.
Moreover, as the solar cell element 40 of FIG. 26, there is one shown in FIG. FIG. 29 is a cross-sectional view of another solar cell element. The i-type amorphous silicon 42 is laminated on both surfaces of the single crystal n-type silicon 41 by the CVD method or the like, and the p-type amorphous silicon 43 and the transparent conductive film 45 are sequentially formed on the one surface by the CVD method or the like. The solar cell element 49 has a structure in which a metal film 47 such as Al or Ag is laminated on the other surface by sputtering or printing. The above-mentioned base material with a conductor layer pattern is adhered to the transparent conductive film 45 by the resin layer 22 so that the conductor layer 19 is in contact therewith.
Moreover, as the solar cell element 40 of FIG. 26, there is one shown in FIG. FIG. 30 is a cross-sectional view of another solar cell element. An i-type amorphous silicon 42 is formed on one surface of the single crystal n-type silicon 41 by a CVD method or the like, a p-type amorphous silicon 43 is formed by a CVD method or the like, and a transparent conductive film 45 is sequentially laminated by a sputtering method or the like. The solar cell element 50 has a structure in which a metal film 47 such as Al or Ag is laminated on the surface by sputtering or printing. The above-mentioned base material with a conductor layer pattern is adhered to the transparent conductive film 45 by the resin layer 22 so that the conductor layer 19 is in contact therewith.

Another embodiment of the solar cell will be described.
FIG. 31 is a cross-sectional view illustrating an example of a solar cell.
The conductor layer 19 is embedded in the resin layer 22 laminated on the support substrate 21 (transparent heat-resistant substrate such as a glass plate). The above structure is an example of the base material with a conductor layer pattern according to the present invention. A transparent conductive film such as ITO is formed on the exposed surface of the conductor layer 19 by sputtering or the like, and grooves are formed by appropriate etching using laser, mechanical polishing of a hard material needle, etc. Is formed. On the transparent conductive film, p-type amorphous silicon 43 is laminated in a specific pattern. Then, an i-type amorphous silicon 42 and an n-type amorphous silicon 44 are laminated so as to overlap with each other, and a groove is formed by appropriate etching such as laser, mechanical polishing of a hard material needle, etc. A pattern is formed. Further, a metal film 47 of Mo or the like is laminated thereon by a sputtering method or the like, and grooves are formed by appropriate etching using a laser, mechanical polishing of a hard material needle or the like to form a certain pattern. The metal film 47 is formed through the side surfaces of the p-type amorphous silicon 43, the i-type amorphous silicon 42, and the n-type amorphous silicon 44 so as to be electrically connected to one adjacent transparent conductive film 47. Thereby, the solar cell 51 is configured.
FIG. 32 is a cross-sectional view showing another example of a solar cell. 31 is a solar cell 54 having a structure in which the metal film 47 side of the solar cell 51 shown in FIG. 31 is sealed with a transparent ethylene-vinyl acetate copolymer 52 and a back sheet 53 is bonded.

FIG. 33 is a cross-sectional view showing another example of a solar cell.
The conductor layer 19 is embedded in the resin layer 22 laminated on the support substrate 21 ((ethylene-vinyl acetate copolymer sheet or ethylene tetrafluoroethylene, etc.)). The above structure is an example of the base material with a conductor layer pattern according to the present invention. A part of the conductor layer 19 is used as the extraction electrode 55.
A certain layer structure is formed on the surface where the conductor layer 19 is exposed so as to repeat a certain pattern. In this constant layer structure, a transparent conductive film 45, a p-type amorphous silicon 43, an i-type amorphous silicon 42, and an n-type amorphous silicon 44 are laminated, and a p-type amorphous silicon germanium 56, an i-type amorphous silicon germanium 57, and an n-type amorphous silicon 44 are stacked. A type amorphous silicon germanium 58 is laminated, and further a metal film 47 (back electrode) is laminated. The transparent conductive film 45 to the metal film 47 are formed on the polyimide film 59 in a certain repeating pattern. I can say that. On the other surface of the polyimide, a back electrode 60 is formed in a specific pattern. In the through hole 61 from the polyimide film 59 to the transparent conductive film and the through hole 62 from the polyimide film 59 to the metal film 47, Metal is deposited so that the transparent conductive film 45 or the metal film 47 and the back electrode 60 are electrically connected to each other. The solar cell 63 configured in this manner is obtained by pressure-bonding and pasting the substrate with a conductor layer pattern according to the present invention to the layer structure below the transparent conductive film. At this time, the resin layer 22 of the base material with the conductor layer pattern is caused to flow so as to seal the layer structure.
A solar cell module can be obtained by supporting the solar cell having the above structure between ethylene tetrafluoroethylene (ETFE) and ETFE or a galvalume steel plate with an ethylene-vinyl acetate copolymer.

FIG. 34 is a cross-sectional view showing another example of a solar cell.
The conductor layer 19 is embedded in the resin layer 22 laminated on the support substrate 21 (a transparent heat-resistant substrate such as a glass plate or an ethylene-vinyl acetate copolymer sheet). The above structure is an example of the base material with a conductor layer pattern according to the present invention. A part of the conductor layer 19 is used as the extraction electrode 55.
A certain layer structure is formed on the surface where the conductor layer 19 is exposed so as to repeat a certain pattern. In this constant layer structure, a transparent conductive film 45, a buffer 64, a semiconductor CIGS light absorption layer 65 made of Cu, In, Ga, and Se are stacked, and a patterned molybdenum back electrode 66 is stacked. . Part of the conductor layer 19 becomes the extraction electrode 55 and the extraction electrode 67. The buffer 64 is an n-type layer such as Cds, ZnO, or InS, and is formed by sputtering, chemical bath deposition, or the like. The CIGS light absorption layer 65 is obtained by forming a precursor by laminating Cu, In, and Ga by a sputtering method, vapor deposition, or the like, annealing the precursor in an H ₂ Se atmosphere, and selenizing. It can be said that a glass plate 68 is laminated on the other surface of the molybdenum back electrode 66. The solar cell 69 configured as described above is obtained by pressure-bonding and pasting the substrate with a conductor layer pattern according to the present invention to the layer structure below the transparent conductive film. At this time, the resin layer 22 of the base material with a conductor layer pattern is caused to flow so as to seal the layer structure. The layer structure is formed by laminating the molybdenum back electrode 66 to the transparent conductive film 45 on the glass plate in the opposite manner as described above. The transparent conductive film 47 is electrically connected to the adjacent molybdenum back electrode 66 through the side surfaces of the CdS buffer 64 and the CIGS light absorption layer 65.
When the support base material 21 is not a transparent heat resistant base material such as a glass plate, the solar cell having the above-described configuration has an outermost layer and is sealed on the support base material 21 side with a transparent ethylene-vinyl acetate copolymer. A solar cell module can be obtained by laminating the glass plates.

  In this invention, the electrical property of a functional element can be improved by connecting the conductive pattern of the base material with a conductive pattern to the functional element which has an electrode (metal electrode or transparent electrode) on the surface. For example, in the case of a solar cell having a transparent electrode on the surface, by connecting a conductive pattern to the transparent electrode, the power generated by the solar cell can be collected with low power loss due to the low resistivity of the conductive pattern. can do. Therefore, it is possible to omit an Ag electrode that is normally used as a collector electrode for a crystalline Si solar cell. Moreover, in a thin film Si solar cell or a CIGS thin film solar cell, the efficiency can be improved in order to suppress the power loss that becomes remarkable in the module size. Furthermore, since the conductive pattern also has a wiring function, no new wiring material is required. For example, a tab wire that is normally used as a wiring for a crystalline Si solar cell can be omitted, and the formation of an extraction electrode can be omitted in a thin film Si solar cell or a CIGS thin film solar cell. As described above, since the conductive pattern is used for the collector electrode and wiring of the solar cell, the material cost is reduced. Furthermore, in the present invention, since the conductive pattern is formed only on a functional element such as a solar cell, the cost for forming the collector electrode and wiring of the solar cell can be significantly reduced.

  In order to keep the conductive pattern connected to the electrode on the functional element surface, it is necessary to maintain the mechanical contact between the conductive pattern and the electrode on the functional element surface. Force must continue to be applied in the direction in which it is pressed against. For example, the output of a solar cell must be stable for a long time, and as a reliability test, the decrease in output power is within 5% even after 1000 hours under high temperature and high humidity of 85 ° C. and 85% RH. It is desirable. In this invention, when the electroconductive pattern of the base material with an electroconductive pattern and the surface electrode of a photovoltaic cell are connected, the function as a collector electrode and wiring is shown, and also stability for several hundred hours is also shown.

  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. 35 shows a concept of an apparatus for continuously depositing metal by electric field plating while continuously rotating the drum electrode when a drum electrode is used as the conductive substrate, and continuously stripping the deposited metal. 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, metal is electrolytically deposited on the surface of the rotator 103, and the conductivity of the surface of the rotator 103 is outside the electrolytic solution 101. The film 107 in which the pressure-sensitive adhesive layer of the film 107 on which the pressure-sensitive adhesive layer is formed is pressure-bonded to the metal 106 deposited in the concave portions of the film 107 by the pressure-bonding roll 108, and the metal 106 is continuously peeled off from the rotating body 103 to form the pressure-sensitive adhesive layer. The metal 106 is transferred to a base material 109 with a conductor layer pattern. This can be wound up on a roll (not shown). Thus, the base material 109 with a conductor layer pattern can be manufactured. In addition, a concave portion and an insulating layer having a geometrical shape drawn thereby are formed on the surface of the rotating body 103. Further, the surface of the rotating body 103 may be etched and cleaned (not shown) after the metal 106 deposited in the concave portion is peeled off from the rotating rotating body 103 and before being immersed in the electrolytic solution 101. . 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, the hoop-like conductive substrate for plating can be used as the conductive substrate for plating used in the present invention. This will be described in detail.
The hoop-shaped conductive substrate for plating can be produced by forming an insulating layer and a recess on the surface of the strip-shaped conductive substrate and then joining the end portions together. As described above, the material forming the surface of the conductive substrate is made of a material with 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 substrate is used, the blackening treatment, rust prevention treatment, transfer and other processes can be performed in one continuous process, so the productivity of the substrate 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. 36 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. After this, 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, 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 laminated with the adhesive layer is moved between the conductive substrate 110 and the pressure roll 137 on the transport roll 128 so that the metal deposited on the conductive recesses 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 conductor layer pattern. The obtained base material 138 with a conductor layer pattern can be wound into a roll. If necessary, the pressure-bonding roll 137 can be heated, and 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.

  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, the cover film used when forming the protective layer on the conductor layer pattern may also serve as a functional layer such as an antireflection layer or a near infrared shielding layer.

  Moreover, the base material with a conductor layer pattern in the present invention is not limited to a continuous plating method using a rotating roll or a hoop as described above, and can be manufactured as 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 cm or less is preferable.

  Moreover, the base material with a conductor layer pattern obtained as described above can be used for use while leaving the adhesiveness of the resin layer, and further, the adhesive layer is laminated on the surface where the conductor layer pattern exists. Can be used for use.

(Pattern specification 1)
A negative film for pattern formation was produced with the following specifications. The line width of the light transmission part is 12 μm, the line pitch is 300 μm, 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), A pattern was formed in a grid shape with a size of 120 mm square.

(Formation of convex pattern)
A resist film (Photech RY3315, manufactured by Hitachi Chemical Co., Ltd.) was bonded to both sides of a 150 mm square stainless steel plate (SUS316L, # 400 polished finish, thickness 500 μm, manufactured by Nisshin Steel Co., Ltd.) (FIG. 11 (a ) But not the same). The bonding conditions were a roll temperature of 105 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Subsequently, the negative film of the pattern specification 1 was left still on the single side | surface of a stainless steel plate. Using an ultraviolet irradiation device, ultraviolet rays were irradiated at 250 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 protrusion resist film (protrusion; height 15 μm) having a line width of 15 to 17 μm, a line pitch of 300 μm, and a bias angle of 45 degrees was obtained on a SUS plate. Note that the entire surface opposite to the surface on which the pattern is formed is exposed and is not developed, and a resist film is formed on the entire surface (corresponding to FIG. 11B but not the same).

(Formation of insulating layer)
A DLC film is formed by a PBII / D apparatus (Type III, manufactured by Kurita Manufacturing Co., Ltd.). A stainless steel substrate with a resist film attached thereto was placed in the chamber, the inside of the chamber was evacuated, and the substrate surface was cleaned with argon gas. Next, hexamethyldisiloxane was introduced into the chamber, and an intermediate layer was formed to a thickness of 0.1 μm. Next, toluene, methane, and acetylene gas were introduced, and a DLC layer was formed on the intermediate layer so as to have a film thickness of 2 to 3 μm (corresponding to FIG. 11C, but not the same).

(Concavity formation; removal of convex pattern with insulating layer attached)
The stainless steel substrate with the insulating layer attached was immersed in an aqueous sodium hydroxide solution (10%, 50 ° C.) and left for 8 hours with occasional rocking. The resist film forming the convex pattern and the DLC film adhering thereto have been peeled off. Since there was a part that was difficult to peel off, the entire surface was peeled off by lightly rubbing with a cloth to obtain a conductive substrate for plating (corresponding to FIG. 11 (d), but not the same).
The shape of the recess was wider toward the opening direction, and the inclination angle of the side surface of the recess was the same as the angle of the boundary surface. The depth of the recess was 2 to 3 μm. Moreover, the width | variety in the bottom part of a recessed part was 15-17 micrometers, and the width | variety (maximum width) in an opening part was 19-23 micrometers. The pitch of the recesses was 300 μm.

(Copper plating)
Furthermore, the surface (back surface) where the pattern of the conductive base material for plating obtained above is not formed
An adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the substrate.
Electrolytic bath for electrolytic copper plating (copper sulfate (pentahydrate) 250 g / L, sulfuric acid 70 g / L, sulfuric acid 70 g / L, cube) using the electroconductive substrate for plating with the adhesive film attached as a cathode and phosphorus-containing copper as an anode light AR (Ebara-Udylite Co., additive) solution of 4 ml / L, immersed in 30 ° C.), a current density over voltage as 10A / dm ² in both electrodes, the recess of the plating conductive substrate Plating was performed until the deposited metal thickness was approximately 6 μm. The plating was formed so as to overflow in and out of the recess of the conductive substrate for plating.

(Preparation of transparent substrate)
Byron UR-1400 (manufactured by Toyobo Co., Ltd.), a thermoplastic resin, on the surface of a polyethylene terephthalate (PET) film (A-4100, manufactured by Toyobo Co., Ltd.), which is a support substrate having a thickness of 100 μm and a 120 mm square. The polyester polyurethane resin is diluted with a mixed solvent of toluene and methyl ethyl ketone.The resin has a glass transition point of 80 ° C.), and is applied so that the film thickness after drying at 100 ° C. is 25 μm. Then, a pressure-sensitive adhesive layer was formed on the support substrate to produce a transparent substrate. The drying condition was 100 ° C. for 10 minutes.

(Transcription and embedding)
After the said transparent base material was pre-heated at 100 degreeC for 5 minute (s), the surface of the adhesive layer and the surface which gave the copper plating of the said electroconductive base material for plating were bonded together using the roll laminator. Lamination conditions were a roll temperature of 150 ° C., a pressure of 0.5 MPa, and a line speed of 0.1 m / min. Subsequently, when the transparent base material bonded to the electroconductive substrate for plating was peeled off, the copper deposited on the electroconductive substrate for plating was transferred to.
A part of the transparent substrate to which copper was transferred was cut out, and the cross section was observed on a scanning electron micrograph (magnification 2000 times). 5 points are selected arbitrarily, and the cross-sectional shape of the conductor layer pattern is as shown in FIG. 5B, the upper upper base width L1 is 15 to 17 μm, the lower base width L2 is 17 to 19 μm, and the angle α Is 45 °, the maximum width L is 21 to 24 μm, the difference between L and L2 is 2 to 3 μm, the upper layer thickness T1 is 2 to 3 μm, the lower layer thickness T2 is 3 to 4 μm, and the overall thickness is 5 to 6 μm It was confirmed that a base material with a conductor layer pattern composed of a grid-like metal pattern having a line pitch of 300 μm was obtained. At the same time, as shown in FIG. 8C, it was confirmed that the entire conductor layer pattern was embedded in the resin layer with its upper surface exposed from the resin layer.
The surface resistance of the obtained base material with a conductor layer pattern was 0.075Ω / □. The surface resistance was measured at a sample size of 50 mm square using a four-probe method surface resistance measuring device Lorester GP MCP-T600 (Mitsubishi Chemical). Further, when the gasket was left on the pattern surface and moved while applying a load of 500 g, there was no abnormality in the pattern surface. Furthermore, as a result of the cross cut test, there was no part where the pattern peeled off.
Even after the above two tests were conducted after 1000 hours at 65 ° C. and 95% RH in the heating and humidification test, there were no abnormalities or peeling portions on the pattern surface.

(Formation of protective film)
The surface of the substrate with the conductor layer pattern obtained above, on which the conductor layer pattern is present, is coated with UV curable resin HITAROID 7983AA3 (manufactured by Hitachi Chemical Co., Ltd.), and a polycarbonate film (macro hole DE, Bayer Co., Ltd.). And the conductor layer pattern is embedded in the UV curable resin and then irradiated with 1 J / cm ² of ultraviolet rays using an ultraviolet lamp to cure the UV curable resin to form a protective film. The base material with a conductor layer pattern was obtained. The obtained base material had a transmittance of 78% and a turbidity of 2.5.

In the same manner as in Example 1, copper plating was applied to the conductive substrate for plating of Example 1 in the same manner as in Example 1.
<Preparation of transparent substrate>
(Composition composition 1)
2-ethylhexyl methacrylate 70 parts by weight Butyl acrylate 15 parts by weight 2-hydroxyethyl methacrylate 10 parts by weight Acrylic acid 5 parts by weight Azobisisobutyronitrile 0.1 part by weight Toluene 60 parts by weight Ethyl acetate 60 parts by weight

Into a 500 cm3 three-necked flask equipped with a thermometer, a cooling pipe, and a nitrogen introduction pipe, the above-mentioned composition 1 is charged, heated to 60 ° C. with gentle stirring, to initiate polymerization, and then bubbled with nitrogen The mixture was stirred at 60 ° C. for 8 hours under reflux to obtain an acrylic resin having a hydroxyl group in the side chain. Thereafter, 5 parts by weight of Karenz MOI (2-isocyanatoethyl methacrylate; manufactured by Showa Denko KK) is added and reacted at 50 ° C. with gentle stirring, and a reactive polymer having a photopolymerizable functional group in the side chain. Solution 1 was obtained.
The obtained reactive polymer 1 had a methacryloyl group in the side chain, and the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography was 800,000. Reactive polymer solution 1 was added to 100 parts by weight (solid content) of 2-methyl-1 [4-methylthio] phenyl] -2-morpholinopropan-1-one (trade names: Irgacure 907, Ciba Geigy ( 1 part by weight, 3 parts by weight of an isocyanate-based crosslinking agent (trade name Coronate L-38ET, manufactured by Nippon Polyurethane Co., Ltd.) and 50 parts by weight of toluene were added to obtain Resin Composition 1.
The obtained resin composition was applied to the surface of a polyethylene terephthalate (PET) film (A-4100, manufactured by Toyobo Co., Ltd.) so that the film thickness after drying at 100 ° C. was 20 μm, and on the support substrate A pressure-sensitive adhesive layer having UV curability was formed on the transparent substrate. The drying condition was 100 ° C. for 10 minutes.
(Transcription and embedding)
Using the same plating plate as in Example 1, copper plating was applied on the conductive substrate for plating in the same manner as in Example 1.
Next, the surface of the pressure-sensitive adhesive layer having UV curability of the transparent substrate and the surface of the conductive substrate for plating subjected to copper plating were bonded using a roll laminator. Lamination conditions were a roll temperature of 30 ° C., a pressure of 0.3 MPa, and a line speed of 1.0 m / min. Subsequently, when the transparent base material bonded to the electroconductive substrate for plating was peeled off, copper deposited on the electroconductive substrate for plating was transferred to the transparent base material.
A part of the transparent substrate to which copper is transferred is cut out and the cross section is taken and observed in a scanning electron micrograph (magnification 2000 times), and the conductor layer pattern has a cross-sectional shape as shown in FIG. It is confirmed that five locations are arbitrarily selected. The thickness T1 of the upper layer is 2 to 3 μm, the thickness T2 of the lower layer is 3 to 4 μm, and the lower portion is buried in the resin layer by 1 to 2 μm on the lower side. It was confirmed.
Furthermore, the surface opposite to the easy adhesion layer of the cover film (A-4100, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm is stuck on the transparent base copper onto which the copper obtained above is transferred with a roll laminate. Combined. Lamination conditions were a roll temperature of 80 ° C., a pressure of 0.3 MPa, and a line speed of 0.5 m / min. Thereafter, from the surface opposite to the surface on which the conductor layer pattern is formed, the cover film is peeled off by irradiating with ultraviolet rays so that the irradiation amount is 1 J / cm ² to obtain a substrate with a conductor layer pattern. It was.
A part of the substrate with the conductor layer pattern was cut out, and the cross section was taken and observed in a scanning electron micrograph (magnification 2000 times). As shown in FIG. Confirm that the upper surface is exposed from the resin layer and is buried in the resin layer, and arbitrarily select five locations. The upper layer width L1 of the upper layer of the conductor layer pattern is 15 to 17 μm. The width L2 is 17 to 19 μm, the angle is 45 °, the maximum width L is 21 to 24 μm, the difference between L and L2 is 2 to 3 μm, the upper layer thickness T1 is 2 to 3 μm, and the lower layer thickness T2 is 3 to 3 μm. It was confirmed that a substrate with a conductor layer pattern composed of a grid-like metal pattern having a thickness of 4 μm, an overall thickness of 5 to 6 μm, and a line pitch of 300 μm was obtained. The aperture ratio of the conductor layer pattern was 84.0%.
The surface resistance of the obtained base material with a conductor layer pattern was 0.075Ω / □.
Further, when the gasket was left on the pattern surface and moved while applying a load of 500 g, there was no abnormality in the pattern surface. Furthermore, as a result of the cross cut test, there was no part where the pattern peeled off.
Even after the above two tests were conducted after 1000 hours at 65 ° C. and 95% RH in the heating and humidification test, there were no abnormalities or peeling portions on the pattern surface. The obtained base material had a transmittance of 78% and a turbidity of 2.8.

(Transcription and embedding)
In the same manner as in Example 1, copper plating was applied to the conductive substrate for plating of Example 1 in the same manner as in Example 1. The surface subjected to copper plating of the conductive substrate, liquid Mu溶 dosage form UV-curable resin (trade name: Adekaoptomer KRX-400, Asahi Denka Co., Ltd.) was 10ml dropwise a width of 100mm . Next, a polyethylene terephthalate (PET) film (A-4100, manufactured by Toyobo Co., Ltd.), which is a supporting substrate having a thickness of 100 μm, was brought into contact with the resin and roll-laminated. Lamination conditions were a roll temperature of 30 ° C., a pressure of 0.1 MPa, and a line speed of 2.0 m / min. Thus, the resin spread uniformly, and a 15 μm liquid UV curable resin layer was formed between the conductive substrate and the substrate film. Thereafter, the pressure-sensitive adhesive layer was cured by irradiating with ultraviolet rays so that the irradiation amount was 1 J / cm ² from the supporting substrate side, and then the transparent substrate was peeled off to obtain a substrate with a conductor layer pattern.
A portion of the substrate with the conductor layer pattern is cut out, and the cross section is taken and observed in a scanning electron micrograph (magnification 2000 times). As shown in FIG. 5B, the cross section of the conductor layer pattern is trapezoidal. Confirm that the conductor layer pattern is embedded in the resin layer with the upper part exposed from the resin layer, and confirm that the thickness of the resin layer is 25 μm. The width L1 of the upper base of the upper part of the conductor layer pattern was 15-17 μm, the width L2 of the lower base was 17-19 μm, and the angle was 45 °. The maximum width L was 21 to 24 μm, and the difference between L and L2 was 2 to 3 μm. It was confirmed that the upper layer thickness T1 was 2-3 μm, the lower layer thickness T2 was 3-4 μm, the overall thickness was 5-6 μm, and the line pitch was 300 μm. The surface resistance of the obtained base material with a conductor layer pattern was 0.075Ω / □. Further, when the gasket was left on the pattern surface and moved while applying a load of 500 g, there was no abnormality in the pattern surface. Furthermore, as a result of the cross cut test, there was no part where the pattern peeled off. Even after the above two tests were conducted after 1000 hours at 65 ° C. and 95% RH in the heating and humidification test, there were no abnormalities or peeling portions on the pattern surface.

(Formation of protective film)
The surface of the substrate with the conductor layer pattern obtained above, on which the conductor layer pattern is present, is coated with UV curable resin HITAROID 7983AA3 (manufactured by Hitachi Chemical Co., Ltd.), and a polycarbonate film (macro hole DE, Bayer Co., Ltd.). And the conductor layer pattern is embedded in the UV curable resin and then irradiated with 1 J / cm ² of ultraviolet rays using an ultraviolet lamp to cure the UV curable resin to form a protective film. The base material with a conductor layer pattern was obtained. The obtained base material had a transmittance of 78% and a turbidity of 2.5.

  In the same manner as in Example 1, a conductive substrate for plating was produced.

(Copper plating)
Furthermore, the surface (back surface) where the pattern of the conductive base material for plating obtained above is not formed
An adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the substrate.
Electrolytic bath for electrolytic copper plating (copper sulfate (pentahydrate) 250 g / L, sulfuric acid 70 g / L, luster 70 g / L) with the conductive substrate for plating with the adhesive film attached as the cathode and phosphorous copper as the anode Soaked in an agent (3-mercapto-1-propanesulfonate) 3 ml / L, surfactant (polyethylene glycol) 10 mL / L in an aqueous solution at 30 ° C. No. ² was plated until the thickness of the metal deposited in the concave portion of the conductive substrate for plating reached approximately 6 μm. The plating was formed so as to overflow in and out of the recess of the conductive substrate for plating.

  A transparent substrate was produced in the same manner as in Example 1.

(Transcription and embedding)
The transparent substrate obtained above was preheated at 100 ° C. for 5 minutes, and then the surface of the pressure-sensitive adhesive layer and the surface subjected to copper plating of the conductive substrate for plating were bonded together using a roll laminator. Lamination conditions were a roll temperature of 150 ° C., a pressure of 0.5 MPa, and a line speed of 0.1 m / min. Subsequently, when the transparent base material bonded to the conductive substrate for plating was peeled off, the copper deposited on the conductive substrate for plating was transferred to the pressure-sensitive adhesive layer of the transparent substrate.
A part of the transparent substrate to which copper was transferred was cut out, and the cross section was observed on a scanning electron micrograph (magnification 2000 times). 5 points are arbitrarily selected, and the cross-sectional shape of the conductor layer pattern is as shown in FIG. 5B, the upper upper base width L1 is 15 to 17 μm, the lower base width L2 is 17 to 19 μm, and the angle α Is 45 °, the maximum width L is 19-22 μm, the difference between L and L2 is 2-3 μm, the upper layer thickness T1 is 2-3 μm, the lower layer thickness T2 is 3-4 μm, and the overall thickness is 6-7 μm. It was confirmed that a base material with a conductor layer pattern composed of a grid-like metal pattern having a line pitch of 300 μm was obtained. Further, the width L3 of the shoulder portion was 1 to 2 μm, the conductor thickness T1 of the shoulder base portion was 2 to 3 μm, and T1 / L3 was 1.5 to 2.0. At the same time as shown in FIG. 8 (c), all of the conductor layer pattern was confirmed that it is embedded in the resin layer with its upper surface is exposed from the resin layer.
The surface resistance of the obtained base material with a conductor layer pattern was 0.075Ω / □. The surface resistance was measured at a sample size of 50 mm square using a four-probe method surface resistance measuring device Lorester GP MCP-T600 (Mitsubishi Chemical). Further, when the gasket was left on the pattern surface and moved while applying a load of 500 g, there was no abnormality in the pattern surface. Furthermore, as a result of the cross cut test, there was no part where the pattern peeled off. Further, the aperture ratio of the mesh pattern was 87%. Even after the above two tests were conducted after 1000 hours at 65 ° C. and 95% RH in the heating and humidification test, there were no abnormalities or peeling portions on the pattern surface.

(Formation of protective film)
The surface of the substrate with the conductor layer pattern obtained above, on which the conductor layer pattern is present, is coated with UV curable resin HITAROID 7983AA3 (manufactured by Hitachi Chemical Co., Ltd.), and a polycarbonate film (macro hole DE, Bayer Co., Ltd.). Manufactured, 75 μm), and the conductor layer pattern was embedded in a UV curable resin, and then 1 J / cm ² using an ultraviolet lamp.
The substrate was provided with a conductor layer pattern having a protective film by curing the UV curable resin by irradiation with UV rays. The obtained base material had a transmittance of 81% and a turbidity of 2.0.

  A transparent substrate was produced in the same manner as in Example 2.

(Plating, transfer and embedding)
Using the same conductive substrate for plating as in Example 4, copper plating was applied on the conductive substrate for plating in the same manner as in Example 4.
Next, the surface of the pressure-sensitive adhesive layer having UV curability of the transparent substrate and the surface of the conductive substrate for plating subjected to copper plating were bonded using a roll laminator. Lamination conditions were a roll temperature of 30 ° C., a pressure of 0.3 MPa, and a line speed of 1.0 m / min. Subsequently, when the transparent base material bonded to the electroconductive substrate for plating was peeled off, copper deposited on the electroconductive substrate for plating was transferred to the transparent base material.
Cut a portion of the transparent substrate copper is transferred, its cross-section, taken scanning electron micrograph (magnification 2,000 times) was observed, the conductive layer pattern is in such cross-sectional shape shown in FIG. 5 (b) sure, also optionally select five positions, the thickness T1 of the upper layer is 2 to 3 [mu] m, the lower portion of the thickness T2 is 3 to 4 [mu] m, buried only the resin layer 1~2μm lower its lower I confirmed.
Furthermore, the surface opposite to the easy adhesion layer of the cover film (A-4100, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm is stuck on the transparent base copper onto which the copper obtained above is transferred with a roll laminate. Combined. Lamination conditions were a roll temperature of 80 ° C., a pressure of 0.3 MPa, and a line speed of 0.5 m / min. Thereafter, from the surface opposite to the surface on which the conductor layer pattern is formed, the cover film is peeled off by irradiating with ultraviolet rays so that the irradiation amount is 1 J / cm ² to obtain a substrate with a conductor layer pattern. It was.
Cut a portion of the conductive layer patterned substrate, the cross-section, taken scanning electron micrograph (magnification 2,000 times) was observed, as shown in FIG. 8 (c), the whole of the conductive layer pattern, the Confirm that the upper surface is exposed from the resin layer and is buried in the resin layer, and arbitrarily select five locations. The upper layer width L1 of the upper layer of the conductor layer pattern is 15 to 17 μm. The width L2 is 17 to 19 μm, the angle is 45 °, the maximum width L is 19 to 22 μm, the difference between L and L2 is 2 to 3 μm, the upper layer thickness T1 is 2 to 3 μm, and the lower layer thickness T2 is 3 to 3 μm. It was confirmed that a substrate with a conductor layer pattern consisting of a grid-like metal pattern having a thickness of 4 μm, an overall thickness of 6 to 7 μm, and a line pitch of 300 μm was obtained. Further, the width L3 of the shoulder portion was 1 to 2 μm, the conductor thickness T1 of the shoulder base portion was 2 to 3 μm, and T1 / L3 was 1.5 to 2.0. The aperture ratio of the conductor layer pattern was 87.0%.
The surface resistance of the obtained base material with a conductor layer pattern was 0.075Ω / □. Further, as a result of the cross-cut test, there was no place where the pattern peeled off.
Even after the above two tests were conducted after 1000 hours at 65 ° C. and 95% RH in the heating and humidification test, there were no abnormalities or peeling portions on the pattern surface. The obtained base material had a transmittance of 81% and a turbidity of 1.9.

  Copper plating was performed on the conductive substrate for plating of Example 4 in the same manner as in Example 4.

<Preparation of substrate (I)>
An adhesive film [base material (I)] was produced.
That is, first, 70% by weight of 2-ethylhexyl acrylate and 20% by weight of ethyl acrylate are used as main monomers, and 6% by weight of hydroxyethyl methacrylate and 4 parts by weight of acrylic acid are polymerized as a functional group monomer by a solution polymerization method. A polymer was synthesized. The synthesized acrylic copolymer had a weight average molecular weight of 300,000 and a glass transition point of -35 ° C.

Obtained by blending 10 parts by weight of a polyfunctional isocyanate crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) with respect to 100 parts by weight of this acrylic copolymer and diluting with toluene to a concentration of 30% by weight. Apply the pressure-sensitive adhesive solution to a PET film with an easy-adhesion layer having a thickness of 50 μm (manufactured by Toyobo Co., Ltd., Cosmo Shine A4100) so that the thickness of the pressure-sensitive adhesive layer when dried is 10 μm. And dried at 100 ° C. for 30 minutes to obtain a substrate (I). Substrate (I) is a pressure-sensitive adhesive layer-carrying substrate, which corresponds to the supporting substrate 21 in FIG. 14.

<Preparation of substrate with holding resin layer and substrate for transfer>
First, 85% by weight of butyl acrylate and 10% by weight of ethyl acrylate are used as main monomers, 5 parts by weight of 2-hydroxyethyl acrylate is used as a functional group monomer, hydrogen peroxide is used as an initiator, and nonion is used as an emulsifier. After emulsion polymerization at 75 ° C. for 3 hours using a surfactant, an acrylic copolymer having a weight average molecular weight of 800,000 and a glass transition point of −47 ° C. was obtained. Next, this was dissolved in toluene so as to be 20% by weight, and 10 parts by weight of a polyfunctional isocyanate crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) was added to 100 parts by weight of the solid content of this solution. A pressure-sensitive adhesive solution was prepared. This was applied to a polyester film separator (manufactured by Toyobo Co., Ltd., trade name E-7002, thickness 25 μm) coated with a silicone release agent so that the film thickness after drying was 25 μm. It was dried for a minute to obtain a separator with a retaining resin layer.
Next, the base material (I) and the separator with the retaining resin layer are bonded so that the adhesive layer of the base material (I) and the retaining resin layer of the separator with the retaining resin layer are bonded, and only the polyester film separator is peeled off. Thus, a substrate with a holding resin layer and a substrate for transfer (corresponding to the substrate 20 in FIG. 13) were produced. The holding resin layer corresponds to the base material 22 of FIG.

<Transfer of metal wiring layer from conductive substrate for plating>
The substrate with a holding resin layer was pressure-bonded onto the conductive substrate for plating on which the metal wiring layer was formed as described above (corresponding to FIG. 14G). Next, when the substrate with the holding resin layer was peeled off, the metal wiring layer was transferred to the holding resin layer. At this point, the substrate with the conductor layer pattern (the substrate with the conductor layer pattern of FIG. 23). The metal wiring layer corresponds to the conductor layer 19 in FIG.

<Lamination of substrate (II)>
A polyethylene terephthalate (PET) film (corresponding to 24 in FIG. 17) as a base material (II) is bonded to the metal wiring layer and the holding resin layer of the holding resin layer-formed base material on which the metal wiring layer is formed. A protected substrate with a conductor layer pattern (corresponding to 25 in FIG. 17) was obtained.
<Peeling of base material (I) and bonding to glass plate [base material (III)]>
The base material (I) is peeled from the holding resin layer (corresponding to FIG. 21 (a)), and a glass plate [base on the holding resin layer surface of the obtained laminate ((corresponding to FIG. 21 (b))). Material (III)] (corresponding to FIG. 21C). Bonding was performed using a roll laminator at a roll temperature of 150 ° C., a pressure of 0.5 MPa, and a line speed of 0.1 m / min. The glass plate corresponds to 31 in FIG.

<Peeling of substrate (II)>
The substrate (II) was peeled from the holding resin layer on the glass. A glass with a metal wiring layer in which the metal wiring layer was held by the holding resin layer was obtained (corresponding to FIG. 21D).
<Embedded state of metal wiring layer>
The cross section of the glass with a metal wiring layer was observed with a scanning electron micrograph (magnification 2000 times).
5 points are selected arbitrarily, and the cross-sectional shape of the metal wiring layer is as shown in FIG. 5B. The upper upper base width L1 is 15 to 17 μm, the lower base width L2 is 17 to 19 μm, and the angle α Is 45 °, the maximum width L is 19-22 μm, the difference between L and L2 is 2-3 μm, the upper layer thickness T1 is 2-3 μm, the lower layer thickness T2 is 3-4 μm, and the overall thickness is 6-7 μm. It was confirmed that a substrate with a metal wiring layer composed of a grid-like metal pattern with a line pitch of 300 μm was obtained. At the same time as shown in FIG. 8 (c), the metal wiring layer is confirmed that the width L1 of the upper portion of the upper base is exposed only 15～17Myuemu, all of the metal wiring layer is embedded in the retaining resin layer did.

  The aperture ratio of the metal wiring layer was 84.0%. Also, no plating breakage occurred during peeling transfer.

  The surface resistance of the obtained base material with a metal wiring layer was 0.075Ω / □. The surface resistance was measured at a sample size of 50 mm square using a four-probe method surface resistance measuring device Lorester GP MCP-T600 (Mitsubishi Chemical).

  Copper plating was performed on the conductive substrate for plating of Example 4 in the same manner as in Example 4.

<Preparation of transparent substrate (transfer substrate)>
The separator film was peeled from one side of a double-sided pressure-sensitive adhesive film (Hitalex DA3025, manufactured by Hitachi Chemical Co., Ltd.) having a pressure-sensitive adhesive layer thickness of 25 μm and bonded to glass. Lamination conditions were a roll temperature of 100 ° C., a pressure of 0.3 MPa, and a line speed of 1.0 m / min. Thereafter, the separator film was peeled off from the other surface of the pressure-sensitive adhesive layer formed on the glass to expose the pressure-sensitive adhesive layer.

<Transfer and embed>
The surface of the pressure-sensitive adhesive layer of the transparent substrate and the surface of the conductive substrate for plating subjected to copper plating were bonded using a roll laminator. Lamination conditions were a roll temperature of 30 ° C., a pressure of 0.3 MPa, and a line speed of 0.1 m / min. Subsequently, when the electroconductive substrate for plating bonded to the transparent substrate was peeled off, copper (conductor layer pattern) deposited on the electroconductive substrate for plating was transferred.

  A part of the transparent substrate to which copper was transferred was cut out, and the cross section was observed on a scanning electron micrograph (magnification 2000 times). 5 points are selected arbitrarily, and the cross-sectional shape of the conductor layer pattern is as shown in FIG. 5B, the upper upper base width L1 is 15 to 17 μm, the lower base width L2 is 17 to 19 μm, and the angle α Is 45 °, the maximum width L is 19-22 μm, the difference between L and L2 is 2-3 μm, the upper layer thickness T1 is 2-3 μm, the lower layer thickness T2 is 3-4 μm, and the overall thickness is 6-7 μm. It was confirmed that a base material with a conductor layer pattern composed of a grid-like metal pattern having a line pitch of 300 μm was obtained. At the same time, as shown in FIG. 8C, it was confirmed that the entire conductor layer pattern was embedded in the resin layer with its upper surface exposed from the resin layer.

  The surface resistance of the obtained base material with a conductor layer pattern was 0.075Ω / □. The surface resistance was measured at a sample size of 50 mm square using a four-probe method surface resistance measuring device Lorester GP MCP-T600 (Mitsubishi Chemical).

  Even after the above two tests were conducted after 1000 hours at 65 ° C. and 95% RH in the heating and humidification test, there were no abnormalities or peeling portions on the pattern surface.

  Copper plating was performed on the electroconductive substrate for plating in the same manner as in Example 4 except that the electroconductive substrate for plating of Example 4 was plated until the plating thickness became approximately 12 μm.

<Preparation of transparent substrate>
The separator film is peeled off from one side of a double-sided adhesive film (Hitalex DA3025, manufactured by Hitachi Chemical Co., Ltd.) having an adhesive layer thickness of 25 μm, and bonded to a PET film (125 μm thickness, A-4100, manufactured by Toyobo Co., Ltd.). It was. Lamination conditions were a roll temperature of 100 ° C., a pressure of 0.3 MPa, and a line speed of 1.0 m / min. Thereafter, the separator film was peeled off from the other surface of the pressure-sensitive adhesive layer formed on the PET film to expose the pressure-sensitive adhesive layer.

<Transfer and embed>
The surface of the pressure-sensitive adhesive layer of the transparent substrate and the surface of the conductive substrate for plating subjected to copper plating were bonded using a roll laminator. Lamination conditions were a roll temperature of 30 ° C., a pressure of 0.3 MPa, and a line speed of 0.1 m / min. Subsequently, when the transparent base material bonded to the conductive substrate for plating was peeled off, the copper deposited on the conductive substrate for plating was transferred to the pressure-sensitive adhesive layer of the transparent substrate.

  A part of the transparent substrate to which copper was transferred was cut out, and the cross section was observed on a scanning electron micrograph (magnification 2000 times). 5 points are selected arbitrarily, and the cross-sectional shape of the conductor layer pattern is as shown in FIG. 5B, the upper upper base width L1 is 15 to 17 μm, the lower base width L2 is 17 to 19 μm, and the angle α Is 45 °, the maximum width L is 24 to 28 μm, the difference between L and L2 is 8 to 10 μm, the upper layer thickness T1 is 2 to 3 μm, the lower layer thickness T2 is 8 to 10 μm, and the total thickness is 11 to 13 μm. It was confirmed that a base material with a conductor layer pattern composed of a grid-like metal pattern having a line pitch of 300 μm was obtained. At the same time, as shown in FIG. 8C, it was confirmed that the entire conductor layer pattern was embedded in the resin layer with its upper surface exposed from the resin layer.

  The surface resistance of the obtained base material with a conductor layer pattern was 0.04Ω / □. The surface resistance was measured at a sample size of 50 mm square using a four-probe method surface resistance measuring device Lorester GP MCP-T600 (Mitsubishi Chemical).

  Even after the above two tests were conducted after 1000 hours at 65 ° C. and 95% RH in the heating and humidification test, there were no abnormalities or peeling portions on the pattern surface.

<Production of solar cell module>
A thin tab wire is soldered to each of the two bus bars on the back surface of the solar cell (manufactured by Advantech, Inc., single crystal Si solar cell) using a soldering iron, and the two thin tab wires are connected to one The thick tab wire (A) was used for solder connection using a soldering iron. The substrate with the conductor layer pattern obtained in Example 8 is bonded to the surface (light-receiving surface) of the solar cell so that the surface on which the conductor layer pattern is formed and the finger electrode and bus bar on the surface of the solar cell are in contact with each other. It was. Lamination conditions were a roll temperature of 100 ° C., a pressure of 0.1 MPa, and a line speed of 0.1 m / min. One thick tab line (B) was bonded to the conductive layer pattern of the base material with the conductive layer pattern bonded to the solar battery cell with a distance of 10 mm from the end of the cell. Lamination conditions were a roll temperature of 100 ° C., a pressure of 0.1 MPa, and a line speed of 0.1 m / min. Although the conductor layer pattern of the base material with a conductor layer pattern is connected to the tab line (B), it is not connected to the tab line (A).
An ethylene vinyl acetate copolymer resin sheet (Solar Eva SC50B, manufactured by Mitsui Chemicals Fabro Co., Ltd.) having the same size as the glass was placed on a white plate heat-treated glass for solar cells having a thickness of 3 mm and a size of 200 mm □, and the above tab wires were connected. The solar battery cell was placed so that the cell surface faced the glass side. The center of the solar battery cell and the center of the glass were placed in alignment, and a thick tab line (A) and a thick tab line (B) were drawn outside the glass. An ethylene vinyl acetate copolymer resin sheet (Solar Eva SC50B, manufactured by Mitsui Chemicals Fabro Co., Ltd.) having the same size as the glass is placed on the solar cell, and a PET film (125 μm thick, A-4100 having the same size as the glass) is placed thereon. , Manufactured by Toyobo Co., Ltd.). These were heated and pressurized at 0.1 MPa and 150 ° C. for 30 minutes with a vacuum pressure laminator to produce a solar cell module.

<High temperature and high humidity test>
The solar cell module was stored at 85 ° C. and 85% RH. When measuring the characteristics, the module taken out from 85 ° C. and 85% RH was stored at 25 ° C. and 60% RH for 6 hours, then immediately (0 hour), and then stored at 85 ° C. and 85% RH for 160 hours. The series resistance was measured after 280 hours storage, 360 hours storage and 470 hours storage . The electrical resistance was measured as characteristics after high-temperature and high-humidity test. For the measurement of the series resistance, the series resistance between the tab wire (A) and the tab wire (B) of the solar cell module was measured by a two-terminal method using an ADVANTEST digital multimeter AD7461A. The results are shown in Table 1.

Comparative Example 1
<Production of solar cell module>
A thin tab wire is soldered to each of the two bus bars on the back surface of the solar cell (manufactured by Advantech, Inc., single crystal Si solar cell) using a soldering iron, and the two thin tab wires are connected to one The thick tab wire (A) was used for solder connection using a soldering iron. A thin tab wire is soldered to each of the two bus bars on the surface (light-receiving surface) of the solar battery cell using a soldering iron, and the two thin tab wires are soldered with one thick tab wire (B). Solder connection was used.
An ethylene vinyl acetate copolymer resin sheet (Solar Eva SC50B, manufactured by Mitsui Chemicals Fabro Co., Ltd.) having the same size as the glass was placed on a white plate heat-treated glass for solar cells having a thickness of 3 mm and a size of 200 mm □, and the above tab wires were connected. The solar battery cell was placed so that the cell surface faced the glass side. The center of the solar battery cell and the center of the glass were placed in alignment, and a thick tab line (A) and a thick tab line (B) were drawn outside the glass. An ethylene vinyl acetate copolymer resin sheet (Solar Eva SC50B, manufactured by Mitsui Chemicals Fabro Co., Ltd.) having the same size as the glass is placed on the solar cell, and a PET film (125 μm thick, A-4100 having the same size as the glass) is placed thereon. , Manufactured by Toyobo Co., Ltd.). These were heated and pressurized at 0.1 MPa and 150 ° C. for 30 minutes with a vacuum pressure laminator to produce a solar cell module.
<High temperature and high humidity test>
The same operation as in Example 9 was performed. The results are shown in Table 1.

各試験時間における比較例１での抵抗値に対する実施例９での抵抗の比（Ｒｔ）を求め、０ｈｒにおける比較例１での抵抗値に対する実施例９での抵抗の比（Ｒ０）からの変化率（抵抗率の変化率、Ｒｔ／Ｒ０）も示した。８５℃８５％ＲＨにて４７０ｈｒ保管しても、保管開始前の直列抵抗と比べて０．４％増加しただけであった。
実施例９において、８５℃８５％ＲＨにて４７０ｈｒ保管しても、保管開始直後（０時間）の直列抵抗と比べて０．４％増加しただけであった。 Table 1 shows the results of the high-temperature and high-humidity test of the solar cell modules of Example 9 and Comparative Example 1.

The ratio (Rt) of the resistance in Example 9 to the resistance value in Comparative Example 1 at each test time was obtained, and the change from the ratio (R0) of resistance in Example 9 to the resistance value in Comparative Example 1 at 0 hr. The rate (rate of change in resistivity, Rt / R0) is also shown. Even when stored at 85 ° C. and 85% RH for 470 hours, it increased only by 0.4% compared to the series resistance before the start of storage.
In Example 9, even when stored at 85 ° C. and 85% RH for 470 hours, it increased only by 0.4% compared to the series resistance immediately after the start of storage (0 hour).

1: Substrate with conductor layer pattern 2: Support base material 3: Resin layer 4: Base material 5: Conductive layer 6: Upper part 7: Lower part 8: Shoulder part 11: Conductive base material for plating 12: Conductive base material 13 : Insulating layer 14: Concave portion 15: Photosensitive resist layer (photosensitive resin layer)
16: Protrusion 17: DLC film 18: Intermediate layer 19: Conductive layer 20: Transfer base material 21: Support base material 22: Resin layer (adhesive layer)
23: Substrate with conductor layer pattern 24: Protective layer (protective substrate)
25: Substrate with a conductor layer pattern whose surface is protected 26: Substrate with a conductor layer pattern (at least part of the maximum width embedded)
27: Resin layer with a conductor layer pattern 28: Transparent conductive film 29: Substrate with a conductor layer pattern having a transparent conductive film on the surface 30: Substrate with a conductor layer pattern with a surface protection from which the support substrate 21 is peeled 31: New support base material 32: Base material with a new conductor layer pattern 33 having a protective base material 33: Upper surface is a base material with a conductor layer pattern in which a conductor layer exposed from the resin layer is laminated 34: Adhesive layer 35: Upper surface is Conductive layer patterned base material on which conductive layers exposed from the resin layer 22 are laminated 40: solar cell element 41: single crystal n-type silicon 42: i-type amorphous silicon 43: p-type amorphous silicon 44: n-type amorphous silicon 45: Transparent conductive film 47: Metal film 52: Transparent ethylene-vinyl acetate copolymer 53: Back sheet 55: Extraction electrode 56: P-type amol Fast silicon germanium 57: i-type amorphous silicon germanium 58: n-type amorphous silicon germanium 59: polyimide film 60: back electrode 61, 62: through hole 64: buffer 65: CIGS light absorption layer of semiconductor 66: patterned molybdenum back electrode 67: Extraction electrode 68: Glass plate 100: Electrolytic bath 101: Electrolytic solution 102: Anode 103: Rotating body 104: Piping 105: Pump 106: Metal 107: Film 108: Crimp roll 109: Substrate with conductor layer pattern 110: Hoop 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 conductor layer pattern

Claims (18)

A substrate with a conductor layer pattern in which a pattern of a conductor layer is laminated on a substrate including a resin layer, and the cross-sectional shape of the conductor layer is continuous with a trapezoidal portion (trapezoidal shape portion) and this portion. A pattern of a conductor layer comprising a portion wider than this portion (maximum width portion) , wherein at least the trapezoidal upper surface or part of the trapezoidal shape is exposed from the resin layer. A base material with a conductor layer pattern, wherein at least a lower part from a part ( maximum width part ) wider than a trapezoidal part continuous to a trapezoidal part is embedded in the resin layer of the base material.   The base material with a conductor layer pattern according to claim 1, wherein a part of the trapezoidal portion having a cross-sectional shape is exposed in the conductor layer.   The base material with a conductor layer pattern according to claim 1, wherein the conductor layer is covered with a resin layer on the entire side surface and part of the upper surface of the trapezoidal shape section having a cross-sectional shape.   The base material with a conductor layer pattern according to any one of claims 1 to 3, wherein an angle of a side surface of the trapezoidal shape portion having a cross-sectional shape of the conductor layer is in a range of 30 ° to 80 °.   The substrate with a conductor layer pattern according to any one of claims 1 to 4, wherein the conductor layer has a thickness in the range of 0.1 to 30 µm. The base material with a conductor layer pattern according to claim 1, wherein the width of the upper side of the trapezoidal shape of the conductor layer pattern is in the range of 0.1 to 40 μm.   The substrate with a conductor layer pattern according to any one of claims 1 to 6, wherein the substrate including the resin layer is formed by laminating a resin layer on a heat-resistant transparent substrate.   The substrate with a conductor layer pattern according to claim 7, wherein the heat-resistant transparent substrate is a glass plate.   The substrate with a conductor layer pattern according to any one of claims 1 to 6, wherein the substrate including the resin layer is formed by laminating a resin layer on a transparent plastic film.   A substrate with a surface-protected conductor layer pattern obtained by laminating a substrate for surface protection or a resin on the surface of the substrate with a conductor layer pattern according to any one of claims 1 to 9, wherein the conductor layer is exposed. . (A) An insulating layer is formed on the surface of the conductive base material, and a conductive pattern for plating in which a concave pattern for forming plating is formed on the insulating layer and becomes wider in the opening direction. the substrate, by plating so as to extend to the outside of the concave portion of that is continuous to the portion and the portion of the cross-sectional shape trapezoidal conductor layer fabricated to form a pattern of the conductor layer composed of a portion of the width wider than the portion And (B) a transfer step of transferring the pattern of the conductor layer deposited on the concave portion of the conductive base material to a base material having a resin layer on the surface, and in the transfer step or after the transfer step, the conductor From a trapezoidal portion continuous to at least the trapezoidal portion of the conductor layer while exposing at least a part of the upper surface of the trapezoidal shape of the layer or a part of the trapezoidal shape of the sectional shape from the resin layer. wide width of a portion (maximum width Preparation of conductive layers patterned substrate for causing embedded in the resin layer of the base material portion of the bottom portion). Resin of the resin layer is a curable resin, the conductive layer pattern, after transferring the substrate having a resin layer on the surface, the conductor layer on the resin layer of the substrate having a resin layer on the surface of at least a cross-sectional shape base The manufacturing method of the base material with a conductor layer pattern of Claim 11 which hardens at least the surface of a resin layer in the state by which a part of shape was embed | buried. (A) An insulating layer is formed on the surface of the conductive base material, and a conductive pattern for plating in which a concave pattern for forming plating is formed on the insulating layer and becomes wider in the opening direction. the substrate, by plating so as to extend to the outside of the concave portion of that is continuous to the portion and the portion of the cross-sectional shape trapezoidal, conductive layer fabrication process for forming a conductor layer pattern composed of a part of the width wider than the portion ,
(B) a step of transferring the conductor layer pattern deposited on the concave portion of the conductive substrate to the substrate (I) having an adhesive resin layer on the surface, and (C) the conductor layer of the obtained substrate with the conductor layer pattern Laminating the substrate (II) on the exposed surface,
In the above transfer step or after the transfer step, at least the cross-sectional shape of the conductor layer pattern is part of the trapezoidal top surface or part of the cross-sectional shape trapezoidal shape is exposed from the adhesive resin layer. A lower portion from a portion ( maximum width portion ) having a width wider than a trapezoidal portion continuous to at least the trapezoidal portion of the conductor layer pattern is embedded in the adhesive resin layer of the substrate (I). A method for producing a surface-protected substrate with a conductor layer pattern.   After carrying out all the steps of the method for producing a substrate with a surface-protected conductor layer pattern according to claim 13, while peeling the substrate (I) of the obtained substrate with a surface-protected conductor layer pattern or A method for producing a surface-protected substrate with a conductor layer pattern comprising a step of laminating a substrate (III) on an exposed adhesive resin layer after peeling.   The method for producing a substrate with a conductor layer pattern according to claim 14, wherein the substrate (III) is a heat-resistant transparent substrate.   The method for producing a substrate with a conductor layer pattern according to claim 15, wherein the heat-resistant transparent substrate is a glass plate.   The electromagnetic wave shielding member which consists of a base material with a conductor layer pattern in any one of Claims 1-10.   An electromagnetic wave shielding plate obtained by bonding the electromagnetic wave shielding member according to claim 17 to a transparent substrate.

Images