JP2011142127A - Solar cell structure and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solar cell structure wherein a conductor layer serving as a collecting electrode, an interconnector or an auxiliary electrode exhibits superior contact characteristics and connection reliability, and further provide a solar cell structure which includes the conductor layer and exhibits superior adhesion reliability. <P>SOLUTION: A base material containing patterned conductor layer and a resin layer where the conductor layer is buried in the resin layer such that the surface of the conductor layer is exposed at least partially to the resin layer is incorporated into the solar cell structure so that the conductor layer serves as the collecting electrode, the interconnector or the auxiliary electrode. The base material is laminated such that the surface where the conductor layer exists faces the electrical extraction surface, and the conductor layer consisting of a transparent conductive film or a metal and constituting an electrical extraction electrode connected with a photoelectric conversion layer or the collecting electrode connected therewith exists on the electrical extraction surface. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a solar cell structure and a manufacturing method thereof.

Examples of types of photoelectric conversion layers used in solar cells include single crystal silicon type, polycrystalline silicon type, amorphous silicon type, CIGS type, CIS type, other compound types, organic thin film types, dye sensitized types, and the like. Can do. In any type, when the photoelectric conversion layer is irradiated with light such as sunlight, a pair of electrons and holes is generated, and the electrons and holes are the junction surfaces of the p-type and n-type semiconductors, and the electrons (−) are Holes (+) collect into the n-type and the p-type, and as a result, an electromotive force is generated between the n-type and the p-type. Electric power can be supplied to the load by electrically connecting the electrode (extraction electrode) for extracting electrons and holes and the load.
Single crystal silicon type and polycrystalline silicon type are generally made of a relatively thin metal on the light receiving surface and a collector electrode, and an interconnector for passing current collected by the collector electrode to adjacent solar cells. A bus bar for connecting the collector electrode and the interconnector is provided, and the internal resistance of the solar battery cell is lowered by these low resistances. A typical example of the current collecting electrode is an Ag finger electrode, and a typical example of an interconnector is a tab. However, since the current collecting electrode, the interconnector, and the bus bar are opaque, the increase in the area thereof decreases the effective area of the solar cell. Therefore, in order to reduce the resistance without increasing the area of these electrodes, it is effective to reduce the specific resistance of the electrode material, decrease the width of the electrode, and increase the thickness. Examples are current collecting electrodes formed by plating (Patent Documents 1 and 2).
In addition, in thin film solar cells such as amorphous silicon type, CIGS type, CIS type, other compound types, organic thin film type, and dye sensitized type, in general, transparent conductive material is used to reduce the surface resistance of the light receiving surface. A film is formed, and the transparent conductive film functions as a collector electrode and an interconnector in the crystalline silicon type. However, since the transparent conductive film has a higher resistance than metal, there is a problem that the internal resistance of the solar battery cell is increased. However, there is a contrivance to reduce the internal resistance by forming an auxiliary electrode. As an auxiliary electrode forming method, an example in which an amorphous silicon type is formed by a spray method (Patent Document 3), an example in which a CIGS type is formed by an evaporation method (Patent Document 4), and an example in which a mesh electrode in an organic thin film type is used (Patent Documents 5 and 6) and examples (Patent Documents 7 and 8) formed by a printing method in a dye-sensitized type.

As a method for forming these electrodes, methods such as a vapor deposition method (photolitho method), a plating method, and a printing method are generally used.
However, (1) the vapor deposition method requires high-quality, but expensive, vacuum equipment, which increases the cost and takes time for the same reason. In addition, there is a problem that masking is also necessary for patterning (see Patent Document 9).
(2) In the plating method, Ni electroless plating or the like is generally performed. However, in the case of patterning, a mask is necessary and ease of peeling is a problem ( (See Patent Document 10).
(3) The printing method is low in cost and can be patterned, and a method in which a silver paste is screen-printed and sintered at a high temperature for contact is put into practical use. However, since the sintering temperature is a high temperature of several hundred degrees, a silver electrode by sintering cannot be obtained with an amorphous silicon type, an organic thin film type with low heat resistance, or with a CIGS type or CIS type with low heat resistance.
(4) Therefore, when the printing method is applied to amorphous silicon type having low heat resistance, organic thin film type, CIGS type having low heat resistance, or CIS type, a silver conductive paste containing a polymer binder is relatively used. It is used after being cured at a low temperature. For this reason, only an electrode having a specific resistance of, for example, 3 × 10 ⁻⁵ Ωcm or more can be obtained. This is more than 10 times the specific resistance of pure silver (specific resistance 1.6 × 10 ⁻⁶ Ωcm), copper (specific resistance 1.7 × 10 ⁻⁶ Ωcm) and aluminum (2.8 × 10 ⁻⁶ Ωcm). The conductivity is inferior. Therefore, if it is attempted to reduce the resistance without changing the area of the electrode, it is necessary to make the electrode 10 times thicker. In order to obtain a thickness of 10 times or more, it is necessary to devise such as making the paste more viscous and reducing the amount of the binder, but in any case, problems such as deterioration of printability will occur. However, the thickness of the electrode that can be substantially produced by screen printing is generally 10 to 20 μm. By repeating screen printing several times, thick film coating is also possible, but the process must be lengthened because the ink must be completely dried, and further alignment problems for printing at the same position may occur. become. Therefore, when the current collecting electrode is provided by the screen printing method, the resistance is generally reduced by increasing the width. Under such circumstances, the current situation is that the current collection electrode using the screen printing method has a large loss of effective area.
(5) Moreover, the electrode or fiber mesh formed off-line by printing etc. may be adhere | attached on a solar cell (refer patent document 11 and patent document 12). In this case, it is necessary to cause the adhesive to flow in the step of curing the adhesive and to ensure contact with the electrode and the solar cell.

JP 2000-277762 A JP 2000-277768 A Japanese Patent Laid-Open No. 06-204532 JP 2000-501232 A JP 2009-0776668 A JP 2006-521700 A JP 2003-297158 A JP 2008-288102 A JP-A-9-275221 JP 2000-223443 A JP 2009-099574 A JP 2006-521700 A

The present invention provides, firstly, a solar cell structure having excellent contact reliability and connection reliability of a conductor layer serving as a collector electrode, an interconnector or an auxiliary electrode, and secondly, a solar cell structure having excellent adhesion reliability and including the conductor layer. A battery structure is provided.
Furthermore, the present invention can be easily applied at a low temperature that can be applied to a method for producing such a solar cell structure with high productivity, and also to the production of a solar cell structure including an element having low heat resistance. A method for producing a solar cell structure is provided.

The present invention relates to the following.
1. A substrate including a patterned conductor layer and a resin layer, the substrate having a conductor layer embedded in the resin layer so that at least a part of the surface of the conductor layer is exposed, and collecting the conductor layer A solar cell structure assembled so as to be an electrode, an interconnector or an auxiliary electrode.
2. Item 2. The solar cell structure according to Item 1, wherein a base material including a patterned conductor layer and a resin layer is laminated so that a surface on which the conductor layer exists faces an electric extraction surface.
3. Item 3. The solar cell structure according to Item 2, wherein a conductive layer to be electrically connected to the conductor layer on the substrate is present on the electric extraction surface.
4). Item 4. The solar cell structure according to Item 3, wherein the conductive layer is an electrical extraction electrode connected to the photoelectric conversion layer or a current collecting electrode connected to the electrical extraction electrode.
5. Item 5. The solar cell structure according to Item 4, wherein the electrical extraction electrode is a transparent conductive film or a conductive metal.
6). Item 6. The solar cell structure according to any one of Items 1 to 5, wherein the conductor layer on the substrate is present on the front surface side or the back surface side of the solar cell structure.
7). Item 7. The solar cell structure according to any one of Items 1 to 6, wherein the resin layer of the substrate is in close contact with the electrical extraction surface.
8). The cross-sectional shape of the conductor layer on the substrate is that the entire cross-sectional shape or the upper part of the cross-sectional shape is trapezoidal, and at least the upper surface or a part of the trapezoidal shape is exposed from the resin layer, Item 8. The solar cell structure according to any one of Items 1 to 7, wherein a lower portion from a significant portion is embedded in the resin layer of the base material.
9. Item 9. The solar cell structure according to Item 8, wherein the trapezoidal shape portion of the cross-sectional shape of the conductor layer has a height of 0.1 to 10 µm and a side surface angle of 30 ° to 80 °.
10. The cross-sectional shape of the conductor layer has a curved surface at the upper part thereof, and the conductor layer has at least a part of the upper surface exposed from the resin layer, and at least a part from the maximum width to the lower part of the base layer. Item 8. The solar cell structure according to any one of Items 1 to 7, which is embedded in a resin layer of the material.
11. Item 11. The solar cell structure according to Item 10, wherein the ratio (T2 / L) of the thickness (T2) of the conductor layer above the maximum width to the maximum width (L) of the conductor layer is in the range of 0.01 to 2.
12 Item 12. The solar cell structure according to any one of Items 1 to 11, wherein the conductor layer has a thickness in the range of 2 to 100 μm.
13. A substrate including a patterned conductor layer and a resin layer, the substrate having a conductor layer embedded in the resin layer so that at least a part of the surface of the conductor layer is exposed, and collecting the conductor layer A method for producing a solar cell structure, wherein the solar cell element is bonded to an electric extraction surface of a solar cell element so as to be an electrode, an interconnector or an auxiliary electrode.
14 Item 14. The solar cell structure according to Item 13, wherein the solar cell element includes a photoelectric conversion layer and an electric extraction electrode connected to the photoelectric conversion layer, and the electric extraction surface is a surface from which the electric extraction electrode or the collector electrode is exposed. Manufacturing method.

The solar cell structure according to the present invention includes an electrical extraction electrode connected to a photoelectric conversion layer or a current collection electrode connected to the current collection electrode, a current collection electrode derived from a substrate including a patterned conductor layer and a resin layer, an interconnector, or The contact property with the auxiliary electrode, the connection reliability, etc. are good, and the adhesion reliability is excellent.
The solar cell structure according to the present invention is produced using a substrate including a patterned conductor layer and a resin layer as an electrode substrate for a solar cell in which the conductor layer functions as a collecting electrode, an interconnector, or an auxiliary electrode. The contact between the electrical extraction electrode present on the electrical extraction surface of the solar cell element or the collector electrode connected to the solar cell element and the conductor layer of the base material, connection reliability, etc. are good. It is not necessary to perform a special adhesion method such as vapor deposition or coating on the electric extraction surface. In addition, the solar cell structure according to the present invention is excellent in adhesion reliability without a decrease in adhesion force on the electrical extraction surface after performing a reliability test such as a heat humidification test or a water resistance test.

  In the base material including the patterned conductor layer and the resin layer in the present invention, when the portion that becomes the maximum width of the conductor layer is buried in the resin layer formed on the base material, the contact area between the resin and the conductor layer is This increases the adhesion of the conductor layer. In particular, the lateral shear adhesion of the conductor layer is improved. Therefore, there is no pattern abnormality with respect to vibration and impact, and there is no deterioration in characteristics even after the manufacturing process and after conveyance. Moreover, the effect excellent also with respect to the adhesive force after performing reliability tests, such as a heat humidification test, and a water resistance test is shown.

In the solar cell structure in the present invention, at least a part of the member having the function of the current collecting electrode, interconnector or auxiliary electrode can be made of a metal having a low specific resistance, so that excellent conductivity can be obtained and the fill factor can be increased. Can be improved.
In the solar cell structure in the present invention, the width of the conductor layer can be narrowed to increase the aperture ratio on the top electrode side, and the reduction of the light receiving area due to the conductor layer can be suppressed.

According to the method for manufacturing a solar cell structure of the present invention, a current collecting electrode that is electrically connected to an electric extraction electrode by bonding a base material including a patterned conductor layer and a resin layer to an electric extraction surface of a solar cell element. Since the interconnector or the auxiliary electrode can be installed, the manufacture thereof is easy and the production efficiency is excellent.
Furthermore, at this time, the current collector electrode, the interconnector or the auxiliary electrode in the solar cell structure can be formed at a low temperature. Therefore, the solar cell element of the present invention is not limited to one having high heat resistance.

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 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. The perspective view which cut off some conductor layers. Sectional drawing of the width direction of the conductor layer shown to Fig.22 (a). Sectional drawing of the width direction of the other example of the conductor layer shown to Fig.22 (a). 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. (C) Sectional drawing which shows a process. (D) Sectional drawing which shows a process and an embedment adjustment process. Sectional drawing which shows an example of the base material with a conductor layer pattern which has an exposed conductor layer. Sectional drawing which shows an example of a base material with a conductor layer pattern in which a base material consists only of a resin layer. Sectional drawing which shows the process of (E). Sectional drawing which shows an example of the base material with a conductor layer pattern obtained through the process of (E). Sectional drawing of the base material with a conductor layer pattern containing the base material for transcription | transfer obtained through another process. Sectional drawing which shows the structure of the solar cell structure using the base material with a conductor layer pattern which concerns on this invention. Sectional drawing which shows another structure of the solar cell structure 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 structure. Sectional drawing which shows the other example of a solar cell structure. Sectional drawing which shows the other example of a solar cell structure. Sectional drawing which shows the other example of a solar cell structure. Sectional drawing which shows the other example of a solar cell structure. Sectional drawing which shows the reference example of a solar cell structure. Sectional drawing which shows the reference example of a solar cell structure. Sectional drawing which shows the other example of a solar cell structure. Sectional drawing which shows the other example of a solar cell structure. Sectional drawing which shows the other example of a solar cell structure. Sectional drawing which shows the other example of a solar cell structure. Sectional drawing which shows the other example of a solar cell structure.

  The substrate containing a patterned conductor layer and a resin layer used in the present invention (hereinafter referred to as “substrate with a conductor layer pattern”) is obtained by laminating a patterned conductor layer on a substrate containing a resin layer. It is. As this conductor layer, there are cross-sectional shapes having a cross-sectional shape as a whole or an upper portion of the cross-sectional shape being trapezoidal (referred to as “conductor layer A”). In the base material with a conductor layer pattern, at least a part of the upper surface of the conductor layer or a part of the trapezoidal shape is exposed from the resin layer, and at least a part below the maximum width is a resin layer of the base material. Preferably, the conductor layer pattern has at least the upper surface of the trapezoidal shape section having a cross-sectional shape exposed from the resin layer, and the conductor layer pattern is a part of the trapezoidal shape section having a cross-sectional shape. May be exposed from the resin layer.

  In the base material with a conductor layer pattern used in the present invention, the conductor layer may have a curved surface at the top of its cross-sectional shape (referred to as “conductor layer B”). It is preferable that at least a part of the upper surface is exposed from the resin layer, and at least a portion below the maximum width is embedded in the resin layer of the base material.

  In the base material with a conductor layer pattern used in the present invention, the conductor layer may have a rectangular cross section (referred to as “conductor layer C”), and at least a part of the surface thereof is a resin layer. Is exposed. Moreover, it is preferable that at least 50 to 100% of the thickness is embedded in the resin layer of the base material.

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.

Accordingly, the resin layer and the supporting substrate constituting the substrate 4 can be appropriately selected depending on how they are used, but when used on the solar light irradiation surface side, a transparent one is preferable. At this time, it is preferable that the base material with a conductor layer pattern in the present invention has light transmittance particularly in the visible region.
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.
In addition, this resin layer may be laminated on the supporting base material, and the base material may be constituted only by the resin layer, but if the base material is constituted only by the resin layer, the entire thickness Is more preferable because it can be made thinner.

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.

Examples of the plastic film include 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 polyether. A film made of plastic such as sulfone, polycarbonate, polyamide, polyimide, acrylic resin 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. Further, considering that the handleability is deteriorated if it is too thin, the thickness of the plastic film is more preferably 5 to 500 μm, and further preferably 15 to 200 μm.
These base materials such as plastic films are more flexible and preferable than glass plates and plastic plates.

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, photosensitizers or photoinitiators added at the time of ultraviolet curing include 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 active energy rays, 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 in which the conductor layer is embedded. In order to bury the conductor layer in the resin more reliably, the thickness of the resin layer is more preferably 1.5 times or more the thickness of burying the conductor layer.

As a dimension of the conductor layer, the thickness (T) of the conductor layer is preferably 2 to 100 μm. If it is less than 2 μm, it tends to be difficult to obtain a sufficiently low resistance as an electrode material. If the thickness exceeds 100 μm, the resistance hardly changes, so that material costs and manufacturing process time increase, which is disadvantageous in terms of cost. Moreover, the thickness of the adhesive needed to embed the conductor layer in the adhesive is increased.
Further, the thickness of the conductor layer pattern is more preferably 80 μm or less, and the time required for forming the metal layer by plating is also shortened. Therefore, the thickness is preferably 60 μm or less from the viewpoint of production of the conductor layer. Moreover, since resistance will become large too much when thickness is too thin, 4 micrometers or more are preferable, 6 micrometers or more are more preferable, and 10 micrometers or more are further more preferable. Therefore, considering the above, it is more preferably 4 to 80 μm, and further preferably 6 to 60 μm.

The width (L) of the conductor layer is preferably 1 to 5000 μm. When the width of the conductor layer is less than 1 μm, the resistance tends to increase. From the viewpoint of conductivity, it is more preferably 3 μm or more, and further preferably 6 μm or more.
The width of the conductor layer may be increased if light transmission does not matter, but in this case as well, it is preferably 5000 μm at the maximum. For example, the width L of the conductor layer as the back electrode having the function of the current collecting electrode and the interconnector of the back contact type solar cell does not require light transmission, but the width (L) of the conductor layer is the back contact. It is limited by the line width, size or pitch of the pattern of the bottom electrode which is the electrical extraction electrode of the solar cell. Therefore, if the width of the conductor layer exceeds 5000 μm, it becomes too large compared to the size of the bottom electrode of the back contact solar cell, and there is a possibility that the adjacent bottom electrodes are short-circuited. Further, in the back contact solar cell, when the width (L) of the conductor layer as the back electrode is lower than 50 μm, it becomes too small than the size of the bottom electrode of the back contact, so that it is difficult to secure a connection area. . From the above viewpoint, the width (L) of the conductor layer as the back electrode of the back contact solar cell is more preferably 100 to 2000 μm, and further preferably 200 to 600 μm.
When light transmittance is required, the width (L) of the conductor layer is preferably 80 μm or less, more preferably 60 μm or less, and even more preferably 40 μm or less. Therefore, the maximum width L of the conductor layer when light transparency is required is preferably 1 to 80 μm, more preferably 3 to 60 μm, and further preferably 6 to 40 μm. However, when the electrode itself is light-shielding, as in the case where the electric extraction electrode on the surface side of the solar cell or a part thereof is an Ag finger electrode, the electrode has an appropriate interval in order to provide light transmittance. At this time, in the portion where the conductor layer and the electrical extraction electrode overlap, if the conductive layer is thinner than the electrical extraction electrode, a new light shielding portion does not occur. Therefore, it is preferable that the width of the conductor layer overlapping the light-shielding electrical extraction electrode is smaller than that (for example, 130 μm or less for an Ag finger electrode). Therefore, the maximum width L of the conductor layer connected to the Ag finger electrode is preferably 1 to 130 μm, more preferably 3 to 100 μm, and further preferably 6 μm to 80 μm.

Various patterns can be used for the conductor layer, and the pattern is appropriately selected depending on the specific 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.
Further, the pattern of the conductor layer is preferably a mesh pattern, a stripe pattern, or a comb pattern for the electrode substrate for a solar cell. The pattern of the conductor layer needs to be conductive when used as a collecting electrode, but it is not always conductive as a part of the collecting electrode or the auxiliary electrode.

The line interval of the conductor layer is appropriately determined depending on the structure of the solar cell.
When the electrical extraction electrode is a solid conductive film such as ITO or a metal film such as aluminum metal (which has a current collecting function as will be described later), the conductor layer on the base material to be overlaid thereon The line spacing of the conductor layer pattern (when used as a collector electrode or its auxiliary electrode or a composite of these and an interconnector) such as a mesh pattern, a stripe pattern, or a comb pattern is 50 μm to It is preferable to be in the range of 4000 μm. If the line spacing is too small, the contact area between the resin layer (adhesive layer) and the electric extraction surface of the solar cell element becomes small, and the adhesive force tends to decrease. On the other hand, if the line spacing is too large, the area of the collecting electrode becomes too small and the resistance becomes large, and electricity extraction tends to be inefficient. When the line interval of the conductor layer in the case where light transmittance is necessary, the aperture ratio is improved and the light transmittance is improved. On the other hand, when the line interval becomes too large, the resistance tends to increase as described above. Therefore, the line spacing of the conductor layer when light transparency is required is more preferably 100 μm to 4000 μm, further preferably 200 to 3500 μm, and particularly preferably 300 to 3000 μm. When the light transmittance is unnecessary, the line interval of the conductor layer is more preferably 100 to 3500 μm, and further preferably 200 to 3000 μm.
When the conductor layer pattern is complicated by a combination of geometric figures surrounded by the conductor layer, the line spacing is converted into a square area based on the repeat unit, and the length of one side Is the line spacing.
When the solar cell element has an electrical extraction electrode, a collector electrode, or a laminate thereof scattered on its electrical extraction surface, the conductor layer on the substrate is used as the collector electrode, interconnector or auxiliary electrode. Or, when used as a composite of these, mesh-like pattern, stripe-like pattern, comb-like pattern, etc., so that each scattered electrode or laminate is in contact with any line of the conductor layer on the substrate The conductor layer pattern lines are arranged, and at the point of contact with the electrode, the conductor layer is preferably prevented from protruding from the electrode, and the gap between the electrodes is preferably the width of the conductor layer described above.
When light transmittance is required, the aperture ratio of the conductor layer is preferably 80% or more, and more preferably 90% or more.

As described above, the conductor layer (A), which is an example of the conductor layer in the present invention, has a trapezoidal cross section or a trapezoidal upper section and a lower section 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 is a conductor layer pattern having a trapezoidal cross-sectional shape, and FIG. 2B is a cross-sectional shape of an upper trapezoidal portion and an ellipse-shaped portion having a lower width than the trapezoidal portion. It is the pattern of the conductor layer 5 which becomes. FIG. 3 is a cross-sectional view in the width direction of the conductor layer 5 shown in FIG. 2 (b). The base of the trapezoidal part 6 and the part of the ellipse-shaped string of the ellipse-shaped part 7 are integrated. 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 that protrudes from the lower base of the trapezoidal portion of the lower ellipsoidal 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.

The dimensions of the conductor layer (A) 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 upper trapezoidal part and an ellipse-shaped part (lower part) wider than the trapezoidal part. In both cases, it is preferable that the upper surface width (the length of the upper base of the trapezoid) L1 and the maximum width L in the cross-sectional shape of the conductor layer pattern are as follows.

The thickness (T) of the conductor layer is as described above.
In the case of the shape in FIG. 5B, the total thickness T of the trapezoidal portion (upper part) thickness T1 and the ellipse-shaped part (lower part) thickness T2 is in the range of 2 to 100 μm. Preferably, there is no further limitation on the values of T1 and T2, but 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 is 1 μm or more. Is more preferable.

The maximum width L of the conductor layer is the same as the width (L) of the conductor layer described above.
In the case of the shape in FIG. 5 (b), the maximum width L of the upper base width L1 and the lower base width L2 of the upper trapezoidal portion is in the above range, and, as will be described later, If the angle satisfies the conditions described later, 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 portion is preferably 1 μm or more. Moreover, when it is the shape in (a) or (b) of FIG. 5, it is preferable that L1 shall be 1 micrometer or more on the manufacturing method mentioned later.

  In FIGS. 5A and 5B, the trapezoidal shape means that the side has an inward inclination as a condition, but the inclination of the side of the trapezoidal shape is the left and right respectively. 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.

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)

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.

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 resin layer of a conductor layer pattern improves.
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 while the upper surface is exposed from the resin layer 3. FIG. The state in which the entire layer 5 is embedded in the resin layer 3 is shown. FIG. 8A shows a trapezoidal portion 6 having an upper cross section and a lower rounded circular portion 7 wider than the upper portion. The state where the entire rounded circular portion 7 (in the depth direction) of the lower portion of the conductor layer integrated in (1) is embedded in the resin layer 3 (the shoulder portion 8 is exposed) is shown. FIG. 8B shows a state in which a similar conductor layer is embedded in the resin layer 3 in a state where a part including the upper surface of the upper trapezoidal portion 6 is exposed from the resin layer 3. FIG. 8C shows a state in which a similar conductor layer is embedded in the resin layer 3 in a state where only the upper surface of the upper trapezoidal portion 6 is exposed from the resin layer 3. In any of these cases, 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 coated so as to cover a part of the upper surface of the conductor layer 5 or the upper trapezoidal portion 6. .

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 is formed by plating on a conductive substrate for 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) In some cases, the substrate is produced by a method including a step of replacing the substrate with another substrate. 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. This conductive substrate for plating is a plate for plating that can be used repeatedly.

  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 30 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 10 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.

Examples of the conductive substrate for plating according to 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, an insulating layer 13 is laminated on a conductive base material 12, and a concave portion 14 is formed in the insulating layer 13. 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 in the conductive substrate for plating of the present invention and the thickness or the depth of the recess are appropriately determined according to the role of the conductor layer pattern 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 conductor layer generated by plating, and similarly corresponds to the conductor layer pattern in the base material with the conductor layer pattern. This corresponds to the pattern of the conductor layer of the substrate with a conductor layer pattern as the battery electrode substrate.

  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. More preferably, it is 0.5-30 micrometers, and it is further more preferable that it is 1-10 micrometers.

When the conductive substrate for plating of the present invention is used to produce an electrode substrate that requires light transmission by a transfer method, the width of the recess 14 as shown in FIG. The width d is preferably 2 to 60 μm and the bottom width d ′ is preferably 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.

  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 base material for plating in the present invention includes a step of forming an insulating layer on the surface of the conductive base material so that a geometric figure is drawn by a concave portion exposing the conductive base material. .
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, the 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.

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 inclination angle 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. 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.
It is preferable to form the intermediate layer 18 on the surface of the conductive substrate 12 on which the convex pattern composed of the protrusions 16 is formed before forming the insulating layer 17 (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. For the electroless plating method, refer to pages 505 to 545 of the above-mentioned “Practical Plating for On-Site Engineers” (edited by the Japan Plating Association, published by Sakai Shoten in 1986).
Furthermore, in order to obtain the reducing action of the reducing agent, it may be necessary to activate the catalyst on the metal surface. When the substrate is a metal such as iron, steel, nickel, etc., these metals have catalytic activity, so they are deposited just by immersing them in the electroless plating solution, but copper, silver or their alloys, and stainless steel In this case, in order to impart catalyst activation, a method is used in which the object to be plated is immersed in an acidic hydrochloric acid solution of palladium chloride and palladium is deposited on the surface by ion substitution.

The electroless plating that can be used in the present invention 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 μΩ · cm), iron (9.8 μΩ · cm), chromium (17 μΩ · cm, all values at 20 ° 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 of the metal layer (plating thickness) formed by plating on the concave portion of the conductive base material is appropriately determined according to the purpose. The thickness is related to the thickness of the conductor layer. As described.

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.) Suitable 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”.
As a support substrate for the transfer substrate, a plastic film is preferable in view of productivity. In some cases, the transfer substrate may be composed only of an adhesive layer.

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. Accordingly, the thickness of the pressure-sensitive adhesive layer is preferably 0.5 μm or more, more preferably 1 μm or more, and further 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. Therefore, the thickness of the pressure-sensitive adhesive layer is preferably 110 μm or less. 90 μm or less is more preferable, and 70 μm or less is more preferable.
When the transfer substrate is bonded to the surface of the conductive substrate for plating on which the conductor layer is formed, depending on the properties of the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is particularly suitable for fluidity or pressure-sensitive adhesiveness. If necessary, it is heated. When the transfer base material has a support base material that holds the pressure-sensitive adhesive layer, the support base material preferably 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 base material 20 prepared separately, which is a support base material (transparent base material) 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 19 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 pressure-sensitive adhesive layer 12 and peeled off from the conductive substrate 11 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.

  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 surfaces to be bonded 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.

FIG. 19 is a cross-sectional view showing an example of the base material with a conductor layer pattern in FIG. 18, and the base material with a conductor layer pattern 26 shown in 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.
The substrate 26 with a conductor layer pattern is used such that the exposed surface of the conductor layer 19 of the exposed resin layer (adhesive layer) 22 is brought into contact with the electric extraction surface of the solar cell element.

  The base material 23 with a conductor layer pattern ((FIG. 14 (h) or FIG. 16)) or the base material 26 with a conductor layer pattern (FIG. 18) also peels off the support base material 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.

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. 20 is a cross-sectional view illustrating an example of a support base material replacement step.
FIG. 20A is a cross-sectional view showing a state where the support base material 21 [base material (I)] of the surface-protected base material with conductor layer pattern 25 shown in FIG. 17 is peeled off.

  FIG. 20B 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. 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.20 (c) is sectional drawing of the base material with a conductor layer pattern by which the new support base material is stuck and the surface is protected. FIG. 20C shows the resin layer 22 on the new support base 31 [base (III)], and the conductor layer 19 that is buried in the resin layer 22 but 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. 20A, in order to peel 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. 20C may be used as it is for an electromagnetic wave shielding film, a film antenna, or 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. 20D 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. 20D shows a substrate 33 with a conductor layer pattern in which the resin layer 22 is embedded on the 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. 20D, 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. 21 is the same as the base material 33 with the conductor layer pattern of FIG. 20 (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. 21 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 that is buried in the upper surface but is exposed from the resin layer 22 is laminated. 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 110 μm or less. It is useless even if it is thicker than necessary. Furthermore, if it is too thin, sufficient adhesive strength cannot be obtained, so 0.5 μm or more is preferable. The thickness of the resin layer is more preferably 1 μm to 90 μm, and further preferably 3 μm to 70 μm. 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.

  Further, in FIGS. 7A, 7B, 8B, and 8C, the entire trapezoidal shape (except 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. For this purpose, T or T1 is preferably 100 μm or less, and more preferably 30 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 0.1 μm or more, more preferably 0.5 μm or more.

  In the base material with a conductor layer pattern in the present invention, in the step of attaching a film on the plating deposited on the conductive base material for plating and the step of attaching a cover film after transfer, the pattern is formed by heating and pressing as necessary. Can be embedded in the resin. In particular, by setting the turbidity of the cover film to be bonded to the pattern surface after transfer to 2.0 or less, a highly transparent base material with a conductor layer pattern can be obtained.

The conductor layer in the present invention may have a cross-sectional shape having a curved surface at the top thereof (conductor layer (B)). This will be described in detail below. In addition, the whole thing of reverse trapezoid shape is also possible.
This will be described with reference to the drawings. FIG. 22 is a perspective view in which a part of the conductor layer is cut off. FIG. 22A shows the conductor layer 5 having a curved surface at the top, and FIG. 22B shows the conductor layer 5 having an inverted trapezoidal section. These are the ones shown in FIG. FIG. 23 is obtained by reversing the one shown in FIG. 3 upside down. Accordingly, the same reference numerals are used, but the upper part and the lower part are different. FIG. 23 is a cross-sectional view of the conductor layer shown in FIG. 22A in the width direction. The cross-sectional shape is continuous with the upper ellipse-shaped portion 7 and the upper portion. The narrow cross section is composed of the lower trapezoidal portion 6, and is integrated with a part of the ellipse string of the upper ellipsoidal portion 7 and the lower bottom of the trapezoidal shape of the lower trapezoidal portion 6. In FIG. 22A and FIG. 23, the lower part has an inverted trapezoidal shape, but is not limited thereto. In the case as shown in FIG. 22A and FIG. 23, the shoulder 8 protruding from the lower base of the lower trapezoidal portion 6 of the upper ellipse-shaped portion 7 can be one 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, it may have a shape represented by (a), (b), or (c) in FIG. 24 (another example of a cross-sectional view in the width direction of the conductor layer shown in FIG. 22A). These are the ones shown in FIG. 4 turned upside down.
22A and 23, the maximum width of the conductor layer is the chord portion of the ellipse-shaped portion 7, but it may be a shape in which the maximum width exists above or below it.
Furthermore, the conductor layer may have a rectangular cross section of the trapezoidal portion 6 in its transverse cross section.

The maximum width (L) of the conductor layer is difficult to say generally, but the maximum width (L) of the conductor layer for the surface electrode for solar cells is preferably 3 to 80 μm, and preferably 6 to 60 μm. More preferably, it is 10 to 40 μm. When light transmission is required, a maximum width (L) of 50 μm or less is preferable. From the viewpoint of conductivity, a maximum width (L) of 1 μm or more is preferable.
Further, the maximum width (L) of the conductor layer for the back electrode for solar cell is preferably 50 to 5000 μm, more preferably 100 to 2000 μm, and particularly preferably 200 to 600 μm. The maximum width (L) in the application of the back electrode for a solar cell is limited by the line width or pitch of the pattern of the connection electrode of the solar battery cell. If the maximum width (L) is too large, the tolerance of the pattern is It tends to decrease and becomes unnecessary. On the other hand, if the maximum width L is too small, the connection area with the connection electrode becomes small, so that the connection strength and conductivity are likely to decrease. The maximum width of the conductor layer may be increased if light transmission does not matter. There is no restriction | limiting in particular in the maximum width of a conductor layer, The magnitude | size may be 5 mm, for example.
The width of the conductor layer is particularly preferably 50 μm or less from the viewpoint of non-visibility of the conductor layer pattern, and 1 μm or more from the viewpoint of conductivity.

The ratio (T2 / L) of the thickness T2 above the maximum width portion of the conductor layer to the maximum width L of the conductor layer (the ellipse-shaped portion in the above example) is in the range of 0.01 to 2. Preferably, it is determined appropriately according to the application.
In any case where the conductor layer is used on the front side (light incident side) of the solar cell, it is preferable that the ratio T2 / L is high because transparency and conductivity are required. However, in the growth of plating, the thickness T2 is increased. Since the maximum width L also increases, it is difficult for the ratio T2 / L to exceed 2. On the other hand, when the ratio T2 / L is too low, the maximum width L for obtaining the cross-sectional area necessary for ensuring the conductivity is too large, so that the transparency tends to be impaired.
When used on the back side (opposite side of the light incident side) of the solar cell structure (especially, the solar cell structure having a large electrical extraction electrode on the back surface), the conductor width of the conductor layer may be large, and the ratio T2 / L Is preferably 0.01 to 0.8, more preferably 0.02 to 0.4, and particularly preferably 0.03 to 0.2. A ratio T2 / L that is too low is not preferable because it is difficult to obtain the thickness T necessary for ensuring conductivity.

  When the cross section is an inverted trapezoid, the maximum width L and the overall thickness T are the same as described above.

The dimensions of the conductor layer will be further described with reference to the drawings.
FIG. 25 shows a cross-sectional view of the conductor layer. FIG. 25 (a) is a cross-sectional view of a conductor layer having a curved surface at the upper part. In this figure, the lower part of the inverted trapezoidal part 6 and the upper part of the ellipse-shaped part 7 wider than this lower part are shown. It is a unity. FIG. 25B is a cross-sectional view of the inverted trapezoidal shape of the conductor layer.

The total thickness T of the conductor layer is as described above.
In the case of the shape in FIG. 25 (a), the total thickness (T) of the conductor layer is the thickness (T1) below the portion of the maximum width (L) and the thickness from the maximum width portion (T2). ).
In the present invention, the ratio (T2 / L) is as described above, but the lower thickness (T1) may be 0 as long as this condition is satisfied. The maximum width L of the conductor layer is as described above.

  In the case of the shape in FIG. 25A, the width L1 of the upper base and the width L2 of the lower base of the lower trapezoidal shape are not particularly limited. As will be described later, according to the conductor layer manufacturing method to be described later, it is necessary to satisfy specific conditions due to restrictions on the manufacturing method. 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.

  In the case of the shape in (a) or (b) of FIG. 25, when importance is attached to light transmittance, L1 is preferably 1 to 80 μm in view of the manufacturing method described later.

  In (a) and (b) of FIG. 25, the reason that the cross-sectional shape is trapezoidal or includes it is a restriction from the manufacturing method described later, but in this case, the side is inside as a condition. The inclination of the trapezoidal side is preferably 30 ° or more and less than 90 °, more preferably 30 ° or more and 80 ° or less, and more preferably 30 ° or more. 60 degrees or less is more preferable, and 40 degrees or more and 60 degrees or less is particularly preferable.

  Moreover, the width | variety of the part whose cross-sectional shape of a conductor layer is trapezoid should just have spread as a whole upwards. It does not necessarily have to spread at a constant gradient α as in the above-mentioned drawing, and it does not have to be narrowed upward and may spread as a whole. In particular, it is preferable not to have a portion where the side surface is perpendicular to the upper or lower side or the lower bottom.

  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. 26, the gradient α has a trapezoidal height h and a trapezoid side width s (horizontal direction of the trapezoidal side width direction). ) And can be obtained from the equation (1).

  The line interval of the conductor layer from the viewpoint of light transmittance is as described above.

  In the present invention, the conductor layer is preferably entirely or partially embedded in the resin layer with at least a part of the upper surface exposed. Thereby, since the anchor effect appears, the adhesiveness to the base material of a conductor layer pattern improves. In order to further improve the adhesion between the resin layer and the conductor layer, T2 is preferably 0.5 μm or more, and more preferably 1 μm or more.

27 and 28 are partial cross-sectional views showing a state in which the conductor layer is embedded in the resin layer.
In FIG. 27 (a), the cross-sectional shape of the conductor layer has a curved surface at the top, and at least a part of the top surface of the conductor layer is exposed from the resin layer 9, and the conductor layer has at least the maximum width. The state from which the part below is embedded in the resin layer 9 of the said base material is shown. FIG. 27 (b) shows a similar state, but shows a state in which a conductor layer having a cross-sectional shape with the upper curved portion of the conductor layer at the end and a substantially flat upper surface is used. FIG. 28A shows a state in which a part of the conductor layer 5 having an inverted trapezoidal cross-sectional shape is embedded in the resin layer 9, and FIG. 28B shows a surface corresponding to the base of the trapezoidal cross-sectional shape being a resin. A state in which the entire conductor layer 5 is embedded in the resin layer 9 while being exposed from the layer 9 is shown.

A substrate with a conductor layer pattern is incorporated into a solar cell structure and used in contact with the electrode extraction surface. At this time, the electrical extraction electrode, current collecting electrode or interconnector connected to the photoelectric conversion layer and the conductor layer are in contact with each other. It is desirable that the area to be contacted is high, and the conductor layer in which most of the upper surface as shown in FIG. 27B is substantially flat with respect to the place where the conductor layer is in contact (particularly when the surface is flat or almost flat) By using this, the contact area between the conductor layer and its contact location can be increased. In addition, when the surface of the electrode extraction surface has a fine uneven structure like the texture structure of the solar cell surface, the entire upper part of the conductor layer or the upper end as shown in FIG. 27 (a) or 27 (b). When there is a curved portion having a large curvature, the contact area can be increased by meshing the fine irregularities of the conductor layer and the fine irregularities of the functional layer at the contact portion.
As shown in FIGS. 27A and 27B, it is desirable that most of the conductor layer is buried in the resin layer while the upper portion of the conductor layer in contact with the electrode extraction surface is exposed. This is because the resin layer can be in contact with a portion other than the contact surface of the electrode extraction surface with the conductor layer, and the contact between the conductor layer and the contact portion can be maintained. Therefore, the ratio (f / T) of the maximum thickness (f) of the portion where the conductor layer is embedded in the resin layer to the thickness (T) of the entire conductor layer is preferably 0.1 to 1.0. .3-1.0 is more preferable, and 0.5-1.0 is most preferable.

Before bringing the substrate with the conductor layer pattern into contact with the electrode extraction surface, in order to realize the above effect, the thickness of the entire conductor layer (T) of the maximum thickness (f) of the portion where the conductor layer is embedded in the resin layer (T ) Is preferably 0.1 to 1.0, more preferably 0.1 to 0.8, and most preferably 0.1 to 0.6.
Moreover, it is preferable that the lower part is embedded in the resin layer at least from the location of the maximum width of the conductor layer.

  FIG. 28 shows a state in which a conductor layer having an inverted trapezoidal cross section is embedded in the resin layer. In FIG. 28 (a), a part is embedded, but the effect of adhesion to the resin layer is small, and in FIG. 28 (b), the conductor layer is entirely embedded with the upper surface exposed. Yes. In this case, it can be said that the adhesion effect with the resin layer is improved as compared with the state of FIG. 28A, but the adhesion with the resin layer as compared with the case of FIG. 27A or 27B. The effect is small.

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
(A) Conducting a conductor layer forming step of forming a conductor layer pattern on the conductive substrate for plating by plating;
(B) a transfer step of transferring the pattern of the conductor layer formed on the conductive substrate for plating to the transfer substrate;
(C) Laminate for producing a laminate by laminating a substrate containing a resin layer on the surface of the transfer substrate having the conductor layer pattern so that the resin layer is in contact with the surface on which the conductor layer pattern exists. Manufactured by a method including an object manufacturing process.
After the step (C), any one of the following steps (i) to (vii) or other steps can be appropriately performed.
(I) (D) A step of peeling the transfer substrate from the laminate obtained in the step (C).
(Ii) (E) A step of peeling off the transfer substrate from the laminate obtained in the step (C), and laminating a protective substrate instead to produce a new laminate.
(Iii) A step of performing the step (E), and then (F) peeling off the protective substrate.
(Iv) Performing the above step (E), and then (G) the obtained new laminate (however, using a substrate including a resin layer and a supporting substrate on the surface as a substrate including a resin layer on the surface) A support substrate obtained by replacing the support substrate with another support substrate.
(V) A step of peeling off the protective substrate (H) after the step (G).
(Vi) (J) Laminate obtained in the step (C) above (however, a substrate obtained by using a substrate containing a resin layer and a supporting substrate on the surface as a substrate containing a resin layer on the surface) The step of exchanging the support substrate in () with another support substrate.
(Vii) A step of performing the step (J) above and (K) peeling off the transfer substrate.
In the above-described method for producing a substrate with a conductor layer pattern, the resin layer is adjusted so as to embed at least a portion below the maximum width of the conductor layer in the step (C) or thereafter. Hereinafter, the process of adjusting in this way is referred to as “embedding adjusting process”. In the step (C), a substrate is prepared by laminating a substrate containing a resin layer on the surface of a transfer substrate having a conductor layer pattern so that the resin layer contacts the surface on which the conductor layer pattern exists. When the resin layer is embedded with at least a portion below the maximum width of the conductor layer, it is also included in the embedding adjustment step.

  First, (A) the conductor layer manufacturing process will be described. This step is the same as the (I) conductor layer manufacturing step relating to the conductor layer (A) described above. The conductive base material for plating that can be used, the plating method that can be used, and the like are the same as described above.

The transfer step (B) includes a resin layer containing a conductive layer (metal deposited on the concave portion of the conductive substrate for plating) formed on the conductive substrate for plating (II) described above. This is the same as the transfer process for transferring to the material. This substrate for transfer has the peelability of the conductor layer pattern for the next step.
As described above, as shown in FIG. 14G, the transfer substrate 20 is pressure-bonded to the plating conductive substrate on which the pattern of the conductor layer 19 is formed with the pressure-sensitive adhesive layer 22 facing. At this time, the pressure-sensitive adhesive layer 22 may come into contact with the insulating layer 17, and the thickness of the conductor layer 19 embedded in the pressure-sensitive adhesive layer 22 can be adjusted by the degree of pressure bonding or the thickness of the pressure-sensitive adhesive layer. The maximum width portion of the conductor layer is preferably exposed so as to be embedded in the resin layer in the next step.
Then, as shown in FIG. 14 (h), when the transfer base material 20 is peeled off, the pattern of the conductor layer 19 adheres to the adhesive layer 22 and is peeled off from the electroconductive substrate for plating. As a result, The said base material 23 with a conductor layer pattern is obtained as a base material for transcription | transfer with a conductor layer pattern, and is provided to the following (C) process.

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 60. It may be performed before peeling from the conductive base material 51, or after peeling, or may be semi-cured before peeling and may be completely cured after peeling.
In particular, when partial curing or complete curing of a pressure-sensitive adhesive containing a curable resin is performed after the transfer substrate 20 is peeled from the plating conductive substrate, a coverlay film, a peelable support, etc. are temporarily laminated. You may do it. Even in these cases, the peelability of the conductor layer pattern is ensured for the step (C).

Next, the following steps (C) will be described with reference to FIGS.
FIG. 29 is a cross-sectional view showing the step (C) of manufacturing the laminate.
(C) As a process, the transfer base material (transfer base material with a conductor layer pattern) 23 having the pattern of the conductor layer 19 obtained as described above is provided with a support base material 36 and a resin layer 37 thereon. 38 (hereinafter referred to as “holding substrate”) is prepared for lamination [FIG. 29 (a)]. Subsequently, these are laminated so that the resin layer 25 of the base material 26 is in contact with the surface of the transfer base material 23 where the conductor layer 19 is present to produce a laminate 39 (FIG. 29B). If the maximum width portion and the lower portion of the conductor layer 19 are embedded in the resin layer 25 at the time of producing the laminate 27, it can be used as a substrate with a conductor layer pattern according to the present invention.

  The holding substrate 38 includes the support substrate 36 and the resin layer 37 thereon, but may not include the support substrate 36 in some cases. About these, the support base material and resin layer which were illustrated above can be used. About the resin layer, the thing similar to the adhesive demonstrated in the transcription | transfer process can be used.

  In this step, the holding substrate includes a supporting substrate and a resin layer thereon, and is the same as the above-described substrate, but the supporting substrate is a plastic film having transparency, or A substrate having transparency and heat resistance such as glass is preferred. The resin layer is preferably a pressure-sensitive adhesive layer.

Next, the process after the (C) process and the embedding adjustment process will be described.
FIG. 30 is a cross-sectional view showing a transfer substrate peeling step and an embedding adjustment step. FIG. 31 is a cross-sectional view showing an example of a base material with a conductor layer pattern having an exposed conductor layer, and FIG. 32 is a cross-sectional view showing an example of a base material with a conductor layer pattern in which the base material is composed only of a resin layer.
After the step (C), as a step (D), the transfer substrate 23 is peeled off to obtain a laminate 40 [FIG. 30 (c)]. At this time, the laminate 40 can be used as a base material with a conductor layer pattern according to the present invention if the maximum width portion and the lower portion of the conductor layer 19 are embedded in the resin layer 37. .

In FIG. 14, FIG. 29 and FIG. 30, the pattern of the conductor layer 19 is successively transferred from the plating conductive base material to the transfer base material and the holding base material.
At this time, the adhesive force between the conductor layer 19 and the resin layer 37 must be higher than the adhesive force between the conductor layer 19 and the resin layer 22. However, in the step (B), the pattern of the conductor layer 19 must be transferred to the resin layer 22 from the conductive substrate for plating. For this reason, 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 for plating. This relationship of adhesive strength is
The adhesive force between the conductor layer 19 and the conductive substrate for plating,
The relationship becomes larger in the order of the adhesive force between the conductor layer 19 and the resin layer 22 and the adhesive force between the conductor layer 19 and the resin layer 37 (this relationship is referred to as “relation 1”).
By satisfying the “relationship 1” by lowering the adhesive force between the conductive layer 19 and the conductive substrate for plating according to the plating conditions and the like, and using the resin layer 25 having an adhesive force higher than that of the resin layer 22. it can.

Alternatively, the adhesive strength of the resin layer 22 in the step (D) is lower than the adhesive strength of the resin layer 22 in the step (B) by curing the resin layer 22 with ultraviolet (UV) irradiation or heat. Then, the step (D) can be carried out. In that case, the relationship of adhesive strength is
The relationship in which the adhesive force between the conductor layer 19 and the conductive base material for plating and the adhesive force between the conductor layer 19 and the resin layer 22 are in this order (this relationship is referred to as “Relationship 2”),
The relationship is divided into two relations: an adhesive force between the conductor layer 19 and the resin layer 22 and an adhesive force between the conductor layer 19 and the resin layer 37 (this relation is referred to as “Relation 3”).
Since the adhesive force between the conductor layer 19 and the conductive base material for plating can be lowered depending on the plating conditions and the like, “Relation 2” is easily satisfied, and the adhesive force of the resin layer 22 after curing is reduced, so that “Relation 3 "Is easier to be satisfied.

Further, in order to transfer the pattern of the conductor layer, the adhesive force between the resin layer 37 and the support base material 36 must be higher than the adhesive force between the resin layer 22 and the resin layer 37. However, in the step (B), the pattern of the conductor layer 19 must be transferred from the conductive substrate for plating to the resin layer 22. Therefore, the adhesive force between the resin layer 25 and the resin layer 22 must be higher than the adhesive force between the resin layer 22 and the conductive substrate for plating. This relationship of adhesive strength is
The adhesive force between the resin layer 22 and the conductive substrate for plating;
The relationship becomes larger in the order of the adhesive force between the resin layer 22 and the resin layer 37 and the adhesive force between the resin layer 37 and the support base material 36 (this relationship is referred to as “Relationship 4”).
Since the adhesive strength between the electroconductive substrate for plating and the resin layer 22 is low, use should be made of a substrate that has been subjected to a treatment for improving adhesion, such as a corona-treated substrate or a substrate with an easy-adhesion layer. Etc., “Relationship 4” can be satisfied.
Alternatively, the adhesive strength of the resin layer 22 in the step (D) is lowered than the adhesive strength of the resin layer 22 in the step (B) by curing the resin layer 22 by UV irradiation or heat. The step (D) can be performed. In that case, the relationship of adhesive strength is
The relationship becomes larger in the order of the adhesive force between the resin layer 37 and the resin layer 22 and the adhesive force between the resin layer 37 and the support base material 36 (this relationship is referred to as “Relationship 5”).
Since the adhesive strength of the cured resin layer 22 is low, “Relationship 5” is satisfied.

As a step of adjusting the thickness of the conductor layer 19 embedded in the resin layer 37 (embedding adjustment step), during or after the above-described holding substrate laminating step, the conductor layer is at least from the maximum width portion to the lower portion. The embedding thickness is adjusted so as to be embedded in the resin layer. This adjustment step may be performed in the step (C) itself (corresponding to FIG. 29B). However, as the step (E), after the step (D) (corresponding to FIG. Instead of peeling the material), a substrate such as a cover film or a peelable substrate is laminated on the surface of the laminate 40 where the conductor layer 19 is present, or a resin is applied and cured or solidified. The thickness of the conductor layer 19 can be adjusted by performing a step of laminating the surface on which the conductor layer pattern exists with the protective base material 41 and applying pressure with a press, a laminator or the like as appropriate. The resin layer preferably exhibits fluidity under pressure, and at this time, the resin layer is heated to give it fluidity as needed. As described above, at least temporarily, the surface-protected substrate 42 with a conductor layer pattern is obtained [FIG. 30 (d)] and can be used in this state. The protective substrate 41 may remain continuously or may be peelable later. (F) As a process, the base material 43 with a conductor layer pattern by which the embedding thickness of the conductor layer was adjusted can be obtained by peeling the protective base material 41 (FIG. 31).
By peeling the support base material 36 from the base material 43 with a conductor layer pattern, a base material 44 with a conductor layer pattern in which the base material consists only of the resin layer 37 can be obtained (FIG. 32). This can be used. The resin layer 37 is a pressure-sensitive adhesive layer, but may have already lost its adhesiveness. In addition, the loss of adhesiveness can be performed by advancing the degree of curing of a curable resin, and can be performed by placing the resin in an environment lower than the glass transition temperature of the resin.
The base materials 43 and 44 with a conductor layer pattern can be used as the base material with a conductor layer pattern in the present invention.
The base materials 43 and 44 with the conductor layer pattern may be used as a solar cell wiring base material (electrode base material) by forming a transparent conductive film such as ITO on the surface of the resin layer 37 on which the conductive layer 19 exists. it can. A photovoltaic cell is finally formed by forming a photoelectric conversion film such as amorphous silicon on the wiring substrate (electrode substrate) for the solar cell and forming a metal electrode layer thereon.

FIG. 33 is a cross-sectional view showing a step (G) which is a step of replacing the support base material. FIG. 34 is a cross-sectional view showing an example of a base material with a conductor layer pattern obtained through the step (G).
When the holding base material has the support base material 36, the support base material 36 of the surface-protected conductor layer-patterned base material 42 obtained in the step (E) is used as a new support base material 46. Can be exchanged. For this purpose, the support substrate 36 is peeled off from the surface-protected conductor layer-patterned substrate 42 to form a laminate 45 (FIG. 33 (e)), and a new support substrate 46 is used instead of the support substrate 36. By sticking, a new surface-protected substrate 47 with a conductor layer pattern is obtained [FIG. 33 (f)]. The surface-protected substrate 47 with a conductor layer pattern can be used in this state. A plastic film is used as the support substrate 36 before replacement, and a rigid support such as a glass plate or a plastic plate is particularly suitable for this method as a new support substrate 46 to be replaced. However, it is not limited to these. Furthermore, as a step (H), the protective substrate 41 is peeled off to obtain a new substrate 48 with a conductor layer pattern (FIG. 34). The substrate 48 with the conductor layer pattern can be used in this state.

In order to replace the support base material 36 with the support base material 46, the following relationship of adhesive force is required.
that is,
The adhesive force between the resin layer 37 and the resin layer 22;
The adhesive force between the resin layer 37 and the support substrate 36;
The relationship becomes larger in the order of the adhesive force between the resin layer 37 and the support substrate 41 and the adhesive force between the resin layer 37 and the support substrate 46 (this relationship is referred to as “relation 6”).
The adhesive strength with the resin layer 22 can be reduced by curing with UV or heat. Therefore, "Relationship 6" can be satisfied by using a heavy release separator for the support base material 36, polyethylene terephthalate for the support base material 29, and glass or an adhesive support base material for the support base material 46. .

FIG. 35 is a cross-sectional view of a substrate 49 with a conductor layer pattern including a transfer substrate obtained through another process.
The same support substrate replacement as described above can be performed using the laminate 39 instead of the laminate 42. That is, as the step (J), the support base material 36 of the laminate 39 obtained in the step (C) is peeled off, and a new support base material 46 is stuck instead, and the laminate (base material with a conductor layer pattern) is attached. ) 49 (FIG. 35). Then, as a (K) process, the base material for transfer (support base material 21 and adhesive layer 22) can be peeled, and the same laminate (base material with a conductor layer pattern) as described above can be obtained. If the thickness of the conductor layer 19 embedded in the resin layer has already been adjusted, the obtained laminate can be used as it is as a substrate with a conductor layer pattern. In addition, a coverlay film and a peelable base material are laminated on the same as described above (a protective base material 41 is laminated as shown in FIG. 30D) to form a protective layer or the conductive layer 19. The embedding thickness in the resin layer can also be adjusted. This protective substrate 41 can be peeled later.
In this case, the following adhesive force relationship is required.
that is,
The relationship becomes larger in the order of the adhesive force between the resin layer 37 and the support base material 36 and the adhesive force between the resin layer 37 and the resin layer 22 (this relationship is referred to as “relation 7”).
“Relationship 7” can be satisfied by using a light release separator for the support substrate 36.

Any process for exchanging the above-mentioned supporting substrate has the following significance.
The pattern of the conductor layer formed on the electroconductive substrate for plating is transferred to the substrate for transfer, and further, with the conductor layer pattern by laminating the substrate for holding or transferring the pattern of the conductor layer to the substrate for holding A substrate is obtained. Therefore, when the base material with a conductor layer pattern obtained in this way is used thereafter, the method for producing a base material with a conductor layer pattern is preferable because the number of steps does not increase, but in this case, considering mass productivity When a flexible resin film is used as a support substrate, it is good, but when a hard material such as a glass plate is used as a substrate material, a continuous production method such as a roll-to-roll method cannot be selected. There are restrictions on the production system. Therefore, a plastic film that can be used as a supporting substrate for the holding substrate and can obtain a roll-shaped conductor layer-supporting substrate is used (for the same reason, a supporting substrate for the transferring substrate). It is also preferable to use a plastic film as the material), and by replacing only the supporting base material with a hard base material such as a glass plate, a hard base material with a conductor layer pattern can be produced without reducing mass productivity, and The pattern of the conductor layer can be easily formed on a hard substrate such as a glass substrate.
The above replacement step is convenient in such a case, and is convenient because the support substrate can be replaced as appropriate.

  In the base material with a conductor layer pattern used in the present invention, the conductor layer having a rectangular cross section (referred to as “conductor layer C”) is formed on the conductive base material by a photolithographic method. It is possible to produce a resist pattern having a metal pattern by forming a metal layer in the groove by plating, forming a metal pattern, and transferring the metal pattern to the transfer substrate. Note that the conductive base material is exposed in the groove, and the cross-sectional shape can be easily made rectangular by a photolithographic method. As the plating method, the above-described plating method can be used. Further, the plating can be transferred to the transfer base material in the same manner as the transfer step described above so as to slightly protrude from the groove. Further processing of the obtained substrate with a conductor layer pattern can be carried out in the same manner as described above. Moreover, the adjustment of the amount of conductor layer embedded in the resin layer can be performed in the same manner as described above.

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 thickness of the conductor layer embedded in the base material with conductor layer pattern 23 shown in FIG. 14 (h) or FIG. The method of blackening the conductor layer 19 of the adjusted one, the 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 both There is a method of performing blackening processing.
Light reflection can be prevented by using a substrate with a conductor layer pattern having a conductor layer pattern that has been blackened in this manner with the black layer as the light incident side.
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.

The utilization to the solar cell structure of the base material with a conductor layer pattern concerning the present invention is explained.
FIG. 36 is a cross-sectional view showing a configuration of a solar cell using a base material with a conductor layer pattern according to the present invention. A solar cell element 50 is sandwiched and laminated between two base materials with a conductor layer pattern composed of a resin layer 25 that embeds and carries a pattern of the conductor layer 19 having an exposed surface [FIG. ]]. Moreover, the support base material 24 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.36 (b)). The solar cell element 50 is laminated so that the exposed pattern of the conductor layer 19 of the base material with the conductor layer pattern is in contact with the electric extraction electrode, the collector electrode or the interconnector of the solar cell element 50.

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 wiring formed on the opposite surface of the adjacent solar cell may be connected by any method, such as connection using a conductive adhesive, connection via conductive particles, or resin layer. Bonding connection with the wiring formed in the opposite surface of the solar cell which adjoins by the adhesiveness of 22 may be sufficient.
These solar cell structures may be further sealed with a transparent sealant.

FIG. 37 is a cross-sectional view showing another configuration of the solar cell structure using the base material with a conductor layer pattern according to the present invention. The solar cell element 50 is formed on a base material with a conductor layer pattern formed of a resin layer 25 that embeds and carries the pattern of the conductor layer 19 having an exposed surface [FIG. 37 (a)]. Moreover, the support base material 24 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.37 (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.
These solar cell structures may be sealed with a transparent sealing agent as described above.

In this invention, a solar cell element means the part remove | excluding the said base material with a conductor layer pattern from the solar cell structure of this invention which functions as a solar cell including the base material with the said conductor layer pattern. The solar cell element includes at least a photoelectric conversion layer and an electric extraction electrode connected to the photoelectric conversion layer.
The photoelectric conversion layer includes a p-type semiconductor layer and an n-type semiconductor layer, and appropriately includes an i-type semiconductor layer and a buffer layer.
In order to take out electrons and holes generated in the photoelectric conversion layer, the electrical extraction electrode is formed so that one side is a positive electrode and the other side is a negative electrode on the photoelectric conversion layer, or the back contact type solar cell Thus, it is formed as a plus electrode and a minus electrode on one side.
Said electric extraction electrode has a function (electric extraction function) which supplies with electricity to the thickness direction of a photovoltaic cell. Therefore, it is preferable that the electrical extraction electrode is formed of a material having high conductivity or a thin material because the resistance can be reduced. The electrical extraction electrode may be two-dimensionally spread in the plane direction for the purpose of conduction in the plane direction (in other words, for the current collecting function), and one-dimensionally with a specific width. Or may be connected by a conductive member in order to make each electrode (the same kind of positive electrode and negative electrode) conductive. For the connection for conducting the electrode, the same material as the electrode or a different material is used. As can be seen from the above, the electrical extraction electrode itself may have a current collecting function.
For example, as an electrical extraction electrode that spreads two-dimensionally in the plane direction, there are a transparent conductive film such as ITO and a solid metal film. In a transparent conductive film such as ITO, the in-plane energization function is limited to a short distance, and the current collection function is inferior. Therefore, it is preferable to reinforce the current collection electrode on the current collection electrode. It can be made to bear on the conductor layer of the base material with a conductor layer pattern in it. Further, as an electrical extraction electrode that extends one-dimensionally with a specific width, there is a conventional so-called Ag finger electrode. In the present invention, the bus bar continuous with the Ag finger electrode is a part of the electrical extraction electrode having a current collecting function.
The solar cell element in the present invention has the above-described electrical extraction electrode, but the current collecting electrode may be separately connected thereto, and an interconnector such as a tab is connected thereto. May be. When connecting the interconnector, the electrical extraction electrode already has a current collecting function or the current extraction electrode is connected to the electrical extraction electrode.
In the present invention, the electric extraction surface includes an electric extraction electrode or a collecting electrode of a solar cell element including at least a photoelectric conversion layer and an electric extraction electrode connected to the photoelectric conversion layer, and at least one of these is exposed. Say the side that is.
In this invention, the said base material with a conductor layer pattern is a current collection electrode or an electrical extraction electrode which has a current collection function as a current collection electrode which connects this electrode by making a conductor layer pattern contact the said electrical extraction electrode. It serves as an interconnector for connecting each electrode by contact, and as an auxiliary electrode for reducing the in-plane resistance by contacting the electrical extraction electrode, current collecting electrode or interconnector of the solar cell element. Thus, it is laminated | stacked on the said electrical extraction surface.
Thus, the conductor layer pattern of the base material with a conductor layer pattern performs the role of energizing the surface of the solar battery cell by contacting the electric extraction surface of the solar battery cell or its auxiliary, and between the solar battery cells. The role to energize or assist it.
More specifically, as the transparent conductive film, a transparent conductive film laminated on a photoelectric conversion layer of a crystalline silicon solar cell having an amorphous silicon layer, an inorganic thin film solar cell (amorphous silicon type, CIGS type, CIS type, The transparent conductive film laminated | stacked on the photoelectric converting layer of other compound types, organic thin film types, dye-sensitized types, etc. is mentioned. By bringing the transparent conductive film and the conductor layer pattern into contact with each other, the energization distance in the cell plane can be increased (the current collecting function can be improved or imparted). The conductor layer pattern on the substrate in the present invention can conduct and reinforce in the in-plane direction on the electric extraction surface of the solar cell element. Furthermore, it is also possible to energize the cells by connecting the conductor layer pattern so as to extend between the cells.
Examples of electrical extraction electrodes having an energization function (electric extraction) in the thickness direction and an in-plane energization function (current collection function) are stacked on the photoelectric conversion layer of a single crystal silicon solar cell or a polycrystalline silicon solar cell. There are Ag finger electrodes and Al solid electrodes.

The solar cell element 50 shown in FIG. 36 will be described.
An example of such a solar cell element 50 is shown in FIG. FIG. 38 is a cross-sectional view of a solar cell element. As shown in FIG. 38, i-type amorphous silicon 52 is laminated on both sides of single-crystal n-type silicon 51 by a CVD method or the like, and one surface thereof is p-type amorphous silicon 53 by the CVD method or the like, and the other side. The solar cell element 56 has a structure in which a surface is n-type amorphous silicon 54 by a CVD method or the like, and a transparent conductive film 55 such as ITO is laminated thereon by a sputtering method or the like. Both the transparent conductive films 55 of the solar cell element 56 are pasted by the resin layer 25 so that the above-mentioned base material with a conductor layer pattern contacts the conductor layer 19. The conductor layer 19 at this time functions as a current collecting electrode. The patterns of the upper and lower conductor layers 19 are a top electrode and a back electrode, respectively.
The solar cell structure having the above structure can be formed into a solar cell module by supporting a plurality of solar cell structures with a transparent ethylene-vinyl acetate copolymer between a glass plate and a back sheet.

The solar cell element 50 shown in FIG. 37 will be described.
As such a solar cell element 50, there is one shown in FIG. FIG. 39 is a cross-sectional view of another solar cell element. The i-type amorphous silicon 52 is laminated on both surfaces of the single crystal n-type silicon 51 by the CVD method or the like, and the p-type amorphous silicon 53 and the transparent conductive film 55 are sequentially formed on the one surface by the CVD method or the like. The solar cell element 58 has a structure in which an n-type amorphous silicon 54 and a metal film 57 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 stuck to the transparent conductive film 55 by the resin layer 25 so that the conductor layer 19 is in contact therewith.
Moreover, as a solar cell element 50 of FIG. 37, there is one shown in FIG. FIG. 40 is a cross-sectional view of another solar cell element. The i-type amorphous silicon 52 is laminated on both surfaces of the single crystal n-type silicon 51 by the CVD method or the like, and the p-type amorphous silicon 53 and the transparent conductive film 55 are sequentially formed on the one surface by the CVD method or the like. The solar cell element 59 has a structure in which a metal film 57 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 55 of the solar cell element 59 by the resin layer 25 so as to contact the conductor layer 19.
Moreover, as a solar cell element 50 of FIG. 37, there is one shown in FIG. FIG. 41 is a cross-sectional view of another solar cell element. An i-type amorphous silicon 52 is deposited on one surface of the single crystal n-type silicon 51 by a CVD method or the like, a p-type amorphous silicon 53 by a CVD method or the like and a transparent conductive film 55 by a sputtering method or the like are sequentially stacked. This is a solar cell element 60 having a structure in which a metal film 57 such as Al or Ag is laminated on the surface by sputtering or printing. The transparent conductive film 55 of the solar cell element 60 is adhered by the resin layer 25 so that the above-described base material with a conductor layer pattern contacts the conductor layer 19.
In these cases, the conductor layer 19 functions as a current collecting electrode. The pattern of conductor layer 19 is the top electrode.

Another aspect of the solar cell structure will be described.
FIG. 42 is a cross-sectional view showing an example of a solar cell structure.
The conductor layer 19 is embedded in the resin layer 25 laminated on the support substrate 24 (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 55 such as ITO is formed on the exposed surface of the conductor layer 19 by sputtering or the like, and a groove is formed by appropriate etching using laser, mechanical polishing of a hard material needle, or the like. Pattern is formed. On the transparent conductive film 55, p-type amorphous silicon 53 is laminated in a specific pattern. Then, the i-type amorphous silicon 52 and the n-type amorphous silicon 54 are laminated by the CVD method so as to overlap therewith, and a groove is formed by appropriate etching such as using laser or mechanical polishing of a hard material needle. A certain pattern is formed. Further, a metal film 57 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 57 is formed through the side surfaces of the p-type amorphous silicon 53, the i-type amorphous silicon 52, and the n-type amorphous silicon 54 so as to be electrically connected to the adjacent transparent conductive film 57 on one side. Thereby, the solar cell structure 61 is comprised.
In this case, the conductor layer 19 functions as an auxiliary electrode that improves the conductivity of the transparent conductive film 55 that is an electrical extraction electrode.
The above structure is a solar cell structure of the type shown in FIG.
FIG. 43 is a cross-sectional view showing another example of the solar cell structure. 42 is a solar cell structure 64 having a structure in which the metal film 57 side of the solar cell structure 61 shown in FIG. 42 is sealed with a transparent ethylene-vinyl acetate copolymer 62 and a back sheet 63 is bonded.

FIG. 44 is a cross-sectional view showing another example of a solar cell structure.
The conductor layer 19 is embedded in the resin layer 25 laminated on the support substrate 24 (such as an ethylene-vinyl acetate copolymer sheet or an ethylene tetrafluoroethylene 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 65.
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 55, a p-type amorphous silicon 53, an i-type amorphous silicon 52, and an n-type amorphous silicon 54 are stacked, and a p-type amorphous silicon germanium 66, an i-type amorphous silicon germanium 67, and an n-type A type amorphous silicon germanium 68 is laminated and a metal film 57 (bottom electrode) is further laminated. The transparent conductive film 55 to the metal film 57 are formed on the polyimide film 69 in a certain repeating pattern. I can say that. On the other surface of the polyimide, a back electrode 70 is formed in a specific pattern, and in the through hole 71 from the polyimide film 69 to the transparent conductive film 55 and the through hole 72 from the polyimide film 59 to the metal film 57. The metal is deposited so that the transparent conductive film 55 or the metal film 57 and the back electrode 70 are electrically connected to each other. The solar cell structure 73 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 25 of the base material with the conductor layer pattern is caused to flow so as to seal the layer structure.
The conductor layer 19 functions as an auxiliary electrode that improves the conductivity of the transparent conductive film 55 that is an electrical extraction electrode (upper electrode).
The above structure is a solar cell structure of the type shown in FIG.
The solar cell structure having the above-described configuration can be formed into a solar cell module by being supported by ethylene-vinyl acetate copolymer between ethylene tetrafluoroethylene (ETFE) and ETFE or a galvalume steel plate.

FIG. 45 is a cross-sectional view showing another example of a solar cell structure.
The conductor layer 19 is embedded in the resin layer 25 laminated on the support substrate 24 (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 65.
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 55, a buffer 74, a semiconductor CIGS light absorption layer 75 made of Cu, In, Ga, and Se are stacked, and a patterned molybdenum back electrode 76 is stacked. . A part of the conductor layer 19 becomes an extraction electrode 65 and an extraction electrode 77. The buffer 74 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 75 is obtained by laminating Cu, In, and Ga by sputtering or vapor deposition to form a precursor, annealing the precursor in an H ₂ Se atmosphere, and selenizing. It can be said that a glass plate 78 is laminated on the other surface of the molybdenum back electrode 76. The solar cell structure 79 configured as described above is obtained by pressure-bonding and pasting the base material 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 25 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 76 to the transparent conductive film 55 on the glass plate in the opposite manner as described above. The transparent conductive film 57 is electrically connected to the adjacent molybdenum back electrode 76 through the side surfaces of the CdS buffer 74 and the CIGS light absorption layer 75.
The conductor layer 19 functions as an auxiliary electrode that improves the conductivity of the transparent conductive film 55 that is an electrical extraction electrode (upper electrode).
The above structure is a solar cell structure of the type shown in FIG.
When the support substrate 24 is not a transparent heat resistant substrate such as a glass plate, the solar cell structure having the above-described configuration is most preferably sealed on the support substrate 24 side with a transparent ethylene-vinyl acetate copolymer. A solar cell module can be obtained by laminating a glass plate as an outer layer.

FIG. 46 is a cross-sectional view (schematic diagram) showing another example of the solar cell structure.
A p-type silicon 81 and an n-type silicon 82 are laminated on one side of the single crystal p-type silicon 80, an aluminum electrode 83 is laminated on the p-type silicon 81, and a silver electrode 84 is laminated on the n-type silicon 82, respectively. The aluminum electrode 83 and the silver electrode 84 are conductive. A thin tab line 85 and a thick tab line 86 for current collection are stacked on the silver electrode 84. The silver electrode 84 is a part of an electrical extraction electrode having a current collecting function. The silver electrode 84 on the n-type silicon layer 82 is laminated only at a specific location in order to solder-connect the thin tab wire 85. The entire back surface other than the silver electrode 84 is covered with a laminate of the aluminum electrode 83 and the p-type silicon layer 81. The material of the thin tab wire 85 and the thick tab wire 86 is a copper wire coated with solder. The aluminum electrode 83, the silver electrode 84, the thin tab line 85, and the thick tab line 86 are one current collecting mechanism. On the other side of the single-crystal p-type silicon 80, an n-type silicon 87 containing high-concentration impurities is laminated on the entire surface, and a silicon nitride passivation film 88 and a silver finger electrode 89 are formed on the n-type silicon 87. Are stacked. The silver finger electrode 89 is laminated on the n-type silicon layer 87, and the silicon nitride passivation film 88 covers the entire surface of the n-type silicon 87 other than the silver finger electrode 89. On top of that, the conductor layer (mesh-like copper wiring 90) of the base material with a conductor layer pattern (copper wiring 90 is laminated on the plastic film 92 via the adhesive 91) according to the present invention is a silver finger electrode. It is laminated so as to contact 89. Therefore, the conductor layer functions as an auxiliary electrode. The conductor layer (for example, mesh copper wiring 90) is in contact with the thicker tab wire 93. Since the solar cell can be electrically connected to a discontinuous conductor, the conductor layer has an interconnector function. The mesh copper wiring 90 may be a striped copper wiring. In this case, the wiring is provided in parallel with the paper surface. However, the conductor layer 19 is conductive as a pattern in a direction parallel to the paper surface. In FIG. 46, only the mesh-like copper wiring is drawn in the direction perpendicular to the paper surface. The plastic film 92 may not be present because it does not contribute to the function of the present invention. The plastic film 92 may be peeled off after being sealed with the ethylene-vinyl acetate copolymer after the copper wiring 90 and the pressure-sensitive adhesive 91 are bonded to the electrical extraction surface. Alternatively, the copper wiring 90 and the pressure-sensitive adhesive 91 from which the plastic film 92 has been peeled off in advance may be fixed to the ethylene-vinyl acetate copolymer and then adhered to the electrical extraction surface. The silver finger electrode 89, the copper wiring 90, and the thick tab wire 93 are another current collecting mechanism. The above configuration is sealed with a transparent ethylene-vinyl acetate copolymer 94, and the entire structure is sandwiched between a PET film 95 and a glass plate 96.
The silver finger electrode 89 is an electrical extraction electrode, and the copper wiring 90 as a conductor layer functions as an auxiliary electrode or a composite of the auxiliary electrode and the interconnector.

  FIG. 47 is a cross-sectional view (schematic diagram) showing a reference example of a solar cell structure. The configuration is the same as that of FIG. 47, but thin tab lines 97 are used instead of the copper wiring 90 (accordingly, the substrate with the conductor layer pattern) in FIG. The material of the thin tab wire 97 is a copper wire coated with solder.

48 to 53 show other examples of the solar cell structure according to the present invention.
In FIG. 48, p-type silicon 81 containing high-concentration impurities is laminated on almost the entire surface on one side of single-crystal p-type silicon 80, and n-type silicon is also present at a specific portion on the same surface (not shown). ). An aluminum electrode 83 is stacked on the entire surface of the p-type silicon 81. An Ag electrode is laminated on the n-type silicon (not shown), and a thin tab line 85 is laminated on the Ag electrode. The aluminum electrode 83 is an electrical extraction electrode having a current collecting function, the thin tab wire 85 is an interconnector, and they are one current collecting mechanism. On the other side of the single crystal p-type silicon 80, an n-type silicon 87 is laminated on the entire surface, and on the n-type silicon 87, a silicon nitride passivation film 88 and a silver finger electrode 89 are laminated. The silver finger electrode 89 is laminated on the n-type silicon layer 87, and the silicon nitride passivation film 88 covers the entire surface of the n-type silicon 87 other than the silver finger electrode 89. On top of that, the conductor layer (mesh-like copper wiring 90) of the base material with the conductor layer pattern according to the present invention (the copper wiring 90 is embedded and carried in the adhesive layer 91) contacts the silver finger electrode 89. It is laminated so that. Therefore, the conductor layer functions as an auxiliary electrode. The conductor layer (for example, the mesh-like copper wiring 90) and the adhesive layer 91 are laminated so as to protrude from the electric extraction surface, but the protruding conductor layer serves as a thin tab line. Since the solar cell can be electrically connected to a discontinuous conductor, the conductor layer has an interconnector function. The mesh copper wiring 90 may be a striped copper wiring. In this case, the wiring is provided in parallel with the paper surface. In FIG. 48, only the mesh-like copper wiring is drawn in a direction perpendicular to the paper surface. The base material with the conductor layer pattern does not have a support base material such as a plastic film, but the support base material has an ethylene-vinyl acetate copolymer after the copper wiring 90 and the adhesive 91 are bonded to the electrical extraction surface. The copper wiring 90 and the pressure-sensitive adhesive 91, which have been peeled off before being sealed with or previously peeled off the supporting base material, are fixed to the ethylene-vinyl acetate copolymer and then adhered to the electrical extraction surface. The silver finger electrode 89 and the copper wiring 90 are another current collecting mechanism. The above configuration is sealed with a transparent ethylene-vinyl acetate copolymer 94, and the entire structure is sandwiched between a PET film 95 and a glass plate 96.
The silver finger electrode 89 is an electrical extraction electrode, and the copper wiring 90 as a conductor layer functions as an auxiliary electrode or a composite of the auxiliary electrode and the interconnector.

In FIG. 49, a p-type silicon 81 containing high-concentration impurities is laminated on the entire surface on one side of a single crystal p-type silicon 80, and an aluminum electrode 83 is laminated on the entire surface of the p-type silicon 81, and an electric extraction electrode A substrate with a conductor layer pattern according to the present invention (copper wiring 90 is embedded and carried in the adhesive layer 91) as an auxiliary electrode (back electrode) on the aluminum electrode 83 is a conductor layer (mesh copper). The wiring 90) is laminated so as to contact the aluminum electrode 83. This is a current collecting mechanism of one of the aluminum electrode 83 and the conductor layer (mesh-like copper wiring 90). Note that n-type silicon may partially exist in the plane in parallel with the p-type silicon, and an Ag electrode may be formed on the n-type silicon layer. The conductor layer (for example, the mesh-like copper wiring 90) and the adhesive layer 91 are laminated so as to protrude from the electric extraction surface, but the protruding conductor layer serves as a thin tab line. Since it can conduct | electrically_connect through the conductor layer to the conductor which is not continuous with the photovoltaic cell, a conductor layer has an interconnector function. The mesh copper wiring 90 may be a striped copper wiring. In this case, the wiring is provided in parallel with the paper surface. However, the conductor layer 19 is conductive as a pattern. In FIG. 48, only the mesh-like copper wiring is drawn in a direction perpendicular to the paper surface. The base material with the conductor layer pattern does not have a support base material such as a plastic film, but the support base material has an ethylene-vinyl acetate copolymer after the copper wiring 90 and the adhesive 91 are bonded to the electrical extraction surface. The copper wiring 90 and the pressure-sensitive adhesive 91, which have been peeled off before being sealed with or previously peeled off the supporting base material, are fixed to the ethylene-vinyl acetate copolymer and then adhered to the electrical extraction surface.
On the other side of the single crystal p-type silicon 80, an n-type silicon 87 is laminated on the entire surface, and on the n-type silicon 87, a silicon nitride passivation film 88 and a silver finger electrode 89 are laminated. The silver finger electrode 89 is laminated on the n-type silicon layer 87, and the silicon nitride passivation film 88 covers the entire surface of the n-type silicon 87 other than the silver finger electrode 89. A thin tab wire 85 is laminated on the silver finger electrode 89. The silver finger electrode 89 is an electric extraction electrode having a current collecting function, the thin tab wire 85 is an interconnector, and they are one current collecting mechanism.
The above configuration is sealed with a transparent ethylene-vinyl acetate copolymer 94, and the entire structure is sandwiched between a PET film 95 and a glass plate 96.

In FIG. 50, a p-type silicon 81 and an n-type silicon 82 are stacked on one side of a single crystal p-type silicon 80. The p-type silicon 81 has an aluminum electrode 83 and a n-type silicon 82 has a silver electrode 84. The aluminum electrode 83 and the silver electrode 84 are respectively laminated and are electrically connected. A thin tab line 85 as an interconnector is laminated on the silver electrode 84. The entire back surface other than the silver electrode 84 is covered with a laminate of the aluminum electrode 83 and the p-type silicon layer 81. The aluminum electrode 83 is an electrical extraction electrode having a current collecting function, the tab wire 85 is an interconnector, and these are one current collecting mechanism.
On the other side of the single crystal p-type silicon 80, an n-type silicon 87 is laminated on the entire surface, and on the n-type silicon 87, a silver finger electrode 89 as an electric extraction electrode (upper electrode) is laminated. ing. And on this silver finger electrode 89, the base material with the conductor layer pattern (copper wiring 90 is formed in a strip shape) according to the present invention including the thin tab wire 85 as the interconnector and the copper wiring 90 as the auxiliary electrode. And embedded in the adhesive 91) are alternately stacked. The silver finger electrode 89, the thin tab wire 85, and the copper wiring 90 form one current collecting mechanism.
The above configuration is sealed with a transparent ethylene-vinyl acetate copolymer 94, and the entire structure is sandwiched between a PET film 95 and a glass plate 96.
The conductor layer (mesh copper wiring 90) may be a striped copper wiring. In this case, the wiring is provided in a direction perpendicular to the paper surface. In FIG. 50, only the mesh-like copper wiring is drawn in a direction perpendicular to the paper surface. The above-mentioned base material with a conductor layer pattern does not have a support base material for the same reason as in FIG.

51, the structure is the same as that of FIG. 50 except that n-type silicon 87 is laminated on the other side of single-crystal p-type silicon 80, and silver fingers are placed on n-type silicon 87. An electrode 89 is stacked. And the base material with a conductor layer pattern (copper wiring 90 is embedded and carried in the adhesive 91) according to the present invention is formed on the entire surface of the electrical extraction surface from above the silver finger electrode 89 and is partially adhered. The agent layer 91 is not present, and the conductor layer 90 is exposed. A thin tab line 85 is formed on the exposed conductor layer 90. In the process, first, a base material with a conductor layer pattern according to the present invention (copper wiring 90 is embedded and carried in an adhesive 91) is laminated on the entire surface of the electrical extraction surface, and the adhesive is strip-shaped in advance. It can be performed by making a notch, laminating and bonding, peeling off the adhesive layer in a strip shape, and laminating the tab wire on the exposed conductor layer. Also, instead of this step, as a substrate with a conductor layer pattern, a conductor layer is formed on the conductive substrate for plating, and the substrate with the conductor layer pattern is produced by transferring the conductor layer pattern to the substrate for transfer. When using a substrate with a conductor layer pattern obtained by using a substrate material on which a pressure-sensitive adhesive layer is not partially formed as a substrate for transfer, this substrate with a conductor layer pattern is silver It can also be formed by a process in which the substrate material with a conductor layer pattern is attached to the electrical extraction surface from above the finger electrode, and then the tab wire is laminated on the exposed conductor layer. .
The exposed conductor layer and the tab wire can be connected by a general connection method such as solder connection or connection through conductive particles.
The silver finger electrode 89 is an electric extraction electrode having a current collecting function, the thin tab wire 85 is an interconnector, the conductor layer 90 is an auxiliary electrode and an interconnector, and these are one current collecting mechanism.
The above configuration is sealed with a transparent ethylene-vinyl acetate copolymer 94, and the entire structure is sandwiched between a PET film 95 and a glass plate 96.
The conductor layer (mesh copper wiring 90) may be a striped copper wiring. In this case, the wiring is provided in a direction perpendicular to the paper surface. In FIG. 50, only the mesh-like copper wiring is drawn in a direction perpendicular to the paper surface. The above-mentioned base material with a conductor layer pattern does not have a support base material for the same reason as in FIG.

FIG. 52 shows a back contact solar cell structure.
A silicon nitride passivation film 88 is formed on one surface of the single crystal p-type silicon 80, and layers of high-concentration impurity-containing p-type silicon 81 and n-type silicon 87 are formed on the opposite surface. It is formed so as to be embedded in. Then, a + electrode 98 is laminated on the p-type silicon 81, a-electrode 99 is laminated on the n-type silicon 87, and a silicon nitride passivation film is formed on portions other than these electrodes. And the base material with a conductor layer pattern based on this invention (The copper wiring 90 is embed | buried and carried in the adhesive 91) is laminated | stacked so that a conductor layer may overlap with these electrodes. The copper wiring 90 functions as a current collecting electrode and an interconnector, but is configured so that the contact with the + electrode 98 and the contact with the − electrode 99 do not conduct.
The above configuration is sealed with a transparent ethylene-vinyl acetate copolymer 94, and the entire structure is sandwiched between a PET film 95 and a glass plate 96.

In FIG. 53, a metal film such as Mo is laminated by sputtering or the like, and a pattern is formed in which a groove is formed and a certain pattern is formed by appropriate etching using laser, mechanical polishing of a hard material needle or the like. The molybdenum back electrode 76 thus formed is formed on one glass plate 78. A CIGS light absorption layer of a semiconductor is formed on the molybdenum back electrode 76 so as to be in contact with one side surface of the molybdenum back electrode 76 in a specific pattern, and a layer of Cds 100 is formed so as to overlap therewith. Further, an n-type zinc oxide 101 and a doped zinc oxide 102 are sequentially formed thereon, and these are sequentially formed so as to cover one side surface of the lower layer, and the doped zinc oxide 102 has a pattern of an adjacent similar layer structure. The conductive molybdenum back electrode 76 is electrically connected and directly connected. In the drawing, such repetition is shown only twice, but is repeated an appropriate number in the right direction. A substrate with a conductor layer pattern according to the present invention (the conductor layer 19 is embedded and carried in the adhesive 20) is laminated on each of the above layer structures. The copper wiring 90 is in contact with the top doped zinc oxide 102 of each layer structure. This conductor layer 19 is a strip-like conductor layer in the horizontal direction and arranged in a direction perpendicular to the paper surface. In this case, the conductor layers are not electrically connected to each other. However, the conductor layers may be electrically connected to each other. Further, the conductor layer 19 may be formed up to the adjacent Mo electrode 76 (right hand on the paper surface). These conductor layers function as auxiliary electrodes that increase the conductivity of the doped zinc oxide 102. Further, the repetitive portion of each layer structure is covered with the adhesive 20 except for the portion covered with the conductor layer 19. For this purpose, when laminating the base material with a conductor layer pattern, pressure is applied to cause the adhesive 20 to flow. After the adhesive 20 covers each layer structure together with the conductor layer 19, the adhesive 20 is solidified or cured. As this pressure-sensitive adhesive, it is preferable to use a photocurable resin because it does not need to be heated at the time of curing.
Thereafter, the top is further sealed with a transparent ethylene-vinyl acetate copolymer 94, and another glass plate 78 is bonded.

  In the present invention, the conductive layer pattern of the substrate with the conductive layer pattern is connected to the solar cell element having the electrical extraction electrode (metal electrode or transparent conductive film) on the surface thereof, thereby connecting the electrical layer generated in the photoelectric conversion layer. The collector electrode function, the interconnect function, and the auxiliary electrode function can be exhibited. For example, in the case of a solar cell having a transparent conductive film on the surface, the conductive pattern is brought into contact with and connected to the transparent conductive film. Current can be collected with low loss. Therefore, in a crystalline Si solar cell in which an Ag electrode is laminated on a transparent conductive film, an Ag electrode that is normally used as a current collecting electrode can be omitted. Moreover, in a thin film Si solar cell or a CIGS thin film solar cell, efficiency can be improved in order to suppress power loss that increases with the cell width. Furthermore, the conductor layer pattern can easily have a wiring function, and if a conductor layer pattern having a wiring function is used, no additional 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. In a thin-film Si solar cell or a CIGS thin-film solar cell, the formation of an electrical extraction electrode formed at the end of the module can be omitted. Thus, since the conductor layer pattern is used for the current collecting electrode, the interconnector or the auxiliary electrode of the solar cell, the material cost thereof is reduced. Furthermore, since the necessary conductor layer pattern can be supplied simply by pasting the base material with the conductor layer pattern of the present invention, for example, it becomes easy to form the collector electrode, interconnector and auxiliary electrode of the solar cell, and the cost is greatly increased. Can be reduced.

  In order to continue connecting the conductor layer pattern to the electrical extraction surface, it is necessary to maintain the mechanical contact between the conductive layer pattern and the electrode on the electrical extraction surface or the interconnector. Force must continue to be applied in the direction of pressing against the interconnector. 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. By laminating the substrate with the conductor layer pattern of the present invention and the solar cell element, the conductor layer pattern and the electrode and the interconnector on the electric extraction surface of the solar cell element can be contacted and connected, As a result, the conductor layer pattern can be supplied to show the function as a current collecting electrode, auxiliary electrode, or interconnector, and stability for 1000 hours or more can also be 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.
Using a rotating body, while continuously peeling the pattern formed by electroplating, rotating the drum electrode when using the drum electrode as the conductive substrate and the process of obtaining the substrate with the conductor layer pattern as a scroll In addition, a method and an apparatus described in International Publication WO2008 / 081904 can be used as an apparatus for continuously depositing metal by electroplating and continuously peeling the deposited metal.

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 having relatively low plating adhesion, such as stainless steel, chrome-plated cast iron, chrome-plated steel, titanium, or titanium-lined material. It is preferable. When a hoop-like conductive base material is used, the process of blackening treatment, rust prevention treatment, transfer, etc. can be processed in one continuous process, so the productivity of the base material with a conductive pattern is high. Moreover, the base material with an electroconductive pattern can be produced continuously, and it can be set as a product as a scroll. The thickness of the hoop-like conductive substrate may be determined as appropriate, but is preferably 100 to 1000 μm.
Using a hoop-like conductive base material, a conductor layer pattern formed by electroplating was continuously peeled off, and a structure was obtained as a scroll, and a hoop-like conductive base material was used as the conductive base material. In some cases, a method and an apparatus described in International Publication WO2008 / 081904 can be used as an apparatus for continuously peeling a conductor layer pattern while depositing it by electroplating.

(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, an adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface (back surface) where the pattern of the conductive substrate for plating obtained above was not formed. 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 Immerse it in 4 ml / L aqueous solution (30 ° C.) with light AR (supplied by Ebara Eugene Light Co., Ltd.), apply voltage to both electrodes to set the current density to 10 A / dm ² , and place it on the concave portion of the conductive substrate for plating. 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, copper 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 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.

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. 10 ml of a liquid useless UV curable resin (trade name: Adekaoptomer KRX-400, manufactured by Asahi Denka Co., Ltd.) was dropped onto the surface of the conductive base material subjected to copper plating. 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.

  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). Arbitrary five points are selected, and the cross-sectional shape of the conductor layer pattern is as shown in FIG. 6B, 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. 9C, 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. 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.

  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.
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 is cut out, and the cross section is taken on a scanning electron micrograph (magnification 2000 times) and observed. 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 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 50 μm thick PET film with an easy-adhesive layer (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). The substrate (I) is a substrate with a pressure-sensitive adhesive layer, and corresponds to the support substrate 21 of FIG.

<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. 20 (a)), and a glass plate [base on the holding resin layer surface of the obtained laminate ((corresponding to FIG. 20 (b))). Material (III)] (corresponding to FIG. 20 (c)). 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 a holding resin layer was obtained (corresponding to FIG. 20D).
<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). Arbitrary five points are selected, and the cross-sectional shape of the metal wiring layer is as shown in FIG. 4B. 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. 7C, it is confirmed that the width L1 of the upper base of the metal wiring layer is exposed by 15 to 17 μm, and the entire metal wiring layer is embedded in the holding 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 Solder connection was performed using a soldering iron with a thick tab wire (A). The substrate with the conductor layer pattern obtained in Example 8 is attached 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. Combined. 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 series resistance was measured by measuring electric resistance as a characteristic after the high temperature and high humidity test. For the measurement, a 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 a digital multimeter AD7461A manufactured by ADVANTEST. 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 Solder connection was performed using a soldering iron with a thick tab wire (A). 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.

  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.

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。

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).

<Preparation of conductive substrate for plating>
First, a conductive substrate for plating was produced.
(Pattern specification 1)
A negative film for pattern formation was produced with the following specifications. The light transmission part has a line width of 9 μm, a line pitch of 250 μm, and a bias angle of 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 9 to 11 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 (c) of FIG. 11 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 9-11 micrometers, and the width | variety (maximum width) in an opening part was 13-16 micrometers. The line pitch of the recesses was 250 μm.

<Formation of conductor layer pattern>
(Copper plating)
Furthermore, an adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface (back surface) where the pattern of the conductive substrate for plating obtained above was not formed. 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 Immerse it in 4 ml / L aqueous solution (30 ° C.) with light AR (supplied by Ebara Eugene Light Co., Ltd.), apply voltage to both electrodes to set the current density to 10 A / dm ² , and place it on the concave portion of the conductive substrate for plating. 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 transfer 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 1 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 3 μm. A pressure-sensitive adhesive layer was formed thereon to produce a transfer substrate. The drying condition was 100 ° C. for 10 minutes.

<Transfer of conductor layer pattern>
Next, the surface of the pressure-sensitive adhesive layer of the transfer substrate and the surface of the conductive substrate for plating that had been subjected to copper plating were bonded using a roll laminator (corresponding to FIG. 14G). 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 transfer substrate bonded to the conductive substrate for plating was peeled off, the copper deposited on the conductive substrate for plating was transferred to the adhesive layer of the transfer substrate (FIG. 14). Corresponding to (h)).

<Preparation of holding substrate>
A holding substrate in which a pressure-sensitive adhesive layer having a thickness of 25 μm and having a double-sided adhesive film (Hitalex DA3025, manufactured by Hitachi Chemical Co., Ltd.) is peeled off and the adhesive layer is formed on the separator film Obtained.

<Preparation of substrate with conductor layer pattern>
(Transfer to holding substrate)
Preparation was made so that the adhesive layer of the holding substrate and the transfer substrate having the pattern of the conductor layer were in contact with each other (corresponding to FIG. 29A). Bonding was performed under lamination conditions of a roll temperature of 30 ° C., a pressure of 0.3 MPa, and a line speed of 1.0 m / min to obtain a laminate. Next, the laminate was irradiated with ultraviolet rays of 1000 mJ / cm ² to promote curing of the pressure-sensitive adhesive layer of the transfer base material, thereby reducing the pressure-sensitive adhesive layer (corresponding to FIG. 29B).
(Replacement of support substrate)
Thereafter, the separator film of the holding substrate incorporated in the laminate is peeled off, and a roll temperature of 100 ° C., a pressure of 0.3 MPa, a line speed of 1 is applied to the glass plate so that the exposed pressure-sensitive adhesive layer is in contact. Bonding was performed under a lamination condition of 0.0 m / min (corresponding to FIG. 35).
(Preparation of a substrate with a conductor layer pattern in which the conductor layer is exposed)
Next, when the transfer substrate (the adhesive layer cured by irradiating ultraviolet rays and the support substrate) was peeled off, the conductive pattern was transferred to the pressure-sensitive adhesive layer formed on the glass, A substrate with a conductor layer pattern (corresponding to FIG. 34) was obtained.

  A part of the obtained base material with a conductor layer pattern 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. 5A, the upper layer thickness T2 is 2 to 4 μm, the lower layer thickness T1 is 2 to 3 μm, and the overall thickness. T is 4 to 6 μm, maximum width L is 15 to 18 μm, lower upper base width L1 is 9 to 11 μm, lower base width L2 is 13 to 16 μm, and the upper layer has a relatively large curvature at both ends of the cross section. The curvature of the curvature at the center of the cross section of the upper layer was very small, almost flat, and the angle α was 45 °. The line pitch of the conductor layer pattern was 250 μm. It confirmed that the base material with a conductor layer pattern which consists of a grid-like metal pattern of such a conductor layer was obtained. In addition, the surface of the central portion of the cross section of the upper layer of the conductor layer and the surfaces of the curved portions at both ends were exposed. The maximum thickness (f) of the portion where the conductor layer pattern was embedded in the resin layer was 3 to 5 μm, and the maximum width portion of the conductor layer pattern was embedded. The ratio (f / T) of d to the thickness (T) of the entire conductor layer pattern was 0.50 to 1.0. The ratio (T2 / L) of the upper layer thickness T2 to the maximum width L of the conductor layer pattern was 0.11 to 0.27.

  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).

(Repeated use)
Using the conductive substrate for plating described above, the copper plating-transfer process was repeated 100 times in the same manner as described above. As a result, there was no change in the precipitation and transferability of the copper plating, and the peeling portion of the insulating layer was also observed. Was not. Moreover, the electroconductive base material for plating was cut off after 100 times of use, and the surface shape of the insulating layer (DLC layer) was observed with an electron microscope, but no change was observed in the shape.

  The same procedure as in Example 10 was performed until <Preparation of conductive substrate for plating>.

<Formation of conductor layer pattern>
(Copper plating)
Furthermore, an adhesive film (Hitalex K-3940B, manufactured by Hitachi Chemical Co., Ltd.) was attached to the surface (back surface) where the pattern of the conductive substrate for plating obtained above was not formed. 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.

<Preparation of transfer substrate> was carried out in the same manner as in Example 1 except that the film thickness after drying at 100 ° C. of the resin composition was 15 μm.
<Transfer of pattern of conductor layer>, <Preparation of substrate for holding> and <Preparation of substrate with conductor layer pattern> were carried out in the same manner as in Example 1.

  A portion of the substrate with the conductor layer pattern 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. 5A, the upper layer thickness T2 is 2 to 4 μm, the lower layer thickness T1 is 2 to 3 μm, and the overall thickness T Is 4 to 6 μm, the maximum width L is 15 to 18 μm, the lower base width L1 is 9 to 11 μm, the lower base width L2 is 13 to 16 μm, and there is a relatively large curvature at both ends of the upper layer cross section. The curvature of the curvature at the center of the cross section of the upper layer was very small, almost flat, and the angle α was 45 °. The line pitch of the conductor layer pattern was 250 μm. It confirmed that the base material with a conductor layer pattern which consists of a grid-like metal pattern of such a conductor layer was obtained. In addition, the surface of the central portion of the cross section of the upper layer of the conductor layer and the surfaces of the curved portions at both ends were exposed. The maximum thickness (f) of the portion where the conductor layer pattern was embedded in the resin layer was 2 to 4 μm, and the maximum width portion of the conductor layer pattern was embedded. The ratio (f / T) to the thickness (T) of the entire conductor layer pattern of f was 0.30 to 1.0. The ratio (T2 / L) of the upper layer thickness T2 to the maximum width L of the conductor layer pattern was 0.11 to 0.27.

<Implantation treatment>
A separator film was bonded onto a conductor layer pattern with a conductor layer pattern under a laminating condition of a roll temperature of 100 ° C., a pressure of 0.5 MPa, and a line speed of 0.1 m / min. Next, when the separator film was peeled off, the flat portion of the upper layer of the conductor layer pattern was exposed. The maximum thickness (f) of the portion where the conductor layer pattern was embedded in the resin layer was 3 to 6 μm, and the maximum width portion of the conductor layer pattern was embedded. The ratio (f / T) to the thickness (T) of the entire conductor layer pattern of f was 0.50 to 1.0.

  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).

  From <Preparation of electroconductive substrate for plating> to <Formation of conductor layer pattern> (copper plating), <Preparation of substrate for transfer> and <Transfer of pattern of conductor layer> were carried out in the same manner as in Example 10.

<Preparation of substrate with conductor layer pattern>
(Preparation of holding substrate and transfer to holding substrate)
On the surface of the base material for transfer having the above-mentioned conductor layer pattern obtained above, the liquid non-solvent UV curable resin (trade name: Adekaoptomer KRX-400, Asahi Denka Co., Ltd.) was dropped 10 ml with a width of 100 mm. 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. As a result, the resin spread uniformly, and a liquid UV curable resin layer of 25 μm was formed between the transfer substrate having the conductor layer pattern and the PET film. Then, after curing the pressure-sensitive adhesive layer by irradiating ultraviolet rays from the PET film side so that the irradiation amount is 1000 mJ / cm ² , the transfer substrate was peeled off, and the pattern of the conductor layer was formed on the PET film. The four formed were transferred to the line-of-sight curable resin layer to obtain a substrate with a conductor layer pattern.

  A portion of the substrate with the conductor layer pattern 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. 5A, the upper layer thickness T2 is 2 to 4 μm, the lower layer thickness T1 is 2 to 3 μm, and the overall thickness T Is 4 to 6 μm, the maximum width L is 15 to 18 μm, the lower base width L1 is 9 to 11 μm, the lower base width L2 is 13 to 16 μm, and there is a relatively large curvature at both ends of the upper layer cross section. The curvature of the curved portion at the center of the cross section of the upper layer was very small, almost flat, and the angle α was 45 °. The line pitch of the conductor layer pattern was 250 μm. It confirmed that the base material with a conductor layer pattern which consists of such a grid-like metal pattern was obtained. In addition, the surface of the central portion of the cross section of the upper layer of the conductor layer and the surfaces of the curved portions at both ends were exposed. The maximum thickness (f) of the portion where the conductor layer pattern was embedded in the resin layer was 3 to 5 μm, and the maximum width portion of the conductor layer pattern was embedded. The ratio (f / T) to the thickness (T) of the entire conductor layer pattern of f was 0.50 to 1.0. The ratio (T2 / L) of the upper layer thickness T2 to the maximum width L of the conductor layer pattern was 0.11 to 0.27.

  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).

  Copper plating was performed on the electroconductive substrate for plating in the same manner as in Example 10 except that the electroconductive substrate for plating of Example 1 was plated until the plating thickness became approximately 14 μm. Preparation> was performed. Thereafter, <production of transfer substrate> and <transfer of conductor layer pattern> were carried out in the same manner as in Example 10.

<Preparation of holding substrate>
A separator film on 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 is peeled off, and is applied to a PET film (125 μm thickness, A-4100, manufactured by Toyobo Co., Ltd.). Pasted together. Lamination conditions were a roll temperature of 100 ° C., a pressure of 0.3 MPa, and a line speed of 1.0 m / min. Then, the separator film was peeled from the other surface of the pressure-sensitive adhesive layer formed on the PET film to obtain a holding substrate having a pressure-sensitive adhesive layer exposed on the PET film.

<Preparation of substrate with conductor layer pattern>
(Transfer to holding substrate)
Preparation was made so that the adhesive layer of the holding substrate and the transfer substrate having the conductor layer pattern obtained above were in contact with each other (corresponding to FIG. 31A). Bonding was performed under a roll temperature of 30 ° C., a pressure of 0.3 MPa, and a line speed of 1.0 m / min, thereby obtaining a laminate. Next, the laminate was irradiated with ultraviolet rays of 1000 mJ / cm ² to promote curing of the pressure-sensitive adhesive layer of the substrate for transfer, thereby reducing the pressure-sensitive adhesive property (corresponding to FIG. 29B).
(Preparation of a substrate with a conductor layer pattern in which the conductor layer is exposed)
Next, when the transfer substrate (the adhesive layer cured by irradiating ultraviolet rays and the supporting substrate) was peeled off, the pattern of the conductor layer was transferred to the pressure-sensitive adhesive layer formed on PET. A substrate with a conductor layer pattern was obtained.

  A part of the obtained base material with a conductor layer pattern 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. 5A, the upper layer thickness T2 is 9 to 12 μm, the lower layer thickness T1 is 2 to 3 μm, and the overall thickness is 12-14 [mu] m, maximum width L is 26-30 [mu] m, lower upper base width L1 is 9-11 [mu] m, lower base width L2 is 13-16 [mu] m, and there is a relatively large curvature at both ends of the upper layer cross section, The curvature of the curved portion at the center of the cross section of the upper layer was very small, almost flat, and the angle α was 45 °. The line pitch of the conductor layer pattern was 250 μm. It confirmed that the base material with a conductor layer pattern which consists of a grid-like metal pattern of such a conductor layer was obtained. In addition, the surface of the central portion of the cross section of the upper layer of the conductor layer and the surfaces of the curved portions at both ends were exposed. The maximum thickness (f) of the portion where the conductor layer pattern was embedded in the resin layer was 10 to 13 μm, and the portion of the maximum width of the conductor layer pattern was embedded. The ratio (f / T) to the thickness (T) of the entire conductor layer pattern of f was 0.70 to 1.0. The ratio (T2 / L) of the thickness T2 of the upper layer to the maximum width L of the conductor layer pattern was 0.30 to 0.46.

  The surface resistance of the obtained base material with a conductor layer pattern was 0.02Ω / □. 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).

<Preparation of conductive substrate for plating> was performed in the same manner as in Example 13. Thereafter, <preparation of transfer substrate>, <transfer of conductor layer pattern>, <preparation of holding substrate>, and <preparation of substrate with conductor layer pattern> were carried out in the same manner as in Example 10.
<Preparation of substrate with conductor layer pattern>
First, (transfer to holding substrate) was performed in the same manner as in Example 1.
(Replacement of support substrate)
Thereafter, the separator film of the holding substrate incorporated in the laminate is peeled off, and the exposed pressure-sensitive adhesive layer is brought into contact with an ethylene vinyl acetate copolymer resin sheet (Solar EVA SC50B, manufactured by Mitsui Chemicals, Inc.). I let you. These were sandwiched between two release PETs (E-7002 (manufactured by Toyobo Co., Ltd.)) and heated and pressurized at 0.1 MPa and 120 ° C. for 4 minutes by a vacuum pressure laminator (corresponding to FIG. 35).
(Preparation of a substrate with a conductor layer pattern in which the conductor layer is exposed)
Next, when the transfer substrate (UV-cured adhesive layer and support substrate) was peeled off, the conductive pattern was transferred to the pressure-sensitive adhesive layer formed on the ethylene vinyl acetate copolymer resin sheet. Thus, a substrate with a conductor layer pattern (corresponding to FIG. 34) was obtained.

  A part of the obtained base material with a conductor layer pattern 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. 5A, the upper layer thickness T2 is 9 to 12 μm, the lower layer thickness T1 is 2 to 3 μm, and the overall thickness is 12-14 [mu] m, maximum width L is 26-30 [mu] m, lower upper base width L1 is 9-11 [mu] m, lower base width L2 is 13-16 [mu] m, and there is a relatively large curvature at both ends of the upper layer cross section, The curvature of the curved portion at the center of the cross section of the upper layer was very small, almost flat, and the angle α was 45 °. The line pitch of the conductor layer pattern was 250 μm. It confirmed that the base material with a conductor layer pattern which consists of a grid-like metal pattern of such a conductor layer was obtained. In addition, the surface of the central portion of the cross section of the upper layer of the conductor layer and the surfaces of the curved portions at both ends were exposed. The maximum thickness (f) of the portion where the conductor layer pattern was embedded in the resin layer was 10 to 13 μm, and the portion of the maximum width of the conductor layer pattern was embedded. The ratio (f / T) to the thickness (T) of the entire conductor layer pattern of f was 0.70 to 1.0. The ratio (T2 / L) of the thickness T2 of the upper layer to the maximum width L of the conductor layer pattern was 0.30 to 0.46.

  The surface resistance of the obtained base material with a conductor layer pattern was 0.02Ω / □. 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).

<Production of solar cell>
The solar cell shown in FIG. 46 was produced.
Solar cell (manufactured by Shot Co., Ltd., single crystal Si solar cell: In FIG. 46, p-type silicon 81 and n-type silicon 82 are laminated on one side of single-crystal p-type silicon 80, and p-type silicon 81 A silver electrode 84 is laminated on each of the aluminum electrode 83 and the n-type silicon 82, and a high-concentration impurity-containing n-type silicon 87 is laminated on the other side of the single crystal p-type silicon 80. A silicon nitride passivation film 88 and a silver finger electrode 89 are laminated on the type silicon 87). Two thin tab wires 85 were soldered to the silver electrode 84 on the back surface using a soldering iron, and one thick tab wire 86 was soldered to the two thin tab wires 85. The conductor layer (copper wiring) 90 and the silver finger electrode 89 on the electric extraction surface of the solar cell element are brought into contact with the surface (light-receiving surface) of the solar battery cell with the base material with the conductor layer pattern obtained in Example 4 above. Pasted together. The lamination was carried out using a vacuum pressure laminator with a laminating temperature of 150 ° C., a pressure of 0.1 MPa, a vacuuming time of 2 minutes, and a pressure holding time of 5 minutes. At the time of this bonding, one thick tab line 93 was simultaneously bonded to the surface on which the conductor layer 90 of the substrate with the conductor layer pattern was formed. The end of the solar cell (the end of the single crystal p-type silicon 80) and the thick tab wire 93 were placed 5 mm apart. The conductor layer 90 of the substrate with the conductor layer pattern is connected to the thick tab line 93, but is not connected to the thick tab line 86.
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 cell and the center of the glass were placed in alignment with each other, and a thick tab line 86 and a thick tab line 93 were placed 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 by a vacuum pressurization laminator to produce a solar cell shown in FIG.

<High temperature and high humidity test>
First, the IV characteristic between the tab wire 86 and the tab wire 93 of the solar cell obtained above was measured using a solar simulator. With the fill factor (FF) as one of the performances as the surface electrode of the conductor layer pattern, the solar cell was measured before and after storage at 85 ° C. and 85% RH for 1000 hours.

  The FF (referred to as “FF of initial value”) measured before storing the solar cell at 85 ° C. and 85% RH was 0.693. After the solar cell was stored at 85 ° C. and 85% RH for 1000 hr, the solar cell was taken out and further stored at 25 ° C. and 60% RH for 12 hours, and then the IV characteristics of the solar cell were measured using a solar simulator. The FF at this time (hereinafter referred to as “1000 hr FF”) was 0.684, which was 98.7% with respect to the initial value FF.

<Temperature cycle test>
Next, the IV characteristic between the tab wire 86 and the tab wire 93 of the solar cell obtained in the same manner as described above was measured using a solar simulator. This solar cell is a process of raising the temperature from -40 ° C to 100 ° C in 10 minutes after 30 minutes at -40 ° C, and lowering the temperature from 100 ° C to -40 ° C in 10 minutes after 30 minutes at 100 ° C. The sample was subjected to a temperature cycle test (using a temperature cycle tester) for one cycle. After the temperature cycle test, the IV characteristics of the solar cell were measured and compared with those before storage.

  The initial value FF of the solar cell was 0.696. This solar cell was stored in the above temperature cycle tester, taken out after 100 cycles, and further stored at 25 ° C. and 60% RH for 12 hours, and then the IV characteristics were measured. The FF at this time (hereinafter referred to as “100-cycle FF”) was 0.693, which was 99.5% of the initial FF. Further, another 100 cycles were stored in a temperature cycle tester and the same measurement was performed. The FF at this time (hereinafter referred to as “200-cycle FF”) was 0.682, which was 98.0% of the initial FF.

  The FF is a characteristic that is strongly influenced by the series resistance and parallel resistance inside the solar cell. For example, if the connection resistance between the conductor layer pattern and the finger electrode is increased, the series resistance increases and the FF decreases. Therefore, it turned out that the conductor layer pattern of this invention maintains favorable connection with the conductor layer of the solar cell surface.

Comparative Example 2
<Production of solar cell>
The solar cell shown in FIG. 47 was produced.
A solar battery cell (manufactured by Shot Co., Ltd., single crystal Si solar battery cell: the same as in Example 15) was used. Two thin tab wires 83 were soldered to the silver electrode 82 on the back surface using a soldering iron, and one thick tab wire 84 (A) was soldered to the two thin tab wires 83. Two thin tab wires 83 are soldered to the surface (light-receiving surface) of the solar battery cell using a soldering iron, and one thick tab wire 84 (B) is soldered to the two thin tab wires. Used for solder connection.
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 obtain the solar cell shown in FIG.
<High temperature and high humidity test>
The same procedure as in Example 15 was performed. The initial value FF was 0.725. The FF of 1000 hr was 0.717, which was 98.9% with respect to the initial value FF.

<Preparation of conductive substrate for plating>
First, a conductive substrate for plating was produced.
(Pattern specification 2)
A negative film for pattern formation was produced with the following specifications. A light transmission portion having a line width of 400 μm, a line pitch of 200 μm, and a pattern composed of a finger electrode pattern and an approximately T-shaped interconnector portion was formed in a size of 200 mm square.
Next, in the same manner as in Example 10, (formation of convex pattern), (formation of insulating layer), (formation of concave portion; removal of convex pattern with an insulating layer attached) were performed.

  Except that the conductive substrate for plating was plated until the plating thickness became 20 μm, copper plating was applied on the conductive substrate for plating in the same manner as in Example 10, and <formation of conductor layer pattern> was performed. It was. Thereafter, <preparation of transfer substrate> was carried out in the same manner as in Example 10 except that the resin composition was coated so that the film thickness after drying at 100 ° C. was 10 μm. Further, <transfer of the pattern of the conductor layer> was performed in the same manner as in Example 10.

<Preparation of substrate with conductor layer pattern>
(Preparation and transfer of holding substrate)
After applying a solvent-free ultraviolet curable resin (ADEKA OPTMER KRX-400, manufactured by ADEKA Corporation) to the conductive layer pattern surface side of the electrode base material, a 50 μm-thick polyethylene naphthalate (PEN) film (Q -51, Teijin DuPont Films Co., Ltd.) was laminated (roll temperature 30 ° C.) on the ultraviolet curable resin surface. Immediately after that, ultraviolet rays were irradiated from the transfer substrate side so that the dose was 1 J / cm ² .
(Preparation of a substrate with a conductor layer pattern in which the conductor layer is exposed)
Next, when the transfer substrate was peeled off, the conductive pattern was transferred to the UV curable resin layer formed on the PEN film, and a substrate with a conductor layer pattern (corresponding to FIG. 34) was obtained. It was. This base material with a conductor layer pattern can be used as an electrode substrate for a solar cell.

  A portion of the substrate with the conductor layer pattern 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. 5A, the upper layer thickness T2 is 16 to 21 μm, the lower layer thickness T1 is 2 to 3 μm, and the overall thickness is 18 to 23 μm, maximum width L is 403 to 410 μm, lower upper base width L1 is 383 to 388 μm, lower base width L2 is 387 to 392 μm, and the curvature of the curved portion at the center of the cross section of the upper layer is very small, It was almost flat and the angle α was 45 °. It was confirmed that an electrode base material composed of a finger electrode pattern having a line pitch of 195 to 200 μm and an approximately T-shaped interconnector portion was obtained. In addition, the surface of the central portion of the cross section of the upper layer of the conductor layer and the surfaces of the curved portions at both ends were exposed. The maximum thickness (f) of the portion where the conductor layer pattern was embedded in the resin layer was 16 to 22 μm, and the portion of the maximum width of the conductor layer pattern was embedded. The ratio (f / T) to the thickness (T) of the entire conductor layer pattern of f was 0.70 to 1.0. The ratio (T2 / L) of the upper layer thickness T2 to the maximum width L of the conductor layer pattern was 0.04 to 0.05.

(Connection with semiconductor substrate)
A semiconductor substrate with a positive electrode and a negative electrode formed in a comb shape on the back was aligned with the electrode substrate so that the electrode portion and the conductor layer pattern portion of the electrode substrate (substrate with a conductor layer pattern) coincided. . Using a vacuum pressure laminator, the electrode on the back surface of the semiconductor substrate and the conductor layer pattern of the electrode substrate are brought into contact with each other at a lamination temperature of 150 ° C., a pressure of 0.1 MPa, a vacuum drawing time of 2 minutes, and a pressure holding time of 5 minutes Pasted together. As a result of observing the connection part from the electrode base material side, it was found that there was almost no entrainment of bubbles or the like, and the electrode base material with a conductor layer pattern adhered well to the semiconductor base material.

(Repeated use)
Using the conductive substrate for plating described above, the copper plating-transfer process was repeated 100 times in the same manner as described above. As a result, there was no change in the precipitation and transferability of the copper plating, and the peeling portion of the insulating layer was also observed. Was not. Moreover, the electroconductive base material for plating was cut off after 100 times of use, and the surface shape of the insulating layer (DLC layer) was observed with an electron microscope, but no change was observed in the shape.

  A commercially available silver paste was formed by screen printing on the surface of the conductor layer of the electrode substrate (substrate with a conductor layer pattern) obtained above so that the thickness was 20 μm and the width was 400 μm. The above-mentioned semiconductor substrate was aligned with the electrode base material so that the electrode portion and the silver paste print portion coincided with each other. After the positive electrode and the negative electrode were partially pressure-bonded, the silver paste was cured by heating at 160 ° C. for 2 hours. As a result of observing the connection portion from the electrode substrate side, there was almost no entrainment of bubbles and the like, and even in this way, the electrode substrate with a conductor layer pattern was able to adhere well to the semiconductor substrate.

As in Example 16, <Preparation of conductive substrate for plating>, <Formation of conductor layer pattern>, <Preparation of transfer substrate>, and <Transfer of pattern of conductor layer> are the same as in Example 10. went.
<Preparation of substrate with conductor layer pattern>
First, (transfer to holding substrate) was performed in the same manner as in Example 10.
(Replacement of support substrate)
Thereafter, the separator film of the holding substrate incorporated in the laminate is peeled off, and the exposed pressure-sensitive adhesive layer is brought into contact with an ethylene vinyl acetate copolymer resin sheet (Solar EVA SC50B, manufactured by Mitsui Chemicals, Inc.). I let you. These were sandwiched between two release PETs (E-7002 (manufactured by Toyobo Co., Ltd.)) and heated and pressurized at 0.1 MPa and 120 ° C. for 4 minutes by a vacuum pressure laminator (corresponding to FIG. 35).
(Preparation of a substrate with a conductor layer pattern in which the conductor layer is exposed)
Next, when the transfer substrate (UV-cured adhesive layer and support substrate) was peeled off, the conductive pattern was transferred to the pressure-sensitive adhesive layer formed on the ethylene vinyl acetate copolymer resin sheet. Thus, a substrate with a conductor layer pattern (corresponding to FIG. 34) was obtained.

  A portion of the substrate with the conductor layer pattern was cut out and the cross section was observed on a scanning electron micrograph (magnification 2000 times). The conductor layer pattern has a cross-sectional shape as shown in FIG. 8B, the upper layer thickness T2 is 16 to 21 μm, the lower layer thickness T1 is 2 to 3 μm, and the overall thickness is arbitrarily selected. 18 to 23 μm, maximum width L is 403 to 410 μm, lower upper base width L1 is 383 to 388 μm, lower base width L2 is 387 to 392 μm, and the curvature of the curved portion at the center of the cross section of the upper layer is very small, It was almost flat and the angle α was 45 °. The line pitch of the conductor layer pattern was 195 to 200 μm. It was confirmed that an electrode base material comprising such a conductor layer finger electrode pattern and a substantially T-shaped interconnector portion was obtained. In addition, the surface of the central portion of the cross section of the upper layer of the conductor layer and the surfaces of the curved portions at both ends were exposed. The maximum thickness (f) of the portion where the conductor layer pattern was embedded in the resin layer was 16 to 22 μm, and the portion of the maximum width of the conductor layer pattern was embedded. The ratio (f / T) to the thickness (T) of the entire conductor layer pattern of f was 0.70 to 1.0. The ratio (T2 / L) of the upper layer thickness T2 to the maximum width L of the conductor layer pattern was 0.04 to 0.05.

(Connection with semiconductor substrate)
The semiconductor substrate on which the positive electrode and the negative electrode were formed in a comb shape on the back surface was aligned with the electrode base material so that the electrode portion and the conductor layer pattern portion of the electrode base material coincided. The PEN film was arrange | positioned at the ethylene vinyl acetate copolymer resin sheet side of the electrode base material. Using a vacuum pressure laminator, the electrode on the back surface of the semiconductor substrate and the conductor layer pattern of the electrode substrate are brought into contact with each other at a lamination temperature of 150 ° C., a pressure of 0.1 MPa, a vacuuming time of 4 minutes, and a pressure holding time of 30 minutes Pasted together. As a result of observing the connection part from the electrode base material side, it was found that there was almost no entrainment of bubbles or the like, and the electrode base material with a conductor layer pattern adhered well to the semiconductor base material.

  A commercially available silver paste was formed by screen printing on the surface of the conductor layer of the electrode substrate (substrate with a conductor layer pattern) obtained above so that the thickness was 20 μm and the width was 400 μm. The above-mentioned semiconductor substrate was aligned with the electrode base material so that the electrode portion and the silver paste print portion coincided with each other. After the positive electrode and the negative electrode were partially pressed, the silver paste and the ethylene vinyl acetate copolymer resin sheet were cured by heating at 160 ° C. for 2 hours. As a result of observing the connection portion from the electrode substrate side, there was almost no entrainment of bubbles and the like, and even in this way, the electrode substrate with a conductor layer pattern was able to adhere well to the semiconductor substrate.

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: Projection 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 30: Substrate with a conductor layer pattern on which the support substrate 21 is peeled 31: New support substrate 32: A substrate with a new conductor layer pattern having a protection substrate 33: Substrate with conductor layer pattern in which conductor layer exposed from resin layer is laminated on upper surface 34: Adhesive layer 35: Substrate with conductor layer pattern in which conductor layer exposed from resin layer 22 is laminated on upper surface 36: Support base material 37: Resin layer 38: Holding base material 39: Laminate 40: Holding base material with conductor layer pattern 41: Protective base material 42: Surface-protected base material with conductor layer pattern 43: Exposed Substrate with conductor layer pattern 44: Substrate with exposed conductor layer pattern (excluding supporting substrate) Resin layer with conductor layer pattern 45: Laminate 46: Another supporting substrate 47: Surface protected conductor layer pattern Emissions substrate with 48: New conductive layer patterned substrate 49: laminate (conductive layer patterned substrate)
50: solar cell element 51: single crystal n-type silicon 52: i-type amorphous silicon 53: p-type amorphous silicon 54: n-type amorphous silicon 55: transparent conductive film 57: metal film 62: transparent ethylene-vinyl acetate copolymer 63: Back sheet 65: Extraction electrode 66: P-type amorphous silicon germanium 67: i-type amorphous silicon germanium 68: n-type amorphous silicon germanium 69: Polyimide film 70: Back electrode 71, 72: Through hole 74: Buffer 75: Semiconductor CIGS Light absorption layer 76: Patterned molybdenum back electrode 77: Extraction electrode 78: Glass plate

Claims (14)

  A substrate including a patterned conductor layer and a resin layer, the substrate having a conductor layer embedded in the resin layer so that at least a part of the surface of the conductor layer is exposed, and collecting the conductor layer A solar cell structure assembled so as to be an electrode, an interconnector or an auxiliary electrode.   The solar cell structure according to claim 1, wherein a base material including a patterned conductor layer and a resin layer is laminated so that a surface on which the conductor layer exists faces an electric extraction surface.   The solar cell structure according to claim 2, wherein a conductive layer to be electrically connected to the conductor layer on the substrate is present on the electric extraction surface.   The solar cell structure according to claim 3, wherein the conductive layer is an electrical extraction electrode connected to the photoelectric conversion layer or a current collecting electrode connected to the electrical extraction electrode.   The solar cell structure according to claim 4, wherein the electrical extraction electrode is a transparent conductive film or a conductive metal.   The solar cell structure in any one of Claims 1-5 which makes the conductor layer on a base material exist in the surface side or back surface side of a solar cell structure.   The solar cell structure according to any one of claims 1 to 6, wherein the resin layer of the substrate is in close contact with the electric extraction surface.   The cross-sectional shape of the conductor layer on the substrate is that the entire cross-sectional shape or the upper part of the cross-sectional shape is trapezoidal, and at least the upper surface or a part of the trapezoidal shape is exposed from the resin layer, The solar cell structure according to any one of claims 1 to 7, wherein a lower portion from a significant portion is embedded in the resin layer of the base material.   9. The solar cell structure according to claim 8, wherein the height of the trapezoidal portion of the cross-sectional shape of the conductor layer is 0.1 to 10 μm, and the angle of the side surface is in the range of 30 ° to 80 °.   The cross-sectional shape of the conductor layer on the substrate has a curved surface at the upper part thereof, and the conductor layer has at least a part of the upper surface exposed from the resin layer and at least a part from the maximum width part to the lower part. Is embedded in the resin layer of the substrate. The solar cell structure according to claim 1.   The solar cell structure according to claim 10, wherein the ratio (T2 / L) of the thickness (T2) of the conductor layer above the maximum width to the maximum width (L) of the conductor layer is in the range of 0.01-2.   The solar cell structure according to claim 1, wherein the conductor layer has a thickness in the range of 2 to 100 μm.   A substrate including a patterned conductor layer and a resin layer, the substrate having a conductor layer embedded in the resin layer so that at least a part of the surface of the conductor layer is exposed, and collecting the conductor layer A method for producing a solar cell structure, wherein the solar cell element is bonded to an electric extraction surface of a solar cell element so as to be an electrode, an interconnector or an auxiliary electrode.   The solar cell structure according to claim 13, wherein the solar cell element includes a photoelectric conversion layer and an electric extraction electrode connected to the photoelectric conversion layer, and the electric extraction surface is a surface from which the electric extraction electrode or the collector electrode is exposed. Body manufacturing method.

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