Laminate and method for manufacturing the same, and copper wiring

Abstract

The present invention relates to a laminate, a method for manufacturing the same, and a copper wiring. A laminate characterized by comprising a support, a coating layer containing copper oxide and phosphorus disposed on a surface formed by the support, and a resin layer disposed in a manner of covering the coating layer.

Description

[0001] This application is a divisional application. The international application number of the original application is PCT / JP2018 / 026835, the international application date is July 18, 2018, the Chinese national application number is 201880046322.6, the entry date into China is January 10, 2020, and the invention title is "Structure with conductive patterned area and method of manufacturing the same, laminate and method of manufacturing the same, and copper wiring". Technical Field

[0002] This invention relates to structures having conductive patterned regions and methods for manufacturing the same, laminates and methods for manufacturing the same, and copper wiring. Background Technology

[0003] A circuit board has a structure on which conductive wiring is applied. The manufacturing method of a circuit board is generally as follows: First, a photoresist is coated on a substrate to which metal foil is bonded. Next, the photoresist is exposed and developed to obtain a substrate-like shape with the desired circuit pattern. Then, the metal foil not covered by the photoresist is removed by chemical etching to form the pattern. This allows the manufacture of a high-performance conductive substrate.

[0004] However, existing methods have drawbacks such as numerous and complex steps, and the need for photoresist materials.

[0005] In contrast, direct wiring printing technology, which uses a dispersion (hereinafter also referred to as "paste material") made by dispersing particles selected from the group consisting of metal particles and metal oxide particles, to directly print the desired wiring pattern on a substrate, has attracted attention. This technology has fewer steps, does not require the use of photoresist materials, and has extremely high productivity.

[0006] As an example of direct printed wiring technology, there is a known technique that prints a paste material onto a support by screen printing or inkjet printing, and then obtains a low-resistance wiring pattern by thermally firing the paste material (see, for example, Patent Document 1).

[0007] Another known method involves coating a paste-like material onto the entire surface of a substrate and selectively thermally burning the paste-like material by irradiating it with a laser in a patterned manner, thereby obtaining the desired wiring pattern (see, for example, Patent Documents 1 and 2).

[0008] In addition, it is known that a method for manufacturing copper wires is to coat a dispersion of agglomerated particles containing cuprous oxide with a thickness of 10 to 20 μm onto a polyethylene terephthalate (PET) support and then sinter it using a laser (see, for example, Patent Document 3). Using this method, no part other than the laser irradiation area is heated, so low heat-resistant resin materials such as PET supports can be used.

[0009] In addition, there are known techniques that use colloidal silica particles as a substrate layer to improve the adhesion between the support and the metallic copper-containing film obtained by firing copper paste (see, for example, Patent Document 4).

[0010] Another known method for manufacturing a multilayer wiring substrate is as follows: a first coating layer is formed on a substrate, a portion of the first coating layer is irradiated with light to form a first conductive portion, a second coating layer is then formed on the first coating layer, and light is irradiated from the second coating layer to the first conductive portion to form a second conductive portion (see, for example, Patent Document 5).

[0011] Another known method involves forming a patterned coating film using a copper or copper oxide dispersion on a substrate and obtaining a conductive film by firing it (see, for example, Patent Document 6).

[0012] Existing technical documents

[0013] Patent documents

[0014] Patent Document 1: International Publication No. 2010 / 024385

[0015] Patent Document 2: Japanese Patent Application Publication No. 5-37126

[0016] Patent Document 3: Japanese Patent No. 5449154

[0017] Patent Document 4: International Publication No. 2016 / 031860

[0018] Patent Document 5: Japanese Patent Application Publication No. 2015-26681

[0019] Patent Document 6: International Publication No. 2015 / 012264 Summary of the Invention

[0020] The problem that the invention aims to solve

[0021] In the direct wiring printing technology described in Patent Documents 1-3, which forms wiring patterns by laser irradiation of a paste-like material, unburned paste-like material remains in areas not irradiated by the laser. This unburned paste-like material is conductive, and electrical insulation between wiring patterns cannot be ensured in this state. Therefore, the unburned paste-like material is removed, and insulating materials such as solder resist are filled between the wiring patterns.

[0022] Therefore, existing direct wiring printing technology requires steps to remove unburned paste material and fill with insulating material, thus reducing the advantages of reducing the number of steps. Furthermore, the need to prepare solvents and rinsing agents for removing the unburned paste material increases manufacturing costs.

[0023] When existing direct wiring printing technology is applied to form wiring patterns on flexible substrates, cracks may occur between the solder resist and the wiring when the resulting circuit board is subjected to thermal cycling tests in low-temperature and high-temperature environments.

[0024] Furthermore, while the colloidal silicon dioxide used in the substrate layer disclosed in Patent Document 4 exhibits excellent adhesion to metals, it has poor adhesion to resins. Therefore, when the substrate material is resin, delamination may occur between the substrate layer and the substrate, resulting in low reliability.

[0025] In the method described in Patent Document 5, an unburned paste-like material composed of copper divalent oxide (CuO) particles and resin binder remains in the area not irradiated by the laser. The copper divalent oxide particles are large, and the resin binder is partially present with the particles. In this state, the electrical insulation between the wiring patterns is insufficient.

[0026] In the structure described in Patent Document 6, the spaces between the wiring patterns are not filled, and electrical insulation between the wiring patterns cannot be ensured in this state. In addition, in a high-humidity environment, air containing moisture can enter between the wiring patterns, which can easily lead to insulation failure.

[0027] The present invention was made in view of the above-mentioned problems, and one of its objectives is to provide a structure with conductive patterned regions and a method for manufacturing the same, which can greatly simplify the manufacturing process, has excellent electrical insulation between conductive patterned regions, and has excellent long-term reliability.

[0028] Furthermore, the present invention was made in view of the above-mentioned problems, and one of its objectives is to provide a laminate and a method for manufacturing the same, which does not require equipment for achieving a vacuum atmosphere or inert gas atmosphere in the photo-firing process of copper oxide, thereby reducing the manufacturing cost of structures with conductive patterned regions.

[0029] Furthermore, one of the objectives of this invention is to provide a copper wiring that can improve the conductivity of the wiring.

[0030] Methods for solving problems

[0031] In order to solve the above-mentioned problems, the inventors conducted repeated in-depth research and completed this invention.

[0032] That is, one aspect of the structure of the present invention is characterized in that it has a support body and a layer disposed on the surface formed by the support body, wherein a conductive patterned region containing copper is adjacent to an insulating region containing copper oxide and phosphorus.

[0033] In addition, another aspect of the structure of the present invention is characterized in that it has a support body and a layer disposed on the surface formed by the support body, wherein a conductive patterned region containing copper is adjacent to an insulating region containing copper oxide and hydrazine or hydrazine hydrate.

[0034] In another aspect, the structure of the present invention is characterized by having a support body and a layer disposed on the surface formed by the support body, wherein a conductive patterned region containing copper is adjacent to an insulating region containing copper oxide, phosphorus and hydrazine or hydrazine hydrate.

[0035] In addition, another aspect of the structure of the present invention is characterized in that it has a support body and a layer disposed on the surface formed by the support body, wherein conductive patterned regions containing copper and phosphorus are adjacent to insulating regions containing copper oxide and phosphorus.

[0036] In addition, one aspect of the laminate of the present invention is characterized in that it comprises a support, a coating layer containing copper oxide and phosphorus disposed on the surface formed by the support, and a resin layer disposed in such a manner as to cover the coating layer.

[0037] In addition, one aspect of the laminate of the present invention is characterized in that it comprises a support, a coating layer comprising copper oxide and hydrazine or hydrazine hydrate disposed on the surface formed by the support, and a resin layer disposed in such a manner as to cover the coating layer.

[0038] In addition, one aspect of the laminate of the present invention is characterized in that it comprises a support, a coating layer containing copper oxide, phosphorus and hydrazine or hydrazine hydrate disposed on the surface formed by the support, and a resin layer disposed in such a manner as to cover the coating layer.

[0039] In addition, one embodiment of the copper wiring of the present invention is a copper wiring comprising reduced copper obtained by reducing copper oxide, phosphorus, and carbon, characterized in that the elemental concentration ratio of phosphorus / copper is 0.02 to 0.30 and the elemental concentration ratio of carbon / copper is 1.0 to 6.0.

[0040] Furthermore, one aspect of the manufacturing method of the structure of the present invention is characterized by comprising the following steps: a step of depositing a coating layer comprising copper oxide and phosphorus-containing organic matter on a surface formed of a support; and a step of selectively irradiating the coating layer with light to reduce the copper oxide to copper, thereby obtaining the support, and a layer in which an insulating region comprising the copper oxide and phosphorus and a conductive pattern region comprising the copper are disposed adjacent to each other on the surface formed of the support.

[0041] Furthermore, one aspect of the manufacturing method of the structure of the present invention is characterized by comprising the following steps: a step of depositing a coating layer comprising copper oxide and hydrazine or hydrazine hydrate on a surface formed of a support; and a step of selectively irradiating the coating layer with light to reduce the copper oxide to copper, thereby obtaining the support and a layer in which an insulating region comprising the copper oxide and hydrazine or hydrazine hydrate and a conductive pattern region comprising copper are disposed adjacent to each other on the surface formed of the support.

[0042] Furthermore, one aspect of the manufacturing method of the structure of the present invention is characterized by comprising the following steps: a step of depositing a coating layer comprising copper oxide, a phosphorus-containing organic compound, and hydrazine or hydrazine hydrate on a surface formed of a support; and a step of selectively irradiating the coating layer with light to reduce the copper oxide to copper, thereby obtaining the support, and a layer in which an insulating region comprising the copper oxide, phosphorus, and hydrazine or hydrazine hydrate and a conductive pattern region comprising copper are disposed adjacent to each other on the surface formed of the support.

[0043] Furthermore, one aspect of the method for manufacturing the laminate of the present invention is characterized by comprising the following steps: a step of depositing a coating layer comprising copper oxide and a phosphorus-containing organic compound on a surface formed of a support; and a step of depositing a resin layer in such a manner as to cover the coating layer.

[0044] In addition, one aspect of the method for manufacturing the laminate of the present invention is characterized by comprising the following steps: a step of depositing a coating layer comprising copper oxide and hydrazine or hydrazine hydrate on a surface formed of a support; and a step of depositing a resin layer in such a manner as to cover the coating layer.

[0045] In addition, one aspect of the method for manufacturing the laminate of the present invention is characterized by comprising the following steps: a step of depositing a coating layer comprising copper oxide, a phosphorus-containing organic compound and comprising hydrazine or hydrazine hydrate on a surface formed of a support; and a step of depositing a resin layer in such a manner as to cover the coating layer.

[0046] The effects of the invention

[0047] According to the present invention, a structure having conductive patterned regions and a method thereof can be provided, which can greatly simplify the manufacturing process, provide excellent electrical insulation between conductive patterned regions, and provide excellent long-term reliability.

[0048] In addition, according to the present invention, a laminate and its manufacturing method can be provided, which do not require equipment for achieving a vacuum atmosphere or inert gas atmosphere in the photo-firing process of copper oxide, thereby reducing the manufacturing cost of structures with conductive patterned regions.

[0049] Furthermore, according to the present invention, a copper wiring can be provided that improves the conductivity of the wiring. Attached Figure Description

[0050] Figure 1 This is a schematic diagram illustrating the relationship between cuprous oxide particles and phosphate salts contained in the insulating region of a structure with a conductive patterned region according to this embodiment.

[0051] Figure 2 This is a cross-sectional schematic diagram showing the structure with a conductive patterned region according to the first embodiment.

[0052] Figure 3 This is a cross-sectional schematic diagram showing the structure with a conductive patterned region according to the second embodiment.

[0053] Figure 4 It is shown that... Figure 3 Cross-sectional schematic diagrams of structures with different conductive patterned regions.

[0054] Figure 5 This is a cross-sectional schematic diagram showing an example of a laminate involved in this embodiment.

[0055] Figure 6 This is a cross-sectional schematic diagram showing an example of a structure having a conductive patterned region manufactured using the laminate involved in this embodiment.

[0056] Figure 7 This is an explanatory diagram (example) showing each step of the manufacturing method of the structure having a conductive patterned area according to the first embodiment.

[0057] Figure 8 This is an explanatory diagram (example) showing each step of the manufacturing method of the structure having a conductive patterned area according to the second embodiment.

[0058] Figure 9 These are electron microscope images used to illustrate the state of cracks in the coating layer of the embodiments.

[0059] Figure 10 These are electron microscope images used to illustrate the state of cracks in the coating layer of the embodiments.

[0060] Figure 11 The image shown is an electron microscope photograph of a cross-section of the layer formed on the support in the embodiment.

[0061] Figure 12A It is a photograph showing the area of ​​a conductive pattern formed on the glass surface.

[0062] Figure 12B yes Figure 12A A schematic diagram.

[0063] Figure 12C From Figure 12A The photo shows the area after the insulation has been removed. Detailed Implementation

[0064] The following is a detailed description of one embodiment of the present invention (hereinafter referred to as "the embodiment").

[0065] <Overview of the structure with conductive patterned regions in this embodiment (structure with conductive patterned regions)>

[0066] The inventors have discovered that when a coating layer containing copper oxide is disposed on the surface of a support, and the coating layer is selectively irradiated with light to reduce the copper oxide to copper to form conductive pattern areas, if the electrical insulation of the areas containing unreduced copper oxide is improved, insulation between conductive pattern areas can be ensured without removing these areas and leaving them as is, and the process of removing these areas is not required, thus completing the present invention.

[0067] That is, the structure with conductive patterned regions according to this embodiment is characterized in that a copper oxide-containing coating layer disposed on the surface of the support contains phosphorus. Then, the coating layer is selectively irradiated with light to form conductive patterned regions, and insulating regions containing copper oxide and phosphorus are provided between the conductive patterned regions.

[0068] Figure 1 This is a schematic diagram illustrating the relationship between copper oxide particles and phosphate salts contained in the insulating region of a structure with a conductive patterned region according to this embodiment. Figure 1 As shown, in the insulating region 1, a phosphate ester salt 3, as an example of a phosphorus-containing organic compound, surrounds a copper oxide particle 2, as an example of copper oxide, with phosphorus 3a facing inward and ester salt 3b facing outward. Since the phosphate ester salt 3 exhibits electrical insulation, it hinders electrical conduction between adjacent copper oxide particles 2.

[0069] Therefore, although the copper oxide particles 2 are semiconductors and conductive, they are covered by phosphate salts 3, which exhibit electrical insulation. Thus, the insulating region 1 exhibits electrical insulation, as observed in cross-section ( Figure 2 In the cross section shown in the vertical direction, insulation between the adjacent conductive pattern regions (described later) on both sides of the insulating region 1 can be ensured.

[0070] On the other hand, in the conductive pattern region, a portion of the coating layer containing copper oxide and phosphorus is irradiated with light, reducing the copper oxide to copper in this portion. The copper obtained by reducing copper oxide in this way is called reduced copper. Additionally, in this portion, a phosphorus-containing organic compound is modified into phosphorus oxide. Among the phosphorus oxides, the aforementioned ester salt 3b (see...) Figure 1 Organic materials such as lasers decompose when heated, and do not exhibit electrical insulation properties.

[0071] In addition, such as Figure 1 As shown, when using copper oxide particles 2, under the heat of a laser or the like, the copper oxide is transformed into reduced copper and simultaneously sintered, with adjacent copper oxide particles 2 becoming integrated with each other. This allows the formation of a region with excellent electrical conductivity (hereinafter referred to as the "conductive pattern region").

[0072] Phosphorus remains in the reduced copper within the conductive pattern region. The phosphorus exists in the form of elemental phosphorus, phosphorus oxides, and phosphorus-containing organic compounds. This residual phosphorus segregation within the conductive pattern region does not raise concerns about increasing the resistance of the conductive pattern region.

[0073] <Construction of a structure with conductive patterned regions: First Embodiment>

[0074] Figure 2 This is a cross-sectional schematic diagram showing a structure with a conductive patterned region according to the first embodiment. For example... Figure 2 As shown, the structure 10 is composed of a support 11 and a layer 14 disposed on the surface formed by the support 11. In the layer 14, an insulating region 12 containing copper oxide and phosphorus is adjacent to a conductive pattern region 13 containing copper. The copper mentioned here is preferably the reduced copper described above. In addition, the phosphorus contained in the insulating region 12 is preferably contained in the form of a phosphorus-containing organic compound.

[0075] This configuration allows for insulation between copper-containing conductive pattern areas using insulating regions containing copper oxide and phosphorus, eliminating the need to remove unburned portions of layer 14 during manufacturing. This reduces manufacturing steps and lowers manufacturing costs as solvents are not required. Furthermore, the use of insulating regions to insulate the conductive pattern areas reduces the likelihood of cracking, improving reliability.

[0076] The constituent elements of the structure with conductive patterned regions according to the first embodiment will be described below.

[0077] <Support>

[0078] The support 11 forms the surface for configuring the layer 14. The shape is not particularly limited.

[0079] To ensure electrical insulation between the conductive pattern regions 13 separated by the insulating region 12, the support 11 is preferably made of an insulating material. However, the support 11 does not necessarily need to be entirely made of insulating material; only the portion forming the surface of the configuration layer 14 needs to be made of insulating material.

[0080] The support 11 can more specifically be a flat plate, a film, or a sheet. A flat plate is, for example, a support (also called a substrate) used in circuit boards such as printed circuit boards. A film or sheet is, for example, a base film used as a thin-film insulator in flexible printed circuit boards.

[0081] The support 11 can be a three-dimensional object. The layer with conductive patterned areas can also be disposed on the curved surface or surface containing slopes, etc., of the three-dimensional object, i.e., the three-dimensional surface.

[0082] Examples of three-dimensional objects include the housings of electrical devices such as mobile phone terminals, smartphones, smart glass, televisions, and personal computers. Other examples of three-dimensional objects in the automotive field include front panels, dashboards, steering wheels, and chassis.

[0083] Furthermore, there is no limitation on the material of the three-dimensional object, and it is preferably selected from at least one of the group consisting of polypropylene resin, polyamide resin, acrylonitrile butadiene styrene resin, polyethylene resin, polycarbonate resin, polyacetal resin, polybutylene terephthalate resin, modified polyphenylene ether resin and polyphenylene sulfide resin.

[0084] <Layer disposed on the surface of the support (layer with conductive patterned areas)>

[0085] In this embodiment, layer 14 can be described as a mixture of insulating region 12 and conductive patterned region 13. In the following text, when simply referred to as "layer," it is sometimes referred to as a layer having conductive patterned regions or a layer disposed on a support.

[0086] Layer 14 can be described as an integrated layer. Alternatively, it can be described as a single layer that is not a multilayer structure. "Integrated" and "single" mean that, in cross-sectional view, adjacent insulating regions 12 and conductive patterned regions 13 are continuous along the surface. "Adjacent" means that no other layers are contained between the insulating regions 12 and the conductive patterned regions 13. "Continuous" means that it does not include, for example, the state observed in a printed circuit board where patterned wiring layers are filled with solder paste as a single layer.

[0087] In this embodiment, a break in the slope can be created between the surface of the insulating region 12 and the surface of the conductive pattern region 13. That is, the thickness decreases during the reduction process from copper oxide to copper, so even in a continuous layer, the film thickness of the conductive region and the insulating region may differ.

[0088] Furthermore, the adjacentity between the insulating region 12 and the conductive pattern region 13 means that the electrical conductivity, particle state (fired and unfired), etc., can gradually change along the surface of the support within the layer, and there can also be a boundary (interface) between the insulating region 12 and the conductive pattern region 13.

[0089] Furthermore, the insulating region 12 and the conductive pattern region 13 are formed from a coating layer of the same composition. That is, the conductive pattern region 13 is formed by laser irradiation of a portion of the coating layer, and therefore, the insulating region 12 and the conductive pattern region 13 contain the same elements such as copper and phosphorus.

[0090] <Insulated Area>

[0091] The insulating region 12 contains copper oxide and phosphorus, exhibiting electrical insulation properties. The insulating region 12 can be considered an un-illuminated region that has not been exposed to light. Alternatively, the insulating region 12 can be considered an un-reduced region where the copper oxide has not been reduced by light irradiation. Furthermore, the insulating region 12 can also be considered an un-fired region that has not been fired by light irradiation.

[0092] <Conductive Pattern Area>

[0093] The conductive pattern region 13 contains copper and exhibits electrical conductivity. The conductive pattern region 13 can be described as an irradiated area or a laser-irradiated area. Alternatively, the conductive pattern region 13 can be described as a reduction region containing reduced copper obtained by reducing copper oxide through light irradiation. Furthermore, the conductive pattern region 13 can also be described as a firing region containing a fired body obtained by firing the insulating region 12 through light irradiation.

[0094] The shape of the conductive pattern area 13 when viewed from above, i.e., the pattern itself, can be any of the following: straight line, curved line, circle, square, or bent shape, without any particular limitation. The pattern is formed by irradiating light through a mask or by drawing with a laser, and therefore is not easily limited by shape.

[0095] The boundary between the insulating region 12 and the conductive pattern region 13 is preferably along the thickness direction of layer 14 in cross-sectional view. Figure 2 The boundary can be a straight line (shown in the up-down direction), but may also have a conical angle; there is no particular limitation. The boundary is not necessarily explicitly defined. For example, when measuring the copper composition near the boundary, there may be a composition transition region that gradually changes from the conductive pattern region 13 side to the insulating region 12 side.

[0096] The conductive pattern region 13 does not need to be completely reproduced in cross-sectional view. For example, it is preferable that there is an unreproduced portion near the support 11. This improves the fit between the conductive pattern region 13 and the support 11.

[0097] like Figure 2 As shown, in this embodiment, the film thickness of the conductive pattern region 13 and the film thickness of the insulating region 12 can differ, for example, by making the insulating region 12 thicker. That is, during the reduction process of copper oxide to copper by laser irradiation, the film thickness of the conductive pattern region 13 is more likely to be thinner than that of the insulating region 12. Due to the difference in film thickness, the surface distance between the conductive pattern region 13 and the conductive pattern region 13 facing the insulating region 12 can be increased, thereby improving the insulation. The film thickness of the insulating region 12 is preferably 0.1 μm to 30 μm or less, more preferably 0.1 μm to 15 μm or less, and even more preferably 0.1 μm to 10 μm or less. In particular, when the film thickness is in the range of 1 μm to 10 μm or less, the insulation of the insulating region 12 can be maintained, and the conductive pattern region 13 with better substrate adhesion and conductivity can be produced by light irradiation as described later, which is therefore preferred. The film thickness of the conductive pattern region 13 is preferably 10% to 90% of the film thickness of the insulating region 12, more preferably 20% to 80%, and even more preferably 30% to 70%. In particular, by making it 30% to 70%, the substrate adhesion can be maintained, and sufficient electrical conductivity can be obtained for electrical wiring applications, which is therefore preferred.

[0098] <Sealing Layer>

[0099] Preferably, an adhesive layer (not shown) is provided between the support 11 and the layer 14 with the conductive patterned area. The adhesive layer can improve the adhesion of the layer 14 to the support 11, prevent the peeling of the insulating area 12 and the conductive patterned area 13, and improve the long-term stability of the structure 10.

[0100] The adhesive layer includes, for example, (i) a layer obtained by roughening the surface formed by the support 11, and (ii) a layer formed by applying a coating layer to the surface formed by the support 11. An example of (i) is a part of the support 11 itself. In this case, other layers (e.g., a primer layer) can be combined with the adhesive layer.

[0101] In the example of (ii), the bonding layer can be a single coating layer or laminated with other layers. Additionally, the coating layer can contain a primer material.

[0102] <Detailed description of structures with conductive patterned areas>

[0103] The various components of the structure 10 involved in this embodiment will be further described in detail below. However, the components are not limited to the specific examples given below.

[0104] (Support structure)

[0105] Specific examples of supports include supports made of inorganic materials (hereinafter referred to as "inorganic supports") or supports made of resin (hereinafter referred to as "resin supports").

[0106] Inorganic supports are made of materials such as glass, silicone resin, mica, sapphire, crystal, clay film, and ceramics. Ceramic materials include, for example, alumina, silicon nitride, silicon carbide, zirconium oxide, yttrium oxide, and aluminum nitride, as well as mixtures of at least two of these. Furthermore, supports made of highly transparent materials such as glass, sapphire, and crystal are particularly suitable as inorganic supports.

[0107] As resin supports, materials such as polypropylene (PP), polyimide (PI), polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), polyester, polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacetal (POM), polyarylate (PAR), polyamide (PA), polyamide-imide (PAI), polyether-imide (PEI), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyphenylene sulfide (PPS), polyetherketone (PEK), polyphthalamide (PPA), polyether nitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, polysiloxane, polymethacrylamide, nitrile rubber, acrylic rubber, polytetrafluoroethylene, epoxy resin, phenolic resin, melamine resin, urea resin, polymethyl methacrylate resin (PMMA), and polybutadiene rubber can be used. Supports composed of olefins, polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene, ethylene-propylene-diene copolymer, butyl rubber, polymethylpentene (PMP), polystyrene (PS), styrene-butadiene copolymer, polyethylene (PE), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polyether ether ketone (PEEK), phenolic varnish, benzocyclobutene, polyvinylphenol, polychloroprene, polyoxymethylene, polysulfone (PSF), polyphenylene sulfone resin (PPSU), cyclic olefin polymer (COP), acrylonitrile-butadiene-styrene resin (ABS), acrylonitrile-styrene resin (AS), nylon resin (PA6, PA66), polybutylene terephthalate resin (PBT), polyether sulfone resin (PESU), polytetrafluoroethylene resin (PTFE), polychlorotrifluoroethylene (PCTFE), and silicone resins, etc.

[0108] In addition, although not distinguished above, resin sheets containing cellulose nanofibers can also be used as supports.

[0109] In particular, the selection of at least one of the group consisting of PI, PET and PEN has excellent adhesion to the layer and the adhesive layer with conductive patterned area, and is readily available in the market and can be obtained at low cost, which is meaningful and preferred from an industry point of view.

[0110] Furthermore, especially in the case of a housing, materials selected from at least one of the group consisting of PP, PA, ABS, PE, PC, POM, PBT, m-PPE, and PPS exhibit excellent adhesion to the layer and adhesive layer having the conductive patterned area, and also possess excellent formability and post-molding mechanical strength. Moreover, they also possess sufficient heat resistance to withstand laser irradiation during the formation of the conductive patterned area, and are therefore preferred.

[0111] The load deformation temperature of the resin support is preferably below 400°C, more preferably below 280°C, and even more preferably below 250°C. Supports with a load deformation temperature below 400°C can be obtained at low cost, which is meaningful and preferred from an industrial point of view. The load deformation temperature is measured, for example, according to JIS K7191.

[0112] The thickness of the support can be, for example, 1 μm to 100 mm, preferably 25 μm to 10 mm, and more preferably 25 μm to 250 μm. If the thickness of the support is less than 250 μm, the manufactured electronic device can be made lightweight, space-saving, and flexible, and is therefore preferred.

[0113] It should be noted that when the support is a shell, its thickness can be, for example, 1μm to 1000mm, preferably 200μm to 100mm or 200μm to 5mm. The inventors have clarified that by selecting a thickness within this range, the mechanical strength and heat resistance after molding can be achieved.

[0114] Regarding the support, or a support including an adhesive layer when the support has an adhesive layer, its transmittance to light with a wavelength of 445 nm is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The upper limit of the light transmittance can be 98% or less. Regarding the wavelength, in addition to 445 nm, wavelengths from near ultraviolet to near infrared, such as 355 nm, 405 nm, 450 nm, 532 nm, and 1064 nm, can also be selected. By increasing the light transmittance at such wavelengths, the coating layer can be fired by irradiation from the support side to form a layer with conductive patterned areas.

[0115] (A layer (with conductive patterned areas) disposed on the surface of the support)

[0116] This layer is formed by adjacent insulating regions containing copper oxide and phosphorus-containing organic matter with conductive patterned regions containing copper.

[0117] (Copper oxide)

[0118] In this embodiment, the copper oxide comprises, for example, cuprous oxide and copper divalent oxide (CuO). Cuprous oxide is particularly preferred because it tends to be easily sintered at low temperatures. Cuprous oxide and copper divalent oxide can be used alone or in combination.

[0119] In addition, copper oxide particles have a core / shell structure, either the core or the shell can be cuprous oxide, or it can contain divalent copper oxide.

[0120] The copper oxide contained in the insulating region is, for example, formed in the form of microparticles. The average particle size of the copper oxide-containing microparticles is 1 nm to 100 nm, more preferably 1 nm to 50 nm, and even more preferably 1 nm to 20 nm. The smaller the particle size, the better the electrical insulation of the insulating region, and therefore it is preferred.

[0121] Copper particles may be included in the insulating region. That is, copper can be added to the dispersion described later. Phosphorus-containing organic matter is also adsorbed on the surface of the copper particles, which can exhibit electrical insulation properties.

[0122] (Phosphorus-containing organic matter)

[0123] The phosphorus contained in the insulating region is preferably a phosphorus-containing organic compound. The phosphorus-containing organic compound is a material that exhibits electrical insulation properties in the insulating region. Preferably, the phosphorus-containing organic compound is capable of fixing copper oxide to the support or adhesive layer. The phosphorus-containing organic compound can be a single molecule or a mixture of two or more molecules. Furthermore, the phosphorus-containing organic compound can adsorb copper oxide particles.

[0124] There are no particular limitations on the number average molecular weight of phosphorus-containing organic compounds, but it is preferably between 300 and 300,000. When the molecular weight is above 300, the electrical insulation properties are excellent.

[0125] Phosphorus-containing organic materials are preferably those that decompose or evaporate easily under the influence of light or heat. By using organic materials that decompose or evaporate easily under the influence of light or heat, it is less likely that organic residue will remain after firing, resulting in conductive patterned areas with low resistivity.

[0126] The decomposition temperature of phosphorus-containing organic compounds is not limited, but is preferably below 600°C, more preferably below 400°C, and even more preferably below 200°C. The boiling point of phosphorus-containing organic compounds is not limited, but is preferably below 300°C, more preferably below 200°C, and even more preferably below 150°C.

[0127] The absorption characteristics of phosphorus-containing organic materials are not limited, but those capable of absorbing light used in firing are preferred. For example, when using a laser as the light source for firing, phosphorus-containing organic materials that can absorb light with wavelengths (center wavelengths) of their emitted light, such as 355nm, 405nm, 445nm, 450nm, 532nm, and 1064nm, are preferred. When the support is resin, wavelengths of 355nm, 405nm, 445nm, and 450nm are particularly preferred.

[0128] Alternatively, the structure can be a phosphate salt of a high molecular weight copolymer having groups that have an affinity for copper oxide. For example, the structure of chemical formula (1) is preferred because it can adsorb copper oxide and has excellent adhesion to the support.

[0129] [Chemistry 1]

[0130] Chemical formula (1)

[0131]

[0132] In chemical formula (1), R is an ester salt.

[0133] As an example of an ester salt, the structure of chemical formula (2) can be cited.

[0134] [Chemistry 2]

[0135] Chemical formula (2)

[0136]

[0137] In addition, as an example of phosphorus-containing organic compounds, the structure of chemical formula (3) can be cited.

[0138] [Chemistry 3]

[0139] Chemical formula (3)

[0140]

[0141] In chemical formula (3), l is an integer from 1 to 20, preferably an integer from 1 to 15, more preferably an integer from 1 to 10; m is an integer from 1 to 2, preferably an integer from 1 to 15, more preferably an integer from 1 to 10; n is an integer from 1 to 20, preferably an integer from 1 to 15, more preferably an integer from 1 to 10.

[0142] As organic structures possessed by phosphorus-containing organic compounds, the following can be used: polyethylene glycol (PEG), polypropylene glycol (PPG), polyimide, polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), polyester, polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacetal, polyarylate (PAR), polyamide (PA), polyamide-imide (PAI), polyetherimide (PEI), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyetherketone (PEK), polyphthalamide (PPA), polyether nitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, polysiloxane, polymethacrylamide, nitrile rubber, and acrylic rubber. The structures include polytetrafluoroethylene, epoxy resin, phenolic resin, melamine resin, urea resin, polymethyl methacrylate resin (PMMA), polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene, ethylene-propylene-diene copolymer, butyl rubber, polymethylpentene (PMP), polystyrene (PS), styrene-butadiene copolymer, polyethylene (PE), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polyetheretherketone (PEEK), phenolic varnish, benzocyclobutene, polyvinylphenol, polychloroprene, polyoxymethylene, polysulfone (PSF), polysulfone, polysulfones, aldehydes, cellulose, linear starch, pullulan, dextrin, dextran, fructose, chitosan, etc. Structures derived from the functional groups of these structures can be used, as well as structures obtained by modifying these structures, and copolymers of these structures can also be used. Phosphorus-containing organic compounds with a framework selected from polyethylene glycol, polypropylene glycol, polyacetal, polybutene, and polysulfide structures are easily decomposed, and no residue is easily left in the conductive patterned area after firing, thus making them preferred.

[0143] As specific examples of phosphorus-containing organic compounds, commercially available materials can be used. Specifically, examples include DISPERBYK (registered trademark)-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-118, DISPERBYK-140, and DISPERBYK-140 manufactured by BYK Chemical Company. RBYK-145, DISPERBYK-168, DISPERBYK-180, DISPERBYK-182, DISPERBYK-187, DISPERBYK-190, DIS PERBYK-191, DISPERBYK-193, DISPERBYK-194N, DISPERBYK-199, DISPERBYK-2000, DISPERBYK-200 1. DISPERBYK-2008, DISPERBYK-2009, DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2013, DISPE RBYK-2015, DISPERBYK-2022, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2152, DISPERBYK-20 55. DISPERBYK-2060, DISPERBYK-2061, DISPERBYK-2164, DISPERBYK-2096, DISPERBYK-2200, BYK (registered trademark)-405, BYK-607, BYK-9076, BYK-9077, BYK-P105, Plysurf (registered trademark) M208F, Plysurf DBS manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., etc. These can be used individually or in combination.

[0144] In the insulating region, copper oxide particles (hereinafter referred to as "copper oxide particles") are mixed with phosphorus-containing organic matter. When the total volume of the copper oxide particles is 100 parts by volume, the content of the phosphorus-containing organic matter can be 5 parts by volume or more and 900 parts by volume or less. The lower limit is preferably 10 parts by volume or more, more preferably 30 parts by volume or more, and even more preferably 60 parts by volume or more. The upper limit is preferably 480 parts by volume or less, more preferably 240 parts by volume or less.

[0145] Converted to parts by weight, the content of phosphorus-containing organic matter is preferably 1 part by weight or more and 150 parts by weight or less relative to 100 parts by weight of copper oxide particles. The lower limit is preferably 2 parts by weight or more, more preferably 5 parts by weight or more, and even more preferably 10 parts by weight or more. The upper limit is preferably 80 parts by weight or less, more preferably 40 parts by weight or less.

[0146] When the content of phosphorus-containing organic matter relative to copper oxide particles is 5 parts by volume or more, or 1 part by weight or more, a film with a submicron thickness can be formed. Furthermore, when the content of phosphorus-containing organic matter is 10 parts by volume or more, or 5 parts by weight or more, a thick film with a thickness of tens of micrometers can be formed as a layer. When the content of phosphorus-containing organic matter is 30 parts by volume or more, or 10 parts by weight or more, a highly flexible layer that is not prone to cracking even when bent can be obtained.

[0147] When the content of phosphorus-containing organic matter relative to copper oxide particles is less than 900 parts by volume or less than 150 parts by weight, a patterned area with good electrical conductivity can be obtained by firing.

[0148] (hydrazine or hydrazine hydrate)

[0149] Hydrazine or hydrazine hydrate can be included in the coating layer or remain in the insulating area, which is an unfired region. Including hydrazine or hydrazine hydrate further improves the dispersion stability of copper oxide and facilitates the reduction of copper oxide during firing, further reducing the resistance of the conductive film. The preferred hydrazine content is as follows.

[0150] 0.0001≦(mass of hydrazine / mass of copper oxide)≦0.10(1)

[0151] Regarding the content of the reducing agent, the resistivity of the copper film decreases when the mass ratio of hydrazine is 0.0001 or higher. Furthermore, the long-term stability of the copper oxide ink is improved when the mass ratio is 0.1 or lower, which is therefore preferred.

[0152] (Mass ratio of copper particles to copper oxide particles in the insulation region)

[0153] In the insulating region, in addition to copper oxide particles, copper particles may also be included. In this case, the mass ratio of copper particles to copper oxide particles (hereinafter referred to as "copper particles / copper oxide particles") is preferably 1.0 or more and 7.0 or less.

[0154] From the perspective of conductivity and crack prevention, it is preferable to make the copper particle / copper oxide particle ratio between 1.0 and 7.0.

[0155] (Average particle size in copper oxide microparticles)

[0156] The average secondary particle size of the copper oxide particles is not particularly limited, but is preferably 500 nm or less, more preferably 200 nm or less, and even more preferably 80 nm or less. The average secondary particle size of the particles is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 15 nm or more.

[0157] The average secondary particle size refers to the average particle size of an aggregate (secondary particle) formed by the aggregation of multiple primary particles. When the average secondary particle size is 500 nm or less, it tends to easily form fine conductive pattern regions on the support, and is therefore preferred. When the average secondary particle size is 5 nm or more, the long-term storage stability of the dispersion is improved, and is therefore preferred. The average secondary particle size can be measured, for example, by transmission electron microscopy or scanning electron microscopy.

[0158] The average primary particle size of the primary particles constituting the secondary particles is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or less. The average primary particle size is preferably 1 nm or more, more preferably 2 nm or more, and even more preferably 5 nm or more.

[0159] When the average primary particle size is below 100 nm, there is a tendency to lower the firing temperature, which will be discussed later. The reason for this low-temperature firing is believed to be that the smaller the particle size, the greater its surface energy, and the lower its melting point.

[0160] Furthermore, a primary particle size of 1 nm or more provides good dispersibility and is therefore preferred. When a wiring pattern is formed on a support, from the perspective of adhesion to the substrate and low resistivity, the average primary particle size is preferably 2 nm to 100 nm, more preferably 5 nm to 50 nm. This tendency is more pronounced when the substrate is resin. The average primary particle size can be measured using a transmission electron microscope or a scanning electron microscope.

[0161] Relative to the unit mass of the region containing copper oxide and phosphorus-containing organic matter, the content of copper oxide particles in the layer disposed on the support is preferably 40% by mass or more, more preferably 55% by mass or more, and even more preferably 70% by mass or more. Furthermore, this content is preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.

[0162] Furthermore, the content of copper oxide particles in the layer disposed on the support is preferably 10% by volume or more, more preferably 15% by volume or more, and even more preferably 25% by volume or more per unit volume. Additionally, this content is preferably 90% by volume or less, more preferably 76% by volume or less, and even more preferably 60% by volume or less.

[0163] When the content of copper oxide particles in the insulating region is 40% by mass or more or 10% by volume or more, the particles fuse together during firing, exhibiting conductivity. Higher concentrations result in higher conductivity, which is preferred. Furthermore, when the content is 98% by mass or less or 90% by volume or less, the layer disposed on the support can adhere to the support or adhesive layer as a film, which is preferred. Additionally, when the content is 95% by mass or less or 76% by volume or less, it adheres more strongly to the support or adhesive layer, which is preferred. Furthermore, when the content is 90% by mass or less or 60% by volume or less, the flexibility of the layer increases, making it less prone to cracking during bending, resulting in high reliability. Moreover, when the content of copper oxide particles in the insulating region is 90% by volume or more, the insulation resistance value of the insulating region decreases, resulting in excellent electrical insulation, which is therefore preferred. As copper oxide, cuprous oxide (Cu₂O) and divalent copper oxide (CuO) are preferred, with cuprous oxide being preferred from the perspectives of low resistivity and light absorption.

[0164] The copper oxide contained in the insulating region in this embodiment can be a commercially available product or a synthetic product. Examples of commercially available products include, for instance, cuprous oxide microparticles with an average primary particle size of 18 nm, sold by EM Japan.

[0165] Examples of methods for synthesizing particles containing cuprous oxide include the following.

[0166] (1) A method of adding water and acetylacetone copper complex to a polyol solvent, temporarily heating and dissolving the organocopper compound, further adding the amount of water required for the reaction, and heating to the reduction temperature of the organocopper for reduction.

[0167] (2) A method of heating an organocopper compound (copper-N-nitrosophenylhydroxylamine complex) at a high temperature of about 300°C in the presence of a protective agent such as hexadecylamine and in an inert atmosphere.

[0168] (3) The method of reducing copper salts dissolved in aqueous solution with hydrazine.

[0169] The method described in (1) above can be carried out, for example, under the conditions described in Angewandte Chemi International Edition, No. 40, Volume 2, p. 359, 2001.

[0170] The method described in (2) above can be carried out, for example, under the conditions described in the Journal of American Chemical Society, 1999, Vol. 121, p. 11595.

[0171] In the method described in (3) above, a binary copper salt can be appropriately used as the copper salt. Examples of such salts include copper acetate (II), copper nitrate (II), copper carbonate (II), copper chloride (II), and copper sulfate (II). The amount of hydrazine used relative to 1 mole of copper salt is preferably 0.2 to 2 moles, more preferably 0.25 to 1.5 moles.

[0172] A water-soluble organic compound can be added to an aqueous solution containing dissolved copper salts. By adding this compound, the melting point of the solution decreases, thus enabling reduction at lower temperatures. Examples of water-soluble organic compounds include alcohols and water-soluble polymers.

[0173] As alcohols, examples include methanol, ethanol, propanol, butanol, hexanol, octanol, decanol, ethylene glycol, propylene glycol, and glycerol. As water-soluble polymers, examples include polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol copolymers.

[0174] In the method described in (3) above, the reduction temperature can be, for example, -20 to 60°C, preferably -10 to 30°C. This reduction temperature can be kept constant during the reaction, or it can be increased or decreased midway. In the initial stage of the reaction where hydrazine is highly reactive, reduction is preferably carried out at temperatures below 10°C, more preferably below 0°C. The reduction time is preferably 30 to 300 minutes, more preferably 90 to 200 minutes. The atmosphere used during reduction is preferably an inert atmosphere such as nitrogen or argon.

[0175] Of the methods (1) to (3) above, method (3) is preferred because it is easy to operate and can produce particles with small particle sizes.

[0176] In the embodiments described above, the insulating region contains copper oxide and phosphorus. In contrast, other embodiments may show a configuration where the insulating region contains copper oxide and hydrazine or hydrazine hydrate, or a configuration where the insulating region contains copper oxide, hydrazine or hydrazine hydrate, and phosphorus. That is, the layer is formed by adjacent conductive patterned regions containing copper and insulating regions containing copper oxide and hydrazine or hydrazine hydrate. Alternatively, the layer may also be formed by adjacent conductive patterned regions containing copper and insulating regions containing copper oxide, hydrazine or hydrazine hydrate, and phosphorus; or by adjacent conductive patterned regions containing copper and phosphorus and insulating regions containing copper oxide, hydrazine or hydrazine hydrate, and phosphorus.

[0177] Thus, in this embodiment, hydrazine or hydrazine hydrate can be included in the insulating region. By including hydrazine or hydrazine hydrate in the coating layer, copper oxide is easily reduced to copper upon exposure to light. By including hydrazine or hydrazine hydrate, low resistance of the reduced copper can be achieved. Hydrazine or hydrazine hydrate remains in the insulating region that is not exposed to light.

[0178] (Conductive pattern area)

[0179] The copper in the conductive pattern region can, for example, exhibit a structure formed by copper particles fused together. Alternatively, it can be a particle-free shape where all particles are fused. Furthermore, it can be a partially particle-shaped structure where most of the particles are fused. As described above, the copper is preferably reduced copper. Additionally, the conductive pattern region preferably comprises a sintered body formed by sintering the insulating region. This improves the conductivity of the conductive pattern region. Furthermore, since the conductive pattern region can be formed by sintering the insulating region, it is easy to form the conductive pattern region, and it is possible to form a "layer" in this embodiment where the conductive pattern region and the insulating region are mixed with good precision.

[0180] In addition to copper, the conductive pattern area may also contain at least one of the following: copper oxide (cuprous oxide, divalent copper oxide, monovalent copper oxide), phosphorus, phosphorus oxide, and phosphorus-containing organic compounds. For example, the surface portion of the conductive pattern area may be a structure formed by fusing copper particles together, while the support portion may be a structure containing copper oxide or phosphorus-containing organic compounds. Thus, the copper oxide or phosphorus-containing organic compounds can create a strong bond between the copper particles, thereby improving the adhesion to the support or adhesive layer, which is preferred.

[0181] Regarding the phosphorus content in the conductive pattern area, the phosphorus / copper element concentration ratio is preferably 0.02 to 0.30, more preferably 0.05 to 0.28, and even more preferably 0.1 to 0.25. Maintaining a phosphorus / copper element concentration ratio of 0.02 or higher suppresses copper oxidation and improves the reliability of copper wiring circuits, which is preferable. Furthermore, maintaining a phosphorus / copper element concentration ratio of 0.30 or lower reduces the resistance value of the conductive pattern area, which is also preferable.

[0182] As described above, the layer in this embodiment can be configured such that conductive patterned regions containing copper and phosphorus are adjacent to insulating regions containing copper oxide and phosphorus. This allows for simultaneous improvement of both the conductivity in the conductive patterned regions and the insulation in the insulating regions. It is believed that in the conductive patterned regions, since phosphorus oxidation occurs before copper oxidation during the manufacturing process, the resistance variation in the conductive patterned regions can be suppressed to a low level.

[0183] The copper content in the conductive pattern area is preferably 50% by volume or more, more preferably 60% by volume or more, even more preferably 70% by volume or more, and can be 100% by volume. By making the copper content 50% by volume or more, the conductivity is improved, and therefore preferred.

[0184] Regarding the surface in the conductive pattern area that contacts the resin layer (described later), its surface may have a roughness of a specified value or higher. Specifically, the surface roughness Ra is preferably 20 nm to 500 nm, more preferably 50 nm to 300 nm, and even more preferably 50 nm to 200 nm. By keeping the roughness within this range, a portion of the resin layer penetrates into the unevenness of the conductive pattern area surface, thereby improving adhesion, which is preferable.

[0185] (Sealed layer)

[0186] In the structure with wiring pattern areas according to this embodiment, it is preferable to have an adhesive layer between the support and the layer with conductive pattern areas. That is, it is preferable to have an adhesive layer on the surface formed by the support, and to arrange the layer with conductive pattern areas on the surface forming the adhesive layer.

[0187] The surface formed by the support is preferably roughened by a sealing layer.

[0188] By roughening the surface formed by the support, the copper oxide and phosphorus-containing organic matter in the layer disposed on the surface of the support, as well as the copper, can be firmly bonded to the surface formed by the support.

[0189] The adhesive layer can be formed by roughening the surface of the support through processes such as coarse grinding, sandblasting, chemical etching, reactive ion etching, plasma treatment, sputtering, and UV ozone treatment. Alternatively, the adhesive layer can also be formed by applying a coating material to the surface formed by the support to roughen the surface. The method used can be appropriately selected based on the material of the support.

[0190] (Coating material)

[0191] Examples of coating materials include organic materials, inorganic materials, and organic-inorganic composite materials.

[0192] The coating material preferably has a binding structure. Examples of binding structures include, for instance, hydroxyl (-OH) groups, amino groups, mercapto groups, phosphate groups, phosphonic acid groups, phosphonate groups, functional groups with a succinimide skeleton, functional groups with a pyrrolidone skeleton, selenol groups, polysulfide groups, polyselenide groups, carboxyl groups, functional groups with an anhydride skeleton, sulfonic acid groups, nitro groups, cyano groups, isocyanate groups, azide groups, silanol groups, silyl ether groups, and hydrogenated silyl groups. Preferably, the binding structure is a group selected from the group consisting of hydroxyl (-OH) groups, amino groups, phosphonic acid groups, and carboxylic acid groups. The -OH group is more preferably an Ar-OH group (Ar refers to an aromatic group) and / or a Si-OH group.

[0193] When the coating material has an Ar-O structure (Ar refers to aromatic compounds) and / or a Si-O structure, it is also preferred from the perspective of adhesion.

[0194] The coating material can be an organic material represented by the following chemical formula group.

[0195] [Chemistry 4]

[0196] Chemical formula (4)

[0197]

[0198] In the above chemical formula set, n is an integer greater than or equal to 1, X is the main framework of the organic material, and R is a functional group. Examples of functional groups represented by R in the above chemical formula set include hydrogen, halogen, alkyl (e.g., methyl, isopropyl, tert-butyl, etc.), aryl (e.g., phenyl, naphthyl, thiophene, etc.), haloaryl (e.g., pentafluorophenyl, 3-fluorophenyl, 3,4,5-trifluorophenyl, etc.), alkenyl, alkynyl, amide, acyl, alkoxy (e.g., methoxy, etc.), aryloxy (e.g., phenoxy, naphthyl, etc.), haloalkyl (e.g., perfluoroalkyl, etc.), thiocyanate, hydroxyl, amino, mercapto, phosphonic acid, phosphonate ester, functional groups with a succinimide framework, functional groups with a pyrrolidone framework, selenol, polysulfide, polyselenoside, carboxylic acid, functional groups with an anhydride framework, sulfonic acid, nitro, cyano, and structures formed by combining these. When the adhesive layer contains organic materials with these bonding structures, it tends to have good adhesion to the support and the layer with conductive patterned regions.

[0199] Organic materials with aromatic structures (Ar) can be appropriately used as organic materials. Organic materials with aromatic structures have high softening and decomposition temperatures, thus suppressing deformation of the support during firing and preventing damage to the layer with conductive patterned regions disposed on the support due to the decomposition gases of the support. Therefore, a conductive film with low resistance can be obtained through firing. As aromatic structures, aromatic hydrocarbons such as benzene, naphthalene, anthracene, tetraphenylene, pentaphenylene, phenanthrene, pyrene, dinaphthalene, and benzo[9,10]phenanthrene can be used; as well as heteroaromatics such as thiophene, thiazole, pyrrole, furan, pyridine, pyrazole, imidazole, pyrazine, pyrimidine, and pyrazine can be used. The number of electrons in the π-electron system of the aromatic structure is preferably 22 or less, more preferably 14 or less, and even more preferably 10 or less. When the number of electrons in the π-electron system is 22 or less, the crystallinity does not become too high, and a soft and smooth dense layer can be obtained. In these aromatic structures, a portion of the hydrogen atoms bonded to the aromatic ring can be replaced by functional groups. Examples of functional groups include halogens, alkyl groups (e.g., methyl, isopropyl, tert-butyl, etc.), aryl groups (e.g., phenyl, naphthyl, thiophene, etc.), haloaryl groups (e.g., pentafluorophenyl, 3-fluorophenyl, 3,4,5-trifluorophenyl, etc.), alkenyl, alkynyl, amide, acyl, alkoxy (e.g., methoxy, etc.), aryloxy (e.g., phenoxy, naphthyl, etc.), haloalkyl groups (e.g., perfluoroalkyl, etc.), thiocyanate, and hydroxyl groups. Organic materials preferably have aromatic hydroxyl groups (Ar-OH groups), and particularly preferably phenolic hydroxyl groups (Ph-OH groups). Furthermore, organic materials with Ar-O structures formed by the bonding of oxygen with aromatic hydroxyl groups to other structures tend to be less prone to decomposition during firing, and are therefore preferred.

[0200] Examples of organic materials include, for instance, polyimide, polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), polyester, polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacetal, polyaryl ester (PAR), polyamide (PA), polyamide-imide (PAI), polyether-imide (PEI), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyetherketone (PEK), polyphthalamide (PPA), polyether nitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, polysiloxane, polymethacrylamide, nitrile rubber, acrylic rubber, polytetrafluoroethylene, epoxy resin, and phenolic resin. The range of materials includes esters, melamine resins, urea resins, polymethyl methacrylate resins (PMMA), polybutene, polypentene, ethylene-propylene copolymers, ethylene-butene-diene copolymers, polybutadiene, polyisoprene, polychloroprene, ethylene-propylene-diene copolymers, nitrile rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, urethane rubber, butyl rubber, fluororubber, polymethylpentene (PMP), polystyrene (PS), styrene-butadiene copolymers, polyethylene (PE), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polyetheretherketone (PEEK), phenolic varnishes, benzocyclobutene, polyvinylphenol, polychloroprene, polyoxymethylene, polysulfone (PSF), and silicone resins. Preferably, the organic material is selected from at least one group consisting of phenolic resins, phenolic varnishes, polyvinylphenol, and polyimide.

[0201] Examples of inorganic materials include metals, alloys, metal oxides, metal nitrides, metal carbides, metal carbon oxides, and metal fluorides. More specifically, examples of inorganic materials include silicon oxide, silver oxide, copper oxide, aluminum oxide, zirconium oxide, titanium oxide, hafnium oxide, tantalum oxide, tin oxide, calcium oxide, cerium oxide, chromium oxide, cobalt oxide, holmium oxide, lanthanum oxide, magnesium oxide, manganese oxide, molybdenum oxide, nickel oxide, antimony oxide, samarium oxide, terbium oxide, tungsten oxide, yttrium oxide, zinc oxide, indium oxide, indium tin oxide (ITO), silver fluoride, silicon fluoride, aluminum fluoride, zirconium fluoride, titanium fluoride, hafnium fluoride, tantalum fluoride, tin fluoride, calcium fluoride, cerium fluoride, cobalt fluoride, holmium fluoride, and lanthanum fluoride. Materials such as magnesium fluoride, manganese fluoride, molybdenum fluoride, nickel fluoride, antimony fluoride, samarium fluoride, terbium fluoride, tungsten fluoride, yttrium fluoride, zinc fluoride, lithium fluoride, lead zirconate titanate (PZT), barium titanate, strontium titanate, copper nitride, silicon nitride, aluminum nitride, titanium nitride, hafnium nitride, tantalum nitride, tin nitride, calcium nitride, cerium nitride, cobalt nitride, holmium nitride, lanthanum nitride, magnesium nitride, manganese nitride, molybdenum nitride, nickel nitride, antimony nitride, samarium nitride, terbium nitride, tungsten nitride, yttrium nitride, zinc nitride, lithium nitride, gallium nitride, SiC, SiCN, and diamond-like carbon (DLC) are preferred. Inorganic materials with hydroxyl groups exhibit excellent adhesion to the support and the layer with conductive patterned regions, and are therefore preferred. In particular, the presence of hydroxyl groups on the surface of metal oxides makes metal oxides preferred. Among metal oxides, inorganic materials with a Si-O structure are particularly preferred.

[0202] More specifically, the inorganic material is preferably at least one selected from the group consisting of silicon oxide, titanium oxide, zirconium oxide, indium tin oxide, and aluminum oxide. Silicon oxide and aluminum oxide are particularly preferred.

[0203] Furthermore, the adhesive layer preferably comprises particles with a particle size of 10 nm to 500 nm. Specifically, the adhesive layer preferably comprises silicon oxide or aluminum oxide particles with a particle size of 10 nm to 500 nm. This increases the specific surface area of ​​the layer after the formation of the conductive patterned region, thereby improving the adhesion to the layer with the conductive patterned region. The particles may also be porous particles.

[0204] Inorganic semiconductors can also be used as inorganic materials. Examples of inorganic semiconductor materials include elemental semiconductors, oxide semiconductors, compound semiconductors, and sulfide semiconductors. Examples of elemental semiconductors include silicon and germanium. Examples of oxide semiconductors include IGZO (indium gallium zinc oxide), IZO (indium zinc oxide), zinc oxide, indium oxide, titanium oxide, tin oxide, tungsten oxide, niobium oxide, and cuprous oxide. Examples of compound semiconductors include gallium arsenide (GaAs), gallium arsenide phosphide (GaAsP), gallium phosphide (GaP), cadmium selenide (CdSe), silicon carbide (SiC), indium antimonide (InSb), and gallium nitride. Examples of sulfide semiconductors include molybdenum sulfide and cadmium sulfide.

[0205] As an organic-inorganic composite material, organic materials and organometallic compounds, for example, in which inorganic particles are dispersed, can be used. As inorganic particles, particles of the aforementioned inorganic materials can be used. Examples of organometallic compounds include silicates, titanates, and aluminates. As silicates, methyl silicate and ethyl silicate can be used.

[0206] Furthermore, the thickness of the sealing layer is preferably 20 μm or less. This prevents warping of the support. More preferably, the film thickness of the sealing layer is 10 μm or less, even more preferably 1 μm or less, and from the perspective of adhesion, preferably 0.01 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more.

[0207] (Primer material)

[0208] The adhesive layer can be formed from a single material, or from a mixture or lamination of two or more materials. For example, the adhesive layer may contain a primer material. Additionally, a primer material layer may be disposed, for example, between a support and a layer made of a coating material, or between a layer made of a coating material and a layer having conductive patterned regions.

[0209] When the adhesive layer includes a layer composed of a primer material, the adhesion tends to be further improved. A layer composed of a primer material can be formed, for example, by a primer treatment that forms a thin layer of primer material on the surface.

[0210] The primer material preferably has a bonding structure. Examples of bonding structures include those described in the section on "(coating materials)" above. By giving the primer material a bonding structure, this bonding structure is incorporated into the adhesive layer, tending to result in high adhesion.

[0211] A bonding layer can be formed by applying a primer to the support and then depositing a layer of coating material. Alternatively, a bonding layer can be formed by depositing a layer of coating material on the support and then applying a primer to that layer. Alternatively, the coating material and primer material can be premixed and deposited on the support to form a bonding layer, or a layer of primer material can be deposited on the support to form a bonding layer. Applying a primer to a layer of coating material increases the density of the surface bonding structure, thus resulting in higher adhesion.

[0212] Examples of primer materials include silane coupling agents, phosphonic acid-based low-molecular-weight materials, and thiol-based materials.

[0213] Examples of silane coupling agents include compounds having functional groups such as vinyl, amino, epoxy, styrene, methacryloyl, acryloyl, isocyanurate, urea, mercapto, isocyanate, and phosphonic acid groups at their ends. Specifically, examples of silane coupling agents include vinylmethoxysilane, vinylethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styrenetrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, N- 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

[0214] Examples of phosphonic acid-based materials include compounds with functional groups such as vinyl, amino, epoxy, styrene, methacryloyl, acryloyl, isocyanurate, urea, mercapto, isocyanate, silyl, silanol, and silyl ether groups at their ends. Specifically, examples of phosphonic acid-based materials include aminomethylphosphonic acid, 2-aminoethylphosphonic acid, O-phosphorylethanolamine, 12-aminododecylphosphonic acid, 12-aminoundecylphosphonate, 6-aminohexylphosphonic acid, 6-aminohexylphosphonate, 12-azidodecylphosphonic acid, (12-dodecylphosphonic acid)N,N-dimethyl-N-octadecylammonium bromide, (12-dodecylphosphonic acid)N,N-dimethyl-N-octadecylammonium chloride, (12-dodecylphosphonic acid)pyridinium bromide, (12-dodecylphosphonic acid)triethylammonium bromide, (12-dodecylphosphonic acid)triethylammonium chloride, 11-hydroxyundecylphosphonic acid, and 12-mercaptododecane. Phosphonic acid, 11-mercaptoundecylphosphonic acid, 11-methacryloyloxyundecylphosphonic acid, 4-nitrobenzylphosphonic acid, 12-phosphono-1-dodecanesulfonic acid, (6-phosphonohexyl)phosphonic acid, 11-phosphonoundecanoic acid, 11-phosphonoundecyl acrylate, propylene diphosphonic acid, 4-aminobenzylphosphonic acid, 1,8-octanediphosphonic acid, 1,10-decyldiphosphonic acid, 6-phosphonohexanoic acid, (1-amino-2-methylpropyl)phosphonic acid, (1-aminopropyl)phosphonic acid, (3-nitrophenyl)phosphonic acid, 1-hydroxyethane-1,1,-diphosphonic acid, 3-aminopropylphosphonic acid, 4-aminobutylphosphonic acid, nitrotri(methylene)triphosphonic acid, and methylene diphosphonic acid, etc.

[0215] As thiol-based materials, compounds with functional groups such as vinyl, amino, epoxy, styrene, methacryl, acryloyl, isocyanurate, urea, isocyanate, silyl, silanol, silyl ether, and phosphonic acid groups at their terminals can be appropriately used. Specifically, examples of thiol-based materials include 4-cyano-1-butanethiol, 1,11-undecanedithiol, 1,16-hexadecanedithiol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2,2'-(ethylenedioxy)diethanedithiol, 2,3-butanedithiol, and 5,5'- Bis(mercaptomethyl)-2,2'-bipyridine, hexa(ethylene glycol)dithiol, tetra(ethylene glycol)dithiol, benzene-1,4-dithiol, (11-mercaptoundecyl)hexa(ethylene glycol), (11-mercaptoundecyl)tetra(ethylene glycol), 1-mercapto-2-propanol, 11-amino-1-undecylthiol, 11-amino-1-undecylthiol hydrochloride, 11-azido-1-undecylthiol, 11-mercapto-1-undecylol, 11-mercapto-2-propanol Undecanoamide, 11-mercaptoundecanoic acid, 11-mercaptoundecylhydroquinone, 11-mercaptoundecylphosphonic acid, 12-mercaptododecanonical acid, 16-amino-1-hexadecylthiol, 16-amino-1-hexadecylthiol hydrochloride, 16-mercaptohexadecanoamide, 16-mercaptohexadecanoic acid, 3-amino-1-propanethiol, 3-amino-1-propanethiol hydrochloride, 3-mercapto-1-propanol, 3-mercaptopropionic acid, 4-mercapto-1-butanol, 6-Amino-1-hexanethiol, 6-amino-1-hexanethiol hydrochloride, 6-mercapto-1-hexanol, 6-mercaptohexanoic acid, 8-amino-1-octanethiol, 8-amino-1-octanethiol hydrochloride, 8-mercapto-1-octanol, 8-mercaptooctanoic acid, 9-mercapto-1-nonanol, 1,4-phenylenediethanethiol, 4,4'-bis(mercaptomethyl)biphenyl, 4,4'-dimercaptobis(diphenylethylene), 4-mercaptobenzoic acid, biphenyl-4,4-dithiol, etc.

[0216] Methods for forming a layer composed of a coating material include coating, vapor deposition, and sol-gel methods. From the perspective of preventing warping of the support, the thickness of the layer composed of the coating material is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 1 μm or less; from the perspective of adhesion, this thickness is preferably 0.01 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more.

[0217] In this embodiment, when the support has an adhesive layer, the phosphorus-containing organic material can have more than one bonding structure. Examples of bonding structures include those described in the "(Coating Material)" section above. As a bonding structure, a structure having at least one selected from the group consisting of hydroxyl, amino, phosphonic acid, phosphonate, and isocyanate groups is particularly preferred. When the layer with the conductive patterned region contains a phosphorus-containing organic material having these bonding structures, the adhesion to the adhesive layer tends to be good.

[0218] <Construction of a structure with conductive patterned regions: Second embodiment>

[0219] Figure 3 This is a cross-sectional schematic diagram showing a structure with a conductive patterned region according to the second embodiment. For example... Figure 3 As shown, the structure 20 with conductive patterned regions includes a support 21 and a layer 24 disposed on the surface formed by the support 21. Furthermore, in layer 24, insulating regions 22 containing copper oxide and phosphorus and conductive patterned regions 23 containing reduced copper are disposed adjacent to each other. Additionally, an oxygen barrier layer 25 is provided as a cover layer 24. The oxygen barrier layer 25 is light-transmitting.

[0220] It should be noted that the insulating region 22 may be composed of copper oxide and hydrazine or hydrazine hydrate, or it may be composed of copper oxide, phosphorus, and hydrazine or hydrazine hydrate. Additionally, the conductive pattern region 23 may be composed of copper and phosphorus. Layer 24 in this embodiment may be configured such that the conductive pattern region 23 containing copper is adjacent to the insulating region 22 containing copper oxide and phosphorus; or the conductive pattern region 23 containing copper is adjacent to the insulating region 22 containing copper oxide and hydrazine or hydrazine hydrate; or the conductive pattern region 23 containing copper and phosphorus is adjacent to the insulating region 22 containing copper oxide and phosphorus. Alternatively, layer 24 may be configured such that the conductive pattern region 23 containing copper is adjacent to the insulating region 22 containing copper oxide, hydrazine or hydrazine hydrate, and phosphorus; or the conductive pattern region 23 containing copper and phosphorus is adjacent to the insulating region 22 containing copper oxide, hydrazine or hydrazine hydrate, and phosphorus.

[0221] The structure 20 in the second embodiment has a resin layer (oxygen barrier layer 25), which is different from the structure 10 in the first embodiment.

[0222] With the configuration of the second embodiment, insulating regions containing copper conductive pattern areas can be used to insulate between each other using insulating regions containing copper oxide and phosphorus-containing organic matter, thus eliminating the need to remove the unburned portion of layer 24 for manufacturing. Therefore, manufacturing steps can be reduced, and manufacturing costs can be lowered since solvents are not required. Furthermore, using insulating regions to insulate the conductive pattern areas reduces the likelihood of cracking, improving reliability.

[0223] Furthermore, since layer 24 is covered by a resin layer (oxygen barrier layer 25), it can protect the conductive pattern area and the insulating area from external stress, thereby improving the long-term reliability of the structure with the conductive pattern area.

[0224] Regarding the configurations of the support 21, insulating region 22, conductive patterned region 23, and layer 24 constituting the structure 20, the configurations of the support 11, insulating region 12, conductive patterned region 13, and layer 14 described above can be applied. Additionally, the structure 20 may also include the aforementioned sealing layer.

[0225] The resin layer is described in detail.

[0226] <Resin Layer>

[0227] like Figure 3 As shown, the resin layer is configured in a manner consistent with the surface of the cover layer 24.

[0228] (Oxygen barrier layer)

[0229] One example of a resin layer is an oxygen barrier layer 25. In the manufacturing method of the structure 20 described later, the oxygen barrier layer 25 prevents the coating layer (described later) from contacting oxygen during light irradiation, thereby promoting the reduction of copper oxide. Therefore, equipment for creating an oxygen-free or low-oxygen atmosphere around the coating layer during light irradiation, such as a vacuum atmosphere or an inert gas atmosphere, is not required, thus reducing manufacturing costs.

[0230] Furthermore, the oxygen barrier layer 25 prevents the conductive pattern area 23 from peeling or scattering due to heat or light exposure. As a result, the structure 20 can be manufactured with a high yield.

[0231] (Sealing material layer)

[0232] Other examples of resin layers are sealing material layers. Figure 4 To show with Figure 3 Cross-sectional schematic diagrams of other examples of structures with different conductive patterned regions. Figure 4 In the structure 30 with conductive patterned areas shown, the sealing material layer 31 replaces the oxygen barrier layer 25 (see reference). Figure 3 To cover the surface of layer 24, in addition to Figure 3The structure 20 shown has the same configuration.

[0233] The sealing material layer 31 is reconfigured, for example, after the oxygen barrier layer 25 is stripped.

[0234] Oxygen barrier layer 25 (reference) Figure 3 It plays a crucial role primarily during manufacturing. In contrast, the sealing material layer 31 protects the conductive patterned area 23 from external stresses in the finished product (the structure 30 with the conductive patterned area itself and the product containing it), thereby improving the long-term stability of the structure 30 with the conductive patterned area.

[0235] In this case, the sealing material layer 31, as an example of a resin layer, preferably has a moisture permeability of 1.0 g / m³. 2 / day or less. This is to ensure long-term stability, fully reduce moisture permeability, thereby preventing moisture from mixing in from the outside of the sealing material layer 31 and inhibiting oxidation of the conductive pattern area 23.

[0236] The sealing material layer 31 is an example of a functional layer that imparts functionality to the structure 30 with conductive patterned areas after the oxygen barrier layer 25 is peeled off. In addition, it can also make the structure 30 resistant to damage when handling the structure 30 with conductive patterned areas, have anti-fouling properties to prevent it from being contaminated by external sources, or make the structure 20 rigid by using a tough resin.

[0237] It should be noted that in this specification, functional layers such as sealing material layers other than oxygen barrier layers are referred to as "other resin layers".

[0238] This embodiment uses the following example for illustration: In the manufacturing method of a structure having a conductive patterned area (described later), an oxygen barrier layer 25 is configured in a manner similar to a coating layer (see reference). Figure 3 After photoforming, the oxygen barrier layer 25 is removed, and a sealing material layer 31, which is an example of other resin layers, is configured in the manner of the cover layer 24 (see reference). Figure 4 That is, structure 20 (refer to...). Figure 3 It can be said that it is used to obtain a structure 30 with conductive patterned areas as a finished product (refer to) Figure 4 The precursor structure of ) is used directly. However, the structure 20, which still retains the oxygen barrier layer 25 as is (see reference) Figure 2 It's fine as a finished product.

[0239] The resin constituting the above-mentioned resin layer preferably has a melting point of 150°C to 300°C. By using such a resin, a safety margin of more than twice that of the actual operating temperature range (maximum 75°C) can be ensured, and it can be thermally melted and laminated during the formation of the resin layer, which is therefore preferred.

[0240] An opening is preferably provided in the resin layer. This opening is provided for electrical connection with the conductive pattern area from the outside, and electrical contacts can be installed in the opening by methods such as metal plating or welding.

[0241] The resin layer will be described in more detail. First, the oxygen barrier layer will be explained. The oxygen barrier layer prevents oxygen from entering the coating layer from the outside during light exposure. For example, the following materials can be used as the oxygen barrier layer. The following materials can be used: polypropylene (PP), polyimide (PI), polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), polyester, polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacetal (POM), polyarylate (PAR), polyamide (PA), polyamide-imide (PAI), polyether-imide (PEI), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyphenylene sulfide (PPS), polyetherketone (PEK), polyphthalamide (PPA), polyether nitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, polysiloxane, polymethacrylamide, nitrile rubber, acrylic rubber, polytetrafluoroethylene, epoxy resin, phenolic resin, melamine resin, urea resin, polymethyl methacrylate resin (PMMA), polybutene, and polypentene. Resin materials composed of ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene, ethylene-propylene-diene copolymer, butyl rubber, polymethylpentene (PMP), polystyrene (PS), styrene-butadiene copolymer, polyethylene (PE), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polyether ether ketone (PEEK), phenolic varnish, benzocyclobutene, polyvinylphenol, polychloroprene, polyoxymethylene, polysulfone (PSF), polyphenylene sulfone resin (PPSU), cyclic olefin polymer (COP), acrylonitrile-butadiene-styrene resin (ABS), acrylonitrile-styrene resin (AS), nylon resin (PA6, PA66), polybutyl terephthalate resin (PBT), polyether sulfone resin (PESU), polytetrafluoroethylene resin (PTFE), polychlorotrifluoroethylene (PCTFE), and silicone resin, etc.

[0242] In addition, an adhesive layer can be provided between the oxygen barrier layer and the coating layer to bond the oxygen barrier layer and the coating layer together.

[0243] Next, other resin layers will be described. As an example of other resin layers, the sealing material layer ensures long-term stability. The sealing material layer preferably has sufficiently low moisture permeability. This is to prevent moisture from mixing in from the outside of the sealing material layer and to inhibit oxidation of the conductive pattern areas. The moisture permeability of the sealing material layer is preferably 1.0 g / m³. 2For doses below / day, 0.5g / m² is preferred. 2 Below / day, further preferably 0.1g / m 2 / day or less. By using a sealing material layer with such a moisture permeability range, resistance changes caused by oxidation of conductive pattern areas can be suppressed in long-term stability tests, for example, at 85°C and 85% humidity.

[0244] The materials that can be used for the sealing material layer can be selected from the same materials as the oxygen barrier layer described above. Alternatively, microparticles composed of silicon oxide or aluminum oxide can be mixed into these materials, or a layer composed of silicon oxide or aluminum oxide can be provided on the surface of these materials as a moisture barrier layer, thereby reducing moisture permeability.

[0245] Furthermore, the sealing material layer does not have to be composed of a single material; multiple of the aforementioned materials can also be used.

[0246] The structure with conductive patterned regions described above is manufactured using a laminate as an intermediate, as described below. That is, in order to obtain the desired structure with conductive patterned regions, the structure of the laminate as an intermediate needs to be optimized. Therefore, the structure of the laminate in this embodiment will be described below.

[0247] <Summary of the laminate in this embodiment>

[0248] The inventors disposed a coating layer containing copper oxide on the surface of a support, and selectively irradiated the coating layer with light to reduce the copper oxide to copper, thereby forming conductive patterned areas. It was found that by improving the electrical insulation of the areas containing unreduced copper oxide, insulation between conductive patterned areas can be ensured without removing these areas and leaving them as is, thus eliminating the need for a process to remove these areas.

[0249] Further discovery revealed that by setting a resin layer on the coating layer, when the copper oxide is fired under light (hereinafter referred to as "light firing"), it is not necessary to use equipment to achieve a vacuum atmosphere or inert gas atmosphere, thereby reducing the manufacturing cost of the structure with the conductive patterned area, thus completing the present invention.

[0250] That is, such as Figure 5 As shown, the laminate 40 in this embodiment is characterized by having a support 41, a coating layer 44 comprising copper oxide and phosphorus disposed on the surface formed by the support 41, and an oxygen barrier layer 45, which is an example of a resin layer disposed in a manner covering the coating layer 44. The oxygen barrier layer 45 is light-transmitting.

[0251] like Figure 5 As shown, an adhesive layer 46 is provided between the coating layer 44 and the oxygen barrier layer 45 as needed.

[0252] like Figure 5 As shown, since the coating layer 44 is covered by the resin layer (oxygen barrier layer 45), it prevents the coating layer 44 from contacting oxygen during photofiring, thus promoting the reduction of copper oxide. Therefore, equipment for creating an oxygen-free or low-oxygen atmosphere around the coating layer 44 is not required during photoirradiation, reducing manufacturing costs. Therefore, by using the laminate of this embodiment, a laminate with the desired conductive patterned area can be manufactured with high precision and at low cost.

[0253] Regarding the support 41 constituting the laminate 40 and the resin layer ( Figure 5 As an example, the oxygen barrier layer 45 in the laminate can be constructed using the aforementioned components of the support 11 and the resin layer (oxygen barrier layer 25). Furthermore, in the laminate 40, the aforementioned adhesive layer may also be included between the support 41 and the coating layer 44.

[0254] The coating layer 44 and the adhesive layer 46 will be described in detail below.

[0255] <Coating Layer>

[0256] The coating layer 44 is formed by coating a dispersion onto the surface of the support 41. The dispersion is formed by dispersing copper oxide in a dispersion medium using phosphorus, which also acts as a dispersant, particularly phosphorus-containing organic matter.

[0257] The detailed preparation methods of phosphorus-containing organic compounds, dispersion media, and dispersions are described below.

[0258] Coating layer 44 and Figure 3 The insulating regions 22 are essentially composed of the same elements.

[0259] In addition, with Figure 1 , Figure 3 Similarly, in the insulating regions 12 and 22 shown, the coating layer 44 contains a mixture of copper oxide particles and phosphorus-containing organic matter. When the total volume of the copper oxide particles is 100 parts by volume, the content of the phosphorus-containing organic matter is preferably 5 parts by volume or more and 900 parts by volume or less. This results in a coating layer 44 that is highly flexible, does not easily crack even when bent, and can form a patterned area with good conductivity through firing.

[0260] Furthermore, the coating layer 44 preferably further comprises copper particles, and the mass ratio of copper particles to copper oxide particles in the coating layer is preferably 1.0 to 7.0 or less. This can suppress the occurrence of cracks and enable the formation of a patterned area with good electrical conductivity through firing.

[0261] Furthermore, the content of copper oxide particles relative to the coating layer 44 is preferably 10% by volume or more and 90% by volume or less. This allows the particles to easily fuse together and exhibit conductivity during the firing of the coating layer 44. Additionally, it enables the coating layer 44 to effectively adhere to the support or adhesive layer.

[0262] Furthermore, the average particle size (average primary particle size) of the copper oxide particles contained in the coating layer 44 is preferably 1 nm or more and 50 nm or less. This allows for a reduction in the firing temperature of the coating layer 44 and an improvement in the dispersibility of the copper oxide particles in the coating layer 44.

[0263] Alternatively, the coating layer 44 can be composed of copper oxide and hydrazine or hydrazine hydrate, or it can be composed of copper oxide, phosphorus-containing organic matter, and hydrazine or hydrazine hydrate. By including hydrazine or hydrazine hydrate, copper oxide can be easily reduced to copper upon exposure to light.

[0264] <Adhesive Layer>

[0265] An adhesive layer 46 is disposed between the coating layer 44 and the oxygen barrier layer 45 as needed, so as to attach the oxygen barrier layer 45 to the surface of the coating layer 44.

[0266] The adhesive strength of the adhesive layer 46 is preferably 5 mN / 10 mm or more and 10 N / 10 mm or less. By making the adhesive strength 5 mN / 10 mm or more and less than 1 N / 10 mm, the oxygen barrier layer 45 can be fixed to the coating layer 44 by the adhesive layer 46, and the oxygen barrier layer 45 can be easily peeled off in subsequent processes. Furthermore, by making the adhesive strength 1 N / 10 mm or more and 10 N / 10 mm or less, the oxygen barrier layer 45 can be firmly fixed to the coating layer 44 by the adhesive layer 46.

[0267] The adhesive layer 46 is an adhesive sheet, adhesive film, or adhesive material. The adhesive contained in the adhesive layer 46 is not particularly limited, and examples include acrylic resin, epoxy resin, and silicone resin.

[0268] When the oxygen barrier layer 45 is a resin film having an adhesive layer 46, it is preferable to easily form the oxygen barrier layer 45 by bonding the resin film to the surface of the coating layer 44. Furthermore, by selecting the adhesive strength as described above, the oxygen barrier layer 45 can be peeled off as needed. By peeling off the oxygen barrier layer 45 in this way, a... Figure 2 The structure shown is structure 10.

[0269] It should be noted that if the oxygen barrier layer 45 is a layer formed by a cured resin, or a layer formed by heating and extruding a thermoplastic resin, the adhesive layer may be omitted.

[0270] In addition, in this embodiment, it is preferable to have a layer containing silicon oxide or aluminum oxide between the coating layer 44 and the resin layer. The layer containing silicon oxide or aluminum oxide can function as a moisture barrier layer, thereby reducing moisture permeability.

[0271] Figure 6 Is using Figure 5 The diagram shows a cross-sectional view of a structure 50 with conductive patterned regions formed by a laminate. (See diagram for reference.) Figure 6 As shown, the structure 50 having a conductive patterned area includes: a support 51; an insulating area 52 containing copper oxide and phosphorus-containing organic matter and a conductive patterned area 53 containing reduced copper disposed adjacent to each other on the surface formed by the support 51; an oxygen barrier layer 55, which is an example of a resin layer, disposed as a cover layer 54; and an adhesive layer 56 sandwiched between the layer 54 and the oxygen barrier layer 55.

[0272] Figure 6 The structure 50 shown, which has a conductive patterned region, is related to... Figure 3 The structure shown in structure 20 is basically the same, but... Figure 6 In this process, an adhesive layer 56 is sandwiched between layer 54 and oxygen barrier layer 55, which is consistent with... Figure 3 different. Figure 6 In this structure, the adhesive layer 56 improves the adhesion between the oxygen barrier layer 55 and the layer 54, enabling the creation of a structure 50 with a conductive patterned area exhibiting excellent durability. Furthermore, by sandwiching a layer containing silicon oxide and aluminum oxide between the oxygen barrier layer 55 and the layer 54, moisture barrier properties can also be improved.

[0273] in addition, Figure 6 Alternatively, the oxygen barrier layer 55 can be replaced with other resin layers as needed. In this case, by pre-applying a weak adhesive to the adhesive layer 56, the oxygen barrier layer 55 can be easily peeled off from the layer 54. An adhesive layer 56, or a layer containing silicon oxide or aluminum oxide, can also be sandwiched between other resin layers and the layer 54. When other layers are directly bonded to the surface of the layer 54 without sandwiching an adhesive layer 56 or a layer containing silicon oxide or aluminum oxide, a solution is obtained. Figure 3 The structure shown is a structure 50 with a conductive patterned region.

[0274] <Overview of copper wiring in this embodiment>

[0275] In the above-described structure, the inventors have developed a copper wiring system composed of conductive patterned regions. Specifically, in this embodiment, the conductive patterned regions of the layers adjacent to the insulating regions are the copper wiring systems described below. Alternatively, in this embodiment, the insulating regions can also be removed to obtain the copper wiring system.

[0276] The copper wiring in this embodiment comprises reduced copper (formed by reducing copper oxide), phosphorus, and carbon. It is characterized in that the phosphorus / copper elemental concentration ratio is 0.02 to 0.30, and the carbon / copper elemental concentration ratio is 1.0 to 6.0. The arithmetic mean surface roughness Ra of the copper wiring is preferably 20 nm to 500 nm.

[0277] As described above, the phosphorus content relative to copper is preferably in the range of 0.02 to 0.30. More preferably, it is in the range of 0.05 to 0.28, and even more preferably, it is in the range of 0.1 to 0.25. Maintaining a phosphorus / copper concentration of 0.02 or higher suppresses copper oxidation and improves the reliability of copper wiring circuits, which is preferable. Furthermore, maintaining a phosphorus / copper concentration of 0.30 or lower reduces the resistance of the wiring, which is also preferable.

[0278] As described above, the carbon content relative to copper is preferably in the range of 1.0 to 6.0. More preferably, it is in the range of 1.5 to 5.5, and even more preferably, it is in the range of 2.0 to 5.0. By making the carbon / copper concentration 1.0 or higher, the flexibility of the copper wiring can be accommodated. In addition, by making the carbon / copper concentration 6.0 or lower, the resistance value of the wiring can be reduced, which is preferred.

[0279] The carbon originates from the residue produced when organic components such as phosphorus-containing organic matter or glycols in the coating layer reduce copper oxide.

[0280] As described above, Ra is preferably 20 nm to 500 nm. Ra is more preferably 50 nm to 300 nm, and even more preferably 50 nm to 200 nm. Ra is the arithmetic mean roughness of the copper wiring surface, and when the copper wiring is covered by a resin layer, it refers to the surface roughness of the surface in contact with the resin layer. By making Ra 20 nm to 500 nm, the adhesion with the resin layer can be improved, which is preferred.

[0281] The copper wiring may further contain nitrogen. The nitrogen / copper elemental concentration ratio is preferably 0.04 to 0.6, more preferably 0.1 to 0.55, and even more preferably 0.2 to 0.5. Maintaining a nitrogen / copper elemental concentration ratio of 0.04 or higher improves the corrosion resistance of the copper wiring, while maintaining a ratio of 0.6 or lower reduces the wiring's resistance, which is preferable. The nitrogen originates from residues generated during the reduction of copper oxide by hydrazine or hydrated hydrazine in the coating layer.

[0282] The copper wiring preferably comprises reduced copper (formed by reducing copper oxide), phosphorus, and carbon, with the concentration ratio of each element, i.e., phosphorus:carbon:copper, preferably in the range of 0.02:1:1 to 0.3:6:1. This concentration ratio is more preferably in the range of 0.05:1.5:1 to 0.28:5.5:1, and even more preferably in the range of 0.1:2:1 to 0.25:5:1. It should be noted that the above ranges are defined with a copper element concentration of 1. By including reduced copper, phosphorus, and carbon within this range, the resistance of the wiring can be reduced, and the oxidation inhibition and flexibility of copper can be maximized.

[0283] The copper wiring preferably contains reduced copper (formed by reducing copper oxide), phosphorus, carbon, and nitrogen, with the concentration ratio of each element, i.e., phosphorus:carbon:nitrogen:copper, preferably in the range of 0.02:1:0.04:1 to 0.3:6:0.6:1. This concentration ratio is more preferably in the range of 0.05:1.5:0.1:1 to 0.28:5.5:0.55:1, and even more preferably in the range of 0.1:2:0.2:1 to 0.25:5:0.5:1. It should be noted that the above ranges are defined with a copper element concentration of 1. By including reduced copper, phosphorus, carbon, and nitrogen within this range, the resistance of the wiring can be reduced, and the oxidation inhibition, flexibility, and corrosion resistance of copper can be maximized.

[0284] Next to Figure 2 The manufacturing method of the first structure 10 shown will be described. The manufacturing method of the first structure 10 mainly includes the following steps.

[0285] (A) A process of applying a coating layer containing copper oxide and phosphorus-containing organic matter to the surface formed by the support.

[0286] (B) A process of selectively irradiating the coating layer with light to reduce copper oxide to copper, thereby obtaining a support, and a layer in which an insulating region containing copper oxide and the aforementioned phosphorus-containing organic matter and a conductive pattern region containing copper are arranged adjacent to each other on the surface of the support.

[0287] In (A) above, a coating layer containing copper oxide and hydrazine or hydrazine hydrate can be deposited on the surface formed by the support. Alternatively, a coating layer containing copper oxide, a phosphorus-containing organic compound, and hydrazine or hydrazine hydrate can be deposited on the surface formed by the support. By including hydrazine or hydrazine hydrate, further reduction using light can be performed, resulting in a copper film with low resistance.

[0288] As shown in (A) above, a coating layer containing copper oxide and phosphorus is first applied to the surface formed by the support. Examples of methods include: (a) coating a dispersion containing copper oxide and a phosphorus-containing organic compound; (b) dispersing copper oxide particles and then coating with a phosphorus-containing organic compound; (c) coating with a phosphorus-containing organic compound and then dispersing copper oxide particles; and so on. Method (a) will be described below as an example, but is not limited to this method.

[0289] (Preparation method of dispersion)

[0290] Next, the preparation method of the dispersion will be explained. First, copper oxide particles are dispersed together with phosphorus-containing organic matter in a dispersion medium to prepare a copper oxide dispersion.

[0291] For example, the copper oxide particles synthesized by the method described in (3) above are soft aggregates, which are not suitable for direct coating and therefore need to be dispersed in a dispersion medium.

[0292] After the synthesis in the above method (3) is terminated, the synthesis solution and copper oxide particles are separated by a known method such as centrifugation. A dispersion medium and a phosphorus-containing organic compound are added to the obtained copper oxide particles, and the copper oxide particles are dispersed in the dispersion medium by stirring using a known method such as a homogenizer.

[0293] In this embodiment, the phosphorus-containing organic compound functions as a dispersant. However, other dispersants may be added, as long as they do not affect the insulating area. Figure 2 The extent to which the electrical insulation of the insulating region 12 shown is affected is determined by the degree of electrical insulation.

[0294] It should be noted that copper oxide particles are not easily dispersed using a dispersion medium, and dispersion may be insufficient. In such cases, the copper oxide can be dispersed using an easily dispersible alcohol (e.g., butanol), then replaced with the desired dispersion medium and concentrated to the desired concentration. As an example, methods such as concentration using a UF membrane, and repeated dilution and concentration using the desired dispersion medium, can be cited.

[0295] (Coating)

[0296] A thin film composed of the dispersion according to this embodiment is formed on the surface of the aforementioned support. More specifically, for example, the dispersion is coated onto the support, and the dispersion medium is removed by drying as needed to form a coating layer. The method for forming this coating layer is not particularly limited, and coating methods such as mold coating, spin coating, slot coating, rod coating, doctor blade coating, spraying, and dip coating can be used. It is preferable to use these methods to coat the dispersion onto the support with a uniform thickness.

[0297] Preferably, the oxygen barrier layer is configured in a manner that covers a coating layer applied to the support. Wherein, as... Figure 2 In the manufacturing method of the structure 10 shown, the configuration of the oxygen barrier layer is not necessary.

[0298] (Firing process)

[0299] As shown in (B) above, in this embodiment, a heat treatment is performed under the following conditions to form a conductive pattern area: the copper oxide in the coating layer is reduced to generate copper particles, and the generated copper particles are fused together to form an integrated structure.

[0300] In this embodiment, selective light irradiation is used in the firing process. In this embodiment, as a light firing method, a flash method using a xenon discharge tube or a laser method can be applied, for example. These methods expose the substrate with high-intensity light for a short time, causing the coating layer formed on the support to reach a high temperature for firing in a short time. Because the firing time is short, there is less damage to the support, making it suitable for resin film substrates with low heat resistance.

[0301] Flashing methods include using a xenon lamp (discharge tube) to instantaneously discharge the charge stored in a capacitor. This method generates a large amount of pulsed light (xenon lamp light) that irradiates a coating layer formed on a support, thereby instantaneously heating the coating layer to a high temperature. The exposure can be adjusted by light intensity, irradiation time, irradiation interval, and number of exposures.

[0302] To form conductive patterned areas, the coating layer can be selectively illuminated by a light source through a mask.

[0303] Despite the different light sources, the same effect can be achieved even when using a laser source. In the case of a laser source, in addition to adjusting the flash pattern, there is also freedom in wavelength selection; the absorption wavelength of the coating layer or the absorption wavelength of the support can be considered for selection.

[0304] In addition, based on the laser method, exposure can be performed by beam scanning, the exposure range can be easily adjusted, and the coating layer can be selectively illuminated (drawn) without the use of a mask.

[0305] As types of laser sources, YAG (yttrium aluminum garnet), YVO (yttrium vanadate), Yb (ytterbium), semiconductor lasers (GaAs, GaAlAs, GaInAs), carbon dioxide, etc. can be used. As lasers, they can not only pick up the fundamental wave but also harmonics as needed.

[0306] In this embodiment, the light source is preferably a laser with a center wavelength of 355 nm to 532 nm. By producing this wavelength, it becomes the wavelength absorbed by the coating layer containing cuprous oxide, thus uniformly generating the reduction of cuprous oxide and obtaining regions with low resistance (conductive pattern regions).

[0307] In this embodiment, by making the support translucent, light can pass through the support, thus enabling proper firing of a portion of the coating layer.

[0308] It should be noted that as long as the coating layer has an oxygen barrier layer on its surface, by making one of the support or the coating layer light-transmitting, light can be passed through the support or through the coating layer through the oxygen barrier layer, and a portion of the coating layer can be properly fired.

[0309] Furthermore, in a configuration where an oxygen barrier layer is disposed on the surface of the coating layer, by removing the oxygen barrier layer after forming the conductive patterned area, a solution can be obtained. Figure 2 The structure shown is 10.

[0310] Reference Figure 7 The manufacturing method of the support having a conductive patterned region according to the first embodiment will be described in more detail. Figure 7 This is an explanatory diagram showing each step of the manufacturing method of the support with conductive patterned areas according to the first embodiment. Figure 7 In (a) of the above, copper acetate is dissolved in a mixed solvent of water and propylene glycol (PG), and hydrazine or hydrazine hydrate is added and stirred.

[0311] then, Figure 7 In steps (b) and (c), the sample is separated into supernatant and precipitate by centrifugation. Next, Figure 7 In step (d), a dispersant and alcohol are added to the obtained precipitate for dispersion.

[0312] Next, Figure 7 In steps (e) and (f), the UF membrane module is used to repeatedly concentrate and dilute the material, and the solvent is replaced to obtain dispersion I containing copper oxide particles.

[0313] Figure 7 In (g) and (h), dispersion I is coated onto a PET support using a spray coating method. Figure 7 On (h) referred to as "PET"), a coating layer containing copper oxide and phosphorus-containing organic matter is formed. Figure 7 (h) is recorded as "Cu2O").

[0314] then, Figure 7In step (i), the coating layer is irradiated with a laser to selectively burn a portion of the coating layer, reducing copper oxide to copper. Figure 7 (i) is recorded as "Cu"). As a result, Figure 7 In (j), an insulating region containing copper oxide and phosphorus was formed on the support. Figure 7 (j) is referred to as “A”) and the conductive pattern area containing copper ( Figure 7 (j) refers to a structure with conductive patterned regions in layers arranged in a mutually adjacent manner.

[0315] In this embodiment, the insulating area can be further removed by cleaning. This results in copper wiring patterned on the support. Figure 7 (k) is referred to as "C"). It should be noted that the copper wiring C is the same layer as the conductive pattern area B. Furthermore, a second resin layer (…) can be used from the copper wiring C up to the support between the copper wiring C… Figure 7 (l) is referred to as “D”) seal. It should be noted that the second resin layer D can be formed in such a way that it at least covers the copper wiring C, which is the conductive pattern area B. The second resin layer is equivalent to the “other resin layers” mentioned above.

[0316] When removing the insulating areas, water or organic solvents such as ethanol, propanol, butanol, isopropanol, methanol, ethylene glycol, glycerol, etc., or ketones, esters, ethers, etc., can be used. From the perspective of cleaning performance of the insulating areas, water, ethanol, propanol, butanol, and isopropanol are particularly preferred. Alternatively, phosphorus-based dispersants can be added to the above solvents. Adding phosphorus-based dispersants can further improve cleaning performance.

[0317] In manufacturing Figure 2 When using structure 10 as shown, do not use Figure 5 The laminate 40 shown, if in an atmosphere such as a vacuum atmosphere, will not have an oxygen barrier layer as an example of a resin layer ( Figure 7 (h)) can also be used to manufacture structure 10. However, by using a laminate containing an oxygen barrier layer, it is not necessary to use equipment to achieve a vacuum atmosphere or an inert gas atmosphere, which can reduce the manufacturing cost of structures with conductive patterned areas.

[0318] Next, in the explanation Figure 3 , Figure 4 , Figure 6 In the manufacturing method of the second structures 20, 30, and 50 shown, it is preferable to use Figure 5 The layer 40 shown.

[0319] That is, the second manufacturing method of the structure having conductive patterned areas has the following steps.

[0320] (C) A process of applying a coating layer containing copper oxide and phosphorus-containing organic matter to the surface formed by the support.

[0321] (D) The process of preparing the resin layer (first resin layer) in accordance with the method of covering the coating layer.

[0322] (E) A process in which light is selectively irradiated onto the coating layer through either the resin layer or the support to reduce copper oxide to copper, thereby obtaining a structure having a support, an insulating region containing copper oxide and phosphorus-containing organic matter on the surface formed by the support and a conductive pattern region containing copper arranged adjacent to each other, and a resin layer having a conductive pattern region formed in a manner covering the layer.

[0323] In (C) above, a coating layer containing copper oxide and hydrazine or hydrazine hydrate can be disposed on the surface formed by the support. Alternatively, a coating layer containing copper oxide, a phosphorus-containing organic compound, and hydrazine or hydrazine hydrate can be disposed on the surface formed by the support. By including hydrazine or hydrazine hydrate, further reduction using light can be performed, resulting in a copper film with low resistance.

[0324] Here, process (C) is the same as process (A) described above. In process (D), a resin layer is formed on the surface of the coating layer. By obtaining processes (C) and (D), a product can be manufactured as... Figure 5 The intermediate layer 40 shown.

[0325] That is, the method for manufacturing the laminate 40 includes the following steps: a step of disposing a coating layer containing copper oxide and a phosphorus-containing organic compound on the surface formed by a support; and a step of disposing a resin layer (oxygen barrier layer 45) in a manner that covers the coating layer. Alternatively, the method for manufacturing the laminate 40 includes the following steps: a step of disposing a coating layer containing copper oxide and hydrazine or hydrazine hydrate on the surface formed by a support; and a step of disposing a resin layer (oxygen barrier layer 45) in a manner that covers the coating layer. Alternatively, the method for manufacturing the laminate 40 includes the following steps: a step of disposing a coating layer containing copper oxide, a phosphorus-containing organic compound, and hydrazine or hydrazine hydrate on the surface formed by a support; and a step of disposing a resin layer (oxygen barrier layer 45) in a manner that covers the coating layer.

[0326] Figure 5In the laminate 40 shown, the oxygen barrier layer 45 is bonded to the coating layer 44 via an adhesive layer 46. The adhesive layer 46 is not essential. For example, if the oxygen barrier layer 45 is formed from a cured resin, or if a thermoplastic resin is heated and then extruded and laminated, the adhesive layer 46 may not be necessary. For instance, the material constituting the oxygen barrier layer can be heated to soften it, and then pressed onto the coating layer under pressure to form the laminate.

[0327] The oxygen barrier layer 45 was shown as an example of a resin layer above. Preferably, the resin layer is an oxygen barrier layer and a resin film having an adhesive layer. Therefore, by adhering the resin film to the surface of the coating layer 44, a simple and appropriate product can be manufactured. Figure 5 The layer 40 shown.

[0328] It should be noted that the adhesive is not particularly limited, and examples include acrylic resins, epoxy resins, and silicone resins.

[0329] Furthermore, the adhesive strength of the adhesive layer is preferably 5 mN / 10 mm or more and 10 N / 10 mm or less. This allows the oxygen barrier layer to be properly fixed to the coating layer via the adhesive layer, and the oxygen barrier layer can be easily peeled off in subsequent processes. Moreover, by setting the adhesive strength to 1 N / 10 mm or more and 10 N / 10 mm or less, the oxygen barrier layer can be firmly fixed to the coating layer via the adhesive layer.

[0330] The above-described firing process is applied to the laminate formed by processes (C) and (D) to form conductive patterned areas.

[0331] In this embodiment, either the oxygen barrier layer or the support is made translucent. Therefore, during the photoirradiation process, light can pass through the oxygen barrier layer or the support to fire a portion of the coating layer.

[0332] Based on the above, it is possible to manufacture Figure 3 The structure shown is 20. Figure 6 The structure 50 shown has a conductive patterned area.

[0333] (Configuration of other resin layers)

[0334] Secondly, the oxygen barrier layer can be replaced with other resin layers as needed. First, the oxygen barrier layer is removed by dissolving it with a solvent. In this case, if the above-mentioned adhesive layer is used, only the adhesive layer can be removed by dissolving it with a solvent. Alternatively, by pre-applying a weak adhesive to peel the oxygen barrier layer from the layer with the conductive pattern area, the oxygen barrier layer can be peeled off even without using a solvent.

[0335] Next, a sealing material layer, as an example of other resin layers, is configured such that the exposed conductive patterned areas are covered by the layer. The sealing material layer can be formed by bonding a resin sheet made of the material constituting the sealing material layer to the coating layer using a separately prepared adhesive.

[0336] Alternatively, the sealing material layer can be formed by heating the material constituting the sealing material layer to soften it, and then pressing it onto the coating layer under pressure for lamination. Furthermore, a photocurable or heat-curable material can be selected, and a coating layer composed of the curable material can be formed on the exposed conductive patterned area of ​​the layer, followed by curing using light or heat.

[0337] Reference Figure 8 The manufacturing method of the support with conductive patterned area according to the second embodiment will be described in more detail. Figure 8 This is an explanatory diagram showing each step of the manufacturing method of the support with conductive patterned areas according to this embodiment. Figure 8 In (a) of the above, copper acetate is dissolved in a mixed solvent of water and propylene glycol (PG), and hydrazine or hydrazine hydrate is added and stirred.

[0338] then, Figure 8 In steps (b) and (c), the sample was separated into supernatant and precipitate by centrifugation. Next, Figure 8 In step (d), a dispersant and alcohol are added to the obtained precipitate for dispersion.

[0339] Next, Figure 8 In steps (e) and (f), the concentration and dilution using the UF membrane module are repeated, and the solvent is replaced to obtain dispersion I containing copper oxide particles.

[0340] Figure 8 In (g) and (h), dispersion I is coated onto a PET support using a spray coating method. Figure 8 On (h) referred to as "PET"), a coating layer containing copper oxide and phosphorus-containing organic matter is formed. Figure 8 (h) is recorded as "Cu2O").

[0341] then, Figure 8 In (i), an oxygen barrier layer is disposed on the coating layer. Figure 8 (i) is recorded as “barrier”.

[0342] then, Figure 8 In (j), the coating layer is irradiated with a laser through an oxygen barrier layer, selectively burning a portion of the coating layer to reduce copper oxide to copper. Figure 8 (j) is recorded as "Cu"). As a result, Figure 8In (k), an insulating region containing copper oxide and phosphorus-containing organic matter was obtained on the support. Figure 8 (k) is marked as "A") and contains a conductive pattern area with copper ( Figure 8 (k) refers to layers that are mutually adjacent to each other and are designated as “B”.

[0343] then, Figure 8 In (l) and (m), the oxygen barrier layer is removed using a solvent, exposing the layer adjacent to the conductive pattern region and the insulating region. Then, Figure 8 In (n), a sealing material layer is used ( Figure 8 (n) is described as "sealed") on the surface of a layer covering the conductive pattern area and the insulating area adjacent to it, from which the following can be obtained Figure 4 The structure shown has a conductive patterned area.

[0344] In this embodiment, the insulating area can be further removed by cleaning. This results in copper wiring patterned on the support. Figure 8 (o) is referred to as "C"). It should be noted that the copper wiring C is the same layer as the conductive pattern area B. Furthermore, a second resin layer (…) can be used from the copper wiring C up to the support between the copper wiring C… Figure 8 (p) is referred to as “D”) seal. It should be noted that the second resin layer D can be formed in such a way that it at least covers the copper wiring C, which is the conductive pattern area B. The second resin layer is equivalent to the “other resin layers” mentioned above.

[0345] When removing the insulating areas, water or organic solvents such as ethanol, propanol, butanol, isopropanol, methanol, ethylene glycol, glycerol, etc., or ketones, esters, ethers, etc., can be used. From the perspective of cleaning performance of the insulating areas, water, ethanol, propanol, butanol, and isopropanol are particularly preferred. Alternatively, phosphorus-based dispersants can be added to the above solvents. Adding phosphorus-based dispersants can further improve cleaning performance.

[0346] It should be noted that the oxygen barrier layer can also be left intact and used as a sealing material layer. In this case, it is possible to manufacture... Figure 3 and Figure 6 The structure shown has a conductive patterned area. Therefore, in the manufacturing method of the structure with a conductive patterned area in this embodiment, the process after removing the oxygen barrier layer is not necessary.

[0347] In the manufacturing method of the structure in this embodiment, after obtaining a layer with conductive patterned areas and insulating areas by light irradiation, as... Figure 7 (k) Figure 8As shown in (o), the insulating region can also be removed from the layer where the conductive pattern region and the insulating region are in close contact. For example, an etching solution that does not dissolve the conductive pattern region but dissolves the insulating region can be used to selectively clean and remove the insulating region. In this embodiment, the boundary between the conductive pattern region and the insulating region can be clearly distinguished, and the insulating region can be appropriately and selectively removed only.

[0348] Furthermore, in this embodiment, as described above, after removing the insulating region from the layer, such as Figure 7 (l) Figure 8 As shown in (p), the second resin layer can be configured to cover the surface of the conductive pattern area. This ensures insulation between the conductive pattern area and other conductive pattern areas. Furthermore, it is effective as a barrier film in terms of the durability of copper wiring. It should be noted that the second resin layer can also be any of the "other resin layers" mentioned above.

[0349] In this embodiment, for example, the insulating region can be removed as described above, leaving copper wiring on the support. The conductive pattern region remaining on the support, containing reduced copper (formed from copper oxide), phosphorus, and carbon, can be manufactured as the copper wiring of this embodiment. Alternatively, even without removing the insulating region, the conductive pattern region and the conductive pattern region within the insulating region can be considered as copper wiring. In this case, in the copper wiring of this embodiment, the phosphorus / copper elemental concentration ratio can be 0.02 to 0.30 or less, the carbon / copper elemental concentration ratio can be 1.0 to 6.0 or less, and Ra is preferably 20 nm to 500 nm or less. To achieve a phosphorus / copper elemental concentration ratio of 0.02 to 0.30 or less, as an example, a coating layer containing copper oxide and a phosphorus-containing organic compound can be prepared, and reduced copper can be obtained from the copper oxide by light irradiation, thereby manufacturing the wiring. The phosphorus / copper elemental concentration ratio can be adjusted by adjusting the ratio of copper oxide to the phosphorus-containing organic compound. To achieve a carbon / copper ratio of 1.0 to 6.0, for example, a coating layer containing copper oxide and organic matter can be prepared, and copper can be reduced from the copper oxide by light irradiation. The elemental concentration ratio of carbon to copper can be adjusted by changing the ratio of copper oxide to organic matter. Furthermore, to achieve a surface Ra of 20 nm to 500 nm for the copper wiring, for example, the desired Ra can be obtained by adjusting the light irradiation intensity, irradiation speed, and irradiation interval.

[0350] Furthermore, in the manufacturing method of the structure or laminate with conductive patterned regions according to this embodiment, the transmittance of the resin layer or support at a wavelength of 445 nm is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The upper limit of the transmittance can be 98% or less. Regarding the wavelength, in addition to 445 nm, wavelengths from near ultraviolet to near infrared, such as 355 nm, 405 nm, 450 nm, 532 nm, and 1064 nm, can also be selected. By increasing the transmittance of light at such wavelengths, the coating layer can be fired by irradiation from the support side to form conductive patterned regions.

[0351] Furthermore, in the manufacturing method of the structure or laminate with conductive patterned regions according to this embodiment, the copper oxide included in the coating layer is preferably cuprous oxide. Therefore, reduced copper can be obtained through a firing process, and a layer in which conductive patterned regions and insulating regions coexist with high precision can be formed.

[0352] In addition, in the manufacturing method of the structure or laminate with conductive patterned area in this embodiment, the phosphorus-containing organic compound contained in the coating layer preferably has a skeleton represented by the following chemical formula (1) (in chemical formula (1), R is an ester salt).

[0353] [Chemistry 5]

[0354] Chemical formula (1)

[0355]

[0356] In chemical formula (1), R is an ester salt.

[0357] The structure of the above chemical formula (1) can adsorb copper oxide and has excellent adhesion to the support. This ensures insulation and effectively prevents peeling between the support and the coating layer.

[0358] Furthermore, in the manufacturing method of the structure or laminate with conductive patterned regions in this embodiment, the case where the support is a three-dimensional object can be illustrated. That is, in this embodiment, the support is not limited to a flat surface, but can be a curved surface or a slope, for example, the surface of a shell or chassis can be used as the support surface to form the structure with conductive patterned regions in this embodiment.

[0359] <Application Example>

[0360] The structure with conductive patterned areas in this embodiment can be suitably applied to wiring materials such as electronic circuit boards (printed circuit boards, RFID, wiring harness replacements in automobiles, etc.), antennas formed in the housings of portable information devices (smartphones, etc.), mesh electrodes (electrode films for electrostatic capacitive touch panels), electromagnetic wave shielding materials, and heat dissipation materials.

[0361] As explained above, the structure with conductive patterned regions according to this embodiment can insulate the conductive patterned regions containing copper with insulating regions containing copper oxide and phosphorus. Therefore, it is unnecessary to remove the unburned portions of the layers disposed on the support for manufacturing, thus reducing manufacturing steps and lowering manufacturing costs since solvents are not required. Furthermore, using insulating regions to insulate the conductive patterned regions reduces the likelihood of cracking, improving reliability.

[0362] Furthermore, according to the manufacturing method of the structure having a conductive patterned area according to this embodiment, a portion of the coating layer containing copper oxide and phosphorus-containing organic matter can be laser-sintered to form the conductive patterned area, and the un-sintered portion can be used for insulation of the conductive patterned area. Therefore, it is unnecessary to remove the un-sintered portion of the coating layer. Thus, manufacturing steps can be reduced, and manufacturing costs can be lowered since solvents are not required. Additionally, since solder resists are not needed for insulation of the conductive patterned area, manufacturing steps can also be reduced accordingly.

[0363] Furthermore, according to the laminate of this embodiment, by covering the coating layer with a resin layer, contact between the coating layer and oxygen can be prevented during photofiring, thus promoting the reduction of copper oxide. Therefore, equipment for creating an oxygen-free or low-oxygen atmosphere around the coating layer during photoirradiation is unnecessary, reducing manufacturing costs. Additionally, since the coating layer is covered with a resin layer, it is protected from external stress, improving processability.

[0364] Furthermore, according to the method for manufacturing laminates according to this embodiment, laminates can be manufactured simply and appropriately by using a process of forming a coating layer containing copper oxide and phosphorus-containing organic matter on the surface of a support and a process of forming a resin layer on the surface of the coating layer.

[0365] Example

[0366] The present invention will be described in more detail below through specific embodiments.

[0367] <Preparation of Dispersions>

[0368] 80g of copper(II) hydrate (Wako Pure Chemical Industries) was dissolved in a mixed solvent consisting of 800g of water and 400g of 1,2-propanediol (Wako Pure Chemical Industries). 20g of hydrazine or hydrazine hydrate (Wako Pure Chemical Industries) was added and stirred. The mixture was then separated into supernatant and precipitate by centrifugation.

[0369] 0.05 g of DISPERBYK-145 (trade name, manufactured by BYK Chemical Company) (BYK-145 in Table 1) as a phosphorus-containing organic compound and 6.6 g of ethanol (Wako Pure Chemical Industries Co., Ltd.) as a dispersion medium were added to 2.8 g of the obtained precipitate, and dispersion was carried out using a homogenizer. Further dilution and concentration were performed repeatedly with ethanol to obtain a dispersion (a) containing cuprous oxide particles (cuprous oxide (I)). The weight of the cuprous oxide particles in the precipitate was determined by vacuum drying, and the results showed that 2.0 g of cuprous oxide particles were present in 2.8 g of precipitate.

[0370] It should be noted that the cuprous oxide particles obtained by vacuum drying were observed by transmission electron microscopy and analyzed by energy dispersive X-ray spectroscopy. The results showed that the cuprous oxide content (volume%) in the cuprous oxide particles was 100 vol% (see Table 1).

[0371] The amount of phosphorus-containing organic matter added to the 2.8 g precipitate was varied according to the description in Table 1, and the same operation as described above was performed to obtain dispersions (b) to (g) containing cuprous oxide particles. The copper oxide content (volume %) in all particles contained in dispersions (b) to (g) was determined, and the result was 100 vol% (see Table 1).

[0372] [Table 1]

[0373]

[0374] In addition, dispersions (h) and (i) were obtained by adding copper powder (average particle size 1 μm, spherical particles) to dispersion (c) in the amounts described in Table 1. The copper oxide content (volume %) in all particles (copper oxide particles and copper powder) contained in dispersions (h) and (i) was determined, and the results were 59.7 vol% and 42.6 vol%, respectively (see Table 1).

[0375] <Sample Preparation>

[0376] [Samples 1-19]

[0377] After UV ozone treatment of the surface of the support, the dispersion is rod coated to achieve the specified thickness and dried at room temperature for 10 minutes to obtain a sample with a coating layer formed on the support.

[0378] Samples 1 to 19 were obtained by changing the type of support, the type of dispersion, and the thickness of the coating layer as shown in Table 2.

[0379] The PET film used as the support is a 100μm thick PET film (manufactured by Toyobo Co., Ltd., Cosmoshine A4100).

[0380] [Sample 20]

[0381] As a support, the surface of a 100μm thick PET film (manufactured by Toyobo Co., Ltd., Cosmoshine A4100) is treated with UV ozone, and then roughened by reactive ion etching (RIE) using oxygen to form an adhesive layer.

[0382] Next, the dispersion (c) was rod-coated onto the adhesive layer to achieve a specified thickness of 0.5 μm, and dried at room temperature for 10 minutes to obtain sample 20.

[0383] [Samples 21-23]

[0384] Except for the change of support type as described in Table 2, samples 21 to 23 were obtained by the same operation as in the case of sample 20 described above. The specific surface area and surface roughness of the obtained adhesive layers were measured and are shown in Table 2.

[0385] As a support, the following PEN film, PI film, and mPPE sheet are used.

[0386] PEN film (manufactured by Teijin Film Solutions, Teonex Q65H, 100μm thickness)

[0387] PI film (manufactured by Toray-DuPont, KAPTON500H, 125μm thickness)

[0388] m-PPE sheet (manufactured by Asahi Kasei Corporation, E1000, 125μm thick)

[0389] [Sample 24]

[0390] As a support, a 100 μm thick PET film (manufactured by Toyobo Co., Ltd., Cosmoshine A4100) was subjected to UV ozone treatment on its surface, and then coated with a coating solution containing silica microparticles (average particle size 25 nm). After drying at room temperature for 30 minutes, a 5 μm thick adhesive layer was formed.

[0391] Then, dispersion (a) was changed to dispersion (c), and otherwise sample 24 was obtained by the same operation as for samples 1 to 19 above.

[0392] [Sample 25]

[0393] As a support, a 100 μm thick PET film (manufactured by Toyobo Co., Ltd., Cosmoshine A4100) was subjected to UV ozone treatment on its surface, and then a coating solution containing alumina microparticles (average particle size 110 nm) was applied using a doctor blade coater. After drying at room temperature for 30 minutes, a 10 μm thick adhesive layer was formed.

[0394] Then, dispersion (a) was changed to dispersion (c), and otherwise sample 25 was obtained by the same operation as for samples 1 to 19 above.

[0395] <Evaluation and Measurement Methods>

[0396] (Evaluation of the film-forming properties of the dispersion)

[0397] The film-forming properties of the coating layer on the obtained samples were observed using a shape measurement laser microscope (KEYENCE, VK-9510). A 10x objective lens was used. The evaluation criteria are as follows. Figure 9 and Figure 10 These are electron microscope images used to illustrate the crack state in the coating layer of the embodiment. Figure 9 An example of a crack-free coating layer is shown. Figure 10 An example of a coating layer with cracks is shown.

[0398] (Evaluation based on laser-assisted firing and conductivity)

[0399] Using an electric scanner, a laser (wavelength 445nm, output 1.2W, continuous wave oscillation (CW)) is irradiated onto the substrate of the sample in an argon atmosphere while moving the focal position at a maximum speed of 300mm / min, thereby obtaining the desired 25mm×1mm conductive pattern area containing copper.

[0400] The method for evaluating conductivity is as follows. Conductivity is evaluated by contacting both ends of the conductive pattern area with a testing machine. The evaluation criteria are as follows.

[0401] ○: Resistance value less than 1kΩ

[0402] △: Resistance value is above 1kΩ and less than 1MΩ

[0403] ×: Resistance value is above 1MΩ

[0404] (Evaluation of firing and conductivity using xenon flash)

[0405] A 30 mm square sample was placed on a sample stage in an argon atmosphere. A light-shielding mask with an opening measuring 25 mm × 1 mm was placed on the mask, and xenon flash (irradiation energy 3 J / cm²) was applied from it. 2(Irradiation time: 4 milliseconds). This results in a 25mm × 1mm conductive patterned area containing copper. The portion of the light-shielding mask that is not an opening is in the same state as before xenon flash irradiation.

[0406] Conductivity is evaluated by contacting both ends of the conductive pattern area with the testing machine. The evaluation criteria are as follows.

[0407] ○: Resistance value less than 1kΩ

[0408] △: Resistance value is above 1kΩ and less than 1MΩ

[0409] ×: Resistance value is above 1MΩ

[0410] In both laser-based and xenon-flame-based firing processes, whichever method can exhibit conductivity in the conductive pattern area can be used as a support for the conductive pattern area.

[0411] (Measurement of insulation resistance)

[0412] Two needle detectors were placed at 5 mm intervals in the unfired insulating area containing cuprous oxide and phosphorus-containing organic matter on each of the fired samples. Using a TOS7200 insulation resistance tester manufactured by Kikusui Electronics Industry Co., Ltd., a DC voltage of 500V was applied between the two needle detectors for 1 minute, and the resistance value at this point was evaluated. The evaluation criteria are as follows.

[0413] ○: Above 5000MΩ

[0414] △: 1MΩ or higher and less than 5000MΩ

[0415] ×: Less than 1MΩ

[0416] (Average particle size)

[0417] The average primary particle size of cuprous oxide particles can be determined using a transmission electron microscope (TEM) or a scanning electron microscope (SEM). The specific procedures are explained below. The sample is cut into appropriate sizes and processed using a Hitachi High-Technologies E-3500 ion mill. The sample is then processed under cooling conditions as needed. The processed sample is then subjected to a conductivity treatment, and the cross-section of the conductive adhesive portion is observed using a Hitachi S-4800 SEM. The primary particle size is measured for all primary particles within an image containing 10 or more particles in a single field of view, and the average value is taken as the average primary particle size.

[0418] The average secondary particle size of cuprous oxide particles can be determined using a transmission electron microscope (TEM) or a scanning electron microscope (SEM). The specific procedures are explained below. The sample is cut into appropriate sizes and subjected to binning (BIB) processing using an ion milling apparatus (Hitachi High-Technologies E-3500). The sample is then subjected to BIB processing under cooling conditions, if necessary. The processed sample is then subjected to a conductivity treatment, and the cross-section of the conductive adhesive portion is observed using a scanning electron microscope (Hitachi S-4800). The secondary particle size of all particles within an image containing 10 or more secondary particles in a single field of view is measured, and their average value is taken as the average secondary particle size.

[0419] (Load deformation temperature)

[0420] The load deformation temperature of the support can be determined using the method according to JIS 7191.

[0421] (Determination of the content (volume%) of cuprous oxide particles, copper powder, and phosphorus-containing organic matter)

[0422] The content (volume %) of cuprous oxide particles, (in the case of inclusion) copper powder, and phosphorus-containing organic matter in the insulating regions of the layer was determined by observing the cross-section of the layer disposed on the support using a scanning electron microscope (SEM).

[0423] Figure 11 An electron microscope image showing a cross-section of the layer disposed on the support in the embodiment. (e.g.) Figure 11 As shown, in electron microscope images, materials with higher electron density appear brighter; therefore, inorganic materials appear brighter than organic materials, and conductive metals appear brighter than oxides. Thus, in a specific observation area within a layer of an electron microscope image, the shape, size, and contrast can be used to distinguish between inorganic cuprous oxide particles and copper powder (hereinafter referred to as "all particles") and phosphorus-containing organic matter. The content of all particles (volume %) can be calculated by multiplying the quotient of the area occupied by all particles in the cross-sectional image of the layer contained in that observation area (hereinafter referred to as "cross-sectional image") and the total area of ​​the layer in the cross-sectional image by 100.

[0424] Furthermore, cuprous oxide particles and copper powder can also be distinguished by shape, size, and contrast. Therefore, the copper oxide content (volume %) in all particles can be calculated by multiplying the quotient of the area occupied by cuprous oxide particles in the cross-sectional image and the area occupied by all particles in the cross-sectional image by 100. Similarly, the copper powder content (volume %) in all particles can be calculated by multiplying the quotient of the area occupied by copper powder in the cross-sectional image and the area occupied by all particles in the cross-sectional image by 100.

[0425] In addition, the content of phosphorus-containing organic matter (volume %) can be obtained by multiplying the quotient of the area occupied by phosphoric acid organic matter in the cross-sectional image and the total area of ​​the layer in the cross-sectional image by 100.

[0426] Image analysis can be performed using image analysis software, such as ImageJ (developed by the National Institutes of Health). In this example, the cross-sectional image is read into ImageJ, converted into a black and white 8-bit image, a default threshold is set, and particle analysis is performed to determine the content of cuprous oxide particles and copper powder.

[0427] (Determination of the content (wt%) of cuprous oxide particles, copper powder and phosphorus-containing organic matter)

[0428] The content (by weight) can be calculated from the content (volume %) obtained from the cross-sectional image, and from the specific gravity of copper oxide, copper, and phosphorus-containing organic matter. The specific gravity of copper oxide, copper, and phosphorus-containing organic matter can be calculated using the following values.

[0429] Copper oxide: 6.0 g / cm³ 3

[0430] Copper: 8.9 g / cm³ 3

[0431] Phosphorus-containing organic matter: 1.0 g / cm³ 3

[0432] For materials other than these, values ​​recorded in chemical handbooks, physicochemical chronologies, etc., can be used.

[0433] Based on the contents (volume %) of cuprous oxide particles, copper powder, and phosphorus-containing organic matter in the insulating regions of the layer as determined in this way, the volume fraction of phosphorus-containing organic matter is calculated when the volume of cuprous oxide particles in the insulating regions of the layer, or the total volume of cuprous oxide particles and copper powder in the case of copper powder, is set to 100 parts by volume, and is shown in Table 2. Similarly, the mass fraction of phosphorus-containing organic matter is calculated when the total mass of cuprous oxide particles in the insulating regions of the layer, or the total mass of cuprous oxide particles and copper powder in the case of copper powder, is set to 100 parts by mass, and is shown in Table 2.

[0434] (Support fit)

[0435] The adhesion between the conductive patterned area obtained by firing and the support is evaluated visually according to the following evaluation criteria.

[0436] ○: The state in which the conductive pattern area is in close contact with the support.

[0437] △: Although some peeling was observed, the overall structure remained tightly fitted with the support.

[0438] ×: The state of the conductive pattern area peeling off from the support [Table 2]

[0439]

[0440] The abbreviations in Table 2 refer to the following compounds: PET: Polyethylene terephthalate resin; PEN: Polyethylene naphthalate resin.

[0441] PI: Polyimide resin

[0442] PP: Polypropylene resin

[0443] PA: Polyamide resin

[0444] ABS: Acrylonitrile butadiene styrene resin

[0445] PE: Polyethylene resin

[0446] PC: Polycarbonate resin

[0447] POM: Polyacetal resin

[0448] PBT: Polybutylene terephthalate resin

[0449] m-PPE: Modified polyphenylene ether resin

[0450] PPS: Polyphenylene sulfide resin

[0451] [Sample 35-40]

[0452] Using the dispersions (a), (c), (d), dispersion (j) (2.8 g precipitate, 0 g copper powder, 2.0 g organic compound BYK145, 6.6 g solvent ethanol), dispersion (k) (2.8 g precipitate, 0 g copper powder, 2.0 g organic compound BYK145, 6.6 g solvent ethanol, 0.01 g hydrazine hydrate) formed by adding hydrazine hydrate to dispersion (c) (2.8 g precipitate, 0 g copper powder, 2.0 g organic compound BYK145, 6.6 g solvent ethanol, 0.1 g hydrazine hydrate) formed by adding hydrazine hydrate to dispersion (c), samples 35-40 with a coating layer of 0.8 μm thickness formed on the PI film of the support were obtained by the same method as sample 1. It should be noted that the ratio of hydrazine mass to copper oxide mass in dispersions (k) and (l) is 0.003 for dispersion (k) and 0.03 for dispersion (l).

[0453] The smoothness of the coating surface of each sample was measured. Regarding the measurement method, the arithmetic mean height Ra over a length of 1000 μm was measured using a stylus-type film thickness gauge (ULVAC DektakXT Co., Ltd.). The evaluation criteria are as follows.

[0454] ○: Ra is less than 30nm

[0455] △: Ra is 30nm or more and less than 100nm

[0456] ×: Ra is below 100nm

[0457] Using an electric scanner, a laser (wavelength 532nm, output 0.45W, continuous wave (CW)) is irradiated onto the substrate of the sample in an argon atmosphere while moving the focal position at a maximum speed of 100 mm / s, thereby obtaining the desired 25 mm × 1 mm conductive pattern area containing copper.

[0458] The film thickness of the conductive pattern region for each sample was measured. Regarding the measurement method, a portion of the conductive pattern region was peeled off to expose the support, and the cross-sectional area of ​​the conductive pattern region remaining on the support was measured using a stylus-type film thickness gauge (ULVAC DektakXT Co., Ltd.). The ratio to the unburned insulation region was then calculated.

[0459] The surface roughness of the conductive pattern region of each sample was measured. Regarding the measurement method, the arithmetic mean height Ra over a length of 1000 μm was measured using a stylus-type film thickness gauge (ULVAC DektakXT Co., Ltd.). The evaluation criteria are as follows.

[0460] ○: Ra is greater than 50nm and less than 200nm

[0461] △: Ra is ≥20nm and <50nm, or ≥200nm and <500nm

[0462] ×: Ra is less than 20nm or greater than 500nm

[0463] The resistance values ​​at both ends of the conductive pattern region were evaluated using a four-terminal measurement method. The evaluation criteria are as follows.

[0464] ○: Resistance value less than 30μΩcm

[0465] △: Resistance value is above 30μΩcm and below 100μΩcm

[0466] ×: Resistance value above 100μΩcm

[0467] (Test of withstand voltage)

[0468] Two conductive pattern areas of the above 25mm×1mm size were arranged with a 1mm interval, and the withstand voltage of the insulating area containing cuprous oxide and phosphorus-containing organic matter and containing hydrazine or hydrazine hydrate, which is located between them as an unburned part, was measured.

[0469] Regarding the testing method, a pin detector was connected to two conductive pattern areas. An AC voltage was applied between the two pin detectors using a withstand voltage tester (TOS5300, manufactured by Kikusui Electronics Industry Co., Ltd.). The voltage was slowly increased, and the voltage at which insulation failure occurred was measured. The evaluation criteria are as follows.

[0470] ○: Withstand voltage above 1.7kV / mm

[0471] △: Withstand voltage above 1kV / mm and less than 1.7kV / mm

[0472] × Withstand voltage less than 1kV / mm

[0473] (Evaluation Results)

[0474] [Samples 1-25]

[0475] In dispersions (a) to (i), no aggregates or precipitates were observed during visual evaluation, and all were well-dispersible dispersions.

[0476] In Sample 1, although delamination was observed in a portion of the conductive pattern area during laser firing, the sample remained tightly bonded to the support as a whole, confirming its conductivity. During xenon flash firing, the dispersion applied during firing was blown away, and a conductive pattern area was not obtained.

[0477] In samples 2–4, 7, and 9–17, the conductive patterned areas adhered closely to the support during laser firing, confirming conductivity. During xenon flash firing, the dispersion applied during firing was blown away, failing to produce conductive patterned areas.

[0478] In samples 5 and 6, the content of phosphorus-containing organic matter in the layer was high, and the conductivity evaluation result was Δ. The cuprous oxide layer placed on the support after firing was in a state of tight adhesion to the support.

[0479] In sample 8, a conductive pattern region with excellent conductivity that is closely fitted to the support was obtained in both laser sintering and xenon flash sintering.

[0480] In samples 18 and 19, conductive patterned areas were obtained through laser burning, but in terms of adhesion with the support, a portion of them were peeled off during laser burning.

[0481] Samples 20-25 have a dense layer, and conductive patterned areas that are densely bonded to the support are obtained in both laser burning and xenon flash burning.

[0482] [Samples 26–34]

[0483] As supports, shells of different materials, without an adhesive layer, as shown in Table 2, were prepared. The shells were curved surfaces in the shape of a mortar with a radius of curvature of 500 mm. The dispersion (c) was coated onto the prepared shells using a spray method to achieve a dry film thickness of 5 μm, resulting in samples 26–34. Then, for samples 26–34, a laser (wavelength 445 nm, output 1.5 W, continuous wave (CW)) was used to irradiate the surface of the shells with an argon atmosphere while moving the focal point at a maximum speed of 300 mm / min. This resulted in a desired 25 mm × 1 mm conductive pattern area containing copper on the surface of the shells. The obtained conductive pattern area exhibited fine cracks in some areas, but remained tightly bonded to the shell, demonstrating excellent conductivity.

[0484] [Sample 35-40]

[0485] Dispersions (j)(k)(l) are dispersions that do not produce agglomerates or precipitates and have good dispersibility during visual evaluation.

[0486] The smoothness of the coating layers in samples 35–40 was evaluated. The evaluation results are shown in Table 3. Due to its smoothness, the coating layer does not exhibit random reflections when illuminated, and it can appropriately absorb light.

[0487] The resistance values ​​of the conductive patterned regions of samples 35–40 were evaluated. The evaluation results are shown in Table 3. Regarding sample 38, the coating layer was ablated during laser irradiation, making it impossible to obtain a suitable conductive patterned region.

[0488] The film thickness of the conductive patterned regions of samples 35–37, 39, and 40 was measured, and the film thickness ratio to that of the unburned insulating region was calculated. The evaluation results are shown in Table 3. The film thickness ratio was in the range of 45–50%.

[0489] The surface roughness of the conductive pattern regions of samples 35–37, 39, and 40 was evaluated. The evaluation results are listed in Table 3. All samples exhibited suitable surface roughness.

[0490] The withstand voltage of the insulation regions of samples 35–37, 39, and 40 was evaluated. The evaluation results are shown in Table 3. Samples 36, 37, 39, and 40 exhibited good withstand voltage.

[0491] A resin layer (PET film: Toyobo Co., Ltd., Cosmoshine A4100, 100µm thickness) serving as a sealing layer was prepared in sample 36. A silicon oxide layer was provided within the resin layer as a moisture barrier. An bonding layer (Lintec Co., Ltd. Optical Adhesive Sheet MO Series) was provided to bond with the layer containing the conductive pattern area disposed on the support. Furthermore, to prevent moisture from entering from the edges of the resin layer, a thermosetting sealing material (AJINOMOTO FINE TECHNO Co., Ltd. AES-210) was used for sealing. A portion of the resin layer was opened to expose the conductive pattern area, and electrodes were placed therein using low-temperature solder (Senju Metal Industries, Ltd. ECO Solder LEO). Under these conditions, an accelerated conductivity degradation test was conducted on the conductive pattern area at 85°C and 85% RH. After 1000 hours, the resistance value was evaluated, and the resistance change rate was less than +5%, indicating good performance. This is believed to be due to the oxidation of phosphorus before copper is oxidized, caused by the presence of trace amounts of oxygen and moisture in the sealed interior during accelerated testing, which suppresses the resistance change in the conductive pattern area.

[0492] As sample 41, a glass wine glass was prepared as a support with a three-dimensional curved surface. The radius of curvature of the wine glass was 35 mm. The wine glass was immersed in a container filled with dispersion (c) and lifted at a certain speed, thereby obtaining a coating layer with a dry film thickness of 2 μm on the outer surface of the wine glass. Then, a laser marker (KEYENCE Co., Ltd. laser marker MD-S9910A) was used to irradiate the coating layer with laser light (wavelength 532 nm, output 0.22 W, pulse repetition frequency 260 kHz) in air at a speed of 20 mm / s. This resulted in a conductive pattern area containing reduced copper on the surface of the wine glass. Figure 12A The photo is shown in the image. Figure 12B A schematic diagram is shown. The resulting conductive patterned region is in close contact with the glass. The resistance value of the conductive patterned region is evaluated as ○, and the voltage withstand capability of the insulating patterned region is evaluated as ○.

[0493] Furthermore, to obtain copper wiring, ethanol, used as a cleaning solvent, was used to remove the coating layer from the insulating areas that were not subjected to laser irradiation. A photograph of the removed coating is shown below. Figure 12C The resistance of the removed copper wiring is rated as 0, which is considered good.

[0494] Similarly, as in the experiment described above, a glass wine glass was prepared as sample 42, serving as a support with a three-dimensional curved surface. The radius of curvature of the wine glass was 35 mm. The wine glass was immersed in a container filled with dispersion (c) and lifted at a certain speed, thereby obtaining a coating layer with a dry film thickness of 2 μm on the outer surface of the wine glass. Then, using a laser marker (KEYENCE MD-U1000C laser marker, different from the one used in the above experiment), the coating layer was irradiated with laser light (wavelength 355 nm, output 0.25 W, pulse repetition frequency 300 kHz) at a speed of 20 mm / s in air. This resulted in a conductive patterned area containing reduced copper on the surface of the wine glass. The obtained conductive patterned area adhered tightly to the glass and exhibited excellent conductivity.

[0495] As sample 43, a micro-adhesive PET film (Lintec SRL-0753) serving as an oxygen-barrier resin layer was adhered to the surface of the coating layer of sample 36. A laser marker (KEYENCE MD-S9910A) was used to irradiate the coating layer through the resin layer in air at a speed of 20 mm / s using a laser (wavelength 532 nm, output 0.22 W, pulse repetition frequency 260 kHz). The resin layer was then removed. The resulting conductive patterned area adhered tightly to the PI film. The resistance value of the conductive patterned area was evaluated as ○, and the withstand voltage of the insulating area was evaluated as ○.

[0496] Furthermore, a resin layer (PET film: Toyobo Co., Ltd., Cosmoshine A4100, 100µm thick) was applied as a sealing material layer, an example of the other resin layers, onto the conductive patterned area and insulating area exposed by removing the resin layer. A silicon oxide layer was provided within the resin layer as a moisture barrier layer, and an bonding layer (Lintec Co., Ltd. Optical Adhesive MO Series) was provided to bond with the layer containing the conductive patterned area disposed on the support. Additionally, to prevent moisture from entering from the edges of the resin layer, a thermosetting sealing material (AJINOMOTO FINE TECHNO Co., Ltd. AES-210) was used for sealing. Furthermore, a portion of the resin layer was opened to expose the conductive patterned area, where electrodes were placed using low-temperature solder (Senju Metal Industries, Ltd. ECO Solder LEO). In this state, an accelerated conductivity degradation test of the conductive patterned area was conducted in an environment of 85°C and 85% RH. After 1000 hours, the resistance value was evaluated, and the resistance change rate was less than +5%, which was considered good. This is believed to be due to the oxidation of phosphorus before copper is oxidized, caused by the presence of trace amounts of oxygen and moisture in the sealed interior during accelerated testing, which suppresses the resistance change in the conductive pattern area.

[0497] [Comparative Example 1]

[0498] Except that polyvinylpyrrolidone (hereinafter referred to as PVP) was used to replace the phosphorus-containing organic matter, a dispersion (x) containing cuprous oxide particles was obtained by the same operation as dispersion (a). It should be noted that the composition of dispersion (x) is 2.8 g of precipitate, 0.2 g of polyvinylpyrrolidone, 6.6 g of ethanol dispersion medium, and the cuprous oxide content in the cuprous oxide particles is 100% by volume.

[0499] Comparative Example 1 was obtained by performing the same operation as for Samples 1 to 19, in which a coating layer of dispersion (x) was formed on a PET film (manufactured by Toyobo Co., Ltd., Cosmoshine A4100) with a thickness of 0.5 μm on a thickness of 100 μm as a support.

[0500] In Comparative Example 1, an electric scanner was used to irradiate the substrate of the sample with a laser (wavelength 445nm, output 1.2W, continuous wave oscillation (CW)) while moving the focal position at a maximum speed of 300mm / min, thereby obtaining the desired 25mm×1mm conductive pattern area containing copper.

[0501] In Comparative Example 1, after firing, two pin detectors were placed at a 5mm interval in the unfired insulation area. Using an insulation resistance tester TOS7200 manufactured by Kikusui Electronics Industry Co., Ltd., a DC voltage of 500V was applied between the two pin detectors for 1 minute, and the resistance value at this time was evaluated. The result showed that the resistance value was less than 1MΩ, indicating insufficient insulation.

[0502] Further, in the same manner as described above, the withstand voltage was measured on the insulation region containing cuprous oxide as an unburned portion, and excluding phosphorus-containing organic matter and hydrazine or hydrazine hydrate. The result was a withstand voltage of 0.9 kV / mm, rated as ×.

[0503] [Comparative Example 2]

[0504] Comparative Example 2 was obtained by using Metalon ICI-021 from Novacentrix, a company that produces a dispersion containing copper divalent oxide particles, instead of a dispersion containing cuprous oxide particles, phosphorus-containing organic matter, and hydrazine or hydrazine hydrate. The same operation as that used for Samples 1 to 19 was employed to form a coating layer with a thickness of 1.0 μm on a PI film (manufactured by Toray-DuPont, KAPTON500H, 125 μm thickness).

[0505] The conductive patterned region was obtained by irradiating the sample with a laser using the same procedure as for samples 35-38.

[0506] The results of the evaluation of each item, performed in the same manner as for samples 35–38, are recorded in Table 3. The smoothness of the coating layer is ×. It is believed that during the coating layer formation process, due to the poor wettability between the dispersion and the support, and the absence of hydrazine or hydrated hydrazine and phosphorus-containing organic matter, the copper oxide particles in the coated layer state exhibited poor dispersibility and agglomeration.

[0507] The resistance value of the conductive pattern area is ×. It is believed that due to the poor smoothness of the coating layer and the absence of hydrazine or hydrated hydrazine and phosphorus-containing organic matter, the reduction and sintering of copper oxide particles using lasers could not be properly achieved.

[0508] The film thickness of the conductive patterned region was measured, and the ratio to the film thickness of the unburned insulating region was calculated. The film thickness ratio was 68%.

[0509] The surface roughness of the conductive pattern area is ×. It is believed that in Comparative Example 2, due to the poor smoothness of the coating layer and the absence of hydrazine or hydrazine hydrate and phosphorus-containing organic matter, the reduction and sintering of copper oxide particles using a laser were not properly achieved, resulting in no particle-to-particle bonding and a rough surface. It should be noted that it is believed that the reduction and sintering of copper oxide particles using a laser cannot be achieved when at least one of hydrazine or hydrazine hydrate and phosphorus-containing organic matter is absent.

[0510] A withstand voltage evaluation of the insulation region was conducted, and the result was Δ. It is believed that in Comparative Example 2, due to the absence of hydrazine or hydrazine hydrate and phosphorus-containing organic matter, the copper oxide particles in the coated state exhibited poor dispersibility and could not adequately demonstrate insulation properties. It should be noted that it is believed that the copper oxide particles in the coated state also exhibited poor dispersibility when at least one of hydrazine or hydrazine hydrate and phosphorus-containing organic matter is absent.

[0511] [Comparative Example 3]

[0512] Using dispersion (c), a coating layer (0.8 μm thick) with two 25 mm × 1 mm patterns arranged in parallel with a 1 mm gap was formed on a borosilicate glass substrate (SCHOTT Tempax) using a reverse transfer method. The coating layer was further reduced by plasma firing to obtain two 25 mm × 1 mm conductive pattern regions containing reduced copper and phosphorus.

[0513] The voltage withstand capability of the two obtained conductive pattern regions was evaluated, and the result was ×. It is believed that this is because the two conductive pattern regions are separated by air and do not contain any insulating area, thus failing to exhibit insulation properties.

[0514] [Determination of phosphorus in conductive patterned regions]

[0515] For Specimen 8, after laser firing was performed as described above, phosphorus in the formed conductive pattern region was measured.

[0516] 1) Specimen manufacturing, XPS measurement

[0517] A small piece of about 3 mm square was cut out from the laser-fired Specimen 8, and an XPS measurement was performed with a 5 mmΦ mask covered. In the XPS measurement, Ar + ion sputtering was used for depth direction analysis.

[0518] <XPS measurement conditions>

[0519] Equipment used: ULVAC-PHI Versa probeII

[0520] Excitation source: mono.AlKα 15 kV × 3.3 mA

[0521] Analysis size: about 200 μmΦ

[0522] Optoelectron extraction angle: 45° ± 20°

[0523] Inlet region: Cu 2p3 / 2, P 2p, C 1s, O 1s, N 1s

[0524] Pass energy: 93.9 eV

[0525] <Ar + Ion sputtering conditions>

[0526] Acceleration voltage: 3 kV

[0527] Specimen current: 1.6 μA

[0528] Specimen size: 2 mm × 2 mm

[0529] Specimen rotation: Yes

[0530] Regarding the results of the XPS measurement, in Specimen 8, it was confirmed that the content of phosphorus relative to copper was 0.127 atom / atom% in atomic composition percentage and 0.062 w / w% in mass percentage.

[0531] For samples 35-37, after laser burning as described above, the phosphorus content in the formed conductive pattern region was measured. The evaluation results are shown in Table 3. It shows that the phosphorus / copper concentration ratio for each sample was 0.02 to 0.30. Similarly, the carbon and nitrogen content in the conductive pattern region were also measured. The evaluation results are shown in Table 3. It shows that the carbon / copper concentration ratio for each sample was 1 to 6. Furthermore, the nitrogen / copper concentration ratio for each sample was 0.04 to 0.6.

[0532] Table 3 is shown below.

[0533]

[0534] It should be noted that the present invention is not limited to the above-described embodiments and examples. Modifications can be made to the above-described embodiments and examples based on the knowledge of those skilled in the art, and the above-described embodiments and examples can be arbitrarily combined; such modifications are also included within the scope of the present invention.

[0535] Industrial applicability

[0536] According to the present invention, the manufacturing process can be greatly simplified, and a structure with conductive patterned regions that has excellent electrical insulation between conductive patterned regions and high reliability can be provided.

[0537] Furthermore, according to the present invention, no equipment for achieving a vacuum atmosphere or inert gas atmosphere is required in the photo-firing process of copper oxide, and a laminate and its manufacturing method can be provided that can reduce the manufacturing cost of the structure.

[0538] Based on the above, the structure and laminate of the present invention can be suitably used as wiring materials, grid electrodes, electromagnetic wave shielding materials, and heat dissipation materials for electronic circuit boards and the like.

[0539] This application is based on Japanese Special Penalties Nos. 2017-139133, 2017-139134, 2017-141518, 2017-141519, 2017-145188, 2017-145188, 2017-145188, and 2018-023239, filed on July 27, 2017. All of these are contained herein.

Claims

1. A laminate for manufacturing a structure having conductive patterned regions, characterized in that, The laminate comprises a support, a coating layer containing copper oxide and a phosphorus-containing organic compound disposed on the surface formed by the support, and a resin layer disposed in a manner covering the coating layer, wherein the phosphorus-containing organic compound has one or more skeletons selected from the group consisting of polyethylene glycol, polypropylene glycol, polyacetal, polybutene, and polysulfide structures. The copper oxide is a microparticle containing copper oxide. When the total volume of the microparticles is 100 parts by volume, the content of the phosphorus-containing organic matter is more than 5 parts by volume and less than 900 parts by volume. Relative to the coating layer, the content of copper oxide microparticles is more than 10% by volume and less than 90% by volume.

2. The laminate as claimed in claim 1, characterized in that, The coating layer is disposed on the support having a three-dimensional surface.

3. The laminate as described in claim 1 or 2, characterized in that, The copper oxide is cuprous oxide.

4. The laminate as described in claim 1 or 2, characterized in that, The phosphorus-containing organic compound is a phosphate salt.

5. A laminate for manufacturing a structure having conductive patterned regions, characterized in that, The laminate comprises a support, a coating layer containing copper oxide, a phosphorus-containing organic compound, and hydrazine or hydrazine hydrate disposed on the surface formed by the support, and a resin layer disposed in a manner covering the coating layer, wherein the phosphorus-containing organic compound has one or more skeletons selected from the group consisting of polyethylene glycol, polypropylene glycol, polyacetal, polybutene, and polysulfide structures. The copper oxide is a microparticle containing copper oxide. When the total volume of the microparticles is 100 parts by volume, the content of the phosphorus-containing organic matter is more than 5 parts by volume and less than 900 parts by volume. Relative to the coating layer, the content of copper oxide microparticles is more than 10% by volume and less than 90% by volume.

6. The laminate as described in claim 5, characterized in that, The coating layer is disposed on the support having a three-dimensional surface.

7. The laminate as described in claim 5 or 6, characterized in that, The copper oxide is cuprous oxide.

8. The laminate as described in claim 5 or 6, characterized in that, The phosphorus-containing organic compound is a phosphate salt.

9. A laminate for a circuit board, characterized in that, The laminate comprises a support, a layer on the surface of the support comprising an insulating region containing copper oxide and a phosphorus-containing organic material and a conductive pattern region containing copper arranged adjacent to each other, and a resin layer formed to cover the layer, wherein the phosphorus-containing organic material has one or more skeletons selected from the group consisting of polyethylene glycol structure, polypropylene glycol structure, polyacetal structure, polybutene structure and polysulfide structure. The copper oxide is a microparticle containing copper oxide. When the total volume of the microparticles is 100 parts by volume, the content of the phosphorus-containing organic matter is more than 5 parts by volume and less than 900 parts by volume. Relative to the insulating area, the content of copper oxide microparticles is more than 10% by volume and less than 90% by volume.

10. The laminate as claimed in claim 9, characterized in that, The insulating region and the conductive pattern region are arranged adjacent to each other in a layer on the support having a three-dimensional surface.

11. The laminate as claimed in claim 9 or 10, characterized in that, The copper oxide is cuprous oxide.

12. The laminate as described in claim 9 or 10, characterized in that, The phosphorus-containing organic compound is a phosphate salt.

13. A laminate for a circuit board, characterized in that, The laminate comprises a support, an insulating region comprising copper oxide, a phosphorus-containing organic compound, and hydrazine or hydrazine hydrate disposed adjacent to each other on the surface formed by the support, and a conductive patterned region comprising copper, and a resin layer formed to cover the layer, wherein the phosphorus-containing organic compound has a framework selected from one or more of the group consisting of polyethylene glycol, polypropylene glycol, polyacetal, polybutene, and polysulfide structures. The copper oxide is a microparticle containing copper oxide. When the total volume of the microparticles is 100 parts by volume, the content of the phosphorus-containing organic matter is more than 5 parts by volume and less than 900 parts by volume. Relative to the insulating area, the content of copper oxide microparticles is more than 10% by volume and less than 90% by volume.

14. The laminate as claimed in claim 13, characterized in that, The insulating region and the conductive pattern region are arranged adjacent to each other in a layer on the support having a three-dimensional surface.

15. The laminate as claimed in claim 13 or 14, characterized in that, The copper oxide is cuprous oxide.

16. The laminate as claimed in claim 13 or 14, characterized in that, The phosphorus-containing organic compound is a phosphate salt.

17. A copper wiring comprising reduced copper (formed by reducing copper oxide), phosphorus, and carbon, characterized in that, The copper wiring is a conductive patterned region formed by selectively irradiating the coating layer in the laminate according to any one of claims 1 to 8, wherein the elemental concentration ratio of phosphorus to copper is 0.02 to 0.30 and the elemental concentration ratio of carbon to copper is 1.0 to 6.

0.

18. The copper wiring as described in claim 17, characterized in that, The arithmetic mean roughness Ra of the copper wiring surface is above 20 nm and below 500 nm.

19. The copper wiring as described in claim 17 or 18, characterized in that, The copper wiring further comprises nitrogen, with a nitrogen / copper elemental concentration ratio of 0.04 to 0.

6.

20. The method for manufacturing a laminated body for manufacturing a structure having conductive patterned regions as described in claim 1, characterized in that, It has the following processes: The process of applying the coating layer containing the copper oxide and the phosphorus-containing organic matter to the surface formed by the support; and The process of preparing a resin layer in a manner that covers the coating layer.

21. The method for manufacturing a laminate as described in claim 20, characterized in that, It further includes the following processes: The process of selectively irradiating the coating layer with light by means of either the resin layer or the support, and depositing an insulating region containing copper oxide and phosphorus-containing organic matter adjacent to a conductive pattern region containing copper on the surface formed by the support.

22. The method for manufacturing a laminate as described in claim 21, characterized in that, The light source is a laser with a center wavelength between 355nm and 532nm.

23. The method for manufacturing a laminate as described in any one of claims 20 to 22, characterized in that, The copper oxide is cuprous oxide.

24. The method for manufacturing a laminate as described in any one of claims 20 to 22, characterized in that, The phosphorus-containing organic compound is a phosphate salt.

25. The method for manufacturing a laminated body for manufacturing a structure having conductive patterned regions as described in claim 5, characterized in that, It has the following processes: The process of depositing a coating layer comprising the copper oxide, the phosphorus-containing organic matter, and hydrazine or hydrazine hydrate on the surface formed by the support; and The process of preparing a resin layer in a manner that covers the coating layer.

26. The method for manufacturing a laminate as described in claim 25, characterized in that, It further includes the following processes: The process of selectively irradiating the coating layer with light by means of either the resin layer or the support, and depositing an insulating region containing copper oxide, phosphorus-containing organic matter and containing hydrazine or hydrazine hydrate adjacent to each other on the surface formed by the support.

27. The method for manufacturing a laminate as described in claim 26, characterized in that, The light source is a laser with a center wavelength between 355nm and 532nm.

28. The method for manufacturing a laminate as described in any one of claims 25 to 27, characterized in that, The copper oxide is cuprous oxide.

29. The method for manufacturing a laminate as described in any one of claims 25 to 27, characterized in that, The phosphorus-containing organic compound is a phosphate salt.

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