CN105517788A - Stacked body, conductive pattern, electronic circuit, and production method for stacked body - Google Patents
Stacked body, conductive pattern, electronic circuit, and production method for stacked body Download PDFInfo
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- CN105517788A CN105517788A CN201480049643.3A CN201480049643A CN105517788A CN 105517788 A CN105517788 A CN 105517788A CN 201480049643 A CN201480049643 A CN 201480049643A CN 105517788 A CN105517788 A CN 105517788A
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- metal level
- duplexer
- supporter
- described metal
- metal
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/046—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/245—Reinforcing conductive patterns made by printing techniques or by other techniques for applying conductive pastes, inks or powders; Reinforcing other conductive patterns by such techniques
- H05K3/246—Reinforcing conductive paste, ink or powder patterns by other methods, e.g. by plating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2266/00—Composition of foam
- B32B2266/04—Inorganic
- B32B2266/045—Metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
Abstract
The present invention provides: a stacked body in which a porous metal layer (B) is formed upon a support body (A), and a metal layer (C) is formed upon the metal layer (B), said stacked body wherein pores in the metal layer (B) are filled with a metal configuring the metal layer (C); and a production method for said stacked body. Also provided are a conductive pattern and an electronic circuit which use the stacked body. In this stacked body, although metal layers of two different kinds are formed upon the support body, excellent adhesive properties are exhibited therebetween.
Description
Technical field
The duplexer that the conductive pattern that the present invention relates to the electronic circuit that can obtain as the wiring for printed base plate, electromagnetic wave shielding, integrated circuit, organic transistor etc. uses and manufacture method thereof.
Background technology
In recent years, along with the high performance of electronic equipment, miniaturization and slimming, the densification of electronic circuit wherein used, integrated circuit, miniaturization and slimming is required consumingly.
As the conductive pattern that may be used in above-mentioned electronic circuit etc., such as there will be a known following conductive pattern, namely, by containing the paint of conductive material in the coating of the surface of supporter and burning till and form conductive material layer in supporting body surface, then, by carrying out plating process to the surface of described conductive material layer, and coating is set on the surface of described conductive material layer (such as with reference to patent document 1 and 2.)。But the conductive material layer of this conductive pattern and the adaptation of coating are abundant not, and passing in time can cause the stripping of coating, have and produce the reduction of electric conductivity, the problem of broken string.
Said, as the duplexer that can be used as conductive pattern, require the duplexer of the excellent adhesion at each interface of supporter and conductive material layer and coating, particularly also do not find out the duplexer of the excellent adhesion at the interface of conductive material layer and coating.
Prior art document
Patent document
Patent document 1: Japanese Laid-Open Patent Publication 60-246695 publication
Patent document 2: Japanese Unexamined Patent Publication 2005-286158 publication
Summary of the invention
Invent problem to be solved
Problem to be solved by this invention is, provides a kind of duplexer, is the duplexer being formed with 2 kinds of metal levels on supporter, and the adaptation of these 2 kinds of metal interlevels is very excellent, and provides the manufacture method of this duplexer.In addition, the conductive pattern, the electronic circuit that employ this duplexer are provided.
For the method for dealing with problems
The present inventor etc. conduct in-depth research to solve the above problems, found that, supporter is formed in the duplexer of 2 kinds of metal levels, if the first metal layer be formed on supporter is set to cavernous metal level and forms the metal being formed at the second metal level on this first metal layer and will be present in the fill gaps in the first metal layer, then the adaptation of these 2 kinds of metal interlevels is very excellent, thus completes the present invention.
Namely, the invention provides a kind of duplexer, it is the duplexer being formed with cavernous metal level (B) on supporter (A), being formed with metal level (C) on described metal level (B), it is characterized in that, be present in the space in described metal level (B) metal being filled with and forming metal level (C), and the manufacture method of this duplexer is being provided.In addition, the conductive pattern, the electronic circuit that employ this duplexer are provided.
Invention effect
Duplexer of the present invention due to the adaptation being formed at 2 kinds of metal interlevels on supporter very excellent, therefore the electric conductivity of metal level can not be passed in time and reduce, and in addition, can not break when being utilized by metal level fine rule to carry out patterning.Thus, the various components uses in the general printed electronic field such as manufacture forming the formation of periphery wiring of RFID etc., the wiring of the electromagnetic wave shielding of plasma scope, integrated circuit, organic transistor as conductive pattern, electronic circuit, organic solar batteries, electric terminal, organic EL, organic transistor, flexible printed board, contactless IC card etc. can be such as suitable for.
Accompanying drawing explanation
Fig. 1 is the cross sectional photograph of the SEM of the duplexer (1) made in embodiment 1, and bright part represents the part having copper (Cu) atom.
Fig. 2 is the cross sectional photograph of the SEM of the duplexer (1) made in embodiment 1, and bright part represents the part having silver (Ag) atom.
Fig. 3 is the cross sectional photograph of the SEM of the duplexer (R1) made in comparative example 1, and bright part represents the part having copper (Cu) atom.
Fig. 4 is the cross sectional photograph of the SEM of the duplexer (R1) made in comparative example 1, and bright part represents the part having silver (Ag) atom.
Detailed description of the invention
Duplexer of the present invention is the duplexer being formed with cavernous metal level (B) on supporter (A), being formed with metal level (C) on described metal level (B), is being present in the space in described metal level (B) metal being filled with and forming metal level (C).
Described supporter (A) becomes the base material of duplexer of the present invention.As the material of described supporter (A), such as, can enumerate polyimides, polyamidoimide, polyamide, PETG, PEN, Merlon, acrylonitrile-butadiene-styrene (ABS) (ABS resin), acrylic resin, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene, polypropylene, polyurethane, cellulose nano-fibrous, silicon, pottery, glass, glass-epoxy resin, glass polyimides, paper phenol etc.
In addition, when duplexer of the present invention is used as conductive pattern, preferably there is the material of insulating properties, therefore as the material of described supporter (A), preferred phenolic resins, fluororesin, polyimide resin, PETG, PEN, glass, glass-epoxy resin, glass polyimides, paper phenol, cellulose nano-fibrous, aluminium oxide, mullite, talcum, forsterite, zirconium dioxide etc.
In addition, as described supporter (A), such as, also can use synthetic fibers such as comprising polyester fiber, Fypro, aramid fibre; The base material of the natural fiber such as cotton, numb etc.Also processing can be implemented in advance to described fiber.
As described supporter (A), when duplexer of the present invention be used to requirement can the purposes of flexibility of warpage, preferably use the soft and supporter of flexibility.Specifically, the supporter of film or sheet is preferably used.
As the supporter of described film or sheet, such as, can enumerate PETG film, polyimide film, poly (ethylene naphthalate) film etc.
When the shape of described supporter (A) be membranaceous or sheet, the thickness of the supporter of membranaceous or sheet is preferably about 1 ~ 5000 μm usually, is more preferably the thickness of about 1 ~ 300 μm.In addition, when duplexer of the present invention being used for flexible printed board etc. and requiring in the component of bendability, as supporter, the membranaceous supporter of the thickness of about 1 ~ 200 μm is preferably used.
For the surface of described supporter (A), in order to improve the adaptation with described metal level (B) further, such as also can utilize the dry treatment methods such as plasma discharge facture, ultraviolet treatment such as Corona discharge Treatment method, employ water, the wet treatment method of acidity or alkaline liquid, organic solvent etc., carry out surface treatment.
Described metal level (B) is formed at the cavernous layer on described supporter (A), has space in this layer.As the metal forming described metal level (B), transition metal or its compound can be enumerated, wherein the transition metal of preferred ion.As the transition metal that this is ionic, copper, silver, gold, nickel, palladium, platinum, cobalt etc. can be enumerated.In the transition metal that these are ionic, copper, silver, the gold conductive pattern that resistance is low owing to obtaining, corrosion resistance is strong, therefore preferably.
In addition, as the metal forming described metal level (C), copper, nickel, chromium, cobalt, tin etc. can be enumerated.In the middle of them, the conductive pattern that resistance is low owing to obtaining, corrosion resistance is strong, therefore preferably copper.
In duplexer of the present invention, be present in the space in described metal level (B) metal being filled with and forming metal level (C), but in order to improve the adaptation of described metal level (B) and described metal level (C) further, preferably until be present in described supporter (A) and the space in the described metal level (B) of the near interface of described metal level (B), be all filled with the metal forming described metal level (C).
As the manufacture method of duplexer of the present invention, such as can enumerate following method, namely, in the upper coating of supporter (A) containing the metal powder of nano-scale and the fluid of dispersant and after burning till and forming metal level (B '), to the organic compound removing comprising dispersant in described metal level (B ') be present in and form space, make cavernous metal level (B), then utilize plating or electroless plating to form described metal level (C).
Described metal level (B) as long as formation in the shape of metal powder of nano-scale used make metal level be cavernous shape, but be preferably particle shape or fibrous shape.In addition, the size of described metal powder uses the size of nano-scale, but specifically, under the shape of metal powder is emboliform situation, in order to fine conductive pattern can be formed, can reduce the resistance value after burning till further, average grain diameter is preferably the scope of 1 ~ 100nm, is more preferably the scope of 1 ~ 50nm.And described " average grain diameter " is the bulk averaged value being diluted, utilize dynamic light scattering determination to go out by described conductive material dispersion good solvent.Microtrac Inc. " NanotracUPA-150 " can be used when this mensuration.
On the other hand, under the shape of metal powder is fibrous situation, in order to form fine conductive pattern, can reduce the resistance value after burning till further, the diameter of fiber is preferably the scope of 5 ~ 100nm, is more preferably the scope of 5 ~ 50nm.In addition, the length of fiber is preferably the scope of 0.1 ~ 100 μm, is more preferably the scope of 0.1 ~ 30 μm.
When the upper formation described metal level (B) of described supporter (A), preferably the method for fluid coating on described supporter (A) of the metal powder of described nano-scale will be dispersed with in a solvent.
The scope being preferably 5 ~ 90 quality % containing ratio of the metal powder of the described nano-scale in described fluid, is more preferably the scope of 10 ~ 60 quality %.
As the composition be engaged in described fluid, comprise the organic compound such as surfactant described later, levelling agent, viscosity modifier, coalescents, defoamer, anticorrisive agent for making the metal powder of nano-scale be scattered in dispersant in solvent or solvent and use as required.
In order to make the metal powder of described nano-scale be scattered in solvent, use the dispersant of low-molecular-weight or HMW.As described dispersant, such as, can enumerate dodecyl mercaptans, 1-octanethiol, triphenylphosphine, lauryl amine, polyethylene glycol, PVP, polyethylene imine based, PVP; The aliphatic acid such as myristic acid, sad, stearic acid; Cholic acid, glycyrrhizic acid, rosin acid (acid of ア PVC Application チ Application) etc. have the condensed ring formula hydrocarbon compound etc. of carboxyl.In the middle of them, owing to can be improved the adaptation of described metal level (B) and metal level described later (C) by the void size increased in described metal level (B), therefore preferred macromolecule dispersing agent, as this macromolecule dispersing agent, preferably the polyalkyleneimine such as polyethylene imine based, polypropylneimine, on described polyalkyleneimine the addition compound etc. of polyalkylene oxide.
As mentioned above, by using macromolecule dispersing agent in described dispersant, compared with low molecule dispersant, the dispersant because removing in described metal level (B) can being increased and the void size formed, the space of the size from nanoscale to submicron order can be formed.In this space, easily fill the metal forming metal level described later (C), the metal of filling becomes anchor, can increase substantially the adaptation of described metal level (B) and metal level described later (C).
In order to the use amount of the metal powder and required described dispersant that disperse described nano-scale is preferably 0.01 ~ 50 mass parts relative to metal powder 100 mass parts of described nano-scale, be more preferably 0.01 ~ 10 mass parts.
In addition, space is formed due to the dispersant more easily removed in described metal level (B), the adaptation of described metal level (B) and metal level described later (C) can be improved further, therefore relative to metal powder 100 mass parts of described nano-scale, be preferably 0.1 ~ 10 mass parts, be more preferably 0.1 ~ 5 mass parts.
As solvent used in described fluid, aqueous medium or organic solvent can be used.As described aqueous medium, such as, can enumerate distilled water, ion exchange water, pure water, ultra-pure water etc.In addition, as described organic solvent, alcoholic compound, ether compound, ester compounds, ketonic compound etc. can be enumerated.
As described alcohol, such as methyl alcohol can be enumerated, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-methyl isophthalic acid-propyl alcohol, 2-butanols, 2-methyl-2-propanol, enanthol, hexanol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alchohol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpinol, dihydroterpineol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, TEG monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Tripropylene glycol monomethyl Ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, Dipropylene glycol mono-n-butyl Ether, Tri(propylene glycol)butyl ether,mixture of isomers etc.
In addition, in described fluid, except above-mentioned metal powder, solvent, spent glycol, diethylene glycol, 1,3-BDO, isoprene etc. can also be made as required.
As described surfactant, general surfactant can be used, such as, can enumerate two (2-ethylhexyl) sulfosuccinate, dodecyl benzene sulfonate, alkyl diphenyl base ether disulfonate, alkylnaphthalene sulfonate, hexametaphosphate etc.
As described levelling agent, general levelling agent can be used, such as, can enumerate silicone compound, acetylenediol based compound, fluorine based compound etc.
As described viscosity modifier, general thickener can be used, such as can enumerate by be adjusted to alkalescence and can the acrylic polymer of thickening or synthetic rubber latex, by making molecular association and can the carbamate resins, hydroxyethylcellulose, carboxymethyl cellulose, methylcellulose, polyvinyl alcohol, rilanit special, amide waxe, oxidic polyethylene, metallic soap, dibenzal sorbitol etc. of thickening.
As described coalescents, general coalescents can be used, such as, can enumerate anion system surfactant (dioctyl sodium sulfosuccinates sodium salt etc.), Hydrophobic nonionic system surfactant (sorbitan monooleate etc.), polyether modified siloxane, silicone oil etc.
As described defoamer, general defoamer can be used, such as, can enumerate silicone-based defoamer, nonionic system surfactant, polyethers, higher alcohol, polymer system surfactant etc.
As described anticorrisive agent, general anticorrisive agent can be used, such as, can enumerate isothiazoline system anticorrisive agent, triazine system anticorrisive agent, imidazoles system anticorrisive agent, pyridine system anticorrisive agent, azole series anticorrisive agent, iodine system anticorrisive agent, pyrithione system anticorrisive agent etc.
The viscosity (value 25 DEG C use Brookfield viscometer to measure) of described fluid is preferably the scope of 0.1 ~ 500000mPas, is more preferably the scope of 0.5 ~ 10000mPas.In addition, when utilizing method coating (printing) the described fluids such as ink jet printing method described later, letterpress reverse printing, its viscosity is preferably the scope of 5 ~ 20mPas.
As the method at the described fluid of the upper coating of described supporter (A), such as, can enumerate ink jet printing method, reversal printing method, silk screen print method, flexographic printing process, spin-coating method, spraying process, stick coating method, mould painting method, slot coated method, rolling method, dip coating etc.
In the middle of these coating processes, when described metal level (B) that formed with the thin-line-shaped patterning of the width of about 0.01 ~ 100 μm required during the densification realizing electronic circuit etc., preferably use ink jet printing method, reversal printing method.
As described ink jet printing method, the device being referred to as ink-jet printer generally can be used.Specifically, KonicaMinoltaEB100, XY100 (KonicaMinoltaIJ Co., Ltd. system), DimatixMaterial printer DMP-3000, DimatixMaterial printer DMP-2831 (Fuji Photo Film Co., Ltd.'s system) etc.
In addition, as reversal printing method, there will be a known letterpress reverse printing method, intaglio plate reversal printing method, such as, can enumerate following method, namely, by the surface of described fluid coating in various blanket, make it the version outstanding with non-setting-out portion to contact, by the surface optionally transfer printing of the fluid corresponding with described non-setting-out portion to described version, form described pattern on the surface of described blanket etc. thus, then, described pattern is gone up (surface) transfer printing to described support body layer (A).
Described metal level (B) is formed on described supporter (A), but in order to the adaptation of the surface of improving described supporter (A) further and described metal level (B), also can in the surperficial primer coating of described supporter (A), dry and after forming prime coat, this prime coat forms described metal level (B).
As described priming paint, such as, can enumerate the priming paint containing the various resins such as carbamate resins, vinylite, carbamate-vinyl compound resin, epoxy resin, imide resin, amide resin, melmac, phenolic resins, polyvinyl alcohol, PVP and solvent.
In the resin used as described priming paint, preferred use carbamate resins, vinylite, carbamate-vinyl compound resin, more preferably the carbamate resins with polyether structure is selected from, there is the carbamate resins of polycarbonate structure, there is the carbamate resins of polyester construction, acrylic resin, and the resin of more than a kind in carbamate-acrylic compounds compound resin, carbamate-acrylic compounds compound resin is owing to obtaining adaptation, electric conductivity, duplexer used in the conductive pattern of fine rule excellence, therefore further preferably.
For the described resin in described priming paint containing ratio, if consider the easness of coating, then the scope of preferred 10 ~ 70 quality %, the more preferably scope of 10 ~ 50 quality %.
In addition, as solvent used in described priming paint, organic solvent, aqueous medium can be enumerated.
As described organic solvent, such as, can enumerate toluene, ethyl acetate, MEK etc., the organic solvent as described aqueous medium, water can be enumerated, mixing with water and their mixture.
As the organic solvent mixed with water, such as, can enumerate the alcohol such as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, butyl cellosolve; The ketone such as acetone, MEK; The ployalkylene glycols such as ethylene glycol, diethylene glycol, propane diols; The alkyl ether of ployalkylene glycol; The lactams etc. such as METHYLPYRROLIDONE.
For the described solvent in described priming paint containing ratio, if consider the easness of coating, then the scope of preferred 25 ~ 85 quality, the more preferably scope of 45 ~ 85 quality %.
In described priming paint, as required, the additive such as crosslinking agent, pH adjusting agent, overlay film formation auxiliary agent, levelling agent, thickener, water-repelling agent, defoamer can also be added.
Described prime coat can by coating part or all of the surface of described supporter (A) and aqueous medium contained in described priming paint, organic solvent equal solvent being removed and formed by priming paint.
As the method on surface described priming paint being coated described supporter (A), such as, can enumerate intaglio plate mode, coating method, silk screen mode, roller mode, rotation mode, spray pattern etc.
For the surface of described prime coat, in order to improve and the adaptation of described metal level (B) further, such as, also can utilize the dry treatment methods such as plasma discharge facture, ultraviolet treatment such as Corona discharge Treatment method, employ water, the wet treatment method of acidity or alkaline liquid, organic solvent etc. carries out surface treatment.
As behind the surface described priming paint being coated described supporter (A), remove the method for solvent contained in this coating layer, be generally the method such as using drying machine to be dried, described solvent is volatilized.As baking temperature, be preferably set to and described solvent can be made to volatilize and the temperature of dysgenic scope can not be caused supporter (A).
The thickness of the prime coat using described priming paint to be formed is different according to the purposes of use duplexer of the present invention, but due to the adaptation of described supporter (A) and described metal level (B) can be improved further, therefore the scope of 10nm ~ 30 μm is preferably, be more preferably the scope of 10nm ~ 1 μm, the more preferably scope of 10nm ~ 500nm.
In addition, described supporter (A) arranges prime coat, due to the adaptation of described supporter (A) and described prime coat can be improved, therefore also can implementing fine concavo-convex formation to the surface of described supporter (A), being attached to the cleaning of the dirt on its surface, for importing the surface treatment etc. of the functional groups such as hydroxyl, carbonyl, carboxyl.Specifically can implement the wet processed etc. of the dry process such as plasma discharge process, UV treatment such as Corona discharge Treatment, the aqueous solution using water, acid/alkali etc. or organic solvent etc.
In order to form described metal level (B), the firing process carried out after coating is containing the fluid of metal powder is in order to be undertaken by closely sealed joint between metal powder contained in described fluid is formed the metal level (B) with electric conductivity.Described burning till preferably carries out about 2 ~ 200 minutes the temperature range of 80 ~ 300 DEG C.Described burning till also can be carried out in an atmosphere, but in order to prevent metal powder to be all oxidized, also can carry out part or all of firing process under reducing atmosphere.Through this firing process, closely sealedly will engage between particle shape used in the formation of described metal level (B) or fibrous metal powder, make described metal level (B) become cavernous layer thus.
In addition, described firing process such as can use baking oven, hot air type drying oven, infrared drying stove, laser irradiation, microwave, illumination to penetrate (flash lamp irradiation device) etc. and carry out.
For the thickness of the metal level utilizing above-mentioned firing process to obtain (B '), if consider the adaptation with metal level described later (C), be then preferably the scope of 10nm ~ 10 μm, be more preferably the scope of 10nm ~ 3 μm.
After above-mentioned firing process, be present in the organic compound comprising dispersant in described metal level (B ') by removing and form space, just can make cavernous described metal level (B).As the method for this removing organic compound, there is the method described metal level (B ') being implemented to the process such as plasma discharge facture, electromagnetic wave irradiation facture, laser treatment with irradiation method, the dissolution process method of being disperseed again by the organic compound comprising dispersant and dissolving with water or organic solvent.These processing methods can be used alone, or combinationally use two or more, due to by combinationally using two or more, can more effectively remove described organic compound, therefore preferably.And said so-called organic compound herein, is be engaged in the composition in described fluid, refers to the organic compounds such as dispersant, solvent, surfactant, levelling agent, viscosity modifier, coalescents, defoamer, anticorrisive agent.
As described plasma discharge facture, such as, can enumerate the vacuum plasma discharge factures etc. such as the atmospheric pressure plasma discharge factures such as Corona discharge Treatment method, the glow discharge facture of carrying out under vacuum or decompression and arc discharge facture.
As described atmospheric pressure plasma discharge facture, the method of carrying out plasma discharge process under oxygen concentration is the atmosphere of 0.1 ~ 25 volume about % can be enumerated, but in order to improve the adaptation of described metal level (B) and metal level (C), easy metal of filling formation metal level (C) in the space that cavernous metal level (B) has simultaneously, oxygen concentration is preferably the scope of 10 ~ 22 volume %, is more preferably about 21 volume % (under air atmosphere).
In addition, too much concavo-convex owing to can not give the surface of described metal level (B), the adaptation of described metal level (B) and metal level (C) can be improved further, therefore preferably under described oxygen concentration, under containing the environment of inactive gas, carry out described atmospheric pressure plasma discharge facture.And, as described inactive gas, can argon gas, nitrogen etc. be enumerated.
As the operable device when utilizing described atmospheric pressure plasma discharge facture to process, such as, can enumerate the atmospheric pressure plasma jet treatment device " AP-T01 " etc. of Sekisui Chemical Co., Ltd.
When utilizing described atmospheric pressure plasma discharge facture to process, as the flow of the gases such as air, be preferably the scope of 5 ~ 50 liters/min.In addition, as power output, be preferably the scope of 50 ~ 500W.In addition, as the processing time, the scope of 1 ~ 500 second is preferably.
In the middle of described atmospheric pressure plasma discharge facture, preferably use Corona discharge Treatment method.As device operable in Corona discharge Treatment method, such as, can enumerate the corona surface modified gneiss device " TEC-4AX " etc. of Kasuga Electric K. K..
When utilizing Corona discharge Treatment method to process, as power output, be preferably the scope of 5 ~ 300W.In addition, the processing time is preferably the scope of 0.5 ~ 600 second.
Above-mentioned plasma discharge facture can until the removing of ground, deep be present in the described organic compound in described metal level (B '), the described organic compound be present in described metal level (B) connecting the near interface being present in described supporter (A) and described metal level (B) can remove, therefore preferably.By using above-mentioned plasma discharge facture, time metal level (C) that state after its formation, in the space that cavernous metal level (B) has, filling with regard to easy the metal forming metal level (C), more easily will forming the metal filled to being present in described supporter (A) and the space in the described metal level (B) of the near interface of described metal level (B) of metal level (C).Thus, the metal forming metal level (C) will enter into the darker part of described metal level (B), play larger anchoring effect, therefore can increase substantially the adaptation of described metal level (B) and metal level described later (C).
Described electromagnetic wave irradiation facture by being irradiated to described metal level (B ') by electromagnetic wave, and at high temperature can heat described metal level (B '), and organic compound is decomposed removing.This electromagnetic wave irradiation process also can utilize electro-magnetic wave absorption to resonate and optionally remove dispersant.The electromagnetic wavelength that prior setting resonate with the described organic compound be present in described metal level (B '), to the electromagnetic wave of the wavelength set by described metal level (B) irradiation.Thus, the absorption to described organic compound will become greatly (resonance), therefore by the electromagnetic intensity of adjustment, can only be removed by dispersant.
Described organic compound in metal level (B '), by irradiating laser to described metal level (B '), can be decomposed removing by described laser treatment with irradiation method.In this laser treatment with irradiation method, the laser instrument that can carry out laser ablation (laserscribe) and process can be used.As the laser instrument that can carry out laser ablation process, YAG laser, CO can be enumerated
2laser instrument, excimer laser, but particularly preferably YAG laser.The light of 0.53 μm of second high frequency that also can obtain according to required use and with nonlinear optical element except fundamental wavelength 1.06 μm.For YAG laser, in order to obtain high-peak power and high-frequency, preferably use pulse laser.
As concrete sharp light-struck method to described metal level (B '), while transport described metal level (B '), while the laser beam lens light gathering will exported from lasing light emitter, the surface to described metal level (B ') is irradiated.Now, polygonal mirror is utilized to move laser beam, with the surface of the described metal level (B ') in laser beam flying conveyance.Thus, just can by described metal level (B ') with high-temperature heating.The power output of the laser of laser treatment with irradiation is preferably 0.1 ~ 100kW, and pulsed frequency (stimulating frequency) is preferably number kHz to tens of kHz, and the duration (pulse width) of 1 pulse is preferably 90 ~ 100nsec.
Described dissolution process method is by being disperseed by the described organic compound be present in described metal level (B ') again and being dissolved in water or organic solvent thus carrying out the method that removes.As described organic solvent, the alcohol series solvents such as methyl alcohol, ethanol, isopropyl alcohol can be enumerated; The aprotic polar solvent such as methyl-sulfoxide, dimethyl formamide, 1-METHYLPYRROLIDONE; Oxolane, MEK, ethyl acetate, エ Network ア ミ De (bright dipping is emerging produces organic solvent) etc.
In addition, in order to described organic compound is disperseed, dissolves, preferably use acid or alkali, more preferably use alkali.As acid, such as, can enumerate sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, oxalic acid, acetic acid, formic acid, propionic acid, butanedioic acid, glutaric acid, tartaric acid, adipic acid etc.The strong acid such as sulfuric acid, nitric acid, hydrochloric acid are preferably used in the middle of them.In addition, when forming metal level (C) described later in the electrolytic copper plating operation employing copper sulphate, also in order to not bring impurity into in rear operation, preferably sulfuric acid is used.
As described alkali, the organic amine such as NaOH or potassium hydroxide, lithium hydroxide, calcium hydroxide, ammonia, triethylamine, pyridine, morpholine can be enumerated; The alkanolamines etc. such as MEA.Wherein, the highly basic such as NaOH, potassium hydroxide is preferably used.
In addition, in order to described organic compound is disperseed, dissolved, also surfactant can be used.As described surfactant, general surfactant can be used, such as, can enumerate two (2-ethylhexyl) sulfosuccinate, alkyl sulfate, alkylbenzenesulfonate, alkyl diphenyl base ether disulfonate etc.These surfactant dissolves demonstrate alkalescence in water, therefore easily remove described organic compound, so be more preferably.
Then, formed because removing described organic compound in described metal level (B ') after there is the cavernous metal level (B) in space described supporter (A) is upper as described above, described metal level (B) is formed metal level (C), just can obtain duplexer of the present invention thus.
The metal level (C) forming duplexer of the present invention is the layer arranged for following object, such as, that is, when described duplexer being used for conductive pattern etc., can not broken string etc. be produced in long-time, form the wiring pattern that the reliability of the powered that can remain good is high.
Described metal level (C) is formed at the layer on described metal level (B), and as its formation method, preferably utilize the method that plating process is formed.As this plating process, such as, can enumerate the dry type plating etc. such as the wet type such as galvanoplastic, electroless plating method plating, sputtering method, vacuum vapour deposition.In addition, also these plating can be combined two or more to form described metal level (C).
In above-mentioned plating process, owing to easily filling the adaptation of metal, the further described metal level of raising (B) and the described metal level (C) forming metal level (C) in the space that cavernous metal level (B) has, the conductive pattern of excellent electric conductivity can be obtained in addition, therefore the preferred wet type such as galvanoplastic, electroless plating method plating, more preferably galvanoplastic.
Above-mentioned electroless plating method such as makes the metals such as copper contained in electroless plating liquid separate out, be formed by the method for the metal film coated electroless plating (overlay film) formed by making electroless plating liquid contact the metal of the described metal level of formation (B).
As described electroless plating liquid, such as, can enumerate the plating solution containing metal, reducing agent and the aqueous mediums such as copper, nickel, chromium, cobalt, tin, organic solvent equal solvent.
As described reducing agent, such as, can enumerate dimethyl amino borane, ortho phosphorous acid, inferior sodium phosphate, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenol etc.
In addition, as described electroless plating liquid, as required, can use containing the monocarboxylic acid such as acetic acid, formic acid; The dicarboxylic acid compounds such as malonic acid, butanedioic acid, adipic acid, maleic acid, fumaric acid; The hydroxy carboxylic acid compounds such as malic acid, lactic acid, glycolic, gluconic acid, citric acid; The amino-acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid, glutamic acid; The plating solution of the complexants such as amines such as the organic acids such as the aminopolycarboxylate compounds such as NTA, EDDA, ethylenediamine tetra-acetic acid, diethylenetriamine pentaacetic acid or these organic acid soluble-salts (sodium salt, sylvite, ammonium salt etc.), ethylenediamine, two sub-second triamines, tetramine.
Described electroless plating liquid preferably uses with the scope of 20 ~ 98 DEG C.
Described galvanoplastic are following methods, namely, such as by being energized under the metal making electrolyte contacts form described metal level (B) or the state utilizing the surface of the described electroless plating (tunicle) formed without electrolytic treatments, and make the metals such as copper contained in described electroplate liquid to the conductive material of the described metal level of the formation being located at negative electrode (B) or utilize the surface of the described electroless plating layer (tunicle) without electrolytic treatments formation to separate out, form electrodeposited coating (metal tunicle).
As described electroplate liquid, such as, can enumerate the plating solution etc. of sulfide, sulfuric acid and the aqueous medium containing metals such as copper, nickel, chromium, cobalt, tin.Specifically, the plating solution containing copper sulphate, sulfuric acid and aqueous medium can be enumerated.
Described electroplate liquid preferably uses with the scope of 20 ~ 98 DEG C.
In above-mentioned electroplating processes method, due to the material that toxicity is high can not be used, good operability, be therefore preferably formed the metal level (C) comprising copper employing galvanoplastic.
In addition, as described dry type plating treatment process, sputtering method, vacuum vapour deposition etc. can be used.Described sputtering method is following method, namely, import inactive gas (mainly argon gas) in a vacuum, voltage is applied to the formation material (target) of metal level (C) and produces glow discharge, then, by described inactive gas atomizing/ionizing, to beat gas ion tempestuously to the surface of the formation material (target) of described metal level (C) at a high speed, the atom and molecule that form the formation material (target) of metal level (C) are ejected and makes it to be attached to the surface of described metal level (B) fiercely, form metal level (C) thus.
As the formation material (target) of described metal level (C) utilizing sputtering method, such as, can enumerate chromium, copper, titanium, silver, platinum, gold, nickel-chromium alloy, stainless steel, copper-zinc alloy, indium tin oxide (ITO), silica, titanium dioxide, niobium oxide, zinc oxide etc.
When utilizing described sputtering method to carry out plating process, such as, magnetic control sputtering device etc. can be used.
The thickness of described metal level (C) is preferably the scope of 1 ~ 50 μm.The thickness of described metal level (C) can be adjusted by the use amount etc. of the processing time of plating treatment process during control formation described metal level (C), current density, plating additive.
The duplexer of the present invention utilizing above-mentioned method to obtain can use as conductive pattern.When duplexer of the present invention is used for conductive pattern, in order to want to be formed needed for position corresponding to pattern form form described metal level (B), coating contains the fluid of described metal powder and burns till, and can manufacture the conductive pattern with required pattern thus.
In addition, described conductive pattern such as can utilize the photoetching process such as subtractive process, semi-additive process or the method for plating manufactures on the printed patterns of metal level (B).
Described subtractive process is following method, namely, on the described metal level (C) of the formation manufactured in advance duplexer of the present invention, form the resist layer of the shape corresponding with required pattern form, utilize development treatment thereafter, dissolve described metal level (C) and the metal level (B) of the part except removing described resist with liquid, form required pattern thus.As described liquid, the liquid containing copper chloride, iron chloride etc. can be used.
Described semi-additive process is following method, namely, form described metal level (B ') described supporter (A) is upper, utilize as required the removing such as plasma discharge process be present in described metal level (B ') comprise the organic compound of dispersant after, the resistance coating of the shape corresponding with required pattern is formed on the surface of the described metal level (B) of gained, then, utilize galvanoplastic, after electroless plating method forms metal level (C), described resistance coating and the described metal level (B) contacted with it are dissolved in the middle removings such as liquid, form required pattern thus.
In addition, on the printed patterns of metal level (B), the method for plating is following method, namely, on described supporter (A), ink-jet method, reversal printing method etc. is utilized to print the pattern of described metal level (B), utilize as required the removing such as plasma discharge process be present in described metal level (B ') comprise the organic compound of dispersant after, on the surface of the described metal level (B) of gained, utilize galvanoplastic, electroless plating method forms described metal level (C), form required pattern thus.
The conductive pattern utilizing above-mentioned method to obtain is due to the adaptation of each interlayer, adaptation particularly between described metal level (B) and described metal level (C) is high, therefore splitting can be suppressed, there is the durability of the excellence of the powered that can remain good, thus may be used for the electronic circuit employing silver-colored black liquid etc., the formation of circuit formation substrate used in integrated circuit etc., organic solar batteries, electric terminal, organic EL, organic transistor, flexible printed board, form the formation of the periphery wiring of RFID etc., in the wiring of the electromagnetic wave shielding of plasma scope etc.Particularly go for the purposes requiring high-durability, such as, may be used for printed circuit board (PCB) (PWB), flexible printed board (FPC), coil type automatically engage (TAB), cover in brilliant film (COF) etc.
Embodiment
Below, the present invention is described in detail to utilize embodiment.
[preparation of priming paint]
Be dropped in the reaction flask possessing reflux condenser, thermometer, mixer in formalin 600 mass parts (content of formaldehyde: 222 mass parts (7.4mol), methanol content: 42 mass parts (1.31mol)) of the methyl alcohol of formaldehyde containing 37 quality % and 7 quality % and add water 200 mass parts and methyl alcohol 350 mass parts (10.92mol) and the solution of homogenising.Then, add 25 quality % sodium hydrate aqueous solutions, after being adjusted to pH10, adding melamine 310 mass parts (2.46mol), liquid temperature is elevated to 85 DEG C, carry out hydroxymethylation (reaction time: 1 hour).
Thereafter, add formic acid and after being adjusted to pH7, be cooled to 60 DEG C, making it to carry out etherification reaction.Add 25 quality % sodium hydrate aqueous solutions gonorrhoea temperature 40 DEG C and be adjusted to pH9, stopping etherification reaction (reaction time: 1 hour).Under the decompression of temperature 50 C, remove remaining methyl alcohol (separating methanol time: 4 hours), obtain the priming paint containing melmac that nonvolatile component is 80 quality %.
And the assay method of described gonorrhoea temperature is the resin gathering 1g, is mixed by this resin with the water 100ml being adjusted to the temperature of specifying.Now, resin is water insoluble and the highest water temperature of when there is gonorrhoea is set to gonorrhoea temperature.
[preparation of fluid (1)]
To in the mixed solvent of ethylene glycol 45 mass parts and ion exchange water 55 mass parts, be used as the addition on polyethylene imine based of the dispersant compound of PEO, thus the silver particles of average grain diameter 30nm is disperseed, prepare the fluid (1) of metal powder containing nano-scale and dispersant thus.
[preparation of fluid (2)]
The fluid (1) obtained utilizing aforesaid operations uses ion exchange water and surfactant, and its viscosity is adjusted to 10mPas, produces the fluid (2) of the electric conductivity ink liquid as ink jet printing thus.
[embodiment 1]
Use spin coater, to the surface of the supporter be made up of polyimide film (TorayDupont Co., Ltd. system " Kapton200H ", thickness 50 μm), to make its dried thickness be the mode of 0.1 μm, be coated with the priming paint utilizing aforesaid operations to prepare.Then, use air drier 120 DEG C of dryings 5 minutes, define prime coat on the surface of polyimide film thus.
Then, to the surface of described prime coat, use ink-jet printer (KonicaMinoltaIJ Co., Ltd. ink-jet testing machine EB100, evaluation printer head KM512L, spray volume 42pL), be coated with the fluid (2) utilizing aforesaid operations to obtain with the area of vertical 10cm, horizontal 5cm comprehensively.Then, carry out burning till for 30 minutes at 250 DEG C, thus form the silver layer (thickness about 1 μm) being equivalent to described metal level (B ').
Then, the process being equivalent to the organic compound in the silver layer of described metal level (B ') for removing is carried out.First, as plasma discharge facture, (Kasuga Electric K. K.'s system " TEC-4AX " implements Corona discharge Treatment (gas: air (oxygen concentration about 21 quality %), gap: 1.5mm, power output: 100W, processing time: 2 seconds) to use corona surface modified gneiss device to the surface of the silver layer being equivalent to described metal level (B ').Then, as dissolution process method, carry out the process of the surfactant by alkalescence of 5 minutes liquid temperature 40 DEG C, remove organic compound thus and obtain the cavernous silver layer being equivalent to metal level (B) with space.As the surfactant of described alkalescence, employ the surfactant (pH=9.3) ICPCleanerSC (Ao Ye Pharmaceutical Co., Ltd system) dilution risen for 150ml/.
Then, the silver layer being equivalent to described metal level (B) obtained utilizing aforesaid operations is set as negative electrode, and phosphorous copper is set as anode, uses the electroplate liquid containing copper sulphate with current density 2A/dm
2carry out plating in 15 minutes, thus the stacked copper coating of thick 8 μm on the surface of described silver layer.As described electroplate liquid, employ copper sulphate 70g/ liter, sulfuric acid 200g/ liter, chlorion 50mg/ liter, additive (wild pharmaceuticals industry (strain) system " ト ッ プ Le チ Na SF-M " difficult to understand) 5ml/ liter.
Utilize above method, obtain the duplexer (1) will respectively folded layer by layer according to the order of supporter (A), prime coat, metal level (B), metal level (C).To the duplexer (1) of gained, SEM (Jeol Ltd.'s system " JSM-7800F ") is used to confirm section.The cross sectional photograph of this duplexer (1) is shown in Fig. 1 (copper (Cu) mapping) and Fig. 2 (silver (Ag) maps).According to the comparison of Fig. 1 and Fig. 2, can confirm: in the silver layer being equivalent to metal level (B), also have copper (Cu) atom forming metal level (C), because this copper atom reaches the near interface of silver layer and the supporter (A) being equivalent to metal level (B), in the space of metal level (B), be therefore filled into the near interface of metal level (B) and supporter (A) as the copper of the metal forming metal level (C).
[embodiment 2]
Except replacing the process by corona surface modified gneiss device (Kasuga Electric K. K.'s system " TEC-4AX "), and carried out beyond electromagnetic wave irradiation process (wavelength 100 μm), utilize the method identical with embodiment 1 to obtain the duplexer (2) will respectively folded layer by layer according to the order of supporter (A), prime coat, metal level (B), metal level (C).To the duplexer (2) of gained, use sem observation identically with embodiment 1, consequently, the near interface being filled into metal level (B) and supporter (A) in the space of metal level (B) as the copper of the metal forming metal level (C) is confirmed.
[embodiment 3]
Except replacing by the process of corona surface modified gneiss device (Kasuga Electric K. K.'s system " TEC-4AX ") and the process by ICPCleaner, and carried out beyond laser treatment with irradiation (power output 6kW), utilize the method identical with embodiment 1 to obtain described supporter (A), prime coat, described metal level (B) and the duplexer (3) folded layer by layer being equivalent to described metal level (C).To the duplexer (3) of gained, use sem observation identically with embodiment 1, consequently, the near interface being filled into metal level (B) and supporter (A) in the space of metal level (B) as the copper of the metal forming metal level (C) is confirmed.
[embodiment 4]
Except replacing the process by corona surface modified gneiss device (Kasuga Electric K. K.'s system " TEC-4AX "), and carry out beyond 5 minutes dippings in sulfuric acid (60ml/ liter), utilize the method identical with embodiment 1 to obtain the duplexer (4) will respectively folded layer by layer according to the order of supporter (A), prime coat, metal level (B), metal level (C).To the duplexer (4) of gained, use sem observation identically with embodiment 1, consequently, the near interface being filled into metal level (B) and supporter (A) in the space of metal level (B) as the copper of the metal forming metal level (C) is confirmed.
[comparative example 1]
Use spin coater, on the surface of the supporter be made up of polyimide film (TorayDupont Co., Ltd. system " Kapton200H ", thick 50 μm), be that the mode of 0.1 μm is coated with the priming paint utilizing aforesaid operations to prepare to make its dried thickness.Then, use air drier 120 DEG C of dryings 5 minutes, define prime coat on the surface of polyimide film thus.
Then, on the surface of described prime coat, silver is set as target, utilizes and while importing argon gas, the silver layer that thickness is about 1 μm is formed to the magnetron sputtering method applying DC voltage between base material and target under vacuo.
Then, the silver layer obtained utilizing aforesaid operations is set as negative electrode, and phosphorous copper is set as anode, uses the electroplate liquid containing copper sulphate with current density 2A/dm
2carry out plating in 15 minutes, thus the stacked copper coating of thick 8 μm on the surface of described silver layer.As described electroplate liquid, employ copper sulphate 70g/ liter, sulfuric acid 200g/ liter, chlorion 50mg/ liter, additive (wild pharmaceuticals industry (strain) system " ト ッ プ Le チ Na SF-M " difficult to understand) 5ml/ liter.
Utilize above method, obtain the duplexer (R1) will respectively folded layer by layer according to the order of supporter (A), prime coat, silver layer, layers of copper.The cross sectional photograph of this duplexer (R1) is shown in Fig. 3 (copper (Cu) mapping) and Fig. 4 (silver (Ag) maps).According to the comparison of Fig. 3 and Fig. 4, can confirm: due in the silver layer being equivalent to metal level (B), there is not copper (Cu) atom of formation metal level (C), the copper therefore as the metal forming metal level (C) does not enter in metal level (B) completely.And, the cross sectional photograph of this duplexer (R1) is shown in Fig. 3 and 4.
The adaptation that < utilizes peel strength to measure evaluates >
Utilize the method according to IPC-TM-650, NUMBER2.4.9, determine peel strength.Wire widths used in mensuration is 1mm, and the angle of this stripping is set to 90 °.And peel strength has the thickness of described coating larger, demonstrates the trend of higher value, and the mensuration of peel strength in the present invention is for benchmark is implemented with measured value during now general coating 8 μm.
< utilizes visual adaptation to evaluate >
Utilize the release surface after the mensuration of peel strength described in visualization, confirm the position at the interface of having peeled off.The position at the interface of having peeled off is set to following 1 ~ 3, when the position at the interface of having peeled off is 2 or 3, is judged as that metal level (B) is good with the adaptation of metal level (C).
1: the interface of metal level (B) and metal level (C)
2: the interface of prime coat and metal level (B)
3: the interface of prime coat and polyimide film (supporter)
The evaluation result obtained utilizing aforesaid operations is concentrated and is shown in table 1.
[table 1]
Due to as duplexer (1) ~ (4) obtained in the embodiment 1 ~ 4 of duplexer of the present invention not from the situation of metal level (B) with the interface peel of metal level (C), there is high-peeling strength, therefore confirm that metal level (B) is very high with the adaptation of metal level (C).
On the other hand, the duplexer (R1) obtained in comparative example 1 corresponds to the silver layer of metal level (B) and the example of non-porous layer.This duplexer (R1) is peeled off from the interface of silver layer (corresponding to metal level (B)) and layers of copper (corresponding to metal level (C)), therefore confirms that the adaptation of 2 metal interlevels does not tolerate actual use.
Claims (9)
1. a duplexer, is characterized in that, is the duplexer being formed with cavernous metal level (B) and being formed with metal level (C) on supporter (A) on described metal level (B),
Be present in the space in described metal level (B) metal being filled with and forming metal level (C).
2. duplexer according to claim 1, wherein,
Until be present in described supporter (A) and the space in the described metal level (B) of the near interface of described metal level (B), be filled with the metal forming described metal level (C).
3. duplexer according to claim 1, wherein,
Form the metal of described metal level (B) for silver, the metal forming described metal level (C) is copper.
4. duplexer according to claim 1, wherein,
Described supporter (A) and described metal level (B) press from both sides stacked across prime coat.
5. a conductive pattern, is characterized in that,
Comprise the duplexer according to any one of Claims 1 to 4.
6. an electronic circuit, is characterized in that,
There is conductive pattern according to claim 5.
7. a manufacture method for duplexer, is characterized in that,
In the upper coating of supporter (A) containing the metal powder of nano-scale and the fluid of dispersant and after carrying out burning till and forming metal level (B '), to the organic compound removing comprising dispersant in described metal level (B ') be present in and form space, make cavernous metal level (B), then utilize plating or electroless plating to form described metal level (C).
8. the manufacture method of duplexer according to claim 7, wherein,
The shape of the metal powder of described nano-scale is particle shape or threadiness.
9. the manufacture method of duplexer according to claim 7, wherein,
The metal powder of described nano-scale is silver,
Described metal level (C) copper coating for utilizing electrolytic copper plating to be formed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-187333 | 2013-09-10 | ||
| JP2013187333 | 2013-09-10 | ||
| PCT/JP2014/073382 WO2015037511A1 (en) | 2013-09-10 | 2014-09-04 | Stacked body, conductive pattern, electronic circuit, and production method for stacked body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105517788A true CN105517788A (en) | 2016-04-20 |
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| CN201480049643.3A Pending CN105517788A (en) | 2013-09-10 | 2014-09-04 | Stacked body, conductive pattern, electronic circuit, and production method for stacked body |
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| Country | Link |
|---|---|
| JP (1) | JP5843123B2 (en) |
| KR (1) | KR20160018843A (en) |
| CN (1) | CN105517788A (en) |
| TW (1) | TW201522071A (en) |
| WO (1) | WO2015037511A1 (en) |
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| CN109563625A (en) * | 2016-08-08 | 2019-04-02 | Dic株式会社 | Laminated body, metal mesh and touch panel |
| CN110753617A (en) * | 2017-07-10 | 2020-02-04 | Dic株式会社 | Laminate, printed wiring board using same, flexible printed wiring board, and molded article |
| CN110785282A (en) * | 2017-07-10 | 2020-02-11 | Dic株式会社 | Laminate, printed wiring board using same, flexible printed wiring board, and molded article |
| CN112714554A (en) * | 2019-10-24 | 2021-04-27 | 嘉联益电子(昆山)有限公司 | Manufacturing method of flexible circuit board, electroplating solution and etching solution |
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| JP6263146B2 (en) * | 2015-04-06 | 2018-01-17 | 株式会社ノリタケカンパニーリミテド | Substrate with conductive film, method for producing the same, and conductive paste for polyimide substrate |
| JP6014792B1 (en) * | 2015-06-24 | 2016-10-25 | 株式会社メイコー | 3D wiring board manufacturing method, 3D wiring board, 3D wiring board base material |
| WO2016208006A1 (en) | 2015-06-24 | 2016-12-29 | 株式会社メイコー | Three-dimensional wiring board production method, three-dimensional wiring board, and substrate for three-dimensional wiring board |
| CN109315069B (en) * | 2016-07-07 | 2021-01-08 | 名幸电子有限公司 | Three-dimensional wiring board, method for manufacturing three-dimensional wiring board, and substrate for three-dimensional wiring board |
| US11612933B2 (en) | 2017-07-06 | 2023-03-28 | Lg Chem, Ltd. | Preparation method for metal foam |
| WO2019013039A1 (en) * | 2017-07-10 | 2019-01-17 | Dic株式会社 | Laminate, printed wiring board in which same is used, flexible printed wiring board, and molded article |
| TWI791769B (en) | 2018-02-27 | 2023-02-11 | 日商迪愛生股份有限公司 | Electronic component packaging and manufacturing method thereof |
| WO2020085136A1 (en) * | 2018-10-22 | 2020-04-30 | Dic株式会社 | Layered body, and layered body manufacturing method |
| TWI710020B (en) * | 2019-10-24 | 2020-11-11 | 嘉聯益科技股份有限公司 | Manufacturing method of flexible circuit board, electroplating solution and etching solution |
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| CN110785282B (en) * | 2017-07-10 | 2022-06-24 | Dic株式会社 | Laminate, printed wiring board using same, flexible printed wiring board, and molded article |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2015037511A1 (en) | 2017-03-02 |
| WO2015037511A1 (en) | 2015-03-19 |
| JP5843123B2 (en) | 2016-01-13 |
| KR20160018843A (en) | 2016-02-17 |
| TW201522071A (en) | 2015-06-16 |
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