WO2019013039A1 - Stratifié, carte de circuit imprimé mettant en œuvre celui-ci, carte de circuit imprimé souple, et article moulé - Google Patents

Stratifié, carte de circuit imprimé mettant en œuvre celui-ci, carte de circuit imprimé souple, et article moulé Download PDF

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Publication number
WO2019013039A1
WO2019013039A1 PCT/JP2018/025166 JP2018025166W WO2019013039A1 WO 2019013039 A1 WO2019013039 A1 WO 2019013039A1 JP 2018025166 W JP2018025166 W JP 2018025166W WO 2019013039 A1 WO2019013039 A1 WO 2019013039A1
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Prior art keywords
layer
mass
acid
laminate
plating
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PCT/JP2018/025166
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English (en)
Japanese (ja)
Inventor
亘 冨士川
深澤　憲正
憲一 平林
白髪　潤
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Dic株式会社
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Publication of WO2019013039A1 publication Critical patent/WO2019013039A1/fr

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Classifications

    • 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
    • B32B15/08—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 synthetic resin
    • 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
    • B32B15/16—Layered products comprising a layer of metal next to a particulate layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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

Definitions

  • the present invention relates to a laminate that can be used for printed wiring boards, flexible printed wiring boards, molded articles, and the like.
  • a coating agent containing a conductive substance is applied to the surface of a support and fired to form a conductive layer on the surface of the support, and then
  • the electroconductive pattern by which the metal layer was provided in the surface of the said conductive layer is known by plating the surface of the said conductive layer (for example, refer patent document 1 and 2).
  • an organic substance such as a dispersant derived from a conductive substance on the surface of the conductive layer or an organic solvent inhibits the adsorption of the plating at the time of forming the electrolytic plating layer, and there is a problem that the adhesion between the conductive layer and the plating layer is reduced.
  • a laminate that can be used as a conductive pattern a laminate excellent in adhesion at each interface between a support, a conductive layer, and a plating layer is required, and in particular, the conductive layer and the plating layer The laminated body which is excellent in the adhesiveness of was not found yet.
  • ABS acrylonitrile-butadiene-styrene copolymer
  • ABS-PC polymer alloy of ABS and polycarbonate
  • hexavalent chromic acid and the like are preferably environmentally unfriendly substances, so it is preferable not to use them, and alternative methods have been developed (see, for example, Patent Document 3).
  • the base material is not limited to ABS or ABS-PC, and a plated film having excellent adhesion can be obtained even with other types of plastic, and It has been required to reduce the use of environmentally hazardous substances.
  • the problem to be solved by the present invention is a laminate excellent in adhesion between a support and a metal layer (metal plating layer) without roughening the surface of the support, and a printed wiring board using the same It is providing a flexible printed wiring board and a molded article.
  • the present inventors have intensively studied to solve the above problems, and as a result, it is a laminate in which a silver nanoparticle layer and a metal plating layer are sequentially laminated on a support, and the metal plating layer is laminated.
  • the above-mentioned problem is achieved by setting the value of the normalized photoelectron yield (1/2 power) at a specific excitation energy to a certain range.
  • the present invention has been completed.
  • the present invention is a laminate in which a silver nanoparticle layer (B) and a metal plating layer (C) are sequentially laminated on a support (A), and the metal plating layer (C) is laminated.
  • the value of the normalized photoelectron yield (1/2 power) at an excitation energy of 5.5 eV is 0.1 or more and 20 or less.
  • the laminate of the present invention is excellent in adhesion between the support and the metal plating layer without roughening the surface of the support, and a metal layer is provided on the smooth surface of various supports. , It is a material that makes use of the metallic luster of the metal layer.
  • the laminate of the present invention is, for example, a printed wiring board, a flexible printed wiring board, a conductive film for a touch panel, a metal mesh for a touch panel, an organic solar cell, an organic EL element, an organic transistor, by patterning a metal layer.
  • a metal layer for example, a printed wiring board, a flexible printed wiring board, a conductive film for a touch panel, a metal mesh for a touch panel, an organic solar cell, an organic EL element, an organic transistor, by patterning a metal layer.
  • It can be suitably used as an RFID such as a noncontact IC card, an electromagnetic wave shield, an LED illumination base, an electronic member such as a digital signage.
  • FCCL flexible printed wiring board applications
  • connectors for connecting wires for optical communication lamp reflectors, electrical components, electric motor peripheral components, battery components, automotive parts, mobile phones, personal computers, mirrors, containers, home appliances, switches, water faucet parts, showers It can be suitably used for molded articles such as heads.
  • the laminate of the present invention is a laminate in which a silver nanoparticle layer (B) and a metal plating layer (C) are sequentially laminated on a support (A), and the metal plating layer (C) is laminated.
  • a silver nanoparticle layer (B) before measurement is measured with a photoelectron spectrometer, the value of the normalized photoelectron yield (1/2 power) at an excitation energy of 5.5 eV is 0.1 or more and 20 or less It is.
  • Examples of the support (A) include polyimide, polyamideimide, polyamide, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (hereinafter abbreviated as "ABS”) resin, ABS and polycarbonate.
  • ABS acrylonitrile-butadiene-styrene
  • Polymer alloy acrylic resin such as methyl poly (meth) acrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, polyethylene, polypropylene, polyurethane, liquid crystal polymer (LCP), poly Ether ether ketone (PEEK), polyphenylene sulfide (PPS), polyphenylene sulfone (PPSU), epoxy resin, cellulose nanofiber, sili Supports made of iron, ceramics, glass, etc., porous supports made of them, steel plates, supports made of metal such as copper, their surfaces are silicon carbide, diamond like carbon, aluminum, copper, titanium, stainless steel etc. And the like.
  • acrylic resin such as methyl poly (meth) acrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, polyethylene
  • the laminate of the present invention is used for a printed wiring board etc.
  • polyimide polyethylene terephthalate, polyethylene naphthalate, liquid crystal polymer (LCP), polyetheretherketone (PEEK), epoxy resin as the support (A)
  • LCP liquid crystal polymer
  • PEEK polyetheretherketone
  • epoxy resin epoxy resin
  • the film-form or sheet-like support which has the bendable softness
  • the thickness is generally preferably 1 ⁇ m to 5,000 ⁇ m, more preferably 1 ⁇ m to 300 ⁇ m, and still more preferably 1 ⁇ m to 200 ⁇ m.
  • the surface of the support (A) can be smooth as required. May form fine irregularities that do not lose their properties, or clean the dirt attached to the surface, or surface-treat for the introduction of functional groups such as hydroxyl, carbonyl and carboxyl groups. .
  • methods such as plasma discharge treatment such as corona discharge treatment, dry treatment such as ultraviolet light treatment, wet treatment using an aqueous solution of water, acid or alkali, an organic solvent or the like may be mentioned.
  • the method of ozone nano bubble processing is mentioned.
  • a primer layer (X) may be formed on the surface of the support (A) as required.
  • the primer resin used for the primer layer (X) is, for example, urethane resin, acrylic resin, urethane-vinyl composite resin, epoxy resin, imide resin, amide resin, amide resin, melamine resin, phenol resin, urea formaldehyde resin, and phenol block
  • the block polyisocyanate used as an agent, polyvinyl alcohol, polyvinyl pyrrolidone etc. are mentioned. These resins can be used alone or in combination of two or more. Moreover, the value of the normalized photoelectron yield (1/2 power) mentioned later can be controlled by the kind of said primer layer (X).
  • primer resins used for the primer layer (X) those using an aminotriazine-modified novolak resin and an epoxy resin in combination, an epoxy resin having an epoxy group and a hydroxyl group, and an acrylic resin having an epoxy group and a hydroxyl group It is preferable because it can be improved.
  • polyvalent carboxylic acid when using the epoxy resin which has an epoxy group and a hydroxyl group, or the acrylic resin which has an epoxy group and a hydroxyl group as primer resin used for the said primer layer (X), it is preferable to use polyvalent carboxylic acid together as a crosslinking agent.
  • the polyvalent carboxylic acid may also be an anhydride.
  • Specific examples of the polyvalent carboxylic acid include aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, mellitic acid, biphenyldicarboxylic acid, biphenyltetracarboxylic acid and naphthalenedicarboxylic acid.
  • Acids and their anhydrides Oxalic acid, malonic acid, succinic acid, methylsuccinic anhydride, ethylsuccinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, maleic acid
  • aliphatic polyvalent carboxylic acids such as fumaric acid and anhydrides thereof.
  • trimellitic anhydride is preferable because adhesion can be further improved.
  • These polyvalent carboxylic acids can be used alone or in combination of two or more.
  • a solvent with the said primer resin, in order to make it the viscosity which is easy to apply, when coating on the surface of the said support body (A), and to use as a primer composition.
  • the solvent include various organic solvents and aqueous media.
  • the organic solvent include toluene, ethyl acetate, methyl ethyl ketone, cyclohexanone and the like, and examples of the aqueous medium include water, an organic solvent miscible with water, and a mixture thereof.
  • organic solvent miscible with water examples include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosolve and butyl cellosolve; ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol, diethylene glycol, propylene And alkylene glycol solvents such as glycol; polyalkylene glycol solvents such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; and lactam solvents such as N-methyl-2-pyrrolidone.
  • alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosolve and butyl cellosolve
  • ketone solvents such as acetone and methyl ethyl ketone
  • the amount of the organic solvent used be appropriately adjusted according to the coating method used when coating on the support (A) described later, and the desired film thickness of the primer layer (X).
  • the primer layer (X) may be formed by applying the primer composition to a part or all of the surface of the support (A) and removing the organic solvent contained in the primer composition. it can.
  • the drying temperature at the time of formation of the said primer layer (X) although based also on the kind of primer resin to be used, 80 degreeC or more is preferable normally. Moreover, as an upper limit of drying temperature, 300 degrees C or less is preferable, 250 degrees C or less is more preferable, and 200 degrees C or less is more preferable.
  • the drying time is usually preferably 1 second or more, more preferably 10 seconds or more, and still more preferably 30 seconds or more. Moreover, as an upper limit of drying time, 24 hours or less are preferable, 4 hours or less are more preferable, and 1 hour or less is more preferable.
  • the range of the drying time is preferably 30 seconds to 30 minutes, more preferably 30 seconds to 300 seconds, and still more preferably 30 seconds to 60 seconds.
  • the film thickness of the primer layer (X) varies depending on the use of the laminate of the present invention, but a range in which the adhesion between the support (A) and the silver nanoparticle layer (B) is further improved is preferable.
  • the thickness of the primer layer is preferably 10 nm or more and 30 ⁇ m or less, more preferably 10 nm or more and 1 ⁇ m or less, and still more preferably 50 nm or more and 500 nm or less.
  • the surface of the primer layer (X) can further improve the adhesion to the metal nanoparticle layer (B), and therefore, if necessary, it can be a dry process such as a plasma discharge treatment method such as corona discharge treatment method or an ultraviolet treatment method
  • the surface treatment may be performed by a treatment method, a wet treatment method using water, an acidic or alkaline chemical solution, an organic solvent or the like. Alternatively, ozone nanobubble treatment may be performed.
  • a primer layer (X) is formed on a support (A) as required, and then a flow containing nano-sized silver nanoparticles (b) After the silver nanoparticle layer (B) is formed by coating the body and removing the organic solvent and the like contained in the fluid by drying, the metal plating is performed by electrolytic plating, electroless plating, or both.
  • the method of forming layer (C) is mentioned.
  • the shape of the silver nanoparticles (b) used for forming the silver nanoparticle layer (B) is preferably particulate or fibrous.
  • the size of the silver nanoparticles (b) is nano-sized, specifically, when the shape of the silver nanoparticles (b) is particulate, a fine conductive pattern can be formed.
  • the average particle diameter is preferably 1 nm or more and 100 nm or less, and more preferably 1 nm or more and 50 nm or less because the resistance value can be further reduced.
  • the “average particle diameter” is a volume average value measured by dynamic light scattering method after diluting the conductive substance with a dispersion good solvent. For this measurement, "Nanotrack UPA-150" manufactured by Microtrac, Inc. can be used.
  • the diameter of the fiber is preferably 5 nm or more and 100 nm or less, and 5 nm or more and 50 nm or less Is more preferred.
  • the length of the fiber is preferably 0.1 ⁇ m to 100 ⁇ m, and more preferably 0.1 ⁇ m to 30 ⁇ m.
  • the content of the metal nanoparticles (b) in the fluid is preferably 1% by mass to 90% by mass, more preferably 1% by mass to 60% by mass, and still more preferably 1% by mass to 10% by mass Is more preferred.
  • a dispersant or solvent for dispersing the silver nanoparticles (b) in a solvent and, if necessary, a surfactant, a leveling agent, a viscosity modifier, which will be described later, Film forming aids, antifoaming agents, preservatives and the like can be mentioned.
  • the value of the normalized photoelectron yield (1/2 power) described later can also be controlled by the types and amounts of the components to be blended into the fluid.
  • a low molecular weight or high molecular weight dispersant examples include dodecanethiol, 1-octanethiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinyl pyrrolidone, polyethylene imine, polyvinyl pyrrolidone; fatty acids such as myristic acid, octanoic acid and stearic acid; cholic acid, Examples thereof include polycyclic hydrocarbon compounds having a carboxyl group such as glycyrrhizic acid and aventic acid.
  • a polymer dispersant is preferable because the adhesion between the silver nanoparticle layer (B) and the metal plating layer (C) can be improved, and examples of the polymer dispersant include polyethylene imine, polypropylene imine, and the like. And a compound obtained by adding a polyoxyalkylene to the polyalkyleneimine, a urethane resin, an acrylic resin, the urethane resin, a compound having a phosphoric acid group in the acrylic resin, and the like.
  • the amount of the dispersing agent used to disperse the silver nanoparticles (b) is preferably 0.01 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the silver nanoparticles (b), and 0. More than 01 mass parts and below 10 mass parts are more preferred.
  • an aqueous medium and an organic solvent can be used as a solvent used for the said fluid.
  • the aqueous medium include distilled water, ion exchanged water, pure water, ultrapure water and the like.
  • an alcohol compound, an ether compound, an ester compound, a ketone compound etc. are mentioned as said organic solvent.
  • Examples of the alcohol compound include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, and the like.
  • ethylene glycol, diethylene glycol, 1,3-butanediol, isoprene glycol and the like can be used as the fluid in addition to the silver nanoparticles (b) and the solvent.
  • a common surfactant can be used as the surfactant, and examples thereof include di-2-ethylhexyl sulfosuccinate, dodecylbenzene sulfonate, alkyl diphenyl ether disulfonate, alkyl naphthalene sulfonate, hexametaphosphoric acid Salt etc. are mentioned.
  • a general leveling agent can be used as the leveling agent, and examples thereof include silicone compounds, acetylene diol compounds, and fluorine compounds.
  • a general thickener can be used as the viscosity modifier.
  • an acrylic polymer or synthetic rubber latex that can be thickened by adjusting to alkalinity, or a urethane that can be thickened by association of molecules Resin, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, polyvinyl alcohol, castor oil with water, amide wax, polyethylene oxide, metal soap, dibenzylidene sorbitol and the like.
  • a general film forming aid can be used, and examples thereof include anionic surfactants (such as dioctyl sulfosuccinic acid ester soda salt) and hydrophobic nonionic surfactants (sorbitan monooleate).
  • anionic surfactants such as dioctyl sulfosuccinic acid ester soda salt
  • hydrophobic nonionic surfactants sorbitan monooleate
  • Etc. polyether-modified siloxane, silicone oil and the like.
  • antifoaming agent a general antifoaming agent can be used, and examples thereof include silicone antifoaming agents, nonionic surfactants, polyethers, higher alcohols, and polymer surfactants.
  • a general preservative can be used, for example, isothiazoline preservative, triazine preservative, imidazole preservative, pyridine preservative, azole preservative, iodine preservative, pyrithione Examples include antiseptics and the like.
  • the viscosity of the fluid (value measured with a B-type viscometer at 25 ° C.) is preferably in the range of 0.1 to 500,000 mPa ⁇ s, and more preferably in the range of 0.2 to 10,000 mPa ⁇ s .
  • the viscosity is preferably in the range of 5 to 20 mPa ⁇ s.
  • a method of coating or printing the fluid on the support (A) or the primer layer (X) for example, an inkjet printing method, a reverse printing method, a screen printing method, an offset printing method, a spin coating method And spray coating, bar coating, die coating, slit coating, roll coating, dip coating, pad printing, flexographic printing, and the like.
  • the silver nanoparticle layer (B) patterned in the shape of a thin line of about 0.01 to 100 ⁇ m which is required when realizing high density of an electronic circuit or the like. It is preferable to use an inkjet printing method or a reverse printing method.
  • an inkjet printer As the inkjet printing method, one generally referred to as an inkjet printer can be used. Specifically, Konica Minolta EB 100, XY 100 (manufactured by Konica Minolta IJ Co., Ltd.), Dymatics Material Printer DMP-3000, Dimatics Material Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.), etc. may be mentioned.
  • the reverse printing method the letterpress reverse printing method and the intaglio reverse printing method are known, and for example, the fluid is coated on the surface of various blankets and brought into contact with a plate in which non-image areas are projected;
  • the pattern is formed on the surface of the blanket or the like by selectively transferring the fluid corresponding to the non-image area onto the surface of the plate, and then the pattern is formed on the support (A).
  • a method of transferring to (surface) may be mentioned.
  • the pad printing method is known about printing of the pattern to a three-dimensional molded article. This is done by placing the ink on the intaglio plate, filling the ink uniformly into the recess by writing with the squeegee, pressing the pad made of silicone rubber or urethane rubber onto the plate loaded with the ink, the pattern on the pad It is a method of transferring and transferring to a three-dimensional molded product.
  • drying temperature at the time of formation of the said silver nanoparticle layer (B) 80 degreeC or more is preferable normally.
  • 300 degrees C or less is preferable, 250 degrees C or less is more preferable, and 200 degrees C or less is more preferable.
  • the drying time is usually preferably 1 second or more, more preferably 10 seconds or more, and still more preferably 30 seconds or more.
  • 24 hours or less are preferable, 4 hours or less are more preferable, and 1 hour or less is more preferable.
  • the range of the drying time is preferably 30 seconds to 30 minutes, more preferably 30 seconds to 300 seconds, and still more preferably 30 seconds to 60 seconds.
  • Mass per unit area of the silver nanoparticle layer (B) is preferably from 1 mg / m 2 or more 30,000 / m 2 or less, 1 mg / m 2 or more 5,000 mg / m 2 or less.
  • the thickness of the silver nanoparticle layer (B) is adjusted by controlling the processing time, the current density, the amount of use of the additive for plating, etc. in the plating process when the metal plating layer (C) is formed. be able to.
  • the value of the normalized photoelectron yield (1/2 power) of the surface of the silver nanoparticle layer (B) can be measured by a photoelectron spectrometer.
  • excitation energy ultraviolet light (for example, a wavelength of 310 to 177 nm) can be used.
  • photoelectron spectrometer for example, “AC-3” manufactured by Riken Keiki Co., Ltd. can be used.
  • the silver nanoparticle layer (B) is formed on a support (A) or the primer layer (X).
  • the surface of the silver nanoparticle layer (B) before laminating the metal plating layer (C) described later is used.
  • the value of the normalized photoelectron yield (1/2 power) at an excitation energy of 5.5 eV is 0.1 or more and 20 or less, preferably 1 or more and 18 or less, and 3 or more and 15 or less. Is more preferably 5 or more and 12 or less.
  • the value of the normalized photoelectron yield (1/2 power) is an indicator of the ease of emission of electrons from the surface of the silver nanoparticle layer (B) at the time of irradiation with excitation energy (ultraviolet light). It correlates with the density of silver nanoparticles on the surface of the nanoparticle layer (B). For example, when the density of silver nanoparticles is high, the value of the normalized photoelectron yield (1/2 power) is high.
  • the present invention provides an optimum silver nano particle by setting the value of normalized photoelectron yield (1/2 power) at excitation energy of 5.5 eV on the surface of the silver nanoparticle layer (B) to 0.1 or more and 20 or less. The density of the particles is used to make the adhesion between the support (A) and the metal plating layer (C) extremely excellent.
  • the metal plating layer (C) constituting the laminate of the present invention is, for example, a reliability capable of maintaining good conductivity without causing disconnection or the like for a long period of time when the laminate is used for a printed wiring board or the like. It is a layer provided for the purpose of forming a highly conductive wiring pattern.
  • metal which comprises the said metal plating layer (C)
  • money, silver, platinum etc. are mentioned.
  • copper is preferable because a laminate can be obtained which has a low electrical resistance and is resistant to corrosion.
  • the method of forming by the plating process is preferable as the formation method.
  • wet plating methods such as an electrolytic plating method which can form the said metal plating layer (C) simply, and an electroless plating method, are mentioned. Also, two or more of these plating methods may be combined. For example, after the electroless plating is performed, electrolytic plating may be performed to form the metal plating layer (C).
  • a metal such as copper contained in the electroless plating solution is deposited by bringing the electroless plating solution into contact with the silver nanoparticles constituting the silver nanoparticle layer (B).
  • Examples of the electroless plating solution include those containing a metal such as copper, nickel, chromium, cobalt, tin, gold, silver and the like, a reducing agent, and a solvent such as an aqueous medium and an organic solvent.
  • reducing agent examples include dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenol and the like.
  • monocarboxylic acids such as acetic acid and formic acid
  • dicarboxylic acid compounds such as malonic acid, succinic acid, adipic acid, maleic acid and fumaric acid
  • malic acid lactic acid and glycol Hydroxycarboxylic acid compounds such as gluconic acid and citric acid
  • amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid and glutamic acid
  • iminodiacetic acid nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc.
  • a complexing agent such as an organic acid such as aminopolycarboxylic acid compound of the above or a soluble salt of such an organic acid (sodium salt, potassium salt, ammonium salt etc.), an amine compound such as ethylenediamine, diethylenetriamine, triethylenetetramine etc. Also It can be used.
  • the electroless plating solution is preferably used in a range of 20 ° C. or more and 98 ° C. or less.
  • the electrolytic plating method is carried out, for example, in a state in which an electrolytic plating solution is in contact with the metal constituting the silver nanoparticle layer (B) or the surface of the electroless plating layer (film) formed by the electroless treatment.
  • a conductive substance constituting the silver nanoparticle layer (B) in which a metal such as copper contained in the electrolytic plating solution is disposed at the cathode by energization, or an electroless plating layer formed by the electroless treatment It is a method of depositing on the surface of (coating) to form an electrolytic plating layer (metal coating).
  • Examples of the electrolytic plating solution include those containing sulfides of metals such as copper, nickel, chromium, cobalt and tin, sulfuric acid, and an aqueous medium. Specifically, those containing copper sulfate, sulfuric acid and an aqueous medium can be mentioned.
  • the electrolytic plating solution is preferably used in the range of 20 ° C. or more and 98 ° C. or less.
  • the metal plating layer (C) As a method of forming the metal plating layer (C), after electroless plating is performed because the film thickness of the metal plating layer (C) can be easily controlled to a desired film thickness from thin film to thick film, The method of electrolytic plating is preferred.
  • the thickness of the metal plating layer (C) is preferably in the range of 1 to 50 ⁇ m.
  • the film thickness of the metal plating layer (C) is adjusted by controlling the processing time, the current density, the use amount of the additive for plating, and the like in the plating treatment step in forming the metal plating layer (C). Can.
  • the laminate of the present invention obtained by the above method can be used as a conductive pattern.
  • a fluid containing silver nanoparticles is used.
  • a conductive pattern having a desired pattern can be manufactured.
  • the conductive pattern can be manufactured by, for example, a photolithographic method such as a subtractive method or a semi-additive method, or a method of plating on a print pattern of a silver nanoparticle layer (B).
  • an etching resist layer having a shape corresponding to a desired pattern shape is formed on the plating layer (C) constituting the laminate of the present invention manufactured in advance, and the development processing thereafter is carried out.
  • This is a method of forming a desired pattern by dissolving and removing the plating layer (C) and the silver nanoparticle layer (B) of the removed portion of the resist with a chemical solution.
  • a chemical solution a chemical solution containing copper chloride, iron chloride or the like can be used.
  • the silver nanoparticle layer (B) is formed on the support (A), surface-treated as necessary, and then the surface has a shape corresponding to a desired pattern.
  • a plating resist layer is formed, and then a metal plating layer (C) is formed by electrolytic plating method and electroless plating method, and then the plating resist layer and the silver nanoparticle layer (B) in contact therewith are used as a chemical solution or the like. It is a method of forming a desired pattern by dissolving and removing.
  • the pattern of the silver nanoparticle layer (B) is printed on the support (A) by an inkjet method, reverse printing method, etc.
  • the metal plating layer (C) is formed on the surface of the obtained silver nanoparticle layer (B) by electrolytic plating method and electroless plating method Is a method of forming a desired pattern.
  • the measurement conditions of the normalized photoelectron yield (1/2 power) of the surface of the silver nanoparticle layer (B) are as follows. Using a photoelectron spectrometer ("AC-3" manufactured by Riken Keiki Co., Ltd.), the measurement conditions are an energy scanning range of 4.0 to 7.0 eV (ultraviolet excitation of wavelength 310 to 177 nm), a set light amount of 10 nm, and a measurement time The measurement was performed at an anode voltage of 2,990 V and a step of 0.1 eV for 10 seconds. The value of the normalized photoelectron yield (1/2 power) at an excitation energy of 5.5 eV was read out of the measured normalized photoelectron yield (1/2 power of the photoelectron yield per unit light quantity).
  • AC-3 photoelectron spectrometer
  • Preparation Example 1 Preparation of Primer Composition (1) Add 750 parts by mass of phenol, 75 parts by mass of melamine, 346 parts by mass of 41.5% by mass formalin, and 1.5 parts by mass of triethylamine to a flask equipped with a thermometer, a condenser, a distillation pipe and a stirrer, The temperature was raised to 100 ° C. with caution. After reacting for 2 hours at 100 ° C. under reflux, the temperature was raised to 180 ° C. over 2 hours while removing water under normal pressure. Then, unreacted phenol was removed under reduced pressure to obtain an aminotriazine-modified novolak resin.
  • primer composition (1) 70 parts by mass of aminotriazine novolak resin and 30 parts by mass of epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation; bisphenol A epoxy resin) are mixed, and then the methyl ethyl ketone has a nonvolatile content of 2% by mass. It diluted and mixed uniformly, and obtained primer composition (1).
  • Preparation Example 2 Preparation of Primer Composition (2) In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst, 200 parts by mass of ethyl acetate is added, and nitrogen is blown up to 90 ° C. The temperature rose. A monomer mixture containing 30 parts by mass of glycidyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 40 parts by mass of styrene and 15 parts by mass of methyl methacrylate under stirring in a reaction vessel heated to 90 ° C.
  • a polymerization initiator solution containing 1 part by mass of azoisobutyronitrile and 20 parts by mass of ethyl acetate was added dropwise over 240 minutes while maintaining the temperature in the reaction vessel at 90 ⁇ 1 ° C. from separate dropping funnels. . After completion of the dropwise addition, after stirring for 120 minutes at the same temperature, the temperature in the reaction vessel was cooled to 30 ° C. Subsequently, ethyl acetate was added to obtain a resin solution having a nonvolatile content of 2% by mass.
  • Preparation Example 3 Preparation of Primer Composition (3)
  • Epoxy resin (“EPICLON 1050” manufactured by DIC Corporation; bisphenol A type epoxy resin, epoxy equivalent 475 g / equivalent) diluted with methyl ethyl ketone to make the non-volatile content 2 mass% solution 11.5 parts by mass of a 2% by mass methyl ethyl ketone solution of acid was uniformly mixed to obtain a primer composition (3).
  • Preparation Example 4 Preparation of Primer Composition (4) 830 parts by mass of terephthalic acid, 830 parts by mass of isophthalic acid, 685 parts by mass of 1,6-hexanediol, neopentyl glycol 604 while introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer Prepare a mass part and 0.5 mass parts of dibutyltin oxide and carry out a polycondensation reaction at 180 ° C to 230 ° C for 15 hours at 230 ° C until the acid value becomes 1 or less. A polyester polyol was obtained.
  • reaction solution was cooled to 40 ° C., and 60 parts by mass of triethylamine was added for neutralization, followed by mixing with 4700 parts by mass of water to obtain a transparent reaction product.
  • the methyl ethyl ketone is removed from the reaction product under reduced pressure at 40 to 60 ° C., and then water is mixed to make the non-volatile content 2% by mass, and a primer composition (4) having a weight average molecular weight of 50,000 is obtained. Obtained.
  • Preparation Example 5 Preparation of Primer Composition (5) In a nitrogen-substituted reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 6.3 parts by mass of 2,2-dimethylol propionic acid and a nurate of 4,4'-diphenylmethane diisocyanate 71.1 After preparing an isocyanate compound by reacting with a mass part in methyl ethyl ketone, a solvent solution of a block polyisocyanate was prepared by supplying 17.8 mass parts of phenol as a blocking agent to the reaction vessel and reacting. Thereafter, methyl ethyl ketone was added to obtain a primer composition (5) having a nonvolatile content of 2% by mass.
  • Polyester polyol obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol and adipic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, hydroxyl group Equivalent of 1,000 g / equivalent), 100 parts by mass, 49.7 parts by mass of 2,2-dimethylol propionic acid, 127.1 parts by mass of 1,4-cyclohexanedimethanol, and 416.8 parts by mass of dicyclohexylmethane diisocyanate; The reaction was carried out in a mixed solvent of 492 parts by mass of methyl ethyl ketone to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
  • aqueous urethane resin dispersion was obtained.
  • the urethane resin obtained here had an acid value of 30 and a weight average molecular weight of 70,000.
  • a vinyl monomer mixture comprising 60 parts by mass of methyl methacrylate, 38 parts by mass of n-butyl acrylate and 2 parts by mass of methacrylic acid in a reaction vessel, and an emulsifier (Aqualon KH- manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 1025 ′ ′, 25 parts by weight of the active ingredient) and a part (5 parts by weight) of a monomer pre-emulsion obtained by mixing 15 parts by weight of deionized water with subsequent addition of potassium persulfate 0.1 The parts by mass were added, and polymerization was carried out for 60 minutes while maintaining the temperature in the reaction vessel at 75 ° C.
  • Preparation Example 7 Preparation of Primer Composition (7)
  • a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst 200 parts by mass of ethyl acetate is added, and nitrogen is blown up to 90 ° C. The temperature rose.
  • a polymerization initiator solution containing 1 part by mass of azoisobutyronitrile and 20 parts by mass of ethyl acetate was added dropwise over 240 minutes while maintaining the temperature in the reaction vessel at 90 ⁇ 1 ° C. from separate dropping funnels. After completion of the dropwise addition, after stirring for 120 minutes at the same temperature, the temperature in the reaction vessel was cooled to 30 ° C. Next, ethyl acetate was added to adjust the non-volatile content to 2% by mass to obtain a primer composition (7).
  • Example 1 described in Japanese Patent No. 4573138, a cationic silver nano consisting of a flake-like lump having an ash green color which is a complex of silver nanoparticles and an organic compound having a cationic group (amino group) I got the particles. Thereafter, the powder of silver nanoparticles was dispersed in a mixed solvent of 45 parts by mass of ethylene glycol and 55 parts by mass of ion-exchanged water to prepare a fluid (1) having 5% by mass of cationic silver nanoparticles. .
  • Example 1 On the surface of a polyimide film ("Kapton 150 EN-C" manufactured by Toray DuPont Co., Ltd .; thickness 38 ⁇ m), the primer composition (1) obtained in Preparation Example 1 was used as a tabletop small coater (RK Print Coat Instrument Co., Ltd.) It applied so that the thickness after the drying might be set to 100 nm using the product made from "K printing prober". Then, a primer layer was formed on the surface of the polyimide film by drying at 150 ° C. for 5 minutes using a hot air drier.
  • a tabletop small coater RK Print Coat Instrument Co., Ltd.
  • the fluid (1) obtained above was applied to the surface of the primer layer formed above using a bar coater. Subsequently, the silver layer (film thickness of 20 nm) corresponded to the said silver nanoparticle layer (B) was formed by drying at 150 degreeC for 5 minutes. The surface of this silver nanoparticle layer was measured by a photoelectron spectrometer, and the normalized photoelectron yield (1/2 power) at an excitation energy of 5.5 eV was 11.
  • the silver layer formed above is immersed in a pre-plating agent (an aqueous solution prepared by mixing 3 parts by mass of palladium chloride, 17 parts by mass of 36 mass% hydrochloric acid, and 80 parts by mass of ion exchange water)
  • a pre-plating agent an aqueous solution prepared by mixing 3 parts by mass of palladium chloride, 17 parts by mass of 36 mass% hydrochloric acid, and 80 parts by mass of ion exchange water
  • Electroless copper plating is performed by immersing in a copper plating solution ("OIC Kappa” manufactured by Okuno Pharmaceutical Co., Ltd., "OIC Kappa", pH 12.5) for 12 minutes, and a copper plating layer (film thickness 0.2 ⁇ m) by electroless plating Formed.
  • the copper plating layer by electroless copper plating obtained above is set on the cathode side, phosphorus-containing copper is set on the anode side, and an electrolytic plating solution containing copper sulfate is used at a current density of 2.5 A / dm 2 By performing electrolytic plating for 30 minutes, a copper plating layer (film thickness 15 ⁇ m) by electrolytic copper plating was formed on the surface of the copper plating layer by electroless copper plating.
  • the electrolytic plating solution 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 50 mg / L of chlorine ion, and 5 ml / L of an additive (“Top Rutina SF-M” manufactured by Okuno Pharmaceutical Co., Ltd.) were used.
  • a combination of a copper plating layer by electroless copper plating and a copper plating layer by electrolytic copper plating formed thereon corresponds to the metal plating layer (C).
  • a laminate (1) in which a support (A), a primer layer (X), a metal nanoparticle layer (B) and a metal plating layer (C) were sequentially laminated was obtained.
  • Example 2 On the surface of a polyimide film (“Kapton 150 EN-C” manufactured by Toray DuPont Co., Ltd .; thickness 38 ⁇ m), the primer composition (2) obtained in Preparation Example 2 was used as a desktop small-sized coater (RK print coat instrument company) It applied so that the thickness after the drying might be set to 100 nm using the product made from "K printing prober". Then, a primer layer was formed on the surface of the polyimide film by drying at 120 ° C. for 5 minutes using a hot air drier.
  • the fluid (1) obtained above was applied to the surface of the primer layer formed above using a bar coater. Then, by drying for 5 minutes at 150 ° C., a silver layer (film thickness 20 nm) corresponding to the metal nanoparticle layer (C) was formed.
  • the normalized photoelectron yield (1/2 power) at an excitation energy of 5.5 eV was 7.
  • electroless copper plating and electrolytic copper plating are performed to obtain a support (A), a primer layer (X), a metal nanoparticle layer (B), and a metal plating layer ( A laminate (2) was obtained in which C) was sequentially laminated.
  • Example 3 On the surface of a polyimide film ("Kapton 150 EN-C” manufactured by Toray DuPont Co., Ltd .; thickness 38 ⁇ m), the primer composition (3) obtained in Preparation Example 3 was used as a tabletop small coater (RK Print Coat Instrument Co., Ltd.) It applied so that the thickness after the drying might be set to 100 nm using the product made from "K printing prober". Then, a primer layer was formed on the surface of the polyimide film by drying at 120 ° C. for 5 minutes using a hot air drier.
  • the fluid (1) obtained above was applied to the surface of the primer layer formed above using a bar coater. Subsequently, the silver layer (film thickness of 20 nm) corresponded to the said metal nanoparticle layer (C) was formed by drying at 250 degreeC for 5 minutes. When the surface of this silver nanoparticle layer was measured by a photoelectron spectrometer, the normalized photoelectron yield (1/2 power) at an excitation energy of 5.5 eV was 1.
  • electroless copper plating and electrolytic copper plating are performed to obtain a support (A), a primer layer (X), a metal nanoparticle layer (B), and a metal plating layer ( C) obtained a laminate (3) sequentially laminated.
  • Example 4 The fluid (1) obtained above was coated on the surface of a polyimide film ("Kapton 150 EN-C" manufactured by Toray DuPont Co., Ltd .; thickness 38 ⁇ m) using a bar coater. Subsequently, the silver layer (film thickness of 100 nm) corresponded to the said metal nanoparticle layer (C) was formed by drying at 200 degreeC for 5 minutes. When the surface of this silver nanoparticle layer was measured by a photoelectron spectrometer, the normalized photoelectron yield (1/2 power) at an excitation energy of 5.5 eV was 19.
  • the support (A), the metal nanoparticle layer (B), and the metal plating layer (C) are sequentially laminated by performing electroless copper plating and electrolytic copper plating.
  • the resulting laminate (4) was obtained.
  • the fluid (1) obtained above was applied to the surface of the primer layer formed above using a bar coater. Subsequently, the silver layer (film thickness of 20 nm) corresponded to the said metal nanoparticle layer (B) was formed by drying at 120 degreeC for 5 minutes. When the surface of this silver nanoparticle layer was measured by a photoelectron spectrometer, the normalized photoelectron yield (1/2 power) at an excitation energy of 5.5 eV was 24.
  • electroless copper plating and electrolytic copper plating are performed to obtain a support (A), a primer layer (X), a metal nanoparticle layer (B), and a metal plating layer ( A laminate (R1) was obtained in which C) was sequentially laminated.
  • the fluid (1) obtained above was applied to the surface of the primer layer formed above using a bar coater. Subsequently, the silver layer (film thickness of 20 nm) corresponded to the said metal nanoparticle layer (C) was formed by drying at 100 degreeC for 5 minutes. When the surface of this silver nanoparticle layer was measured by a photoelectron spectrometer, the normalized photoelectron yield (1/2 power) at an excitation energy of 5.5 eV was 35.
  • electroless copper plating and electrolytic copper plating are performed to obtain a support (A), a primer layer (X), a metal nanoparticle layer (B), and a metal plating layer ( A laminate (R2) was obtained in which C) was sequentially laminated.
  • the fluid (1) obtained above was applied to the surface of the primer layer formed above using a bar coater. Subsequently, the silver layer (film thickness of 20 nm) corresponded to the said metal nanoparticle layer (C) was formed by drying at 110 degreeC for 5 minutes. When the surface of this silver nanoparticle layer was measured by a photoelectron spectrometer, the normalized photoelectron yield (1/2 power) at an excitation energy of 5.5 eV was 36.
  • electroless copper plating and electrolytic copper plating are performed to obtain a support (A), a primer layer (X), a metal nanoparticle layer (B), and a metal plating layer ( A laminate (R3) was obtained in which C) was sequentially laminated.
  • the fluid (1) obtained above was applied to the surface of the primer layer formed above using a bar coater. Subsequently, the silver layer (film thickness of 20 nm) corresponded to the said metal nanoparticle layer (C) was formed by drying at 120 degreeC for 5 minutes. When the surface of this silver nanoparticle layer was measured by a photoelectron spectrometer, the normalized photoelectron yield (1/2 power) at an excitation energy of 5.5 eV was 43.
  • electroless copper plating and electrolytic copper plating are performed to obtain a support (A), a primer layer (X), a metal nanoparticle layer (B), and a metal plating layer ( A laminate (R4) in which C) was sequentially laminated was obtained.
  • the peel strength of each of the obtained laminates was measured using "Autograph AGS-X 500N" manufactured by Shimadzu Corporation.
  • the lead width used for measurement was 5 mm, and the peel angle was 90 °.
  • the measurement of the peel strength in the present invention was performed based on the measurement value at a thickness of 15 ⁇ m of the metal plating layer.
  • the adhesion was evaluated according to the following criteria from the value of the peel strength before heating measured above.
  • the retention ratio before and after heating was calculated, and heat resistance was evaluated according to the following criteria.
  • the normalized photoelectron yield (1/2 power) of the surface of the silver nanoparticle layer of Examples 1 to 4 and the measurement results of peel strength before and after heating, and the evaluation results of adhesion and heat resistance are shown in Table 1.
  • the results of measurement of the normalized photoelectron yield (1/2 power) of the surface of the silver nanoparticle layer of Comparative Examples 1 to 4 and the peel strength before and after heating, and the evaluation results of adhesion and heat resistance are shown in Table 2.
  • the laminates (1) to (4) obtained in Examples 1 to 4, which are laminates of the present invention, have normalized photoelectron yield (1/2 power) of the silver nanoparticle layer at an excitation energy of 5.5 eV. Since the value of is 0.1 or more and 20 or less, the initial (pre-heating) adhesion is sufficiently high, and it can be confirmed that the decrease in peel strength after heating is slight and the heat resistance is also excellent. .
  • the laminates (R1) to (R4) obtained in Comparative Examples 1 to 4 are examples in which the value of the normalized photoelectron yield (1/2 power) at an excitation energy of 5.5 eV exceeds 20. However, it was confirmed that the initial adhesion (before heating) and the peel strength after heating were low.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

L'invention fournit un stratifié, une carte de circuit imprimé mettant en œuvre celui-ci, une carte de circuit imprimé souple, et un article moulé. Ledit stratifié est obtenu par stratification sur un corps de support (A) dans l'ordre d'une couche de nanoparticules d'argent (B) et d'une couche de placage métallique (C), et est caractéristique en ce que la valeur du rendement de photoémission d'électrons normalisé (puissance 1/2) lorsqu'une énergie d'excitation de 5,5eV est appliquée est supérieure ou égale à 0,1 et inférieure ou égale à 20, dans le cas où la surface de ladite couche de nanoparticules d'argent (B) avant stratification de ladite couche de placage métallique (C) est mesurée par un spectromètre photoélectronique. Ce stratifié présente une adhérence suffisante entre le corps de support et un film de placage, sans rugosification de la surface du corps de support.
PCT/JP2018/025166 2017-07-10 2018-07-03 Stratifié, carte de circuit imprimé mettant en œuvre celui-ci, carte de circuit imprimé souple, et article moulé WO2019013039A1 (fr)

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WO2008105480A1 (fr) * 2007-03-01 2008-09-04 Ajinomoto Co., Inc. Film pour un transfert de film métallique, procédé de transfert d'un film métallique, et procédé de fabrication d'une plaque de circuits imprimés
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WO2014050657A1 (fr) * 2012-09-28 2014-04-03 Dic株式会社 Stratifié, motif conducteur, et circuit électrique
WO2015037511A1 (fr) * 2013-09-10 2015-03-19 Dic株式会社 Corps empilé, réseau conducteur, circuit électronique et procédé de production de corps empilé
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JP2016007797A (ja) * 2014-06-25 2016-01-18 Dic株式会社 積層体、導電性パターン、電子回路及び積層体の製造方法
JP2016112704A (ja) * 2014-12-11 2016-06-23 Dic株式会社 導電性積層体及びその製造方法
WO2016098596A1 (fr) * 2014-12-16 2016-06-23 株式会社カネカ Composition de résine photodurcissable et thermodurcissable, produit durci et stratifié
JP2016120604A (ja) * 2014-12-24 2016-07-07 Dic株式会社 積層体、導電性パターン及び電子回路
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007231125A (ja) * 2006-02-28 2007-09-13 Kaneka Corp 熱硬化性樹脂組成物およびその利用
WO2008105480A1 (fr) * 2007-03-01 2008-09-04 Ajinomoto Co., Inc. Film pour un transfert de film métallique, procédé de transfert d'un film métallique, et procédé de fabrication d'une plaque de circuits imprimés
WO2008105481A1 (fr) * 2007-03-01 2008-09-04 Ajinomoto Co., Inc. Procédé de fabrication d'une carte de circuits imprimés
JP2011025532A (ja) * 2009-07-24 2011-02-10 Ajinomoto Co Inc 金属膜付きフィルム
WO2013146195A1 (fr) * 2012-03-28 2013-10-03 Dic株式会社 Motif électroconducteur, circuit électrique, blindage contre les ondes électromagnétiques et procédé de fabrication d'un motif électroconducteur
WO2014050657A1 (fr) * 2012-09-28 2014-04-03 Dic株式会社 Stratifié, motif conducteur, et circuit électrique
WO2015037511A1 (fr) * 2013-09-10 2015-03-19 Dic株式会社 Corps empilé, réseau conducteur, circuit électronique et procédé de production de corps empilé
JP2015156459A (ja) * 2014-02-21 2015-08-27 Dic株式会社 積層体、導電性パターン及び電子回路
JP2016007797A (ja) * 2014-06-25 2016-01-18 Dic株式会社 積層体、導電性パターン、電子回路及び積層体の製造方法
JP2016112704A (ja) * 2014-12-11 2016-06-23 Dic株式会社 導電性積層体及びその製造方法
WO2016098596A1 (fr) * 2014-12-16 2016-06-23 株式会社カネカ Composition de résine photodurcissable et thermodurcissable, produit durci et stratifié
JP2016120604A (ja) * 2014-12-24 2016-07-07 Dic株式会社 積層体、導電性パターン及び電子回路
WO2016208672A1 (fr) * 2015-06-26 2016-12-29 Dic株式会社 Corps stratifié, article moulé, profil électroconducteur, circuit électronique et blindage électromagnétique

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