WO2015137132A1 - Shield film, shield printed wiring board, and methods for producing same - Google Patents

Shield film, shield printed wiring board, and methods for producing same Download PDF

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Publication number
WO2015137132A1
WO2015137132A1 PCT/JP2015/055570 JP2015055570W WO2015137132A1 WO 2015137132 A1 WO2015137132 A1 WO 2015137132A1 JP 2015055570 W JP2015055570 W JP 2015055570W WO 2015137132 A1 WO2015137132 A1 WO 2015137132A1
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WO
WIPO (PCT)
Prior art keywords
layer
printed wiring
wiring board
group
conductive
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PCT/JP2015/055570
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French (fr)
Japanese (ja)
Inventor
白髪　潤
亘 冨士川
村川　昭
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Dic株式会社
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Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2015541353A priority Critical patent/JPWO2015137132A1/en
Publication of WO2015137132A1 publication Critical patent/WO2015137132A1/en

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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
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0216—Reduction of cross-talk, noise or electromagnetic interference
    • H05K1/0218—Reduction of cross-talk, noise or electromagnetic interference by printed shielding conductors, ground planes or power plane
    • H05K1/0224—Patterned shielding planes, ground planes or power planes
    • 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
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0215—Grounding of printed circuits by connection to external grounding means

Definitions

  • the present invention relates to a shield film used for a printed wiring board, a shield printed wiring board using the shield film, and a manufacturing method thereof.
  • the signal transmission path of the printed wiring board is also considered to be shielded in order to reduce the influence on the other parts due to the noise generated by itself and not to be affected by the noise generated from the other parts.
  • a method for forming the shield for example, in a printed wiring board having a signal wiring and a ground wiring on an insulating substrate, a metal thin film layer having a high conductivity and a high electromagnetic wave shielding effect as a shielding material on the signal wiring cover layer And a shielded printed wiring board having a structure in which the ground wiring of the printed wiring board and the metal thin film layer are conducted through a conductive adhesive has been proposed (for example, see Patent Document 1).
  • the above-mentioned shielded printed wiring board can solve the problem of noise countermeasures inside the equipment, but the means for matching the impedance with other equipment to be connected by controlling the impedance of the printed wiring board is a signal wiring pattern.
  • the problem can be solved only by reducing the width, and the degree of freedom of the pattern of the signal wiring is limited.
  • an electromagnetic wave shielding sheet used for a wiring board having signal wiring contains a thermosetting resin composition having a glass transition temperature of 0 to 150 ° C., and can flow under conditions of a temperature of 150 ° C. and a pressure of 1 kg / cm 2.
  • An electromagnetic wave shielding sheet having a bonding layer having insulation and a conductive layer provided on one surface of the bonding layer and having a plurality of openings has been proposed (for example, see Patent Document 2).
  • the impedance of the printed wiring board is adjusted by providing an opening in the conductive layer and directly connecting to the ground wiring of the printed wiring board through a through hole provided in the printed wiring board.
  • the conductive layer of the electromagnetic wave shielding sheet and the ground wiring of the printed wiring board are directly connected, so the hardness of the conductive layer, the line width of the pattern, the printed wiring
  • the connection reliability is insufficient.
  • the line width of the pattern of the conductive layer of the electromagnetic wave shielding sheet is made thicker than the ground wiring of the printed wiring board, it becomes difficult to connect the conductive layer and the ground wiring. Since the adhesion area of the layer becomes very small, there is a problem that connection reliability becomes insufficient.
  • the connection reliability is insufficient.
  • the insulating protective layer of the printed wiring board is thick, the height of the through hole provided on the ground wiring also increases, and if the conductive layer of the electromagnetic wave shield sheet is not flexible, the conductive layer is disconnected at the step of the through hole. There was also a problem to do.
  • the present inventors have established a conductive adhesive layer, a patterned copper plating layer on a printed wiring board provided with a signal wiring, a ground wiring, and an insulating protective layer, By providing a shield film composed of an insulating protective layer, the impedance of the printed wiring board can be controlled without reducing the pattern width of the signal wiring, and the connection reliability between the shielding film and the ground wiring of the printed wiring board is improved.
  • the present invention was completed.
  • the present invention is a shield film for a printed wiring board in which signal wiring, ground wiring, and a first insulating protective layer are provided on a base insulating base material, and is laminated on the entire surface of the first insulating protective layer.
  • a shield film comprising the layer (A) formed by using the conductive adhesive layer, the copper plating layer, and a second insulating protective layer on the layer (A), and the shield film.
  • the present invention relates to a shield printed wiring board. Moreover, it is related with the manufacturing method of the said shield film and a shield printed wiring board.
  • the shield film and shield printed wiring board of the present invention are related to the impedance control required for a printed wiring board used at a high frequency, and are not controlled only by the pattern width of the signal wiring, but the copper plating layer pattern on the shield film side.
  • the aperture ratio one factor of impedance control, impedance matching can be achieved while maintaining the freedom of the line width of the signal wiring. Therefore, for example, it can be suitably used as a shield printed wiring board used inside an electronic apparatus such as a mobile phone, a notebook computer, a smartphone, a tablet computer, a wearable device, a digital still camera, and a digital video camera.
  • FIG. 1 shows a cross section of a shielded printed wiring board according to the present invention.
  • FIG. 2 shows a cross section of the shield printed wiring board of the present invention, in which a polymer layer is provided between the second insulating protective layer and a layer formed using conductive ink.
  • the shield film of the present invention is a shield film for a printed wiring board in which a signal wiring, a ground wiring, and a first insulating protective layer are provided on a base insulating base material, A conductive adhesive layer laminated on the entire surface of the first insulating protective layer; A copper plating layer patterned with a film thickness of 0.2 to 20 ⁇ m and an aperture ratio of 10 to 90% on the conductive adhesive layer; A layer (A) formed using a conductive ink on the copper plating layer; It has a 2nd insulating protective layer on the said conductive adhesive layer, the said copper plating layer, and the said layer (A).
  • the base insulating base material is a base material for a printed wiring board.
  • the material of the base insulating base material include, for example, polyester resins such as polyimide, polyamideimide, polyamide, and polyethylene terephthalate, polyethylene naphthalate, polycarbonate, ABS (acrylonitrile-butadiene-styrene) resin, acrylic resin such as polymethyl methacrylate, Fluorine resin such as phenol resin, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene, polypropylene, polyurethane, LCP (liquid crystal polymer), PEEK (polyether ether ketone) resin, PEI (polyether imide) resin , PPS (polyphenylene sulfide) resin, PSF (polysulfone) resin, PES (polyethersulfone) resin, polyarylate resin, PBT ( Ribbylene terephthalate)
  • the base insulating base material for example, a base material made of synthetic fibers such as polyester fiber, polyamide fiber, and aramid fiber; natural fibers such as cotton and hemp can be used.
  • the fibers may be processed in advance.
  • the base insulating substrate it is preferable to use a flexible and flexible support when the shield printed wiring board of the present invention to be described later is used for applications that require bending flexibility. Specifically, it is preferable to use a film or sheet-like support.
  • Examples of the film or sheet-like base insulating base material include a polyethylene terephthalate film, a polyimide film, a polyethylene naphthalate film, and an LCP (liquid crystal polymer) film.
  • the base insulating base material improves the adhesion with signal wiring and ground wiring, which will be described later, so that the surface is roughened by sandblasting, solvent treatment, etc. (Corona discharge treatment, atmospheric pressure plasma treatment), chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet ray / electron beam irradiation treatment, oxidation treatment, etc. can be used.
  • the thickness of the film or sheet support is preferably about 1 to 5,000 ⁇ m, and preferably about 1 to 300 ⁇ m. It is more preferable that When the conductive pattern of the present invention is used for a flexible printed circuit board or the like that requires flexibility, it is preferable to use a film-like material having a thickness of about 1 to 200 ⁇ m as the base insulating base material. .
  • a commercially available copper-clad base material can be used in order to form signal wiring and ground wiring described later.
  • copper other than a wiring part can be removed by an etching process to form a wiring pattern.
  • the signal wiring and ground wiring can be made of the above-described copper-based wiring, and may be composed of other conductive materials, for example, by printing conductive ink mainly composed of silver. It is also possible to use the formed wiring pattern. Further, the conductive ink pattern can be made into a wiring by thickening it by copper plating, nickel plating or the like.
  • the shield printed wiring board of the present invention is provided with a first insulating protective layer on the signal wiring and the ground wiring.
  • the first insulating protective layer include a polyimide film or the like coated with an adhesive, a photosensitive coverlay film or the like having a photosensitivity and capable of forming a pattern by exposure and development, a liquid coverlay.
  • an insulating protective layer can be formed by applying a liquid material such as a photosensitive liquid coverlay or a solder resist.
  • the shield film of the present invention includes a conductive adhesive layer laminated on the entire surface of the first insulating protective layer, a film thickness of 0.2 to 20 ⁇ m, and an aperture ratio of 10 to 90 on the conductive adhesive layer. It is a shield film characterized by having a metal layer patterned by% and a second insulating protective layer.
  • the conductive adhesive layer is made of an adhesive resin containing a conductive substance.
  • the conductive substance include metal plating such as copper, silver, nickel, and aluminum, metal whiskers, and silver plating on copper powder.
  • These conductive materials can be used alone or in combination of two or more.
  • the adhesive resin includes styrene resin, vinyl acetate resin, polyester resin, polyolefin resin such as polyethylene and polypropylene, amide resin, amideimide resin, styrene-butadiene resin, acrylonitrile-butadiene resin, (meth) acryl-butadiene resin, (meth )
  • Thermoplastic resins such as acrylic resins and urethane resins; Thermosetting resins such as phenol resins, epoxy resins, melamine resins, and alkyd resins; UV curable resins such as urethane acrylates, epoxy acrylates, and acrylic acrylates.
  • These adhesive resins can be used alone or in combination of two or more.
  • the shield film of the present invention has a copper plating layer patterned with a film thickness of 0.2 to 20 ⁇ m and an aperture ratio of 10 to 90% on the conductive adhesive layer.
  • the pattern of the copper plating layer is not particularly limited, but can be appropriately selected according to required shielding properties, impedance to be controlled, and the like.
  • the specific pattern of the copper plating layer is preferably a mesh pattern, and the shape of the opening is a triangle such as a regular triangle, an isosceles triangle, a right triangle; a square, a rectangle, a rhombus, a parallelogram, a trapezoid, and the like.
  • the openings are arranged at equal intervals because of excellent shielding properties against electromagnetic waves.
  • the aperture ratio of the pattern is preferably in the range of 10 to 90%.
  • the aperture ratio is an important factor in controlling the impedance of the shield printed wiring board. When the aperture ratio is less than 10%, the impedance can be controlled without adjusting the line width of the signal wiring of the shield printed wiring board. When the range becomes small and the aperture ratio exceeds 90%, the effect of shielding the electromagnetic waves of the shield printed wiring board becomes small.
  • the film thickness of the copper plating layer is in the range of 0.2 to 20 ⁇ m.
  • the film thickness of the copper plating layer is less than 0.2 ⁇ m, the effect of shielding the electromagnetic wave of the shield printed wiring board is reduced.
  • the film thickness of the copper plating layer exceeds 20 ⁇ m, the shield printed wiring board itself is required to be thinned. In addition, it is difficult to satisfy the requirements, and when used as a flexible printed wiring board, there is a problem that the flexibility is greatly lowered.
  • the film thickness of the copper plating layer is a factor related to the control of the impedance of the shield printed wiring board, and is preferably in the range of 0.2 to 8 ⁇ m.
  • Examples of the method of forming the copper plating layer include a method of removing the pattern of the opening from the copper foil by etching, but this method has a problem that the manufacturing method is complicated and the copper plating layer is difficult to be thinned. . Therefore, in the present invention, the copper plating layer can be easily patterned with a desired aperture ratio, and the degree of freedom in design in controlling the impedance is increased. Therefore, a layer formed using a conductive ink described later. After producing the pattern in (A), the copper plating layer is formed thereon.
  • the conductive ink is used for producing a pattern as a base of a copper plating layer as described above, and is excellent in adhesion to a copper plating layer formed on the copper plating layer and plating deposition at the time of copper plating. Therefore, those containing metal nanoparticles as the conductive substance (a2) are preferable. Furthermore, since the said metal nanoparticle is excellent in adhesiveness with the 2nd insulating protective layer mentioned later, it is preferable that it is the metal nanoparticle disperse
  • the polymer dispersant is preferably a polymer having a functional group coordinated to the metal nanoparticles.
  • the functional group include a carboxyl group, an amino group, a cyano group, an acetoacetoxy group, a phosphorus atom-containing group, a thiol group, a thiocyanato group, and a glycinato group.
  • the metal nanoparticles include a transition metal or a compound thereof, and an ionic transition metal is preferable among the transition metals.
  • the ionic transition metal include metals such as copper, silver, gold, nickel, palladium, platinum, and cobalt, and composites of these metals. These metal nanoparticles can be used alone or in combination of two or more. Among these metal nanoparticles, silver nanoparticles are preferable from the viewpoints of handling problems such as oxidative degradation and cost.
  • the conductive substance (a2) contained in the conductive ink can use a plating nucleating agent in place of the metal nanoparticles.
  • a plating nucleating agent in place of the metal nanoparticles.
  • an oxide of the transition metal, a metal whose surface is coated with an organic substance, or the like can be used.
  • These plating nucleating agents can be used alone or in combination of two or more.
  • the transition metal oxide is usually in an inactive (insulating) state.
  • the metal is exposed by treatment with a reducing agent such as dimethylaminoborane to impart activity (conductivity). be able to.
  • examples of the metal whose surface is coated with the organic substance include those in which a metal is contained in resin particles (organic substance) formed by an emulsion polymerization method or the like. These are usually in an inactive (insulating) state. However, for example, by removing the organic substance using a laser or the like, the metal can be exposed to impart activity (conductivity).
  • the conductive substance (a2) is preferably in the form of particles having an average particle diameter of about 1 to 100 nm, preferably having an average particle diameter of 1 to 50 nm. Compared to the case of using a conductive material having an average particle size of 1, a fine conductive pattern can be formed, and the resistance value after firing described later can be further reduced, which is more preferable.
  • the average particle diameter is a volume average value measured by a dynamic light scattering method after diluting the conductive substance (a2) with a dispersion good solvent. For this measurement, “Nanotrack UPA” manufactured by Microtrack Corporation can be used.
  • the layer (A) formed using the conductive ink is formed on the second insulating protective layer described later, but the adhesion between the surface of the second insulating protective layer described later and the layer (A) is improved.
  • the polymer forming the second insulating protective layer preferably has a reactive functional group [Y] described later.
  • the polymer forming the second insulating protective layer described later does not have the reactive functional group [Y] described later, the polymer is applied to the surface of the second insulating protective layer, dried, and dried. After providing the molecular layer (B), the adhesiveness between the surface of the second insulating protective layer described later and the layer (A) can be further improved by forming the layer (A) thereon. .
  • the polymer forming the polymer layer (B) preferably has a reactive functional group [Y] described later.
  • the conductive ink further improves the adhesion between the copper plating layer and a second insulating protective layer described later. Therefore, what contains the compound (a1) which has reactive functional group [X], and the said electroconductive substance (a2) is preferable.
  • the reactive functional group [X] possessed by the compound (a1) is involved in binding to the reactive functional group [Y] described later, and specific examples include an amino group, an amide group, and an alkylolamide group. , Carboxyl group, anhydrous carboxyl group, carbonyl group, acetoacetoxy group, epoxy group, alicyclic epoxy group, oxetane ring, vinyl group, allyl group, (meth) acryloyl group, (blocked) isocyanate group, (alkoxy) silyl group Etc., silsesquioxane compounds, and the like.
  • the reactive functional group [X] is preferably a basic nitrogen atom-containing group in order to further improve the adhesion to the second insulating protective layer described later.
  • Examples of the basic nitrogen atom-containing group in the compound having a basic nitrogen atom-containing group include an imino group, a primary amino group, and a secondary amino group.
  • the compound (a1) having a plurality of basic nitrogen atom-containing groups in one molecule one of the basic nitrogen atom-containing groups is described later when the pattern of the layer (A) is formed.
  • the reactive functional group [Y] of the polymer forming the second insulating protective layer or the polymer forming the polymer layer (B) is in the layer (A)
  • the conductive material (a2) such as silver contained in and can further improve the adhesion between the finally obtained copper plating layer and the second insulating protective layer.
  • the compound (a1) having a basic nitrogen atom-containing group can further improve the dispersion stability of the conductive substance (a2) and the adhesion to the second insulating protective layer described later, a polyalkyleneimine, or A polyalkyleneimine having a polyoxyalkylene structure containing an oxyethylene unit is preferred.
  • the polyalkyleneimine having the above may be a linear bond of polyethyleneimine and polyoxyalkylene, and the polyoxyalkylene is present in the side chain of the main chain composed of polyethyleneimine. May be grafted.
  • polyalkyleneimine having the polyoxyalkylene structure examples include a block copolymer of polyethyleneimine and polyoxyethylene, and an addition reaction of ethylene oxide with a part of imino group present in the main chain of polyethyleneimine.
  • examples thereof include those obtained by introducing a polyoxyethylene structure, those obtained by reacting an amino group possessed by polyalkyleneimine, a hydroxyl group possessed by polyoxyethylene glycol, and an epoxy group possessed by an epoxy resin.
  • Examples of commercially available products of the polyalkyleneimine include “PAO2006W”, “PAO306”, “PAO318”, “PAO718” and the like of “Epomin (registered trademark) PAO series” manufactured by Nippon Shokubai Co., Ltd.
  • the number average molecular weight of the polyalkyleneimine is preferably in the range of 3,000 to 30,000.
  • the reactive functional group [X] of the compound (a1) is a carboxyl group, an amino group, a cyano group, an acetoacetoxy group, a phosphorus atom-containing group, a thiol group, a thiocyanato group, a glycinato group, etc. Since the functional group also functions as a functional group that coordinates with the metal nanoparticles, the compound (a1) can also be used as a polymer dispersant for the metal nanoparticles.
  • the conductive ink preferably has an appropriate viscosity using a solvent in order to impart printability in various printing methods described later.
  • a solvent include aqueous media such as distilled water, ion-exchanged water, pure water, and ultrapure water; and organic solvents such as alcohol solvents, ether solvents, ketone solvents, and ester solvents.
  • Examples of the alcohol solvent or ether solvent include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol.
  • Examples of the ketone solvent include acetone, cyclohexanone, methyl ethyl ketone, and the like.
  • Examples of the ester solvent include ethyl acetate, butyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-butyl acetate and the like.
  • other organic solvents include hydrocarbon solvents such as toluene, particularly hydrocarbon solvents having 8 or more carbon atoms.
  • hydrocarbon solvent having 8 or more carbon atoms examples include nonpolar solvents such as octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, mesitylene, ethylbenzene, dodecylbenzene, tetralin, and trimethylbenzenecyclohexane.
  • nonpolar solvents such as octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, mesitylene, ethylbenzene, dodecylbenzene, tetralin, and trimethylbenzenecyclohexane.
  • a solvent such as mineral spirit or solvent naphtha, which is a mixed solvent, can be used in combination.
  • the conductive ink can be produced, for example, by mixing the polymer dispersant, the conductive substance, and, if necessary, the solvent. Specifically, an ion solution of the conductive substance prepared in advance is added to a medium in which a compound having a polyalkyleneimine chain, a hydrophilic segment, and a hydrophobic segment is dispersed, and the metal ions are reduced. Can be manufactured by.
  • the conductive ink may contain a surfactant, an erasing agent, or the like, if necessary, in order to improve the dispersion stability of the conductive substance in a solvent such as an aqueous medium or an organic solvent and the wettability to the coated surface.
  • Foaming agents, rheology modifiers, etc. may be added.
  • the conductive ink is printed on a second insulating protective layer to be described later to form a pattern composed of the layer (A).
  • Examples of the method for printing the conductive ink include an inkjet printing method, Examples include reverse printing, flexographic printing, screen printing, gravure printing, and gravure offset printing.
  • the ink jet printing method is preferable.
  • an ink jet printer As the ink jet printing method, what is generally called an ink jet printer can be used. Specific examples include “Konica Minolta EB100, XY100” (manufactured by Konica Minolta IJ Co., Ltd.), “Dimatics Material Printer DMP-3000, DMP-2831” (manufactured by Fuji Film Co., Ltd.), and the like.
  • the conductive ink is applied to the surface of various blankets, and is brought into contact with a plate from which a non-image portion protrudes.
  • the pattern is formed on the surface of the blanket or the like by selectively transferring the conductive ink corresponding to the image area to the surface of the plate, and then the pattern is formed on the second insulating protective layer ( And a method of transferring to the surface).
  • the polymer layer (B) when the polymer layer (B) is provided for the purpose of further improving the adhesion between the surface of the second insulating protective layer described later and the layer (A), the polymer layer (B)
  • the polymer that forms a resin include various resins such as urethane resin, vinyl resin, urethane-vinyl composite resin, epoxy resin, imide resin, amide resin, melamine resin, phenol resin, polyvinyl alcohol, and polyvinylpyrrolidone, and a solvent. The thing to contain is mentioned.
  • urethane resin urethane resin
  • vinyl resin urethane-vinyl composite resin
  • urethane resin vinyl resin, and urethane-vinyl composite resin
  • Urethane resin having a polyether structure Urethane resin having a polyether structure, urethane resin having a polycarbonate structure, urethane resin having a polyester structure, and acrylic resin
  • one or more resins selected from the group consisting of urethane-acrylic composite resins are more preferable.
  • a urethane-acrylic composite resin is more preferable because a conductive pattern having excellent adhesion and conductivity can be obtained.
  • the polymer forming the polymer layer (B) is reactive with the reactive functional group [X].
  • the compound (b1) having a functional group [Y] having Examples of the compound (b1) having the reactive functional group [Y] include an amino group, an amide group, an alkylolamide group, a carboxyl group, an anhydrous carboxyl group, a carbonyl group, an acetoacetoxy group, an epoxy group, and an alicyclic epoxy.
  • Examples of the method for applying the polymer forming the polymer layer (B) to the surface of the second insulating protective layer described later include a gravure method, a coating method, a screen method, a roller method, a rotary method, and a spray method. Can be mentioned.
  • the surface of the second insulating protective layer to be described later is improved in adhesion with the polymer layer (B), for example, plasma discharge treatment method such as corona discharge treatment method; dry treatment such as ultraviolet treatment method.
  • plasma discharge treatment method such as corona discharge treatment method
  • dry treatment such as ultraviolet treatment method.
  • Surface treatment may be performed by a wet treatment method using water, an acidic or alkaline chemical solution, an organic solvent, or the like.
  • a method of volatilizing the solvent is common.
  • the drying temperature is preferably set to a temperature that allows the solvent to be volatilized and does not adversely affect the support (A).
  • the thickness of the polymer (B) layer formed using the polymer (B) is preferably in the range of 5 to 5000 nm because the adhesion between the second insulating protective layer and the metal layer can be further improved. A range of 10 to 500 nm is more preferable.
  • the polymer (B) can be used as it is as the second insulating protective layer, and further, the polymer (B) can be mixed and used in the second insulating protective layer. In this case, the polymer (B) needs to be present in a portion of the second insulating protective layer that contacts the conductive ink (A).
  • the baking step performed after applying the conductive ink to form a pattern as a plating base with the conductive ink is to adhere and bond the conductive substances contained in the conductive ink.
  • the firing is preferably performed at a temperature range of 80 to 300 ° C. for about 1 to 200 minutes.
  • the firing temperature be in the range of 100 to 200 ° C.
  • the firing may be performed in the air, part or all of the firing step may be performed in a reducing atmosphere in order to prevent all of the conductive material from being oxidized.
  • the baking step can be performed using, for example, an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, microwave, light irradiation (flash irradiation apparatus), or the like.
  • the pattern comprising the layer (A) as the plating base formed using the conductive ink by the above method contains a conductive substance in the range of 80 to 99.9% by mass in the pattern.
  • the polymer dispersant is preferably contained in the range of 0.1 to 20% by mass.
  • the thickness of the plating base pattern which is the layer (A) formed using the conductive ink is preferably in the range of 50 to 2,000 nm because a conductive pattern having low resistance and excellent conductivity can be formed.
  • the layer (A) formed using the conductive ink as a conductive layer on the shield film side is used as a plating base pattern, and a film thickness of 0.2 is formed thereon. It has a copper plating layer patterned with a thickness of ⁇ 20 ⁇ m and an aperture ratio of 10 ⁇ 90%.
  • Patent Document 2 as a conductive layer, a method of printing conductive ink or conductive paste in a predetermined pattern on a base film, a method of forming an opening by etching a metal foil, It is disclosed that a metal layer having a predetermined pattern is formed by vapor deposition or sputtering, and that a wire mesh is used as such a conductive layer.
  • Patent Document 2 discloses that the material of the conductive layer is preferably a metal such as gold, silver, or copper and an alloy thereof, a conductive filler-containing resin, a conductive polymer, or the like. ing.
  • the layer (A) in which the pattern is formed with the conductive ink is used as a plating base, and a copper plating layer obtained by performing copper plating thereon is used. All points can be solved.
  • Examples of the method for forming the copper plating layer include wet plating methods such as an electrolytic plating method and an electroless plating method, and the copper plating layer may be formed by combining two or more of these plating methods.
  • the adhesion between the pattern of the layer (A) and the copper plating layer formed by the plating method is further improved, and a pattern having excellent conductivity can be obtained.
  • a wet plating method such as an electroless plating method is preferable, and an electrolytic plating method is more preferable because of excellent productivity and mechanical properties of the obtained metal film.
  • the electroless plating method for example, by bringing an electroless plating solution into contact with a conductive material constituting the pattern of the layer (A), copper metal contained in the electroless plating solution is precipitated, and the metal coating is used.
  • This is a method of forming an electroless plating layer (film).
  • Examples of the electroless plating solution include copper, a reducing agent, and a solvent such as an aqueous medium or 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, glycol Hydroxycarboxylic acid compounds such as acid, gluconic acid, citric acid
  • amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid, glutamic acid
  • iminodiacetic acid nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc.
  • complexing agents such as organic acids such as aminopolycarboxylic acid compounds or soluble salts of these organic acids (sodium salts, potassium salts, ammonium salts, etc.), amine compounds such as ethylenediamine, diethylenetriamine, and triethylenetetramine. It is possible to use the thing.
  • the electroless plating solution is preferably used in the range of 20 to 98 ° C.
  • the electrolytic plating method for example, electricity is supplied in a state where an electrolytic plating solution is in contact with the surface of the metal constituting the conductive layer (A) or the electroless plating layer (coating) formed by the electroless treatment.
  • a metal such as copper contained in the electrolytic plating solution is used to form a conductive material constituting the conductive layer (A) placed on the cathode or the electroless plating layer (coating) formed by the electroless treatment.
  • This is a method of depositing on the surface and forming an electrolytic plating layer (metal coating).
  • Examples of the electrolytic plating solution include those containing copper sulfide, sulfuric acid, and an aqueous medium. Specifically, what contains copper sulfate, sulfuric acid, and an aqueous medium is mentioned.
  • the electrolytic plating solution is preferably used in the range of 20 to 98 ° C.
  • the plating method is preferably an electrolytic plating method because it is easy to work without using a highly toxic substance. Electrolytic copper plating is preferable because it can shorten the plating time and control the thickness of the plating as compared with electroless copper plating. Furthermore, the copper plating layer obtained by electrolytic copper plating has excellent mechanical properties, is difficult to break even when bent, and has excellent flexibility. It is preferable to use the formed copper plating layer.
  • the copper plating layer may be formed by laminating another metal plating layer on the copper plating layer.
  • a nickel plating layer, a gold plating layer, or a tin plating layer is provided, the surface of the copper plating layer is deteriorated by oxidation or corroded. Can be prevented.
  • the thickness of the copper plating layer formed by the above plating method is preferably in the range of 0.2 to 20 ⁇ m because it is excellent in conductivity as a conductive layer and can meet the demands for thinning the shield printed wiring board.
  • the thickness of the layer can be adjusted by controlling the processing time, current density, the amount of plating additive used, etc. in the copper plating process. .
  • a second insulating protective layer is provided on the metal layer pattern.
  • the second insulating protective layer comprises an insulating resin sheet or film, or an insulating resin coating layer.
  • the insulating resin sheet or film include polyester film, polyolefin film, polyimide film, polyamideimide film, polyphenylene sulfide film, polyethylene naphthalate film, LCP (liquid crystal polymer) film, and polycycloolefin film.
  • Insulating resin coating layers include styrene resins, vinyl acetate resins, polyester resins, polyolefin resins such as polyethylene and polypropylene, amide resins, amideimide resins, styrene-butadiene resins, acrylonitrile-butadiene resins, and (meth) acryl-butadiene resins.
  • UV rays composed of thermoplastic resins such as (meth) acrylic resin and urethane resin, thermosetting resins such as phenolic resin, epoxy resin, melamine resin and alkyd resin, urethane-acrylate, epoxy-acrylate, acrylic-acrylate, etc.
  • a curable resin or the like can be used alone or in combination of two or more.
  • thermosetting resin or an ultraviolet curable resin is preferable, and an epoxy resin, a urethane resin
  • an epoxy resin, a urethane resin It is preferable to use a polyester resin, a melamine resin, an acrylic resin, urethane-acrylate, epoxy acrylate, acrylic-acrylate, etc. alone, in combination of two or more, or in combination with a crosslinking agent.
  • urethane resin is included.
  • a conductive ink is formed directly on the second insulating protective layer or after the polymer layer (B) is formed on the second insulating protective layer.
  • a conductive ink is formed directly on the second insulating protective layer or after the polymer layer (B) is formed on the second insulating protective layer.
  • the formation method of the said polymer layer (B) and the said layer (A) is as having mentioned above.
  • the second insulating protective layer can be an insulating resin sheet or film, or an insulating resin coating layer. However, when the second insulating protective layer is manufactured by coating the insulating resin, it is supported. A release film can be used as the substrate.
  • a plastic film or release paper can be used as the release film.
  • the plastic film include a polyester film, a polyolefin film, a polyimide film, and a film in which a silicone release layer, a fluorine release layer, an olefin release layer, and the like are further provided on these films. It is done.
  • the release paper include those in which a sealing layer is provided on a paper substrate and then a silicone release layer, a fluorine release layer, and an olefin release layer are provided thereon.
  • said 2nd insulation protective layer formed by coating what coated resin etc. which were illustrated above can be used, for example, an insulating resin is applied to the said peeling film, it is dried, and resin is needed as needed. Can be cured by heat curing and ultraviolet curing to produce the second insulating protective layer.
  • a conductive adhesive layer is formed on the copper plating layer.
  • the conductive adhesive layer specifically, those described above can be used.
  • the conductive adhesive layer can be formed by applying the conductive adhesive on the copper plating layer pattern and drying it as necessary.
  • the shield film obtained in this manner can be used as a shield film that is attached to the outermost surface of the shield printed wiring board of the present invention.
  • the manufacturing method of the shield printed wiring board of the present invention will be described.
  • the printed wiring board constituting the shield printed wiring board of the present invention is formed with signal wiring and ground wiring on a printed wiring board substrate, and a first insulating protective layer is provided thereon, and the first insulating protective layer is A ground wire having a partly exposed via is used.
  • the shield printed wiring board of the present invention is a flexible printed wiring board (FPC), a single-sided FPC having a printed circuit only on one side of the base film, and a double-sided FPC having a printed circuit on both sides of the base film Multi-layer FPC in which a plurality of such FPCs are laminated, Flexboard (registered trademark) having a multilayer component mounting portion and a cable portion, a flex rigid board having a rigid member constituting the multilayer portion, or a tape carrier A TAB tape or the like for the package can be adopted as appropriate.
  • FPC flexible printed wiring board
  • a single-sided FPC having a printed circuit only on one side of the base film and a double-sided FPC having a printed circuit on both sides of the base film
  • Multi-layer FPC in which a plurality of such FPCs are laminated
  • Flexboard registered trademark
  • Flexboard having a multilayer component mounting portion and a cable portion
  • the conductive adhesive layer of the shield film of the present invention is disposed so as to be in contact, and the printed wiring board and the shield film are shielded by pressing in a direction approaching each other.
  • the shield printed wiring board of the present invention can be manufactured by flowing the conductive adhesive layer of the film and connecting it to the ground layer of the printed wiring board.
  • the printed wiring board and the shield film are pressurized to cause the conductive adhesive layer to flow and join with the ground layer of the printed wiring board, it can be heated, and the conductive adhesive can be thermoset.
  • the heating conditions can be adjusted according to the curing conditions of the resin.
  • the heating temperature is usually preferably in the range of 50 to 250 ° C.
  • the shield printed wiring board of the present invention may have a configuration in which a shield film is attached to one side of the printed wiring board or a configuration in which shield films are attached to both sides.
  • conductive ink (1) By dispersing silver particles having an average particle diameter of 20 nm in a mixed solvent of 35 parts by mass of ethylene glycol and 65 parts by mass of ion-exchanged water, using a compound in which polyoxyethylene is added to polyethyleneimine as a dispersant, metal nanoparticles are dispersed. A metal nanoparticle dispersion containing particles and a polymer dispersant having a basic nitrogen atom-containing group as a reactive functional group was prepared. Next, ion-exchanged water and a surfactant were added to the obtained metal nanoparticle dispersion, and the viscosity was adjusted to 11 mPa ⁇ s to prepare a conductive ink (1) for inkjet printing.
  • polyester polyol polyol obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol and adipic acid in a nitrogen-substituted container equipped with a thermometer, nitrogen gas inlet tube and stirrer Polyol, a hydroxyl group equivalent of 1,000 g / equivalent
  • 17.4 parts by mass of 2,2-dimethylolpropionic acid 17.4 parts by mass of 1,4-cyclohexanedimethanol
  • 106.2 parts by mass of dicyclohexylmethane diisocyanate By mixing and reacting in 178 parts by mass, an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.
  • a vinyl monomer mixture containing 60 parts by mass of methyl methacrylate, 10 parts by mass of n-butyl acrylate and 30 parts by mass of glycidyl methacrylate, and azoisobutyro
  • a polymerization initiator solution containing 1 part by mass of nitrile and 20 parts by mass of ethyl acetate was dropped and polymerized from another dropping funnel over 240 minutes while maintaining the temperature in the reaction vessel at 80 ⁇ 1 ° C.
  • polyester polyol polyol obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol and adipic acid in a nitrogen-substituted container equipped with a thermometer, nitrogen gas inlet tube and stirrer Polyol, hydroxyl group equivalent 1000 g / equivalent), 17.4 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol and 106.2 parts by mass of dicyclohexylmethane diisocyanate, and 178 parts by mass of methyl ethyl ketone.
  • a urethane resin having an isocyanate group at the molecular end was obtained. Subsequently, methyl ethyl ketone was added to the obtained urethane resin to obtain an organic solvent solution of a urethane resin having a solid content of 50% by mass.
  • Example 1 As a printed wiring board, a wiring composed of a ground copper wiring pattern with a copper thickness of 12 ⁇ m and a line width of 500 ⁇ m and a signal copper wiring pattern with a copper thickness of 12 ⁇ m and a line width of 200 ⁇ m is formed on a polyimide base film.
  • the first insulating protective layer having a film thickness of 27.5 ⁇ m is formed of an adhesive layer having a film thickness of 15 ⁇ m and a polyimide film layer having a film thickness of 12.5 ⁇ m.
  • a printed wiring board having a 400 ⁇ m square opening in the ground wiring portion was used.
  • the second insulating protective layer resin produced above is applied so that the film thickness after drying is 5 ⁇ m, and dried to form a second insulating protective layer. Formed.
  • the polymer layer (B-1) resin produced above was applied so that the film thickness after drying was 0.2 ⁇ m, and dried to form a polymer layer (B-1).
  • the conductive ink (1) obtained above is applied onto the second insulating protective layer on which the polymer layer (B-1) formed by the above method is laminated, by an inkjet printer (manufactured by Konica Minolta IJ Co., Ltd.).
  • a grid pattern having a line width of 90 ⁇ m and an aperture ratio of 82% was printed for the purpose of setting the characteristic impedance of the shield printed wiring board to 50 ⁇ using an inkjet test machine EB100, an evaluation printer head KM512L, and a discharge amount of 14 pL.
  • a layer (having a thickness of 0.8 ⁇ m) made of the conductive ink (1) having a lattice pattern with an aperture ratio of 82% was formed.
  • the layer made of the conductive ink (1) obtained above is set as a cathode, phosphorous copper is set as an anode, and an electroplating solution containing copper sulfate is used at a current density of 2 A / dm 2 .
  • electrolytic copper plating for 10 minutes, a copper plating layer having a thickness of 5 ⁇ m was laminated on the surface of the layer made of conductive ink.
  • the copper electroplating solution 70 g / liter of copper sulfate, 200 g / liter of sulfuric acid, 50 mg / liter of chloride ions, and 5 ml / liter of additives (“Top Lucina SF-M” manufactured by Okuno Pharmaceutical Co., Ltd.) were used.
  • the line width of the lattice pattern after electrolytic copper plating was 100 ⁇ m, and the aperture ratio was 80%.
  • the conductive adhesive produced in Synthesis Example 3 is dried on the copper plating layer having a lattice pattern of 80% formed on the second insulating protective layer obtained above.
  • the film was applied to a thickness of 5 ⁇ m and dried to prepare a shield film.
  • the printed wiring board obtained by opening the ground wiring part obtained above and the shielding film obtained above are formed on the insulating protective layer of the printed wiring board, and the conductive adhesive layer of the shielding film.
  • the printed wiring board and the shield film are pressed in a direction approaching each other (pressure: 1.96 MPa, heating temperature: 150 ° C., treatment time: 30 minutes), and the shield film is conductive.
  • the conductive adhesive layer was allowed to flow and connected to the ground layer of the printed wiring board to produce a shield printed wiring board.
  • Example 2 instead of the printed wiring board used in Example 1, the line width of the signal copper wiring is set to the line width described in Table 1, and instead of the shield film used in Example 1, the opening of the copper plating layer of the shield film A shield printed wiring board was produced in the same manner as in Example 1 except that the aperture ratio described in Table 1 was used for the purpose of setting the ratio to the characteristic impedance of the shield printed wiring board of 50 ⁇ .
  • Example 1 a printed wiring board having a line width of the signal copper wiring pattern described in Table 1 was used.
  • the film thickness after drying the resin for the second insulating protective layer obtained above on a rolled copper foil having a film thickness of 5 ⁇ m so that the aperture ratio becomes 0%. was applied to a thickness of 5 ⁇ m and dried to form a second insulating protective layer.
  • the surface of the rolled copper foil opposite to the surface on which the second insulating protective layer is formed is coated with the conductive adhesive obtained above so as to have a film thickness after drying of 5 ⁇ m, and dried to obtain an aperture ratio.
  • a shield film having a 0% copper layer was prepared.
  • the line width of the signal copper wiring pattern described in Table 1 is used, and the printed wiring board having a 400 ⁇ m square opening in the ground wiring part and the shield film obtained above are insulated from the printed wiring board. It arrange
  • Comparative Example 2 instead of the printed wiring board used in Comparative Example 1, the line width of the signal copper wiring pattern was changed to the line width described in Table 1, and the comparative example with an aperture ratio of 0% was made in the same manner as in Comparative Example 1. A shield printed wiring board was produced.
  • Comparative Conductive Ink (R1) 333 parts by mass of the resin solution for conductive ink for comparison obtained above and 20 parts by mass of bisphenol A type epoxy resin (“JER828” manufactured by Mitsubishi Chemical Corporation) were stirred and mixed to obtain a resin composition solution.
  • a resin composition solution 180 parts by mass of a conductive filler (“AgXF-301” manufactured by Fukuda Metal Foil Powder Co., Ltd.) is added and mixed by stirring to a total of 100 parts by mass of the polyurethane polyurea resin and the epoxy resin.
  • a comparative conductive ink (R1) containing 300 parts by mass of a conductive filler was obtained.
  • a comparative conductive ink (R1) obtained as described above was formed on a release-treated polyester film, a line width of 100 ⁇ m, an aperture ratio of 25%, and a film thickness after drying of 5 ⁇ m. It screen-printed so that it might become a pattern, and it dried and formed the conductive layer.
  • the resin for bonding layer obtained above was applied on the release-treated polyester film so that the film thickness after drying was 15 ⁇ m and dried.
  • the conductive layer formed on the releasable film and the bonding layer formed on the releasable film were bonded together to produce a shield film.
  • the wiring width of the signal copper wiring pattern is set to the line width shown in Table 1, and a 400 ⁇ m square opening is provided in the ground wiring portion.
  • the metal layer of the shield film (copper plating layer)
  • the characteristic impedance of the shield printed wiring board could be controlled to 50 ⁇ .
  • the pattern width of the signal copper wiring of the printed wiring board is 100 nm, and the opening ratio of the metal layer (copper plating layer) of the shield film is 0% (overall copper plating layer).
  • the characteristic impedance of this shield printed wiring board was 30 ⁇ and could not be controlled to 50 ⁇ .
  • the aperture ratio of the metal layer (copper plating layer) of the shield film was set to 0% (entire copper plating layer) as in Comparative Example 1, and the pattern of the signal copper wiring on the printed wiring board
  • the width is set to 20 ⁇ m and the characteristic impedance is controlled to 50 ⁇ .
  • the communication width of the printed wiring board compared to the shielded printed wiring board of the example was reduced by reducing the pattern width of the signal copper wiring to 20 ⁇ m. There is a problem that transmission loss increases as the speed increases.
  • the shield printed wiring board of the present invention has the desired characteristics by adjusting the opening ratio of the metal layer of the shield film even when the pattern width of the signal copper wiring of the printed wiring board is changed. It was confirmed that the impedance could be adjusted.
  • the shield printed wiring board of Comparative Example 3 is an example in which there is no essential conductive adhesive layer in the shield printed wiring board of the present invention.
  • This shielded printed wiring board has a problem in connection reliability between the conductive layer on the shield film side and the ground wiring on the printed wiring side.

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  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Structure Of Printed Boards (AREA)

Abstract

The present invention provides a shield film for use in a printed wiring board and having signal wiring, ground wiring and a first insulating protective layer provided on a base insulating substrate, the shield film being characterized by having: a conductive adhesive layer layered across the entire surface of the first insulating protective film; a patterned copper plating layer having an aperture ratio of 10-90%, having a film thickness of 0.2-20μm, and positioned on the conductive adhesive layer; a layer (A) formed on the copper plating layer by using a conductive ink; and a second insulating protective layer formed on the conductive adhesive layer, the copper plating layer, and the layer (A). This shield film has high shielding properties for noise reduction, and is capable of controlling the impedance of the printed wiring board without decreasing the pattern width of the signal wiring.

Description

シールドフィルム、シールドプリント配線板及びそれらの製造方法SHIELD FILM, SHIELD PRINTED WIRING BOARD AND METHOD FOR PRODUCING THEM
　本発明は、プリント配線板に用いるシールドフィルム、該シールドフィルムを用いたシールドプリント配線板及びそれらの製造方法に関するものである。 The present invention relates to a shield film used for a printed wiring board, a shield printed wiring board using the shield film, and a manufacturing method thereof.
　近年、電子機器業界では、ＵＳＢ２．０、ｉＥＥＥ１３９４、ＨＤＭＩ（登録商標）等の高速伝送を必要とする規格が日進月歩で策定され、高速シリアル通信が多く採用されている。また、機器内の伝送方式も作動伝送のひとつであるＬＶＤＳ（Ｌｏｗ　Ｖｏｌｔａｇｅ　Ｄｉｆｆｅｒｅｎｔｉａｌ　Ｓｉｇｎａｌ）伝送が多くの機器で採用されてきており、機器間インターフェースのインピーダンス整合が重要となっている。最近では、さらに信号の高速化が要求されており、機器間のインターフェースでインピーダンスが整合していないと、伝送路端で反射が生じ、信号波と反射波の重畳により波形ひずみが発生し、信号の伝送損失が大きくなる問題がある。特に、使用する周波数が高くなると、インピーダンス不整合による反射波の影響が大きくなるため、高い周波数で使用するプリント配線板には、インピーダンスを制御し、接続される他の基板や部品とインピーダンスが整合した状態で使用することが必要となる。 In recent years, in the electronic equipment industry, standards requiring high-speed transmission such as USB 2.0, iEEE 1394, HDMI (registered trademark), etc., have been steadily developed, and high-speed serial communication is often adopted. In addition, LVDS (Low Voltage Differential Signal) transmission, which is one of operation transmissions, is adopted in many devices, and impedance matching of the interface between devices is important. Recently, there has been a demand for higher signal speed, and if the impedance is not matched at the interface between devices, reflection occurs at the end of the transmission path, and waveform distortion occurs due to superposition of the signal wave and the reflected wave. There is a problem that the transmission loss increases. In particular, since the influence of reflected waves due to impedance mismatching increases as the frequency used increases, the impedance of the printed wiring board used at high frequencies is controlled and matched with other boards and components to be connected. It is necessary to use it in the state.
　また、電子機器の小型化に伴いプリント配線板には薄型化の要求が高まっている。プリント配線板が薄型化すると、信号線とグランド層との距離が近くなり、信号線の容量成分が増加し、同一のインピーダンスを保つためには信号線の線幅（パターン幅）を細くして容量成分を減少させる必要がある。しかし、信号線のパターン幅が細くなると抵抗損失の増加、直流抵抗の増加などの問題があるため、一定のパターン幅を保った状態でインピーダンスを制御することが要求されている。 Also, with the miniaturization of electronic devices, there is an increasing demand for thinner printed wiring boards. When the printed wiring board is made thinner, the distance between the signal line and the ground layer becomes closer, the capacitance component of the signal line increases, and in order to maintain the same impedance, the line width (pattern width) of the signal line is reduced. It is necessary to reduce the capacitive component. However, when the pattern width of the signal line becomes narrow, there are problems such as an increase in resistance loss and an increase in DC resistance, and therefore it is required to control the impedance while maintaining a constant pattern width.
　一方、電子機器の高性能化に伴い、機器内部でもノイズ対策が重要になってきている。プリント配線板の信号伝達経路も、自身が出すノイズによる他の部品への影響を低減し、他の部品から発せられたノイズの影響を受けないためにシールド化が検討されている。このシールド化の方法としては、例えば、絶縁基板上に信号配線とグランド配線を有するプリント配線板において、信号配線のカバー層の上にシールド材として導電性が高く電磁波の遮蔽効果が高い金属薄膜層が設けられ、導電性接着剤を介してプリント配線板のグランド配線と金属薄膜層が導通した構造のシールドプリント配線板が提案されている（例えば、特許文献１参照。）。 On the other hand, with the improvement in performance of electronic devices, noise countermeasures have become important inside the devices. The signal transmission path of the printed wiring board is also considered to be shielded in order to reduce the influence on the other parts due to the noise generated by itself and not to be affected by the noise generated from the other parts. As a method for forming the shield, for example, in a printed wiring board having a signal wiring and a ground wiring on an insulating substrate, a metal thin film layer having a high conductivity and a high electromagnetic wave shielding effect as a shielding material on the signal wiring cover layer And a shielded printed wiring board having a structure in which the ground wiring of the printed wiring board and the metal thin film layer are conducted through a conductive adhesive has been proposed (for example, see Patent Document 1).
　しかし、上記のシールドプリント配線板では、機器内部のノイズ対策の課題は解決できるが、プリント配線板のインピーダンスを制御して、接続する他の機器とのインピーダンスを整合させる手段は、信号配線のパターン幅を小さくすることでしか解決できず、信号配線のパターンの自由度が制限されてしまうという問題があった。 However, the above-mentioned shielded printed wiring board can solve the problem of noise countermeasures inside the equipment, but the means for matching the impedance with other equipment to be connected by controlling the impedance of the printed wiring board is a signal wiring pattern. The problem can be solved only by reducing the width, and the degree of freedom of the pattern of the signal wiring is limited.
　また、信号配線を有する配線板に用いられる電磁波シールドシートとして、ガラス転移温度が０～１５０℃の熱硬化性樹脂組成物を含有し、温度１５０℃かつ圧力１ｋｇ／ｃｍ２の条件で流動可能な絶縁性を備える接合層と、前記接合層の一方の面に設けられ、複数の開口部を備える導電層とを有する電磁波シールドシートが提案されている（例えば、特許文献２参照。）。この電磁波シールドシートでは、前記導電層に開口部を設け、プリント配線板に設けた貫通孔を通じてプリント配線板のグランド配線と直接接続することで、プリント配線板のインピーダンスを調整する。 Further, as an electromagnetic wave shielding sheet used for a wiring board having signal wiring, it contains a thermosetting resin composition having a glass transition temperature of 0 to 150 ° C., and can flow under conditions of a temperature of 150 ° C. and a pressure of 1 kg / cm 2. An electromagnetic wave shielding sheet having a bonding layer having insulation and a conductive layer provided on one surface of the bonding layer and having a plurality of openings has been proposed (for example, see Patent Document 2). In this electromagnetic wave shielding sheet, the impedance of the printed wiring board is adjusted by providing an opening in the conductive layer and directly connecting to the ground wiring of the printed wiring board through a through hole provided in the printed wiring board.
　しかし、上記の電磁波シールドシートを用いたプリント配線板では、電磁波シールドシートの導電層とプリント配線板のグランド配線との接続が直接行われるため、導電層の硬さ及びパターンの線幅、プリント配線板に設ける貫通孔の大きさ等に制限があり、さらに接続信頼性が不十分であるという問題があった。例えば、電磁波シールドシートの導電層のパターンの線幅を、プリント配線板のグランド配線より太くした場合、導電層とグランド配線の接続が難しくなり、仮に直接接続ができたとしても、熱硬化性樹脂層の接着面積が非常に小さくなるため接続信頼性が不十分となる問題があった。また、プリント配線板のグランド配線上に設ける貫通孔が小さい場合も同様に、接続信頼性が不十分となる。さらに、プリント配線板の絶縁保護層が厚いとグランド配線の上に設けた貫通孔の高さも高くなり、電磁波シールドシートの導電層が柔軟性に乏しい場合は、貫通孔の段差で導電層が断線する問題もあった。 However, in the printed wiring board using the electromagnetic wave shielding sheet, the conductive layer of the electromagnetic wave shielding sheet and the ground wiring of the printed wiring board are directly connected, so the hardness of the conductive layer, the line width of the pattern, the printed wiring There is a problem that the size of the through hole provided in the plate is limited, and the connection reliability is insufficient. For example, when the line width of the pattern of the conductive layer of the electromagnetic wave shielding sheet is made thicker than the ground wiring of the printed wiring board, it becomes difficult to connect the conductive layer and the ground wiring. Since the adhesion area of the layer becomes very small, there is a problem that connection reliability becomes insufficient. Similarly, when the through hole provided on the ground wiring of the printed wiring board is small, the connection reliability is insufficient. Furthermore, if the insulating protective layer of the printed wiring board is thick, the height of the through hole provided on the ground wiring also increases, and if the conductive layer of the electromagnetic wave shield sheet is not flexible, the conductive layer is disconnected at the step of the through hole. There was also a problem to do.
特開平７－１２２８８２号公報Japanese Patent Laid-Open No. 7-122882 特開２０１３－１６８６４３号公報JP 2013-168643 A
　本発明が解決しようとする課題は、プリント配線板に用いることができ、ノイズ対策として高いシールド性を有し、かつ、プリント配線板のインピーダンスを信号配線のパターン幅を小さくしなくても制御できるシールドフィルムを提供することである。また、前記シールドフィルムと、プリント配線板のグランド配線との接続信頼性に優れ、インピーダンスの制御における設計の自由度が高いシールドプリント配線板を提供することである。さらには、前記シールドフィルム及びシールドプリント配線板の製造方法を提供することである。 The problem to be solved by the present invention can be used for a printed wiring board, has a high shielding property as a noise countermeasure, and can control the impedance of the printed wiring board without reducing the pattern width of the signal wiring. It is to provide a shield film. Another object of the present invention is to provide a shielded printed wiring board having excellent connection reliability between the shield film and the ground wiring of the printed wiring board and having a high degree of design freedom in impedance control. Furthermore, it is providing the manufacturing method of the said shield film and a shield printed wiring board.
　本発明者らは、上記の課題を解決すべく鋭意研究した結果、信号配線とグランド配線及び絶縁保護層が設けられたプリント配線板に、導電性接着剤層、パターン化された銅めっき層、絶縁保護層で構成されるシールドフィルムを設けることで、プリント配線板のインピーダンスが信号配線のパターン幅を小さくしなくても制御でき、さらにシールドフィルムとプリント配線板のグランド配線との接続信頼性にも優れることを見出し、本発明を完成した。 As a result of diligent research to solve the above problems, the present inventors have established a conductive adhesive layer, a patterned copper plating layer on a printed wiring board provided with a signal wiring, a ground wiring, and an insulating protective layer, By providing a shield film composed of an insulating protective layer, the impedance of the printed wiring board can be controlled without reducing the pattern width of the signal wiring, and the connection reliability between the shielding film and the ground wiring of the printed wiring board is improved. The present invention was completed.
　すなわち、本発明は、ベース絶縁基材上に信号配線とグランド配線及び第一絶縁保護層が設けられたプリント配線板用のシールドフィルムであって、前記第一絶縁保護層上の全面に積層された導電性接着剤層と、前記導電性接着剤層上に膜厚０．２～２０μｍ、開口率１０～９０％でパターン化された銅めっき層と、前記銅めっき層上に導電性インクを用いて形成した層（Ａ）と、前記導電性接着剤層及び前記銅めっき層及び前記層（Ａ）上に第二絶縁保護層とを有することを特徴とするシールドフィルム及びこのシールドフィルムを有するシールドプリント配線板に関するものである。また、前記シールドフィルム及びシールドプリント配線板の製造方法に関するものである。 That is, the present invention is a shield film for a printed wiring board in which signal wiring, ground wiring, and a first insulating protective layer are provided on a base insulating base material, and is laminated on the entire surface of the first insulating protective layer. A conductive adhesive layer, a copper plating layer patterned with a film thickness of 0.2 to 20 μm and an aperture ratio of 10 to 90% on the conductive adhesive layer, and a conductive ink on the copper plating layer. A shield film comprising the layer (A) formed by using the conductive adhesive layer, the copper plating layer, and a second insulating protective layer on the layer (A), and the shield film. The present invention relates to a shield printed wiring board. Moreover, it is related with the manufacturing method of the said shield film and a shield printed wiring board.
　本発明のシールドフィルム及びシールドプリント配線板は、高い周波数で使用するプリント配線板に求められるインピーダンスの制御に関し、信号配線のパターン幅のみで制御するのではなく、シールドフィルム側の銅めっき層パターンの開口率をインピーダンス制御の１つの因子とすることで、信号配線の線幅の自由度を維持しながらインピーダンスの整合を取ることができる。従って、例えば、携帯電話、ノート型パソコン、スマートフォン、タブレット型パソコン、ウェアラブルデバイス、デジタルスチルカメラ、デジタルビデオカメラなどの電子機器の内部で使用されるシールドプリント配線板として好適に使用することができる。 The shield film and shield printed wiring board of the present invention are related to the impedance control required for a printed wiring board used at a high frequency, and are not controlled only by the pattern width of the signal wiring, but the copper plating layer pattern on the shield film side. By making the aperture ratio one factor of impedance control, impedance matching can be achieved while maintaining the freedom of the line width of the signal wiring. Therefore, for example, it can be suitably used as a shield printed wiring board used inside an electronic apparatus such as a mobile phone, a notebook computer, a smartphone, a tablet computer, a wearable device, a digital still camera, and a digital video camera.
図１は、本発明のシールドプリント配線板の断面を表したものである。FIG. 1 shows a cross section of a shielded printed wiring board according to the present invention. 図２は、本発明のシールドプリント配線板の断面を表したもので、第二絶縁保護層と導電性インクを用いて形成した層との間に高分子層を設けたものである。FIG. 2 shows a cross section of the shield printed wiring board of the present invention, in which a polymer layer is provided between the second insulating protective layer and a layer formed using conductive ink.
　本発明のシールドフィルムは、ベース絶縁基材上に信号配線とグランド配線及び第一絶縁保護層が設けられたプリント配線板用のシールドフィルムであって、
前記第一絶縁保護層上の全面に積層された導電性接着剤層と、
前記導電性接着剤層上に膜厚０．２～２０μｍ、開口率１０～９０％でパターン化された銅めっき層と、
前記銅めっき層上に導電性インクを用いて形成した層（Ａ）と、
前記導電性接着剤層及び前記銅めっき層及び前記層（Ａ）上に第二絶縁保護層とを有するものである。 The shield film of the present invention is a shield film for a printed wiring board in which a signal wiring, a ground wiring, and a first insulating protective layer are provided on a base insulating base material,
A conductive adhesive layer laminated on the entire surface of the first insulating protective layer;
A copper plating layer patterned with a film thickness of 0.2 to 20 μm and an aperture ratio of 10 to 90% on the conductive adhesive layer;
A layer (A) formed using a conductive ink on the copper plating layer;
It has a 2nd insulating protective layer on the said conductive adhesive layer, the said copper plating layer, and the said layer (A).
　前記ベース絶縁基材は、プリント配線板の基材となるものである。前記ベース絶縁基材の材質としては、例えば、ポリイミド、ポリアミドイミド、ポリアミド、ポリエチレンテレフタレート等のポリエステル樹脂、ポリエチレンナフタレート、ポリカーボネート、ＡＢＳ（アクリロニトリル－ブタジエン－スチレン）樹脂、ポリメチルメタクリレート等のアクリル樹脂、フェノール樹脂、ポリフッ化ビニリデン等のフッ素樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール、ポリエチレン、ポリプロピレン、ポリウレタン、ＬＣＰ（液晶ポリマー）、ＰＥＥＫ（ポリエーテルエーテルケトン）樹脂、ＰＥＩ（ポリエーテルイミド）樹脂、ＰＰＳ（ポリフェニレンサルファイド）樹脂、ＰＳＦ（ポリサルフォン）樹脂、ＰＥＳ（ポリエーテルサルフォン）樹脂、ポリアリレート樹脂、ＰＢＴ（ポリブチレンテレフタレート）樹脂、シリコーン樹脂、不飽和ポリエステル樹脂、ポリアセタール、ナイロン、セラミックス、アルミナ、ムライト、ステアタイト、フォルステライト、ジルコニア、ガラス、ガラス・エポキシ樹脂、ガラスポリイミド、紙フェノール、セルロースナノファイバー等が挙げられる。 The base insulating base material is a base material for a printed wiring board. Examples of the material of the base insulating base material include, for example, polyester resins such as polyimide, polyamideimide, polyamide, and polyethylene terephthalate, polyethylene naphthalate, polycarbonate, ABS (acrylonitrile-butadiene-styrene) resin, acrylic resin such as polymethyl methacrylate, Fluorine resin such as phenol resin, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene, polypropylene, polyurethane, LCP (liquid crystal polymer), PEEK (polyether ether ketone) resin, PEI (polyether imide) resin , PPS (polyphenylene sulfide) resin, PSF (polysulfone) resin, PES (polyethersulfone) resin, polyarylate resin, PBT ( Ribbylene terephthalate) resin, silicone resin, unsaturated polyester resin, polyacetal, nylon, ceramics, alumina, mullite, steatite, forsterite, zirconia, glass, glass / epoxy resin, glass polyimide, paper phenol, cellulose nanofiber, etc. Can be mentioned.
　また、前記ベース絶縁基材としては、例えば、ポリエステル繊維、ポリアミド繊維、アラミド繊維等の合成繊維；綿、麻等の天然繊維などからなる基材を用いることもできる。前記繊維には、予め加工が施されていてもよい。 As the base insulating base material, for example, a base material made of synthetic fibers such as polyester fiber, polyamide fiber, and aramid fiber; natural fibers such as cotton and hemp can be used. The fibers may be processed in advance.
　前記ベース絶縁基材としては、後述する本発明のシールドプリント配線板が、折り曲げ可能な柔軟性を求められる用途に用いられる場合、柔軟でフレキシブルな支持体を用いることが好ましい。具体的には、フィルムまたはシート状の支持体を用いることが好ましい。 As the base insulating substrate, it is preferable to use a flexible and flexible support when the shield printed wiring board of the present invention to be described later is used for applications that require bending flexibility. Specifically, it is preferable to use a film or sheet-like support.
　フィルムまたはシート状のベース絶縁基材としては、例えば、ポリエチレンテレフタレートフィルム、ポリイミドフィルム、ポリエチレンナフタレートフィルム、ＬＣＰ（液晶ポリマー）フィルム等が挙げられる。 Examples of the film or sheet-like base insulating base material include a polyethylene terephthalate film, a polyimide film, a polyethylene naphthalate film, and an LCP (liquid crystal polymer) film.
　また、前記ベース絶縁基材は、後述する信号配線やグランド配線との密着性を向上するため、必要に応じて、その表面をサンドブラスト法、溶剤処理法等による表面の凹凸化処理、電気的処理（コロナ放電処理、大気圧プラズマ処理）、クロム酸処理、火炎処理、熱風処理、オゾン・紫外線・電子線照射処理、酸化処理等により処理をしたものを使用することができる。 In addition, the base insulating base material improves the adhesion with signal wiring and ground wiring, which will be described later, so that the surface is roughened by sandblasting, solvent treatment, etc. (Corona discharge treatment, atmospheric pressure plasma treatment), chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet ray / electron beam irradiation treatment, oxidation treatment, etc. can be used.
　前記ベース絶縁基材の形状がフィルム状またはシート状の場合、フィルム状またはシート状の支持体の厚さは、通常、１～５，０００μｍ程度であることが好ましく、１～３００μｍ程度の厚さであることがより好ましい。また、本発明の導電性パターンをフレキシブルプリント基板等の屈曲性を求められるものに用いる場合には、前記ベース絶縁基材として、１～２００μｍ程度の厚さのフィルム状のものを用いることが好ましい。 When the shape of the base insulating substrate is a film or sheet, the thickness of the film or sheet support is preferably about 1 to 5,000 μm, and preferably about 1 to 300 μm. It is more preferable that When the conductive pattern of the present invention is used for a flexible printed circuit board or the like that requires flexibility, it is preferable to use a film-like material having a thickness of about 1 to 200 μm as the base insulating base material. .
　前記ベース絶縁基材としては、後述する信号配線やグランド配線を形成するために、市販の銅張基材を使用することができる。銅張基材を使用する場合、銅張基材上にレジスト材を設け、フォトマスクでパターンを露光した後、エッチング処理で配線部以外の銅を取り除いて配線パターンを形成することができる。 As the base insulating base material, a commercially available copper-clad base material can be used in order to form signal wiring and ground wiring described later. When using a copper clad base material, after providing a resist material on a copper clad base material and exposing a pattern with a photomask, copper other than a wiring part can be removed by an etching process to form a wiring pattern.
　また、信号配線やグランド配線は、前述の銅を主成分とした配線が使用できるとともに、その他の導電性物質で構成されていても良く、例えば、銀を主体とする導電性インクを印刷して形成した配線パターンを使用することも可能である。また、この導電性インクのパターン上に銅めっきやニッケルめっき等で厚膜化して配線とすることもできる。 The signal wiring and ground wiring can be made of the above-described copper-based wiring, and may be composed of other conductive materials, for example, by printing conductive ink mainly composed of silver. It is also possible to use the formed wiring pattern. Further, the conductive ink pattern can be made into a wiring by thickening it by copper plating, nickel plating or the like.
　本発明のシールドプリント配線板は、信号配線とグランド配線の上に第一絶縁保護層が設けられる。この第一絶縁保護層としては、ポリイミドフィルム等の片面に接着剤を塗布したものや、感光性カバーレイフィルム等の感光性を有しており露光現像によりパターンが形成できるものや、液状カバーレイ、感光性液状カバーレイ、ソルダーレジスト等の液状の材料を塗工して絶縁保護層を形成することもできる。 The shield printed wiring board of the present invention is provided with a first insulating protective layer on the signal wiring and the ground wiring. Examples of the first insulating protective layer include a polyimide film or the like coated with an adhesive, a photosensitive coverlay film or the like having a photosensitivity and capable of forming a pattern by exposure and development, a liquid coverlay. Alternatively, an insulating protective layer can be formed by applying a liquid material such as a photosensitive liquid coverlay or a solder resist.
　次に、本発明のシールドフィルムは、第一絶縁保護層上の全面に積層される導電性接着剤層と、前記導電性接着剤層上に膜厚０．２～２０μｍ、開口率１０～９０％でパターン化された金属層と、第二絶縁保護層を有することを特徴とするシールドフィルムである。 Next, the shield film of the present invention includes a conductive adhesive layer laminated on the entire surface of the first insulating protective layer, a film thickness of 0.2 to 20 μm, and an aperture ratio of 10 to 90 on the conductive adhesive layer. It is a shield film characterized by having a metal layer patterned by% and a second insulating protective layer.
　前記導電性接着剤層は、導電性物質を含有する接着性樹脂からなり、導電性物質としては、例えば、銅、銀、ニッケル、アルミニウム等の金属粉や金属ウィスカー、銅粉に銀めっきを施した銀コート銅粉、ニッケル粉に銀めっきを施した銀コートニッケル粉、ニッケル粉に金めっきを施した金コートニッケル粉、カーボン、樹脂粒子やガラスビーズに金属めっきを施したフィラー等が挙げられる。これらの導電性物質は、１種で用いることも２種以上併用することもできる。 The conductive adhesive layer is made of an adhesive resin containing a conductive substance. Examples of the conductive substance include metal plating such as copper, silver, nickel, and aluminum, metal whiskers, and silver plating on copper powder. Silver-coated copper powder, silver-coated nickel powder obtained by applying silver plating to nickel powder, gold-coated nickel powder obtained by applying gold plating to nickel powder, fillers obtained by applying metal plating to carbon, resin particles and glass beads, etc. . These conductive materials can be used alone or in combination of two or more.
　前記接着性樹脂は、スチレン樹脂、酢酸ビニル樹脂、ポリエステル樹脂、ポリエチレンやポリプロピレン等のポリオレフィン樹脂、アミド樹脂、アミドイミド樹脂、スチレン－ブタジエン樹脂、アクリロニトリル－ブタジエン樹脂、（メタ）アクリル－ブタジエン樹脂、（メタ）アクリル樹脂、ウレタン樹脂等の熱可塑性樹脂；フェノール樹脂、エポキシ樹脂、メラミン樹脂、アルキッド樹脂等の熱硬化性樹脂；ウレタンアクリレート、エポキシアクリレート、アクリルアクリレート等の紫外線硬化型樹脂などが挙げられる。これらの接着性樹脂は、１種で用いることも２種以上併用することもできる。 The adhesive resin includes styrene resin, vinyl acetate resin, polyester resin, polyolefin resin such as polyethylene and polypropylene, amide resin, amideimide resin, styrene-butadiene resin, acrylonitrile-butadiene resin, (meth) acryl-butadiene resin, (meth ) Thermoplastic resins such as acrylic resins and urethane resins; Thermosetting resins such as phenol resins, epoxy resins, melamine resins, and alkyd resins; UV curable resins such as urethane acrylates, epoxy acrylates, and acrylic acrylates. These adhesive resins can be used alone or in combination of two or more.
　本発明のシールドフィルムは、前記導電性接着剤層上に膜厚０．２～２０μｍ、開口率１０～９０％でパターン化された銅めっき層を有する。前記銅めっき層のパターンとしては、その形状には特に制限はないが、要求されるシールド性、制御するインピーダンス等に応じて適宜選択することができる。前記銅めっき層の具体的なパターンとしては、メッシュ状のパターンが好ましく、開口部の形状は、正三角形、二等辺三角形、直角三角形等の三角形；正方形、長方形、菱形、平行四辺形、台形等の四角形；（正）五角形、（正）六角形、（正）八角形、（正）十二角形等の（正）ｎ角形（ｎは５以上の整数）；円、楕円、星形などの幾何学図形が挙げられる。開口部は、等間隔で配置されていることが、電磁波のシールド性に優れるため好ましい。また、パターンの開口率は１０～９０％の範囲とすることが好ましい。開口率は、シールドプリント配線板のインピーダンスを制御する上で重要な因子となるが、開口率が１０％未満の場合、シールドプリント配線板の信号配線の線幅を調整することなくインピーダンスを制御できる範囲が小さくなり、開口率が９０％を超えると、シールドプリント配線板の電磁波をシールドする効果が小さくなる。 The shield film of the present invention has a copper plating layer patterned with a film thickness of 0.2 to 20 μm and an aperture ratio of 10 to 90% on the conductive adhesive layer. The pattern of the copper plating layer is not particularly limited, but can be appropriately selected according to required shielding properties, impedance to be controlled, and the like. The specific pattern of the copper plating layer is preferably a mesh pattern, and the shape of the opening is a triangle such as a regular triangle, an isosceles triangle, a right triangle; a square, a rectangle, a rhombus, a parallelogram, a trapezoid, and the like. (Positive) pentagons, (positive) hexagons, (positive) octagons, (positive) dodecagons, etc. (positive) n-gons (n is an integer greater than or equal to 5); circles, ellipses, stars, etc. Examples include geometric figures. It is preferable that the openings are arranged at equal intervals because of excellent shielding properties against electromagnetic waves. The aperture ratio of the pattern is preferably in the range of 10 to 90%. The aperture ratio is an important factor in controlling the impedance of the shield printed wiring board. When the aperture ratio is less than 10%, the impedance can be controlled without adjusting the line width of the signal wiring of the shield printed wiring board. When the range becomes small and the aperture ratio exceeds 90%, the effect of shielding the electromagnetic waves of the shield printed wiring board becomes small.
　前記銅めっき層の膜厚は０．２～２０μｍの範囲である。銅めっき層の膜厚が０．２μｍ未満の場合、シールドプリント配線板の電磁波をシールドする効果が小さくなり、銅めっき層の膜厚が２０μｍを超えるとシールドプリント配線板自体を薄型化するという要求を満たすことが難しくなるとともに、フレキシブルプリント配線板として使用する場合においては、屈曲性が大幅に低下する問題がある。また、銅めっき層の膜厚は、シールドプリント配線板のインピーダンスの制御にも関係する因子であり、０．２～８μｍの範囲とすることが好ましい。 The film thickness of the copper plating layer is in the range of 0.2 to 20 μm. When the film thickness of the copper plating layer is less than 0.2 μm, the effect of shielding the electromagnetic wave of the shield printed wiring board is reduced. When the film thickness of the copper plating layer exceeds 20 μm, the shield printed wiring board itself is required to be thinned. In addition, it is difficult to satisfy the requirements, and when used as a flexible printed wiring board, there is a problem that the flexibility is greatly lowered. The film thickness of the copper plating layer is a factor related to the control of the impedance of the shield printed wiring board, and is preferably in the range of 0.2 to 8 μm.
　前記銅めっき層の形成方法としては、銅箔から開口部のパターンをエッチング処理で取り除く方法が挙げられるが、この方法では製造方法が複雑となることや、銅めっき層を薄膜化しにくい問題がある。そこで、本発明では、前記銅めっき層を所望とする開口率でパターン化することが容易で、インピーダンスの制御における設計の自由度が高くなることから、後述する導電性インクを用いて形成した層（Ａ）でパターンを作製した後、その上に前記銅めっき層を形成する。 Examples of the method of forming the copper plating layer include a method of removing the pattern of the opening from the copper foil by etching, but this method has a problem that the manufacturing method is complicated and the copper plating layer is difficult to be thinned. . Therefore, in the present invention, the copper plating layer can be easily patterned with a desired aperture ratio, and the degree of freedom in design in controlling the impedance is increased. Therefore, a layer formed using a conductive ink described later. After producing the pattern in (A), the copper plating layer is formed thereon.
　前記導電性インクは、上記の通り銅めっき層の下地としてパターンを作製するために使用されるが、その上に形成する銅めっき層との密着性や、銅めっき時のめっき析出性に優れることから、導電性物質（ａ２）として金属ナノ粒子を含有するものが好ましい。さらに、前記金属ナノ粒子は、後述する第二絶縁保護層との密着性に優れることから、高分子分散剤により分散された金属ナノ粒子であることが好ましい。 The conductive ink is used for producing a pattern as a base of a copper plating layer as described above, and is excellent in adhesion to a copper plating layer formed on the copper plating layer and plating deposition at the time of copper plating. Therefore, those containing metal nanoparticles as the conductive substance (a2) are preferable. Furthermore, since the said metal nanoparticle is excellent in adhesiveness with the 2nd insulating protective layer mentioned later, it is preferable that it is the metal nanoparticle disperse | distributed with the polymer dispersing agent.
　前記高分子分散剤は、金属ナノ粒子に配位する官能基を有する高分子が好ましい。前記官能基としては、例えば、カルボキシル基、アミノ基、シアノ基、アセトアセトキシ基、リン原子含有基、チオール基、チオシアナト基、グリシナト基等が挙げられる。 The polymer dispersant is preferably a polymer having a functional group coordinated to the metal nanoparticles. Examples of the functional group include a carboxyl group, an amino group, a cyano group, an acetoacetoxy group, a phosphorus atom-containing group, a thiol group, a thiocyanato group, and a glycinato group.
　前記金属ナノ粒子としては、遷移金属またはその化合物が挙げられ、前記遷移金属の中でもイオン性の遷移金属が好ましい。前記イオン性の遷移金属としては、例えば、銅、銀、金、ニッケル、パラジウム、白金、コバルト等の金属やこれら金属の複合体が挙げられる。これらの金属ナノ粒子は、１種で用いることも２種以上併用することもできる。また、これらの金属ナノ粒子の中でも、特に酸化劣化などの取り扱い上の問題点が少ないことやコストの面から、銀ナノ粒子が好ましい。 Examples of the metal nanoparticles include a transition metal or a compound thereof, and an ionic transition metal is preferable among the transition metals. Examples of the ionic transition metal include metals such as copper, silver, gold, nickel, palladium, platinum, and cobalt, and composites of these metals. These metal nanoparticles can be used alone or in combination of two or more. Among these metal nanoparticles, silver nanoparticles are preferable from the viewpoints of handling problems such as oxidative degradation and cost.
　また、前記導電性インクに含まれる導電性物質（ａ２）は、金属ナノ粒子に代えて、めっき核剤を用いることもできる。その場合には、前記遷移金属の酸化物、有機物によって表面被覆された金属等を使用することができる。これらのめっき核剤は、１種で用いることも２種以上併用することもできる。 In addition, the conductive substance (a2) contained in the conductive ink can use a plating nucleating agent in place of the metal nanoparticles. In that case, an oxide of the transition metal, a metal whose surface is coated with an organic substance, or the like can be used. These plating nucleating agents can be used alone or in combination of two or more.
　前記遷移金属の酸化物は、通常、不活性（絶縁）な状態であるが、例えば、ジメチルアミノボラン等の還元剤を用いて処理することによって金属を露出させ、活性（導電性）を付与することができる。 The transition metal oxide is usually in an inactive (insulating) state. For example, the metal is exposed by treatment with a reducing agent such as dimethylaminoborane to impart activity (conductivity). be able to.
　また、前記有機物によって表面被覆された金属としては、乳化重合法等によって形成した樹脂粒子（有機物）中に金属を内在させたものが挙げられる。これらは、通常、不活性（絶縁）な状態であるが、例えば、レーザー等を用いて前記有機物を除去することによって、金属を露出させ、活性（導電性）を付与することできる。 Further, examples of the metal whose surface is coated with the organic substance include those in which a metal is contained in resin particles (organic substance) formed by an emulsion polymerization method or the like. These are usually in an inactive (insulating) state. However, for example, by removing the organic substance using a laser or the like, the metal can be exposed to impart activity (conductivity).
　前記導電性物質（ａ２）としては、１～１００ｎｍ程度の平均粒子径を有する粒子状のものを使用することが好ましく、１～５０ｎｍの平均粒子径を有するものを使用することが、マイクロメートルオーダーの平均粒子径を有する導電性物質を用いる場合と比較して、微細な導電性パターンが形成でき、後述する焼成後の抵抗値をより低下できることからより好ましい。なお、本発明において、平均粒子径は、前記導電性物質（ａ２）を分散良溶媒にて希釈し、動的光散乱法により測定した体積平均値である。この測定にはマイクロトラック社製「ナノトラックＵＰＡ」を用いることができる。 The conductive substance (a2) is preferably in the form of particles having an average particle diameter of about 1 to 100 nm, preferably having an average particle diameter of 1 to 50 nm. Compared to the case of using a conductive material having an average particle size of 1, a fine conductive pattern can be formed, and the resistance value after firing described later can be further reduced, which is more preferable. In the present invention, the average particle diameter is a volume average value measured by a dynamic light scattering method after diluting the conductive substance (a2) with a dispersion good solvent. For this measurement, “Nanotrack UPA” manufactured by Microtrack Corporation can be used.
　前記導電性インクを用いて形成した層（Ａ）は、後述する第二絶縁保護層の上に形成されるが、後述する第二絶縁保護層の表面と前記層（Ａ）との密着性をより向上するため、この第二絶縁保護層を形成する高分子は、後述する反応性官能基［Ｙ］を有しているものが好ましい。 The layer (A) formed using the conductive ink is formed on the second insulating protective layer described later, but the adhesion between the surface of the second insulating protective layer described later and the layer (A) is improved. In order to further improve, the polymer forming the second insulating protective layer preferably has a reactive functional group [Y] described later.
　また、後述する第二絶縁保護層を形成する高分子が、後述する反応性官能基［Ｙ］を有していない場合でも、第二絶縁保護層の表面に高分子を塗布、乾燥して高分子層（Ｂ）を設けた後、その上に前記層（Ａ）を形成することで、後述する第二絶縁保護層の表面と前記層（Ａ）との密着性をより向上することができる。また、前記高分子層（Ｂ）を形成する高分子は、後述する反応性官能基［Ｙ］を有しているものが好ましい。 Even when the polymer forming the second insulating protective layer described later does not have the reactive functional group [Y] described later, the polymer is applied to the surface of the second insulating protective layer, dried, and dried. After providing the molecular layer (B), the adhesiveness between the surface of the second insulating protective layer described later and the layer (A) can be further improved by forming the layer (A) thereon. . The polymer forming the polymer layer (B) preferably has a reactive functional group [Y] described later.
　後述する反応性官能基［Ｙ］を有する高分子層（Ｂ）を設ける場合には、前記導電性インクとしては、前記銅めっき層と後述する第二絶縁保護層との密着性をさらに向上させるため、反応性官能基［Ｘ］を有する化合物（ａ１）及び前記導電性物質（ａ２）を含有するものが好ましい。 When the polymer layer (B) having a reactive functional group [Y] described later is provided, the conductive ink further improves the adhesion between the copper plating layer and a second insulating protective layer described later. Therefore, what contains the compound (a1) which has reactive functional group [X], and the said electroconductive substance (a2) is preferable.
　前記化合物（ａ１）が有する反応性官能基［Ｘ］は、後述する反応性官能基［Ｙ］との結合に関与するものであり、具体例としては、アミノ基、アミド基、アルキロールアミド基、カルボキシル基、無水カルボキシル基、カルボニル基、アセトアセトキシ基、エポキシ基、脂環エポキシ基、オキセタン環、ビニル基、アリル基、（メタ）アクリロイル基、（ブロック化）イソシアネート基、（アルコキシ）シリル基等を有する化合物、シルセスキオキサン化合物等が挙げられる。 The reactive functional group [X] possessed by the compound (a1) is involved in binding to the reactive functional group [Y] described later, and specific examples include an amino group, an amide group, and an alkylolamide group. , Carboxyl group, anhydrous carboxyl group, carbonyl group, acetoacetoxy group, epoxy group, alicyclic epoxy group, oxetane ring, vinyl group, allyl group, (meth) acryloyl group, (blocked) isocyanate group, (alkoxy) silyl group Etc., silsesquioxane compounds, and the like.
　特に、後述する第二絶縁保護層との密着性をより向上させるため、前記反応性官能基［Ｘ］が塩基性窒素原子含有基であることが好ましい。 In particular, the reactive functional group [X] is preferably a basic nitrogen atom-containing group in order to further improve the adhesion to the second insulating protective layer described later.
　前記塩基性窒素原子含有基を有する化合物中の塩基性窒素原子含有基としては、例えばイミノ基、１級アミノ基、２級アミノ基等が挙げられる。 Examples of the basic nitrogen atom-containing group in the compound having a basic nitrogen atom-containing group include an imino group, a primary amino group, and a secondary amino group.
　また、１分子中に複数の塩基性窒素原子含有基を有する化合物（ａ１）を用いることで、前記塩基性窒素原子含有基の一方は、前記層（Ａ）のパターンを形成した際に、後述する第二絶縁保護層を形成する高分子、または前記高分子層（Ｂ）を形成する高分子が有する反応性官能基［Ｙ］との結合に関与し、他方は、前記層（Ａ）中に含まれる銀等の導電性物質（ａ２）との相互作用に寄与し、最終的に得られる前記銅めっき層と第二絶縁保護層との密着性をさらに向上できるため好ましい。 Further, by using the compound (a1) having a plurality of basic nitrogen atom-containing groups in one molecule, one of the basic nitrogen atom-containing groups is described later when the pattern of the layer (A) is formed. Involved in bonding with the reactive functional group [Y] of the polymer forming the second insulating protective layer or the polymer forming the polymer layer (B), and the other is in the layer (A) This is preferable because it contributes to the interaction with the conductive material (a2) such as silver contained in and can further improve the adhesion between the finally obtained copper plating layer and the second insulating protective layer.
　前記塩基性窒素原子含有基を有する化合物（ａ１）は、前記導電性物質（ａ２）の分散安定性、及び後述する第二絶縁保護層との密着性をより向上できることから、ポリアルキレンイミン、または、オキシエチレン単位を含むポリオキシアルキレン構造を有するポリアルキレンイミンが好ましい。 Since the compound (a1) having a basic nitrogen atom-containing group can further improve the dispersion stability of the conductive substance (a2) and the adhesion to the second insulating protective layer described later, a polyalkyleneimine, or A polyalkyleneimine having a polyoxyalkylene structure containing an oxyethylene unit is preferred.
　前記を有するポリアルキレンイミンとしては、ポリエチレンイミンとポリオキシアルキレンとが、直鎖状の結合したものであってもよく、前記ポリエチレンイミンからなる主鎖に対して、その側鎖に前記ポリオキシアルキレンがグラフトしたものであってもよい。 The polyalkyleneimine having the above may be a linear bond of polyethyleneimine and polyoxyalkylene, and the polyoxyalkylene is present in the side chain of the main chain composed of polyethyleneimine. May be grafted.
　前記ポリオキシアルキレン構造を有するポリアルキレンイミンの具体例としては、ポリエチレンイミンとポリオキシエチレンとのブロック共重合体、ポリエチレンイミンの主鎖中に存在するイミノ基の一部にエチレンオキサイドを付加反応させてポリオキシエチレン構造を導入したもの、ポリアルキレンイミンが有するアミノ基と、ポリオキシエチレングリコールが有する水酸基と、エポキシ樹脂が有するエポキシ基とを反応させたもの等が挙げられる。 Specific examples of the polyalkyleneimine having the polyoxyalkylene structure include a block copolymer of polyethyleneimine and polyoxyethylene, and an addition reaction of ethylene oxide with a part of imino group present in the main chain of polyethyleneimine. Examples thereof include those obtained by introducing a polyoxyethylene structure, those obtained by reacting an amino group possessed by polyalkyleneimine, a hydroxyl group possessed by polyoxyethylene glycol, and an epoxy group possessed by an epoxy resin.
　前記ポリアルキレンイミンの市販品としては、株式会社日本触媒製の「エポミン（登録商標）ＰＡＯシリーズ」の「ＰＡＯ２００６Ｗ」、「ＰＡＯ３０６」、「ＰＡＯ３１８」、「ＰＡＯ７１８」等が挙げられる。 Examples of commercially available products of the polyalkyleneimine include “PAO2006W”, “PAO306”, “PAO318”, “PAO718” and the like of “Epomin (registered trademark) PAO series” manufactured by Nippon Shokubai Co., Ltd.
　前記ポリアルキレンイミンの数平均分子量は、３，０００～３０，０００の範囲が好ましい。 The number average molecular weight of the polyalkyleneimine is preferably in the range of 3,000 to 30,000.
　前記化合物（ａ１）が有する反応性官能基［Ｘ］が、カルボキシル基、アミノ基、シアノ基、アセトアセトキシ基、リン原子含有基、チオール基、チオシアナト基、グリシナト基等である場合は、これらの官能基は金属ナノ粒子と配位する官能基としても機能するため、前記化合物（ａ１）は金属ナノ粒子の高分子分散剤としても用いることができる。 When the reactive functional group [X] of the compound (a1) is a carboxyl group, an amino group, a cyano group, an acetoacetoxy group, a phosphorus atom-containing group, a thiol group, a thiocyanato group, a glycinato group, etc. Since the functional group also functions as a functional group that coordinates with the metal nanoparticles, the compound (a1) can also be used as a polymer dispersant for the metal nanoparticles.
　前記導電性インクは、後述する各種印刷方式での印刷適性を付与するため、溶媒を用いて適正な粘度にすることが好ましい。前記溶媒としては、例えば、蒸留水、イオン交換水、純水、超純水等の水性媒体；アルコール溶剤、エーテル溶剤、ケトン溶剤、エステル溶剤等の有機溶剤が挙げられる。 The conductive ink preferably has an appropriate viscosity using a solvent in order to impart printability in various printing methods described later. Examples of the solvent include aqueous media such as distilled water, ion-exchanged water, pure water, and ultrapure water; and organic solvents such as alcohol solvents, ether solvents, ketone solvents, and ester solvents.
　前記アルコール溶剤またはエーテル溶剤としては、例えば、メタノール、エタノール、ｎ－プロパノール、イソプロピルアルコール、ｎ－ブタノール、イソブチルアルコール、ｓｅｃ－ブタノール、ｔｅｒｔ－ブタノール、ヘプタノール、ヘキサノール、オクタノール、ノナノール、デカノール、ウンデカノール、ドデカノール、トリデカノール、テトラデカノール、ペンタデカノール、ステアリルアルコール、アリルアルコール、シクロヘキサノール、テルピネオール、ターピネオール、ジヒドロターピネオール、２－エチル－１，３－ヘキサンジオール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオール、グリセリン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、テトラエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノブチルエーテル等が挙げられる。 Examples of the alcohol solvent or ether solvent include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol. , Tridecanol, tetradecanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydroterpineol, 2-ethyl-1,3-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, Propylene glycol, dipropylene glycol, 1,2-butanediol, 1 3-butanediol, 1,4-butanediol, 2,3-butanediol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, Tetraethylene glycol 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 monobutyl ether, tripropylene Glycol monobutyl ether.
　前記ケトン溶剤としては、例えば、アセトン、シクロヘキサノン、メチルエチルケトン等が挙げられる。また、前記エステル溶剤としては、例えば、酢酸エチル、酢酸ブチル、３―メトキシブチルアセテート、３－メトキシ－３－メチル－ブチルアセテート等が挙げられる。さらに、その他の有機溶剤として、トルエン等の炭化水素溶剤、特に炭素原子数８以上の炭化水素溶剤が挙げられる。 Examples of the ketone solvent include acetone, cyclohexanone, methyl ethyl ketone, and the like. Examples of the ester solvent include ethyl acetate, butyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-butyl acetate and the like. Furthermore, other organic solvents include hydrocarbon solvents such as toluene, particularly hydrocarbon solvents having 8 or more carbon atoms.
　前記炭素原子数８以上の炭化水素溶剤としては、例えば、オクタン、ノナン、デカン、ドデカン、トリデカン、テトラデカン、シクロオクタン、キシレン、メシチレン、エチルベンゼン、ドデシルベンゼン、テトラリン、トリメチルベンゼンシクロヘキサン等の非極性溶剤が挙げられ、他の溶媒と必要に応じて組み合わせて用いることができる。さらに、混合溶剤であるミネラルスピリット、ソルベントナフサ等の溶媒を併用することもできる。 Examples of the hydrocarbon solvent having 8 or more carbon atoms include nonpolar solvents such as octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, mesitylene, ethylbenzene, dodecylbenzene, tetralin, and trimethylbenzenecyclohexane. Can be used in combination with other solvents as necessary. Furthermore, a solvent such as mineral spirit or solvent naphtha, which is a mixed solvent, can be used in combination.
　前記導電性インクは、例えば、前記高分子分散剤と、前記導電性物質と、必要に応じて前記溶媒とを混合することによって製造することができる。具体的には、ポリアルキレンイミン鎖と、親水性セグメントと、疎水性セグメントとを有する化合物を分散した媒体中に、予め調製した前記導電性物質のイオン溶液を加え、該金属イオンを還元することによって製造することができる。 The conductive ink can be produced, for example, by mixing the polymer dispersant, the conductive substance, and, if necessary, the solvent. Specifically, an ion solution of the conductive substance prepared in advance is added to a medium in which a compound having a polyalkyleneimine chain, a hydrophilic segment, and a hydrophobic segment is dispersed, and the metal ions are reduced. Can be manufactured by.
　また、前記導電性インクには、水性媒体、有機溶剤等の溶媒中における導電性物質の分散安定性、被塗布面への濡れ性を向上するために、必要に応じて、界面活性剤、消泡剤、レオロジー調整剤等を加えてもよい。 In addition, the conductive ink may contain a surfactant, an erasing agent, or the like, if necessary, in order to improve the dispersion stability of the conductive substance in a solvent such as an aqueous medium or an organic solvent and the wettability to the coated surface. Foaming agents, rheology modifiers, etc. may be added.
　本発明では後述する第二絶縁保護層の上に前記導電性インクを印刷して層（Ａ）からなるパターンを形成するが、前記導電性インクを印刷する方法としては、例えば、インクジェット印刷法、反転印刷法、フレキソ印刷法、スクリーン印刷法、グラビア印刷法、グラビアオフセット印刷法等が挙げられる。これらの印刷法の中でも、シールドプリント配線板のインピーダンスを制御するために銅めっき層のパターンを変更する場合において、パターンに応じた印刷版を作製する必要がなく、パターンの変更に容易に対応できるため、インクジェット印刷法が好ましい。 In the present invention, the conductive ink is printed on a second insulating protective layer to be described later to form a pattern composed of the layer (A). Examples of the method for printing the conductive ink include an inkjet printing method, Examples include reverse printing, flexographic printing, screen printing, gravure printing, and gravure offset printing. Among these printing methods, when changing the pattern of the copper plating layer in order to control the impedance of the shield printed wiring board, it is not necessary to prepare a printing plate corresponding to the pattern, and can easily cope with the pattern change. Therefore, the ink jet printing method is preferable.
　前記インクジェット印刷法としては、一般にインクジェットプリンターといわれるものを使用することができる。具体的には、「コニカミノルタＥＢ１００、ＸＹ１００」（コニカミノルタＩＪ株式会社製）、「ダイマティックス・マテリアルプリンターＤＭＰ－３０００、ＤＭＰ－２８３１」（富士フィルム株式会社製）等が挙げられる。 As the ink jet printing method, what is generally called an ink jet printer can be used. Specific examples include “Konica Minolta EB100, XY100” (manufactured by Konica Minolta IJ Co., Ltd.), “Dimatics Material Printer DMP-3000, DMP-2831” (manufactured by Fuji Film Co., Ltd.), and the like.
　また、高精細な金属層のパターンを作製する場合には、細線の印刷精度に優れる反転印刷法が好ましい。 In addition, when producing a high-definition metal layer pattern, a reverse printing method that is excellent in fine line printing accuracy is preferable.
　反転印刷法としては、凸版反転印刷法、凹版反転印刷法が知られており、例えば、各種ブランケットの表面に前記導電性インクを塗布し、非画線部が突出した版と接触させ、前記非画線部に対応する導電性インクを前記版の表面に選択的に転写させることによって、前記ブランケット等の表面に前記パターンを形成し、次いで、前記パターンを、前記第二絶縁保護層の上（表面）に転写させる方法が挙げられる。 As the reversal printing method, a letterpress reversal printing method and an intaglio reversal printing method are known.For example, the conductive ink is applied to the surface of various blankets, and is brought into contact with a plate from which a non-image portion protrudes. The pattern is formed on the surface of the blanket or the like by selectively transferring the conductive ink corresponding to the image area to the surface of the plate, and then the pattern is formed on the second insulating protective layer ( And a method of transferring to the surface).
　また、上記のように、後述する第二絶縁保護層の表面と前記層（Ａ）との密着性をより向上する目的で高分子層（Ｂ）を設ける場合に、前記高分子層（Ｂ）を形成する高分子としては、例えば、ウレタン樹脂、ビニル樹脂、ウレタン－ビニル複合樹脂、エポキシ樹脂、イミド樹脂、アミド樹脂、メラミン樹脂、フェノール樹脂、ポリビニルアルコール、ポリビニルピロリドン等の各種樹脂と溶媒とを含有するものが挙げられる。 Further, as described above, when the polymer layer (B) is provided for the purpose of further improving the adhesion between the surface of the second insulating protective layer described later and the layer (A), the polymer layer (B) Examples of the polymer that forms a resin include various resins such as urethane resin, vinyl resin, urethane-vinyl composite resin, epoxy resin, imide resin, amide resin, melamine resin, phenol resin, polyvinyl alcohol, and polyvinylpyrrolidone, and a solvent. The thing to contain is mentioned.
　前記高分子（Ｂ）として用いる樹脂の中でも、ウレタン樹脂、ビニル樹脂、ウレタン－ビニル複合樹脂が好ましく、ポリエーテル構造を有するウレタン樹脂、ポリカーボネート構造を有するウレタン樹脂、ポリエステル構造を有するウレタン樹脂、アクリル樹脂、及び、ウレタン－アクリル複合樹脂からなる群より選ばれる１種以上の樹脂がより好ましい。また、ウレタン－アクリル複合樹脂は、密着性、導電性に優れた導電性パターンが得られるのでさらに好ましい。 Among the resins used as the polymer (B), urethane resin, vinyl resin, and urethane-vinyl composite resin are preferable. Urethane resin having a polyether structure, urethane resin having a polycarbonate structure, urethane resin having a polyester structure, and acrylic resin And one or more resins selected from the group consisting of urethane-acrylic composite resins are more preferable. A urethane-acrylic composite resin is more preferable because a conductive pattern having excellent adhesion and conductivity can be obtained.
　前記導電性インク中に前記反応性官能基［Ｘ］を有する化合物（ａ１）を含有する場合、前記高分子層（Ｂ）を形成する高分子は、反応性官能基［Ｘ］との反応性を有する官能基［Ｙ］を有する化合物（ｂ１）であることが好ましい。前記反応性官能基［Ｙ］を有する化合物（ｂ１）としては、例えば、アミノ基、アミド基、アルキロールアミド基、カルボキシル基、無水カルボキシル基、カルボニル基、アセトアセトキシ基、エポキシ基、脂環エポキシ基、オキセタン環、ビニル基、アリル基、（メタ）アクリロイル基、（ブロック化）イソシアネート基、（アルコキシ）シリル基等を有する化合物、シルセスキオキサン化合物などが挙げられる。 When the conductive ink contains the compound (a1) having the reactive functional group [X], the polymer forming the polymer layer (B) is reactive with the reactive functional group [X]. The compound (b1) having a functional group [Y] having Examples of the compound (b1) having the reactive functional group [Y] include an amino group, an amide group, an alkylolamide group, a carboxyl group, an anhydrous carboxyl group, a carbonyl group, an acetoacetoxy group, an epoxy group, and an alicyclic epoxy. Group, oxetane ring, vinyl group, allyl group, (meth) acryloyl group, (blocked) isocyanate group, (alkoxy) silyl group-containing compound, silsesquioxane compound and the like.
　特に、前記導電性インク（Ａ）中の前記反応性官能基［Ｘ］を有する化合物（ａ１）が、前記塩基性窒素原子含有基を有する化合物（ａ１）の場合、前記高分子層（Ｂ）を形成する高分子は、反応性官能基［Ｙ］として、カルボキシル基、カルボニル基、アセトアセトキシ基、エポキシ基、脂環エポキシ基、アルキロールアミド基、イソシアネート基、ビニル基、（メタ）アクリロイル基、アリル基であることが、最終的に得られる前記金属層と前記第二絶縁保護層との密着性を向上できるので好ましい。 In particular, when the compound (a1) having the reactive functional group [X] in the conductive ink (A) is the compound (a1) having the basic nitrogen atom-containing group, the polymer layer (B) As a reactive functional group [Y], a polymer that forms a carboxyl group, a carbonyl group, an acetoacetoxy group, an epoxy group, an alicyclic epoxy group, an alkylolamide group, an isocyanate group, a vinyl group, a (meth) acryloyl group An allyl group is preferable because adhesion between the finally obtained metal layer and the second insulating protective layer can be improved.
　前記高分子層（Ｂ）を形成する高分子を後述する第二絶縁保護層の表面に塗布する方法としては、例えば、グラビア方式、コーティング方式、スクリーン方式、ローラー方式、ロータリー方式、スプレー方式等が挙げられる。 Examples of the method for applying the polymer forming the polymer layer (B) to the surface of the second insulating protective layer described later include a gravure method, a coating method, a screen method, a roller method, a rotary method, and a spray method. Can be mentioned.
　また、後述する第二絶縁保護層の表面は、前記高分子層（Ｂ）との密着性をより向上するため、例えば、コロナ放電処理法等のプラズマ放電処理法；紫外線処理法等の乾式処理法；水、酸性またはアルカリ性薬液、有機溶剤等を用いた湿式処理法によって、表面処理されていてもよい。 Further, the surface of the second insulating protective layer to be described later is improved in adhesion with the polymer layer (B), for example, plasma discharge treatment method such as corona discharge treatment method; dry treatment such as ultraviolet treatment method. Method: Surface treatment may be performed by a wet treatment method using water, an acidic or alkaline chemical solution, an organic solvent, or the like.
　前記高分子層（Ｂ）を形成する高分子を後述する第二絶縁保護層の表面に塗布した後、その塗布層に含まれる溶媒を除去する方法としては、例えば乾燥機を用いて乾燥させ、前記溶媒を揮発させる方法が一般的である。乾燥温度としては、前記溶媒を揮発させることが可能で、かつ支持体（Ａ）に悪影響を与えない範囲の温度に設定することが好ましい。 After applying the polymer forming the polymer layer (B) to the surface of the second insulating protective layer described later, as a method of removing the solvent contained in the coating layer, for example, using a dryer, A method of volatilizing the solvent is common. The drying temperature is preferably set to a temperature that allows the solvent to be volatilized and does not adversely affect the support (A).
　前記高分子（Ｂ）を用いて形成する高分子（Ｂ）層の厚さは、前記第二絶縁保護層と前記金属層との密着性をより向上できることから、５～５０００ｎｍの範囲が好ましく、１０～５００ｎｍの範囲がより好ましい。 The thickness of the polymer (B) layer formed using the polymer (B) is preferably in the range of 5 to 5000 nm because the adhesion between the second insulating protective layer and the metal layer can be further improved. A range of 10 to 500 nm is more preferable.
　また、前記高分子（Ｂ）をそのまま前記第二絶縁保護層として使用することも可能であり、さらに、前記第二絶縁保護層に前記高分子（Ｂ）を混合して使用することも可能であるが、この場合、前記高分子（Ｂ）が前記第二絶縁保護層の前記導電性インク（Ａ）と接触する部分に存在する必要がある。 Further, the polymer (B) can be used as it is as the second insulating protective layer, and further, the polymer (B) can be mixed and used in the second insulating protective layer. In this case, the polymer (B) needs to be present in a portion of the second insulating protective layer that contacts the conductive ink (A).
　次に、前記導電性インクで、めっき下地としてのパターンを形成するために前記導電性インクを塗布した後に行う焼成工程は、前記導電性インク中に含まれる導電性物質同士を密着し接合することで導電性を有するめっき下地パターンを形成するために行う。前記焼成は、８０～３００℃の温度範囲で、１～２００分程度行うことが好ましい。ここで、前記第二絶縁保護層との密着性に優れためっき下地パターンを得るためには、前記焼成の温度を１００～２００℃の範囲にすることがより好ましい。 Next, the baking step performed after applying the conductive ink to form a pattern as a plating base with the conductive ink is to adhere and bond the conductive substances contained in the conductive ink. In order to form a plating base pattern having conductivity. The firing is preferably performed at a temperature range of 80 to 300 ° C. for about 1 to 200 minutes. Here, in order to obtain a plating base pattern having excellent adhesion to the second insulating protective layer, it is more preferable that the firing temperature be in the range of 100 to 200 ° C.
　前記焼成は大気中で行っても良いが、導電性物質のすべてが酸化することを防止するため、焼成工程の一部または全部を還元雰囲気下で行ってもよい。 Although the firing may be performed in the air, part or all of the firing step may be performed in a reducing atmosphere in order to prevent all of the conductive material from being oxidized.
　また、前記焼成工程は、例えば、オーブン、熱風式乾燥炉、赤外線乾燥炉、レーザー照射、マイクロウェーブ、光照射（フラッシュ照射装置）等を用いて行うことができる。 The baking step can be performed using, for example, an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, microwave, light irradiation (flash irradiation apparatus), or the like.
　上記のような方法により、前記導電性インクを用いて形成された前記めっき下地としての層（Ａ）からなるパターンは、前記パターン中に８０～９９．９質量％の範囲で導電性物質を含有し、０．１～２０質量％の範囲で高分子分散剤を含有するものであることが好ましい。 The pattern comprising the layer (A) as the plating base formed using the conductive ink by the above method contains a conductive substance in the range of 80 to 99.9% by mass in the pattern. In addition, the polymer dispersant is preferably contained in the range of 0.1 to 20% by mass.
　前記導電性インクを用いて形成した層（Ａ）である前記めっき下地パターンの厚さは、低抵抗で導電性に優れた導電性パターンを形成できることから、５０～２，０００ｎｍの範囲が好ましい。 The thickness of the plating base pattern which is the layer (A) formed using the conductive ink is preferably in the range of 50 to 2,000 nm because a conductive pattern having low resistance and excellent conductivity can be formed.
　次に、本発明のシールドフィルム及びシールドプリント配線板では、シールドフィルム側の導電層として、前記導電性インクを用いて形成した層（Ａ）をめっき下地パターンとして、その上に膜厚０．２～２０μｍ、開口率１０～９０％でパターン化された銅めっき層を有する。一方、前記特許文献２では、導電層として、導電性インキまたは導電性ペーストを基材フィルム上に所定のパターンで印刷する方法、金属箔にエッチング処理することで開口部を形成する方法、金属の蒸着またはスパッタリングにより所定のパターンの金属層を形成する方法により作製したもの、さらにはこのような導電層として、金網を使用することが開示されている。また、前記特許文献２では、導電層の素材は、金、銀、または銅等の金属及びその合金、または、導電性フィラー含有樹脂、導電性高分子等を使用することが好ましいことが開示されている。しかし、導電層の素材として、導電性インキまたは導電性ペーストとして、導電性フィラー含有樹脂を使用した場合は、導電層自体の導電性が乏しく、プリント配線板としての伝送損失を悪化させることが知られている。また、金属箔にエッチング処理をすることで開口部を形成する方法では、製造工程が複雑となり、シールドプリント配線板が高価になることや、導電層の膜厚を任意に調整（薄膜化）することが困難となる。また、金属の蒸着またはスパッタリングにより所定のパターンの金属層を形成する方法では、導電層の膜厚が薄いものしか形成できず、さらに、開口部をパターン化する方法についても課題を有する。また、金属の金網を使用する方法では、導電層のパターンを細線化することが困難であり、開口部の面積を小さくすることに制約を受ける。本発明では、シールドフィルム側の導電層として、前記導電性インクでパターンを形成した層（Ａ）をめっき下地とし、その上に銅めっきを行った銅めっき層を使用することで、前述の問題点を全て解決することができる。 Next, in the shield film and shield printed wiring board of the present invention, the layer (A) formed using the conductive ink as a conductive layer on the shield film side is used as a plating base pattern, and a film thickness of 0.2 is formed thereon. It has a copper plating layer patterned with a thickness of ˜20 μm and an aperture ratio of 10˜90%. On the other hand, in Patent Document 2, as a conductive layer, a method of printing conductive ink or conductive paste in a predetermined pattern on a base film, a method of forming an opening by etching a metal foil, It is disclosed that a metal layer having a predetermined pattern is formed by vapor deposition or sputtering, and that a wire mesh is used as such a conductive layer. Patent Document 2 discloses that the material of the conductive layer is preferably a metal such as gold, silver, or copper and an alloy thereof, a conductive filler-containing resin, a conductive polymer, or the like. ing. However, when a conductive filler-containing resin is used as a conductive layer material or conductive paste as a conductive layer material, the conductive layer itself is poorly conductive and deteriorates transmission loss as a printed wiring board. It has been. Moreover, in the method of forming the opening by etching the metal foil, the manufacturing process becomes complicated, the shield printed wiring board becomes expensive, and the thickness of the conductive layer is arbitrarily adjusted (thinned). It becomes difficult. Further, in the method of forming a metal layer having a predetermined pattern by metal vapor deposition or sputtering, only a thin conductive layer can be formed, and there is also a problem with a method of patterning openings. Further, in the method using a metal wire mesh, it is difficult to make the pattern of the conductive layer thin, and there is a restriction in reducing the area of the opening. In the present invention, as the conductive layer on the shield film side, the layer (A) in which the pattern is formed with the conductive ink is used as a plating base, and a copper plating layer obtained by performing copper plating thereon is used. All points can be solved.
　前記銅めっき層の形成方法としては、例えば、電解めっき法、無電解めっき法等の湿式めっき法が挙げられ、これらのめっき法を２つ以上組み合わせて前記銅めっき層を形成してもよい。 Examples of the method for forming the copper plating layer include wet plating methods such as an electrolytic plating method and an electroless plating method, and the copper plating layer may be formed by combining two or more of these plating methods.
　前記めっき法の中でも、前記層（Ａ）のパターンと、前記めっき法で形成した銅めっき層との密着性がより向上し、また、導電性に優れたパターンが得られることから、電解めっき法、無電解めっき法等の湿式めっき法が好ましく、生産性や得られる金属膜の力学的特性に優れることから、電解めっき法がより好ましい。 Among the plating methods, the adhesion between the pattern of the layer (A) and the copper plating layer formed by the plating method is further improved, and a pattern having excellent conductivity can be obtained. A wet plating method such as an electroless plating method is preferable, and an electrolytic plating method is more preferable because of excellent productivity and mechanical properties of the obtained metal film.
　前記無電解めっき法は、例えば、前記層（Ａ）のパターンを構成する導電性物質に、無電解めっき液を接触させることで、無電解めっき液中に含まれる銅金属を析出させ金属皮膜からなる無電解めっき層（被膜）を形成する方法である。 In the electroless plating method, for example, by bringing an electroless plating solution into contact with a conductive material constituting the pattern of the layer (A), copper metal contained in the electroless plating solution is precipitated, and the metal coating is used. This is a method of forming an electroless plating layer (film).
　前記無電解めっき液としては、例えば、銅と、還元剤と、水性媒体、有機溶剤等の溶媒とを含有するものが挙げられる。 Examples of the electroless plating solution include copper, a reducing agent, and a solvent such as an aqueous medium or an organic solvent.
　前記還元剤としては、例えば、ジメチルアミノボラン、次亜燐酸、次亜燐酸ナトリウム、ジメチルアミンボラン、ヒドラジン、ホルムアルデヒド、水素化ホウ素ナトリウム、フェノール等が挙げられる。 Examples of the reducing agent include dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenol and the like.
　また、前記無電解めっき液としては、必要に応じて、酢酸、蟻酸等のモノカルボン酸；マロン酸、コハク酸、アジピン酸、マレイン酸、フマール酸等のジカルボン酸化合物；リンゴ酸、乳酸、グリコール酸、グルコン酸、クエン酸等のヒドロキシカルボン酸化合物；グリシン、アラニン、イミノジ酢酸、アルギニン、アスパラギン酸、グルタミン酸等のアミノ酸化合物；イミノジ酢酸、ニトリロトリ酢酸、エチレンジアミンジ酢酸、エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸等のアミノポリカルボン酸化合物などの有機酸、またはこれらの有機酸の可溶性塩（ナトリウム塩、カリウム塩、アンモニウム塩等）、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン等のアミン化合物等の錯化剤を含有するものを使用することができる。 In addition, as the electroless plating solution, if necessary, 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, glycol Hydroxycarboxylic acid compounds such as acid, gluconic acid, citric acid; amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid, glutamic acid; iminodiacetic acid, nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc. Contains complexing agents such as organic acids such as aminopolycarboxylic acid compounds or soluble salts of these organic acids (sodium salts, potassium salts, ammonium salts, etc.), amine compounds such as ethylenediamine, diethylenetriamine, and triethylenetetramine. It is possible to use the thing.
　前記無電解めっき液は、２０～９８℃の範囲で使用することが好ましい。 The electroless plating solution is preferably used in the range of 20 to 98 ° C.
　前記電解めっき法は、例えば、前記導電層（Ａ）を構成する金属、または、前記無電解処理によって形成された無電解めっき層（被膜）の表面に、電解めっき液を接触した状態で通電することにより、前記電解めっき液中に含まれる銅等の金属を、カソードに設置した前記導電層（Ａ）を構成する導電性物質または前記無電解処理によって形成された無電解めっき層（被膜）の表面に析出させ、電解めっき層（金属被膜）を形成する方法である。 In the electrolytic plating method, for example, electricity is supplied in a state where an electrolytic plating solution is in contact with the surface of the metal constituting the conductive layer (A) or the electroless plating layer (coating) formed by the electroless treatment. Thus, a metal such as copper contained in the electrolytic plating solution is used to form a conductive material constituting the conductive layer (A) placed on the cathode or the electroless plating layer (coating) formed by the electroless treatment. This is a method of depositing on the surface and forming an electrolytic plating layer (metal coating).
　前記電解めっき液としては、例えば、銅の硫化物と、硫酸と、水性媒体とを含有するもの等が挙げられる。具体的には、硫酸銅と硫酸と水性媒体とを含有するものが挙げられる。 Examples of the electrolytic plating solution include those containing copper sulfide, sulfuric acid, and an aqueous medium. Specifically, what contains copper sulfate, sulfuric acid, and an aqueous medium is mentioned.
　前記電解めっき液は、２０～９８℃の範囲で使用することが好ましい。 The electrolytic plating solution is preferably used in the range of 20 to 98 ° C.
　前記めっき処理の方法は、毒性の高い物質を用いることなく、作業性がよいため、電解めっき法が好ましい。また、電解銅めっきは、無電解銅めっきと比較して、めっき時間が短縮でき、めっきの膜厚の制御が容易であることから好ましい。さらに、電解銅めっきにより得られる銅めっき層は、力学的特性に優れ、折り曲げても破断し難い、優れたフレキシビリティーを有することから、フレキシブルプリント配線板に使用する場合、電解銅めっき法で形成した銅めっき層を用いることが好ましい。 The plating method is preferably an electrolytic plating method because it is easy to work without using a highly toxic substance. Electrolytic copper plating is preferable because it can shorten the plating time and control the thickness of the plating as compared with electroless copper plating. Furthermore, the copper plating layer obtained by electrolytic copper plating has excellent mechanical properties, is difficult to break even when bent, and has excellent flexibility. It is preferable to use the formed copper plating layer.
　前記銅めっき層は、銅めっき層の上にさらに別の金属のめっき層が積層されていてもよく、ニッケルめっき層や金めっき層、スズめっき層を設けると銅めっき層表面の酸化劣化や腐食が防止できる。 The copper plating layer may be formed by laminating another metal plating layer on the copper plating layer. When a nickel plating layer, a gold plating layer, or a tin plating layer is provided, the surface of the copper plating layer is deteriorated by oxidation or corroded. Can be prevented.
　前記めっき法で形成した銅めっき層の厚さは、導電層としての導電性に優れることと、シールドプリント配線板への薄膜化の要求に対応できることから、０．２～２０μｍの範囲が好ましい。また、電解めっき法により銅めっき層を形成する場合、その層の厚さは、銅めっき処理工程における処理時間、電流密度、めっき用添加剤の使用量等を制御することによって調整することができる。 The thickness of the copper plating layer formed by the above plating method is preferably in the range of 0.2 to 20 μm because it is excellent in conductivity as a conductive layer and can meet the demands for thinning the shield printed wiring board. In addition, when a copper plating layer is formed by an electrolytic plating method, the thickness of the layer can be adjusted by controlling the processing time, current density, the amount of plating additive used, etc. in the copper plating process. .
　本発明のシールドプリント配線板は、前記金属層パターンの上に第二絶縁保護層が設けられている。第二絶縁保護層としては、絶縁樹脂のシートまたはフィルム、または絶縁樹脂の塗工層からなる。絶縁樹脂のシートまたはフィルムとしては、ポリエステルフィルム、ポリオレフィンフィルム、ポリイミドフィルム、ポリアミドイミドフィルム、ポリフェニレンサルファイドフィルム、ポリエチレンナフタレートフィルム、ＬＣＰ（液晶ポリマー）フィルム、ポリシクロオレフィンフィルム等が挙げられる。絶縁樹脂の塗工層としては、スチレン樹脂、酢酸ビニル樹脂、ポリエステル樹脂、ポリエチレンやポリプロピレン等のポリオレフィン樹脂、アミド樹脂、アミドイミド樹脂、スチレン－ブタジエン樹脂、アクリロニトリル－ブタジエン樹脂、（メタ）アクリル－ブタジエン樹脂、（メタ）アクリル樹脂、ウレタン樹脂等の熱可塑性樹脂や、フェノール樹脂、エポキシ樹脂、メラミン樹脂、アルキッド樹脂等の熱硬化性樹脂や、ウレタン－アクリレート、エポキシ－アクリレート、アクリル－アクリレート等から成る紫外線硬化型樹脂等を単独で、または２種以上を組み合わせて使用することができる。これらの中でも、プリント配線板を搭載する電子機器を製造する際における過酷な熱条件（例えば、はんだリフロー時）を考慮すると、熱硬化性樹脂や紫外線硬化性樹脂が好ましく、エポキシ樹脂、ウレタン樹脂、ポリエステル樹脂、メラミン樹脂、アクリル樹脂、ウレタン－アクリレート、エポキシアクリレート、アクリル－アクリレート等を単独で、または２種以上を組み合わせて、または架橋剤などと組み合わせて使用することが好ましい。また、フレキシブルなシールドプリント配線板として使用される場合は、ウレタン樹脂を含んでいることが好ましい。 In the shielded printed wiring board of the present invention, a second insulating protective layer is provided on the metal layer pattern. The second insulating protective layer comprises an insulating resin sheet or film, or an insulating resin coating layer. Examples of the insulating resin sheet or film include polyester film, polyolefin film, polyimide film, polyamideimide film, polyphenylene sulfide film, polyethylene naphthalate film, LCP (liquid crystal polymer) film, and polycycloolefin film. Insulating resin coating layers include styrene resins, vinyl acetate resins, polyester resins, polyolefin resins such as polyethylene and polypropylene, amide resins, amideimide resins, styrene-butadiene resins, acrylonitrile-butadiene resins, and (meth) acryl-butadiene resins. UV rays composed of thermoplastic resins such as (meth) acrylic resin and urethane resin, thermosetting resins such as phenolic resin, epoxy resin, melamine resin and alkyd resin, urethane-acrylate, epoxy-acrylate, acrylic-acrylate, etc. A curable resin or the like can be used alone or in combination of two or more. Among these, in consideration of harsh thermal conditions (for example, during solder reflow) when manufacturing an electronic device on which a printed wiring board is mounted, a thermosetting resin or an ultraviolet curable resin is preferable, and an epoxy resin, a urethane resin, It is preferable to use a polyester resin, a melamine resin, an acrylic resin, urethane-acrylate, epoxy acrylate, acrylic-acrylate, etc. alone, in combination of two or more, or in combination with a crosslinking agent. Moreover, when using as a flexible shield printed wiring board, it is preferable that urethane resin is included.
　本発明のシールドフィルムの製造方法としては、例えば、前記第二絶縁保護層の上に直接、または前記第二絶縁保護層の上に前記高分子層（Ｂ）を形成した上に、導電性インクを用いて開口率１０～９０％の層（Ａ）からなるパターンを形成し、その上に電解銅めっきを施して銅めっき層を形成し、その上に導電性接着剤層を形成する方法が挙げられる。なお、前記高分子層（Ｂ）及び前記層（Ａ）の形成方法は、前述した通りである。 As a method for producing the shield film of the present invention, for example, a conductive ink is formed directly on the second insulating protective layer or after the polymer layer (B) is formed on the second insulating protective layer. Is used to form a pattern composed of a layer (A) having an aperture ratio of 10 to 90%, to form a copper plating layer by applying electrolytic copper plating thereon, and to form a conductive adhesive layer thereon. Can be mentioned. In addition, the formation method of the said polymer layer (B) and the said layer (A) is as having mentioned above.
　前記第二絶縁保護層は、前述のように絶縁樹脂のシートまたはフィルムや、絶縁樹脂の塗工層が使用できるが、絶縁樹脂を塗工して第二絶縁保護層を製造する場合は、支持基材として剥離フィルムを用いることができる。 As described above, the second insulating protective layer can be an insulating resin sheet or film, or an insulating resin coating layer. However, when the second insulating protective layer is manufactured by coating the insulating resin, it is supported. A release film can be used as the substrate.
　前記剥離フィルムとしては、プラスチックフィルムや剥離紙を用いることできる。前記プラスチックフィルムとしては、例えば、ポリエステルフィルム、ポリオレフィンフィルム、ポリイミドフィルム等が挙げられ、さらにこれらのフィルムにシリコーン系離型層、フッ素系離型層、オレフィン系離型層等を設けたフィルムも挙げられる。前記剥離紙としては、例えば、紙基材の上に目止め層が設けた後、その上にシリコーン系離型層、フッ素系離型層、オレフィン系離型層を設けたものが挙げられる。 As the release film, a plastic film or release paper can be used. Examples of the plastic film include a polyester film, a polyolefin film, a polyimide film, and a film in which a silicone release layer, a fluorine release layer, an olefin release layer, and the like are further provided on these films. It is done. Examples of the release paper include those in which a sealing layer is provided on a paper substrate and then a silicone release layer, a fluorine release layer, and an olefin release layer are provided thereon.
　塗工により形成した前記第二絶縁保護層としては、例えば、前述で例示した樹脂等を塗工したものが使用でき、前記剥離フィルムに絶縁樹脂を塗工し、乾燥し、必要に応じて樹脂を加熱硬化、紫外線硬化で硬化させて第二絶縁保護層を製造することができる。 As said 2nd insulation protective layer formed by coating, what coated resin etc. which were illustrated above can be used, for example, an insulating resin is applied to the said peeling film, it is dried, and resin is needed as needed. Can be cured by heat curing and ultraviolet curing to produce the second insulating protective layer.
　本発明のシールドフィルムの製造方法では、前記銅めっき層の上に導電性接着剤層を形成する。導電性接着剤層としては、具体的には前述したものが使用でき、導電性接着剤を銅めっき層パターンの上に塗工して、必要に応じて乾燥して形成することができる。このようにして得られるシールドフィルムは、本発明のシールドプリント配線板の最表面に貼り付けられるシールドフィルムとして用いることができる。 In the shield film manufacturing method of the present invention, a conductive adhesive layer is formed on the copper plating layer. As the conductive adhesive layer, specifically, those described above can be used. The conductive adhesive layer can be formed by applying the conductive adhesive on the copper plating layer pattern and drying it as necessary. The shield film obtained in this manner can be used as a shield film that is attached to the outermost surface of the shield printed wiring board of the present invention.
　本発明のシールドプリント配線板の製造方法について説明する。本発明のシールドプリント配線板を構成するプリント配線板は、プリント配線板基材上に信号配線及びグランド配線を形成し、その上に第一絶縁保護層が設けられ、前記第一絶縁保護層は前記グランド配線の一部が露出したビアを有しているものを用いる。また、本発明のシールドプリント配線板をフレキシブルプリント配線板（ＦＰＣ）とする場合は、ベースフィルムの一方の面にのみプリント回路を有する片面型ＦＰＣ、ベースフィルムの両面にプリント回路を有する両面型ＦＰＣ、この様なＦＰＣが複数層積層された多層型ＦＰＣ、多層部品搭載部とケーブル部を有するフレクスボード（登録商標）、多層部を構成する部材を硬質なものとしたフレックスリジッド基板、あるいは、テープキャリアパッケージのためのＴＡＢテープ等を適宜採用して実施することができる。 The manufacturing method of the shield printed wiring board of the present invention will be described. The printed wiring board constituting the shield printed wiring board of the present invention is formed with signal wiring and ground wiring on a printed wiring board substrate, and a first insulating protective layer is provided thereon, and the first insulating protective layer is A ground wire having a partly exposed via is used. When the shield printed wiring board of the present invention is a flexible printed wiring board (FPC), a single-sided FPC having a printed circuit only on one side of the base film, and a double-sided FPC having a printed circuit on both sides of the base film Multi-layer FPC in which a plurality of such FPCs are laminated, Flexboard (registered trademark) having a multilayer component mounting portion and a cable portion, a flex rigid board having a rigid member constituting the multilayer portion, or a tape carrier A TAB tape or the like for the package can be adopted as appropriate.
　前記プリント配線板の第一絶縁保護層の上に、本発明のシールドフィルムの導電性接着剤層が接するように配置し、プリント配線板とシールドフィルムとを互いに接近する方向に加圧することによりシールドフィルムの導電性接着剤層を流動させてプリント配線板のグランド層と接続することにより、本発明のシールドプリント配線板を製造することができる。前記プリント配線板と前記シールドフィルムを加圧して、導電性接着剤層を流動させてプリント配線板のグランド層と接合する際には加熱することもでき、前記導電性接着剤が熱硬化可能な樹脂を含有するものである場合、その樹脂の硬化条件に応じて加熱条件を調整することができる。加熱する場合の温度は、通常５０～２５０℃の範囲が好ましい。 On the first insulating protective layer of the printed wiring board, the conductive adhesive layer of the shield film of the present invention is disposed so as to be in contact, and the printed wiring board and the shield film are shielded by pressing in a direction approaching each other. The shield printed wiring board of the present invention can be manufactured by flowing the conductive adhesive layer of the film and connecting it to the ground layer of the printed wiring board. When the printed wiring board and the shield film are pressurized to cause the conductive adhesive layer to flow and join with the ground layer of the printed wiring board, it can be heated, and the conductive adhesive can be thermoset. In the case of containing a resin, the heating conditions can be adjusted according to the curing conditions of the resin. The heating temperature is usually preferably in the range of 50 to 250 ° C.
　なお、本発明のシールドプリント配線板は、プリント配線板の片面にシールドフィルムを貼り付けた構成や、両面にシールドフィルムを貼り付けた構成でもよい。 The shield printed wiring board of the present invention may have a configuration in which a shield film is attached to one side of the printed wiring board or a configuration in which shield films are attached to both sides.
　以下、実施例により本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail by way of examples.
［導電性インク（１）の調製］
　エチレングリコール３５質量部と、イオン交換水６５質量部との混合溶媒に、分散剤としてポリエチレンイミンにポリオキシエチレンが付加した化合物を用いて平均粒径２０ｎｍの銀粒子を分散させることによって、金属ナノ粒子と、反応性官能基として塩基性窒素原子含有基を有する高分子分散剤とを含有する金属ナノ粒子分散液を調製した。次いで、得られた金属ナノ粒子分散液に、イオン交換水及び界面活性剤を添加して、その粘度を１１ｍＰａ・ｓに調整することによって、インクジェット印刷用の導電性インク（１）を調製した。 [Preparation of conductive ink (1)]
By dispersing silver particles having an average particle diameter of 20 nm in a mixed solvent of 35 parts by mass of ethylene glycol and 65 parts by mass of ion-exchanged water, using a compound in which polyoxyethylene is added to polyethyleneimine as a dispersant, metal nanoparticles are dispersed. A metal nanoparticle dispersion containing particles and a polymer dispersant having a basic nitrogen atom-containing group as a reactive functional group was prepared. Next, ion-exchanged water and a surfactant were added to the obtained metal nanoparticle dispersion, and the viscosity was adjusted to 11 mPa · s to prepare a conductive ink (1) for inkjet printing.
［第二絶縁保護層用樹脂の製造］
　温度計、窒素ガス導入管及び攪拌器を備えた窒素置換された容器中で、ポリエステルポリオール１００質量部（１，４－シクロヘキサンジメタノールとネオペンチルグリコールとアジピン酸とを反応させて得られたポリエステルポリオール、水酸基当量１，０００ｇ／当量）と２，２―ジメチロールプロピオン酸１７．４質量部と１，４－シクロヘキサンジメタノール２１．７質量部とジシクロヘキシルメタンジイソシアネート１０６．２質量部とを、メチルエチルケトン１７８質量部中で混合し反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。 [Manufacture of resin for second insulating protective layer]
100 parts by mass of polyester polyol (polyester obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol and adipic acid in a nitrogen-substituted container equipped with a thermometer, nitrogen gas inlet tube and stirrer Polyol, a hydroxyl group equivalent of 1,000 g / equivalent), 17.4 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol, and 106.2 parts by mass of dicyclohexylmethane diisocyanate. By mixing and reacting in 178 parts by mass, an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.
　次いで、上記で得られたウレタンプレポリマーの有機溶剤溶液に、トリエチルアミンを１３．３質量部加えることで前記ウレタン樹脂が有するカルボキシル基の一部または全部を中和し、さらに水２７７質量部を加え十分に攪拌することにより、カルボキシル基を有するウレタン樹脂の水分散液を得た。 Next, 13.3 parts by mass of triethylamine was added to the organic solvent solution of the urethane prepolymer obtained above to neutralize part or all of the carboxyl groups of the urethane resin, and 277 parts by mass of water was further added. By sufficiently stirring, an aqueous dispersion of urethane resin having a carboxyl group was obtained.
　上記で得られたウレタン樹脂の水分散液に、２５質量％のエチレンジアミン水溶液を８質量部加え、攪拌することによって、ウレタン樹脂を鎖伸長させ、次いでエージング・脱溶剤することによって、固形分３０質量％のウレタン樹脂の水分散液を得た。次いで、得られたウレタン樹脂の水分散液３３３質量部に、ソルビトールポリグリシジルエーテル（エポキシ当量１７０）３０質量部を加えて混合し、第二絶縁保護層用樹脂溶液を得た。 By adding 8 parts by mass of a 25% by mass ethylenediamine aqueous solution to the aqueous dispersion of the urethane resin obtained above and stirring, the urethane resin is chain-extended, and then aging / desolvent to obtain a solid content of 30% by mass. % Aqueous dispersion of urethane resin was obtained. Next, 30 parts by mass of sorbitol polyglycidyl ether (epoxy equivalent 170) was added to 333 parts by mass of the obtained aqueous dispersion of urethane resin and mixed to obtain a resin solution for the second insulating protective layer.
［高分子層（Ｂ－１）用樹脂の製造］
　攪拌機、還流冷却管、窒素導入管、温度計、単量体混合物滴下用滴下漏斗及び重合触媒滴下用滴下漏斗を備えた反応容器に、酢酸エチル１８０質量部を入れ、窒素を吹き込みながら８０℃まで昇温した。８０℃まで昇温した反応容器内に、攪拌下、メタクリル酸メチル６０質量部、アクリル酸ｎ－ブチル１０質量部及びメタクリル酸グリシジル３０質量部を含有するビニル単量体混合物と、アゾイソブチロニトリル１質量部及び酢酸エチル２０質量部を含有する重合開始剤溶液を、各々別の滴下漏斗から反応容器内温度を８０±１℃に保ちながら２４０分間かけて滴下し重合した。滴下終了後、同温度にて１２０分間攪拌した後、前記反応容器内の温度を３０℃に冷却し、次いで、不揮発分が１０質量％になるように酢酸エチルを加えて、反応性官能基としてエポキシ基を含有する高分子層（Ｂ－１）用樹脂を得た。 [Manufacture of polymer layer (B-1) resin]
Into a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, dropping funnel for dropping the monomer mixture and dropping funnel for dropping the polymerization catalyst, 180 parts by mass of ethyl acetate was added and the temperature was increased to 80 ° C. while blowing nitrogen. The temperature rose. In a reaction vessel heated to 80 ° C., with stirring, a vinyl monomer mixture containing 60 parts by mass of methyl methacrylate, 10 parts by mass of n-butyl acrylate and 30 parts by mass of glycidyl methacrylate, and azoisobutyro A polymerization initiator solution containing 1 part by mass of nitrile and 20 parts by mass of ethyl acetate was dropped and polymerized from another dropping funnel over 240 minutes while maintaining the temperature in the reaction vessel at 80 ± 1 ° C. After completion of the dropwise addition, the mixture was stirred at the same temperature for 120 minutes, and then the temperature in the reaction vessel was cooled to 30 ° C., and then ethyl acetate was added so that the nonvolatile content was 10% by mass to obtain a reactive functional group. A resin for the polymer layer (B-1) containing an epoxy group was obtained.
［導電性接着剤用樹脂の製造］
　温度計、窒素ガス導入管及び攪拌器を備えた窒素置換された容器中で、ポリエステルポリオール１００質量部（１，４－シクロヘキサンジメタノールとネオペンチルグリコールとアジピン酸とを反応させて得られたポリエステルポリオール、水酸基当量１０００ｇ／当量）と２，２―ジメチロールプロピオン酸１７．４質量部と１，４－シクロヘキサンジメタノール２１．７質量部とジシクロヘキシルメタンジイソシアネート１０６．２質量部とを、メチルエチルケトン１７８質量部中で混合し反応させることによって、分子末端にイソシアネート基を有するウレタン樹脂を得た。次いで、得られたウレタン樹脂にメチルエチルケトンを加え、固形分５０質量％のウレタン樹脂の有機溶剤溶液を得た。 [Manufacture of resin for conductive adhesive]
100 parts by mass of polyester polyol (polyester obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol and adipic acid in a nitrogen-substituted container equipped with a thermometer, nitrogen gas inlet tube and stirrer Polyol, hydroxyl group equivalent 1000 g / equivalent), 17.4 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol and 106.2 parts by mass of dicyclohexylmethane diisocyanate, and 178 parts by mass of methyl ethyl ketone. By mixing and reacting in the part, a urethane resin having an isocyanate group at the molecular end was obtained. Subsequently, methyl ethyl ketone was added to the obtained urethane resin to obtain an organic solvent solution of a urethane resin having a solid content of 50% by mass.
［導電性接着剤の調製］
　上記で得られたウレタン樹脂の有機溶剤溶液２００質量部に、ビスフェノールＡ型エポキシ樹脂（エポキシ当量１８０）２０質量部を加えて混合し、さらに、銀フィラー（大研化学工業株式会社製「Ｓ－２０１」）８０質量部を加えて混合し、導電性接着剤を調製した。 [Preparation of conductive adhesive]
To 200 parts by mass of the organic resin solution of urethane resin obtained above, 20 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 180) is added and mixed, and further, a silver filler (“S— 201 ") 80 parts by mass was added and mixed to prepare a conductive adhesive.
（実施例１）
　プリント配線基板として、ポリイミド製のベースフィルムに、銅厚１２μｍ、線幅５００μｍのグランド用銅配線パターンと、銅厚１２μｍ、線幅２００μｍの信号用銅配線パターンとからなる配線が形成され、信号配線とグランド配線の線間をそれぞれ１００μｍ、回路長１００ｍｍとし、さらに膜厚１５μｍの接着剤層と、膜厚１２．５μｍのポリイミド製フィルム層で膜厚２７．５μｍの第一絶縁保護層が形成され、グランド配線部に４００μｍ角の開口部が設けられたプリント配線板を用いた。 Example 1
As a printed wiring board, a wiring composed of a ground copper wiring pattern with a copper thickness of 12 μm and a line width of 500 μm and a signal copper wiring pattern with a copper thickness of 12 μm and a line width of 200 μm is formed on a polyimide base film. The first insulating protective layer having a film thickness of 27.5 μm is formed of an adhesive layer having a film thickness of 15 μm and a polyimide film layer having a film thickness of 12.5 μm. A printed wiring board having a 400 μm square opening in the ground wiring portion was used.
　シールドフィルムとして、離型処理されたポリエステルフィルム上に、上記で製造した第二絶縁保護層用樹脂を乾燥後の膜厚が５μｍとなるように塗工し、乾燥して第二絶縁保護層を形成した。次いで、上記で製造した高分子層（Ｂ－１）用樹脂を乾燥後の膜厚が０．２μｍとなるように塗工し、乾燥して高分子層（Ｂ－１）を形成した。 As a shield film, on the release-treated polyester film, the second insulating protective layer resin produced above is applied so that the film thickness after drying is 5 μm, and dried to form a second insulating protective layer. Formed. Next, the polymer layer (B-1) resin produced above was applied so that the film thickness after drying was 0.2 μm, and dried to form a polymer layer (B-1).
　次に、上記方法で形成した高分子層（Ｂ－１）が積層された第二絶縁保護層の上に、上記で得られた導電性インク（１）をインクジェットプリンター（コニカミノルタＩＪ株式会社製インクジェット試験機ＥＢ１００、評価用プリンタヘッドＫＭ５１２Ｌ、吐出量１４ｐＬ）を用い、シールドプリント配線板の特性インピーダンスを５０Ωとすることを目的として、線幅９０μｍ、開口率８２％の格子パターンを印刷した。次いで、１２０℃で２０分間焼成することによって、開口率８２％の格子パターンを形成した導電性インク（１）からなる層（膜厚０．８μｍ）を形成した。 Next, the conductive ink (1) obtained above is applied onto the second insulating protective layer on which the polymer layer (B-1) formed by the above method is laminated, by an inkjet printer (manufactured by Konica Minolta IJ Co., Ltd.). A grid pattern having a line width of 90 μm and an aperture ratio of 82% was printed for the purpose of setting the characteristic impedance of the shield printed wiring board to 50Ω using an inkjet test machine EB100, an evaluation printer head KM512L, and a discharge amount of 14 pL. Next, by baking at 120 ° C. for 20 minutes, a layer (having a thickness of 0.8 μm) made of the conductive ink (1) having a lattice pattern with an aperture ratio of 82% was formed.
　次に、上記で得られた導電性インク（１）からなる層を陰極に設定し、含リン銅を陽極に設定し、硫酸銅を含有する電解めっき液を用いて電流密度２Ａ／ｄｍ２で１０分間電解銅めっきを行うことによって、導電性インクからなる層の表面に、厚さ５μｍの銅めっき層を積層した。前記銅電解めっき液としては、硫酸銅７０ｇ／リットル、硫酸２００ｇ／リットル、塩素イオン５０ｍｇ／リットル、添加剤（奥野製薬工業(株)製「トップルチナＳＦ－Ｍ」）５ｍｌ／リットルを使用した。電解銅めっき後の格子パターンの線幅は１００μｍ、開口率は８０％であった。 Next, the layer made of the conductive ink (1) obtained above is set as a cathode, phosphorous copper is set as an anode, and an electroplating solution containing copper sulfate is used at a current density of 2 A / dm 2 . By performing electrolytic copper plating for 10 minutes, a copper plating layer having a thickness of 5 μm was laminated on the surface of the layer made of conductive ink. As the copper electroplating solution, 70 g / liter of copper sulfate, 200 g / liter of sulfuric acid, 50 mg / liter of chloride ions, and 5 ml / liter of additives (“Top Lucina SF-M” manufactured by Okuno Pharmaceutical Co., Ltd.) were used. The line width of the lattice pattern after electrolytic copper plating was 100 μm, and the aperture ratio was 80%.
　次に、上記で得られた第二絶縁保護層の上に形成された開口率８０％の格子パターンの銅めっき層の上に、上記合成例３で製造した導電性接着剤を乾燥後の膜厚５μｍとなるように塗工し、乾燥してシールドフィルムを作製した。 Next, the conductive adhesive produced in Synthesis Example 3 is dried on the copper plating layer having a lattice pattern of 80% formed on the second insulating protective layer obtained above. The film was applied to a thickness of 5 μm and dried to prepare a shield film.
　次に、上記で得られたグランド配線部に開口部が設けられたプリント配線板と上記で得られたシールドフィルムを、プリント配線板の絶縁保護層の上に、シールドフィルムの導電性接着剤層が接するように配置し、プリント配線板とシールドフィルムとを互いに接近する方向に加圧（圧力：１．９６ＭＰａ、加熱温度：１５０℃、処理時間：３０分間）して圧着し、シールドフィルムの導電性接着剤層を流動させてプリント配線板のグランド層と接続し、シールドプリント配線板を作製した。 Next, the printed wiring board obtained by opening the ground wiring part obtained above and the shielding film obtained above are formed on the insulating protective layer of the printed wiring board, and the conductive adhesive layer of the shielding film. The printed wiring board and the shield film are pressed in a direction approaching each other (pressure: 1.96 MPa, heating temperature: 150 ° C., treatment time: 30 minutes), and the shield film is conductive. The conductive adhesive layer was allowed to flow and connected to the ground layer of the printed wiring board to produce a shield printed wiring board.
（実施例２～４）
　実施例１で用いたプリント配線板の代わりに、信号用銅配線の線幅を表１に記載した線幅とし、実施例１で用いたシールドフィルムの代わりに、シールドフィルムの銅めっき層の開口率をシールドプリント配線板の特性インピーダンスを５０Ωとすることを目的として、表１に記載した開口率とした以外は、実施例１と同様にシールドプリント配線板を作製した。 (Examples 2 to 4)
Instead of the printed wiring board used in Example 1, the line width of the signal copper wiring is set to the line width described in Table 1, and instead of the shield film used in Example 1, the opening of the copper plating layer of the shield film A shield printed wiring board was produced in the same manner as in Example 1 except that the aperture ratio described in Table 1 was used for the purpose of setting the ratio to the characteristic impedance of the shield printed wiring board of 50Ω.
（比較例１）
　実施例１で用いたプリント配線板の代わりに、信号用銅配線パターンの線幅を表１に記載した線幅としたプリント配線板を使用した。また、実施例１で用いたシールドフィルムの代わりに、開口率が０％となるように、膜厚５μｍの圧延銅箔に上記で得られた第二絶縁保護層用樹脂を乾燥後の膜厚が５μｍとなるように塗工し、乾燥して第二絶縁保護層を形成した。次いで、圧延銅箔の第二絶縁保護層を形成した面とは反対面に、上記で得られた導電性接着剤を乾燥後の膜厚５μｍとなるように塗工し、乾燥して開口率０％の銅層を有するシールドフィルムを作製した。 (Comparative Example 1)
Instead of the printed wiring board used in Example 1, a printed wiring board having a line width of the signal copper wiring pattern described in Table 1 was used. In addition, instead of the shield film used in Example 1, the film thickness after drying the resin for the second insulating protective layer obtained above on a rolled copper foil having a film thickness of 5 μm so that the aperture ratio becomes 0%. Was applied to a thickness of 5 μm and dried to form a second insulating protective layer. Next, the surface of the rolled copper foil opposite to the surface on which the second insulating protective layer is formed is coated with the conductive adhesive obtained above so as to have a film thickness after drying of 5 μm, and dried to obtain an aperture ratio. A shield film having a 0% copper layer was prepared.
　次に、表１に記載した信号用銅配線パターンの線幅とし、グランド配線部に４００μｍ角の開口部が設けられたプリント配線板と、上記で得られたシールドフィルムを、プリント配線板の絶縁保護層の上に、シールドフィルムの導電性接着剤層が接するように配置し、プリント配線板とシールドフィルムとを互いに接近する方向に加圧（圧力：１．９６ＭＰａ、加熱温度：１５０℃、処理時間：３０分間）して圧着し、シールドフィルムの導電性接着剤層を流動させてプリント配線板のグランド層と接続し、シールドプリント配線板を作製した。 Next, the line width of the signal copper wiring pattern described in Table 1 is used, and the printed wiring board having a 400 μm square opening in the ground wiring part and the shield film obtained above are insulated from the printed wiring board. It arrange | positions so that the conductive adhesive layer of a shield film may contact | connect on a protective layer, and a printed wiring board and a shield film are pressurized in the direction which mutually approaches (pressure: 1.96 MPa, heating temperature: 150 degreeC, process (Time: 30 minutes) and pressure-bonded, and the conductive adhesive layer of the shield film was flowed to be connected to the ground layer of the printed wiring board to produce a shield printed wiring board.
（比較例２）
　比較例１で用いたプリント配線板に代えて、信号用銅配線パターンの線幅を表１に記載した線幅とした以外は、前記比較例１と同様にして、開口率０％の比較用シールドプリント配線板を作製した。 (Comparative Example 2)
Instead of the printed wiring board used in Comparative Example 1, the line width of the signal copper wiring pattern was changed to the line width described in Table 1, and the comparative example with an aperture ratio of 0% was made in the same manner as in Comparative Example 1. A shield printed wiring board was produced.
［比較用の導電性インク（Ｒ１）用樹脂の製造］
　攪拌機、温度計、還流冷却器、滴下装置、及び窒素導入管を備えた反応容器に、アジピン酸、テレフタル酸、及び３－メチル－１，５－ペンタンジオールから得られる数平均分子量が１００６であるジオール４１４質量部、ジメチロールブタン酸８質量部、イソホロンジイソシアネート１４５質量部、及びトルエン４０質量部を仕込み、窒素雰囲気下９０℃で３時間反応させた。次いで、この反応溶液に、さらにトルエン３００質量部を加えて、末端にイソシアネート基を有するウレタンプレポリマーの溶液を得た。 [Manufacture of Resin for Conductive Ink (R1) for Comparison]
The number average molecular weight obtained from adipic acid, terephthalic acid, and 3-methyl-1,5-pentanediol is 1006 in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping device, and nitrogen introduction tube. A diol (414 parts by mass), dimethylolbutanoic acid (8 parts by mass), isophorone diisocyanate (145 parts by mass) and toluene (40 parts by mass) were charged and reacted at 90 ° C. for 3 hours in a nitrogen atmosphere. Next, 300 parts by mass of toluene was further added to the reaction solution to obtain a urethane prepolymer solution having an isocyanate group at the terminal.
　次に、イソホロンジアミン２７質量部、ジ－ｎ－ブチルアミン３質量部、２－プロパノール３４２質量部及びトルエン５７６質量部を混合した混合物に、上記で得られたウレタンプレポリマーの溶液８１６質量部を添加し、７０℃で３時間反応させてポリウレタンポリウレア樹脂の溶液を得た。これに、トルエン１４４質量部、及び２－プロパノール７２質量部を加えて、ポリウレタンポリウレア樹脂の固形分３０質量％である比較用の導電性インク（Ｒ１）用樹脂溶液を得た。 Next, 816 parts by mass of the urethane prepolymer solution obtained above was added to a mixture of 27 parts by mass of isophoronediamine, 3 parts by mass of di-n-butylamine, 342 parts by mass of 2-propanol and 576 parts by mass of toluene. And reacted at 70 ° C. for 3 hours to obtain a polyurethane polyurea resin solution. To this, 144 parts by mass of toluene and 72 parts by mass of 2-propanol were added to obtain a resin solution for a conductive ink (R1) for comparison having a solid content of 30% by mass of the polyurethane polyurea resin.
［比較用の導電性インク（Ｒ１）の調製］
　上記で得られた比較用の導電性インク用樹脂溶液３３３質量部、及びビスフェノールＡ型エポキシ樹脂（三菱化学株式会社製「ＪＥＲ８２８」）２０質量部を攪拌混合し、樹脂組成物溶液を得た。この樹脂組成物溶液３５３質量部に、導電フィラー（福田金属箔粉工業株式会社製「ＡｇＸＦ－３０１」）１８０質量部を加えて攪拌混合し、ポリウレタンポリウレア樹脂とエポキシ樹脂との合計１００質量部に対して、導電フィラー３００質量部を含有する比較用の導電性インク（Ｒ１）を得た。 [Preparation of Comparative Conductive Ink (R1)]
333 parts by mass of the resin solution for conductive ink for comparison obtained above and 20 parts by mass of bisphenol A type epoxy resin (“JER828” manufactured by Mitsubishi Chemical Corporation) were stirred and mixed to obtain a resin composition solution. To 353 parts by mass of this resin composition solution, 180 parts by mass of a conductive filler (“AgXF-301” manufactured by Fukuda Metal Foil Powder Co., Ltd.) is added and mixed by stirring to a total of 100 parts by mass of the polyurethane polyurea resin and the epoxy resin. In contrast, a comparative conductive ink (R1) containing 300 parts by mass of a conductive filler was obtained.
［接合層用樹脂の製造］
　上記の導電性インク（Ｒ１）用樹脂と同様にして製造したポリウレタンポリウレア樹脂溶液３３３質量部に対して、ビスフェノールＡ型エポキシ樹脂２０質量部を加えて、接合層用樹脂を得た。 [Manufacture of resin for bonding layers]
20 parts by mass of a bisphenol A type epoxy resin was added to 333 parts by mass of the polyurethane polyurea resin solution produced in the same manner as the resin for the conductive ink (R1) to obtain a resin for a bonding layer.
（比較例３）
　シールドフィルムの作製として、離型処理されたポリエステルフィルム上に、上記で得られた比較用の導電性インク（Ｒ１）を、線幅１００μｍ、開口率２５％、乾燥後の膜厚が５μｍの格子パターンになるようにスクリーン印刷し、乾燥して導電層を形成した。次いで、離型処理されたポリエステルフィルム上に、上記で得られた接合層用樹脂を乾燥後の膜厚が１５μｍとなるように塗工し、乾燥した。次いで、離型性フィルム上に形成した導電層と、離型性フィルム上に形成した接合層とを貼り合わせてシールドフィルムを作製した。 (Comparative Example 3)
As a shield film, a comparative conductive ink (R1) obtained as described above was formed on a release-treated polyester film, a line width of 100 μm, an aperture ratio of 25%, and a film thickness after drying of 5 μm. It screen-printed so that it might become a pattern, and it dried and formed the conductive layer. Next, the resin for bonding layer obtained above was applied on the release-treated polyester film so that the film thickness after drying was 15 μm and dried. Next, the conductive layer formed on the releasable film and the bonding layer formed on the releasable film were bonded together to produce a shield film.
　次に、実施例１で用いたプリント配線板の代わりに、信号用銅配線パターンの線幅を表１に記載した線幅とし、そのグランド配線部に４００μｍ角の開口部が設けられたプリント配線板と、上記で得られたシールドフィルムを、プリント配線板の絶縁保護層の上に、シールドフィルムの導電層が接するように配置し、プリント配線板とシールドフィルムとを互いに接近する方向に加圧（圧力：１．９６ＭＰａ、加熱温度：１５０℃、処理時間：３０分間）して圧着し、シールドフィルムの接合層を流動させてプリント配線板のグランド層と接続し、導電性接着剤層が無い比較用シールドプリント配線板を作製した。 Next, instead of the printed wiring board used in Example 1, the wiring width of the signal copper wiring pattern is set to the line width shown in Table 1, and a 400 μm square opening is provided in the ground wiring portion. Place the board and the shield film obtained above on the insulation protective layer of the printed wiring board so that the conductive layer of the shield film is in contact, and press the printed wiring board and the shield film in a direction approaching each other (Pressure: 1.96 MPa, heating temperature: 150 ° C., treatment time: 30 minutes) and then bonded, the shield film bonding layer is flowed to connect with the ground layer of the printed wiring board, and there is no conductive adhesive layer A comparative shield printed wiring board was produced.
［特性インピーダンスの測定］
　上記の実施例、比較例で得られたシールドプリント配線板について、ネットワークアナライザＥ５０７１Ｃ（アジレント・テクノロジーズ社製）を用いて特性インピーダンスの測定を行った。 [Measurement of characteristic impedance]
About the shield printed wiring board obtained by said Example and comparative example, characteristic impedance was measured using network analyzer E5071C (made by Agilent Technologies).
［シールドフィルムとプリント配線板のグランド配線との接続信頼性の評価］
　上記の実施例、比較例で得られたシールドプリント配線板について、部品接続時のはんだリフロー工程を想定し、２４０℃で２５秒間のリフロー炉を通過させ、その後２５℃までシールドプリント配線板を冷却するリフロー操作を５回繰り返し、その前後のシールドフィルムとプリント配線板のグランド配線間の電気抵抗率の測定を行い、電気抵抗率の変化率（リフロー炉通過前の体積抵抗値／リフロー炉通過後の体積抵抗値）を算出し、以下の基準に従って評価した。
［評価基準］
　Ａ：８０％以上
　Ｂ：５０％以上、８０％未満
　Ｃ：１０％以上、５０％未満
　Ｄ：１０％未満 [Evaluation of connection reliability between shield film and printed circuit board ground wiring]
For the shield printed wiring boards obtained in the above examples and comparative examples, a solder reflow process at the time of component connection is assumed, and the shield printed wiring board is cooled to 25 ° C. after passing through a reflow furnace at 240 ° C. for 25 seconds. Repeat the reflow operation 5 times, measure the electrical resistivity between the shield film before and after the ground wiring of the printed wiring board, and change rate of electrical resistivity (volume resistance value before passing through the reflow furnace / after passing through the reflow furnace) Volume resistance value) was calculated and evaluated according to the following criteria.
[Evaluation criteria]
A: 80% or more B: 50% or more, less than 80% C: 10% or more, less than 50% D: Less than 10%
　上記で評価した結果をまとめたものを表１に示す。 Table 1 summarizes the results evaluated above.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　上記の表１中の実施例１～４のシールドプリント配線板は、プリント配線板の信号用銅配線のパターン幅を５０～２００μｍに変化させた場合においても、シールドフィルムの金属層（銅めっき層）の開口率を調整することで、シールドプリント配線板の特性インピーダンスを５０Ωに制御することができた。 In the shield printed wiring boards of Examples 1 to 4 in Table 1 above, even when the pattern width of the signal copper wiring of the printed wiring board is changed to 50 to 200 μm, the metal layer of the shield film (copper plating layer) ), The characteristic impedance of the shield printed wiring board could be controlled to 50Ω.
　一方、比較例１のシールドプリント配線板は、プリント配線板の信号用銅配線のパターン幅を１００ｎｍとし、シールドフィルムの金属層（銅めっき層）の開口率を０％（全面銅めっき層）とした例である。このシールドプリント配線板の特性インピーダンスは３０Ωになり、５０Ωに制御することができなかった。 On the other hand, in the shield printed wiring board of Comparative Example 1, the pattern width of the signal copper wiring of the printed wiring board is 100 nm, and the opening ratio of the metal layer (copper plating layer) of the shield film is 0% (overall copper plating layer). This is an example. The characteristic impedance of this shield printed wiring board was 30Ω and could not be controlled to 50Ω.
　比較例２のシールドプリント配線板は、比較例１と同様にシールドフィルムの金属層（銅めっき層）の開口率を０％（全面銅めっき層）とし、プリント配線板の信号用銅配線のパターン幅を２０μｍとし、特性インピーダンスを５０Ωに制御した例である。このシールドプリント配線板は、特性インピーダンスを５０Ωに制御できたものの、プリント配線板の信号用銅配線のパターン幅を２０μｍまで細くしたことにより、実施例のシールドプリント配線板と比較して、通信速度が速くなるに従い、伝送損失が増大する問題があった。 In the shield printed wiring board of Comparative Example 2, the aperture ratio of the metal layer (copper plating layer) of the shield film was set to 0% (entire copper plating layer) as in Comparative Example 1, and the pattern of the signal copper wiring on the printed wiring board In this example, the width is set to 20 μm and the characteristic impedance is controlled to 50Ω. Although this shielded printed wiring board was able to control the characteristic impedance to 50Ω, the communication width of the printed wiring board compared to the shielded printed wiring board of the example was reduced by reducing the pattern width of the signal copper wiring to 20 μm. There is a problem that transmission loss increases as the speed increases.
　上記の結果から、本発明のシールドプリント配線板は、プリント配線板の信号用銅配線のパターン幅を変化させた場合においても、シールドフィルムの金属層の開口率を調整することで、所望の特性インピーダンスに調整することが可能であることが確認できた。 From the above results, the shield printed wiring board of the present invention has the desired characteristics by adjusting the opening ratio of the metal layer of the shield film even when the pattern width of the signal copper wiring of the printed wiring board is changed. It was confirmed that the impedance could be adjusted.
　また、比較例３のシールドプリント配線板は、本発明のシールドプリント配線板では必須の導電性接着剤層がない構成での例である。このシールドプリント配線板では、シールドフィルム側の導電層と、プリント配線側のグランド配線の接続信頼性に問題があった。 Further, the shield printed wiring board of Comparative Example 3 is an example in which there is no essential conductive adhesive layer in the shield printed wiring board of the present invention. This shielded printed wiring board has a problem in connection reliability between the conductive layer on the shield film side and the ground wiring on the printed wiring side.
　１・・・・シールドフィルム
　２・・・・第二絶縁保護層
　２’・・・高分子層
　３・・・・導電性インクを用いて形成した層
　４・・・・開口部を有する銅めっき層
　５・・・・導電性接着剤層
　６・・・・第一絶縁保護層
　７・・・・プリント配線板基材
　８・・・・信号配線
　９・・・・グランド配線
　１０・・・第一絶縁保護層除去部（グランド配線と開口部を有する銅めっき層との導通部）
　１１・・・プリント配線板
　１２・・・シールドプリント配線板 DESCRIPTION OF SYMBOLS 1 ... Shield film 2 ... 2nd insulation protective layer 2 '... Polymer layer 3 ... Layer formed using conductive ink 4 ... Copper plating with opening Layer 5... Conductive adhesive layer 6... First insulating protective layer 7... Printed wiring board base material 8... Signal wiring 9. One insulating protective layer removal part (conducting part between ground wiring and copper plating layer with opening)
11 ... Printed wiring board 12 ... Shield printed wiring board

Claims (12)

  1. 　ベース絶縁基材上に信号配線とグランド配線及び第一絶縁保護層が設けられたプリント配線板用のシールドフィルムであって、
    前記第一絶縁保護層上の全面に積層された導電性接着剤層と、
    前記導電性接着剤層上に膜厚０．２～２０μｍ、開口率１０～９０％でパターン化された銅めっき層と、
    前記銅めっき層上に導電性インクを用いて形成した層（Ａ）と、
    前記導電性接着剤層及び前記銅めっき層及び前記層（Ａ）上に第二絶縁保護層とを有することを特徴とするシールドフィルム。     A shield film for a printed wiring board in which a signal wiring, a ground wiring, and a first insulating protective layer are provided on a base insulating base material,
    A conductive adhesive layer laminated on the entire surface of the first insulating protective layer;
    A copper plating layer patterned with a film thickness of 0.2 to 20 μm and an aperture ratio of 10 to 90% on the conductive adhesive layer;
    A layer (A) formed using a conductive ink on the copper plating layer;
    A shield film comprising a second insulating protective layer on the conductive adhesive layer, the copper plating layer, and the layer (A).
  2. 　前記導電性インクが、導電性物質（ａ２）として金属ナノ粒子を主成分とするインクである請求項１記載のシールドフィルム。 The shield film according to claim 1, wherein the conductive ink is an ink mainly composed of metal nanoparticles as a conductive substance (a2).
  3. 　前記金属ナノ粒子が、高分子分散剤により分散されたものである請求項２記載のシールドフィルム。 The shield film according to claim 2, wherein the metal nanoparticles are dispersed by a polymer dispersant.
  4. 　前記第二絶縁保護層と前記導電性インクを用いて形成した層（Ａ）との間に高分子層（Ｂ）を有するものである請求項１～３のいずれか１項記載のシールドフィルム。 The shield film according to any one of claims 1 to 3, further comprising a polymer layer (B) between the second insulating protective layer and the layer (A) formed using the conductive ink.
  5. 　前記導電性インクが、反応性官能基［Ｘ］を有する化合物（ａ１）及び導電性物質（ａ２）を含有する導電性インクであり、
    かつ、前記高分子層（Ｂ）が、反応性官能基［Ｙ］を有する化合物（ｂ１）を含有する高分子からなる層であり、
    前記導電性インクに含まれる前記化合物（ａ１）が有する反応性官能基［Ｘ］と、前記高分子層（Ｂ）に含まれる前記化合物（ｂ１）が有する反応性官能基［Ｙ］とを反応させることによって結合を形成したものである請求項４記載のシールドフィルム。     The conductive ink is a conductive ink containing a compound (a1) having a reactive functional group [X] and a conductive substance (a2),
    And the polymer layer (B) is a layer composed of a polymer containing the compound (b1) having a reactive functional group [Y],
    The reactive functional group [X] of the compound (a1) contained in the conductive ink reacts with the reactive functional group [Y] of the compound (b1) contained in the polymer layer (B). The shield film according to claim 4, which is formed by bonding.
  6. 　前記導電性インクが、反応性官能基［Ｘ］として塩基性窒素原子含有基を有する化合物（ａ１）及び導電性物質（ａ２）を含有する導電性インクである請求項５記載のシールドフィルム。 The shield film according to claim 5, wherein the conductive ink is a conductive ink containing a compound (a1) having a basic nitrogen atom-containing group as a reactive functional group [X] and a conductive substance (a2).
  7. 　前記塩基性窒素原子含有基を有する化合物（ａ１）が、ポリアルキレンイミン、または、オキシエチレン単位を含むポリオキシアルキレン構造を有するポリアルキレンイミンである請求項６記載のシールドフィルム。 The shield film according to claim 6, wherein the compound (a1) having a basic nitrogen atom-containing group is a polyalkyleneimine or a polyalkyleneimine having a polyoxyalkylene structure containing an oxyethylene unit.
  8. 　前記反応性官能基［Ｙ］が、ケト基、エポキシ基、カルボキシル基、Ｎ－アルキロール基、イソシアネート基、ビニル基、（メタ）アクリロイル基、アリル基からなる群より選ばれる１種以上である請求項５～７のいずれか１項記載のシールドフィルム。 The reactive functional group [Y] is at least one selected from the group consisting of a keto group, an epoxy group, a carboxyl group, an N-alkylol group, an isocyanate group, a vinyl group, a (meth) acryloyl group, and an allyl group. The shield film according to any one of claims 5 to 7.
  9. 　請求項１～８のいずれか１項記載のシールドフィルムを有することを特徴とするシールドプリント配線板。 A shield printed wiring board comprising the shield film according to any one of claims 1 to 8.
  10. 　第二絶縁保護層上または第二絶縁保護層上に設けた高分子層（Ｂ）上に、
    導電性インクで開口率１０～９０％のパターンを形成し、
    その上に電解銅めっきを施して銅めっき層を形成し、
    その上に導電性接着剤層を形成することを特徴とするシールドフィルムの製造方法。     On the second insulating protective layer or the polymer layer (B) provided on the second insulating protective layer,
    A pattern with an aperture ratio of 10 to 90% is formed with conductive ink,
    On top of that, electrolytic copper plating is applied to form a copper plating layer,
    A method for producing a shield film, comprising forming a conductive adhesive layer thereon.
  11. 　前記導電性インク（Ａ）として金属ナノ粒子を主成分とするインクを用い、インクジェット印刷で開口率１０～９０％のパターンを形成する請求項１０記載のシールドフィルムの製造方法。 The method for producing a shield film according to claim 10, wherein an ink having metal nanoparticles as a main component is used as the conductive ink (A), and a pattern having an aperture ratio of 10 to 90% is formed by ink jet printing.
  12. 　信号配線とグランド配線及び絶縁保護層が設けられ、前記絶縁保護層はグランド配線の一部が露出したビアを有するプリント配線板において、
    プリント配線板の絶縁保護層の上に、請求項１～８のいずれか１項記載のシールドフィルムを、導電性接着剤層が前記プリント配線板の絶縁保護層に接するように配置し、プリント配線板とシールドフィルムとを互いに接近する方向に加圧することによりシールドフィルムの導電性接着剤層を流動させてプリント配線板のグランド層と接続することを特徴とするシールドプリント配線板の製造方法。     A signal wiring, a ground wiring, and an insulating protective layer are provided, and the insulating protective layer is a printed wiring board having a via in which a part of the ground wiring is exposed,
    A shield film according to any one of claims 1 to 8 is disposed on an insulating protective layer of a printed wiring board so that a conductive adhesive layer is in contact with the insulating protective layer of the printed wiring board. A method for producing a shielded printed wiring board, wherein the conductive adhesive layer of the shield film is caused to flow by pressurizing the board and the shield film toward each other to be connected to the ground layer of the printed wiring board.
PCT/JP2015/055570 2014-03-10 2015-02-26 Shield film, shield printed wiring board, and methods for producing same WO2015137132A1 (en)

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