WO2017195621A1 - Metal nanoparticle ink for flexography and method for producing laminate using same - Google Patents
Metal nanoparticle ink for flexography and method for producing laminate using same Download PDFInfo
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- WO2017195621A1 WO2017195621A1 PCT/JP2017/016716 JP2017016716W WO2017195621A1 WO 2017195621 A1 WO2017195621 A1 WO 2017195621A1 JP 2017016716 W JP2017016716 W JP 2017016716W WO 2017195621 A1 WO2017195621 A1 WO 2017195621A1
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- metal nanoparticle
- flexographic printing
- ink
- metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41F—PRINTING MACHINES OR PRESSES
- B41F5/00—Rotary letterpress machines
- B41F5/24—Rotary letterpress machines for flexographic printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/02—Letterpress printing, e.g. book printing
- B41M1/04—Flexographic printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
Definitions
- the present invention relates to a metal nanoparticle ink for flexographic printing that can be used for manufacturing electronic circuits, antenna wiring, electromagnetic wave shields, and the like.
- Examples of the metal nanoparticle ink that can be used for manufacturing the electronic circuit and the like include, for example, a cellulose substrate using a conductive aqueous ink composed of water, conductive particles, a water-soluble resin, a surfactant, and an antifoaming agent.
- a method of forming a conductive pattern using a flexographic printing method has been proposed (for example, see Patent Document 1).
- Patent Document 1 A method of forming a conductive pattern using a flexographic printing method has been proposed (for example, see Patent Document 1).
- ink repelling or metal nanoparticles become non-uniform due to the coffee stain phenomenon, and a uniform pattern is printed. There was a problem that I could not.
- the metal nanoparticle ink for flexographic printing is capable of producing a uniform pattern that is less likely to cause ink repelling when printed on a substrate that hardly absorbs a solvent, and has a high accuracy and stability. And a method for producing a laminate using the ink.
- the present inventors have increased the alcohol content in the aqueous medium contained in the metal nanoparticle ink for flexographic printing, so that the pattern is stably highly accurate and uniform.
- the present invention has been completed.
- the present invention relates to a metal nanograph for flexographic printing comprising a composite of metal nanoparticles (A) and an organic compound (B), and an aqueous medium (C) containing water and a monoalcohol having 1 to 3 carbon atoms.
- the present invention provides a method for producing a laminate comprising printing the metal nanoparticle ink for flexographic printing on a surface of a base material by a flexographic printing method, and a reactive functional group (Y) on the surface of the base material.
- the organic compound (B) After forming the primer layer (D) containing the resin (d) having, the organic compound (B) has a reactive functional group (X) that reacts with the reactive functional group (Y) to form a bond.
- a method for producing a laminate characterized in that the metal nanoparticle ink for flexographic printing is printed by a flexographic printing method, and further a metal nano for flexographic printing of a laminate obtained by the method for producing the laminate.
- Another object of the present invention is to provide a method for producing a laminate, in which a metal plating layer (E) is further formed by electroless plating and / or electrolytic plating on the surface of an ink layer formed of particle ink.
- the metal nanoparticle ink for flexographic printing of the present invention is used, for example, the metal nanoparticle ink containing metal particles is hard to be repelled on a substrate surface that does not absorb a solvent such as an organic film, and the accuracy is stable. High metal nanoparticle patterns can be produced.
- flexographic printing enables continuous printing on a substrate in a roll-to-roll manner, and a pattern of metal nanoparticles can be produced with high efficiency.
- the metal nanoparticle ink for flexographic printing according to the present invention is, for example, an electronic circuit densified by lamination, an inorganic or organic solar cell that needs to be bonded to another member, an organic EL element, an organic transistor, a flexible It can be suitably used in the manufacture of various electronic members such as printed circuit boards, RFIDs such as non-contact IC cards, etc., peripheral wiring members, and electromagnetic wave shields.
- the metal nanoparticle ink for flexographic printing of the present invention contains a composite of metal nanoparticles (A) and an organic compound (B), and an aqueous medium (C) containing water and a monoalcohol having 1 to 3 carbon atoms.
- the metal nanoparticles (A) include transition metals or compounds thereof.
- transition metals are preferable, and examples thereof include copper, silver, gold, nickel, palladium, platinum, and cobalt.
- copper, silver, and gold are preferable because they can form a metal nanoparticle pattern that has low electrical resistance and is resistant to corrosion, and silver is more preferable.
- the average particle diameter of the metal nanoparticles (A) is preferably in the range of 1 to 100 nm and more preferably in the range of 1 to 50 nm because a fine metal nanoparticle pattern can be formed and the resistance value can be further reduced.
- the “average particle diameter” is a volume average value obtained by diluting the metal nanoparticles (A) with a good dispersion solvent and measuring by a dynamic light scattering method. This average particle diameter can be measured by, for example, “Nanotrack UPA-150” manufactured by Nikkiso Co., Ltd.
- organic compound (B) those having a cationic group or an anionic group are preferable because dispersibility of the metal nanoparticles in an aqueous medium is improved.
- the cationic group include amino groups and quaternary ammonium bases.
- the anionic group include a carboxyl group, a carboxylate group, a phosphoric acid group, a phosphorous acid group, a sulfonic acid group, a sulfonate group, a sulfinic acid group, and a sulfenic acid group.
- the complex with the metal nanoparticles (A) using the organic compound (B) having the anionic group can be obtained, for example, by the method described in Japanese Patent No. 5648232.
- the organic compound (B) is preferably a compound having both a functional group coordinated to a metal and a hydrophilic group.
- Examples of the functional group that coordinates to the metal include a pyridinium group, a triphenylphosphine group, a nitric acid group, a carboxyl group, an acetylacetonato group, an amino group, a thiol group, a thioether group, and a thiocyanate group.
- amino groups and carboxyl groups are preferred because they have a high coordination power to metals and are easily released from the metal after printing, and are in a configuration that allows bidentate coordination with the metal.
- Group and carboxyl group are preferred.
- hydrophilic group examples include nonionic groups in addition to the above anionic groups and cationic groups.
- nonionic group examples include a polyoxyalkylene chain, a polyvinyl alcohol chain, a polyvinylpyrrolidone chain, and the like, and a polyoxyethylene chain is preferable because of its high affinity for water.
- a complex with the metal nanoparticles (A) using the organic compound (B) having a polyethyleneimine chain and a polyoxyethylene chain can be obtained, for example, by the method described in Japanese Patent No. 5648229.
- the amino group (imino group) in the polyethyleneimine chain functions as a cationic group.
- the reactivity which resin (d) used for the said primer layer (D) has as said organic compound (B) What has the reactive functional group (X) which reacts with a functional group (Y) and forms a bond is preferable.
- Examples of the functional group (X) include a carboxyl group, an isocyanate group, a blocked isocyanate group, an epoxy group, a hydroxyl group, an oxazoline group, an N-methylol group, an N-alkoxymethylol group, an amino group, and an alkoxysilyl group.
- the organic compound (B) may have two or more of these functional groups.
- the functional group (X) is an amino group
- an organic compound having the polyethyleneimine chain is used as the organic compound (B), and the amino group (imino group) in the polyethyleneimine chain is converted to the functional group (X). It can be.
- An acrylic resin obtained by polymerizing an acrylic monomer having the functional group (X) can also be used as the organic compound (B) having the functional group (X).
- examples of the raw material for the acrylic resin include (meth) acrylic acid, ⁇ -carboxyethyl (meth) acrylate, 2- (meth) acryloylpropionic acid, crotonic acid, and itaconic acid.
- the functional group (X) is an isocyanate group
- a monomer having a blocked isocyanate group such as “Karenz MOI-BM” manufactured by Showa Denko KK is used as a raw material for the acrylic resin.
- the functional group (X) is an epoxy group
- a monomer having an epoxy group such as glycidyl (meth) acrylate or allyl glycidyl ether is used as a raw material for the acrylic resin.
- the functional group (X) is a hydroxyl group
- a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used as a raw material for the acrylic resin.
- the functional group (X) is an oxazoline group
- a monomer having an oxazoline group such as 2-isopropenyl-2-oxazoline is used as a raw material for the acrylic resin.
- the functional group (X) is an N-methylol group
- a monomer having an N-methylol group such as N-methylol (meth) acrylamide is used as a raw material for the acrylic resin.
- examples of the raw material for the acrylic resin include N-methoxymethylol (meth) acrylamide, N-ethoxymethylol (meth) acrylamide, and N-propoxymethylol (meth) acrylamide.
- N-alkoxymethylol groups such as N-isopropoxymethylol (meth) acrylamide, Nn-butoxymethylol (meth) acrylamide, N-isobutoxymethylol (meth) acrylamide, and N-pentoxymethylol (meth) acrylamide Use monomers.
- the functional group (X) is an amino group
- a monomer having an amino group such as N, N-dimethylaminoethyl methacrylate is used as a raw material for the acrylic resin.
- the functional group (X) is an alkoxysilyl group
- a monomer having an alkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane is used as a raw material for the acrylic resin.
- the acrylic resin may be copolymerized with an acrylic monomer other than the monomer having the above functional group.
- the acrylic resin can be produced by a known method, and among them, the solution polymerization method is preferable because the dispersion stability of the metal nanoparticles is improved.
- (meth) acrylate refers to one or both of acrylate and methacrylate
- (meth) acrylamide refers to one or both of acrylamide and methacrylamide
- Examples of the method for producing the composite of the metal nanoparticles (A) and the organic compound (B) used in the present invention include the methods described in Japanese Patent Nos. 5648232 and 5648229.
- the powder of the composite of the metal nanoparticles (A) and the organic compound (B) can be obtained by freeze-drying an aqueous dispersion of the composite.
- the aqueous medium (C) used in the present invention contains water and a monoalcohol having 1 to 3 carbon atoms, and the content of the monoalcohol having 1 to 3 carbon atoms contained therein is 45% by mass or more. belongs to.
- Examples of the monoalcohol having 1 to 3 carbon atoms include methanol, ethanol, n-propanol, and isopropanol. By using these monoalcohols, it is possible to suppress ink repellency and unevenness of metal nanoparticles due to the coffee stain phenomenon.
- the content of the monoalcohol having 1 to 3 carbon atoms in the aqueous medium (C) is 45% by mass or more, preferably 45 to 95% by mass. Further, in order to print with the metal nanoparticle content of the ink described later and the ink viscosity at that time, the content of the monoalcohol is more preferably in the range of 60 to 90% by mass.
- the aqueous medium (C) includes alcohol solvents such as ethyl carbitol, ethyl cellosolve and butyl cellosolv; ketones such as acetone and methyl ethyl ketone, as necessary.
- Solvent alkylene glycol solvent such as ethylene glycol, diethylene glycol, propylene glycol, butyl glycol; glycerin; alkyl ether of polyalkylene glycol; water-soluble solvent such as lactam solvent such as N-methyl-2-pyrrolidone may be used.
- the content of the metal nanoparticles (A) used in the present invention in the ink is preferably in the range of 1 to 60% by mass. Further, when the metal plating layer (E) is formed in the plating process described later, the content of the metal nanoparticles (A) in the ink can further suppress the adverse effect on the metal plating layer obtained in the plating process. A range of 1 to 20% by mass is more preferable.
- the viscosity of the metal nanoparticle ink for flexographic printing of the present invention is preferably in the range of 0.1 to 300 mPa ⁇ s. Further, when the metal plating layer (E) is formed in the plating process described later, the content of the metal nanoparticles (A) in the ink is preferably in the range of 1 to 20% by mass as described above.
- the viscosity of the printing metal nanoparticle ink is preferably in the range of 0.1 to 25 mPa ⁇ s. Further, the viscosity of the metal nanoparticle ink for flexographic printing is more preferably in the range of 0.1 to 10 mPa ⁇ s because it easily follows the fine irregularities of the substrate.
- the metal nanoparticle ink for flexographic printing according to the present invention contains a specific amount of a predetermined monoalcohol, so that the ink repellency and the metal nanoparticle may be a coffee stain phenomenon. Can suppress non-uniformity.
- the viscosity of the ink in the present invention is a value measured with an E-type viscometer (measurement temperature: 25 ° C., cone rotor: 1 ° 34 ′ ⁇ R24, rotation speed: 50 rpm).
- the metal nanoparticle ink for flexographic printing of the present invention comprises a dispersion stability of a complex of the metal nanoparticle (A) and the organic compound (B) in an aqueous medium (C), a base material, or a primer layer (D described later).
- a pH adjuster, a surfactant, an antifoaming agent, a rheology adjuster, a leveling agent, etc. are used as necessary. May be.
- the metal nanoparticle ink for flexographic printing according to the present invention can be directly printed on a substrate to be printed to form a laminate, but a primer layer (D) is previously formed on the surface of the substrate and printed on the surface. By doing so, a laminate having higher adhesion between the substrate and the ink layer can be obtained, which is preferable.
- the base material examples include polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polycarbonate resin, acrylonitrile-butadiene-styrene (ABS) resin, and acrylic such as poly (meth) acrylate.
- polyvinylidene fluoride resin polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polycarbonate resin, polyethylene resin, polypropylene resin, urethane resin, liquid crystal polymer (LCP), polyether ether ketone (PEEK) resin, polyphenylene sulfide (PPS) resin, polyphenylene sulfone (PPSU) resin, cellulose nanofiber, base material made of silicon, ceramics, glass, etc., from them That the porous base material, steel, substrate made of metal such as copper, their surface silicon carbide, diamond-like carbon, aluminum, copper, or the like can be used and titanium deposition treated substrate.
- an electroconductive material for a base material it can use as a base material in this invention by forming the primer layer (D) mentioned later as the insulating layer on the surface.
- the laminated body manufactured by this invention when using the laminated body manufactured by this invention for a circuit board etc., it consists of a polyimide, a polyethylene terephthalate, a polyethylene naphthalate, a liquid crystal polymer (LCP), polyetheretherketone (PEEK), glass, a cellulose nanofiber, etc. It is preferable to use a substrate.
- the laminate produced according to the present invention is used for applications requiring flexibility, it is preferable to use a film-like or sheet-like substrate rich in flexibility as the substrate.
- Examples of the film-like or sheet-like base material include a polyethylene terephthalate film, a polyimide film, and a polyethylene naphthalate film.
- the film-like or sheet-like base material preferably has a thickness of 1 to 2,000 ⁇ m because the laminate produced according to the present invention can be reduced in weight and thickness.
- a thickness of ⁇ 100 ⁇ m is more preferable.
- a thickness of 1 to 80 ⁇ m is more preferable.
- the resin (d) forming the primer layer (D) has the functional group (Y) that reacts with the functional group (X) contained in the organic compound (B) to form a chemical bond.
- the resin type is not limited, but a urethane resin, an acrylic resin, or a combination thereof is preferable.
- the resin (d) can be used alone or in combination of two or more.
- Examples of the functional group (Y) include a carboxyl group, an isocyanate group, a blocked isocyanate group, an epoxy group, a hydroxyl group, an oxazoline group, an N-methylol group, an N-alkoxymethylol group, an amino group, and an alkoxysilyl group. Can be mentioned.
- the resin (d) may have two or more of these functional groups.
- the carboxyl group may be derived from an acid anhydride.
- the amino group may be any of primary to tertiary amino groups.
- the resin (d) for example, those described in Japanese Patent No. 5382279 can be used.
- the method described in the publication can also be used for introducing the functional group (Y) into the resin (d).
- the combination in which the reactive functional group (X) of the organic compound (B) and the reactive functional group (Y) of the resin (d) react efficiently to form a bond is preferable.
- the functional group (X) is a carboxyl group
- the functional group (Y) is preferably an epoxy group
- the functional group (X) is an isocyanate group or a blocked isocyanate group
- the functional group (Y ) Is preferably a hydroxyl group or an amino group
- the functional group (X) is an epoxy group
- the functional group (Y) is preferably a carboxyl group or an amino group
- the functional group (X) is an oxazoline group
- the functional group (Y) is preferably a carboxyl group
- the functional group (Y) is preferably an isocyanate group or a blocked isocyanate group
- the functional group (X) is a methylol group or an N-alkoxy group.
- the functional group (Y) is preferably a methylol group, an N-alkoxymethylol group or an amino group
- the functional group (X) In the case of an amino group, the functional group (Y) is preferably an epoxy group, an isocyanate group, a blocked isocyanate group, an N-methylol group, or an N-alkoxymethylol group.
- the functional group (X) is an alkoxysilyl group
- the functional group (Y) is preferably an alkoxysilyl group.
- a soft rubber plate is used because plate making and printing are simple.
- the flexographic printing method used is preferred.
- an anilox roll is used to uniformly transfer ink to a plate.
- the thickness of the ink layer after printing and drying can be adjusted.
- the thickness of the ink layer is preferably 100 nm or less.
- the number of anilox rolls is preferably in the range of 160 to 600 lines / cm, and more preferably in the range of 200 to 400 lines / cm.
- the cell volume is preferably in the range of 2 to 6 cm 3 / m 2 .
- the printing speed is preferably adjusted in the range of 20 to 200 m / min, and the printing speed is set in the range of 30 to 150 m / min in consideration of print quality and productivity.
- the substrate may be conveyed by a single sheet, but in the case of a continuous substrate such as a film substrate wound by a roll, it can also be conveyed by a roll-to-roll.
- the primer layer (D) is subjected to a heat treatment as necessary.
- the said functional group (Y) which the said resin (d) contained reacts with the said functional group (X) which the said organic compound (B) contained in the said metal nanoparticle ink for flexographic printing reacts, and the said primer It is possible to further improve the adhesion between the layer (D) and the ink layer.
- the temperature of the heat treatment is preferably in the range of 50 to 300 ° C. for 2 to 200 minutes.
- the said heat processing may be performed in air
- the heat treatment can be performed by, for example, an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, microwave, light irradiation, or the like.
- Electroless plating is further performed on the surface of the ink layer of the laminate obtained by printing the metal nanoparticle ink for flexographic printing of the present invention on the surface of the substrate or the primer layer (D) formed on the substrate. And / or it can also be set as the laminated body which formed the metal plating layer (E) by electrolytic plating.
- the electroless plating and the electroplating can be performed independently, but after the electroless plating, the electroplating may be performed.
- the electroless plating and electrolytic plating for forming the metal plating layer (E) can be performed by a known method.
- the laminate obtained by the production method of the present invention can maintain good electrical conductivity without being peeled off from the primer layer (D) even if the laminate is subjected to a plating process, and is excellent.
- Peripheral wiring that forms circuit forming substrates used in electronic circuits, integrated circuits, etc., organic solar cells, electronic book terminals, organic EL, organic transistors, flexible printed circuit boards, RFID, etc. It is suitably used for forming an electromagnetic wave and for electromagnetic wave shielding.
- the laminate subjected to the plating treatment does not cause disconnection or the like over a long period of time and can maintain good electrical conductivity and can form a highly reliable wiring pattern, for example, a flexible printed circuit board (FPC), It can be used for applications generally called copper clad laminates (CCL) such as automatic tape bonding (TAB), chip-on-film (COF), and printed wiring board (PWB).
- FPC flexible printed circuit board
- CCL copper clad laminates
- TAB automatic tape bonding
- COF chip-on-film
- PWB printed wiring board
- a polymerization initiator (0.3 parts by weight of “Perbutyl O” manufactured by NOF Corporation) was added twice and stirred for 12 hours at 80 ° C. Water was added to the resulting resin solution and the solution was transferred. After phase emulsification and desolvation under reduced pressure, water was added to adjust the concentration to obtain an aqueous solution of an acrylic polymer having a glycidyl group with a non-volatile content of 76.8% by mass. The weight average molecular weight measured by chromatography was 4,200 in terms of polystyrene, and the acid value was 96.2 mgKOH / g.
- a reducing agent solution consisting of 85 mass% N, N-diethylhydroxylamine 5.56 g (53.0 mmol), the acrylic polymer obtained above (corresponding to 106 mg of a non-volatile material), and water 15 g was prepared. Separately, the acrylic polymer obtained above (corresponding to 106 mg of non-volatile material) was dissolved in 5 g of water, and a solution of 6 g (35.3 mmol) of silver nitrate in 10 g of water was added thereto and stirred well. The reducing agent solution was added dropwise to this mixture at room temperature (25 ° C.) over 2 hours. The obtained reaction mixture was concentrated at 40 ° C.
- an aqueous dispersion of silver nanoparticles having a nonvolatile content of about 30% by mass The particle size of the silver nanoparticles was estimated from 10 to 40 nm from the TEM image. Further, the dispersion was left to stand in a freezer at ⁇ 40 ° C. for one day and frozen, and this was treated with a freeze dryer (“FDU-2200” manufactured by Tokyo Rika Kikai Co., Ltd.) for 24 hours, thereby obtaining silver nanoparticles.
- An anionic silver nanoparticle consisting of grey-green metallic luster flake-like lumps, which is a composite of an anionic group (phosphate group) and an organic compound having a glycidyl group, was obtained.
- Example 1 By mixing 5 g of anionic silver nanoparticles obtained in Production Example 1, 45 g of ethanol, 29 g of ion-exchanged water, and 0.1 g of a leveling agent (“KF-351A” manufactured by Shin-Etsu Silicone Co., Ltd.) and stirring for 3 hours A metal nanoparticle ink (1) for flexographic printing (alcohol content of 1 to 3 carbon atoms in an aqueous medium: 69% by mass, silver content: 4.7% by mass, viscosity: 1.0 mPa ⁇ s) was prepared.
- a leveling agent (“KF-351A” manufactured by Shin-Etsu Silicone Co., Ltd.
- the metal nanoparticle ink for flexographic printing (1) obtained above is applied to the surface of a polyimide film (“Kapton150ENC” manufactured by Toray DuPont Co., Ltd., 50 ⁇ m thick), and the flexographic printing machine (“Flexiproof 100 manufactured by Matsuo Sangyo Co., Ltd.”) is used. ”,
- a square solid pad part with a side of 2 mm is connected to both ends of a straight line parallel to the printing direction with a line width of 100 ⁇ m and a length of 64 mm at the midpoint of one side. 1 (FIG. 1), a pattern in which the pattern in FIG. 1 is a straight line orthogonal to the printing direction (FIG. 2), and a solid solid pattern with a side of 60 mm (FIG. 3) at a printing speed of 50 m / min.
- the laminated body was obtained by drying at 120 degreeC for 10 minute (s).
- Example 2 5 g of the cationic silver nanoparticles obtained in Production Example 2, 63 g of methanol, 29 g of ion-exchanged water, 3 g of glycerin, and 0.1 g of a leveling agent (“KF-351A” manufactured by Shin-Etsu Silicone Co., Ltd.) were mixed and stirred for 3 hours.
- a leveling agent (“KF-351A” manufactured by Shin-Etsu Silicone Co., Ltd.)
- KF-351A a leveling agent manufactured by Shin-Etsu Silicone Co., Ltd.
- Example 3 Methyl ethyl ketone solution of the primer layer resin having a carboxyl group obtained in Production Example 3 was added to a polyimide film (“Kapton 150ENC” manufactured by Toray DuPont Co., Ltd., thickness 50 ⁇ m) so that the dry film thickness was 0.3 ⁇ m.
- the substrate was coated with a spin coater and dried at 80 ° C. for 3 minutes using a hot air drier to obtain a substrate on which a primer layer was formed.
- the obtained metal nanoparticle ink for flexographic printing (3) was printed in the same manner as in Example 1 on the surface of the primer layer of the substrate on which the primer layer obtained above was formed. Next, by drying at 120 ° C. for 10 minutes, a laminate in which the carboxyl group in the primer layer of the substrate and the glycidyl group in the anionic silver nanoparticles reacted and bonded was obtained.
- the ink (R1) obtained above was printed in the same manner as in Example 1 on the surface of the primer layer of the base material on which the primer layer obtained in the same manner as in Example 3 was formed. Next, by drying at 120 ° C. for 10 minutes, a laminate in which the carboxyl group in the primer layer of the substrate and the glycidyl group in the anionic silver nanoparticles reacted and bonded was obtained.
- Examples 4 to 10 and Comparative Examples 2 to 4 Using the cationic silver nanoparticles obtained in Production Example 2, the same procedure as in Example 1 was carried out except that the composition was changed to the compositions shown in Tables 2 and 3, and metal nanoparticle inks for flexographic printing (4) to ( 10) and (R2) to (R4) were prepared.
- Methyl ethyl ketone solution of the primer layer resin having a glycidyl group obtained in Production Example 4 is a polyimide film ("Kapton150ENC" manufactured by Toray DuPont Co., Ltd.) so that the thickness of the primer layer after drying is 0.1 ⁇ m.
- a polyimide film roll base material on which a primer layer is formed is coated on a surface having a thickness of 50 ⁇ m and a length of 1000 m using a small-diameter gravure coater and dried at 80 ° C. for 3 minutes using a hot air dryer. Obtained.
- Example 4 Using the metal nanoparticle ink for flexographic printing (4) obtained in Example 4 on the surface of the primer layer of the base material on which the primer layer obtained above was formed, using a flexographic printing machine ("SOLOFLEX" manufactured by WINDMOELLER & HOLSCHER) In the same manner as in Example 1, a printing pattern (FIGS. 1 to 3) was printed at 1000 m with a printing speed of 100 m / min and roll-to-roll. Next, by drying at 120 ° C. for 10 minutes, a laminate in which the glycidyl group in the primer layer of the base material and the amino (imino) group in the cationic silver nanoparticles reacted and bonded was obtained.
- SOLOFLEX manufactured by WINDMOELLER & HOLSCHER
- the electrolytic plating solution used contained 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 50 mg / L of chloride ions, and 5 g / L of Top Lucina SF (brightener manufactured by Okuno Pharmaceutical Co., Ltd.).
- the surface of the solid plating layer of the printed pattern obtained by laminating the obtained copper plating layer was randomly photographed at a magnification of 180 ⁇ using a microscope (“VHX-900” manufactured by Keyence Corporation).
- a valuation treatment was performed, and the area ratio of plating film defects was evaluated.
- B There was a defect in the range of less than 1%.
- C There was a defect in the range of 1% or more and less than 10%.
- D There was a defect in the range of 10% or more and less than 30%.
- E There was a defect in the range of 30% or more.
- Example 11 The laminate obtained in Example 11 was first immersed in an electroless copper plating solution ("OIC Copper” manufactured by Okuno Seiyaku Co., Ltd., pH 12.5) at 55 ° C for 20 minutes to form an electroless copper plating film (thickness). 0.5 ⁇ m) was formed. Next, by performing electroplating for 15 minutes at a current density of 2 A / dm 2 using an electroplating solution containing copper sulfate with the surface of the solid portion of the printed pattern (FIG. 3) as a cathode and phosphorous copper as an anode, A copper plating layer having a thickness of 8 ⁇ m was laminated on the surface of the conductive layer.
- an electroless copper plating solution ("OIC Copper” manufactured by Okuno Seiyaku Co., Ltd., pH 12.5) at 55 ° C for 20 minutes to form an electroless copper plating film (thickness). 0.5 ⁇ m) was formed.
- the electrolytic plating solution used contained 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 50 mg / L of chloride ions, and 5 g / L of Top Lucina SF (brightener manufactured by Okuno Pharmaceutical Co., Ltd.). About the plating layer surface of the solid part of the printing pattern which laminated
- the electrolytic plating solution used contained 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 50 mg / L of chloride ions, and 5 g / L of Top Lucina SF (brightener manufactured by Okuno Pharmaceutical Co., Ltd.).
- tester electrodes were applied to the pad portions of two types of printed patterns (FIGS. 1 and 2) obtained by laminating the obtained copper plating layers, and the disconnection ratio in 40 (20 ⁇ 2 patterns) was evaluated.
- Example 11 The laminate obtained in Example 11 was first immersed in an electroless copper plating solution ("OIC Copper” manufactured by Okuno Seiyaku Co., Ltd., pH 12.5) at 55 ° C for 20 minutes to form an electroless copper plating film (thickness). 0.5 ⁇ m) was formed.
- an electroless copper plating solution ("OIC Copper” manufactured by Okuno Seiyaku Co., Ltd., pH 12.5)
- a pattern (FIG. 1) in which a square solid pad portion having a side of 2 mm is connected to both ends of a straight line having a line width of 100 ⁇ m and a length of 6 cm obtained above at the midpoint of one side, and a space between the pad portions of 1 mm is 20 mm.
- the electroconductive layer is formed by performing electroplating at a current density of 2 A / dm 2 for 15 minutes using an electroplating solution containing copper sulfate using the surface of the regular pattern (FIG. 2) as a cathode, phosphorous copper as an anode, and copper sulfate.
- a copper plating layer having a thickness of 8 ⁇ m was laminated on the surface of the substrate.
- the electrolytic plating solution used contained 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 50 mg / L of chloride ions, and 5 g / L of Top Lucina SF (brightener manufactured by Okuno Pharmaceutical Co., Ltd.).
- a set of printing patterns is arbitrarily selected from the two types of printing patterns (FIGS. 1 and 2) obtained by laminating the obtained copper plating layer, and tester electrodes are applied to the pad portions of the printing patterns.
- the disconnection ratio in the book (20 pieces ⁇ 2 patterns) was evaluated.
- Table 1 summarizes the results of evaluation of the composition of the metal nanoparticle ink for flexographic printing, the type of resin used for the primer layer (D) formed on the substrate surface (denoted by the number of the production example), and printability. Shown in ⁇ 3.
- Example 11 is an example of using an actual flexographic printing machine using the metal nanoparticle ink of the present invention, but can be flex-printed by roll-to-roll without any problem and has good printability. I was able to confirm.
- Example 3 it was confirmed that a metal plating layer could be laminated without any problem by electrolytic plating, and that the metal plating layer had a high current conduction rate.
- Example 11 the metal plating layer was laminated by electroless plating, and then the metal plating layer was further thickened by electrolytic plating. Similarly, the metal plating layer can be laminated without any problem. It was confirmed that the layer had a high current rate.
- the print patterns obtained in Comparative Examples 1 to 4 are examples in which the content of the alcohol having 1 to 3 carbon atoms in the aqueous medium (C) is less than 45% by mass. These printing patterns have poor printability on the substrate and primer layer, and repel immediately after printing, so that there is a problem that a plating layer having a desired pattern cannot be laminated.
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Abstract
Description
温度計、攪拌機、滴下漏斗、窒素導入管及び還流冷却器を備えた四つ口フラスコに、メチルエチルケトン(以下、MEK)32質量部及びエタノール32質量部を仕込んで、窒素気流中、攪拌しながら80℃に昇温した。次に、ホスホオキシエチルメタクリレート20質量部、メトキシポリエチレングリコールメタクリレート(分子量1,000)70質量部、グリシジルメタクリレート10質量部、メルカプトプロピオン酸メチル4.1質量部、MEK80質量部からなる混合物、及び重合開始剤(和光純薬株式会社製品「V-65」、2,2’-アゾビス(2,4-ジメチルバレロニトリル))0.5質量部、MEK5質量部からなる混合物をそれぞれ2時間かけて滴下した。滴下終了後、4時間ごとに重合開始剤(日油株式会社製「パーブチルO」0.3質量部を2回添加し、80℃で12時間攪拌した。得られた樹脂溶液に水を加え転相乳化し、減圧脱溶剤した後、水を加えて濃度を調整して、不揮発物含量76.8質量%のグリシジル基を有するアクリル重合体の水溶液が得られた。該樹脂のゲルパーミエーション・クロマトグラフィーにより測定された重量平均分子量はポリスチレン換算で4,200、酸価は96.2mgKOH/gであった。 [Production Example 1: Production of anionic silver nanoparticles]
A four-necked flask equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser was charged with 32 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) and 32 parts by mass of ethanol. The temperature was raised to ° C. Next, a mixture composed of 20 parts by mass of phosphooxyethyl methacrylate, 70 parts by mass of methoxypolyethylene glycol methacrylate (molecular weight 1,000), 10 parts by mass of glycidyl methacrylate, 4.1 parts by mass of methyl mercaptopropionate, 80 parts by mass of MEK, and polymerization A mixture of 0.5 parts by weight of initiator (Wako Pure Chemical Industries Ltd. product “V-65”, 2,2′-azobis (2,4-dimethylvaleronitrile)) and 5 parts by weight of MEK was added dropwise over 2 hours. did. After the completion of the addition, every 4 hours, a polymerization initiator (0.3 parts by weight of “Perbutyl O” manufactured by NOF Corporation) was added twice and stirred for 12 hours at 80 ° C. Water was added to the resulting resin solution and the solution was transferred. After phase emulsification and desolvation under reduced pressure, water was added to adjust the concentration to obtain an aqueous solution of an acrylic polymer having a glycidyl group with a non-volatile content of 76.8% by mass. The weight average molecular weight measured by chromatography was 4,200 in terms of polystyrene, and the acid value was 96.2 mgKOH / g.
特許第4573138号公報記載の実施例1にしたがって、銀ナノ粒子とカチオン性基(アミノ基)を有する有機化合物の複合体である灰緑色の金属光沢があるフレーク状の塊からなるカチオン性銀ナノ粒子を得た。 [Production Example 2: Production of cationic silver nanoparticles]
According to Example 1 described in Japanese Patent No. 4573138, a cationic silver nanoparticle comprising a grey-green metallic luster flaky mass, which is a composite of silver nanoparticles and an organic compound having a cationic group (amino group) Particles were obtained.
攪拌機、還流冷却管、窒素導入管、温度計及び滴下漏斗を備えた反応容器に、メチルエチルケトン450質量部、メチルメタクリレート46質量部、n-ブチルアクリレート45質量部、メタクリル酸9質量部を混合したアクリル単量体混合物100質量部のうちの5質量部を仕込んだ後、過酸化ベンゾイル0.5重量部を添加した。次いで、反応容器内温度を80℃に保ちながら、前記アクリル単量体混合物の残りの95質量部を120分間かけて滴下して重合することにより、カルボキシル基を有するプライマー層用樹脂のメチルエチルケトン溶液を得た。 [Production Example 3: Production of resin for primer layer having carboxyl group]
Acrylic mixed with 450 parts by mass of methyl ethyl ketone, 46 parts by mass of methyl methacrylate, 45 parts by mass of n-butyl acrylate, and 9 parts by mass of methacrylic acid in a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer and dropping funnel. After charging 5 parts by mass of 100 parts by mass of the monomer mixture, 0.5 part by weight of benzoyl peroxide was added. Next, while maintaining the temperature in the reaction vessel at 80 ° C., the remaining 95 parts by mass of the acrylic monomer mixture was dropped over 120 minutes to polymerize the methyl ethyl ketone solution of the primer layer resin having a carboxyl group. Obtained.
攪拌機、還流冷却管、窒素導入管、温度計及び滴下漏斗を備えた反応容器に、メチルエチルケトン450質量部、メチルメタクリレート46質量部、n-ブチルアクリレート45質量部、グリシジルメタクリレート9質量部を混合したアクリル単量体混合物100質量部のうちの5質量部を仕込んだ後、過酸化ベンゾイル0.5重量部を添加した。次いで、反応容器内温度を80℃に保ちながら、前記アクリル単量体混合物の残りの95質量部を120分間かけて滴下して重合することにより、グリシジル基を有するプライマー層用樹脂のメチルエチルケトン溶液を得た。 [Production Example 4: Production of resin for primer layer having glycidyl group]
Acrylic mixed with 450 parts by mass of methyl ethyl ketone, 46 parts by mass of methyl methacrylate, 45 parts by mass of n-butyl acrylate, and 9 parts by mass of glycidyl methacrylate in a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer and dropping funnel. After charging 5 parts by mass of 100 parts by mass of the monomer mixture, 0.5 part by weight of benzoyl peroxide was added. Next, while maintaining the temperature in the reaction vessel at 80 ° C., the remaining 95 parts by mass of the acrylic monomer mixture is dropped and polymerized over 120 minutes, whereby a methyl ethyl ketone solution of the primer layer resin having a glycidyl group is obtained. Obtained.
製造例1で得られたアニオン性銀ナノ粒子5g、エタノール45g、イオン交換水29g、及びレベリング剤(信越シリコーン株式会社製「KF-351A」)0.1gを混合し、3時間攪拌することによって、フレキソ印刷用金属ナノ粒子インク(1)(水性媒体中の炭素原子数1~3のアルコール含有率69質量%、銀含有率4.7質量%、粘度1.0mPa・s)を調製した。 [Example 1]
By mixing 5 g of anionic silver nanoparticles obtained in Production Example 1, 45 g of ethanol, 29 g of ion-exchanged water, and 0.1 g of a leveling agent (“KF-351A” manufactured by Shin-Etsu Silicone Co., Ltd.) and stirring for 3 hours A metal nanoparticle ink (1) for flexographic printing (alcohol content of 1 to 3 carbon atoms in an aqueous medium: 69% by mass, silver content: 4.7% by mass, viscosity: 1.0 mPa · s) was prepared.
製造例2で得られたカチオン性銀ナノ粒子5g、メタノール63g、イオン交換水29g、グリセリン3g、及びレベリング剤(信越シリコーン株式会社製「KF-351A」)0.1gを混合し、3時間攪拌することによって、フレキソ印刷用金属ナノ粒子インク(2)(水性媒体中の炭素原子数1~3のアルコールの含有率68質量%、銀含有率4.8質量%、粘度1.5mPa・s)を調製した。得られたフレキソ印刷用金属ナノ粒子インク(2)を用いて、実施例1と同様に行い積層体を得た。 [Example 2]
5 g of the cationic silver nanoparticles obtained in Production Example 2, 63 g of methanol, 29 g of ion-exchanged water, 3 g of glycerin, and 0.1 g of a leveling agent (“KF-351A” manufactured by Shin-Etsu Silicone Co., Ltd.) were mixed and stirred for 3 hours. By doing so, the metal nanoparticle ink for flexographic printing (2) (the content of the alcohol having 1 to 3 carbon atoms in the aqueous medium is 68% by mass, the silver content is 4.8% by mass, and the viscosity is 1.5 mPa · s). Was prepared. Using the obtained metal nanoparticle ink for flexographic printing (2), a laminate was obtained in the same manner as in Example 1.
製造例3で得られたカルボキシル基を有するプライマー層用樹脂のメチルエチルケトン溶液を、乾燥膜厚が0.3μmになるように、ポリイミドフィルム(東レ・デュポン株式会社製「Kapton150ENC」、厚さ50μm)の表面に、スピンコーターを用いて塗工し、熱風乾燥機を用いて80℃で3分間乾燥することによって、プライマー層を形成した基材を得た。 [Example 3]
Methyl ethyl ketone solution of the primer layer resin having a carboxyl group obtained in Production Example 3 was added to a polyimide film (“Kapton 150ENC” manufactured by Toray DuPont Co., Ltd., thickness 50 μm) so that the dry film thickness was 0.3 μm. The substrate was coated with a spin coater and dried at 80 ° C. for 3 minutes using a hot air drier to obtain a substrate on which a primer layer was formed.
製造例1で得られたアニオン性銀ナノ粒子5g、エタノール9g、イオン交換水86g、及びレベリング剤(信越シリコーン株式会社製「KF-351A」)0.1gを混合し、3時間攪拌することによって、フレキソ印刷用金属ナノ粒子インク(R1)(水性媒体中の炭素原子数1~3のアルコール含有率9質量%、銀含有率4.5質量%、粘度1.0mPa・s、)を調製した。 [Comparative Example 1]
By mixing 5 g of anionic silver nanoparticles obtained in Production Example 1, 9 g of ethanol, 86 g of ion-exchanged water, and 0.1 g of a leveling agent (“KF-351A” manufactured by Shin-Etsu Silicone Co., Ltd.), and stirring for 3 hours A metal nanoparticle ink (R1) for flexographic printing (alcohol content of 1 to 3 carbon atoms in aqueous medium: 9% by mass, silver content: 4.5% by mass, viscosity: 1.0 mPa · s) was prepared. .
製造例2で得られたカチオン性銀ナノ粒子を用いて、表2及び3に示した組成に変更した以外は、実施例1と同様に行い、フレキソ印刷用金属ナノ粒子インク(4)~(10)及び(R2)~(R4)を調製した。 [Examples 4 to 10 and Comparative Examples 2 to 4]
Using the cationic silver nanoparticles obtained in Production Example 2, the same procedure as in Example 1 was carried out except that the composition was changed to the compositions shown in Tables 2 and 3, and metal nanoparticle inks for flexographic printing (4) to ( 10) and (R2) to (R4) were prepared.
製造例4で得られたグリシジル基を有するプライマー層用樹脂のメチルエチルケトン溶液を、乾燥後のプライマー層の膜厚が0.1μmになるように、ポリイミドフィルム(東レ・デュポン株式会社製「Kapton150ENC」、厚さ50μm、長さ1000m)の表面に、小径グラビアコーターを用いて塗工し、熱風乾燥機を用いて80℃で3分間乾燥することによって、プライマー層を形成したポリイミドフィルムのロール基材を得た。 [Example 11]
Methyl ethyl ketone solution of the primer layer resin having a glycidyl group obtained in Production Example 4 is a polyimide film ("Kapton150ENC" manufactured by Toray DuPont Co., Ltd.) so that the thickness of the primer layer after drying is 0.1 μm. A polyimide film roll base material on which a primer layer is formed is coated on a surface having a thickness of 50 μm and a length of 1000 m using a small-diameter gravure coater and dried at 80 ° C. for 3 minutes using a hot air dryer. Obtained.
上記の実施例1~11及び比較例1~4で得られた積層体それぞれについて、下記の方法により、印刷適性の評価を行った。 [Evaluation of printability]
The printability of each of the laminates obtained in Examples 1 to 11 and Comparative Examples 1 to 4 was evaluated by the following method.
上記で得られた印刷パターン(図3)のベタ部をマイクロスコープ(キーエンス社製VHX-900)を用い、倍率180倍にて無作為に写真撮影後2値化処理を行い、インクがはじいた面積比率を評価した。
A:インクが全くはじかなかった。
B:インクが1%未満の範囲ではじいた。
C:インクが1%以上10%未満の範囲ではじいた。
D:インクが10%以上30%未満の範囲ではじいた。
E:インクが30%以上の範囲ではじいた。 [Evaluation method of ink printability]
Using a microscope (VHX-900 manufactured by Keyence Co., Ltd.), the solid portion of the printed pattern (Fig. 3) obtained above was randomly binarized after taking a photograph at a magnification of 180 times, and the ink was repelled. The area ratio was evaluated.
A: The ink did not repel at all.
B: The ink was repelled in the range of less than 1%.
C: The ink was repelled in the range of 1% or more and less than 10%.
D: The ink was repelled in the range of 10% to less than 30%.
E: The ink was repelled in the range of 30% or more.
実施例1~10及び比較例1~4で得られた積層体について、上記で得られた印刷パターン(図3)のベタ部の表面を陰極とし、含リン銅を陽極として、硫酸銅を含む電解めっき液を用いて電流密度2A/dm2で15分間電解めっきを行うことによって、前記導電層の表面に厚さ8μmの銅めっき層を積層した。なお、電解めっき液は、硫酸銅70g/L、硫酸200g/L、塩素イオン50mg/L、トップルチナSF(奥野製薬工業株式会社製の光沢剤)5g/Lを含むものを用いた。次いで、得られた銅めっき層を積層した印刷パターンのベタ部のめっき層表面をマイクロスコープ(株式会社キーエンス製「VHX-900」)を用い、倍率180倍にて無作為に写真撮影後、2値化処理を行い、めっき膜欠陥の面積比率を評価した。
A:全く欠陥がなかった
B:1%未満の範囲で欠陥があった。
C:1%以上10%未満の範囲で欠陥があった。
D:10%以上30%未満の範囲で欠陥があった。
E:30%以上の範囲で欠陥があった。 [Method for evaluating plating film defects]
For the laminates obtained in Examples 1 to 10 and Comparative Examples 1 to 4, the surface of the solid portion of the printed pattern (FIG. 3) obtained above was used as a cathode, phosphorous copper was used as an anode, and copper sulfate was included. A copper plating layer having a thickness of 8 μm was laminated on the surface of the conductive layer by performing electrolytic plating for 15 minutes at a current density of 2 A / dm 2 using an electrolytic plating solution. The electrolytic plating solution used contained 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 50 mg / L of chloride ions, and 5 g / L of Top Lucina SF (brightener manufactured by Okuno Pharmaceutical Co., Ltd.). Next, the surface of the solid plating layer of the printed pattern obtained by laminating the obtained copper plating layer was randomly photographed at a magnification of 180 × using a microscope (“VHX-900” manufactured by Keyence Corporation). A valuation treatment was performed, and the area ratio of plating film defects was evaluated.
A: There was no defect. B: There was a defect in the range of less than 1%.
C: There was a defect in the range of 1% or more and less than 10%.
D: There was a defect in the range of 10% or more and less than 30%.
E: There was a defect in the range of 30% or more.
実施例1~10及び比較例1~4で得られた積層体について、上記で得られた線幅100μm、長さ6cmの直線の両端に一辺が2mmの正方形のベタのパッド部を一辺の中点で接続した印刷パターン(図1)及びパッド部間を1mmで20本ならべた印刷パターン(図2)の表面を陰極とし、含リン銅を陽極として、硫酸銅を含む電解めっき液を用いて電流密度2A/dm2で15分間電解めっきを行うことによって、前記導電層の表面に厚さ8μmの銅めっき層を積層した。なお、電解めっき液は、硫酸銅70g/L、硫酸200g/L、塩素イオン50mg/L、トップルチナSF(奥野製薬工業株式会社製の光沢剤)5g/Lを含むものを用いた。次いで、得られた銅めっき層を積層した2種の印刷パターン(図1及び2)のパッド部にテスターの電極をあて、40本(20本×2パターン)中の断線した比率を評価した。 [Evaluation method of power supply rate after plating layer lamination]
For the laminates obtained in Examples 1 to 10 and Comparative Examples 1 to 4, square solid pad portions each having a side of 2 mm on both ends of the straight line having a line width of 100 μm and a length of 6 cm obtained above were placed in one side. Using an electroplating solution containing copper sulfate, with the surface of the printed pattern (FIG. 1) connected at the dots and the printed pattern (FIG. 2) with 20 pads arranged at 1 mm between the pads as the cathode and phosphorous copper as the anode By performing electroplating for 15 minutes at a current density of 2 A / dm 2 , a copper plating layer having a thickness of 8 μm was laminated on the surface of the conductive layer. The electrolytic plating solution used contained 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 50 mg / L of chloride ions, and 5 g / L of Top Lucina SF (brightener manufactured by Okuno Pharmaceutical Co., Ltd.). Next, tester electrodes were applied to the pad portions of two types of printed patterns (FIGS. 1 and 2) obtained by laminating the obtained copper plating layers, and the disconnection ratio in 40 (20 × 2 patterns) was evaluated.
Claims (8)
- 金属ナノ粒子(A)及び有機化合物(B)の複合体と、水及び炭素原子数1~3のモノアルコールを含む水性媒体(C)とを含有するフレキソ印刷用金属ナノ粒子インクであって、前記水性媒体(C)中の炭素原子数1~3のモノアルコールの含有率が45質量%以上であることを特徴とするフレキソ印刷用金属ナノ粒子インク。 A metal nanoparticle ink for flexographic printing comprising a composite of metal nanoparticles (A) and an organic compound (B), and an aqueous medium (C) containing water and a monoalcohol having 1 to 3 carbon atoms, The metal nanoparticle ink for flexographic printing, wherein the content of monoalcohol having 1 to 3 carbon atoms in the aqueous medium (C) is 45% by mass or more.
- 前記金属ナノ粒子(A)のインク中の含有率が1~20質量%の範囲である請求項1記載のフレキソ印刷用金属ナノ粒子インク。 The metal nanoparticle ink for flexographic printing according to claim 1, wherein the content of the metal nanoparticle (A) in the ink is in the range of 1 to 20% by mass.
- 粘度が0.1~25mPa・sの範囲である請求項1又は2項記載のフレキソ印刷用金属ナノ粒子インク。 The metal nanoparticle ink for flexographic printing according to claim 1 or 2, wherein the viscosity is in the range of 0.1 to 25 mPa · s.
- 前記有機化合物(B)が、カチオン性基又はアニオン性基を有するものである請求項1~3のいずれか1項記載のフレキソ印刷用金属ナノ粒子インク。 The metal nanoparticle ink for flexographic printing according to any one of claims 1 to 3, wherein the organic compound (B) has a cationic group or an anionic group.
- 前記金属ナノ粒子(A)の金属種が、銀、金、銅又はパラジウムである請求項1~4のいずれか1項記載のフレキソ印刷用金属ナノ粒子インク。 The metal nanoparticle ink for flexographic printing according to any one of claims 1 to 4, wherein the metal species of the metal nanoparticle (A) is silver, gold, copper or palladium.
- 基材表面に、請求項1~5のいずれか1項記載のフレキソ印刷用金属ナノ粒子インクをフレキソ印刷法により印刷することを特徴とする積層体の製造方法。 A method for producing a laminate, wherein the metal nanoparticle ink for flexographic printing according to any one of claims 1 to 5 is printed on a surface of a base material by a flexographic printing method.
- 基材表面に、反応性官能基(Y)を有する樹脂(d)を含有するプライマー層(D)を形成した後、前記有機化合物(B)が反応性官能基(Y)と反応して結合を形成する反応性官能基(X)を有するものである請求項1~5のいずれか1項記載のフレキソ印刷用金属ナノ粒子インクをフレキソ印刷法により印刷することを特徴とする積層体の製造方法。 After forming a primer layer (D) containing a resin (d) having a reactive functional group (Y) on the surface of the substrate, the organic compound (B) reacts with the reactive functional group (Y) to bind. 6. A laminate having the reactive functional group (X) for forming a metal film, the metal nanoparticle ink for flexographic printing according to any one of claims 1 to 5 printed by a flexographic printing method Method.
- 請求項6又は7記載の積層体の製造方法により得られた積層体のフレキソ印刷用金属ナノ粒子インクで形成されたインク層の表面に、さらに無電解めっき及び/又は電解めっきにより金属めっき層(E)を形成することを特徴とする積層体の製造方法。 A metal plating layer (100) is further formed by electroless plating and / or electrolytic plating on the surface of the ink layer formed with the metal nanoparticle ink for flexographic printing of the laminate obtained by the method for producing a laminate according to claim 6 or 7. E) is formed, and the manufacturing method of the laminated body characterized by the above-mentioned.
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