WO2021193679A1 - Plated object having pattern-shaped electroless plating layer - Google Patents

Plated object having pattern-shaped electroless plating layer Download PDF

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Publication number
WO2021193679A1
WO2021193679A1 PCT/JP2021/012115 JP2021012115W WO2021193679A1 WO 2021193679 A1 WO2021193679 A1 WO 2021193679A1 JP 2021012115 W JP2021012115 W JP 2021012115W WO 2021193679 A1 WO2021193679 A1 WO 2021193679A1
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Prior art keywords
layer
electroless plating
catalyst
catalyst layer
pattern
Prior art date
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PCT/JP2021/012115
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French (fr)
Japanese (ja)
Inventor
悠人 中澤
達也 中辻
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株式会社イオックス
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Publication date
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Publication of WO2021193679A1 publication Critical patent/WO2021193679A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

Definitions

  • the present invention relates to a plated product having a pattern-shaped electroless plating layer.
  • Patent Document 1 a catalytic treatment liquid containing a catalytic metal complex ion is adhered to the surface of a base material, and then the surface of the base material is irradiated with light using a pattern mask having a circuit pattern to be formed.
  • a method of deactivating the catalytic activity of an irradiated portion and then immersing the base material in an electroless plating bath to form a plating circuit in an unirradiated portion not irradiated with light is disclosed.
  • a plating circuit is formed in the light-unirradiated part by the pattern mask, but on the other hand, in the light-irradiated part, the catalyst treatment liquid (treatment liquid containing Pd complex ion as a catalyst) is used as hydrochloric acid, sulfuric acid, etc. Needs to be removed with acid.
  • the catalyst treatment liquid treatment liquid containing Pd complex ion as a catalyst
  • the present invention newly provides a plated product having a pattern-shaped electroless plating layer.
  • the present inventor has made a catalyst composition containing (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a binder on the surface of a base material in a plated product.
  • a new plated product having a catalyst layer made of the above and having a pattern-shaped electroless plating layer on the surface of the catalyst layer has been developed.
  • the present invention is the following plated product.
  • Item 1 It ’s a plated product, A catalyst layer composed of a catalyst composition containing (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a binder is provided on the surface of the base material. A plated product having a pattern-shaped electroless plating layer on the surface of the catalyst layer.
  • Item 2 The plated product according to Item 1, wherein the catalyst layer is provided on the entire surface of the base material.
  • Item 3 In the pattern-shaped electroless plating layer, on the surface of the catalyst layer, The part that is not irradiated with UV and has an electroless plating layer, In the part that is UV-irradiated and there is no electroless plating layer, Item 2.
  • the plated product according to Item 1 or 2 which is an electroless plating layer having a pattern shape.
  • Item 4 In the pattern-shaped electroless plating layer, on the surface of the catalyst layer, The part that is masked, is not irradiated with UV, and has an electroless plating layer, In the part without masking, UV irradiation, and no electroless plating layer Item 3.
  • the base material is a substrate, and the base material is a substrate.
  • the electroless plating layer is a conductor circuit.
  • the plated product according to any one of Items 1 to 4, which is a circuit board.
  • Item 6. It is a manufacturing method of plated products.
  • a step of removing the masking layer After the UV irradiation step, a step of removing the masking layer, (5) After the step of removing the masking layer, a step of forming a pattern-shaped electroless plating layer, A method for manufacturing a plated product, including.
  • Item 7 In the step of forming the catalyst layer, Item 6.
  • Item 8 In the step of forming the pattern-shaped electroless plating layer, on the surface of the catalyst layer, The masking layer is formed to form the electroless plating layer without UV irradiation. By not forming the masking layer and not forming the electroless plating layer by irradiating with the UV.
  • Item 6. The method for producing a plated product according to Item 6 or 7, wherein a pattern-shaped electroless plating layer is formed.
  • the base material is a substrate, and the electroless plating layer is a conductor circuit.
  • the present invention can newly provide a plated product having a pattern-shaped electroless plating layer.
  • the present invention can provide a plated product in which the catalyst layer is insulating and does not require a step of removing the catalyst layer.
  • the present invention is a plated product that forms a pattern-shaped electroless plating layer (conductor circuit) by masking technology, and can form finer circuit wiring.
  • a catalyst layer is formed on the base material (metalloid coating, etc.).
  • (2) masking (metal plate, etc.) is performed.
  • (3) light irradiation (UV irradiation, etc.) is performed.
  • (5) the mask (masked part) is removed.
  • (6) electroless plating (Cu plating, etc.) is performed.
  • the masked portion is not UV-irradiated (UV-unirradiated portion), is not deactivated, and plating (electroless Cu) is deposited.
  • the unmasked portion is UV-irradiated (UV-irradiated portion), deactivated, and plating does not precipitate.
  • (7) a conductor circuit is formed.
  • the catalyst layer is composed of a catalyst composition containing (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a binder, and is insulating. It is possible to provide a plated product that does not require a removal step.
  • the present invention is a plated product that forms a pattern-shaped electroless plating layer (conductor circuit) by masking technology, and can form finer circuit wiring.
  • the catalyst treatment liquid contains a catalyst metal (Pd, etc.) complex ion as a catalyst, which represents conductivity. If the catalyst treatment liquid remains in the UV-irradiated portion or the UV-irradiated portion, the UV-irradiated portion exhibits conductivity even in a portion that does not form a circuit, so that a short circuit occurs as a circuit. For that reason, in the prior art, it is necessary to remove the catalyst treatment liquid from the UV-irradiated portion with an acid such as hydrochloric acid or sulfuric acid.
  • an acid such as hydrochloric acid or sulfuric acid.
  • the portion masking the catalyst layer is a UV-unirradiated portion, the catalyst layer is not deactivated, and an electrolytically-free plating layer (conductor circuit) is formed, and (b) the catalyst.
  • a plated product that enables pattern formation of a conductor circuit, including a portion that is not masked with respect to the layer becomes a UV irradiation portion, the catalyst layer is deactivated, and a non-electrolytic plating layer (conductor circuit) is not formed.
  • the catalyst layer is insulating, so that it is possible to form a pattern of a conductor circuit without removing the catalyst layer, and (d) even if the catalyst layer exists, it itself. Can provide a plated product that does not exhibit conductivity and does not short-circuit.
  • the catalyst layer is transparent, and a transparent plated product can be provided.
  • the present invention has a pattern shape, it is possible to preferably provide a plated product that does not require steps such as photoetching and pattern printing for forming a circuit pattern.
  • the plated product of the present invention is preferably a circuit board having a patterned conductor circuit, wherein the base material is a substrate and the electroless plating layer is a conductor circuit.
  • the present invention can provide a new plated material (circuit board, printed wiring board) that enables pattern formation of a conductor circuit.
  • the plated product of the present invention has a catalyst layer composed of (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a catalyst composition on the surface of a base material.
  • a pattern-shaped electroless plating layer is provided on the surface of the catalyst layer.
  • the surface of the catalyst layer is not UV-irradiated, and the portion having the electroless plating layer and the electroless plating layer are UV-irradiated.
  • a pattern-shaped electroless plating layer is formed at the portion where there is no space.
  • the surface of the catalyst layer is masked and not irradiated with UV, and the portion having the electroless plating layer is not masked.
  • the part that is UV-irradiated and does not have the electroless plating layer forms a pattern-shaped electroless plating layer.
  • the base material is preferably a substrate
  • the electroless plating layer is a conductor circuit and a circuit board.
  • the catalyst layer is preferably insulating, and a step of removing the catalyst layer is unnecessary.
  • the catalyst layer is preferably transparent.
  • an electroless plating layer (circuit) is formed on the mask layer (UV unirradiated portion), so that a circuit pattern can be formed.
  • the plated product of the present invention has a pattern-shaped electroless plating layer (conductor circuit) that does not require steps such as photoetching and pattern printing for circuit pattern formation and does not require a step of removing the catalyst layer. ..
  • the plated product of the present invention has a catalyst layer on the surface of the base material, and has a pattern-shaped electroless plating layer on the surface of the catalyst layer.
  • the material of the base material (preferably a substrate, a circuit board) is preferably an insulating substrate, and plastic (resin), glass, ceramics, or the like is used.
  • the base material is preferably a substrate and a circuit board.
  • the material of the base material (board) preferably has a uniform thickness (height) in terms of ease of masking.
  • ABS resin acrylonitrile-butadiene-styrene copolymer resin
  • the plastics are preferably polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and polylactic acid esters; acrylic resins such as polymethylmethacrylate (PMMA); polycarbonate (PC); Polyvinyl chloride; Polyester; Polyester; Polyesterimide; Polyacetal; Polyether ether ketone; Cyclic polyolefin with norbornen skeleton; Polyphenylene sulfide; Liquid crystal polymer; Cycloolefin polymer (COP); Modified polyphenyl ether; Polysulfone; Phenol; Poly Phthalamide (PPA); polyallylate or the like is used.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • Polyvinyl chloride Polyester
  • Polyester Polyesterimide
  • Polyacetal Polyacetal
  • Polyether ether ketone Cyc
  • polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polybutadiene, polybutene, polyisoprene, polychloroprene, polyisobutylene, and polyisoprene are used.
  • PTFE polytetrafluoroethylene
  • ETFE tetrafluoroethylene-ethylene copolymer
  • FEP fluoroethylene-fluorinated propylene copolymer
  • PFA perfluoroalkoxy alkanes
  • the ceramics include glass, alumina and the like.
  • wood fiber, glass fiber, asbestos, polyester fiber, vinylon fiber, rayon fiber, polyolefin fiber and the like are used.
  • the base material When plastic, ceramics, etc. are used as the base material, it is preferably used after appropriately forming an insulating property with a primer or the like.
  • a conductive substance such as a metal
  • it is preferably used as the base material after forming insulation with a primer or the like.
  • the base material is preferably a substrate, and the electroless plating layer described later is a conductor circuit and a circuit board.
  • the plated product of the present invention has a catalyst layer on the surface of the base material, and has a pattern-shaped electroless plating layer on the surface of the catalyst layer.
  • the catalyst layer preferably comprises a catalyst composition containing (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a binder.
  • the plated product of the present invention preferably has the catalyst layer on the entire surface of the base material.
  • the catalyst layer comprises (i) a catalyst composition containing a composite of metal particles and a dispersant.
  • the metal particles are preferably palladium particles, gold particles, silver particles, or platinum particles.
  • the complex of the metal particles and the dispersant is preferably a palladium complex (Pd complex) containing palladium particles (Pd particles).
  • the composite of the metal particles and the dispersant is preferably used as metal particles in the presence of a dispersant such as a polycarboxylic acid-based dispersant, a block copolymer type polymer dispersant having a hydroxyl group or a carboxyl group.
  • a dispersant such as a polycarboxylic acid-based dispersant, a block copolymer type polymer dispersant having a hydroxyl group or a carboxyl group.
  • a dispersant such as a polycarboxylic acid-based dispersant, a block copolymer type polymer dispersant having a hydroxyl group or a carboxyl group.
  • a dispersant such as a polycarboxylic acid-based dispersant, a block copolymer type polymer dispersant having a hydroxyl group or a carboxyl group.
  • Pd ions palladium ions supplied from a palladium compound (Pd compound) such as palladium chlor
  • the metal particles function as a electroless plating catalyst, and are preferably of noble metals such as palladium particles (Pd particles), gold particles (Au particles), silver particles (Ag particles), and platinum particles (Pt particles). It is ultrafine particles, more preferably Pd particles.
  • the Pd particles can be preferably obtained by reducing Pd ions supplied from the Pd compound with a reducing agent in the presence of the dispersant (liquid phase reduction method).
  • the Pd compound preferably, palladium chloride (Pd chloride), palladium sulfate, palladium nitrate, palladium acetate, palladium benzoate, palladium salicylate, palladium paratoluenesulfonate, palladium perchlorate, palladium benzenesulfonate and the like are used.
  • the Pd compound can be used alone or in combination of two or more.
  • the reducing agent is preferably primary, secondary or tertiary amines such as hydrazine hydrate (hydrazine monohydrate), sodium borohydride, N, N dimethylethanolamine, diethanolamine, triethanolamine, and ascorbin. Endiols such as acid and 2,3-dihydroxymaleic acid are used.
  • the method for reducing the Pd ion is preferably a method in which the dispersant and the Pd ion are present in a solvent (the solvent below) and then the reducing agent is added to the solvent, whereby the Pd ion and the reducing agent are added. Can contact with and reduce Pd ions.
  • the average particle size of the Pd complex preferably has a spherical structure with an average particle size of about 20 nm to 300 nm as a whole.
  • the average particle size of the Pd composite is measured with a particle size analyzer (Otsuka Electronics Co., Ltd., FPAR-1000) (weight-based average diameter).
  • the metal particles function as an electroless plating catalyst, and are preferably ultrafine particles of precious metals such as Pd particles, Au particles, Ag particles, and Pt particles.
  • platinum ions (Pt ions) supplied from a platinum compound (Pt compound, noble metal compound) such as platinum chloride (IV) are preferably hydrazine hydride in the presence of a dispersant. Obtained by reduction with secondary or tertiary amines such as lat.
  • the catalyst layer preferably comprises (ii) a catalyst composition containing a solvent.
  • the solvent is preferably one that can disperse a metal complex (Pd complex or the like) and has an excellent affinity with the following binders.
  • the solvent is preferably selected from the viewpoint of the viscosity of the catalyst composition, the evaporation rate, and the like, and is satisfied that the catalyst composition adheres well to the substrate.
  • the solvent is preferably water, alcohols such as methanol, ethanol, isopropyl alcohol (IPA), 1-butyl alcohol, isobutyl alcohol; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diacetone alcohol (4). -Hydroxy-4-methyl-2-pentanone), ketones such as cyclohexanone; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether; aromatic carboxylic acid esters such as methyl benzoate, ethyl benzoate and methyl salicylate.
  • alcohols such as methanol, ethanol, isopropyl alcohol (IPA), 1-butyl alcohol, isobutyl alcohol
  • MEK methyl ethyl ketone
  • MIBK methyl isobutyl ketone
  • Classes aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane, n-heptane and mineral spirit; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate, butyl Glycol ether esters such as carbitol acetate; alkanol esters such as ethyl acetate and butyl acetate; 2-phenoxyethanol (ethylene glycol phenyl ether) and the like are used.
  • a solvent having a slow evaporation rate is preferably used in consideration of printability, paintability, and leveling process after printing / painting.
  • the solvent having a slow evaporation rate preferably diacetone alcohol, cyclohexanone, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate, butyl carbitol acetate, 2-phenoxyethanol and the like are used.
  • the solvent water, an aprotic polar solvent such as N-methylpyrrolidone, or the like is preferably used from the viewpoint that the metal complex (Pd complex or the like) in the catalyst composition can be dispersed well.
  • the aprotonic polar solvent is preferably an aprotonic polar solvent such as N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc); dimethylsulfoxide; ⁇ . -Use butyrolactone or the like.
  • NMP N-methylpyrrolidone
  • DMF N-dimethylformamide
  • DMAc N-dimethylacetamide
  • dimethylsulfoxide ⁇ . -Use butyrolactone or the like.
  • the solvent can be used alone or in combination of two or more.
  • the catalyst layer preferably comprises (iii) a catalyst composition containing a binder.
  • the binder preferably has good electroless plating reactivity from the viewpoints of the viscosity of the catalyst composition, the adhesion between the catalyst composition and the substrate (PET film, ABS substrate, etc.), curing conditions, and the like. Select one.
  • the binder is preferably one that is dispersed or dissolved in the solvent.
  • the binder is preferably an acetal resin (POM), an epoxy resin, an ester resin, an acrylic resin, a urethane resin, an amide resin (PA, polyamide, nylon), an imide resin (polymethyl), an amide imide resin (PAI, polyamideimide), and the like.
  • POM acetal resin
  • PA polyamide
  • PA polyamide
  • PAI polyamide imide resin
  • the vinyl chloride-vinyl acetate copolymer (vinyl chloride / vinyl acetate-based modified resin) is a copolymer resin of vinyl chloride and vinyl acetate or the like.
  • At least one selected from the group consisting of an epoxy resin, a urethane resin, an amidoimide resin, and a vinyl chloride-vinyl acetate copolymer is used, and two or more of them can be used in combination.
  • Epoxy resin, urethane resin and amideimide resin are particularly preferably used as the binder.
  • a curing agent in combination with the binder, if necessary.
  • a curing agent in combination, the effect of UV irradiation can be exhibited in a shorter time, so that the pattern can be made clearer.
  • the curing agent is not particularly limited and can be appropriately selected according to the binder resin to be used.
  • isocyanate, amide resin, phenol resin, mercaptan, imidazole, kettimin, oxazoline, carbodiimide, epoxy and the like are preferably used.
  • additives such as fillers and thickeners may be used in the catalyst composition, if necessary.
  • filler silica, alumina or the like is preferably used.
  • thickener an inorganic thickener such as smectite clay mineral, an organic thickener such as cellulose nanofiber, or the like is preferably used.
  • the particle size of the additives such as the filler and the thickener is not particularly limited.
  • additives such as a filler having a smaller particle size and a thickener are preferably used.
  • the particle size of the additive such as the filler and the thickener is preferably 100 nm or less, more preferably 10 nm or less.
  • the catalyst composition is preferably applied on a substrate (circuit substrate) by a bar coating method, a spin coating method, a dip coating method, a spray coating, or a gravure coating.
  • a catalyst layer is formed by coating and drying by a known means such as a method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, and a gravure reverse roll coating method.
  • the catalyst composition is applied onto a substrate (circuit board) by a bar coating method, a spin coating method, or a gravure reverse roll coating method, and the catalyst composition is dried. To form a catalyst layer.
  • the thickness of the catalyst layer is preferably 20 ⁇ m from the viewpoint that electroless plating can be performed satisfactorily, the reactivity of electroless plating can be obtained, and a plating film can be satisfactorily formed on the base material (substrate). It is about 0.01 ⁇ m to 10 ⁇ m, more preferably about 0.01 ⁇ m to 10 ⁇ m.
  • the portion to be masked with respect to the catalyst layer is a UV-unirradiated portion, the catalyst layer is not deactivated, an electrolytic-free plating layer (conductor circuit) is formed, and the catalyst layer is masked. It is possible to provide a plated product capable of forming a pattern of a conductor circuit, including a portion not provided as a UV-irradiated portion, the catalyst layer being deactivated, and a non-electrolytic plating layer (conductor circuit) not being formed.
  • the plated product of the present invention preferably has the catalyst layer on the entire surface of the base material.
  • the catalyst layer is insulating, it is possible to form a pattern of a conductor circuit without removing the catalyst layer, and even if the catalyst layer is present, it itself exhibits conductivity. Instead, it becomes a plated product that does not short-circuit.
  • the plated product of the present invention preferably removes the masking (masking layer) having a light transmitting pattern according to the plating circuit.
  • the plated product of the present invention has a catalyst layer on the surface of the base material, and has a pattern-shaped electroless plating layer on the surface of the catalyst layer.
  • the surface of the catalyst layer is not UV-irradiated and has an electroless plating layer, and is UV-irradiated without the electroless plating layer.
  • the part forms an electroless plating layer with a pattern shape.
  • the surface of the catalyst layer is masked to form a mask layer, and the portion is not irradiated with UV and has an electroless plating layer.
  • the part is UV-irradiated without masking and does not form a mask layer, and the part without the electroless plating layer becomes a pattern-shaped electroless plating layer (conductor circuit).
  • the pattern shape and mask layer preferably, a metal plate, a glass plate, a film or the like having a light transmitting pattern according to the plating circuit, or a resin such as a resist is pattern-printed and used as a mask.
  • a metal plate or the like having no light transmission masking can be performed according to the plating circuit.
  • a catalyst treatment liquid containing a catalytic metal complex ion is adhered to the surface of the base material to form a catalyst layer, and then a pattern mask having a circuit pattern to be formed is used on the surface of the base material.
  • Light is irradiated (UV irradiation) to deactivate the catalytic activity of the light-irradiated part, and then the base material is electroless plated (immersed in a bath, etc.), and the unirradiated part (masking part) is not irradiated with light. )
  • UV irradiation UV irradiation
  • the base material is electroless plated (immersed in a bath, etc.), and the unirradiated part (masking part) is not irradiated with light.
  • the plated product of the present invention uses a catalyst treatment liquid (catalyst composition) containing a catalytic metal (palladium (Pd) or the like) complex ion, and the light-irradiated portion (UV-irradiated portion) deactivates the catalytic activity to generate light.
  • a plating circuit is formed in the unirradiated portion (UV unirradiated portion).
  • the pattern shape and mask layer preferably have a light transmitting pattern according to the plating circuit to be formed.
  • the light used for the light irradiation is preferably ultraviolet light (UV light), visible light, or the like, and is light that can inactivate the catalyst in the catalyst composition (catalyst treatment liquid) adhering to the surface of the base material. Is used.
  • the light used for the light irradiation is preferably ultraviolet rays (UV light), and is an electromagnetic wave of invisible light having a wavelength of about 10 nm to 400 nm, that is, shorter than visible light and longer than soft X-ray.
  • the light used for the light irradiation is more preferably ultraviolet rays (UV light), and is an electromagnetic wave having a wavelength of about 10 nm to 300 nm.
  • the light source of the ultraviolet light is preferably a high-pressure mercury lamp, a metal halide lamp, or an ultraviolet LED lamp.
  • the light source may be an ultraviolet (UV) laser.
  • the ultraviolet (UV) laser is preferably UV-YAG, DUV-YAG or excimer.
  • the ultraviolet (UV) laser is more preferably DUV-YAG or excimer.
  • Integrated light quantity of the ultraviolet light preferably, 1mJ / cm 2 ⁇ 20,000mJ / cm 2, more preferably, 1mJ / cm 2 ⁇ 2,000mJ / cm 2, more preferably, 1 mJ / cm 2 ⁇ It is 1,000 mJ / cm 2 .
  • the catalytic activity of the portion irradiated with light (UV irradiation) is inactivated according to the circuit pattern to be formed.
  • the catalytic activity of the unirradiated portion (masking portion) that has not been irradiated with light remains, and electroless plating is formed on the portion, so that a plating circuit can be formed.
  • Electroless plating layer (circuit board)
  • the base material is a substrate and the electroless plating layer is a conductor circuit as a circuit board.
  • the portion to be masked (metal plate portion) with respect to the catalyst layer becomes a UV unirradiated portion, the catalyst layer is not deactivated, an electrolytically-free plating layer (conductor circuit) is formed, and the catalyst layer is formed.
  • the portion that is not masked with respect to the catalyst layer becomes a UV irradiation portion, the catalyst layer is deactivated, and the electroless plating layer (conductor circuit) is not formed.
  • the present invention thus produces a plated product that enables pattern formation of a conductor circuit.
  • circuit board of the present invention it is preferable to form pattern plating on the substrate by performing electroless plating on the catalyst layer (masking portion (metal plate portion)) that has not been deactivated. can.
  • the catalyst layer formed by the catalyst composition has good reactivity of electroless plating, and the obtained electroless plating film has no unevenness and is excellent in adhesion and appearance.
  • the electroless plating layer is preferably a conductor circuit (conductivity).
  • the plating solution preferably forms a conductor circuit (conductivity) and uses copper, gold, silver, nickel or the like.
  • a plating solution containing copper or nickel is preferably used because of the relationship with the catalyst layer (catalyst film).
  • the plating conditions are preferably such that the catalyst layer (catalyst film) has very good reactivity of electroless plating, so that it is not necessary to increase the concentration of the reducing agent or the concentration of the alkaline component in the plating solution. Therefore, the life of the plating solution is long, and the plating is selectively deposited according to the pattern of the catalyst layer. That is, the catalyst (catalyst film) formed from the catalyst composition is excellent in pattern forming ability.
  • the thickness of the electroless plating layer is preferably about 0.05 ⁇ m to 10 ⁇ m, and more preferably about 0.1 ⁇ m to 6 ⁇ m.
  • the treatment temperature is preferably about 25 ° C to 65 ° C, and the treatment time is preferably about 10 to 60 minutes. Is.
  • a precipitation film thickness of about 0.3 ⁇ m to 3 ⁇ m can be formed.
  • the treatment temperature is preferably about 55 ° C. to 70 ° C.
  • the precipitation rate is preferably about 5 ⁇ m / hr (60 ° C.). be.
  • the treatment temperature is preferably about 30 ° C. to 95 ° C.
  • the precipitation rate is preferably about 3 ⁇ m / hr at a bath temperature of 30 ° C. At a bath temperature of 90 ° C, it is about 20 ⁇ m / hr.
  • the catalyst composition has high reactivity of electroless plating, especially when a substrate such as ABS is targeted, and has good adhesion that can withstand multi-layer plating up to plating. Can be realized.
  • the reactivity of electroless plating is good, it is not necessary to increase the concentration of the reducing agent in electroless plating, and it is not necessary to raise the reaction temperature of electroless plating. Furthermore, it does not require an etching process with harmful substances.
  • a catalyst layer is formed on the surface of a printed wiring board or the like of an electronic device, and a film for electroless plating is formed (exposed) in a pattern.
  • a metal wiring circuit is preferably formed by electroless plating on a printed wiring board or the like of an electronic device.
  • the manufacturing method of the plated product of the present invention is as follows. (1) A step of forming a catalyst layer composed of (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a catalyst composition containing a binder on the surface of a base material. (2) A step of forming a masking layer on the surface of the catalyst layer after the step of forming the catalyst layer. (3) After the step of forming the masking layer, the step of irradiating the catalyst layer and the surface of the masking layer with UV. (4) After the UV irradiation step, a step of removing the masking layer, (5) After the step of removing the masking layer, a step of forming a pattern-shaped electroless plating layer is included.
  • the catalyst layer is formed on the entire surface of the base material.
  • the masking layer is formed on the surface of the catalyst layer, and the UV irradiation is not performed, and the electroless plating layer is not applied.
  • a pattern-shaped electroless plating layer is formed by forming the plating layer and not forming the masking layer and irradiating the UV to form the electroless plating layer.
  • the base material is a substrate
  • the electroless plating layer is a conductor circuit and a circuit board.
  • the catalyst composition is applied onto the base material (circuit substrate), preferably by the bar coating method or spin coating.
  • the catalyst layer is coated and dried by known means such as a method, a dip coating method, a spray coating, a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, and a gravure reverse roll coating method to form a catalyst layer.
  • the catalyst layer is preferably formed on the entire surface of the base material.
  • the catalyst composition is applied onto a substrate (circuit board) by a bar coating method, a spin coating method, or a gravure reverse roll coating method, and the catalyst composition is dried. To form a catalyst layer.
  • the thickness of the catalyst layer is preferably 20 ⁇ m from the viewpoint that electroless plating can be performed satisfactorily, the reactivity of electroless plating can be obtained, and a plating film can be satisfactorily formed on the base material (substrate). It is about 0.01 ⁇ m to 10 ⁇ m, more preferably about 0.01 ⁇ m to 10 ⁇ m.
  • Step of forming a masking layer on the surface of the catalyst layer preferably, a metal plate or the like having a light transmitting pattern corresponding to the plating circuit is used on the catalyst layer.
  • the pattern shape and the mask layer (masking) can preferably be masked according to the plating circuit by using a metal plate having no light transmission.
  • a plate, glass plate, film, etc., or a resin such as a resist is printed in a pattern and used as a mask.
  • the light used for light irradiation is preferably ultraviolet light (UV light).
  • the catalyst in the catalyst composition (catalyst treatment liquid) attached to the surface of the material is inactivated.
  • the light used for the light irradiation is preferably electromagnetic waves (UV light), preferably has a wavelength of about 10 nm to 400 nm, more preferably has a wavelength of about 10 nm to 300 nm, that is, shorter than visible light and longer than soft X-rays. It is an electromagnetic wave of invisible light.
  • the light source of the ultraviolet light is preferably a high-pressure mercury lamp, a metal halide lamp, or an ultraviolet LED lamp.
  • the light source may be an ultraviolet (UV) laser.
  • the ultraviolet (UV) laser is preferably UV-YAG, DUV-YAG or excimer.
  • the ultraviolet (UV) laser is more preferably DUV-YAG or excimer.
  • Integrated light quantity of the ultraviolet light preferably, 1mJ / cm 2 ⁇ 20,000mJ / cm 2, more preferably, 1mJ / cm 2 ⁇ 2,000mJ / cm 2, more preferably, 1 mJ / cm 2 ⁇ It is 1,000 mJ / cm 2 .
  • the plated product of the present invention preferably has a masking (masking layer) having a light transmitting pattern corresponding to the plating circuit, and if it is a metal plate, the metal plate is removed. good.
  • a masking layer other than a metal plate for example, a glass plate or a film, it may be removed.
  • the masking layer is preferably formed on the surface of the catalyst layer, and the electroless plating layer is not irradiated with UV.
  • the electroless plating layer (conductor) having a pattern shape is formed on the base material (conductor). Circuit) is formed.
  • circuit board of the present invention it is preferable to form pattern plating on the substrate by performing electroless plating on the catalyst layer (masking portion (metal plate portion)) that has not been deactivated. can.
  • the catalyst layer formed by the catalyst composition has good reactivity of electroless plating, and the obtained electroless plating film has no unevenness and is excellent in adhesion and appearance.
  • the electroless plating layer is preferably a conductor circuit (conductivity).
  • the plating solution preferably forms a conductor circuit (conductivity) and uses copper, gold, silver, nickel or the like.
  • a plating solution containing copper or nickel is preferably used because of the relationship with the catalyst layer (catalyst film).
  • the plating conditions are preferably such that the catalyst layer (catalyst film) has very good reactivity of electroless plating, so that it is not necessary to increase the concentration of the reducing agent or the concentration of the alkaline component in the plating solution. Therefore, the life of the plating solution is long, and the plating is selectively deposited according to the pattern of the catalyst layer. That is, the catalyst (catalyst film) formed from the catalyst composition is excellent in pattern forming ability.
  • the thickness of the electroless plating layer is preferably about 0.05 ⁇ m to 10 ⁇ m, and more preferably about 0.1 ⁇ m to 6 ⁇ m.
  • the treatment temperature is preferably about 25 ° C to 65 ° C, and the treatment time is preferably about 10 to 60 minutes. Is.
  • a precipitation film thickness of about 0.3 ⁇ m to 3 ⁇ m can be formed.
  • the treatment temperature is preferably about 55 ° C. to 70 ° C.
  • the precipitation rate is preferably about 5 ⁇ m / hr (60 ° C.). be.
  • the treatment temperature is preferably about 30 ° C. to 95 ° C.
  • the precipitation rate is preferably about 3 ⁇ m / hr at a bath temperature of 30 ° C. At a bath temperature of 90 ° C, it is about 20 ⁇ m / hr.
  • pretreatment may be performed as necessary before forming the electroless plating layer.
  • the base material after the previous step is subjected to treatments such as alkaline degreasing, acidic degreasing, and acid activity.
  • the catalyst layer is formed on the surface of the base material (catalyst treatment liquid is adhered), and the masking layer is formed on the catalyst layer. Then, light is irradiated (UV irradiation) through the pattern mask. By this light irradiation (UV irradiation), the catalytic metal ion deactivates the catalytic activity in the irradiated portion (UV irradiated portion) exposed to light.
  • the base material is electroless plated (for example, immersed in a bath). Pd 2+ will be described as an example of the catalyst metal ion.
  • the unirradiated portion (UV unirradiated portion) that is pattern masked and not irradiated with light
  • Pd metal is present and electroless plating is performed.
  • plating metals such as Cu and Ni are deposited on the surface of the base material, and a plating circuit (conductor circuit) is formed.
  • a pattern-shaped plating circuit is formed in the light-unirradiated part (UV unirradiated part) by the pattern mask.
  • a plating circuit (conductor circuit) is not formed in the portion irradiated with light (UV irradiated portion).
  • the plated product of the present invention is divided into a catalytically active portion (plating circuit forming portion) of the non-light-irradiated portion and an inactive portion by light irradiation by using a specific catalyst treatment liquid, a pattern mask, and light irradiation. After that, the metal for the plating circuit can be deposited on the catalytically active portion to form the plating circuit.
  • the plated product of the present invention has an insulating catalyst layer, so that it is possible to form a pattern of a conductor circuit without removing the catalyst layer, and even if the catalyst layer exists, it itself. Is a plated product that does not exhibit conductivity and does not short-circuit.
  • the plated product of the present invention does not need to use a resist mask.
  • the plated product of the present invention is not limited in the type of base material, and can form a plating circuit having excellent electrical characteristics.
  • Example 1 Manufacture of plated products (circuit board) -A catalyst layer composed of a catalyst composition containing (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a binder of the present invention.-Masking with a metal mask
  • a process for forming a catalyst layer on the surface of a base material (board) A polyethylene naphthalate (PEN) film was used as a circuit board. First, this PEN film was corona-treated. The discharge amount of the corona treatment was 160 W / m 2 / min. By coating the surface of this PEN film with Metalloid ML-240LV (manufactured by IOX) with a bar coater, a coating film (catalyst layer) containing a Pd catalyst was formed. The thickness of the catalyst layer was 0.4 ⁇ m.
  • the metalloid ML-240LV is a composition (catalyst composition) composed of (i) a complex of Pd particles (metal particles) and a dispersant, (ii) a solvent, and (iii) an epoxy resin (binder). Is.
  • Step of Forming a Masking Layer on the Surface of the Catalyst Layer A metal mask was put on the surface of the PEN film on which the catalyst layer was formed in order to form the masking layer.
  • the metal mask has a pattern with a mask width of 0.1 mm.
  • the obtained sample has a conductive layer (electroless plating layer, conductor circuit) only in the portion not irradiated with UV.
  • ⁇ Example 2> Manufacture of plated products (circuit board) -A catalyst layer composed of a catalyst composition containing (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a binder of the present invention.-A mask in which a pattern is formed of stainless steel on quartz glass. Masking by
  • a process for forming a catalyst layer on the surface of a base material (board) A polyethylene naphthalate (PEN) film was used as a circuit board. First, this PEN film was corona-treated. The discharge amount of the corona treatment was 160 W / m 2 / min. By coating the surface of this PEN film with Metalloid ML-240LV (manufactured by IOX) with a bar coater, a coating film (catalyst layer) containing a Pd catalyst was formed. The thickness of the catalyst layer was 0.4 ⁇ m.
  • the metalloid ML-240LV is a composition (catalyst composition) composed of (i) a complex of Pd particles (metal particles) and a dispersant, (ii) a solvent, and (iii) an epoxy resin (binder). Is.
  • the obtained sample has a conductive layer (electroless plating layer, conductor circuit) only in the portion not irradiated with UV.
  • the catalyst layer of the present invention becomes insulating by the masking technique, and it is possible to provide a plated product having a pattern-shaped electroless plating layer.
  • a pattern-shaped electroless plating layer can be formed, and a plated product (circuit component, circuit board) forming finer circuit wiring can be produced. Can be evaluated.
  • a process for forming a catalyst layer on the surface of a base material (board) A polyethylene terephthalate (PET) film was used as a circuit board. First, this PET film was corona-treated. The discharge amount of the corona treatment was 160 W / m 2 / min. This PET film is immersed in a catalyst layer-imparting solution (Catalyst C-7 manufactured by Okuno Pharmaceutical Co., Ltd.) at 35 ° C for 3 minutes, and then immersed in an activation accelerator solution (Accelerator X manufactured by Okuno Pharmaceutical Co., Ltd.) at 35 ° C for 3 minutes. By doing so, a catalyst layer was formed.
  • a catalyst layer-imparting solution Catalyst C-7 manufactured by Okuno Pharmaceutical Co., Ltd.
  • an activation accelerator solution Accelelerator X manufactured by Okuno Pharmaceutical Co., Ltd.
  • Step of Forming a Masking Layer on the Surface of the Catalyst Layer A metal mask was put on the surface of the PET film on which the catalyst layer was formed in order to form the masking layer.
  • the mask has a pattern in which the width of the mask is 0.1 mm.
  • Step of forming an electroless plating layer (conductor circuit) with a pattern shape The film with a catalyst layer treated with UV light is placed in an electroless Cu plating solution (OPC copper HFS manufactured by Okuno Pharmaceutical Co., Ltd.) at 40 ° C for 20 minutes. When immersed, an electroless copper plating layer was formed on the entire surface of the base material. The thickness of the electroless Cu layer was 1.0 ⁇ m. As a result, the obtained sample (PET film) has a conductive layer (electroless plating layer, conductor circuit) in both the UV-irradiated portion and the non-UV-irradiated portion.
  • OPC copper HFS manufactured by Okuno Pharmaceutical Co., Ltd.
  • the catalyst layer of the prior art does not have an insulating property, a conductive layer is formed, and a pattern-shaped electroless plating layer cannot be formed satisfactorily.

Abstract

The present invention provides a novel plated object that has a pattern-shaped electroless plating layer. The plated object has pattern-shaped electroless plating layer.

Description

パターン形状の無電解めっき層を有するめっき物Plated product with pattern-shaped electroless plating layer
　本発明は、パターン形状の無電解めっき層を有するめっき物に関する。 The present invention relates to a plated product having a pattern-shaped electroless plating layer.
　特許文献1には、基材の表面に、触媒金属錯イオンを含有する触媒処理液を付着させ、次いで形成すべき回路パターンを有するパターンマスクを用いて基材表面に光を照射して、光照射部分の触媒活性を失活させ、その後基材を無電解めっき浴中に浸漬して光が照射されていない未照射部分にめっき回路を形成する方法が開示されている。この技術では、パターンマスクによる光未照射部分にめっき回路を形成するが、一方で、光が照射された部分では触媒処理液（触媒としてPd錯イオンを含む処理液）を、塩酸、硫酸等の酸によって除去する必要がある。 In Patent Document 1, a catalytic treatment liquid containing a catalytic metal complex ion is adhered to the surface of a base material, and then the surface of the base material is irradiated with light using a pattern mask having a circuit pattern to be formed. A method of deactivating the catalytic activity of an irradiated portion and then immersing the base material in an electroless plating bath to form a plating circuit in an unirradiated portion not irradiated with light is disclosed. In this technology, a plating circuit is formed in the light-unirradiated part by the pattern mask, but on the other hand, in the light-irradiated part, the catalyst treatment liquid (treatment liquid containing Pd complex ion as a catalyst) is used as hydrochloric acid, sulfuric acid, etc. Needs to be removed with acid.
特開平6-77626号公報Japanese Patent Application Laid-Open No. 6-77626
　本発明は、新たに、パターン形状の無電解めっき層を有するめっき物を提供する。 The present invention newly provides a plated product having a pattern-shaped electroless plating layer.
　本発明者は、鋭意検討した結果、めっき物において、基材の表面に、（i）金属粒子と分散剤との複合体、（ii）溶媒、及び（iii）バインダーを含有する触媒組成物から成る触媒層を有し、前記触媒層の表面に、パターン形状の無電解めっき層を有する、新たなめっき物を開発した。 As a result of diligent studies, the present inventor has made a catalyst composition containing (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a binder on the surface of a base material in a plated product. A new plated product having a catalyst layer made of the above and having a pattern-shaped electroless plating layer on the surface of the catalyst layer has been developed.
　即ち、本発明は、次のめっき物である。 That is, the present invention is the following plated product.
　項１．
　めっき物であって、
　基材の表面に、（i）金属粒子と分散剤との複合体、（ii）溶媒、及び（iii）バインダーを含有する触媒組成物から成る触媒層を有し、
　前記触媒層の表面に、パターン形状の無電解めっき層を有する、めっき物。 Item 1.
It ’s a plated product,
A catalyst layer composed of a catalyst composition containing (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a binder is provided on the surface of the base material.
A plated product having a pattern-shaped electroless plating layer on the surface of the catalyst layer.
　項２．
　前記基材の表面に、前記触媒層を、全面に有する、前記項1に記載のめっき物。 Item 2.
Item 2. The plated product according to Item 1, wherein the catalyst layer is provided on the entire surface of the base material.
　項３．
　前記パターン形状の無電解めっき層では、前記触媒層の表面に、
　UV照射されず、無電解めっき層が有る部分と、
　UV照射されて、無電解めっき層が無い部分とで、
　パターン形状の無電解めっき層と成る、前記項1又は2に記載のめっき物。 Item 3.
In the pattern-shaped electroless plating layer, on the surface of the catalyst layer,
The part that is not irradiated with UV and has an electroless plating layer,
In the part that is UV-irradiated and there is no electroless plating layer,
Item 2. The plated product according to Item 1 or 2, which is an electroless plating layer having a pattern shape.
　項４．
　前記パターン形状の無電解めっき層では、前記触媒層の表面に、
　マスキングされて、前記UV照射されず、無電解めっき層が有る部分と、
　マスキングされず、前記UV照射されて、無電解めっき層が無い部分とで、
　パターン形状の無電解めっき層と成る、前記項3に記載のめっき物。 Item 4.
In the pattern-shaped electroless plating layer, on the surface of the catalyst layer,
The part that is masked, is not irradiated with UV, and has an electroless plating layer,
In the part without masking, UV irradiation, and no electroless plating layer
Item 3. The plated product according to Item 3, which is an electroless plating layer having a pattern shape.
　項５．
　前記基材は、基板であり、
　前記無電解めっき層は、導体回路であり、
　回路基板である、前記項1～4のいずれかに記載のめっき物。 Item 5.
The base material is a substrate, and the base material is a substrate.
The electroless plating layer is a conductor circuit.
The plated product according to any one of Items 1 to 4, which is a circuit board.
　項６．
　めっき物の製造方法であって、
　（1）基材の表面に、（i）金属粒子と分散剤との複合体、（ii）溶媒、及び（iii）バインダーを含有する触媒組成物から成る触媒層を形成する工程、
　（2）前記触媒層を形成する工程の後、前記触媒層の表面にマスキング層を形成する工程、
　（3）前記マスキング層を形成する工程の後、前記触媒層及び前記マスキング層の表面にUV照射する工程、
　（4）前記UV照射する工程の後、マスキング層を除去する工程、
　（5）前記マスキング層を除去する工程の後、パターン形状の無電解めっき層を形成する工程、
を含む、めっき物の製造方法。 Item 6.
It is a manufacturing method of plated products.
(1) A step of forming a catalyst layer composed of (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a catalyst composition containing a binder on the surface of a base material.
(2) A step of forming a masking layer on the surface of the catalyst layer after the step of forming the catalyst layer.
(3) After the step of forming the masking layer, the step of irradiating the catalyst layer and the surface of the masking layer with UV.
(4) After the UV irradiation step, a step of removing the masking layer,
(5) After the step of removing the masking layer, a step of forming a pattern-shaped electroless plating layer,
A method for manufacturing a plated product, including.
　項７．
　前記触媒層を形成する工程では、
　前記基材の表面に、前記触媒層を、全面に形成する、前記項6に記載のめっき物の製造方法。 Item 7.
In the step of forming the catalyst layer,
Item 6. The method for producing a plated product according to Item 6, wherein the catalyst layer is formed on the entire surface of the base material.
　項８．
　前記パターン形状の無電解めっき層を形成する工程では、前記触媒層の表面に、
　前記マスキング層を形成して、前記UV照射せず、無電解めっき層を形成することと、
　前記マスキング層を形成せず、前記UV照射して、無電解めっき層を形成しないこととで、
　パターン形状の無電解めっき層を形成する、前記項6又は7に記載のめっき物の製造方法。 Item 8.
In the step of forming the pattern-shaped electroless plating layer, on the surface of the catalyst layer,
The masking layer is formed to form the electroless plating layer without UV irradiation.
By not forming the masking layer and not forming the electroless plating layer by irradiating with the UV.
Item 6. The method for producing a plated product according to Item 6 or 7, wherein a pattern-shaped electroless plating layer is formed.
　項９．
　前記基材は、基板であり
　前記無電解めっき層は、導体回路であり、
　回路基板である、前記項6～8のいずれかに記載のめっき物の製造方法。 Item 9.
The base material is a substrate, and the electroless plating layer is a conductor circuit.
The method for manufacturing a plated product according to any one of Items 6 to 8, which is a circuit board.
　本発明は、新たに、パターン形状の無電解めっき層を有するめっき物を提供できる。 The present invention can newly provide a plated product having a pattern-shaped electroless plating layer.
　本発明は、触媒層は絶縁性であり、触媒層を除去する工程が不要である、めっき物を提供できる。 The present invention can provide a plated product in which the catalyst layer is insulating and does not require a step of removing the catalyst layer.
　本発明は、マスキング技術により、パターン形状の無電解めっき層（導体回路）を形成するめっき物であり、より微細な回路配線を形成することができる。 The present invention is a plated product that forms a pattern-shaped electroless plating layer (conductor circuit) by masking technology, and can form finer circuit wiring.
本発明のめっき物を説明する図である。本発明の光パターニングを説明する。（1）基材に触媒層を形成（メタロイド塗工等）する。次に、（2）マスキング（金属板等）する。次に、（3）光照射（UV照射等）する。次に、（5）マスク（マスキングした部分）除去する。次に、（6）無電解めっき（Cuめっき等）する。（i）マスキングされる部分は、UV照射されず（UV未照射部分）、失活せず、めっき（無電解Cu）が析出する。（ii）マスキングされない部分は、UV照射され（UV照射部分）、失活し、めっきが析出しない。次に、（7）導体回路を形成する。It is a figure explaining the plated article of this invention. The optical patterning of the present invention will be described. (1) A catalyst layer is formed on the base material (metalloid coating, etc.). Next, (2) masking (metal plate, etc.) is performed. Next, (3) light irradiation (UV irradiation, etc.) is performed. Next, (5) the mask (masked part) is removed. Next, (6) electroless plating (Cu plating, etc.) is performed. (I) The masked portion is not UV-irradiated (UV-unirradiated portion), is not deactivated, and plating (electroless Cu) is deposited. (Ii) The unmasked portion is UV-irradiated (UV-irradiated portion), deactivated, and plating does not precipitate. Next, (7) a conductor circuit is formed.
　以下に本発明を詳細に説明する。但し、この実施の形態は、発明の趣旨がより良く理解できる説明であり、特に指定のない限り、発明内容を限定するものではない。 The present invention will be described in detail below. However, this embodiment is an explanation in which the gist of the invention can be better understood, and the content of the invention is not limited unless otherwise specified.
　本発明は、触媒層は、（i）金属粒子と分散剤との複合体、（ii）溶媒、及び（iii）バインダーを含有する触媒組成物から成り、絶縁性であることから、触媒層を除去する工程が不要である、めっき物を提供できる。 In the present invention, the catalyst layer is composed of a catalyst composition containing (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a binder, and is insulating. It is possible to provide a plated product that does not require a removal step.
　本発明は、マスキング技術により、パターン形状の無電解めっき層（導体回路）を形成するめっき物であり、より微細な回路配線を形成することができる。 The present invention is a plated product that forms a pattern-shaped electroless plating layer (conductor circuit) by masking technology, and can form finer circuit wiring.
　従来技術（特開平6-77626号公報）では、触媒処理液は、触媒として触媒金属（Pd等）錯イオンを含み、これは導電性を表す。その触媒処理液が、UV照射部分やUV未照射部分で残ると、そのUV照射部分は回路を形成しない部分であっても、導電性を表すので、回路として短絡を起こす。従来技術は、その理由から、UV照射部分に対して、塩酸、硫酸等の酸によって、その触媒処理液を除去することが必要である。 In the prior art (Japanese Patent Laid-Open No. 6-77626), the catalyst treatment liquid contains a catalyst metal (Pd, etc.) complex ion as a catalyst, which represents conductivity. If the catalyst treatment liquid remains in the UV-irradiated portion or the UV-irradiated portion, the UV-irradiated portion exhibits conductivity even in a portion that does not form a circuit, so that a short circuit occurs as a circuit. For that reason, in the prior art, it is necessary to remove the catalyst treatment liquid from the UV-irradiated portion with an acid such as hydrochloric acid or sulfuric acid.
　本発明は、（ア）触媒層に対してマスキングする部分は、UV未照射部分と成り、触媒層は失活せず、無電解めっき層（導体回路）が形成されること、（イ）触媒層に対してマスキングしない部分は、UV照射部分と成り、触媒層は失活し、無電解めっき層（導体回路）が形成されないことを含む、導体回路のパターン形成を可能とするめっき物を提供できる。 In the present invention, (a) the portion masking the catalyst layer is a UV-unirradiated portion, the catalyst layer is not deactivated, and an electrolytically-free plating layer (conductor circuit) is formed, and (b) the catalyst. Provided is a plated product that enables pattern formation of a conductor circuit, including a portion that is not masked with respect to the layer becomes a UV irradiation portion, the catalyst layer is deactivated, and a non-electrolytic plating layer (conductor circuit) is not formed. can.
　本発明は、また、（ウ）触媒層は絶縁性であることから、その触媒層を除去すること無く、導体回路のパターン形成を可能とし、（エ）触媒層が存在しても、それ自体が導電性を表さず、短絡しないめっき物を提供できる。 In the present invention, (c) the catalyst layer is insulating, so that it is possible to form a pattern of a conductor circuit without removing the catalyst layer, and (d) even if the catalyst layer exists, it itself. Can provide a plated product that does not exhibit conductivity and does not short-circuit.
　本発明は、好ましくは、触媒層は透明であり、透明なめっき物を提供できる。 In the present invention, preferably, the catalyst layer is transparent, and a transparent plated product can be provided.
　本発明は、パターン形状を有することから、好ましくは、回路のパターン形成に、フォトエッチング、パターン印刷等の工程が不要であるめっき物を提供できる。 Since the present invention has a pattern shape, it is possible to preferably provide a plated product that does not require steps such as photoetching and pattern printing for forming a circuit pattern.
　本発明のめっき物は、好ましくは、前記基材は基板であり、前記無電解めっき層は導体回路である、パターン形状の導体回路を有する回路基板である。 The plated product of the present invention is preferably a circuit board having a patterned conductor circuit, wherein the base material is a substrate and the electroless plating layer is a conductor circuit.
　（1）めっき物（回路基板）
　本発明は、新たな、導体回路のパターン形成を可能とするめっき物（回路基板、プリント配線板）を提供できる。 (1) Plated material (circuit board)
The present invention can provide a new plated material (circuit board, printed wiring board) that enables pattern formation of a conductor circuit.
　本発明のめっき物は、基材の表面に、（i）金属粒子と分散剤との複合体、（ii）溶媒、及び（iii）バインダーを含有する触媒組成物から成る触媒層を有し、前記触媒層の表面に、パターン形状の無電解めっき層を有する。 The plated product of the present invention has a catalyst layer composed of (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a catalyst composition on the surface of a base material. A pattern-shaped electroless plating layer is provided on the surface of the catalyst layer.
　本発明のめっき物は、好ましくは、前記パターン形状の無電解めっき層では、前記触媒層の表面に、UV照射されず、無電解めっき層が有る部分と、UV照射されて、無電解めっき層が無い部分とで、パターン形状の無電解めっき層と成る。 In the plated product of the present invention, preferably, in the pattern-shaped electroless plating layer, the surface of the catalyst layer is not UV-irradiated, and the portion having the electroless plating layer and the electroless plating layer are UV-irradiated. A pattern-shaped electroless plating layer is formed at the portion where there is no space.
　本発明のめっき物は、好ましくは、前記パターン形状の無電解めっき層では、前記触媒層の表面に、マスキングされて、前記UV照射されず、無電解めっき層が有る部分と、マスキングされず、前記UV照射されて、無電解めっき層が無い部分とで、パターン形状の無電解めっき層と成る。 In the plated product of the present invention, preferably, in the electroless plating layer having the pattern shape, the surface of the catalyst layer is masked and not irradiated with UV, and the portion having the electroless plating layer is not masked. The part that is UV-irradiated and does not have the electroless plating layer forms a pattern-shaped electroless plating layer.
　本発明のめっき物は、好ましくは、前記基材は、基板であり、前記無電解めっき層は、導体回路であり、回路基板である。 In the plated product of the present invention, the base material is preferably a substrate, and the electroless plating layer is a conductor circuit and a circuit board.
　本発明のめっき物は、好ましくは、触媒層は絶縁性であり、触媒層を除去する工程が不要である。前記触媒層は、好ましくは、透明である。 In the plated product of the present invention, the catalyst layer is preferably insulating, and a step of removing the catalyst layer is unnecessary. The catalyst layer is preferably transparent.
　本発明のめっき物は、マスク層（UV未照射部）に無電解めっき層（回路）が形成されるので、回路のパターン形成を可能とする。 In the plated product of the present invention, an electroless plating layer (circuit) is formed on the mask layer (UV unirradiated portion), so that a circuit pattern can be formed.
　本発明のめっき物は、回路のパターン形成に、フォトエッチング、パターン印刷等の工程が不要であり、触媒層の除去の工程も不要である、パターン形状の無電解めっき層（導体回路）を有する。 The plated product of the present invention has a pattern-shaped electroless plating layer (conductor circuit) that does not require steps such as photoetching and pattern printing for circuit pattern formation and does not require a step of removing the catalyst layer. ..
　（2）基材（基板）
　本発明のめっき物は、基材の表面に触媒層を有し、前記触媒層の表面にパターン形状の無電解めっき層を有する。 (2) Substrate (board)
The plated product of the present invention has a catalyst layer on the surface of the base material, and has a pattern-shaped electroless plating layer on the surface of the catalyst layer.
　前記基材（好ましくは、基板、回路基板）の材料は、好ましくは、絶縁基板であり、プラスチック（樹脂）、ガラス、セラミックス等を用いる。 The material of the base material (preferably a substrate, a circuit board) is preferably an insulating substrate, and plastic (resin), glass, ceramics, or the like is used.
　前記基材は、好ましくは、基板であり、回路基板である。 The base material is preferably a substrate and a circuit board.
　前記基材（基板）の材料は、マスク処理のし易さの点で、好ましくは、均一な厚み（高さ）を有する。 The material of the base material (board) preferably has a uniform thickness (height) in terms of ease of masking.
　前記プラスチックとして、好ましくは、アクリロニトリル-ブタジエン-スチレンの共重合樹脂(ABS樹脂)等を用いる。 As the plastic, preferably an acrylonitrile-butadiene-styrene copolymer resin (ABS resin) or the like is used.
　前記プラスチックとして、好ましくは、ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート(PBT)、ポリエチレンナフタレート（PEN）、ポリ乳酸エステル等のポリエステル；ポリメチルメタクリレート(PMMA)等のアクリル樹脂；ポリカーボネート(PC)；ポリ塩化ビニル；ポリアミド；ポリイミド；ポリエーテルイミド；ポリアセタール；ポリエーテルエーテルケトン；ノルボルネン骨格を有する環状ポリオレフィン；ポリフェニレンスルファイド；液晶ポリマー；シクロオレフィンポリマー（COP）；変性ポリフェニルエーテル；ポリスルホン；フェノール；ポリフタルアミド（PPA）；ポリアリレート等を用いる。 The plastics are preferably polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and polylactic acid esters; acrylic resins such as polymethylmethacrylate (PMMA); polycarbonate (PC); Polyvinyl chloride; Polyester; Polyester; Polyesterimide; Polyacetal; Polyether ether ketone; Cyclic polyolefin with norbornen skeleton; Polyphenylene sulfide; Liquid crystal polymer; Cycloolefin polymer (COP); Modified polyphenyl ether; Polysulfone; Phenol; Poly Phthalamide (PPA); polyallylate or the like is used.
　前記プラスチックとして、好ましくは、ポリエチレン(PE)、ポリプロピレン(PP)、ポリスチレン(PS)、ポリブタジエン、ポリブテン、ポリイソプレン、ポリクロロプレン、ポリイソブチレン、ポリイソプレン等のポリオレフィン等を用いる。 As the plastic, preferably, polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polybutadiene, polybutene, polyisoprene, polychloroprene, polyisobutylene, and polyisoprene are used.
　前期プラスチックとして、好ましくは、ポリテトラフルオロエチレン（PTFE）、テトラフルオロエチレン-エチレン共重合体（ETFE）、フッ化エチレン-フッ化プロピレン共重合体（FEP）、ペルフルオロアルコキシフッ素樹脂（PFA）などのフッ素樹脂を用いる。 As early-stage plastics, preferably, polytetrafluoroethylene (PTFE), tetrafluoroethylene-ethylene copolymer (ETFE), fluoroethylene-fluorinated propylene copolymer (FEP), perfluoroalkoxy alkanes (PFA) and the like are used. Fluororesin is used.
　前記セラミックスとして、好ましくは、ガラス、アルミナ等が挙げられる。また、基材として不織布を使用する場合、木質繊維、ガラス繊維、石綿、ポリエステル繊維、ビニロン繊維、レーヨン繊維、ポリオレフィン繊維等を用いる。 Preferred examples of the ceramics include glass, alumina and the like. When a non-woven fabric is used as the base material, wood fiber, glass fiber, asbestos, polyester fiber, vinylon fiber, rayon fiber, polyolefin fiber and the like are used.
　前記基材としてプラスチック、セラミックス等を使用する場合、好ましくは、適宜プライマー等で絶縁性を形成した上で、使用する。 When plastic, ceramics, etc. are used as the base material, it is preferably used after appropriately forming an insulating property with a primer or the like.
　前記基材として金属等の導電性物質を使用する場合、好ましくは、プライマー等で絶縁性を形成した上で、基材として用いる。 When a conductive substance such as a metal is used as the base material, it is preferably used as the base material after forming insulation with a primer or the like.
　本発明のめっき物は、前記基材は、好ましくは、基板であり、後述する無電解めっき層は、導体回路であり、回路基板である。 In the plated product of the present invention, the base material is preferably a substrate, and the electroless plating layer described later is a conductor circuit and a circuit board.
　（3）触媒層
　本発明のめっき物は、基材の表面に触媒層を有し、前記触媒層の表面にパターン形状の無電解めっき層を有する。前記触媒層は、好ましくは、（i）金属粒子と分散剤との複合体、（ii）溶媒、及び（iii）バインダーを含有する触媒組成物から成る。 (3) Catalyst layer The plated product of the present invention has a catalyst layer on the surface of the base material, and has a pattern-shaped electroless plating layer on the surface of the catalyst layer. The catalyst layer preferably comprises a catalyst composition containing (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a binder.
　本発明のめっき物は、好ましくは、前記基材の表面に、前記触媒層を、全面に有する。 The plated product of the present invention preferably has the catalyst layer on the entire surface of the base material.
　（i）金属粒子と分散剤との複合体
　本発明のめっき物では、前記触媒層は、（i）金属粒子と分散剤との複合体を含有する触媒組成物から成る。 (I) Composite of metal particles and dispersant In the plated product of the present invention, the catalyst layer comprises (i) a catalyst composition containing a composite of metal particles and a dispersant.
　前記金属粒子は、好ましくは、パラジウム粒子、金粒子、銀粒子、又は、白金粒子である。前記金属粒子と分散剤との複合体は、好ましくは、パラジウム粒子（Pd粒子）を含むパラジウム複合体（Pd複合体）である。 The metal particles are preferably palladium particles, gold particles, silver particles, or platinum particles. The complex of the metal particles and the dispersant is preferably a palladium complex (Pd complex) containing palladium particles (Pd particles).
　前記金属粒子と分散剤との複合体は、好ましくは、例えば、ポリカルボン酸系分散剤、ヒドロキシル基又はカルボキシル基を有するブロック共重合体型高分子分散剤等の分散剤の存在下、金属粒子として、例えば、塩化パラジウム（塩化Pd）等のパラジウム化合物（Pd化合物）から供給されるパラジウムイオン（Pdイオン）を、ヒドラジンヒドラート等の2級又は3級アミン類で還元することによって得ることができる。 The composite of the metal particles and the dispersant is preferably used as metal particles in the presence of a dispersant such as a polycarboxylic acid-based dispersant, a block copolymer type polymer dispersant having a hydroxyl group or a carboxyl group. , For example, it can be obtained by reducing palladium ions (Pd ions) supplied from a palladium compound (Pd compound) such as palladium chloride (Pd chloride) with secondary or tertiary amines such as hydrazine hydride. ..
　前記金属粒子は、無電解めっき触媒として機能するものであり、好ましくは、パラジウム粒子（Pd粒子）、金粒子（Au粒子）、銀粒子（Ag粒子）、白金粒子（Pt粒子）等の貴金属の超微粒子であり、より好ましくは、Pd粒子である。 The metal particles function as a electroless plating catalyst, and are preferably of noble metals such as palladium particles (Pd particles), gold particles (Au particles), silver particles (Ag particles), and platinum particles (Pt particles). It is ultrafine particles, more preferably Pd particles.
　前記Pd粒子は、好ましくは、前記分散剤の存在下、Pd化合物から供給されるPdイオンを、還元剤を用いて還元することによって得ることができる（液相還元法）。 The Pd particles can be preferably obtained by reducing Pd ions supplied from the Pd compound with a reducing agent in the presence of the dispersant (liquid phase reduction method).
　前記Pd化合物は、好ましくは、塩化パラジウム（塩化Pd）、硫酸パラジウム、硝酸パラジウム、酢酸パラジウム、安息香酸パラジウム、サリチル酸パラジウム、パラトルエンスルホン酸パラジウム、過塩素酸パラジウム、ベンゼンスルホン酸パラジウム等を用いる。Pd化合物は、1種又は2種以上を組み合わせて使用することができる。 As the Pd compound, preferably, palladium chloride (Pd chloride), palladium sulfate, palladium nitrate, palladium acetate, palladium benzoate, palladium salicylate, palladium paratoluenesulfonate, palladium perchlorate, palladium benzenesulfonate and the like are used. The Pd compound can be used alone or in combination of two or more.
　前記還元剤は、好ましくは、ヒドラジンヒドラート（ヒドラジン1水和物）、水素化ホウ素ナトリウム、N,Nジメチルエタノールアミン、ジエタノールアミン、トリエタノールアミン等の1級、2級又は3級アミン類、アスコルビン酸、2,3-ジヒドロキシマレイン酸等のエンジオール類を用いる。 The reducing agent is preferably primary, secondary or tertiary amines such as hydrazine hydrate (hydrazine monohydrate), sodium borohydride, N, N dimethylethanolamine, diethanolamine, triethanolamine, and ascorbin. Endiols such as acid and 2,3-dihydroxymaleic acid are used.
　前記Pdイオンを還元する方法は、好ましくは、溶媒（下記の溶媒）中に分散剤及びPdイオンを存在させた後、還元剤を前記溶媒中に加える方法であり、これによりPdイオンと還元剤とが接触し、Pdイオンを還元することができる。 The method for reducing the Pd ion is preferably a method in which the dispersant and the Pd ion are present in a solvent (the solvent below) and then the reducing agent is added to the solvent, whereby the Pd ion and the reducing agent are added. Can contact with and reduce Pd ions.
　前記Pd複合体中のPd粒子と分散剤との重量比は、好ましくは、Pd粒子：分散剤＝50：50～95：5程度であり、より好ましくは、Pd粒子：分散剤＝65：35～85：15程度である。 The weight ratio of the Pd particles to the dispersant in the Pd complex is preferably about Pd particles: dispersant = 50:50 to 95: 5, and more preferably Pd particles: dispersant = 65:35. It is about 85:15.
　前記Pd複合体の平均粒子径は、好ましくは、全体としては平均粒子径20nm～300nm程度の球形状の構造を有している。前記Pd複合体の平均粒子径は、粒径アナライザー（大塚電子株式会社、FPAR-1000）で測定する（重量基準平均径）。 The average particle size of the Pd complex preferably has a spherical structure with an average particle size of about 20 nm to 300 nm as a whole. The average particle size of the Pd composite is measured with a particle size analyzer (Otsuka Electronics Co., Ltd., FPAR-1000) (weight-based average diameter).
　前記金属粒は、無電解めっき触媒として機能するものであり、好ましくは、Pd粒子、Au粒子、Ag粒子、Pt粒子等の貴金属の超微粒子である。 The metal particles function as an electroless plating catalyst, and are preferably ultrafine particles of precious metals such as Pd particles, Au particles, Ag particles, and Pt particles.
　前記金属粒子として、Pt粒子を用いる時、好ましくは、分散剤の存在下、塩化白金（IV）等の白金化合物（Pt化合物、貴金属化合物）から供給される白金イオン（Ptイオン）を、ヒドラジンヒドラート等の2級又は3級アミン類で還元することによって得る。 When Pt particles are used as the metal particles, platinum ions (Pt ions) supplied from a platinum compound (Pt compound, noble metal compound) such as platinum chloride (IV) are preferably hydrazine hydride in the presence of a dispersant. Obtained by reduction with secondary or tertiary amines such as lat.
　（ii）溶媒
　本発明のめっき物では、前記触媒層は、好ましくは、（ii）溶媒を含有する触媒組成物から成る。 (Ii) Solvent In the plated product of the present invention, the catalyst layer preferably comprises (ii) a catalyst composition containing a solvent.
　前記溶媒（分散媒）は、好ましく、金属複合体（Pd複合体等）を分散させることができ、また、下記のバインダーとの親和性に優れているものである。前記溶媒は、好ましくは、触媒組成物の粘度、蒸発速度等の観点で選択し、また、触媒組成物が、基板と良好に密着する点を満足さものである。 The solvent (dispersion medium) is preferably one that can disperse a metal complex (Pd complex or the like) and has an excellent affinity with the following binders. The solvent is preferably selected from the viewpoint of the viscosity of the catalyst composition, the evaporation rate, and the like, and is satisfied that the catalyst composition adheres well to the substrate.
　前記溶媒は、好ましくは、水、メタノール、エタノール、イソプロピルアルコール（IPA）、1-ブチルアルコール、イソブチルアルコール等のアルコール類；アセトン、メチルエチルケトン（MEK）、メチルイソブチルケトン（MIBK）、ジアセトンアルコール（4-ヒドロキシ-4-メチル-2-ペンタノン）、シクロヘキサノン等のケトン類；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ブチルエーテル等のグリコールエーテル類；安息香酸メチル、安息香酸エチル、サリチル酸メチル等の芳香族カルボン酸エステル類；トルエン、キシレン等の芳香族炭化水素類；n-へキサン、n-へプタン、ミネラルスピリット等の脂肪族炭化水素類；メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート、メチルカルビトールアセテート、ブチルカルビトールアセテート等のグリコールエーテルエステル類；酢酸エチル、酢酸ブチル等のアルカノールエステル類；2-フェノキシエタノール（エチレングリコールフェニルエーテル）等を用いる。 The solvent is preferably water, alcohols such as methanol, ethanol, isopropyl alcohol (IPA), 1-butyl alcohol, isobutyl alcohol; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diacetone alcohol (4). -Hydroxy-4-methyl-2-pentanone), ketones such as cyclohexanone; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether; aromatic carboxylic acid esters such as methyl benzoate, ethyl benzoate and methyl salicylate. Classes; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane, n-heptane and mineral spirit; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate, butyl Glycol ether esters such as carbitol acetate; alkanol esters such as ethyl acetate and butyl acetate; 2-phenoxyethanol (ethylene glycol phenyl ether) and the like are used.
　前記溶媒は、好ましくは、印刷性及び塗装性、印刷・塗装後のレベリング過程を考慮して、蒸発速度が遅い溶媒を使用する。前記蒸発速度が遅い溶媒として、好ましくは、ジアセトンアルコール、シクロヘキサノン、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート、メチルカルビトールアセテート、ブチルカルビトールアセテート、2-フェノキシエタノール等を用いる。 As the solvent, a solvent having a slow evaporation rate is preferably used in consideration of printability, paintability, and leveling process after printing / painting. As the solvent having a slow evaporation rate, preferably diacetone alcohol, cyclohexanone, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate, butyl carbitol acetate, 2-phenoxyethanol and the like are used.
　前記溶媒は、触媒組成物中の金属複合体（Pd複合体等）を良好に分散させることができるという観点から、好ましくは、水、N-メチルピロリドン等の非プロトン性極性溶媒等を用いる。 As the solvent, water, an aprotic polar solvent such as N-methylpyrrolidone, or the like is preferably used from the viewpoint that the metal complex (Pd complex or the like) in the catalyst composition can be dispersed well.
　前記非プロトン性極性溶媒は、好ましくは、N-メチルピロリドン（NMP）、N,N-ジメチルホルムアミド（DMF）、N,N-ジメチルアセトアミド（DMAc）等の非プロトン性極性溶媒；ジメチルスルホキシド；γ-ブチロラクトン等を用いる。 The aprotonic polar solvent is preferably an aprotonic polar solvent such as N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc); dimethylsulfoxide; γ. -Use butyrolactone or the like.
　前記溶媒は、1種又は2種以上を組み合わせて使用することができる。 The solvent can be used alone or in combination of two or more.
　（iii）バインダー
　本発明のめっき物では、前記触媒層は、好ましくは、（iii）バインダーを含有する触媒組成物から成る。 (Iii) Binder In the plated product of the present invention, the catalyst layer preferably comprises (iii) a catalyst composition containing a binder.
　前記バインダーは、好ましくは、触媒組成物の粘度、触媒組成物と基板（PETフィルム、ABS基材等）との密着性、硬化条件等の観点から、良好に無電解めっきの反応性が得られるものを選択する。前記バインダーは、好ましくは、前記溶媒に分散又は溶解するものである。 The binder preferably has good electroless plating reactivity from the viewpoints of the viscosity of the catalyst composition, the adhesion between the catalyst composition and the substrate (PET film, ABS substrate, etc.), curing conditions, and the like. Select one. The binder is preferably one that is dispersed or dissolved in the solvent.
　前記バインダーは、好ましくは、アセタール樹脂（POM）、エポキシ樹脂、エステル樹脂、アクリル樹脂、ウレタン樹脂、アミド樹脂（PA、ポリアミド、ナイロン）、イミド樹脂（ポリイミド）、アミドイミド樹脂（PAI、ポリアミドイミド）、シェラック樹脂、メラミン樹脂、尿素樹脂、硝化綿、アルキド樹脂、石油樹脂、ロジン系樹脂、スチレン／マレイン酸樹脂、シリコン樹脂、塩ビ-酢ビ共重合体、アクリルモノマー／オリゴマー及びオレフィン樹脂（ポリオレフィン）等を用いる。 The binder is preferably an acetal resin (POM), an epoxy resin, an ester resin, an acrylic resin, a urethane resin, an amide resin (PA, polyamide, nylon), an imide resin (polymethyl), an amide imide resin (PAI, polyamideimide), and the like. Shelac resin, melamine resin, urea resin, nitrified cotton, alkyd resin, petroleum resin, rosin resin, styrene / maleic acid resin, silicon resin, vinyl chloride-vinegar bipolymer, acrylic monomer / oligomer, olefin resin (polyolefin), etc. Is used.
　前記塩ビ-酢ビ共重合体（塩化ビニル・酢酸ビニル系変性樹脂）は、塩化ビニルと酢酸ビニル等との共重合樹脂である。 The vinyl chloride-vinyl acetate copolymer (vinyl chloride / vinyl acetate-based modified resin) is a copolymer resin of vinyl chloride and vinyl acetate or the like.
　前記バインダーは、より好ましくは、エポキシ樹脂、ウレタン樹脂、アミドイミド樹脂、及び塩ビ-酢ビ共重合体からなる群から選ばれた少なくとも1種を用い、2種以上を組み合わせて使用することもできる。前記バインダーは、特に好ましくは、エポキシ樹脂、ウレタン樹脂及びアミドイミド樹脂を使用する。 More preferably, at least one selected from the group consisting of an epoxy resin, a urethane resin, an amidoimide resin, and a vinyl chloride-vinyl acetate copolymer is used, and two or more of them can be used in combination. Epoxy resin, urethane resin and amideimide resin are particularly preferably used as the binder.
　前記バインダーは、必要に応じて、硬化剤を併用する方が好ましい。硬化剤を併用することで、より短時間でUV照射による効果を発現できるため、よりパターンの鮮明化が可能になる。 It is preferable to use a curing agent in combination with the binder, if necessary. By using a curing agent in combination, the effect of UV irradiation can be exhibited in a shorter time, so that the pattern can be made clearer.
　前記硬化剤は、特に限定されず、使用するバインダー樹脂に合わせて適宜選択することが可能である。前記硬化剤は、好ましくは、イソシアネート、アミド樹脂、フェノール樹脂、メルカプタン、イミダゾール、ケティミン、オキサゾリン、カルボジイミド、エポキシ等を用いる。 The curing agent is not particularly limited and can be appropriately selected according to the binder resin to be used. As the curing agent, isocyanate, amide resin, phenol resin, mercaptan, imidazole, kettimin, oxazoline, carbodiimide, epoxy and the like are preferably used.
　本発明では、前記触媒組成物には、必要に応じて、フィラー、増粘剤等の添加物を使用しても良い。前記フィラーは、好ましくは、シリカ、アルミナ等を用いる。前記増粘剤は、好ましくは、スメクタイト系粘土鉱物等の無機増粘剤、セルロースナノファイバー等の有機系増粘剤等を用いる。 In the present invention, additives such as fillers and thickeners may be used in the catalyst composition, if necessary. As the filler, silica, alumina or the like is preferably used. As the thickener, an inorganic thickener such as smectite clay mineral, an organic thickener such as cellulose nanofiber, or the like is preferably used.
　前記フィラー、増粘剤等の添加物の粒子径は、特に限定されない。本発明では、導体回路として微細配線を形成する場合では、好ましくは、粒子径がより小さいフィラー、増粘剤等の添加物を用いる。その理由から、フィラー、増粘剤等の添加物の粒子径は、好ましくは、100nm以下であり、より好ましくは、10nm以下である。 The particle size of the additives such as the filler and the thickener is not particularly limited. In the present invention, when forming fine wiring as a conductor circuit, additives such as a filler having a smaller particle size and a thickener are preferably used. For that reason, the particle size of the additive such as the filler and the thickener is preferably 100 nm or less, more preferably 10 nm or less.
　（iv）触媒層の形成方法
　本発明のめっき物では、前記触媒組成物を、基材（回路基板）上に、好ましくは、バーコート法、スピンコート法、ディップコート法、スプレー塗布、グラビアコート法、ロールコート法、コンマコート法、グラビア印刷法、スクリーン印刷法、グラビアリバースロールコーティング法等の公知の手段により、塗布・乾燥させて、触媒層を形成する。 (Iv) Method for Forming Catalyst Layer In the plated product of the present invention, the catalyst composition is preferably applied on a substrate (circuit substrate) by a bar coating method, a spin coating method, a dip coating method, a spray coating, or a gravure coating. A catalyst layer is formed by coating and drying by a known means such as a method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, and a gravure reverse roll coating method.
　前記触媒層の形成は、より好ましくは、基材（回路基板）上に、前記触媒組成物を、バーコート法、スピンコート法、若しくはグラビアリバースロールコーティング法により塗布し、触媒組成物を乾燥させて、触媒層を形成する。 To form the catalyst layer, more preferably, the catalyst composition is applied onto a substrate (circuit board) by a bar coating method, a spin coating method, or a gravure reverse roll coating method, and the catalyst composition is dried. To form a catalyst layer.
　前記触媒層の厚みは、好ましくは、良好に無電解めっきを行い、無電解めっきの反応性を得ることができ、基材（基板）にめっき皮膜を良好に形成することができる点から、20μm以下程度であり、より好ましくは、0.01μm～10μm程度である。 The thickness of the catalyst layer is preferably 20 μm from the viewpoint that electroless plating can be performed satisfactorily, the reactivity of electroless plating can be obtained, and a plating film can be satisfactorily formed on the base material (substrate). It is about 0.01 μm to 10 μm, more preferably about 0.01 μm to 10 μm.
　本発明は、触媒層に対して、マスキングする部分は、UV未照射部分と成り、触媒層は失活せず、無電解めっき層（導体回路）が形成されること、触媒層に対してマスキングしない部分は、UV照射部分と成り、触媒層は失活し、無電解めっき層（導体回路）が形成されないことを含む、導体回路のパターン形成を可能とするめっき物を提供できる。 In the present invention, the portion to be masked with respect to the catalyst layer is a UV-unirradiated portion, the catalyst layer is not deactivated, an electrolytic-free plating layer (conductor circuit) is formed, and the catalyst layer is masked. It is possible to provide a plated product capable of forming a pattern of a conductor circuit, including a portion not provided as a UV-irradiated portion, the catalyst layer being deactivated, and a non-electrolytic plating layer (conductor circuit) not being formed.
　本発明のめっき物は、好ましくは、前記基材の表面に、前記触媒層を、全面に有する。本発明のめっき物では、触媒層は絶縁性であることから、その触媒層を除去すること無く、導体回路のパターン形成を可能とし、触媒層が存在しても、それ自体が導電性を表さず、短絡しないめっき物と成る。 The plated product of the present invention preferably has the catalyst layer on the entire surface of the base material. In the plated product of the present invention, since the catalyst layer is insulating, it is possible to form a pattern of a conductor circuit without removing the catalyst layer, and even if the catalyst layer is present, it itself exhibits conductivity. Instead, it becomes a plated product that does not short-circuit.
　本発明のめっき物は、好ましくは、めっき回路に応じた光透過模様を有するマスキング（マスキング層）を除去すれば良い。 The plated product of the present invention preferably removes the masking (masking layer) having a light transmitting pattern according to the plating circuit.
　（4）パターン形状及びマスク層（マスキング）
　本発明のめっき物は、基材の表面に触媒層を有し、前記触媒層の表面にパターン形状の無電解めっき層を有する。 (4) Pattern shape and mask layer (masking)
The plated product of the present invention has a catalyst layer on the surface of the base material, and has a pattern-shaped electroless plating layer on the surface of the catalyst layer.
　前記基材において、前記パターン形状の無電解めっき層では、好ましくは、前記触媒層の表面に、UV照射されず、無電解めっき層が有る部分と、UV照射されて、無電解めっき層が無い部分とで、パターン形状の無電解めっき層と成る。 In the base material, in the electroless plating layer having the pattern shape, preferably, the surface of the catalyst layer is not UV-irradiated and has an electroless plating layer, and is UV-irradiated without the electroless plating layer. The part forms an electroless plating layer with a pattern shape.
　前記基材において、前記パターン形状の無電解めっき層では、好ましくは、前記触媒層の表面に、マスキングされて、マスク層を形成し、その部分はUV照射されず、無電解めっき層が有る部分と、マスキングされず、マスク層を形成せず、その部分はUV照射されて、無電解めっき層が無い部分とで、パターン形状の無電解めっき層（導体回路）と成る。 In the base material, in the electroless plating layer having the pattern shape, preferably, the surface of the catalyst layer is masked to form a mask layer, and the portion is not irradiated with UV and has an electroless plating layer. The part is UV-irradiated without masking and does not form a mask layer, and the part without the electroless plating layer becomes a pattern-shaped electroless plating layer (conductor circuit).
　前記パターン形状及びマスク層（マスキング）は、好ましくは、めっき回路に応じた光透過模様を有する金属板、ガラス板、フィルム等、若しくはレジスト等の樹脂をパターン印刷し、マスクとしたものを用いる。光透過性が無い金属板等を用いることで、めっき回路に応じたマスキングを行うことができる。 As the pattern shape and mask layer (masking), preferably, a metal plate, a glass plate, a film or the like having a light transmitting pattern according to the plating circuit, or a resin such as a resist is pattern-printed and used as a mask. By using a metal plate or the like having no light transmission, masking can be performed according to the plating circuit.
　本発明のめっき物は、基材の表面に、触媒金属錯イオンを含有する触媒処理液を付着させ、触媒層を形成し、次いで形成すべき回路パターンを有するパターンマスクを用いて基材表面に光を照射（UV照射）して、光照射部分の触媒活性を失活させ、その後基材を無電解めっきして（浴中に浸漬等）、光が照射されていない未照射部分（マスキング部分）にめっき回路を形成する方法である。 In the plated product of the present invention, a catalyst treatment liquid containing a catalytic metal complex ion is adhered to the surface of the base material to form a catalyst layer, and then a pattern mask having a circuit pattern to be formed is used on the surface of the base material. Light is irradiated (UV irradiation) to deactivate the catalytic activity of the light-irradiated part, and then the base material is electroless plated (immersed in a bath, etc.), and the unirradiated part (masking part) is not irradiated with light. ) Is a method of forming a plating circuit.
　本発明のめっき物は、触媒金属（パラジウム（Pd）等）錯イオンを含有する触媒処理液（触媒組成物）を用い、光照射部分（UV照射部分）は触媒活性を失活させて、光の未照射部分（UV未照射部分）にめっき回路を形成する。 The plated product of the present invention uses a catalyst treatment liquid (catalyst composition) containing a catalytic metal (palladium (Pd) or the like) complex ion, and the light-irradiated portion (UV-irradiated portion) deactivates the catalytic activity to generate light. A plating circuit is formed in the unirradiated portion (UV unirradiated portion).
　前記パターン形状及びマスク層（マスキング、パターンマスク）は、好ましくは、形成しようとするめっき回路に応じた光透過模様を有している。 The pattern shape and mask layer (masking, pattern mask) preferably have a light transmitting pattern according to the plating circuit to be formed.
　前記光照射に用いる光として、好ましくは、紫外線光（UV光）、可視光等であり、基材表面に付着させた触媒組成物（触媒処理液）中の触媒を失活させることができる光を用いる。 The light used for the light irradiation is preferably ultraviolet light (UV light), visible light, or the like, and is light that can inactivate the catalyst in the catalyst composition (catalyst treatment liquid) adhering to the surface of the base material. Is used.
　前記光照射に用いる光は、好ましくは、紫外線（UV光）であり、波長が10nm～400nm程度、即ち可視光線より短く軟X線より長い不可視光線の電磁波である。前記光照射に用いる光は、より好ましくは、紫外線（UV光）であり、波長が10nm～300nm程度の電磁波である。 The light used for the light irradiation is preferably ultraviolet rays (UV light), and is an electromagnetic wave of invisible light having a wavelength of about 10 nm to 400 nm, that is, shorter than visible light and longer than soft X-ray. The light used for the light irradiation is more preferably ultraviolet rays (UV light), and is an electromagnetic wave having a wavelength of about 10 nm to 300 nm.
　前記紫外線光（UV光）の光源は、好ましくは、高圧水銀ランプ、メタルハライドランプ、紫外線LEDランプである。 The light source of the ultraviolet light (UV light) is preferably a high-pressure mercury lamp, a metal halide lamp, or an ultraviolet LED lamp.
　また、前記光源は紫外（UV）レーザーであってもよい。前記紫外（UV）レーザーは、好ましくは、UV-YAG、DUV-YAGもしくはエキシマである。前記紫外（UV）レーザーは、より好ましくは、DUV-YAGもしくはエキシマである。 Further, the light source may be an ultraviolet (UV) laser. The ultraviolet (UV) laser is preferably UV-YAG, DUV-YAG or excimer. The ultraviolet (UV) laser is more preferably DUV-YAG or excimer.
　前記紫外線光（UV光）の積算光量は、好ましくは、1mJ／cm2～20,000mJ／cm2、より好ましくは、1mJ／cm2～2,000mJ／cm2、更に好ましくは、1mJ／cm2～1,000mJ／cm2である。 Integrated light quantity of the ultraviolet light (UV light), preferably, 1mJ / cm 2 ~ 20,000mJ / cm 2, more preferably, 1mJ / cm 2 ~ 2,000mJ / cm 2, more preferably, 1 mJ / cm 2 ~ It is 1,000 mJ / cm 2 .
　前記基材表面に形成された触媒層では、形成すべき回路パターンに応じて、光を照射（UV照射）した部分は、その触媒活性が失活される。前記触媒層では、一方で、光が照射されていない未照射部分（マスキング部分）は、その触媒活性は残り、その部分に無電解めっきが形成されて、めっき回路を形成することができる。 In the catalyst layer formed on the surface of the base material, the catalytic activity of the portion irradiated with light (UV irradiation) is inactivated according to the circuit pattern to be formed. On the other hand, in the catalyst layer, the catalytic activity of the unirradiated portion (masking portion) that has not been irradiated with light remains, and electroless plating is formed on the portion, so that a plating circuit can be formed.
　（5）無電解めっき層（回路基板）
　本発明のめっき物は、前記基材を基板とし、前記無電解めっき層を導体回路として、回路基板とすることが好ましい。 (5) Electroless plating layer (circuit board)
In the plated product of the present invention, it is preferable that the base material is a substrate and the electroless plating layer is a conductor circuit as a circuit board.
　本発明は、触媒層に対して、マスキングする部分（金属板部分）は、UV未照射部分と成り、触媒層は失活せず、無電解めっき層（導体回路）が形成され、触媒層に対して、触媒層に対してマスキングしない部分は、UV照射部分と成り、触媒層は失活し、無電解めっき層（導体回路）が形成されない。本発明は、こうして、導体回路のパターン形成を可能とするめっき物を作製する。 In the present invention, the portion to be masked (metal plate portion) with respect to the catalyst layer becomes a UV unirradiated portion, the catalyst layer is not deactivated, an electrolytically-free plating layer (conductor circuit) is formed, and the catalyst layer is formed. On the other hand, the portion that is not masked with respect to the catalyst layer becomes a UV irradiation portion, the catalyst layer is deactivated, and the electroless plating layer (conductor circuit) is not formed. The present invention thus produces a plated product that enables pattern formation of a conductor circuit.
　本発明の回路基板では、好ましくは、失活していない触媒層（マスキングする部分（金属板部分））に対して、無電解めっきを行うことで、基板の上にパターンめっきを形成することができる。 In the circuit board of the present invention, it is preferable to form pattern plating on the substrate by performing electroless plating on the catalyst layer (masking portion (metal plate portion)) that has not been deactivated. can.
　前記触媒組成物によって形成された触媒層は、無電解めっきの反応性がよく、得られた無電解めっき皮膜はむらがなく、密着性及び外観性に優れる。 The catalyst layer formed by the catalyst composition has good reactivity of electroless plating, and the obtained electroless plating film has no unevenness and is excellent in adhesion and appearance.
　本発明の回路基板では、前記無電解めっき層は、導体回路（導通）であることが好ましい。 In the circuit board of the present invention, the electroless plating layer is preferably a conductor circuit (conductivity).
　前記めっき液は、好ましくは、導体回路（導通）を形成し、銅、金、銀、ニッケル等を用いる。前記めっき液は、好ましくは、触媒層（触媒膜）との関係から、銅又はニッケルを含むめっき液を用いる。 The plating solution preferably forms a conductor circuit (conductivity) and uses copper, gold, silver, nickel or the like. As the plating solution, a plating solution containing copper or nickel is preferably used because of the relationship with the catalyst layer (catalyst film).
　前記めっき条件は、好ましくは、触媒層（触媒膜）は無電解めっきの反応性が非常に良好である為、めっき液の還元剤濃度やアルカリ成分濃度を高める必要がない。その為、めっき液の寿命が長持ちし、触媒層のパターン通りにめっきが選択的に析出される。即ち、触媒組成物から形成される触媒（触媒膜）は、パターン形成能に優れる。 The plating conditions are preferably such that the catalyst layer (catalyst film) has very good reactivity of electroless plating, so that it is not necessary to increase the concentration of the reducing agent or the concentration of the alkaline component in the plating solution. Therefore, the life of the plating solution is long, and the plating is selectively deposited according to the pattern of the catalyst layer. That is, the catalyst (catalyst film) formed from the catalyst composition is excellent in pattern forming ability.
　前記無電解めっき層（めっき皮膜）の厚みは、好ましくは、0.05μm～10μm程度であり、より好ましくは、0.1μm～6μm程度である。 The thickness of the electroless plating layer (plating film) is preferably about 0.05 μm to 10 μm, and more preferably about 0.1 μm to 6 μm.
　無電解めっき処理で、無電解銅（Cu）めっき浴を用いる時は、その処理温度は、好ましくは、25℃～65℃程度であり、その処理時間は、好ましくは、10分～60分程度である。この無電解めっき処理により、0.3μm～3μm程度の析出膜厚を形成することができる。 When an electroless copper (Cu) plating bath is used in the electroless plating treatment, the treatment temperature is preferably about 25 ° C to 65 ° C, and the treatment time is preferably about 10 to 60 minutes. Is. By this electroless plating treatment, a precipitation film thickness of about 0.3 μm to 3 μm can be formed.
　無電解めっき処理で、無電解ニッケルボロン浴を用いる時は、その処理温度は、好ましくは、55℃～70℃程度であり、その析出速度は、好ましくは、5μm／hr（60℃）程度である。 When an electroless nickel boron bath is used in the electroless plating treatment, the treatment temperature is preferably about 55 ° C. to 70 ° C., and the precipitation rate is preferably about 5 μm / hr (60 ° C.). be.
　無電解めっき処理で、無電解ニッケルりん浴を用いる時は、その処理温度は、好ましくは、30℃～95℃程度であり、好ましくは、析出速度が浴温30℃では3μm／hr程度であり、浴温90℃では20μm／hr程度である。 When an electroless nickel phosphorus bath is used in the electroless plating treatment, the treatment temperature is preferably about 30 ° C. to 95 ° C., and the precipitation rate is preferably about 3 μm / hr at a bath temperature of 30 ° C. At a bath temperature of 90 ° C, it is about 20 μm / hr.
　（6）回路基板
　本発明の回路基板では、前記触媒組成物は、特にABS等の基板を対象とする時に、無電解めっきの反応性が高く、めっきまでの多層めっきに耐え得る良好な密着性を実現できる。 (6) Circuit board In the circuit board of the present invention, the catalyst composition has high reactivity of electroless plating, especially when a substrate such as ABS is targeted, and has good adhesion that can withstand multi-layer plating up to plating. Can be realized.
　本発明の回路基板では、無電解めっきの反応性は良く、無電解めっきにおける還元剤の濃度を高める必要が無く、また無電解めっきの反応温度を上げる必要もない。更に、また有害な物質によるエッチング工程を必要としない。 In the circuit board of the present invention, the reactivity of electroless plating is good, it is not necessary to increase the concentration of the reducing agent in electroless plating, and it is not necessary to raise the reaction temperature of electroless plating. Furthermore, it does not require an etching process with harmful substances.
　本発明の回路基板では、好ましくは、電子機器のプリント配線板等の表面に、触媒層を形成し、無電解用めっきを施すための皮膜をパターン形成（露出）する。その無電解めっき用の皮膜（触媒層）が形成された配線板に対して、無電解めっきを行うことで、配線板に電子回路形成用の無電解めっき皮膜を形成する。本発明の回路基板では、好ましくは、電子機器のプリント配線板等で、無電解めっきを行うことにより金属配線回路を形成する。 In the circuit board of the present invention, preferably, a catalyst layer is formed on the surface of a printed wiring board or the like of an electronic device, and a film for electroless plating is formed (exposed) in a pattern. By performing electroless plating on the wiring board on which the film (catalyst layer) for electroless plating is formed, an electroless plating film for forming an electronic circuit is formed on the wiring board. In the circuit board of the present invention, a metal wiring circuit is preferably formed by electroless plating on a printed wiring board or the like of an electronic device.
　（7）めっき物（回路基板）の製造方法
　本発明のめっき物の製造方法は、
　（1）基材の表面に、（i）金属粒子と分散剤との複合体、（ii）溶媒、及び（iii）バインダーを含有する触媒組成物から成る触媒層を形成する工程、
　（2）前記触媒層を形成する工程の後、前記触媒層の表面にマスキング層を形成する工程、
　（3）前記マスキング層を形成する工程の後、前記触媒層及び前記マスキング層の表面にUV照射する工程、
　（4）前記UV照射する工程の後、マスキング層を除去する工程、
　（5）前記マスキング層を除去する工程の後、パターン形状の無電解めっき層を形成する工程、を含む。 (7) Manufacturing method of plated product (circuit board) The manufacturing method of the plated product of the present invention is as follows.
(1) A step of forming a catalyst layer composed of (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a catalyst composition containing a binder on the surface of a base material.
(2) A step of forming a masking layer on the surface of the catalyst layer after the step of forming the catalyst layer.
(3) After the step of forming the masking layer, the step of irradiating the catalyst layer and the surface of the masking layer with UV.
(4) After the UV irradiation step, a step of removing the masking layer,
(5) After the step of removing the masking layer, a step of forming a pattern-shaped electroless plating layer is included.
　本発明のめっき物の製造方法は、好ましくは、前記触媒層を形成する工程では、前記基材の表面に、前記触媒層を、全面に形成する。 In the method for producing a plated product of the present invention, preferably, in the step of forming the catalyst layer, the catalyst layer is formed on the entire surface of the base material.
　本発明のめっき物の製造方法は、好ましくは、前記パターン形状の無電解めっき層を形成する工程では、前記触媒層の表面に、前記マスキング層を形成して、前記UV照射せず、無電解めっき層を形成することと、前記マスキング層を形成せず、前記UV照射して、無電解めっき層を形成しないこととで、パターン形状の無電解めっき層を形成する。 In the method for producing a plated product of the present invention, preferably, in the step of forming the electroless plating layer having the pattern shape, the masking layer is formed on the surface of the catalyst layer, and the UV irradiation is not performed, and the electroless plating layer is not applied. A pattern-shaped electroless plating layer is formed by forming the plating layer and not forming the masking layer and irradiating the UV to form the electroless plating layer.
　本発明のめっき物の製造方法は、好ましくは、前記基材は、基板であり、前記無電解めっき層は、導体回路であり、回路基板である。 In the method for producing a plated product of the present invention, preferably, the base material is a substrate, and the electroless plating layer is a conductor circuit and a circuit board.
　・（1）基材の表面に触媒層を形成する工程
　本発明のめっき物では、上記の通り、前記触媒組成物を、基材（回路基板）上に、好ましくは、バーコート法、スピンコート法、ディップコート法、スプレー塗布、グラビアコート法、ロールコート法、コンマコート法、グラビア印刷法、スクリーン印刷法、グラビアリバースロールコーティング法等の公知の手段により、塗布・乾燥させて、触媒層を形成する。 (1) Step of forming a catalyst layer on the surface of a base material In the plated product of the present invention, as described above, the catalyst composition is applied onto the base material (circuit substrate), preferably by the bar coating method or spin coating. The catalyst layer is coated and dried by known means such as a method, a dip coating method, a spray coating, a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, and a gravure reverse roll coating method to form a catalyst layer. Form.
　前記触媒層は、好ましくは、前記基材の表面の全面に形成する。 The catalyst layer is preferably formed on the entire surface of the base material.
　前記触媒層の形成は、より好ましくは、基材（回路基板）上に、前記触媒組成物を、バーコート法、スピンコート法、若しくはグラビアリバースロールコーティング法により塗布し、触媒組成物を乾燥させて、触媒層を形成する。 To form the catalyst layer, more preferably, the catalyst composition is applied onto a substrate (circuit board) by a bar coating method, a spin coating method, or a gravure reverse roll coating method, and the catalyst composition is dried. To form a catalyst layer.
　前記触媒層の厚みは、好ましくは、良好に無電解めっきを行い、無電解めっきの反応性を得ることができ、基材（基板）にめっき皮膜を良好に形成することができる点から、20μm以下程度であり、より好ましくは、0.01μm～10μm程度である。 The thickness of the catalyst layer is preferably 20 μm from the viewpoint that electroless plating can be performed satisfactorily, the reactivity of electroless plating can be obtained, and a plating film can be satisfactorily formed on the base material (substrate). It is about 0.01 μm to 10 μm, more preferably about 0.01 μm to 10 μm.
　・（2）触媒層の表面にマスキング層を形成する工程
　本発明のめっき物では、上記の通り、好ましくは、めっき回路に応じた光透過模様を有する金属板等を用いて、触媒層の上に置くことで、光透過性が無い金属板により、めっき回路に応じたマスキングを行うことができる
　前記パターン形状及びマスク層（マスキング）は、好ましくは、めっき回路に応じた光透過模様を有する金属板、ガラス板、フィルム等、若しくはレジスト等の樹脂をパターン印刷し、マスクとしたものを用いる。 (2) Step of forming a masking layer on the surface of the catalyst layer In the plated product of the present invention, as described above, preferably, a metal plate or the like having a light transmitting pattern corresponding to the plating circuit is used on the catalyst layer. The pattern shape and the mask layer (masking) can preferably be masked according to the plating circuit by using a metal plate having no light transmission. A plate, glass plate, film, etc., or a resin such as a resist is printed in a pattern and used as a mask.
　・（3）触媒層及びマスキング層の表面にUV照射する工程
　本発明のめっき物では、上記の通り、好ましくは、光照射に用いる光として、好ましくは、紫外線光（UV光）を用い、基材表面に付着させた触媒組成物（触媒処理液）中の触媒を失活させる。前記光照射に用いる光は、好ましくは、紫外線（UV光）であり、好ましくは、波長が10nm～400nm程度、より好ましくは、波長が10nm～300nm程度、即ち可視光線より短く軟X線より長い不可視光線の電磁波である。 (3) Step of irradiating the surfaces of the catalyst layer and the masking layer with UV In the plated product of the present invention, as described above, the light used for light irradiation is preferably ultraviolet light (UV light). The catalyst in the catalyst composition (catalyst treatment liquid) attached to the surface of the material is inactivated. The light used for the light irradiation is preferably electromagnetic waves (UV light), preferably has a wavelength of about 10 nm to 400 nm, more preferably has a wavelength of about 10 nm to 300 nm, that is, shorter than visible light and longer than soft X-rays. It is an electromagnetic wave of invisible light.
　前記紫外線光（UV光）の光源は、好ましくは、高圧水銀ランプ、メタルハライドランプ、紫外線LEDランプである。 The light source of the ultraviolet light (UV light) is preferably a high-pressure mercury lamp, a metal halide lamp, or an ultraviolet LED lamp.
　また、前記光源は紫外（UV）レーザーであってもよい。前記紫外（UV）レーザーは、好ましくは、UV-YAG、DUV-YAGもしくはエキシマである。前記紫外（UV）レーザーは、より好ましくは、DUV-YAGもしくはエキシマである。 Further, the light source may be an ultraviolet (UV) laser. The ultraviolet (UV) laser is preferably UV-YAG, DUV-YAG or excimer. The ultraviolet (UV) laser is more preferably DUV-YAG or excimer.
　前記紫外線光（UV光）の積算光量は、好ましくは、1mJ／cm2～20,000mJ／cm2、より好ましくは、1mJ／cm2～2,000mJ／cm2、更に好ましくは、1mJ／cm2～1,000mJ／cm2である。 Integrated light quantity of the ultraviolet light (UV light), preferably, 1mJ / cm 2 ~ 20,000mJ / cm 2, more preferably, 1mJ / cm 2 ~ 2,000mJ / cm 2, more preferably, 1 mJ / cm 2 ~ It is 1,000 mJ / cm 2 .
　・（4）マスキング層を除去する工程
　本発明のめっき物は、好ましくは、めっき回路に応じた光透過模様を有するマスキング（マスキング層）を、金属板であれば、その金属板を除去すれば良い。マスキング層として金属板以外、例えば、ガラス板、フィルムを使った場合も、それを除去すれば良い。 (4) Step of removing the masking layer The plated product of the present invention preferably has a masking (masking layer) having a light transmitting pattern corresponding to the plating circuit, and if it is a metal plate, the metal plate is removed. good. When a masking layer other than a metal plate, for example, a glass plate or a film, is used, it may be removed.
　・（5）パターン形状の無電解めっき層を形成する工程
　本発明のめっき物は、好ましくは、前記触媒層の表面に、前記マスキング層を形成して、前記UV照射せず、無電解めっき層（導体回路）を形成することと、前記マスキング層を形成せず、前記UV照射して、無電解めっき層を形成しないこととで、基材（基板）にパターン形状の無電解めっき層（導体回路）を形成する。 (5) Step of forming an electroless plating layer having a pattern shape In the plated product of the present invention, the masking layer is preferably formed on the surface of the catalyst layer, and the electroless plating layer is not irradiated with UV. By forming the (conductor circuit) and not forming the masking layer and not forming the electroless plating layer by irradiating the UV, the electroless plating layer (conductor) having a pattern shape is formed on the base material (conductor). Circuit) is formed.
　本発明の回路基板では、好ましくは、失活していない触媒層（マスキングする部分（金属板部分））に対して、無電解めっきを行うことで、基板の上にパターンめっきを形成することができる。 In the circuit board of the present invention, it is preferable to form pattern plating on the substrate by performing electroless plating on the catalyst layer (masking portion (metal plate portion)) that has not been deactivated. can.
　前記触媒組成物によって形成された触媒層は、無電解めっきの反応性がよく、得られた無電解めっき皮膜はむらがなく、密着性及び外観性に優れる。 The catalyst layer formed by the catalyst composition has good reactivity of electroless plating, and the obtained electroless plating film has no unevenness and is excellent in adhesion and appearance.
　本発明の回路基板では、前記無電解めっき層は、導体回路（導通）であることが好ましい。 In the circuit board of the present invention, the electroless plating layer is preferably a conductor circuit (conductivity).
　前記めっき液は、好ましくは、導体回路（導通）を形成し、銅、金、銀、ニッケル等を用いる。前記めっき液は、好ましくは、触媒層（触媒膜）との関係から、銅又はニッケルを含むめっき液を用いる。 The plating solution preferably forms a conductor circuit (conductivity) and uses copper, gold, silver, nickel or the like. As the plating solution, a plating solution containing copper or nickel is preferably used because of the relationship with the catalyst layer (catalyst film).
　前記めっき条件は、好ましくは、触媒層（触媒膜）は無電解めっきの反応性が非常に良好である為、めっき液の還元剤濃度やアルカリ成分濃度を高める必要がない。その為、めっき液の寿命が長持ちし、触媒層のパターン通りにめっきが選択的に析出される。即ち、触媒組成物から形成される触媒（触媒膜）は、パターン形成能に優れる。 The plating conditions are preferably such that the catalyst layer (catalyst film) has very good reactivity of electroless plating, so that it is not necessary to increase the concentration of the reducing agent or the concentration of the alkaline component in the plating solution. Therefore, the life of the plating solution is long, and the plating is selectively deposited according to the pattern of the catalyst layer. That is, the catalyst (catalyst film) formed from the catalyst composition is excellent in pattern forming ability.
　前記無電解めっき層（めっき皮膜）の厚みは、好ましくは、0.05μm～10μm程度であり、より好ましくは、0.1μm～6μm程度である。 The thickness of the electroless plating layer (plating film) is preferably about 0.05 μm to 10 μm, and more preferably about 0.1 μm to 6 μm.
　無電解めっき処理で、無電解銅（Cu）めっき浴を用いる時は、その処理温度は、好ましくは、25℃～65℃程度であり、その処理時間は、好ましくは、10分～60分程度である。この無電解めっき処理により、0.3μm～3μm程度の析出膜厚を形成することができる。 When an electroless copper (Cu) plating bath is used in the electroless plating treatment, the treatment temperature is preferably about 25 ° C to 65 ° C, and the treatment time is preferably about 10 to 60 minutes. Is. By this electroless plating treatment, a precipitation film thickness of about 0.3 μm to 3 μm can be formed.
　無電解めっき処理で、無電解ニッケルボロン浴を用いる時は、その処理温度は、好ましくは、55℃～70℃程度であり、その析出速度は、好ましくは、5μm／hr（60℃）程度である。 When an electroless nickel boron bath is used in the electroless plating treatment, the treatment temperature is preferably about 55 ° C. to 70 ° C., and the precipitation rate is preferably about 5 μm / hr (60 ° C.). be.
　無電解めっき処理で、無電解ニッケルりん浴を用いる時は、その処理温度は、好ましくは、30℃～95℃程度であり、好ましくは、析出速度が浴温30℃では3μm／hr程度であり、浴温90℃では20μm／hr程度である。 When an electroless nickel phosphorus bath is used in the electroless plating treatment, the treatment temperature is preferably about 30 ° C. to 95 ° C., and the precipitation rate is preferably about 3 μm / hr at a bath temperature of 30 ° C. At a bath temperature of 90 ° C, it is about 20 μm / hr.
　本発明では、無電解めっき層を形成する工程において、無電解めっき層を形成する前に、必要に応じて、前処理を行っても良い。前記前処理は、好ましくは、例えば、前工程後の基材に対して、アルカリ脱脂、酸性脱脂、酸活性等の処理を施す。 In the present invention, in the step of forming the electroless plating layer, pretreatment may be performed as necessary before forming the electroless plating layer. In the pretreatment, for example, the base material after the previous step is subjected to treatments such as alkaline degreasing, acidic degreasing, and acid activity.
　（8）めっき物（回路基板）の利用性
　本発明のめっき物（回路基板）では、基材表面に前記触媒層を形成し（触媒処理液を付着させ）、その上に前記マスキング層を形成し、パターンマスクを介して光を照射（UV照射）する。この光照射（UV照射）により、光が当った照射部分（UV照射部分）では、触媒金属イオンがその触媒活性を失活する。次に、前記基材を無電解めっき（例えば、浴中に浸漬）する。触媒金属イオンとしてPd2+を例に挙げて説明する。パターンマスクされて、光が照射されていない未照射部分（UV未照射部分）では、Pd金属が存在し、無電解めっきされる。このPd金属、即ち触媒金属の働きによって、基材表面にCu、Ni等のめっき金属が析出し、めっき回路（導体回路）が形成される。 (8) Usability of Plated Material (Circuit Board) In the plated material (circuit board) of the present invention, the catalyst layer is formed on the surface of the base material (catalyst treatment liquid is adhered), and the masking layer is formed on the catalyst layer. Then, light is irradiated (UV irradiation) through the pattern mask. By this light irradiation (UV irradiation), the catalytic metal ion deactivates the catalytic activity in the irradiated portion (UV irradiated portion) exposed to light. Next, the base material is electroless plated (for example, immersed in a bath). Pd 2+ will be described as an example of the catalyst metal ion. In the unirradiated portion (UV unirradiated portion) that is pattern masked and not irradiated with light, Pd metal is present and electroless plating is performed. By the action of this Pd metal, that is, the catalyst metal, plating metals such as Cu and Ni are deposited on the surface of the base material, and a plating circuit (conductor circuit) is formed.
　パターンマスクによる光未照射部分（UV未照射部分）に、パターン形状のめっき回路が形成される。一方、光が照射された部分（UV照射部分）は、めっき回路（導体回路）が形成されない。 A pattern-shaped plating circuit is formed in the light-unirradiated part (UV unirradiated part) by the pattern mask. On the other hand, a plating circuit (conductor circuit) is not formed in the portion irradiated with light (UV irradiated portion).
　本発明のめっき物は、特定の触媒処理液とパターンマスクと光照射とを用いることによって、光未照射部分の触媒活性部分（めっき回路形成部分）と、光照射による不活性部分とに区分し、その後、触媒活性部分にめっき回路用金属を析出させて、めっき回路を形成することかできる。 The plated product of the present invention is divided into a catalytically active portion (plating circuit forming portion) of the non-light-irradiated portion and an inactive portion by light irradiation by using a specific catalyst treatment liquid, a pattern mask, and light irradiation. After that, the metal for the plating circuit can be deposited on the catalytically active portion to form the plating circuit.
　本発明のめっき物は、従来技術と異なり、触媒層は絶縁性であることから、その触媒層を除去すること無く、導体回路のパターン形成を可能とし、触媒層が存在しても、それ自体が導電性を表さず、短絡しないめっき物と成る。 Unlike the prior art, the plated product of the present invention has an insulating catalyst layer, so that it is possible to form a pattern of a conductor circuit without removing the catalyst layer, and even if the catalyst layer exists, it itself. Is a plated product that does not exhibit conductivity and does not short-circuit.
　本発明のめっき物は、従来技術と異なり、レジストマスクを用いる必要がない。本発明のめっき物は、基材の種類の制限を受けることが無く、電気特性に優れるめっき回路を形成することができる。 Unlike the prior art, the plated product of the present invention does not need to use a resist mask. The plated product of the present invention is not limited in the type of base material, and can form a plating circuit having excellent electrical characteristics.
　以下に、実施例及び比較例を示して本発明を具体的に説明する。但し、本発明は実施例に限定されない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.
　＜実施例1＞
　めっき物の製造（回路基板）
　・本発明の（i）金属粒子と分散剤との複合体、（ii）溶媒、及び（iii）バインダーを含有する触媒組成物から成る触媒層
　・メタルマスクによるマスキング <Example 1>
Manufacture of plated products (circuit board)
-A catalyst layer composed of a catalyst composition containing (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a binder of the present invention.-Masking with a metal mask
　（1）基材（基板）の表面に触媒層を形成する工程
　回路基板として、ポリエチレンナフタレート（PEN）フィルムを用いた。はじめに、このPENフィルムにコロナ処理を行った。前記コロナ処理の放電量は160W／m2／minとした。このPENフィルムの表面に、メタロイドML-240LV(IOX社製)をバーコーターで塗工することにより、Pd触媒を含有する塗膜（触媒層）を形成した。前記触媒層の厚みは0.4μmとした。前記メタロイドML-240LVは、（i）Pd粒子（金属粒子）と分散剤との複合体、（ii）溶媒、及び（iii）エポキシ樹脂（バインダー）とから構成される組成物（触媒組成物）である。 (1) A process for forming a catalyst layer on the surface of a base material (board) A polyethylene naphthalate (PEN) film was used as a circuit board. First, this PEN film was corona-treated. The discharge amount of the corona treatment was 160 W / m 2 / min. By coating the surface of this PEN film with Metalloid ML-240LV (manufactured by IOX) with a bar coater, a coating film (catalyst layer) containing a Pd catalyst was formed. The thickness of the catalyst layer was 0.4 μm. The metalloid ML-240LV is a composition (catalyst composition) composed of (i) a complex of Pd particles (metal particles) and a dispersant, (ii) a solvent, and (iii) an epoxy resin (binder). Is.
　（2）触媒層の表面にマスキング層を形成する工程
　前記触媒層が形成されたPENフィルムの表面にマスキング層を形成するため、メタルマスクを被せた。メタルマスクは、マスクの幅が0.1mmのパターンをもつ。 (2) Step of Forming a Masking Layer on the Surface of the Catalyst Layer A metal mask was put on the surface of the PEN film on which the catalyst layer was formed in order to form the masking layer. The metal mask has a pattern with a mask width of 0.1 mm.
　（3）UV照射する工程
　前記マスキング層を形成した触媒層付きPENフィルムに、高圧水銀ランプによるUV照射を行った。積算光量は300mJ／cm2とした。 (3) UV Irradiation Step The PEN film with a catalyst layer on which the masking layer was formed was UV-irradiated with a high-pressure mercury lamp. The integrated light intensity was set to 300 mJ / cm 2 .
　（4）マスキング層を除去する工程
　前記UV光照射処理されたマスキング層を形成した触媒層付きPENフィルムから、被せていたメタルマスクを取り除いた。 (4) Step of Removing the Masking Layer The metal mask covered with the catalyst layer was removed from the PEN film with the catalyst layer on which the masking layer treated with UV light was formed.
　（5）パターン形状の無電解めっき層（導体回路）を形成する工程
　触媒層の表面で、マスキング層を形成した部分は、UV照射されず、無電解めっき層が形成される。触媒層の表面で、マスキング層を形成しない部分は、UV照射されて、無電解めっき層が形成される。こうして、パターン形状の無電解めっき層（導体回路）を形成する。 (5) Process for forming a pattern-shaped electroless plating layer (conductor circuit) On the surface of the catalyst layer, the portion where the masking layer is formed is not irradiated with UV, and an electroless plating layer is formed. The portion of the surface of the catalyst layer that does not form the masking layer is irradiated with UV to form an electroless plating layer. In this way, a pattern-shaped electroless plating layer (conductor circuit) is formed.
　前記UV光処理された触媒層付きフィルムを、無電解Cuめっき液（奥野製薬社製OPCカッパーHFS）に40℃×20分浸漬することで、UV照射されていない部分にのみCuめっきを形成した。前記無電解Cu層の厚みは1.0μmとした。これにより、得られたサンプル（PENフィルム）は、UV照射されていない部分にのみ導電層（無電解めっき層、導体回路）を有する。 By immersing the film with a catalyst layer treated with UV light in an electroless Cu plating solution (OPC Copper HFS manufactured by Okuno Pharmaceutical Co., Ltd.) at 40 ° C. for 20 minutes, Cu plating was formed only on the portion not irradiated with UV. .. The thickness of the electroless Cu layer was 1.0 μm. As a result, the obtained sample (PEN film) has a conductive layer (electroless plating layer, conductor circuit) only in the portion not irradiated with UV.
　（6）密着性の確認
　前記パターン形成された導体回路に対して、テープ剥離試験を行い、基材に対する導体回路の密着性を評価した。 (6) Confirmation of Adhesion A tape peeling test was performed on the conductor circuit in which the pattern was formed, and the adhesion of the conductor circuit to the substrate was evaluated.
　結果、実施例のめっき物では、基材に対して、導体回路部分の剥離は見られなかった。 As a result, in the plated product of the example, no peeling of the conductor circuit portion was observed with respect to the base material.
　＜実施例2＞
　めっき物の製造（回路基板）
　・本発明の（i）金属粒子と分散剤との複合体、（ii）溶媒、及び（iii）バインダーを含有する触媒組成物から成る触媒層
　・石英ガラス上にステンレスでパターンが形成されたマスクによるマスキング <Example 2>
Manufacture of plated products (circuit board)
-A catalyst layer composed of a catalyst composition containing (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a binder of the present invention.-A mask in which a pattern is formed of stainless steel on quartz glass. Masking by
　（1）基材（基板）の表面に触媒層を形成する工程
　回路基板として、ポリエチレンナフタレート（PEN）フィルムを用いた。はじめに、このPENフィルムにコロナ処理を行った。前記コロナ処理の放電量は160W／m2／minとした。このPENフィルムの表面に、メタロイドML-240LV(IOX社製)をバーコーターで塗工することにより、Pd触媒を含有する塗膜（触媒層）を形成した。前記触媒層の厚みは0.4μmとした。前記メタロイドML-240LVは、（i）Pd粒子（金属粒子）と分散剤との複合体、（ii）溶媒、及び（iii）エポキシ樹脂（バインダー）とから構成される組成物（触媒組成物）である。 (1) A process for forming a catalyst layer on the surface of a base material (board) A polyethylene naphthalate (PEN) film was used as a circuit board. First, this PEN film was corona-treated. The discharge amount of the corona treatment was 160 W / m 2 / min. By coating the surface of this PEN film with Metalloid ML-240LV (manufactured by IOX) with a bar coater, a coating film (catalyst layer) containing a Pd catalyst was formed. The thickness of the catalyst layer was 0.4 μm. The metalloid ML-240LV is a composition (catalyst composition) composed of (i) a complex of Pd particles (metal particles) and a dispersant, (ii) a solvent, and (iii) an epoxy resin (binder). Is.
　（2）触媒層の表面にマスキング層を形成する工程
　前記触媒層が形成されたPENフィルムの表面にマスキング層を形成するため、石英ガラス上にステンレスでパターンが形成されたマスクを被せた。前記マスクは、マスクの幅が0.1mmのパターンをもつ。 (2) Step of Forming a Masking Layer on the Surface of the Catalyst Layer In order to form a masking layer on the surface of the PEN film on which the catalyst layer was formed, a mask having a pattern formed of stainless steel was put on quartz glass. The mask has a pattern in which the width of the mask is 0.1 mm.
　（3）UV照射する工程
　前記マスキング層を形成した触媒層付きPENフィルムに、高圧水銀ランプによるUV照射を行った。積算光量は300mJ／cm2とした。 (3) UV Irradiation Step The PEN film with a catalyst layer on which the masking layer was formed was UV-irradiated with a high-pressure mercury lamp. The integrated light intensity was set to 300 mJ / cm 2 .
　（4）マスキング層を除去する工程
　前記UV光照射処理されたマスキング層を形成した触媒層付きPENフィルムから、被せていた石英ガラスのマスクを取り除いた。 (4) Step of Removing the Masking Layer The mask of the quartz glass covered was removed from the PEN film with the catalyst layer on which the masking layer treated with UV light was formed.
　（5）パターン形状の無電解めっき層（導体回路）を形成する工程
　触媒層の表面で、マスキング層を形成した部分は、UV照射されず、無電解めっき層が形成される。触媒層の表面で、マスキング層を形成しない部分は、UV照射されて、無電解めっき層が形成される。こうして、パターン形状の無電解めっき層（導体回路）を形成する。 (5) Process for forming a pattern-shaped electroless plating layer (conductor circuit) On the surface of the catalyst layer, the portion where the masking layer is formed is not irradiated with UV, and an electroless plating layer is formed. On the surface of the catalyst layer, the portion where the masking layer is not formed is irradiated with UV to form an electrolytically electroless plating layer. In this way, a pattern-shaped electroless plating layer (conductor circuit) is formed.
　前記UV光処理された触媒層付きフィルムを、無電解Cuめっき液（奥野製薬社製OPCカッパーHFS）に40℃×20分浸漬することで、UV照射されていない部分にのみCuめっきを形成した。前記無電解Cu層の厚みは1.0μmとした。これにより、得られたサンプル（PENフィルム）は、UV照射されていない部分にのみ導電層（無電解めっき層、導体回路）を有する。 By immersing the film with a catalyst layer treated with UV light in an electroless Cu plating solution (OPC Copper HFS manufactured by Okuno Pharmaceutical Co., Ltd.) at 40 ° C. for 20 minutes, Cu plating was formed only on the portion not irradiated with UV. .. The thickness of the electroless Cu layer was 1.0 μm. As a result, the obtained sample (PEN film) has a conductive layer (electroless plating layer, conductor circuit) only in the portion not irradiated with UV.
　（6）密着性の確認
　前記パターン形成された導体回路に対して、テープ剥離試験を行い、基材に対する導体回路の密着性を評価した。 (6) Confirmation of Adhesion A tape peeling test was performed on the conductor circuit in which the pattern was formed, and the adhesion of the conductor circuit to the substrate was evaluated.
　結果、実施例のめっき物では、基材に対して、導体回路部分の剥離は見られなかった。 As a result, in the plated product of the example, no peeling of the conductor circuit portion was observed with respect to the base material.
　本発明の触媒層を用いると、マスキング技術により、その触媒層は絶縁性と成り、良好に、パターン形状の無電解めっき層を有するめっき物を提供できる。本発明のマスキング技術により、パターン形状の無電解めっき層（導体回路）を形成することができ、より微細な回路配線を形成するめっき物（回路部品、回路基板）を作製することができると、評価できる。 When the catalyst layer of the present invention is used, the catalyst layer becomes insulating by the masking technique, and it is possible to provide a plated product having a pattern-shaped electroless plating layer. According to the masking technique of the present invention, a pattern-shaped electroless plating layer (conductor circuit) can be formed, and a plated product (circuit component, circuit board) forming finer circuit wiring can be produced. Can be evaluated.
　＜比較例1＞
　めっき物の製造（回路基板）
　・従来技術の触媒層
　・メタルマスクによるマスキング <Comparative example 1>
Manufacture of plated products (circuit board)
・ Conventional catalyst layer ・ Masking with metal mask
　（1）基材（基板）の表面に触媒層を形成する工程
　回路基板として、ポリエチレンテレフタラート（PET）フィルムを用いた。はじめに、このPETフィルムにコロナ処理を行った。前記コロナ処理の放電量は160W／m2／minとした。このPETフィルムを触媒層付与液（奥野製薬社製キャタリストC-7）に35℃×3分浸漬した後、活性化促進剤溶液（奥野製薬社製アクセレーターX）に35℃×3分浸漬することにより、触媒層を形成した。 (1) A process for forming a catalyst layer on the surface of a base material (board) A polyethylene terephthalate (PET) film was used as a circuit board. First, this PET film was corona-treated. The discharge amount of the corona treatment was 160 W / m 2 / min. This PET film is immersed in a catalyst layer-imparting solution (Catalyst C-7 manufactured by Okuno Pharmaceutical Co., Ltd.) at 35 ° C for 3 minutes, and then immersed in an activation accelerator solution (Accelerator X manufactured by Okuno Pharmaceutical Co., Ltd.) at 35 ° C for 3 minutes. By doing so, a catalyst layer was formed.
　（2）触媒層の表面にマスキング層を形成する工程
　前記触媒層が形成されたPETフィルムの表面にマスキング層を形成するため、メタルマスクを被せた。前記マスクは、マスクの幅が0.1mmのパターンをもつ。 (2) Step of Forming a Masking Layer on the Surface of the Catalyst Layer A metal mask was put on the surface of the PET film on which the catalyst layer was formed in order to form the masking layer. The mask has a pattern in which the width of the mask is 0.1 mm.
　（3）UV照射する工程
　前記マスキング層を形成した触媒層付きPETフィルムに、高圧水銀ランプによるUV照射を行った。積算光量は300mJ／cm2とした。 (3) UV Irradiation Step The PET film with a catalyst layer on which the masking layer was formed was UV-irradiated with a high-pressure mercury lamp. The integrated light intensity was set to 300 mJ / cm 2 .
　（4）マスキング層を除去する工程
　前記UV光照射処理されたマスキング層を形成した触媒層付きPETフィルムから、被せていたメタルマスクを取り除いた。 (4) Step of Removing the Masking Layer The metal mask covered with the catalyst layer was removed from the PET film with the catalyst layer on which the masking layer treated with UV light was formed.
　（5）パターン形状の無電解めっき層（導体回路）を形成する工程
　前記UV光処理された触媒層付きフィルムを、無電解Cuめっき液（奥野製薬社製OPCカッパーHFS）に40℃×20分浸漬したところ、基材の全面に無電解銅めっき層が形成された。前記無電解Cu層の厚みは1.0μmとした。これにより、得られたサンプル（PETフィルム）は、UV照射されている部分、UV照射されていない部分のどちらにも導電層（無電解めっき層、導体回路）を有する。 (5) Step of forming an electroless plating layer (conductor circuit) with a pattern shape The film with a catalyst layer treated with UV light is placed in an electroless Cu plating solution (OPC copper HFS manufactured by Okuno Pharmaceutical Co., Ltd.) at 40 ° C for 20 minutes. When immersed, an electroless copper plating layer was formed on the entire surface of the base material. The thickness of the electroless Cu layer was 1.0 μm. As a result, the obtained sample (PET film) has a conductive layer (electroless plating layer, conductor circuit) in both the UV-irradiated portion and the non-UV-irradiated portion.
　従来技術の触媒層では、その触媒層は絶縁性と成らず、導電層を形成し、良好に、パターン形状の無電解めっき層を形成することが出来ない。 In the catalyst layer of the prior art, the catalyst layer does not have an insulating property, a conductive layer is formed, and a pattern-shaped electroless plating layer cannot be formed satisfactorily.

Claims (9)

  1. 　めっき物であって、
    　基材の表面に、（i）金属粒子と分散剤との複合体、（ii）溶媒、及び（iii）バインダーを含有する触媒組成物から成る触媒層を有し、
    　前記触媒層の表面に、パターン形状の無電解めっき層を有する、めっき物。     It ’s a plated product,
    A catalyst layer composed of a catalyst composition containing (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a binder is provided on the surface of the base material.
    A plated product having a pattern-shaped electroless plating layer on the surface of the catalyst layer.
  2. 　前記基材の表面に、前記触媒層を、全面に有する、請求項1に記載のめっき物。 The plated product according to claim 1, which has the catalyst layer on the entire surface of the base material.
  3. 　前記パターン形状の無電解めっき層では、前記触媒層の表面に、
    　UV照射されず、無電解めっき層が有る部分と、
    　UV照射されて、無電解めっき層が無い部分とで、
    　パターン形状の無電解めっき層と成る、請求項1又は2に記載のめっき物。     In the pattern-shaped electroless plating layer, on the surface of the catalyst layer,
    The part that is not irradiated with UV and has an electroless plating layer,
    In the part that is UV-irradiated and there is no electroless plating layer,
    The plated product according to claim 1 or 2, which is an electroless plating layer having a pattern shape.
  4. 　前記パターン形状の無電解めっき層では、前記触媒層の表面に、
    　マスキングされて、前記UV照射されず、無電解めっき層が有る部分と、
    　マスキングされず、前記UV照射されて、無電解めっき層が無い部分とで、
    　パターン形状の無電解めっき層と成る、請求項3に記載のめっき物。     In the pattern-shaped electroless plating layer, on the surface of the catalyst layer,
    The part that is masked, is not irradiated with UV, and has an electroless plating layer,
    In the part without masking, UV irradiation, and no electroless plating layer
    The plated product according to claim 3, which is an electroless plating layer having a pattern shape.
  5. 　前記基材は、基板であり、
    　前記無電解めっき層は、導体回路であり、
    　回路基板である、請求項1～4のいずれかに記載のめっき物。     The base material is a substrate, and the base material is a substrate.
    The electroless plating layer is a conductor circuit.
    The plated product according to any one of claims 1 to 4, which is a circuit board.
  6. 　めっき物の製造方法であって、
    　（1）基材の表面に、（i）金属粒子と分散剤との複合体、（ii）溶媒、及び（iii）バインダーを含有する触媒組成物から成る触媒層を形成する工程、
    　（2）前記触媒層を形成する工程の後、前記触媒層の表面にマスキング層を形成する工程、
    　（3）前記マスキング層を形成する工程の後、前記触媒層及び前記マスキング層の表面にUV照射する工程、
    　（4）前記UV照射する工程の後、マスキング層を除去する工程、
    　（5）前記マスキング層を除去する工程の後、パターン形状の無電解めっき層を形成する工程、
    を含む、めっき物の製造方法。     It is a manufacturing method of plated products.
    (1) A step of forming a catalyst layer composed of (i) a composite of metal particles and a dispersant, (ii) a solvent, and (iii) a catalyst composition containing a binder on the surface of a base material.
    (2) A step of forming a masking layer on the surface of the catalyst layer after the step of forming the catalyst layer.
    (3) After the step of forming the masking layer, the step of irradiating the catalyst layer and the surface of the masking layer with UV.
    (4) After the UV irradiation step, a step of removing the masking layer,
    (5) After the step of removing the masking layer, a step of forming a pattern-shaped electroless plating layer,
    A method for manufacturing a plated product, including.
  7. 　前記触媒層を形成する工程では、前記基材の表面に、
    　前記触媒層を、全面に形成する、請求項6に記載のめっき物の製造方法。     In the step of forming the catalyst layer, on the surface of the base material,
    The method for producing a plated product according to claim 6, wherein the catalyst layer is formed on the entire surface.
  8. 　前記パターン形状の無電解めっき層を形成する工程では、前記触媒層の表面に、
    　前記マスキング層を形成して、前記UV照射せず、無電解めっき層を形成することと、
    　前記マスキング層を形成せず、前記UV照射して、無電解めっき層を形成しないこととで、
    　パターン形状の無電解めっき層を形成する、請求項6又は7に記載のめっき物の製造方法。     In the step of forming the pattern-shaped electroless plating layer, on the surface of the catalyst layer,
    The masking layer is formed to form the electroless plating layer without UV irradiation.
    By not forming the masking layer and not forming the electroless plating layer by irradiating with the UV.
    The method for producing a plated product according to claim 6 or 7, wherein an electroless plating layer having a pattern shape is formed.
  9. 　前記基材は、基板であり
    　前記無電解めっき層は、導体回路であり、
    　回路基板である、請求項6～8のいずれかに記載のめっき物の製造方法。     The base material is a substrate, and the electroless plating layer is a conductor circuit.
    The method for manufacturing a plated product according to any one of claims 6 to 8, which is a circuit board.
PCT/JP2021/012115 2020-03-25 2021-03-24 Plated object having pattern-shaped electroless plating layer WO2021193679A1 (en)

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JP7323884B1 (en) 2022-08-08 2023-08-09 株式会社イオックス Coating composition for electroless plating having photosensitivity, plated article having pattern-shaped electroless plating layer, and method for producing plated article having pattern-shaped electroless plating layer

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JP2014065909A (en) * 2012-03-02 2014-04-17 Iox:Kk Coating material composition for electroless plating
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