WO2017130373A1 - 基板上への回路形成方法 - Google Patents

基板上への回路形成方法 Download PDF

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Publication number
WO2017130373A1
WO2017130373A1 PCT/JP2016/052625 JP2016052625W WO2017130373A1 WO 2017130373 A1 WO2017130373 A1 WO 2017130373A1 JP 2016052625 W JP2016052625 W JP 2016052625W WO 2017130373 A1 WO2017130373 A1 WO 2017130373A1
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WIPO (PCT)
Prior art keywords
substrate
circuit
plating
coating film
substrate according
Prior art date
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PCT/JP2016/052625
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English (en)
French (fr)
Inventor
大祐 佐土原
西川　賢一
鈴木　啓太
公太 伊部
勝己 下田
Original Assignee
株式会社Ｊｃｕ
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Publication date
Application filed by 株式会社Ｊｃｕ filed Critical 株式会社Ｊｃｕ
Priority to PCT/JP2016/052625 priority Critical patent/WO2017130373A1/ja
Priority to EP16887960.9A priority patent/EP3409814A4/en
Priority to US16/072,091 priority patent/US10966327B2/en
Priority to CN201680078732.XA priority patent/CN108463576B/zh
Priority to JP2017563491A priority patent/JP6893478B2/ja
Priority to KR1020187021740A priority patent/KR102644596B1/ko
Publication of WO2017130373A1 publication Critical patent/WO2017130373A1/ja

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4661—Adding a circuit layer by direct wet plating, e.g. electroless plating; insulating materials adapted therefor
    • 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
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/208—Multistep pretreatment with use of metal first
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
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    • 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
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    • C23C18/1601—Process or apparatus
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    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/072—Electroless plating, e.g. finish plating or initial plating
    • 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
    • H05K3/181—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 by electroless plating
    • H05K3/182—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 by electroless plating characterised by the patterning method
    • H05K3/185—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 by electroless plating characterised by the patterning method by making a catalytic pattern by photo-imaging

Definitions

  • the present invention relates to a method for forming a circuit on a substrate and the like.
  • Non-Patent Document 1 ⁇ Circuit formation on a substrate using plating requires a number of steps. For example, when the substrate is a resin, the following steps are performed (Non-Patent Document 1).
  • ⁇ Subtractive method> (A1) Etching or the like on the substrate to roughen the surface (A2) Giving hydrophilicity to the substrate with a conditioner (A3) Giving a catalyst on the substrate (A4) Electroless copper or electroless Ni plating on the substrate (A5) Electrolytic copper plating is performed on the substrate. (A6) A resist pattern is formed on the electrolytic copper plating. (A7) Unnecessary electrolytic and electroless plating stripping and resist stripping are performed to form a circuit.
  • the entire surface and partial plating for decorative plating on the substrate using plating need to go through a number of steps as in the case of circuit formation on the substrate.
  • an object of the present invention is to provide a new method capable of forming a circuit by performing metal plating on a desired portion on a substrate with few steps regardless of the type of the substrate.
  • the present inventors have used a coating film containing a silicon oligomer and a catalytic metal in forming a circuit.
  • the present invention has been completed by finding that metal plating can be performed on these parts and a circuit can be formed.
  • the present invention when performing circuit formation by plating on the substrate, Including a step of applying a coating film containing a silicon oligomer and a catalytic metal on the substrate, then activating the catalytic metal in the coating film to develop autocatalytic properties, and then performing electroless plating.
  • a circuit forming method on a substrate is characterized.
  • the present invention is characterized in that a substrate, a coating film containing a silicon oligomer and a catalytic metal, electroless plating, and electrolytic plating obtained by the circuit forming method on the substrate are laminated in this order. Circuit.
  • the inventors of the present invention irradiate visible light and ultraviolet light of 450 nm or less to a desired site where a coating film containing a silicon oligomer and a catalytic metal is to be plated, so that the catalytic metal in the coating film is autocatalytic.
  • the present invention has been completed by discovering that it is possible to perform electroless plating.
  • a desired part to be plated is irradiated with visible light and ultraviolet light of 450 nm or less to form the catalytic metal in the coating film.
  • This is a method for plating on a base material, characterized in that self-catalytic properties are developed and then electroless plating is performed.
  • the present invention by using a coating film containing a silicon oligomer and a catalytic metal for circuit formation, it is not necessary to perform pretreatment or the like on each substrate. It is possible to reduce the number of steps of metal plating on the part.
  • the present invention is used for manufacturing a semiconductor circuit, it is possible to form a circuit with fewer steps than in the past.
  • the desired portion of the substrate can be obtained by irradiating visible light and ultraviolet rays of 450 nm or less to a desired portion to be plated with a coating film containing a silicon oligomer and a catalytic metal provided on the substrate.
  • the part can be plated.
  • the present invention can be used to plate a desired portion of the substrate.
  • Example 2 is a photograph of a substrate after plating obtained in Example 1.
  • 4 is a photograph of a substrate after plating obtained in Example 2.
  • 4 is a photograph of a substrate after plating obtained in Example 3.
  • 4 is a photograph of a substrate after plating obtained in Example 4.
  • the method of forming a circuit on a substrate of the present invention (hereinafter referred to as “method of the present invention”) is to form a circuit on a substrate by plating. After applying a coating film containing a silicon oligomer and a catalytic metal on the substrate, an activation process of the catalytic metal in the coating film is performed to develop autocatalytic properties, and then an electroless plating process may be included. .
  • the substrate used in the method of the present invention is a coating film containing a silicon oligomer and a catalytic metal, has good adhesion, and can exhibit self-catalytic properties by an activation treatment, so the material is not particularly limited,
  • resin, glass, etc. any of wood, paper, etc., which has been conventionally considered to be difficult to plate, may be used.
  • resin and glass are preferable. Examples of this resin include ABS, polypropylene, polyethylene, polycarbonate, epoxy resin, phenol resin, and urethane resin. These resins can be used alone or in combination of two or more.
  • fillers such as an inorganic oxide, inorganic nitride, and inorganic sulfide
  • one or more of these fillers can be added to the resin.
  • the filler In the conventional circuit formation method, when a resin to which a filler is added is used, the filler must be removed by immersion in an alkaline solution or a roughening process such as a desmear process must be performed. Then that is not necessary.
  • a method for applying a coating film containing a silicon oligomer and a catalyst metal is not particularly limited, and examples thereof include a method of treating a substrate with a coating agent containing the following catalyst-containing metal silicon oligomer.
  • tetraalkoxysilane A polyhydric alcohol having a hydroxy group bonded to at least the n, n + 1 position or the n, n + 2 position (where n is an integer of 1 or more), In the presence of catalytic metal, It is treated with a coating agent containing a catalyst-containing metal silicon oligomer obtained by a condensation reaction.
  • the tetraalkoxysilane is not particularly limited, and examples thereof include tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane. Among these, tetraethoxysilane is preferable. These tetraalkoxysilanes may be used alone or in combination of two or more.
  • the polyhydric alcohol having a hydroxy group bonded to at least the n, n + 1 position or the n, n + 2 position is not particularly limited.
  • n is an integer of 1 to 3.
  • examples thereof include divalent to tetravalent alcohols, preferably divalent to trivalent alcohols in which n is an integer of 1 to 2.
  • polyhydric alcohols include, for example, ethylene glycol, 1,2-propanediol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 2-methyl-1,3-propylene glycol, 1,2-pentylene glycol, 1,3-pentylene glycol, 2,3-pentylene glycol, dihydric alcohols such as 2,4-pentylene glycol, glycerin, etc. And tetrahydric alcohols such as erythritol. Of these polyhydric alcohols, dihydric alcohols are preferred, ethylene glycol and / or 1,3-propylene glycol are more preferred, and ethylene glycol is particularly preferred. These polyhydric alcohols can be used alone or in combination of two or more.
  • the catalytic metal is not a metal having a catalytic action for the condensation reaction of tetraalkoxysilane and polyhydric alcohol, but a metal having an autocatalytic action for the deposition reaction of plating described later. Therefore, it is different from the metal catalyst referred to in WO2014 / 20785 and WO2014 / 207886.
  • Examples of such catalytic metals include iron, nickel, cobalt, copper, palladium, silver, gold, platinum, and the like.
  • iron, nickel, cobalt, copper, and palladium are preferable, iron, nickel, copper, and palladium are more preferable, and palladium is particularly preferable.
  • the catalyst metal is preferably present in the state of being dissolved in the polyhydric alcohol during the condensation reaction.
  • iron chloride, nickel chloride, copper chloride, palladium chloride, gold chloride It is preferable to use a metal salt containing a catalytic metal such as III), silver chloride (I), platinum chloride (IV).
  • a catalytic metal such as III
  • silver chloride (I) platinum chloride (IV)
  • the catalytic metal If the catalytic metal is difficult to dissolve in the polyhydric alcohol, it may be dissolved in advance in an inorganic acid such as hydrochloric acid.
  • These catalytic metals can be used alone or in combination of two or more, and in that case, it is preferable to contain at least palladium.
  • a method for subjecting the above tetraalkoxysilane and polyhydric alcohol to a condensation reaction in the presence of a catalytic metal is not particularly limited.
  • 0.01 to 20 g / kg of catalytic metal is added to the polyhydric alcohol, preferably After adding and dissolving at 0.1 to 10 g / kg, the mixture is heated to the reaction temperature while stirring, and tetraalkoxysilane is further added and reacted.
  • the reaction temperature is 25 to 150 ° C., preferably 30 to 70 ° C.
  • the reaction time is 30 minutes to 8 hours, preferably 2 hours to 4 hours.
  • the tetraalkoxysilane and the polyhydric alcohol are separated into two layers before the condensation reaction, but when the reaction is completed, one layer is formed. Also good.
  • the thus obtained catalyst-containing metal silicon oligomer is obtained by incorporating a catalyst metal into a silicon oligomer obtained by condensation reaction of 2 to 4 of tetraalkoxysilane and 1 to 13 of polyhydric alcohol.
  • the catalyst-containing metal silicon oligomer is a product obtained by condensation reaction of an alkoxy group of tetraalkoxysilane and one or two of n, n + 1-position or n, n + 2-position hydroxy group present in the polyhydric alcohol. It has a partial structure as shown in the following (a) to (d).
  • the catalyst metal exists between oxygen atoms, and is presumed to be stabilized by forming a 5-membered ring structure or a 6-membered ring structure having the catalyst metal as a vertex. . Therefore, the catalyst-containing metal silicon oligomer of the present invention does not show any catalyst metal precipitation even after one year has passed after the production.
  • Such a catalyst-containing metal silicon oligomer can be identified by known methods such as NMR such as 1 HNMR and 29 SiNMR, IR and MASS. Specifically for NMR, the alcohol produced by the condensation reaction of tetraalkoxysilane and polyhydric alcohol is confirmed by 1 HNMR, and further, the number of silicon in the catalyst-containing metal silicon oligomer is confirmed by 29 SiNMR, Catalyst-containing metal silicon oligomers can be identified. In addition, the catalytic metal is taken into the silicon oligomer can be confirmed by the fact that no precipitation of the catalytic metal is observed after a certain period of time has elapsed after the silicon oligomer has been generated, for example, after one year.
  • This catalyst-containing metal silicon oligomer can be treated on the surface of the substrate as a coating agent in the same manner as conventional silicon oligomers.
  • the substrate is treated with a coating agent and then activated to give the substrate autocatalytic properties and conductivity. be able to.
  • the coating agent containing the catalyst-containing metal silicon oligomer only needs to contain the catalyst-containing metal silicon oligomer.
  • two or more kinds of catalyst-containing metal silicon oligomers having different catalyst metals may be used in combination. It is preferable to use a catalyst-containing metal silicon oligomer prepared in the presence of two or more catalyst metals because the catalytic action of the catalyst metal is enhanced.
  • the combination of the catalytic metals is not particularly limited, but for example, a combination of palladium and one or more selected from iron, nickel, cobalt, and copper is preferable.
  • the coating agent may contain, for example, a solvent added to a conventionally known coating agent, a resin for improving wettability to the substrate, and the like.
  • a coating agent can be prepared by appropriately stirring and mixing the above components.
  • the solvent added to the coating agent is not particularly limited, and examples thereof include water, isopropyl alcohol, and ethyl cellosolve.
  • the catalyst-containing metal silicon oligomer of the present invention can be stably stored even in the presence of water when diluted with a glycol-based solvent such as polyethylene glycol or ethyl cellosolve.
  • a glycol-based solvent such as polyethylene glycol or ethyl cellosolve.
  • polyethylene glycol 200 to 1000, preferably polyethylene glycol 200, as a glycol solvent it can be stably stored for a long time even in the presence of moisture.
  • the resin added to the coating agent is not particularly limited as long as it is soluble or dispersible in the coating agent, and examples thereof include acrylic resins, urethane resins, phenol resins, and epoxy resins. Can be mentioned. Among these resins, acrylic resins are preferable, methacrylic acid alkyl ester copolymers, colloidal silica / acrylic composites, ethylene / acrylic acid copolymer ammonium salts are more preferable, and methacrylic acid alkyl ester copolymers. Is particularly preferred. These resins can be used alone or in combination of two or more. These resins may be either a solution or a powder. These resins are blended in the coating agent in an amount of 50% by mass (hereinafter simply referred to as “%”) or less, preferably 0.1 to 50%, more preferably 1 to 20%.
  • % 50% by mass
  • a colorant, a friction coefficient adjusting agent, a film thickener, and other additives that impart functionality may be blended in the coating agent as long as the effect of the catalyst-containing metal silicon oligomer is not impaired.
  • the method of treating the substrate with the above coating agent may be the same as a conventionally known coating agent, and for example, the entire surface of the substrate may be treated by an immersion method such as a dip and spin method or a spray method such as a spray coating method. After the treatment, it may be dried as it is or with warm air.
  • the thickness of the coating is not particularly limited as long as it covers the entire surface of the substrate.
  • the coating film containing the silicon oligomer and the catalytic metal is applied on the substrate as described above, the catalytic metal in the coating film is activated to exhibit autocatalytic properties.
  • the activation treatment of the catalyst metal may be appropriately performed according to the characteristics of the substrate.
  • Examples of the activation treatment include irradiation with visible light and ultraviolet light of 450 nm or less, heating, chemical reduction, and the like. These activation processes may be appropriately combined.
  • irradiation with visible light and ultraviolet light of 450 nm or less is preferable because it does not depend on the type of substrate, and it is particularly preferable to irradiate light with a wavelength of 254 nm to 365 nm that does not generate ozone.
  • the irradiation with visible light and ultraviolet rays of 450 nm or less may be performed for several minutes using an ultraviolet irradiator such as a DUV exposure light source device (UIS-2511DUZ8-AUM01: manufactured by USHIO).
  • an ultraviolet irradiator such as a DUV exposure light source device (UIS-2511DUZ8-AUM01: manufactured by USHIO).
  • the heating is not particularly limited.
  • the temperature may be maintained for about 10 minutes to 2 hours in an oven, an electric furnace, or the like.
  • the atmosphere of the heat treatment is not particularly limited and may be air. After heating, it may be allowed to cool.
  • the chemical reduction is not particularly limited, and may be immersed in an aqueous solution containing a reducing agent for about 1 to 3 minutes.
  • a reducing agent include hypophosphorous acid, dimethylamine borane, formaldehyde, sodium borohydride, hydrazine and the like. These reducing agents can be used alone or in combination of two or more. After chemical reduction, washing and drying may be performed.
  • the catalyst metal in the coating film also exhibits autocatalytic properties.
  • electroless plating is performed.
  • the type of electroless plating is not particularly limited, and examples thereof include electroless copper plating, electroless nickel plating, and electroless copper-nickel plating.
  • the electroless plating conditions are not particularly limited because they may be appropriately set in accordance with the required plating thickness. For example, conditions such as pH of about 9, liquid temperature of about 40 ° C., and processing time of about 7 minutes are included. Can be mentioned.
  • the circuit can be formed on the substrate by including the above-described method (process) of the present invention.
  • process As a method of forming a circuit on a substrate by plating, various known methods can be mentioned.
  • the activation treatment is performed only on the circuit formation portion on the substrate during the activation process of the catalytic metal, and then there is no process.
  • a circuit can be formed on the substrate by electrolytic plating and further electrolytic plating.
  • the kind of electrolytic plating is not specifically limited, For example, electrolytic copper plating etc. are mentioned.
  • the conditions for electrolytic plating are not particularly limited because they may be set as appropriate according to the required plating thickness, and examples include conditions such as about 3 to 60 A at about 3 A / dm 2 .
  • Examples of the method for performing the activation process only on the circuit forming portion include, for example, a method in which a coating film is applied only to the circuit forming portion on the substrate using a mask or the like on the substrate, For example, there is a method in which activation processing is performed only on a circuit formation portion on a substrate.
  • a method in which a coating film is applied to the entire surface of the substrate and activation processing is performed only on a circuit formation portion on the substrate using a mask or the like is preferable.
  • the activation processing is performed by irradiation with visible light and ultraviolet rays of 450 nm or less.
  • the activation process is preferably performed only on the circuit formation portion on the substrate.
  • the activation treatment is performed on the substrate, preferably the entire surface of the substrate during the activation of the catalytic metal.
  • the electrolytic plating for example, the following steps (a1) to (e1), (a2) to (e2), and the like can be performed to form a circuit on the substrate.
  • the steps (a1) to (e1) correspond to a circuit formation method generally called a semi-additive method
  • the steps (a2) to (e2) correspond to a circuit formation method generally called a subtractive method.
  • A1 A step of providing a dry film at a non-circuit forming portion (b1) A step of performing electroplating on the circuit forming portion (c1) A step of removing the dry film (d1) A step of removing electroless plating at the non-circuit forming portion ( e1) The process of removing the coating film at the non-circuit formation site
  • the step of providing a dry film on the non-circuit forming portion is not particularly limited.
  • UV exposure and development is performed using a general photosensitive resist at the non-circuit forming portion of electroless plating. What is necessary is just to provide a dry film using.
  • the step of performing electrolytic plating on the circuit formation site (b1) subsequent to step (a1) is not particularly limited. For example, it may be immersed in an electrolytic plating solution and plated under normal conditions until a desired thickness is obtained. .
  • the kind of electrolytic plating solution is not specifically limited, For example, electrolytic copper plating etc. are mentioned. By this step, plating is performed only on the circuit forming portion.
  • the process of removing a dry film following a process (b1) is not specifically limited, According to the kind of dry film, what is necessary is just to process with the organic solvent, alkaline aqueous solution, etc. which can melt
  • the treatment method is not particularly limited, and may be immersion, spraying, or the like.
  • the process of removing the electroplating of the non-circuit formation site following the process (c1) is not particularly limited, and may be treated with an acid or the like that can dissolve the electroplating.
  • the kind of acid is not specifically limited, For example, if electrolytic plating is copper, a sulfuric acid etc. will be mentioned.
  • the method of a process is not specifically limited, Immersion, spraying, etc. may be sufficient.
  • the step (e1) of removing the coating film at the non-circuit formation site following the step (d1) is not particularly limited.
  • a carbon-oxygen bond (OC) between silicon atoms in the coating film and The coating film may be decomposed and removed by irradiating the non-circuit forming site with a sufficient energy to cut the carbon-carbon bond (C—C) using a mask or the like.
  • the energy sufficient for breaking the carbon-oxygen bond between silicon atoms in the coating film is 3.7 eV or more, and the energy sufficient for breaking the carbon-carbon bond is 3.6 eV or more. .
  • the energy given to the coating film is 3.6 eV or more for cutting the carbon-carbon bond, preferably 8.7 eV or less for cutting the silicon-oxygen bond (Si—O), and 3.6 to 4. 0 eV is more preferable.
  • This energy may be irradiated for about 10 minutes. Whether or not such energy is applied is determined by, for example, testing whether the coating film can be removed without affecting the substrate by irradiating the substrate with the coating film with energy. Can be confirmed.
  • the energy for decomposing such a coating film can be given by, for example, plasma, ultraviolet light, laser, etc., but is preferably given by plasma.
  • energy irradiation can be performed with an ultraviolet irradiator as long as it is ultraviolet light.
  • an ultraviolet irradiator as long as it is ultraviolet light.
  • it if it is a laser, it can carry out with laser irradiation devices, such as a solid laser, a gas laser, and a semiconductor laser.
  • Dry etching can be performed by plasma of a mixed gas containing a halogen compound generated under a pressure lower than atmospheric pressure, for example, low vacuum plasma or high vacuum plasma.
  • a mixed gas containing a halogen compound generated under a pressure lower than atmospheric pressure, for example, low vacuum plasma or high vacuum plasma.
  • the halogen compound include carbon tetrafluoride.
  • the gas mixed with the halogen compound include nitrogen gas, oxygen gas, and rare gas.
  • a general plasma etching apparatus can be used for dry etching.
  • the coating film at the non-circuit formation site can be removed, but the catalyst metal remaining at the non-circuit formation site of the substrate may be further removed with a solution that dissolves the catalyst metal.
  • the solution for dissolving the catalyst metal is not particularly limited, but for example, an acidic aqueous solution is preferable.
  • an acidic aqueous solution for example, an inorganic acid such as hydrochloric acid or sulfuric acid can be used.
  • the substrate may be immersed in a solution that dissolves the catalyst metal.
  • the step (a2) of performing electroplating is not particularly limited.
  • it may be immersed in an electroplating solution and plated under normal conditions until a desired thickness is obtained.
  • the kind of electrolytic plating solution is not specifically limited, For example, electrolytic copper plating etc. are mentioned. Through this process, the entire surface of the substrate is plated.
  • the step (b2) of providing a dry film at the circuit formation site following the step (a2) is not particularly limited.
  • UV exposure development using a general photosensitive resist is used for the circuit formation site of electrolytic plating.
  • a dry film may be provided.
  • the step of removing electroless plating and electrolytic plating at the non-circuit formation site following step (b2) is not particularly limited, and may be treated with an acid or the like that can dissolve electroless plating or electrolytic plating.
  • an acid or the like that can dissolve electroless plating or electrolytic plating.
  • the kind of acid is not specifically limited, For example, if electrolytic plating is copper, a sulfuric acid etc. will be mentioned.
  • the method of a process is not specifically limited, Immersion, spraying, etc. may be sufficient.
  • the step (d2) of removing the coating film at the non-circuit formation site following the step (c2) can be performed in the same manner as the step (e1).
  • the desired metal to be plated is irradiated with visible light or ultraviolet light of 450 nm or less to make the catalytic metal in the coating film self-catalytic. If it is made to express and then electroless plating is performed, plating can be performed on a desired portion of the substrate. Further, after electroless plating, various types of electrolytic plating may be performed.
  • the substrate is not particularly limited, and the same substrate as that described above can be used.
  • a mask or the like is used, or a silicon oligomer and a catalytic metal are contained only in a desired part to be plated in advance.
  • a coating film to be applied may be applied.
  • the carbon-oxygen bond (OC) and / or carbon between the silicon atoms in the coating film is the same as in the steps (e1) and (d2).
  • the coating film may be decomposed and removed by irradiating with sufficient energy to cut carbon bonds (CC) using a mask or the like. The metal may be removed.
  • Example 1 Selective plating on substrate (1):
  • the ABF substrate (GX-T31: Ajinomoto) was degreased (SK-18: JCU) for 1.5 minutes at 60 ° C. and then dried.
  • this ABF substrate was immersed in the coating agent obtained in Production Example 2 for 10 seconds and dried at room temperature for 5 minutes. Then, it baked for 20 minutes at 70 degreeC, and it stood to cool and provided the coating film. After allowing to cool, the entire surface of the ABF substrate was irradiated with ultraviolet light having a wavelength of 365 nm for 5 minutes to develop the catalytic metal self-catalytic property.
  • electroless nickel plating was performed by immersing in an electroless nickel plating solution (Skylite PB-606: manufactured by JCU) at 80 ° C. for 2 minutes. After plating, the dry film is attached to the right half of the substrate (on the electroless nickel plating) and then plated at 25 ° C for a copper sulfate plating solution (Cubelight EP-30: manufactured by JCU) at 3 A / dm 2 for 40 minutes. Went. After plating, the dry film is removed with an aqueous sodium hydroxide solution, and further etching is performed with sulfuric acid to remove unnecessary electroless copper plating under the dry film. Finally, a plasma processing apparatus (Oumi: manufactured by JCU) is used. The coating film under the electroless copper plating was removed.
  • an electroless nickel plating solution Skylite PB-606: manufactured by JCU
  • plating was deposited only on the portion where the dry film was not pasted, and the other portion remained as the substrate (FIG. 1). This indicates that the plating can be selectively performed on the substrate, and that the circuit can be formed by this method.
  • Example 2 Selective plating on substrate (2):
  • the ABF substrate (GX-T31: Ajinomoto) was degreased (SK-18: JCU) for 1.5 minutes at 60 ° C. and then dried.
  • this ABF substrate was immersed in the coating agent obtained in Production Example 3 for 10 seconds and dried at room temperature for 5 minutes. Then, it baked for 20 minutes at 70 degreeC, and it stood to cool and provided the coating film. After allowing to cool, the entire surface of the ABF substrate was irradiated with ultraviolet light having a wavelength of 365 nm for 5 minutes to develop the catalytic metal self-catalytic property.
  • electroless nickel plating was performed by immersing in an electroless nickel plating solution (Skylite PB-606: manufactured by JCU) at 80 ° C. for 2 minutes. After that, plating was performed at 3 A / dm 2 for 40 minutes on a copper sulfate plating solution (Cubelite EP-30: manufactured by JCU) at 25 ° C.
  • an electroless nickel plating solution Skylite PB-606: manufactured by JCU
  • plating was performed at 3 A / dm 2 for 40 minutes on a copper sulfate plating solution (Cubelite EP-30: manufactured by JCU) at 25 ° C.
  • a dry film is attached to the right half of the substrate (on the copper sulfate plating), then etching with sulfuric acid is performed to remove unnecessary copper sulfate plating and electroless nickel plating, and plasma processing equipment (Oumi: manufactured by JCU) ) was used to remove the coating film under the electroless nickel plating, and finally the dry film was removed with an aqueous sodium hydroxide solution.
  • the plating remained only on the part where the dry film was pasted, and the other part remained as the substrate (FIG. 2). This indicates that the plating can be selectively performed on the substrate, and that the circuit can be formed by this method.
  • Example 3 Selective plating on substrate (3): The glass substrate was degreased (SK-18: manufactured by JCU) at 60 ° C. for 1.5 minutes and then dried. Next, this glass substrate was immersed in the coating agent obtained in Production Example 10 for 10 seconds and dried at room temperature for 5 minutes. Then, it baked for 20 minutes at 180 degreeC, and it stood to cool and provided the coating film. In addition, the autocatalytic property of the catalytic metal was expressed by this firing. Thereafter, it was immersed in an electroless copper nickel plating solution (AISL-570: manufactured by JCU) at 40 ° C. for 5 minutes to perform electroless copper nickel plating. Thereafter, it was baked at 180 ° C. for 20 minutes, and further plated at 20 ° C.
  • AISL-570 electroless copper nickel plating solution
  • a copper sulfate plating solution Cubelite EP-30: manufactured by JCU.
  • a dry film is attached to the right half of the substrate (on top of copper sulfate plating), then etching with sulfuric acid is performed to remove copper sulfate plating and electroless copper nickel plating, and plasma processing equipment (Oumi: manufactured by JCU) was used to remove the coating film, and finally the dry film was removed with an aqueous sodium hydroxide solution.
  • plating was deposited only on the portion where the dry film was pasted, and the portion other than that remained as the substrate (FIG. 3). This indicates that the plating can be selectively performed on the substrate, and that the circuit can be formed by this method.
  • Example 4 Selective plating on substrate (4):
  • the ABF substrate (GX-T31: Ajinomoto) was degreased (SK-18: JCU) for 1.5 minutes at 60 ° C. and then dried.
  • this ABF substrate was immersed in the coating agent obtained in Production Example 3 for 10 seconds and dried at room temperature for 5 minutes. Then, it baked at 70 degreeC for 20 minute (s), stood to cool, and provided the coating film. After standing to cool, a glass photomask on which a circuit pattern was drawn was placed on the ABF substrate and irradiated with ultraviolet rays having a wavelength of 365 nm for 5 minutes.
  • the method of the present invention can be used for forming circuits such as integrated circuits. more than

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Abstract

基板の種類によらず少ない工程で基板上への所望の部位へ金属めっきを行い回路形成できる新しい方法を提供する。基板上にめっきで回路形成を行うにあたり、　基板上に、シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜を施した後、コーティング皮膜中の触媒金属の活性化処理を行い自己触媒性を発現させ、次いで、無電解めっきを行う工程を含むことを特徴とする基板上への回路形成方法。

Description

基板上への回路形成方法
　本発明は、基板上への回路形成方法等に関する。
　めっきを利用した基板上への回路形成は、多数の工程を経る必要がある。例えば、基板が樹脂の場合、次のような工程で行われている（非特許文献１）。
＜サブトラクティブ法＞
（Ａ１）基板上にエッチング等を行い、表面を荒らす
（Ａ２）基板にコンディショナーで親水性を付与する
（Ａ３）基板上への触媒を付与
（Ａ４）基板に無電解銅または無電解Ｎｉめっきを行う
（Ａ５）基板に電解銅めっきを行う。
（Ａ６）電解銅めっき上にレジストパターンを形成する。
（Ａ７）不要な電解および無電解めっきの剥離とレジストの剥離を行い、回路を形成する
＜セミアディティブ法＞
（Ｂ１）基板上にエッチング等を行い、表面を荒らす
（Ｂ２）基板にコンディショナーで親水性を付与する
（Ｂ３）基板上への触媒を付与
（Ｂ４）基板に無電解銅または無電解Ｎｉめっきを行う
（Ｂ５）無電解めっき上にレジストパターンを形成した後、電解銅めっきを行う
（Ｂ６）不要なレジストとその下の無電解めっきの剥離を行い、回路を形成する
　また、めっきを利用した基板上への装飾用めっき用の全面および部分めっきも、上記基板上への回路形成と同様に、多数の工程を経る必要がある。
　このように種々の基板上へ、回路形成を含めた所望の部位へ金属めっきするには基板にあわせた多数の工程を経なければならなかった。
斉藤囲ら、「新めっき技術」関東学院大学出版会、Ｐ２８１～２９２
　従って、本発明は、基板の種類によらず少ない工程で基板上への所望の部位へ金属めっきを行い回路形成できる新しい方法を提供することを課題とする。
　本発明者らは、上記課題を解決するために鋭意研究した結果、回路形成の際に、シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜を利用することにより、基板の種類によらず少ない工程で所望の部位へ金属めっきが行え、回路を形成できることを見出し、本発明を完成させた。
　すなわち、本発明は、基板上にめっきで回路形成を行うにあたり、
　基板上に、シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜を施した後、コーティング皮膜中の触媒金属の活性化処理を行い自己触媒性を発現させ、次いで、無電解めっきを行う工程を含むことを特徴とする基板上への回路形成方法である。
　また、本発明は、上記基板上への回路形成方法で得られる、基板、シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜、無電解めっき、電解めっきがこの順で積層されていることを特徴とする回路である。
　また、本発明者らは、シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜のめっきを施したい所望の部位に４５０ｎｍ以下の可視光および紫外線を照射することにより、コーティング皮膜中の触媒金属が自己触媒性を発現することおよびそれにより無電解めっきが行えるようになることを見出し、本発明を完成させた。
　すなわち、本発明は、基材を、シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜を施した後、めっきを施したい所望の部位に４５０ｎｍ以下の可視光および紫外線を照射してコーティング皮膜中の触媒金属に自己触媒性を発現させ、次いで、無電解めっきを行うことを特徴とする基材へのめっき方法である。
　本発明によれば、回路形成にシリコンオリゴマーおよび触媒金属を含有するコーティング皮膜を利用することにより、各基板への前処理等を行わなくても良くなるため、基板の種類によらず基板の所望の部位への金属めっきをする工程を少なくできる。
　そのため、本発明を半導体の回路製造に利用すれば、従来よりも工程が少なく回路形成をすることができる。
　また、本発明によれば、基材に設けられたシリコンオリゴマーおよび触媒金属を含有するコーティング皮膜のめっきを施したい所望の部位に４５０ｎｍ以下の可視光および紫外線を照射することにより、基材の所望の部位にめっきをすることができる。
　そのため、本発明は基材の所望の部位にめっきをするのに利用できる。
実施例１で得られためっき後の基板の写真である。 実施例２で得られためっき後の基板の写真である。 実施例３で得られためっき後の基板の写真である。 実施例４で得られためっき後の基板の写真である。
　本発明の基板上への回路形成方法（以下、「本発明方法」という）は、基板上にめっきで回路形成を行うにあたり、
　基板上に、シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜を施した後、コーティング皮膜中の触媒金属の活性化処理を行い自己触媒性を発現させ、次いで、無電解めっきを行う工程を含めばよい。
　本発明方法に用いられる基板は、シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜が、良好な付着性があり、活性化処理により自己触媒性を発現させることができるためその素材は特に限定されず、金属、樹脂、ガラス等の他、従来は難めっき性とされていた、木、紙等の何れでもよい。これらの中でも樹脂、ガラスが好ましい。この樹脂としては、例えば、ＡＢＳ、ポリプロピレン、ポリエチレン、ポリカーボネート、エポキシ系樹脂、フェノール系樹脂、ウレタン系樹脂等が挙げられる。これら樹脂は１種または２種以上を用いることができる。なお、これら樹脂には無機酸化物、無機窒化物、無機硫化物等のフィラーを添加させたものを用いることが密着性等の点から好ましい。これらフィラーは樹脂に１種または２種以上を添加させることができる。なお、従来の回路形成方法においては、フィラーが添加された樹脂を用いた場合、アルカリ溶液への浸漬にてフィラーを除去するかデスミア処理等で粗化処理を行わなければならないが、本発明方法ではその必要はない。
　本発明方法において、シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜を施す方法は、特に限定されず、例えば、基板を以下の含触媒金属シリコンオリゴマーを含有するコーティング剤で処理する方法が挙げられる。
　具体的には、テトラアルコキシシランと、
　少なくともｎ,ｎ＋１位またはｎ,ｎ＋２位（ただしｎは１以上の整数）にヒドロキシ基が結合した多価アルコールとを、
　触媒金属の存在下、
　縮合反応させることにより得られる含触媒金属シリコンオリゴマーを含有するコーティング剤で処理する。
　上記テトラアルコキシシランは、特に限定されず、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラブトキシシラン等が挙げられ、これらの中でもテトラエトキシシランが好ましい。これらテトラアルコキシシランは１種または２種以上を組み合わせてもよい。
　また、上記少なくともｎ,ｎ＋１位またはｎ,ｎ＋２位（ただしｎは１以上の整数）にヒドロキシ基が結合した多価アルコールは、特に限定されず、例えば、ｎが１～３の整数である２価～４価のアルコール、好ましくはｎが１～２の整数である２～３価のアルコール等が挙げられる。これら多価アルコールの具体例としては、例えば、エチレングリコール、１,２－プロパンジオール、１,３－プロピレングリコール、１,２－ブチレングリコール、１,３－ブチレングリコール、２,３－ブチレングリコール、２－メチル－１,３－プロピレングリコール、１,２－ペンチレングリコール、１,３－ペンチレングリコール、２,３－ペンチレングリコール、２,４－ペンチレングリコール等の２価アルコール、グリセリン等の３価アルコール等、エリスリトール等の４価アルコールが挙げられる。これらの多価アルコールの中でも２価アルコールが好ましく、エチレングリコールおよび／または１,３－プロピレングリコールがより好ましく、エチレングリコールが特に好ましい。これら多価アルコールは１種または２種以上を組み合わせて用いることができる。
　更に、上記触媒金属は、テトラアルコキシシランと多価アルコールの縮合反応について触媒作用を有する金属ではなく、後記するめっきの析出反応について自己触媒作用を有する金属である。そのため、ＷＯ２０１４／２０７８８５やＷＯ２０１４／２０７８８６でいうところの金属触媒とは異なるものである。このような触媒金属としては、例えば、鉄、ニッケル、コバルト、銅、パラジウム、銀、金、白金等が挙げられる。これらの触媒金属の中でも、鉄、ニッケル、コバルト、銅、パラジウムが好ましく、鉄、ニッケル、銅、パラジウムがより好ましく、パラジウムが特に好ましい。なお、上記触媒金属は縮合反応の際に、上記多価アルコールに溶解させた状態で存在させることが好ましく、その場合には、例えば、塩化鉄、塩化ニッケル、塩化銅、塩化パラジウム、塩化金（III）、塩化銀（I）、塩化白金（IV）等の触媒金属を含む金属塩を利用することが好ましい。なお、多価アルコールに触媒金属が溶解し難い場合には、予め塩酸等の無機酸に溶解させておいてもよい。これら触媒金属は１種または２種以上を組み合わせて用いることができ、その場合には、パラジウムを少なくとも含むことが好ましい。
　上記したテトラアルコキシシランと、多価アルコールとを、触媒金属の存在下、縮合反応させる方法は特に限定されず、例えば、上記多価アルコールに、触媒金属を０.０１～２０ｇ／ｋｇ、好ましくは０.１～１０ｇ／ｋｇで添加、溶解させた後、反応温度まで撹拌しながら加熱し、更に、テトラアルコキシシランを添加し、反応させればよい。反応温度は２５～１５０℃、好ましくは３０～７０℃であり、反応時間は３０分～８時間、好ましくは２時間～４時間である。なお、上記反応の際には、テトラアルコキシシランと多価アルコールをモル比で４：１～１：４、好ましくは１：２～１：４で反応させることが重要である。これによりテトラアルコキシシランとテトラアルコキシシランの間に多価アルコールが取り込まれる。
　なお、上記反応の際には、アルコールが生成するが、このアルコールを分留しないことにより重合反応が制御されるので、アルコールを分留しないことが好ましい。
　また、上記反応において、テトラアルコキシシランと多価アルコールを縮合反応させる前は２層に分離しているが、反応が完了すると１層になるため、１層になった時点で反応を終了させてもよい。
　このようにして得られる含触媒金属シリコンオリゴマーは、テトラアルコキシシランの２～４と、多価アルコールの１～１３が縮合反応したシリコンオリゴマーに触媒金属が取り込まれたものである。
　なお、含触媒金属シリコンオリゴマーは、テトラアルコキシシランのアルコキシ基と、多価アルコールに存在するｎ,ｎ＋１位またはｎ,ｎ＋２位のヒドロキシ基の１つまたは２つが縮合反応したものであり、例えば、下記（ａ）～（ｄ）の様な部分構造を有している。そして、本発明の含触媒金属シリコンオリゴマーにおいて、触媒金属は酸素原子間に存在し、触媒金属を頂点とする５員環構造または６員環構造を形成し、安定化しているものと推測される。そのため、本発明の含触媒金属シリコンオリゴマーは生成後、１年経過しても触媒金属の沈殿は認められない。
Figure JPOXMLDOC01-appb-C000001
　このような含触媒金属シリコンオリゴマーは、１ＨＮＭＲ、２９ＳｉＮＭＲ等のＮＭＲ、ＩＲ、ＭＡＳＳ等の公知の方法により同定することができる。具体的にＮＭＲであれば、テトラアルコキシシランと多価アルコールの縮合反応により生成したアルコールを１ＨＮＭＲで確認し、更に、含触媒金属シリコンオリゴマー中のシリコンの数を２９ＳｉＮＭＲで確認することにより、含触媒金属シリコンオリゴマーを同定することができる。また、シリコンオリゴマーに触媒金属が取り込まれていることは、シリコンオリゴマーを生成した後、一定期間経過後、例えば、１年経過後に触媒金属の沈殿が認められないことにより確認することができる。
　この含触媒金属シリコンオリゴマーは、従来のシリコンオリゴマーと同様に、コーティング剤として、基板の表面等に処理をすることができる。特にこの含触媒金属シリコンオリゴマーは、その構造中に触媒金属が取り込まれているため、基板をコーティング剤で処理した後、活性化処理を行うことにより、基板に自己触媒性や導電性を付与することができる。
　含触媒金属シリコンオリゴマーを含有するコーティング剤は、含触媒金属シリコンオリゴマーを含有さえしていればよいが、例えば、含まれる触媒金属が異なる２種類以上の含触媒金属シリコンオリゴマーを組み合わせて用いたり、含触媒金属シリコンオリゴマーの調製の際に２種以上の触媒金属の存在下で調製したものを用いることにより、触媒金属の触媒作用が増強されるため好ましい。また、触媒金属の組み合わせとしては、特に限定されないが、例えば、パラジウムと、鉄、ニッケル、コバルト、銅から選ばれる１種以上との組み合わせが好ましい。
　上記コーティング剤は、例えば、従来公知のコーティング剤に添加される溶媒、基板への濡れ性を向上させるための樹脂等を含有させてもよい。このようなコーティング剤は、上記成分を適宜、撹拌、混合することにより調製することができる。
　上記コーティング剤に添加される溶媒としては特に限定されず、例えば、水、イソプロピルアルコール、エチルセロソルブ等が挙げられる。なお、本発明の含触媒金属シリコンオリゴマーは、例えば、ポリエチレングリコールやエチルセロソルブ等のグリコール系溶媒で希釈すると水分存在下でも安定に保存することができる。特にグリコール系溶媒として、ポリエチレングリコール２００～１０００、好ましくはポリエチレングリコール２００を用いることにより、水分存在下でも長期間安定に保存することができる。
　また、上記コーティング剤に添加される樹脂としては、コーティング剤に可溶、もしくは分散するものであれば特に限定されず、例えば、アクリル系樹脂、ウレタン系樹脂、フェノール系樹脂、エポキシ系樹脂等が挙げられる。また、これらの樹脂の中でもアクリル系樹脂が好ましく、メタアクリル酸アルキルエステル共重合体、コロイダルシリカ・アクリル複合体、エチレン・アクリル酸共重合物アンモニウム塩がより好ましく、メタアクリル酸アルキルエステル共重合体が特に好ましい。これらの樹脂は１種または２種以上を用いることができる。また、これらの樹脂は溶液状のものでも粉末状のもののどちらでも構わない。これらの樹脂は、コーティング剤に５０質量％（以下、単に「％」という）以下、好ましくは０.１～５０％、より好ましくは１～２０％配合する。
　更に、上記コーティング剤には含触媒金属シリコンオリゴマーの効果を損なわない範囲で、着色剤、摩擦係数調整剤、増膜剤、その他機能性付与するような添加剤を配合してもよい。
　上記コーティング剤で基板を処理する方法は、従来公知のコーティング剤と同様でよく、例えば、ディップアンドスピン法等の浸漬法、スプレーコーティング法等の噴霧法等で基板の全面を処理すればよい。上記処理後は、そのままあるいは温風等で乾燥させればよい。また、コーティングの厚さは特に限定されず、基板の全面を覆ってさえいればよい。
　上記のようにして基板上に、シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜を施した後は、コーティング皮膜中の触媒金属の活性化処理を行い自己触媒性を発現させる。
　触媒金属の活性化処理は、活性化処理は基板の特性に合わせて、適宜行えばよい。活性化処理としては、例えば、４５０ｎｍ以下の可視光および紫外線の照射、加熱、化学還元等が挙げられる。これらの活性化処理は適宜組み合わせて行ってもよい。これら活性化処理の中でも基板の種類によらないため４５０ｎｍ以下の可視光および紫外線の照射が好ましいく、特にオゾンが生成されない２５４ｎｍ～３６５ｎｍの光を照射することが好ましい。
　上記４５０ｎｍ以下の可視光および紫外線の照射は、例えば、ＤＵＶ露光光源装置（UIS-2511DUZ8-AUM01：ウシオ電機製）等の紫外線照射器等を用いて数分間程度行えばよい。
　上記加熱は、特に限定されず、例えば、オーブン、電気炉等で上記温度を１０分～２時間程度維持すればよい。加熱処理の雰囲気は特に限定されず、空気でよい。加熱後は、放冷等すればよい。
　上記化学還元は、特に限定されず、例えば、還元剤を含む水溶液等に１～３分程度浸漬すればよい。還元剤としては、例えば、次亜リン酸、ジメチルアミンボラン、ホルムアルデヒド、水素化ホウ素ナトリウム、ヒドラジン等が挙げられる。これらの還元剤は１種または２種以上を用いることができる。化学還元後は水洗、乾燥等をすればよい。
　以上のような触媒金属の活性化処理により、コーティング皮膜中の触媒金属も自己触媒性が発現する。
　この触媒金属の活性化処理に次いで、無電解めっきを行う。無電解めっきの種類は特に限定されず、例えば、無電解銅めっき、無電解ニッケルめっき、無電解銅－ニッケルめっき等が挙げられる。また、無電解めっきの条件は、要求されるめっきの厚さにあわせて適宜設定すればよいため特に限定されず、例えば、ｐＨ９程度、液温４０℃程度、処理時間７分程度等の条件が挙げられる。
　基板上にめっきで回路形成を行うにあたり、以上説明した本発明方法（工程）を含めば、基板上へ回路を形成することができる。基板上にめっきで回路形成する方法としては、公知の種々の方法が挙げられる。
　具体的に、本発明方法を利用して基板上にめっきで回路形成する方法としては、触媒金属の活性化処理の際に、活性化処理を基板上の回路形成部位のみに行い、その後、無電解めっきを行い、更に電解めっきを行っても基板上へ回路を形成することができる。電解めっきの種類は特に限定されず、例えば、電解銅めっき等が挙げられる。また、電解めっきの条件も要求されるめっきの厚さにあわせて適宜設定すればよいため特に限定されず、例えば、３Ａ／ｄｍ２程度にて１０～６０分程度等の条件が挙げられる。活性化処理を回路形成部位のみ行う方法としては、例えば、基板上にマスク等を利用してコーティング被膜を基板上の回路形成部位のみに施す方法、基板の全面にコーティング被膜を施し、マスク等を利用して活性化処理を基板上の回路形成部位のみ行う方法等が挙げられる。これらの方法の中でも基板の全面にコーティング被膜を施し、マスク等を利用して活性化処理を基板上の回路形成部位のみ行う方法が好ましく、特に活性化処理を４５０ｎｍ以下の可視光および紫外線の照射で行い、活性化処理を基板上の回路形成部位のみ行う方法が好ましい。
　また、本発明方法を利用して基板上にめっきで回路形成する別の方法としては、触媒金属の活性化処理の際に、活性化処理を基板上に、好ましくは基板の全面に行い、無電解めっきを行った後、例えば、次の工程（ａ１）～（ｅ１）、（ａ２）～（ｅ２）等を行うことにより基板上に回路を形成することができる。なお、工程（ａ１）～（ｅ１）は、一般にセミアディティブ法と呼ばれる回路形成法に該当し、工程（ａ２）～（ｅ２）は、一般にサブトラクティブ法と呼ばれる回路形成法に該当する。
（ａ１）非回路形成部位にドライフィルムを設ける工程
（ｂ１）回路形成部位に電解めっきを行う工程
（ｃ１）ドライフィルムを除去する工程
（ｄ１）非回路形成部位の無電解めっきを除去する工程
（ｅ１）非回路形成部位のコーティング皮膜を除去する工程
（ａ２）電解めっきを行う工程
（ｂ２）回路形成部位にドライフィルムを設ける工程
（ｃ２）非回路形成部位の無電解めっきおよび電解めっきを除去する工程
（ｄ２）非回路形成部位のコーティング皮膜を除去する工程
（ｅ２）ドライフィルムを除去する工程
　上記工程のうち、（ａ１）非回路形成部位にドライフィルムを設ける工程は、特に限定されず、例えば、無電解めっきの非回路形成部位に一般的な感光性レジストを用いてＵＶによる露光現像を利用してドライフィルムを設ければよい。
　工程（ａ１）に続く、（ｂ１）回路形成部位に電解めっきを行う工程は、特に限定されず、例えば、電解めっき液に浸漬し、所望の厚さとなるまで通常の条件でめっきを行えばよい。電解めっき液の種類は特に限定されず、例えば、電解銅めっき等が挙げられる。この工程により回路形成部位のみにめっきがされる。
　工程（ｂ１）に続く、（ｃ１）ドライフィルムを除去する工程は、特に限定されず、ドライフィルムの種類にあわせて、適宜それを溶解し得る有機溶剤、アルカリ性水溶液等で処理すればよい。処理の方法は特に限定されず、浸漬、スプレー等でよい。
　工程（ｃ１）に続く、（ｄ１）非回路形成部位の電解めっきを除去する工程は、特に限定されず、電解めっきを溶解し得る酸等で処理すればよい。酸の種類は特に限定されないが、例えば、電解めっきが銅であれば硫酸等が挙げられる。また、処理の方法は特に限定されず、浸漬、スプレー等でよい。
　工程（ｄ１）に続く、（ｅ１）非回路形成部位のコーティング皮膜を除去する工程は、特に限定されないが、例えば、前記コーティング皮膜中のシリコン原子間にある炭素－酸素結合（Ｏ－Ｃ）および／または炭素－炭素結合（Ｃ－Ｃ）を切断するのに十分なエネルギーをマスク等を利用して非回路形成部位に照射して前記コーティング皮膜を分解し、除去すればよい。
　前記コーティング皮膜中のシリコン原子間にある炭素－酸素結合を切断するのに十分なエネルギーは３.７ｅＶ以上であり、炭素－炭素結合を切断するのに十分なエネルギーは、３.６ｅＶ以上である。前記コーティング皮膜中のシリコン原子間にある炭素－酸素結合および／または炭素－炭素結合が切断されれば、前記コーティング皮膜は分解する。そのため、前記コーティング皮膜に与えるエネルギーとしては、炭素－炭素結合を切断する３.６ｅＶ以上であり、ケイ素－酸素結合（Ｓｉ－Ｏ）を切断する８.７ｅＶ以下が好ましく、３.６～４.０ｅＶがより好ましい。このエネルギーは１０分程度照射すればよい。なお、このようなエネルギーを与えているかどうかは、例えば、上記コーティング皮膜を設けた基板にエネルギーを照射することにより、基板には影響を与えず、コーティング皮膜のみが除去できるかどうかを試すことにより確認することができる。
　このような上記コーティング皮膜を分解するエネルギーは、例えば、プラズマ、紫外線、レーザー等で与えることができるが、プラズマで与えることが好ましい。
　具体的に、エネルギーの照射は、紫外線であれば、紫外線照射器で行うことができる。また、レーザーであれば、固体レーザー、ガスレーザー、半導体レーザー等のレーザー照射器で行うことができる。
　更に、プラズマであれば、いわゆるドライエッチングで行うことができる。ドライエッチングは、大気圧以下の圧力下で発生させたハロゲン化合物を含む混合気体のプラズマ、例えば、低真空プラズマ、高真空プラズマで行うことができる。ハロゲン化合物としては、四フッ化炭素等が挙げられる。また、ハロゲン化合物と混合される気体としては、窒素ガス、酸素ガス、希ガス等が挙げられる。なお、ドライエッチングは一般的なプラズマエッチング装置が利用できる。
　上記のようにして非回路形成部位のコーティング皮膜を除去することができるが、その後、更に、基板の非回路形成部位に残った触媒金属を、触媒金属を溶解する溶液で除去してもよい。
　触媒金属を溶解する溶液は、特に限定されないが、例えば、酸性水溶液が好ましい。水溶液を酸性にするためには、例えば、塩酸、硫酸等の無機酸を用いることができる。基板の非回路形成部位に残った触媒金属を、触媒金属を溶解する溶液で除去するには、触媒金属を溶解する溶液中に基板を浸漬等すればよい。
　これらの操作により非回路形成部位のコーティング皮膜や、触媒金属が完全に除去される。この工程をすることにより、基板上に回路のみが残る。
　また、上記工程のうち、（ａ２）電解めっきを行う工程は、特に限定されず、例えば、電解めっき液に浸漬し、所望の厚さとなるまで通常の条件でめっきを行えばよい。電解めっき液の種類は特に限定されず、例えば、電解銅めっき等が挙げられる。この工程により基板の全面にめっきがされる。
　工程（ａ２）に続く、（ｂ２）回路形成部位にドライフィルムを設ける工程は、特に限定されず、例えば、電解めっきの回路形成部位に一般的な感光性レジストを用いてＵＶによる露光現像を利用してドライフィルムを設ければよい。
　工程（ｂ２）に続く、（ｃ２）非回路形成部位の無電解めっきおよび電解めっきを除去する工程は、特に限定されず、無電解めっきや電解めっきを溶解し得る酸等で処理すればよい。酸の種類は特に限定されないが、例えば、電解めっきが銅であれば硫酸等が挙げられる。また、処理の方法は特に限定されず、浸漬、スプレー等でよい。
　工程（ｃ２）に続く、（ｄ２）非回路形成部位のコーティング皮膜を除去する工程は、工程（ｅ１）と同様にして行うことができる。
　工程（ｄ２）に続く、（ｅ２）ドライフィルムを除去する工程は、工程（ｃ１）と同様にして行うことができる。この工程をすることにより、基板上に回路のみが残る。
　上記工程（ａ１）～（ｅ１）あるいは（ａ２）～（ｅ２）の間や後には、洗浄、乾燥等の通常行われる処理を行ってもよい。
　更に、上記工程（ａ１）～（ｅ１）あるいは（ａ２）～（ｅ２）を終えた後は、本発明方法の一部または全部を繰り返し行ってもよい。
　以上の工程により、基板上に、基板、シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜、無電解めっき、電解めっきがこの順で積層されている回路を得ることができる。
　なお、基材をシリコンオリゴマーおよび触媒金属を含有するコーティング皮膜を施した後、めっきを施したい所望の部位に４５０ｎｍ以下の可視光および紫外線を照射してコーティング皮膜中の触媒金属に自己触媒性を発現させ、次いで、無電解めっきを行えば、基材の所望の部位にめっきを施すことができる。また、無電解めっき後は、種々の電解めっき等を施してもよい。
　上記基材としては特に限定されず、上記した基板と同様のものを用いることができる。　また、めっきを施したい所望の部位に４５０ｎｍ以下の可視光および紫外線を照射するには、マスク等を利用するか、予め基材のめっきを施したい所望の部位にのみシリコンオリゴマーおよび触媒金属を含有するコーティング皮膜を施しておけばよい。
　また、基材のめっきを所望しない部位については、上記工程（ｅ１）や（ｄ２）と同様にして、前記コーティング皮膜中のシリコン原子間にある炭素－酸素結合（Ｏ－Ｃ）および／または炭素－炭素結合（Ｃ－Ｃ）を切断するのに十分なエネルギーをマスク等を利用して照射して前記コーティング皮膜を分解し、除去してもよいし、更に、触媒金属を溶解する溶液で触媒金属を除去してもよい。
　以下、実施例を挙げて本発明を詳細に説明するが、本発明はこれら実施例に何ら限定されるものではない。
製　造　例　１
　　　含パラジウムシリコンオリゴマーの調製：
　予め１.７ｇの塩酸に溶解させた塩化パラジウム１.７ｇを、エチレングリコール３３６ｇに添加した後、撹拌し、溶解させた。これにテトラエトキシシラン５６４ｇを添加し、マントルヒーターで５０℃に加温しながら２時間撹拌し、縮合反応させて反応物を得た。なお、この反応の際に生成するアルコールは分留しなかった。また、この反応の前は、エチレングリコールとテトラエトキシシランは混和せずに、２層に分離していたが、２時間縮合反応後は、単一層となった。そのため、この反応の反応率は１００％であることがわかった。
　反応後冷却を行い反応物を得た。反応前と反応後に１ＨＮＭＲおよび２９ＳｉＮＭＲを測定した。１ＨＮＭＲにおいて、反応終了後のスペクトルには１.１および３.５ｐｐｍ付近にエタノール由来のピークが現れていた。このエタノールは、テトラエトキシシランのエトキシ基とエチレングリコールとの縮合反応が起こった結果、生成したものと考えられた。
　また、２９ＳｉＮＭＲにおいて、反応前のスペクトルでは－８２ｐｐｍ付近にテトラエトキシシラン由来の単一ピークのみ現れていたのものが、反応終了後のスペクトルでは－９０ｐｐｍから－８０ｐｐｍの範囲に複数のピークが表れていた。これから分子中のＳｉの数は２～４と考えられた。
　更に、上記で得られたシリコンオリゴマーは１年経過してもパラジウムの沈殿は認められなかった。これからシリコンオリゴマーの構造中に、パラジウムが取り込まれていると考えられた。（以下、これを「含Ｐｄシリコンオリゴマー」という）。
製　造　例　２
　　　コーティング剤の調製（１）：
　アクリル樹脂（ニガゾールＰＫ８０１２Ｐ：日本カーバイト社製）１０質量％、製造例１で得られた含Ｐｄシリコンオリゴマーを１２.５質量％（金属濃度３００ｐｐｍ）となるように添加、混合してコーティング剤を得た。
製　造　例　３
　　　コーティング剤の調製（２）：
アクリル樹脂（ニガゾールＰＫ８０１２Ｐ：日本カーバイト社製）１０質量％、製造例１で得られた含Ｐｄシリコンオリゴマーを１２.５質量％（金属濃度３００ｐｐｍ）となるように添加、混合してコーティング剤を得た。
実　施　例　１
　　　基板上への選択的なめっき（１）：
　ＡＢＦ基板（ＧＸ－Ｔ３１：味の素製）を、６０℃で１.５分間脱脂（ＳＫ－１８：ＪＣＵ製）を行った後、乾燥させた。次にこのＡＢＦ基板を製造例２で得たコーティング剤に１０秒間浸漬し、５分間室温で乾燥した。その後、７０℃で２０分間焼成をし、放冷してコーティング皮膜を設けた。放冷後、ＡＢＦ基板の全面に波長３６５ｎｍの紫外線を５分間照射して、触媒金属の自己触媒性を発現させた。紫外線照射後、８０℃の無電解ニッケルめっき液（スカイライトＰＢ－６０６：ＪＣＵ製）に２分間浸漬し、無電解ニッケルめっきを行った。めっき後、ドライフィルムを基板の右半分（無電解ニッケルめっきの上）に貼り付けた後、２５℃の硫酸銅めっき液（キューブライトＥＰ－３０：ＪＣＵ製）に３Ａ／ｄｍ２で４０分間めっきを行った。めっき後、ドライフィルムを水酸化ナトリウム水溶液で除去し、更に、硫酸でエッチングを行い、ドライフィルムの下の不要な無電解銅めっきを除去し、最後にプラズマ処理装置（大海：ＪＣＵ製）を用いて無電解銅めっきの下のコーティング皮膜を除去した。
　これらの操作により、ドライフィルムを貼り付けなかった部分にのみめっきが析出し、そうでない部分は基板のままであった（図１）。これにより基板上へ選択的にめっきができることが示され、ひいてはこの方法により回路が形成できることが示された。
実　施　例　２
　　基板上への選択的なめっき（２）：
　ＡＢＦ基板（ＧＸ－Ｔ３１：味の素製）を、６０℃で１.５分間脱脂（ＳＫ－１８：ＪＣＵ製）を行った後、乾燥させた。次にこのＡＢＦ基板を製造例３で得たコーティング剤に１０秒間浸漬し、５分間室温で乾燥した。その後、７０℃で２０分間焼成をし、放冷してコーティング皮膜を設けた。放冷後、ＡＢＦ基板の全面に、波長３６５ｎｍの紫外線を５分間照射して、触媒金属の自己触媒性を発現させた。紫外線照射後、８０℃の無電解ニッケルめっき液（スカイライトＰＢ－６０６：ＪＣＵ製）に２分間浸漬し、無電解ニッケルめっきを行った。その後２５℃の硫酸銅めっき液（キューブライトＥＰ－３０：ＪＣＵ製）に３Ａ／ｄｍ２で４０分間めっきを行った。めっき後、ドライフィルムを基板の右半分（硫酸銅めっきの上）に貼り付けた後、硫酸でエッチングを行い不要な硫酸銅めっきおよび無電解ニッケルめっきを除去し、プラズマ処理装置（大海：ＪＣＵ製）を用いて無電解ニッケルめっきの下のコーティング皮膜を除去し、最後にドライフィルムを水酸化ナトリウム水溶液で除去した。
　これらの操作により、ドライフィルムを貼り付けた部分にのみめっきが残り、そうでない部分は基板のままであった（図２）。これにより基板上へ選択的にめっきができることが示され、ひいてはこの方法により回路が形成できることが示された。
実　施　例　３
　　　基板上への選択的なめっき（３）：
　ガラス基板を、６０℃で１.５分間脱脂（ＳＫ－１８：ＪＣＵ製）を行った後、乾燥させた。次にこのガラス基板を製造例３で得たコーティング剤に１０秒間浸漬し、５分間室温で乾燥した。その後、１８０℃で２０分間焼成をし、放冷してコーティング皮膜を設けた。なお、この焼成により、触媒金属の自己触媒性を発現させた。その後４０℃の無電解銅ニッケルめっき液（ＡＩＳＬ－５７０：ＪＣＵ製）に５分間浸漬し、無電解銅ニッケルめっきを行った。その後１８０℃で２０分間焼成し、更に、２０℃の硫酸銅めっき液（キューブライトＥＰ－３０：ＪＣＵ製）に３Ａ／ｄｍ２で４０分間めっきを行った。めっき後、ドライフィルムを基板の右半分（硫酸銅めっきの上）に貼り付けた後、硫酸でエッチングを行い硫酸銅めっきと無電解銅ニッケルめっきを除去し、プラズマ処理装置（大海：ＪＣＵ製）を用いてコーティング皮膜を除去し、最後にドライフィルムを水酸化ナトリウム水溶液で除去した。
　これらの操作により、ドライフィルムを貼り付けた部分にのみめっきが析出し、そうでない部分は基板のままであった（図３）。これにより基板上へ選択的にめっきができることが示され、ひいてはこの方法により回路が形成できることが示された。
実　施　例　４
　　　基板上への選択的なめっき（４）：
　ＡＢＦ基板（ＧＸ－Ｔ３１：味の素製）を、６０℃で１.５分間脱脂（ＳＫ－１８：ＪＣＵ製）を行った後、乾燥させた。次にこのＡＢＦ基板を製造例３で得たコーティング剤に１０秒間浸漬し、５分間室温で乾燥した。その後、７０℃で２０分間焼成をし、放冷し、コーティング皮膜を設けた。放冷後、ＡＢＦ基板上に回路パターンの描かれたガラスのフォトマスクを重ね、波長３６５ｎｍの紫外線を５分間照射した。紫外線照射後、マスクを取り、８０℃の無電解ニッケルめっき液（スカイライトＰＢ－６０６：ＪＣＵ製）に２分間浸漬し、無電解ニッケルめっきを行うことで、露光部のみに無電解ニッケルの析出を確認した（図４）。
　本発明方法は、集積回路等の回路形成に利用することができる。
　　　　　　　　　　　　　　　　　　　　　　　　　　　　以　　上

Claims (18)

  1. 　基板上にめっきで回路形成を行うにあたり、
    　基板上に、シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜を施した後、コーティング皮膜中の触媒金属の活性化処理を行い自己触媒性を発現させ、次いで、無電解めっきを行う工程を含むことを特徴とする基板上への回路形成方法。
  2. 　無電解めっきを行った後、次の工程（ａ１）～（ｅ１）
    （ａ１）非回路形成部位にドライフィルムを設ける工程
    （ｂ１）回路形成部位に電解めっきを行う工程
    （ｃ１）ドライフィルムを除去する工程
    （ｄ１）非回路形成部位の無電解めっきを除去する工程
    （ｅ１）非回路形成部位のコーティング皮膜を除去する工程
    を行う請求項１に記載の基板上への回路形成方法。
  3. 　無電解めっきを行った後、次の工程（ａ２）～（ｅ２）
    （ａ２）電解めっきを行う工程
    （ｂ２）回路形成部位にドライフィルムを設ける工程
    （ｃ２）非回路形成部位の無電解めっきおよび電解めっきを除去する工程
    （ｄ２）非回路形成部位のコーティング皮膜を除去する工程
    （ｅ２）ドライフィルムを除去する工程
    を行う請求項１に記載の基板上への回路形成方法。
  4. 　コーティング皮膜中の触媒金属の活性化処理を回路形成部位のみに行う請求項１に記載の基板上への回路形成方法。
  5. 　シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜が、
    　テトラアルコキシシランと、
    　少なくともｎ,ｎ＋１位またはｎ,ｎ＋２位（ただしｎは１以上の整数）にヒドロキシ基が結合した多価アルコールとを、
    　触媒金属の存在下、
    　縮合反応させることにより得られる含触媒金属シリコンオリゴマーで形成するものである請求項１～４の何れかに記載の基板上への回路形成方法。
  6. 　縮合反応の際に生成するアルコールを分留しないものである請求項５に記載の基板上への回路形成方法。
  7. 　テトラアルコキシシランが、テトラメトキシシラン、テトラエトキシシランおよびテトラブトキシシランからなる群から選ばれる１種または２種以上である請求項５に記載の基板上への回路形成方法。
  8. 　少なくともｎ,ｎ＋１位またはｎ,ｎ＋２位（ただしｎは１以上の整数）にヒドロキシ基が結合した多価アルコールが、エチレングリコールおよび／または１,３－プロピレングリコールである請求項５に記載の基板上への回路形成方法。
  9. 　触媒金属が、鉄、ニッケル、コバルト、銅およびパラジウムからなる群から選ばれる１種または２種以上である請求項５に記載の基板上への回路形成方法。
  10. 　触媒金属の活性化処理が、４５０ｎｍ以下の可視光および紫外線の照射である請求項１～９の何れかに記載の基板上への回路形成方法。
  11. 　基板が、樹脂またはガラスである請求項１～１０の何れかに記載の基板上への回路形成方法。
  12. 　基板が、樹脂に、無機酸化物、無機窒化物および無機硫化物から選ばれるフィラーの１種または２種以上を添加したものである請求項１１に記載の基板上への回路形成方法。
  13. 　樹脂が、ＡＢＳ、ポリプロピレン、ポリエチレン、ポリカーボネート、エポキシ系樹脂、フェノール系樹脂およびウレタン系樹脂からなる群から選ばれる１種または２種以上である請求項１１または１２に記載の基板上への回路形成方法。
  14. 　請求項１～１３の何れかに記載の基板上への回路形成方法で得られる、基板、シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜、無電解めっき、電解めっきがこの順で積層されていることを特徴とする回路。
  15. 　基材を、シリコンオリゴマーおよび触媒金属を含有するコーティング皮膜を施した後、めっきを施したい所望の部位に４５０ｎｍ以下の可視光および紫外線を照射してコーティング皮膜中の触媒金属に自己触媒性を発現させ、次いで、無電解めっきを行うことを特徴とする基材へのめっき方法。
  16. 　基材が、樹脂またはガラスである請求項１５に記載の基材へのめっき方法。
  17. 　基材が、樹脂に、無機酸化物、無機窒化物および無機硫化物から選ばれるフィラーの１種または２種以上を添加したものである請求項１６に記載の基材へのめっき方法。
  18. 　樹脂が、ＡＢＳ、ポリプロピレン、ポリエチレン、ポリカーボネート、エポキシ系樹脂、フェノール系樹脂およびウレタン系樹脂からなる群から選ばれる１種または２種以上である請求項１６または１７に記載の基材へのめっき方法。
     
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