WO2012133297A1 - Stratifié à film métallique et son procédé de fabrication, stratifié à film métallique texturé et son procédé de fabrication - Google Patents

Stratifié à film métallique et son procédé de fabrication, stratifié à film métallique texturé et son procédé de fabrication Download PDF

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Publication number
WO2012133297A1
WO2012133297A1 PCT/JP2012/057739 JP2012057739W WO2012133297A1 WO 2012133297 A1 WO2012133297 A1 WO 2012133297A1 JP 2012057739 W JP2012057739 W JP 2012057739W WO 2012133297 A1 WO2012133297 A1 WO 2012133297A1
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group
layer
metal film
plated
plating
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PCT/JP2012/057739
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English (en)
Japanese (ja)
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季彦 松村
加納　丈嘉
哲文 高本
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富士フイルム株式会社
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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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • H05K3/387—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive for electroless plating
    • 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
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • 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
    • C23C18/1646—Characteristics of the product obtained
    • 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
    • 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
    • C23C18/1689—After-treatment
    • 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
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, 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
    • C23C18/18—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
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • 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

Definitions

  • the present invention relates to a laminate having a metal film and a manufacturing method thereof, and a laminate having a patterned metal film and a manufacturing method thereof.
  • a metal wiring board in which wiring with a metal pattern is formed on the surface of an insulating substrate has been widely used for electronic components and semiconductor elements.
  • a “subtractive method” is mainly used.
  • a photosensitive layer that is exposed by irradiation with actinic rays is provided on a metal film formed on the surface of the substrate, the photosensitive layer is exposed imagewise, and then developed to form a resist image.
  • the metal film is etched to form a metal pattern, and finally the resist is removed.
  • adhesion between the substrate and the metal pattern is expressed by an anchor effect generated by providing irregularities on the substrate surface. For this reason, when the obtained metal pattern is used as a metal wiring, there is a problem that high frequency characteristics are deteriorated due to the unevenness of the substrate interface portion of the metal pattern.
  • a strong acid such as chromic acid
  • Patent Document 1 a method is known in which a polymer layer having high adhesion to the substrate is formed on the substrate, the polymer layer is plated, and the resulting metal film is etched. According to this method, the adhesion between the substrate and the metal film can be improved without roughening the surface of the substrate.
  • An object of this invention is to provide the manufacturing method of the laminated body which has a metal film in which generation
  • Another object of the present invention is to provide a method for producing a laminate having a patterned metal film using the laminate obtained from the production method and a laminate having a patterned metal film.
  • the present inventors have formed the layer to be plated using a predetermined polymer, and then contacted the layer to be plated with an alkaline aqueous solution containing a predetermined component to thereby solve the above problems. I found that it can be solved. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • a composition for forming a layer to be plated containing a polymer having at least one group selected from the group consisting of a group represented by formula (X) and a (meth) acrylamide group, which will be described later, and an ionic polar group A contact layer forming step for forming a layer to be plated on the substrate by applying energy to the composition for forming a layer to be plated on the substrate; An alkaline aqueous solution contact step in which an aqueous alkaline solution containing amino alcohol and a surfactant and having a pH of 10 to 14 is brought into contact with the layer to be plated; A catalyst application step of applying a plating catalyst or a precursor thereof to the layer to be plated after the alkaline aqueous solution contact step; A method for producing a laminate having a metal film, comprising: a plating process for performing a plating process on a layer to be plated to which a plating catalyst or a precursor thereof is applied, and forming a metal film on the layer
  • a wiring board comprising: a laminate having the patterned metal film according to (5); and an insulating layer provided on the laminate having the patterned metal film.
  • production of the nodule was suppressed can be provided.
  • the manufacturing method of the laminated body which has a patterned metal film using the laminated body obtained by this manufacturing method, and the laminated body which has a patterned metal film can also be provided.
  • FIG. 1 A) to (D) are schematic cross-sectional views from the substrate to the laminate showing the respective manufacturing steps in order in the method for producing a laminate and a laminate having a patterned metal film of the present invention.
  • FIG. 1 A) to (D) are schematic cross-sectional views sequentially showing one embodiment of the etching process of the laminate of the present invention.
  • (A) to (E) are schematic cross-sectional views sequentially showing other aspects of the etching process of the laminate of the present invention.
  • a feature of the present invention is that a layer to be plated is formed using a specific polymer, and then the layer to be plated is brought into contact with an aqueous alkaline solution containing a predetermined component.
  • the inventors of the present invention diligently studied the problems of the prior art, and found that no uncured portions remaining in the layer to be plated after formation of the layer to be plated by applying energy or components having insufficient surface hardening were nodules. Found to be related to outbreak.
  • the uncured portion or decomposition product flows into the plating solution when the layer to be plated is in contact with the plating solution. It was found that the plating solution was contaminated, resulting in the generation of nodules.
  • the desired layer is formed by washing a layer to be plated formed with a predetermined polymer using an alkaline aqueous solution containing amino alcohol and a surfactant and having a predetermined pH. It was found that the effect can be obtained.
  • the manufacturing method of the laminated body which has a metal film of this invention is equipped with four processes, a to-be-plated layer formation process, an alkaline aqueous solution contact process, a catalyst provision process, and a plating process. Below, the material used at each process and the procedure of each process are explained in full detail.
  • the to-be-plated layer forming step is a composition for forming a to-be-plated layer including a polymer having at least one group selected from the group consisting of a group represented by the formula (X) and a (meth) acrylamide group and an ionic polar group.
  • a step of forming a layer to be plated on the substrate by applying energy to the composition for forming a layer to be plated on the substrate. More specifically, in this step, a substrate 10 is prepared as shown in FIG. 1A, and a layer 12 to be plated is formed on the substrate 10 as shown in FIG.
  • the to-be-plated layer formed by this process adsorbs (attaches) the plating catalyst or its precursor in the catalyst application process described later, depending on the function of the ionic polar group contained in the polymer. That is, the layer to be plated functions as a good receiving layer for the plating catalyst or its precursor.
  • a polymerizable group such as a group represented by the formula (X) and a (meth) acrylamide group is used for bonding between polymers and chemical bonding with a substrate.
  • excellent adhesion appears between the metal film (plating film) formed on the surface of the layer to be plated and the substrate.
  • any conventionally known substrate can be used as long as it has shape retention.
  • the surface has a function which can be chemically bonded with the polymer mentioned later.
  • the substrate itself can form a chemical bond with the polymer by applying energy (for example, exposure), or an intermediate layer on the substrate that can form a chemical bond with the layer to be plated by applying energy.
  • an adhesion auxiliary layer described later may be provided.
  • the material of the substrate is not particularly limited.
  • polymer materials for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polyvinyl acetal, Polyimide, epoxy resin, bismaleimide resin, polyphenylene oxide, liquid crystal polymer, polytetrafluoroethylene, etc.
  • metal material for example, metal alloy, metal-containing material, pure metal, or the like.
  • a mixture of aluminum, zinc, copper and the like, an alloy, or an alloy thereof), other materials eg, paper, paper laminated with plastic), a combination thereof, or the like.
  • the laminate of the present invention can be applied to semiconductor packages, various electric wiring boards and the like.
  • the following substrate containing an insulating resin specifically, a substrate made of an insulating resin (insulating substrate) or a layer made of an insulating resin (insulating resin) It is preferable to use a substrate having a layer) on the surface (substrate with an insulating layer).
  • a known insulating resin composition is used.
  • the insulating resin may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof.
  • the thermosetting resin include an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, a bismaleimide resin, a polyolefin resin, an isocyanate resin, and an ABS resin.
  • epoxy resin examples include cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, biphenol F type epoxy resin, naphthalene type epoxy resin, dicyclo
  • examples thereof include pentadiene type epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, triglycidyl isocyanurate, and alicyclic epoxy resins. These may be used alone or in combination of two or more.
  • thermoplastic resin examples include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and the like.
  • the substrate may have metal wiring on one side or both sides.
  • the metal wiring may be formed in a pattern with respect to the surface of the substrate or may be formed on the entire surface. Typically, those formed by a subtractive method using an etching process and those formed by a semi-additive method using electrolytic plating may be used, and those formed by any method may be used. Examples of the material constituting the metal wiring include copper, silver, tin, palladium, gold, nickel, chromium, tungsten, indium, zinc, and gallium.
  • a substrate having such a metal wiring for example, a double-sided or single-sided copper-clad laminate (CCL) or a copper film of this copper-clad laminate is used as a pattern, and these are flexible substrates.
  • CCL double-sided or single-sided copper-clad laminate
  • a copper film of this copper-clad laminate is used as a pattern, and these are flexible substrates.
  • It may be a rigid substrate.
  • an insulating substrate having a metal wiring layer and an insulating layer in this order on the surface may be used as the substrate of the present invention. In that case, two or more metal wiring layers and insulating layers may be alternately laminated.
  • the substrate may contain various additives as long as the effects of the present invention are not impaired.
  • fillers such as inorganic particles (for example, glass fibers, silica particles, alumina, clay, talc, aluminum hydroxide, calcium carbonate, mica, wollastonite) and silane compounds (for example, silane coupling agents) And silane adhesives), organic fillers (eg, cured epoxy resins, crosslinked benzoguanamine resins, crosslinked acrylic polymers), plasticizers, surfactants, viscosity modifiers, colorants, curing agents, impact strength modifiers, adhesives Examples include a property-imparting agent, an antioxidant, and an ultraviolet absorber.
  • composition for forming a layer to be plated includes a polymer containing a group represented by the formula (X) described later or a (meth) acrylamide group and an ionic polar group.
  • a polymer containing a group represented by the formula (X) described later or a (meth) acrylamide group and an ionic polar group includes a polymer containing a group represented by the formula (X) described later or a (meth) acrylamide group and an ionic polar group.
  • the polymer used in the present invention has at least one group selected from the group consisting of a group represented by the formula (X) and a (meth) acrylamide group and an ionic polar group. First, each group contained will be described in detail.
  • R 12 to R 16 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • the substituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group substituted with a methoxy group, a chlorine atom, a bromine atom, or a fluorine atom.
  • a hydrogen atom is preferable in that the effect of the present invention is more excellent. That is, the group represented by the formula (X) is preferably an allyl group.
  • the group represented by the formula (X) and the (meth) acrylamide group are functional groups capable of forming a chemical bond between polymers or between a polymer and a substrate by applying energy.
  • the layer to be plated formed by applying energy has sufficient resistance (alkali resistance) to an aqueous alkali solution described later.
  • the ionic polar group is a group that interacts with a plating catalyst or a precursor thereof described later, and examples thereof include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a boronic acid group, or a salt thereof.
  • a carboxylic acid group is preferable from the viewpoint of moderate acidity (does not decompose other functional groups).
  • the weight average molecular weight of the polymer is not particularly limited, but is preferably 1000 or more and 700,000 or less, and more preferably 2000 or more and 200,000 or less. In particular, from the viewpoint of polymerization sensitivity, it is preferably 20000 or more. Further, the degree of polymerization of the polymer is not particularly limited, but it is preferable to use a polymer of 10-mer or more, and more preferably a polymer of 20-mer or more. Moreover, 7000-mer or less is preferable, 3000-mer or less is more preferable, 2000-mer or less is still more preferable, 1000-mer or less is especially preferable.
  • a unit having a polymerizable group represented by the following formula (a) (hereinafter, also referred to as a polymerizable group unit as appropriate), and an ionic polarity represented by the following formula (b)
  • a copolymer containing a unit having a group hereinafter also referred to as an ionic polar group unit as appropriate.
  • a unit means a repeating unit.
  • R 1 , R 2 and R 4 each independently represent a hydrogen atom or a methyl group.
  • the methyl group may be substituted with another substituent (for example, a halogen atom).
  • R 3 represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining these.
  • the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. Of these, those having 1 to 10 carbon atoms are preferable.
  • the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
  • X and Y each independently represent a single bond or a substituted or unsubstituted divalent organic group.
  • the divalent organic group include a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a substituted or unsubstituted divalent aromatic hydrocarbon group (preferably having 6 carbon atoms).
  • —O—, —S—, —SO 2 —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof Group for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.
  • the substituted or unsubstituted divalent aliphatic hydrocarbon group for example, an alkylene group
  • a methylene group, an ethylene group, a propylene group, or a butylene group, or these groups are a methoxy group, a chlorine atom, or a bromine atom.
  • substituted or unsubstituted divalent aromatic hydrocarbon group an unsubstituted phenylene group or a phenylene group substituted with a methoxy group, a chlorine atom, a bromine atom, a fluorine atom or the like is preferable.
  • X and Y are preferably a single bond, an ester group (—COO—), an amide group (—CONH—), an ether group (—O—), or a substituted or unsubstituted divalent aromatic hydrocarbon group. More preferred are a single bond, an ester group (—COO—), and an amide group (—CONH—).
  • L 1 and L 2 each independently represent a single bond or a substituted or unsubstituted divalent organic group.
  • L 1 is preferably a single bond, a divalent aliphatic hydrocarbon group, or a divalent organic group having a urethane bond or a urea bond (for example, an aliphatic hydrocarbon group). 9 is preferred.
  • the total number of carbon atoms of L 1 means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L 1. More specifically, the structure of L 1 is preferably a structure represented by the following formula (1-1) or formula (1-2).
  • R a and R b each independently represent two or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom. It is a divalent organic group formed by using.
  • a substituted or unsubstituted alkylene group for example, a methylene group, an ethylene group, a propylene group, or a butylene group
  • an alkyleneoxy group or a polyoxyalkylene group for example, an ethylene oxide group, a diethylene oxide group, a triethylene oxide group
  • Tetraethylene oxide group, dipropylene oxide group, tripropylene oxide group, tetrapropylene oxide group for example, a substituted or unsubstituted alkylene group (for example, a methylene group, an ethylene group, a propylene group, or a butylene group), or an alkyleneoxy group or a polyoxyalkylene group (for example, an ethylene oxide group, a diethylene oxide group, a tri
  • L 2 is preferably a single bond, a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these.
  • the group obtained by combining the alkylene group and the aromatic group may further be via an ether group, an ester group, an amide group, a urethane group, or a urea group.
  • L 2 preferably has a single bond or a total carbon number of 1 to 15, and is particularly preferably unsubstituted.
  • the total number of carbon atoms of L 2 means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L 2.
  • a methylene group an ethylene group, a propylene group, a butylene group, a phenylene group, and those groups substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, etc., The group which combined these is mentioned.
  • W represents an ionic polar group.
  • the definition of this functional group is the same as the above-mentioned definition.
  • a preferred embodiment of the polymerizable group unit represented by the above formula (a) includes a unit represented by the following formula (c).
  • R 1 , R 2 , R 3 , and L 1 are the same as the definition of each group in the unit represented by the formula (a).
  • Z represents an oxygen atom or NR (R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms).
  • L 1 is preferably an unsubstituted alkylene group or a divalent organic group (particularly an alkylene group) having a urethane bond or a urea bond, and has 1 to 9 carbon atoms in total. Those are particularly preferred.
  • W, R 4 and L 2 are the same as the definition of each group in the unit represented by the formula (b).
  • Q represents an oxygen atom or NR ′ (R ′ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms).
  • L 2 in the formula (d) is preferably a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these.
  • the connecting site with the ionic polar group in L 2 is preferably a divalent organic group having a linear, branched, or cyclic alkylene group.
  • the valent organic group preferably has 1 to 10 carbon atoms.
  • the connecting portion between the ionic polar group in L 2 in Formula (d) is preferably a divalent organic group having an aromatic group, among others, of the divalent
  • the organic group preferably has a total carbon number of 6 to 15.
  • W and R 4 are the same as the definition of each group in the unit represented by the formula (b).
  • R 11 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • the substituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group substituted with a methoxy group, a chlorine atom, a bromine atom, or a fluorine atom.
  • R 11 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom.
  • the definitions of R 12 to R 16 are as described above.
  • X 1 each independently represents a single bond, an ester group, an amide group, or a phenylene group.
  • an ester group and an amide group are preferable from the viewpoint of plating properties, and an amide group is preferable from the viewpoint of alkali solution resistance.
  • L 11 represents a single bond or a divalent organic group.
  • a bivalent organic group it is synonymous with the bivalent organic group described by X and Y mentioned above.
  • L 11 is preferably a divalent organic group other than —COO— from the viewpoint of the alkaline solution resistance of the layer to be plated, and further, —O— is 1 from the viewpoint of adhesion of the metal film.
  • One or more aliphatic hydrocarbon groups having 10 to 13 carbon atoms are preferred.
  • the aliphatic hydrocarbon group may be substituted with a polar group such as a hydroxyl group.
  • the polymerizable group unit (specifically, the units represented by the formula (a) and the formula (g)) is preferably contained in an amount of 5 to 50 mol% with respect to all units in the polymer. Preferably, it is 5 to 40 mol%. If it is less than 5 mol%, the reactivity (curability, polymerizability) may be lowered, and if it exceeds 50 mol%, gelation tends to occur during synthesis and synthesis is difficult.
  • the ionic polar group unit is preferably contained in an amount of 5 to 95 mol%, more preferably 10 to 85%, based on the total unit in the polymer, from the viewpoint of adsorptivity to the plating catalyst or its precursor. Mol%.
  • the said polymer may have another functional group in the range which does not impair the effect of this invention other than the group represented by Formula (X), a (meth) acrylamide group, and an ionic polar group.
  • a functional group that interacts with a plating catalyst excluding an ionic polar group or a precursor thereof (hereinafter also referred to as an interactive group as appropriate) can be used.
  • an interactive group a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group or the like that can form a coordination with a plating catalyst or a precursor thereof can be used.
  • Examples of interactive groups include non-dissociable functional groups (functional groups that do not generate protons by dissociation).
  • Examples of interactive groups include amino groups, amide groups, imide groups, urea groups, tertiary amino groups, amidino groups, triazine rings, triazole rings, benzotriazole groups, imidazole groups, benzimidazole groups, quinoline groups, Pyridine group, pyrimidine group, pyrazine group, solooline group, quinoxaline group, purine group, triazine group, piperidine group, piperazine group, pyrrolidine group, pyrazole group, aniline group, group containing alkylamine structure, group containing isocyanuric structure, nitro Group, nitroso group, azo group, diazo group, azide group, cyano group, cyanate group (R—O—CN) and other nitrogen-containing functional groups; ether group, carbonate group, carbonyl group, ester group, N-oxide structure -Containing functional groups, oxygen-containing functional groups such as S-oxide structures; thiophene groups,
  • Equation (Y) the polyoxyalkylene group represented by the following formula
  • V represents an alkylene group and R c represents an alkyl group.
  • n represents a number from 1 to 30. * Represents a bonding position.
  • the alkylene group preferably has 1 to 3 carbon atoms, and specific examples include an ethylene group and a propylene group.
  • the alkyl group preferably has 1 to 10 carbon atoms, and specific examples include a methyl group and an ethyl group.
  • n represents a number of 1 to 30, preferably 3 to 23.
  • n represents an average value, and the numerical value can be measured by a known method (NMR) or the like.
  • the said polymer may contain the unit which has an interactive group represented with a following formula (f).
  • each R 5 independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • the alkyl group preferably has 1 to 2 carbon atoms. Examples of the alkyl group include a methyl group and an ethyl group.
  • U represents a single bond or a substituted or unsubstituted divalent organic group.
  • the definition of a bivalent organic group is synonymous with the divalent organic group represented by X and Y mentioned above.
  • a single bond an ester group (—COO—), an amide group (—CONH—), an ether group (—O—), a substituted or unsubstituted divalent aromatic hydrocarbon group, and the like are preferable.
  • L 3 represents a single bond or a substituted or unsubstituted divalent organic group. Defining divalent organic group has the same meaning as divalent organic group represented by L 1 and L 2 as described above. Among these, L 3 is preferably a divalent aliphatic hydrocarbon group (for example, an alkylene group).
  • V represents a functional group (for example, a cyano group or an ether group) that interacts with a plating catalyst excluding an ionic polar group or a precursor thereof.
  • the content is 10 to 70 mol% with respect to all the units in the polymer from the viewpoint of adsorptivity such as a plating catalyst. Is more preferably 20 to 60 mol%, particularly preferably 30 to 50 mol%.
  • the polymer include, for example, polymers described in paragraphs [0065] to [0070] of JP-A-2006-135271 as a polymer having a radical polymerizable group and an ionic polar group.
  • the polymer having a radically polymerizable group a functional group that interacts with the plating catalyst or its precursor, and an ionic polar group
  • the polymers described in paragraphs [0030] to [0108] of US2010-080964 are used. it can.
  • the method for synthesizing the polymer is not particularly limited, and the monomer used may be a commercially available product or one synthesized by combining known synthesis methods.
  • the above polymer can be synthesized with reference to the methods described in paragraphs [0120] to [0164] of Japanese Patent Publication No. 2009-7662.
  • the content of the polymer in the composition for forming a plating layer is not particularly limited, but is preferably 1 to 50% by mass, more preferably 5 to 30% by mass with respect to the total amount of the composition. If it is in the said range, it is excellent in the handleability of a composition and it is easy to control the layer thickness of a to-be-plated layer.
  • composition for forming a layer to be plated may contain a solvent as necessary.
  • Solvents that can be used are not particularly limited. For example, alcohol solvents such as water, methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerin, propylene glycol monomethyl ether, acids such as acetic acid, ketones such as acetone, methyl ethyl ketone, and cyclohexanone.
  • Solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as methyl acetate and ethyl acetate, carbonate solvents such as dimethyl carbonate and diethyl carbonate Besides these, ether solvents, glycol solvents, amine solvents, thiol solvents, halogen solvents and the like can be mentioned. Of these, amide solvents, ketone solvents, nitrile solvents, and carbonate solvents are preferable.
  • acetone dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, propionitrile, N-methylpyrrolidone, and dimethyl are preferred.
  • Carbonate is preferred.
  • the content of the solvent is preferably 50 to 98% by mass, more preferably 70 to 95% by mass with respect to the total amount of the composition. If it is in the said range, it is excellent in the handleability of a composition and it is easy to control the layer thickness of a to-be-plated layer.
  • additives In the composition for forming a layer to be plated of the present invention, other additives (for example, polymerization initiator, sensitizer, curing agent, polymerization inhibitor, antioxidant, antistatic agent, ultraviolet absorber, filler, particle) Flame retardants, surfactants, lubricants, plasticizers, etc.) may be added as necessary.
  • additives for example, polymerization initiator, sensitizer, curing agent, polymerization inhibitor, antioxidant, antistatic agent, ultraviolet absorber, filler, particle
  • Flame retardants, surfactants, lubricants, plasticizers, etc. may be added as necessary.
  • the method for bringing the composition for forming a plating layer on the substrate into contact with the substrate is not particularly limited, and the method for laminating the composition for forming the plating layer directly on the substrate or the composition for forming the plating layer contains a solvent.
  • a method of applying the composition on a substrate can be used. From the viewpoint of easily controlling the thickness of the obtained layer to be plated, a method of applying the composition on the substrate is preferable.
  • the method of application is not particularly limited, and specific methods include spin coater, dip coater, double roll coater, slit coater, air knife coater, wire bar coater, slide hopper, spray coating, blade coater, doctor coater, squeeze coater, Known methods such as a reverse roll coater, a transfer roll coater, an extrusion coater, a curtain coater, a die coater, a gravure roll coating method, an extrusion coating method, and a roll coating method can be used. From the viewpoint of handleability and production efficiency, the composition for forming a layer to be plated is applied and dried on the substrate (or adhesion auxiliary layer) to remove the remaining solvent to form a composition layer containing a polymer. Embodiments are preferred.
  • the coating amount is 0.1 g / m 2 in terms of solid content from the viewpoint of sufficient interaction formation with a plating catalyst or a precursor thereof described later. 10 g / m 2 is preferable, and 0.5 g / m 2 to 5 g / m 2 is particularly preferable.
  • the remaining solvent may be removed by leaving it at 20 to 40 ° C. for 0.5 to 2 hours between application and drying.
  • the method for applying energy to the composition for forming a layer to be plated on the substrate is not particularly limited, but for example, heating or exposure is preferably used.
  • curing proceeds through a reaction between the polymers or between the polymer and the substrate in the composition for forming a layer to be plated, and a layer to be plated is formed.
  • light irradiation with a UV lamp, visible light, or the like is used.
  • the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
  • the radiation electron beam, X-ray, ion beam, far-infrared ray, g-line, i-line, Deep-UV light, high-density energy beam (laser beam) and the like can be used.
  • Specific examples generally used include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
  • the exposure time varies depending on the reactivity of the polymer and the light source, but is usually between 10 seconds and 5 hours.
  • the exposure energy may be about 10 to 8000 mJ, and is preferably in the range of 100 to 3000 mJ.
  • a blower dryer an oven, an infrared dryer, a heating drum, or the like can be used.
  • the thickness of the layer to be plated is not particularly limited, but is preferably 0.01 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m, from the viewpoint of the adhesion of the metal film to the substrate. Further, preferably 0.05 ⁇ 20g / m 2 in dry film thickness, particularly more preferably 0.1 ⁇ 6g / m 2.
  • the content of the polymer in the layer to be plated is preferably 2 to 100% by mass, and more preferably 10 to 100% by mass with respect to the total amount of the layer to be plated.
  • the pattern when applying energy, may be provided with energy, and then a non-energy-irradiated portion may be removed by a known development process to form a patterned layer to be plated.
  • the alkaline aqueous solution contacting step is a step of removing the uncured portion of the plated layer by bringing the plated layer formed in the above step into contact with an alkaline aqueous solution having a pH of 10 to 14 containing amino alcohol and a surfactant. .
  • contamination of the plating solution described later is suppressed, and generation of nodules is suppressed.
  • the alkaline aqueous solution used in this step contains amino alcohol.
  • the amino alcohol is not particularly limited as long as it is a compound having an amino group and a hydroxyl group.
  • monoethanolamine such as amine, N, N-diethylethanolamine, N, N-dibutylethanolamine and derivatives thereof, diethanolamine such as diethanolamine, N-methyldiethanolamine, N-butyldiethanolamine and derivatives thereof, triethanolamine, hydroxyethyl Examples thereof include piperazine and derivatives thereof.
  • monoethanolamines or diethanolamines are preferable because they are excellent in permeability to the layer to be plated and the generation of nodules is further suppressed.
  • the content of amino alcohol in the alkaline aqueous solution is appropriately selected according to the type used, but is preferably 0.1 to 50% by mass, and preferably 1 to 15% by mass with respect to the total amount of the alkaline aqueous solution. It is more preferable.
  • the alkaline aqueous solution contains a surfactant.
  • a surfactant By including the compound, the permeability of the alkaline aqueous solution is promoted, and the removability of the uncured portion of the plated layer and the component with insufficient curing of the plated layer surface is improved.
  • the type of the surfactant used is not particularly limited, and examples thereof include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.
  • anionic surfactant examples include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl ether sulfate, alkyl or alkenyl ether carboxylate, amino acid type surfactant, N- Examples include acylamino acid type surfactants, alkyl or alkenyl phosphate esters and salts thereof.
  • Nonionic surfactants include, for example, polyoxyalkylene alkyls or alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters, Examples include alkylamine oxide.
  • Examples of the cationic surfactant include alkyl cationic surfactants, amide type quaternary cationic surfactants, ester type quaternary cationic surfactants, and the like.
  • amphoteric surfactants include carboxyl-type amphoteric surfactants and sulfobetaine-type amphoteric surfactants.
  • a nonionic surfactant is preferable at the point which generation
  • the content of the surfactant in the alkaline aqueous solution is appropriately selected according to the type used, but is preferably 0.1 to 10% by mass with respect to the total amount of the alkaline aqueous solution, and 1 to 5% by mass. More preferably.
  • the mass ratio (surfactant content / surfactant content) between the surfactant and amino alcohol in the aqueous alkali solution is preferably 10/1 to 1/5 in that generation of nodules is further suppressed. / 1-1 to 1/1 is more preferable.
  • the pH of the alkaline aqueous solution is 10-14. If it is in the said range, generation
  • Water is usually used as the solvent used in the alkaline aqueous solution.
  • organic solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin and propylene glycol monomethyl ether, acids such as acetic acid, hydroxyacetic acid and aminocarboxylic acid, ketones such as acetone and methyl ethyl ketone
  • Solvent amide solvents such as formamide, dimethylacetamide, N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, carbonate solvents such as dimethyl carbonate and diethyl carbonate, and glycol solvents).
  • the alkaline aqueous solution may contain an inorganic base.
  • the kind in particular is not restrict
  • the content of the inorganic base is preferably adjusted to a range where the pH is in the above range.
  • the contact method of a to-be-plated layer and the said alkaline aqueous solution is not restrict
  • coating alkaline aqueous solution on a to-be-plated layer are mentioned.
  • the contact time between the layer to be plated and the aqueous alkali solution is appropriately selected depending on the type of the alkaline solution used, but is preferably 1 to 60 minutes and more preferably 2 to 20 minutes in terms of productivity and nodule suppression.
  • the liquid temperature of the aqueous alkali solution at the time of contact is not particularly limited, it is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, in terms of more excellent removability of uncured parts and components that are easily decomposed by the electroless plating solution. 60 to 80 ° C is more preferable.
  • the planar shape of the metal film obtained as it is 60 degreeC or more is more excellent.
  • a plating catalyst or a precursor thereof is applied to the layer to be plated from which the uncured product has been removed in the alkaline aqueous solution contact step.
  • the polymer-derived ionic polar group adheres (adsorbs) the applied plating catalyst or its precursor depending on its function.
  • a plating catalyst or a precursor thereof is applied in the layer to be plated and on the surface of the layer to be plated.
  • a plating catalyst or its precursor what functions as a catalyst or an electrode of a plating process in the plating process mentioned later is mentioned.
  • a plating catalyst or its precursor is determined by the kind of plating process in a plating process, it is preferable that it is an electroless-plating catalyst or its precursor.
  • the material (electroless plating catalyst or its precursor etc.) used at this process is explained in full detail, and the procedure of this process is explained in full detail after that.
  • any catalyst can be used as long as it becomes an active nucleus at the time of electroless plating.
  • a metal (Ni) having catalytic ability for autocatalytic reduction reaction. And those known as metals capable of electroless plating with a lower ionization tendency).
  • Specific examples include Pd, Ag, Cu, Ni, Al, Fe, and Co. Of these, Ag and Pd are particularly preferable because of their high catalytic ability.
  • This electroless plating catalyst may be used as a metal colloid.
  • a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be controlled by the surfactant or protective agent used here.
  • the electroless plating catalyst precursor used in this step can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction.
  • the metal ions of the metals mentioned as the electroless plating catalyst are mainly used.
  • the metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction.
  • the metal ion, which is an electroless plating catalyst precursor may be used as an electroless plating catalyst after being applied to the layer to be plated and before being immersed in the electroless plating bath, by separately changing to a zero-valent metal by a reduction reaction.
  • the electroless plating catalyst precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.
  • the metal ion that is the electroless plating catalyst precursor is preferably applied to the layer to be plated using a metal salt.
  • the metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO 3 ) n , MCl n , M 2 / n (SO 4 ), M 3 / n (PO 4 ) (M represents an n-valent metal atom), and the like.
  • a metal ion the thing which said metal salt dissociated can be used suitably. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions. Among them, those capable of multidentate coordination are preferable, and in particular, functionalities capable of coordination. In view of the number of types of groups and catalytic ability, Ag ions and Pd ions are preferred.
  • a palladium compound can be mentioned.
  • This palladium compound acts as a plating catalyst (palladium) or a precursor thereof (palladium ions), which serves as an active nucleus during plating treatment and serves to precipitate a metal.
  • the palladium compound is not particularly limited as long as it contains palladium and acts as a nucleus in the plating process, and examples thereof include a palladium (II) salt, a palladium (0) complex, and a palladium colloid.
  • silver or silver ion is mentioned as another preferable example.
  • silver ions those obtained by dissociating silver compounds as shown below can be suitably used.
  • Specific examples of the silver compound include silver nitrate, silver acetate, silver sulfate, silver carbonate, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, silver chloranilate, silver salicylate, silver diethyldithiocarbamate, Examples thereof include silver diethyldithiocarbamate and silver p-toluenesulfonate.
  • silver nitrate is preferable from the viewpoint of water solubility.
  • a zero-valent metal can also be used as a catalyst used for direct electroplating without performing electroless plating on the layer to be plated.
  • a plating catalyst or its precursor is provided to a to-be-plated layer as a dispersion liquid or a solution (plating catalyst liquid).
  • An organic solvent or water is used as a solvent for the plating catalyst solution.
  • the organic solvent used for the plating catalyst solution is not particularly limited as long as it is a solvent that can penetrate into the layer to be plated. Specifically, acetone, methyl acetoacetate, ethyl acetoacetate, ethylene glycol diacetate, cyclohexanone, Acetylacetone, acetophenone, 2- (1-cyclohexenyl) cyclohexanone, propylene glycol diacetate, triacetin, diethylene glycol diacetate, dioxane, N-methylpyrrolidone, dimethyl carbonate, dimethyl cellosolve, and the like can be used.
  • the method for applying the plating catalyst or its precursor to the layer to be plated is not particularly limited.
  • a plating catalyst solution (a dispersion in which a metal is dispersed in an appropriate dispersion medium, or a solution containing metal ions dissolved in an appropriate solvent and dissociated metal ions) is prepared, and the plating catalyst solution is applied to the layer to be plated.
  • a method of immersing a substrate on which a layer to be plated is formed in a plating catalyst solution.
  • the contact time between the layer to be plated and the plating catalyst solution is preferably about 30 seconds to 24 hours, and more preferably about 1 minute to 1 hour.
  • the temperature of the plating catalyst solution at the time of contact is preferably about 10 to 60 ° C., more preferably about 10 to 30 ° C.
  • the amount of adsorption of the plating catalyst of the layer to be plated or its precursor varies depending on the type of plating bath used, the type of catalytic metal, the type of ionic polar group of the layer to be plated, the method of use, etc. 5 to 1000 mg / m 2 is preferable, 10 to 800 mg / m 2 is more preferable, and 20 to 600 mg / m 2 is particularly preferable.
  • a plating process is a process of performing a plating process with respect to the to-be-plated layer which the plating catalyst obtained by the catalyst provision process or its precursor adsorb
  • electroless plating from the point of the adhesive improvement of a metal film.
  • electrolytic plating is further performed after the electroless plating.
  • the plating suitably performed in this process will be described.
  • Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
  • the electroless plating in this step is performed, for example, by rinsing the substrate provided with the electroless plating catalyst to remove excess electroless plating catalyst (metal) and then immersing it in an electroless plating bath.
  • a known electroless plating bath can be used.
  • the electroless plating bath is preferably an alkaline electroless plating bath (preferably having a pH of about 9 to 14) from the viewpoint of availability.
  • the substrate to which the electroless plating catalyst precursor is applied is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated in the layer to be plated, the substrate is washed with water to remove excess. After removing the precursor (metal salt, etc.), it is immersed in an electroless plating bath. In this case, reduction of the plating catalyst precursor and subsequent electroless plating are performed in the electroless plating bath.
  • the electroless plating bath used here a known electroless plating bath can be used as described above.
  • the reduction of the electroless plating catalyst precursor may be performed as a separate step before electroless plating by preparing a catalyst activation liquid (reducing liquid) separately from the embodiment using the electroless plating liquid as described above.
  • the catalyst activation liquid is a liquid in which a reducing agent capable of reducing an electroless plating catalyst precursor (mainly metal ions) to zero-valent metal is dissolved, and the concentration of the reducing agent with respect to the whole liquid is 0.1 to 50% by mass. Preferably, 1 to 30% by mass is more preferable.
  • the reducing agent it is possible to use a boron-based reducing agent such as sodium borohydride or dimethylamine borane, or a reducing agent such as formaldehyde or hypophosphorous acid. When dipping, keep the concentration of the electroless plating catalyst or its precursor near the surface of the layer to be plated in contact with the electroless plating catalyst or its precursor, and soak it with stirring or shaking. Is preferred.
  • composition of a general electroless plating bath for example, in addition to a solvent (for example, water), 1. 1. metal ions for plating; 2. reducing agent; Additives (stabilizers) that improve the stability of metal ions are mainly included.
  • the plating bath may contain known additives such as a plating bath stabilizer.
  • the organic solvent used in the plating bath needs to be a solvent that can be used in water, and from this point, ketones such as acetone and alcohols such as methanol, ethanol, and isopropanol are preferably used.
  • the types of metals used in the electroless plating bath for example, copper, tin, lead, nickel, gold, silver, palladium, and rhodium are known. Among them, copper and gold are particularly preferable from the viewpoint of conductivity. preferable. Moreover, the optimal reducing agent and additive are selected according to the said metal.
  • the film thickness of the metal film formed by electroless plating can be controlled by the metal ion concentration of the plating bath, the immersion time in the plating bath, or the temperature of the plating bath. From the viewpoint, it is preferably 0.1 ⁇ m or more, and more preferably 0.2 to 2 ⁇ m. However, when performing electroplating to be described later using a metal film formed by electroless plating as a conductive layer, it is preferable that a film of at least 0.1 ⁇ m or more is uniformly applied.
  • the immersion time in the plating bath is preferably about 1 minute to 6 hours, and more preferably about 1 minute to 3 hours.
  • electrolytic plating electrolytic plating (electroplating)
  • the plating catalyst or its precursor applied in the above step has a function as an electrode
  • electrolytic plating can be performed on the layer to be plated to which the catalyst or its precursor is applied. it can.
  • the formed metal film may be used as an electrode, and further electrolytic plating may be performed.
  • a new metal film having an arbitrary thickness can be easily formed on the electroless plating film having excellent adhesion to the substrate.
  • the metal film can be formed to a thickness according to the purpose, which is suitable for applying the metal film to various applications.
  • a conventionally known method can be used as a method of electrolytic plating.
  • the metal used for electrolytic plating include copper, chromium, lead, nickel, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, and silver are preferable, and copper is more preferable. preferable.
  • the film thickness of the metal film obtained by electrolytic plating can be controlled by adjusting the metal concentration contained in the plating bath, the current density, or the like.
  • the thickness of the metal film is preferably 0.5 ⁇ m or more, more preferably 1 to 30 ⁇ m from the viewpoint of conductivity.
  • the laminated body 16 (laminated body with a metal film) provided with the board
  • the obtained laminate 16 can be used in various fields, for example, electric / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical, coal, petroleum, rubber, leather, automobile. It can be used in a wide range of industrial fields such as precision equipment, wood, building materials, civil engineering, furniture, printing and musical instruments.
  • printers personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic notebooks, cards, holders, stationery, etc.
  • Office equipment OA equipment, washing machine, refrigerator, vacuum cleaner, microwave oven, lighting equipment, game machine, iron, kotatsu and other household appliances, TV, VTR, video camera, radio cassette, tape recorder, mini-disc, CD player, speaker , AV equipment such as liquid crystal displays, connectors, relays, capacitors, switches, printed boards, coil bobbins, semiconductor sealing materials, LED sealing materials, electric wires, cables, transformers, deflection yokes, distribution boards, semiconductor chips, various electrical wiring Board, FPC, COF, TAB, 2-layer CCL (Copper Clad Lami nate) materials, electrical wiring materials, multilayer wiring boards, motherboards, antennas, electromagnetic wave prevention films, electrical and electronic parts such as watches, and communication equipment.
  • AV equipment such as liquid crystal displays, connectors, relays, capacitors, switches, printed boards, coil bobbins, semiconductor sealing materials, LED sealing materials, electric wires, cables, transformers, deflection yokes, distribution boards, semiconductor chips, various electrical wiring Board, FPC, COF,
  • the smoothness at the interface between the metal film and the layer to be plated has been improved, for example, ornaments (eyeglass frames, automobile ornaments, jewelry, play enclosures, western dishes, water fittings, lighting fixtures, etc.)
  • ornaments eyeglass frames, automobile ornaments, jewelry, play enclosures, western dishes, water fittings, lighting fixtures, etc.
  • the present invention can be applied to various applications such as applications (for example, for wiring boards and printed wiring boards) that need to ensure high frequency transmission.
  • Pattern formation process As needed, you may implement the process of etching a metal film in pattern shape with respect to the laminated body obtained above, and forming a patterned metal film. More specifically, as shown in FIG. 1D, in this step, a patterned metal film 18 is formed on the plated layer 12 by removing unnecessary portions of the metal film 14. . In this step, a metal film having a desired pattern can be generated by removing unnecessary portions of the metal film formed over the entire substrate surface by etching. Any method can be used to form this pattern. Specifically, a generally known subtractive method (a patterned mask is provided on a metal film and an unformed region of the mask is etched).
  • the mask is removed to form a patterned metal film
  • a semi-additive method (a plating process is performed so that a patterned mask is provided on the metal film, and a metal film is formed in a non-mask formation region) , Removing the mask, and performing an etching process to form a patterned metal film).
  • the subtractive method is to provide a resist layer on the formed metal film, form the same pattern as the metal film pattern part by pattern exposure and development, and use the resist pattern as a mask to form the metal film by etching.
  • This is a method of removing and forming a patterned metal film. Any material can be used as the resist, and negative, positive, liquid, and film-like materials can be used.
  • etching method any method used at the time of manufacturing a printed wiring board can be used, and wet etching, dry etching, and the like can be used, and may be arbitrarily selected. In terms of operation, wet etching is preferable from the viewpoint of simplicity of the apparatus.
  • an etching solution for example, an aqueous solution of cupric chloride, ferric chloride, or the like can be used.
  • FIG. 2 shows an aspect of an etching process using a subtractive method.
  • a laminate including the substrate 10, the insulating resin layer 22, the layer to be plated 12, and the metal film 14 shown in FIG.
  • metal wiring 20 is provided on the surface of the substrate 10 and inside thereof.
  • the insulating resin layer 22 and the metal wiring 20 are components added as necessary.
  • the metal film 14 is provided on one side of the substrate 10, but it may be provided on both sides.
  • a patterned mask 24 is provided on the metal film 14. Thereafter, as shown in FIG.
  • the metal film 14 in the region where the mask is not provided is removed by an etching process (for example, dry etching or wet etching) to obtain a patterned metal film 18.
  • the mask 24 is removed to obtain the laminate of the present invention (see FIG. 2D).
  • the semi-additive method is to provide a resist layer on the formed metal film, form the same pattern as the non-metal film pattern part by pattern exposure and development, perform electroplating using the resist pattern as a mask, This is a method of forming a patterned metal film by performing quick etching after removing the resist pattern and removing the metal film in a pattern.
  • the resist, the etching solution, etc. can use the same material as the subtractive method.
  • the above-described method can be used as the electrolytic plating method.
  • FIG. 3 shows an aspect of an etching process using a semi-additive method.
  • a laminate including the substrate 10 having the metal wiring 20, the insulating resin layer 22, the layer to be plated 12, and the metal film 14 shown in FIG. 3A is prepared.
  • a patterned mask 24 is provided on the metal film 14.
  • electrolytic plating is performed to form a metal film in a region where the mask 24 is not provided, thereby obtaining the metal film 14b. Thereafter, as shown in FIG.
  • the mask 24 is removed, and an etching process (for example, dry etching or wet etching) is performed on the uneven metal film 14b including the protrusions and the recesses.
  • the recess is removed, and a laminate including the patterned metal film 18 is obtained as shown in FIG.
  • the layer to be plated may be removed together by a known means (for example, dry etching).
  • the laminate having the patterned metal film obtained above can be used for various applications.
  • the present invention can be applied to various uses such as semiconductor chips, various electric wiring boards, FPC, COF, TAB, antennas, multilayer wiring boards, and mother boards. Especially, it can utilize suitably as a wiring board.
  • the wiring board including the laminate of the present invention and the insulating layer can form wiring with excellent adhesion to a smooth substrate, has high frequency characteristics, and even between fine wiring, Excellent insulation reliability.
  • the insulating layer a known material can be used, and examples thereof include a known interlayer insulating film and a solder resist layer.
  • the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, and 80 g of raw material A was obtained by distilling off ethyl acetate.
  • 47.4 g of raw material A, 22 g of pyridine, and 150 mL of ethyl acetate were placed in a 500 mL three-necked flask and cooled in an ice bath.
  • 25 g of acrylic acid chloride was added dropwise while adjusting the internal temperature to 20 ° C. or lower. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction.
  • the acid value of the obtained polymer A was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer A was 3 0.9 mmol / g.
  • the obtained polymer A was identified using an IR measuring machine (manufactured by Horiba, Ltd.). The measurement was performed by dissolving the polymer in acetone and using KBr crystals. As a result of IR measurement, a peak was observed in the vicinity of 2240 cm ⁇ 1 and it was found that acrylonitrile, which is a nitrile unit, was introduced into the polymer. Moreover, it was found from the acid value measurement that acrylic acid was introduced as a carboxylic acid unit. Further, it was dissolved in heavy DMSO (dimethyl sulfoxide) and measured by Bruker 300 MHz NMR (AV-300). 4.
  • DMSO dimethyl sulfoxide
  • a peak corresponding to the nitrile group-containing unit is broadly observed at 2.5-0.7 ppm (5H min), and a peak corresponding to the polymerizable group-containing unit is 7.8-8.1 ppm (1H min). 8-5.6 ppm (1H min), 5.4-5.2 ppm (1H min), 4.2-3.9 ppm (2H min), 3.3-3.5 ppm (2H min), 2.5- A broad peak was observed at 0.7 ppm (6 H min), and a peak corresponding to a carboxylic acid group unit was observed broad at 2.5-0.7 ppm (3 H min), and a polymerizable group-containing unit: a nitrile group-containing unit: The carboxylic acid group unit was found to be 25:28:47 (mol ratio).
  • the reaction solution was cooled to room temperature, reprecipitated with hexane / ethyl acetate, the solid matter was taken out, and 5 g of polymer B (weight average molecular weight 12,000) having the following structural formula was obtained.
  • the acid value of the obtained polymer B was measured using a potentiometric automatic titration apparatus (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1M sodium hydroxide aqueous solution as a titrant, the acid value of the polymer B was It was 4.48 mmol / g.
  • the obtained polymer B was dissolved in DMSO, and measurement was performed using an KBr crystal with an IR measuring device (manufactured by Horiba, Ltd.). As a result of IR measurement, no peak was observed in the vicinity of 2240 cm ⁇ 1 , and it was found that the cyano group was not contained in the polymer B. Moreover, it was found from the acid value measurement that acrylic acid was introduced as a carboxylic acid unit. Further, it was dissolved in heavy DMSO (dimethyl sulfoxide) and measured by Bruker 300 MHz NMR (AV-300).
  • the reaction solution was cooled to room temperature, reprecipitated with water, and the solid matter was taken out to obtain 8 g of polymer C (weight average molecular weight 45,000) having the following structural formula.
  • the acid value of the obtained polymer C was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer C was It was 4.31 mmol / g.
  • the obtained polymer C was dissolved in acetone, and measurement was performed using an KBr crystal with an IR measuring machine (manufactured by Horiba, Ltd.). As a result of IR measurement, no peak was observed in the vicinity of 2240 cm ⁇ 1 , and it was found that the cyano group was not contained in the polymer C. Moreover, it was found from the acid value measurement that acrylic acid was introduced as a carboxylic acid unit. Further, it was dissolved in heavy DMSO (dimethyl sulfoxide) and measured by Bruker 300 MHz NMR (AV-300).
  • DMSO dimethyl sulfoxide
  • Example 1 [Preparation of base insulating substrate] An epoxy insulating film (GX-13, 45 ⁇ m) manufactured by Ajinomoto Fine Techno Co. on a glass epoxy substrate (trade name: FR-4, manufactured by Matsushita Electric Works Co., Ltd.) at a pressure of 0.2 MPa. An electrical insulating layer was formed on the substrate by heating and pressing using a vacuum laminator under the condition of 110 ° C. for adhesion. Thereafter, heat treatment was performed at 170 ° C. for 1 hour, and the electrical insulating layer was thermally layered to obtain a substrate A1.
  • GX-13 epoxy insulating film manufactured by Ajinomoto Fine Techno Co. on a glass epoxy substrate (trade name: FR-4, manufactured by Matsushita Electric Works Co., Ltd.) at a pressure of 0.2 MPa.
  • An electrical insulating layer was formed on the substrate by heating and pressing using a vacuum laminator under the condition of 110 ° C. for adhesion. Thereafter, heat
  • a composition for forming a layer to be plated which will be described later, was applied onto the substrate A1 by a spin coating method so as to have a thickness of 1.0 ⁇ m, and then dried at 80 to 120 ° C.
  • the composition layer-forming composition layer on the substrate A1 is irradiated with ultraviolet light having a wavelength of 254 nm at room temperature using an exposure machine (ultraviolet irradiation device, UVX-02516S1LP01, manufactured by USHIO INC.). The whole surface was exposed for minutes (energy amount: 5 J).
  • the substrate with the layer to be plated is immersed in an alkaline aqueous solution A (liquid temperature: 60 ° C., pH: 13.6) having the following composition for 5 minutes. Then, the uncured portion of the layer to be plated was removed by washing.
  • substrate A2 which has board
  • composition for plating layer formation ⁇ Polymer A 3.1g ⁇ Baking soda 2.0g ⁇ Water 24.6g 1-methoxy-2-propanol 12.3 g
  • the substrate A2 was immersed in an aqueous solution containing 0.1% by mass of palladium nitrate for 10 minutes and then washed with distilled water. It was 0.10 g / m ⁇ 2 > when the adsorption amount of the palladium ion at this time was measured with the ICP emission spectrometer (made by Shimadzu Corporation).
  • Electroless plating treatment Substrate A2 after the application of the plating catalyst (metal salt) was immersed in an electroless plating bath (alkaline: pH 12.5) having the following composition for 6 hours to form an electroless copper plating layer having a thickness of 0.4 ⁇ m.
  • Electrolytic plating treatment The substrate on which the electroless copper plating layer was formed was immersed in an electrolytic copper plating bath having the following composition, and electroplating was performed for about 20 minutes under a current density of 3 A / dm 2 .
  • the thickness of the copper plating layer (metal film) after the electrolytic plating was about 18 ⁇ m.
  • the metal film was etched by immersing the substrate on which the resist pattern was formed in an FeCl 2 / HCl aqueous solution (temperature 37 ° C.) to remove the copper plating existing in the resist pattern non-formation region. Thereafter, a 4 mass% NaOH aqueous solution was applied at 50 ° C. and a spray pressure of 2 kg / m 2 for 2 minutes to peel off the resist pattern to obtain a patterned metal film.
  • Solder resist (PFR800; manufactured by Taiyo Ink Mfg. Co., Ltd.) is vacuum-laminated on a laminate having a patterned metal film under the conditions of 110 ° C. and 0.2 MPa, and light of 420 mJ is obtained with an exposure machine having a center wavelength of 365 nm. Irradiated with energy. Next, the substrate was subjected to a heat treatment at 80 ° C./10 minutes, and then developed by applying a NaHCO 3 : 10% aqueous solution to the substrate surface at a spray pressure of 2 kg / m 2 and dried.
  • PFR800 manufactured by Taiyo Ink Mfg. Co., Ltd.
  • the substrate was again irradiated with light energy of 1000 mJ with an exposure machine having a center wavelength of 365 nm. Finally, a heat treatment at 150 ° C./1 hr was performed to obtain a wiring board coated with a solder resist.
  • Example 2 A wiring board was obtained according to the same procedure as in Example 1 except that the temperature of the alkaline aqueous solution was changed to 45 ° C. and the uncured portion of the layer to be plated was washed and removed.
  • Examples 3, 4, and 5> A wiring board was obtained according to the same procedure as in Example 1 except that the types of alcoholamine and surfactant were changed as described in Table 1.
  • the surfactants used were polyoxyethylene polyoxypropylene glycol (manufactured by Kao Corporation, Emulgen PP-290) and sodium laurate (manufactured by Wako Pure Chemical Industries, Ltd.).
  • Example 7 A wiring substrate was obtained according to the same procedure as in Example 1 except that an alkaline aqueous solution C (pH: 13.6) having the following composition was used instead of the alkaline aqueous solution A.
  • Alkaline aqueous solution C 3-aminoethanol 3g ⁇ Poly (oxyethylene) octylphenyl ether 8g (Wako Pure Chemical Industries, Ltd.) ⁇ Sodium hydroxide 2g ⁇ 87 g of water
  • Example 8 Polymer A in the composition for forming a layer to be plated used in [Formation of layer to be plated] is replaced with polymer B, and poly (oxyethylene) octylphenyl ether in an aqueous alkali solution is sorbitan monostearate (Raodol, manufactured by Kao Corporation).
  • a wiring board was obtained according to the same procedure as in Example 1 except that it was replaced with (AS-10V).
  • Example 9 A wiring board was obtained according to the same procedure as in Example 1 except that the polymer A in the composition for forming a layer to be used used in [Forming the layer to be plated] was replaced with the polymer C.
  • Example 2 A wiring board was obtained according to the same procedure as in Example 1 except that an alkaline aqueous solution E (pH: 13.6) was used instead of the alkaline aqueous solution A used in [Plating layer formation].
  • the alkaline aqueous solution E does not contain a surfactant.
  • Example 3 A wiring board was obtained according to the same procedure as in Example 1 except that the alkaline aqueous solution F (pH: 13.6) was used instead of the alkaline aqueous solution A used in [Plating layer formation].
  • the alkaline aqueous solution F does not contain amino alcohol.
  • Example 5 A wiring substrate was obtained according to the same procedure as in Example 1 except that the polymer A in the composition for forming a layer to be used used in [Forming the layer to be plated] was replaced with the comparative polymer 1.
  • pH means the pH of the alkaline aqueous solution used.
  • the surface shape of the metal film in the obtained laminate was excellent.
  • the surface shape of the metal film was more excellent when the temperature of the alkaline aqueous solution used was 60 ° C. or higher.
  • the surface shape of a metal film is more excellent when monoethanolamine is used as alcoholamine to be used.
  • the planar shape of a metal film is more excellent. Except for nonionic surfactants, it is presumed that they are easily adsorbed by the layer to be plated and easily flow out into the plating solution.
  • Example 1 and 6 it was confirmed that the surface shape of a metal film is more excellent when pH of alkaline aqueous solution is higher (especially pH12 or more). Further, from comparison between Examples 1 and 7, it was confirmed that the surface shape of the metal film was better when the content of the surfactant was in the range of 1 to 5% by mass. It is presumed that if the amount of the surfactant is too large, the outflow into the plating solution increases.
  • Comparative Examples 1 to 3 the desired effect was not obtained when the alcohol amine or the surfactant was not contained in the alkaline aqueous solution. Further, as shown in Comparative Example 4, the desired effect could not be obtained unless the pH of the alkaline aqueous solution was within the predetermined range. Furthermore, as shown in Comparative Example 5, when a polymer having no predetermined functional group was used, the film thickness of the plated layer was large after contact with the alkaline aqueous solution, and the surface state of the resulting metal film was also inferior.
  • Substrate 12 Plated layers 14, 14b: Metal film 16: Laminate 18: Patterned metal film 20: Metal wiring 22: Insulating resin layer 24: Mask

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Abstract

La présente invention a pour objet un procédé de fabrication d'un stratifié à film métallique, le procédé étant conçu pour empêcher la formation de nodules. Un tel procédé de fabrication comprend : une étape de formation d'une couche cible de placage au cours de laquelle une composition de formation d'une couche cible de placage comportant un polymère contenant un groupe fonctionnel prescrit est utilisée pour former une couche cible de placage sur un substrat ; une étape de mise en contact d'une solution aqueuse alcaline au cours de laquelle une solution aqueuse alcaline contenant un composant prescrit est mise en contact avec la couche cible de placage ; une étape d'application d'un catalyseur au cours de laquelle un catalyseur de placage ou un précurseur associé est appliqué à la couche cible de placage dont des parties non durcies ont été retirées ; et une étape de placage au cours de laquelle il est réalisé un placage permettant de former un film métallique sur la couche cible de placage.
PCT/JP2012/057739 2011-03-29 2012-03-26 Stratifié à film métallique et son procédé de fabrication, stratifié à film métallique texturé et son procédé de fabrication WO2012133297A1 (fr)

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KR102144643B1 (ko) * 2016-08-19 2020-08-13 후지필름 가부시키가이샤 피도금층 형성용 조성물, 피도금층, 피도금층 부착 기판, 도전성 필름, 터치 패널 센서, 터치 패널

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JP2009280905A (ja) * 2008-04-23 2009-12-03 Fujifilm Corp めっき用積層フィルム、表面金属膜材料の作製方法及び表面金属膜材料
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JP2010229536A (ja) * 2009-03-30 2010-10-14 Nippon Mining & Metals Co Ltd 無電解めっき前処理剤及びこれを用いた無電解めっき前処理方法
JP2010239080A (ja) * 2009-03-31 2010-10-21 Fujifilm Corp 導電膜の形成方法、プリント配線板の製造方法及び導電膜材料

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Publication number Priority date Publication date Assignee Title
JP2019196421A (ja) * 2018-05-07 2019-11-14 株式会社日本触媒 光学材料用樹脂組成物及びその用途
JP7160554B2 (ja) 2018-05-07 2022-10-25 株式会社日本触媒 光学材料用樹脂組成物及びその用途

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