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WO2011118797A1 - Composition permettant de former une couche de placage, matériau de film métallique de surface et procédé de fabrication de ce dernier ainsi que matériau de motif métallique et procédé de fabrication de dernier - Google Patents

Composition permettant de former une couche de placage, matériau de film métallique de surface et procédé de fabrication de ce dernier ainsi que matériau de motif métallique et procédé de fabrication de dernier Download PDF

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Publication number
WO2011118797A1
WO2011118797A1 PCT/JP2011/057417 JP2011057417W WO2011118797A1 WO 2011118797 A1 WO2011118797 A1 WO 2011118797A1 JP 2011057417 W JP2011057417 W JP 2011057417W WO 2011118797 A1 WO2011118797 A1 WO 2011118797A1
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WO
WIPO (PCT)
Prior art keywords
group
layer
polymer
substrate
plating
Prior art date
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Ceased
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PCT/JP2011/057417
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English (en)
Japanese (ja)
Inventor
季彦 松村
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Fujifilm Corp
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Fujifilm Corp
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Publication of WO2011118797A1 publication Critical patent/WO2011118797A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C23C18/1601—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
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • 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
    • 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
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment

Definitions

  • the present invention relates to a composition for forming a layer to be plated, a surface metal film material and a manufacturing method thereof, and a metal pattern material and a manufacturing method thereof. More specifically, a composition for forming a layer to be plated containing a polymer having a predetermined type of functional group, a surface metal film material and a metal pattern material obtained by using the composition for forming a layer to be plated, and production thereof Regarding the method.
  • 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.
  • the adhesion between the substrate and the metal film is expressed by an anchor effect generated by providing irregularities on the substrate surface. For this reason, there is a problem that the high frequency characteristics when used as a metal wiring are deteriorated due to unevenness of the obtained metal pattern on the substrate interface.
  • a viscoelastic resin composition containing glycidyl methacrylate, a synthetic rubber having specific physical properties, and a curable component has been proposed (for example, Patent Document 1).
  • This resin composition has flexible properties and is useful as an interlayer insulating film.
  • sufficient adhesion cannot be achieved without surface roughening treatment. Roughening is necessary and is insufficient for forming fine wiring.
  • the adhesion between the substrate or the insulating resin film and the wiring pattern becomes a problem.
  • a polyimide varnish layer that is an insulating resin is formed on a copper foil and a resin film with a metal layer is formed by a thermal reaction
  • the adhesion is due to the adhesion between the copper foil layer and the polyimide varnish layer.
  • the surface of the copper foil is processed to have unevenness and the adhesion effect is exhibited by the anchor effect.
  • the method of forming copper on polyimide by sputtering has a problem in that sufficient adhesion cannot be obtained, and a vacuum apparatus is required and the film formation rate is low, resulting in high costs.
  • Non-Patent Document 1 a method for improving the adhesion between the substrate and the metal film without roughening the surface of the substrate has been proposed (see, for example, Non-Patent Document 1).
  • the graft polymer has a polar group, moisture absorption and desorption are likely to occur due to temperature and humidity changes, and as a result, the formed metal film and substrate are deformed. Had.
  • a metal pattern obtained by using this method is used as a wiring of a metal wiring board
  • a graft polymer having a polar group remains at the interface portion of the board, and moisture, ions, etc. are easily retained.
  • high insulation between wirings (metal patterns) is required, and there is a demand for further improvement in insulation reliability between wirings. It is.
  • the present invention has been made in view of the above-mentioned drawbacks of the prior art, and an object thereof is to achieve the following object. That is, the first object of the present invention is to provide a composition for forming a layer to be plated that can achieve high adhesion with a plating film (metal film) formed on the surface and can form a polymer layer having excellent insulation reliability. And providing a laminate having a polymer layer obtained by using the composition.
  • the second object of the present invention is to provide a surface metal film material having excellent adhesion between the polymer layer and the metal film, a method for producing the same, and an insulation reliability in a non-formed region of the metal pattern using the material. Another object is to provide a metal pattern material.
  • a third object of the present invention is to provide a wiring board that has excellent adhesion to the insulating resin of the wiring, and excellent insulation reliability between the wirings even if the wiring is fine.
  • ⁇ 1> a radical polymerizable group; A non-dissociative functional group that interacts with the plating catalyst or its precursor; A composition for forming a layer to be plated, comprising a polymer containing an epoxy group, an oxetanyl group, an isocyanate group, a blocked isocyanate group, a primary amino group, and at least one functional group selected from the group consisting of secondary amino groups.
  • the polymer is a polymer including a unit represented by formula (1) described later, a unit represented by formula (2) described later, and a unit represented by formula (3) described below.
  • ⁇ 4> A laminate having a substrate and a polymer layer formed from the composition for forming a layer to be plated according to any one of ⁇ 1> to ⁇ 3> on the substrate.
  • ⁇ 5> (a1) forming a polymer layer on the substrate using the composition for forming a plated layer according to any one of ⁇ 1> to ⁇ 3>; (A2) providing a plating catalyst or a precursor thereof to the polymer layer; (A3) a step of plating the plating catalyst or a precursor thereof; The manufacturing method of the surface metal film material which has a plating film on the surface provided with.
  • ⁇ 6> The method for producing a surface metal film material according to ⁇ 5>, wherein the step (a1) is performed by directly chemically bonding the polymer in the polymer layer on a substrate.
  • ⁇ 7> The method for producing a surface metal film material according to ⁇ 5> or ⁇ 6>, wherein electroless plating is performed in the step (a3).
  • ⁇ 8> A surface metal film material obtained by the method for producing a surface metal film material according to any one of ⁇ 5> to ⁇ 7>.
  • ⁇ 9> Manufacture of a metal pattern material having a step of etching a plating film of a surface metal film material obtained by the method for manufacturing a surface metal film material according to any one of ⁇ 5> to ⁇ 7> Method.
  • ⁇ 10> A metal pattern material obtained by the method for producing a metal pattern material according to ⁇ 9>.
  • ⁇ 11> A wiring board comprising the metal pattern material according to ⁇ 10> and an insulating layer containing an epoxy resin on the metal pattern material.
  • the composition for to-be-plated layer formation which can achieve the high adhesiveness with the plating film formed on the surface, and can form the polymer layer excellent in insulation reliability And a laminate having a polymer layer formed from the composition.
  • a surface metal film material having excellent adhesion between the polymer layer and the metal film, a manufacturing method thereof, and a metal pattern having excellent insulation reliability in a non-formation region of the metal pattern using the material. Material can be provided.
  • the composition for forming a layer to be plated of the present invention, the surface metal film material obtained using the composition and the production method thereof, the metal pattern material and the production method thereof will be described below.
  • a polymer having a predetermined functional group such as an epoxy group
  • a plated film having excellent adhesion, a metal pattern having excellent insulation reliability between wirings, and the like can be obtained.
  • the present inventors as one of the causes of insufficient insulation reliability between metal wirings in the prior art, a metal wiring board and a metal It has been found that the adhesiveness with an insulating layer formed of an epoxy resin or the like covering the wiring is not always sufficient.
  • the polymer used in the present invention includes a radical polymerizable group, a non-dissociable functional group that interacts with the plating catalyst or its precursor, an epoxy group, an oxetanyl group, an isocyanate group, a blocked isocyanate group, and a primary amino group. , And at least one functional group selected from the group consisting of secondary amino groups (hereinafter also referred to as “specific functional group”).
  • the polymer used in the present invention contains a radically polymerizable group. By having such a group, excellent adhesion to the substrate described later is exhibited, and a film having excellent strength can be obtained by a crosslinking reaction in the film.
  • the kind in particular of radically polymerizable group is not restrict
  • a methacrylic acid ester group (methacryloyloxy group), an acrylic acid ester group (acryloyloxy group), a vinyl group, and a styryl group are preferable, and an acryloyl group and a methacryloyl group are particularly preferable.
  • Non-dissociative functional group that interacts with the plating catalyst or its precursor includes a non-dissociative functional group that forms an interaction with a plating catalyst or a precursor thereof described later. By including this group, excellent adsorptivity such as a plating catalyst described later is achieved, and as a result, a plating film having a sufficient thickness can be obtained during the plating process.
  • the non-dissociable functional group means a functional group in which the functional group does not generate a proton by dissociation.
  • a functional group has a function of interacting with a plating catalyst or a precursor thereof, or a metal, but does not have high water absorption and hydrophilicity like a dissociative polar group (hydrophilic group). Therefore, there is little variation in the adhesion of the plating layer due to changes in humidity.
  • the non-dissociable functional group is preferably a group capable of forming a coordination with a metal ion, a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group, a phosphorus-containing functional group, or the like.
  • imide group pyridine group, tertiary amino group, ammonium group, pyrrolidone group, amidino group, group containing triazine ring structure, group containing isocyanuric structure, nitro group, nitroso group, azo group, diazo group
  • a nitrogen-containing functional group such as azide group, cyano group, cyanate group (R—O—CN), ether group, carbonyl group, ester group, group containing N-oxide structure, group containing S-oxide structure, etc.
  • Phosphorus-containing functional groups such as sulfur-containing functional groups, phosphine groups, phosphate groups and phosphoramide groups, and halogens such as chlorine and bromine Group including children, and an unsaturated ethylene group.
  • an imidazole group, a urea group, or a thiourea group may be used as long as it is non-dissociative due to the relationship with an adjacent atom or atomic group.
  • it may be a functional group derived from a compound having an inclusion ability such as cyclodextrin and crown ether.
  • an ether group more specifically, —O— (CH 2 ) n —O— (n is an integer of 1 to 13). Structure
  • a cyano group is particularly preferable, and a cyano group is more preferable.
  • the higher the polarity the higher the water absorption rate.
  • the cyano groups interact in the polymer layer so as to cancel each other's polarity, the layer becomes dense and the entire polymer layer Therefore, the water absorption is lowered.
  • the cyano group is solvated, the interaction between the cyano groups is eliminated, and the plating catalyst can interact. Therefore, a polymer layer having a cyano group is preferable in that it exhibits low performance while exhibiting contradictory performance that interacts well with the plating catalyst.
  • the non-dissociative functional group may be contained only 1 type, and 2 or more types of different types of functional groups may be contained.
  • the polymer used in the present invention contains at least one functional group (specific functional group) selected from the group consisting of epoxy groups, oxetanyl groups, isocyanate groups, blocked isocyanate groups, primary amino groups, and secondary amino groups. Is done.
  • the functional group selected from the group consisting of epoxy groups, oxetanyl groups, isocyanate groups, blocked isocyanate groups, primary amino groups, and secondary amino groups.
  • the specific functional group is an epoxy group, an oxetanyl group, an isocyanate group, a blocked isocyanate group, a primary amino group, or a secondary amino group. From the viewpoint of better adhesion to the epoxy resin-containing insulating layer and the point of water absorption An epoxy group and an oxetanyl group are more preferable.
  • the group may be included in the polymer alone or two or more groups may be included.
  • a unit having a radically polymerizable group (repeating unit), a unit having a non-dissociative functional group, and a unit having a radically polymerizable group from the viewpoint of easy synthesis and better adhesion to a substrate
  • a copolymer (a ternary polymer) including a unit having a specific functional group is preferable.
  • a polymer (copolymer) containing a unit represented by the formula (1), a unit represented by the formula (2), and a unit represented by the formula (3) can be given.
  • R 1 to R 4 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • R 1 to R 4 are a substituted or unsubstituted alkyl group
  • an alkyl group having 1 to 4 carbon atoms is preferable, and an alkyl group having 1 to 2 carbon atoms is more preferable.
  • examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group
  • examples of the substituted alkyl group include a methoxy group, a hydroxy group, and a halogen atom (for example, a chlorine atom).
  • a bromine atom, a fluorine atom) and the like and a methyl group, an ethyl group, a propyl group, and a butyl group.
  • R 1 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
  • R 2 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
  • R 3 is preferably a hydrogen atom.
  • R 4 is preferably a hydrogen atom.
  • Y and Z 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).
  • the organic group may have a substituent such as a hydroxy group as long as the effects of the invention are not impaired.
  • Examples of the substituted or unsubstituted divalent aliphatic hydrocarbon group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, or a methoxy group, a hydroxy group, and a halogen atom (for example, , Chlorine atom, bromine atom, fluorine atom) and the like.
  • substituted or unsubstituted divalent aromatic hydrocarbon group phenylene substituted with an unsubstituted phenylene group, a methoxy group, a hydroxy group, a halogen atom (for example, a chlorine atom, a bromine atom, or a fluorine atom) Groups are preferred.
  • Y and Z are preferably an ester group (—COO—), an amide group (—CONH—), an ether group (—O—), or a substituted or unsubstituted divalent aromatic hydrocarbon group.
  • L 1 represents a substituted or unsubstituted divalent organic group.
  • the definition of the divalent organic group is synonymous with the organic group represented by the above Y and Z, for example, a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic A hydrocarbon group, —O—, —S—, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof. It is done.
  • L 1 is preferably an unsubstituted alkylene group or a divalent organic group having a urethane bond or urea bond, more preferably an unsubstituted alkylene group or a divalent organic group having a urethane bond, and the total number of carbon atoms. Those having 1 to 9 are particularly 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 Formula (1-1) or Formula (1-2).
  • R a and R b each independently use two or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom Is a divalent organic group formed.
  • a preferred embodiment of the unit represented by the formula (1) is a unit represented by the formula (4).
  • R 1 , R 2 , Z and L 1 are the same as the definitions of each group in the unit represented by the formula (1).
  • T 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).
  • a preferred embodiment of the unit represented by formula (4) is a unit represented by formula (5).
  • R 1 , R 2 , and L 1 are the same as the definitions of each group in the unit represented by formula (1).
  • T and Q each 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).
  • T and Q are preferably oxygen atoms.
  • L 1 is preferably an unsubstituted alkylene group or a divalent organic group having a urethane bond or a urea bond, and a divalent organic group having a urethane bond. Are more preferable, and those having 1 to 9 carbon atoms are particularly preferable.
  • R 5 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • the substituted or unsubstituted alkyl group represented by R 5 has the same meaning as the substituted or unsubstituted alkyl group represented by R 1 to R 4 described above.
  • R 5 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
  • X and L 2 each independently represents a single bond or a substituted or unsubstituted divalent organic group.
  • the definition of the divalent organic group is synonymous with the divalent organic group represented by Z and Y described above, for example, a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent group.
  • Aromatic hydrocarbon group —O—, —S—, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof Etc.
  • X preferably includes a single bond, an ester group (—COO—), an amide group (—CONH—), an ether group (—O—), or a substituted or unsubstituted divalent aromatic hydrocarbon group. And more preferably a single bond, an ester group (—COO—), or an amide group (—CONH—).
  • L 2 is preferably 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 1 to 15 total carbon atoms, and 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.
  • a preferred embodiment of the unit represented by the formula (2) is a unit represented by the formula (6).
  • R ⁇ 5 > and L ⁇ 2 > are the same as the definition of each group in the unit represented by Formula (2).
  • U 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 Formula (6) is preferably a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these.
  • the linking site with the cyano group in L 2 is preferably a divalent organic group having a linear, branched, or cyclic alkylene group.
  • the organic group preferably has a total carbon number of 1 to 10.
  • it is preferable that the linkage site to the cyano group in L 2 in Formula (6) is a divalent organic group having an aromatic group, and among them, the divalent organic group
  • the total number of carbon atoms is preferably 6 to 15.
  • R 6 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • R 6 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
  • L 3 represents a substituted or unsubstituted divalent organic group.
  • the definition of the divalent organic group represented by L 3 is synonymous with the divalent organic group represented by Z and Y.
  • L 3 is preferably an alkylene group.
  • W represents a single bond or a substituted or unsubstituted divalent organic group.
  • the definition of the divalent organic group represented by W is synonymous with the divalent organic group represented by Z and Y.
  • Preferred examples of W include an ester group (—COO—), an amide group (—CONH—), an ether group (—O—), or a substituted or unsubstituted divalent aromatic hydrocarbon group.
  • V represents an epoxy group, an oxetanyl group, an isocyanate group (—NCO), a blocked isocyanate group, a primary amino group (—NH 2 ), or a secondary amino group.
  • an epoxy group, an oxetanyl group, and a blocked isocyanate group are preferable.
  • the oxetanyl group a group represented by the formula (8) is preferable.
  • R C represents a hydrogen atom or an alkyl group.
  • the secondary amino group is preferably a group represented by —NHR d (R d represents an alkyl group, preferably having 1 to 8 carbon atoms).
  • an epoxy group an alicyclic epoxy group is also included.
  • the blocked isocyanate group as used herein refers to a group in which an isocyanate group is blocked with a protective group and can be easily removed by heat or moisture to generate an isocyanate group.
  • an isocyanate group blocked with a blocking agent such as alcohols, phenols, oximes, triazoles and caprolactams is preferred.
  • Alcohols include methanol, ethanol, propanol, hexanol, lauryl alcohol, t-butanol, cyclohexanol and the like.
  • phenols include xylenol, naphthol, 4-methyl-2,6-di-t-butylphenol and the like.
  • oximes include 2,6-dimethyl-4-heptanone oxime, methyl ethyl ketoxime, 2-heptanone oxime and the like.
  • 3,5-dimethylpyrazole, 1,2,4-triazole and the like can be preferably used.
  • methyl ethyl ketoxime and 3,5-dimethylpyrazole are preferable as the blocking agent.
  • a monomer having a blocked isocyanate group Karenz MOI-BM (trade name: Showa Denko Co., Ltd.), Karenz MOI-BP (trade name: Showa Denko Co., Ltd.), etc. are commercially available and can be suitably used. it can.
  • a preferred embodiment of the unit represented by formula (3) is a unit represented by formula (7).
  • V, R ⁇ 6 > and L ⁇ 3 > are the same as the definition of each group in the unit represented by Formula (3).
  • 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).
  • the content of the unit represented by the formula (1) in the polymer is not particularly limited, but it is 5 to 50 mol% with respect to all units (100 mol%) in terms of better adhesion to the substrate described later. Is preferable, and 5 to 40 mol% is more preferable. When the amount is less than 5 mol%, the reactivity (curability and polymerizability) may be lowered. When the amount exceeds 50 mol%, gelation tends to occur during the synthesis of the polymer, and the control of the reaction becomes difficult.
  • the content of the unit represented by the formula (2) in the polymer is not particularly limited, but is preferably 5 to 94 mol% with respect to all units (100 mol%) in terms of adsorptivity to the plating catalyst and the like. 10 to 80 mol% is more preferable.
  • the content of the unit represented by the formula (3) in the polymer is not particularly limited, but is 1 to 50 mol with respect to all units (100 mol%) in terms of better adhesion to the insulating layer described later. % Is preferable, and 5 to 30 mol% is more preferable.
  • the weight average molecular weight of the polymer of this invention is not specifically limited, 1000 or more and 700,000 or less are preferable, More preferably, it is 2000 or more and 200,000 or less. In particular, from the viewpoint of polymerization sensitivity, the weight average molecular weight of the polymer of the present invention is preferably 20000 or more. Moreover, as a polymerization degree of the polymer of this invention, it is preferable to use a 10-mer or more thing, More preferably, it is a 20-mer or more thing. 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.
  • 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 polymer of the present invention can be synthesized with reference to the method described in paragraphs [0120] to [0164] of Japanese Patent Application Publication No. 2009-7762.
  • the following methods are preferably exemplified.
  • a monomer having a radical polymerizable group a monomer having a non-dissociative functional group, and a method of copolymerizing a monomer having a specific functional group
  • a monomer having a non-dissociative functional group a monomer having a specific functional group
  • a method of copolymerizing a monomer having a radical polymerizable group precursor and then introducing a radical polymerizable group by treatment with a base or the like iii) a monomer having a non-dissociable functional group, a monomer having a specific functional group, and Examples thereof include a method in which a monomer having a reactive group for introducing a radical polymerizable group is copolymerized to introduce a radical polymerizable group.
  • the kind of polymerization reaction at the time of synthesis is not particularly limited, and it is preferably carried out by radical polymerization.
  • the monomer used in the above may be a commercially available product or a known substance. For example, as a monomer having a non-dissociable functional group, paragraphs [0081] to [0084] of JP-A-2009-7662. And the like.
  • A is an organic group having a polymerizable group
  • R 1 to R 3 are each independently a hydrogen atom or a monovalent organic group
  • B and C are each independently removed by elimination reaction.
  • One of A and B is a hydrogen atom, and the other represents a halogen atom, a sulfonate group, an ether group, or a thioether group.
  • the elimination reaction here means that C is extracted by the action of a base and B is eliminated.
  • B is preferably eliminated as an anion and C as a cation.
  • Preferred examples of the base include alkali metal hydrides, hydroxides or carbonates, organic amine compounds, and metal alkoxide compounds.
  • examples of the monomer having a reactive group for introducing a radical polymerizable group include monomers having a carboxyl group, a hydroxyl group, an epoxy group, or an isocyanate group as the reactive group.
  • the polymer having a hydroxyl group in the side chain and, using a compound having an isocyanate group and a radical polymerizable, L in 1 by adding the isocyanate groups to the hydroxyl groups It is preferable to form a urethane bond.
  • Examples of the monomer having a non-dissociable functional group include cyanomethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, 3-cyanopropyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, and 1-cyanoethyl (meta). ) Acrylate and the like.
  • polymer in the present invention are shown below, but are not limited thereto.
  • the weight average molecular weights of these specific examples are all in the range of 3000 to 150,000.
  • composition for forming a layer to be plated of the present invention contains the polymer.
  • the content of the polymer in the composition for forming a layer to be plated is not particularly limited, but is preferably 2 to 50% by mass and more preferably 5 to 30% by mass with respect to the total amount of the composition. If it is in the said range, the handleability of a composition will be excellent and it will be easy to control the layer thickness of the polymer layer mentioned later.
  • the composition for forming a plated layer of the present invention may contain a solvent in addition to the polymer.
  • solvents that can be used include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, and propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, formamide, dimethylacetamide, Amide solvents such as N-methylpyrrolidone, nitrile solvents such as acetonitrile and propyronitrile, ester solvents such as methyl acetate and ethyl acetate, carbonate solvents such as dimethyl carbonate and diethyl carbonate, and other ether solvents A solvent, a glycol solvent, an amine solvent, a thiol solvent, a halogen solvent, etc.
  • amide solvents amide solvents, ketone solvents, nitrile solvents, and carbonate solvents are preferable. Specifically, acetone, dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, propionitrile, N-methylpyrrolidone, and dimethyl carbonate are preferable. .
  • a solvent having a boiling point of 50 to 150 ° C. for ease of handling.
  • these solvents may be used alone or in combination.
  • the composition may include a surfactant, a plasticizer, a polymerization inhibitor, a curing agent / curing accelerator, a flame retardant (for example, a phosphorus flame retardant), a diluent as necessary.
  • a surfactant for example, a phosphorus flame retardant
  • a plasticizer for example, a polymerization inhibitor
  • a curing agent / curing accelerator for example, a phosphorus flame retardant
  • a flame retardant for example, a phosphorus flame retardant
  • a diluent for example, a phosphorus flame retardant
  • thixotropic agents, pigments, antifoaming agents, leveling agents, coupling agents and the like may be added.
  • the composition can be contacted in a liquid state by any method.
  • the coating amount when the polymer layer is formed by the coating method is 0.1 g / m in terms of solid content from the viewpoint of sufficient interaction with the plating catalyst or its precursor and the point of obtaining a uniform coating film. 2 to 10 g / m 2 is preferable, and 0.5 g / m 2 to 5 g / m 2 is particularly preferable.
  • the composition for forming a plated layer of the present invention is useful for forming a receiving layer of a plated metal on an arbitrary solid surface. Therefore, a laminate comprising a polymer layer formed using the composition for forming a layer to be plated of the present invention on an arbitrary substrate is useful for forming a plating film with good adhesion on the substrate.
  • the method for producing the surface metal film material of the present invention is not particularly limited, but it is preferably produced through the following steps (a1) to (a3).
  • (A1) a step of forming a polymer layer (layer to be plated) on the substrate using the composition for forming a layer to be plated
  • (a2) a step of applying a plating catalyst or a precursor thereof to the polymer layer
  • the step (a1) is preferably performed by directly chemically bonding the above-described polymer on the substrate.
  • the plating step in the step (a3) is an electroless plating step.
  • each step will be described.
  • the step (a1) is a step of producing a polymer layer on the substrate using the above composition, and includes a non-dissociative functional group, a radical polymerizable group, and a specific that form an interaction with the plating catalyst or its precursor. It is preferably carried out by directly chemically bonding a polymer having a functional group to the substrate surface. By this step, a laminate having a polymer layer on the substrate can be obtained.
  • a substrate on which a polymerization initiator layer containing a polymerization initiator or having a functional group capable of initiating polymerization is formed on a base material (a1-1)
  • it is a step of forming a polymer layer made of the polymer.
  • the polymer is directly bonded to the substrate surface by applying energy after bringing the polymer into contact with the polymerization initiation layer (or adhesion auxiliary layer). It is preferable that it is a process.
  • energy may be provided to the composition on a board
  • Graft polymerization is a method of synthesizing a graft (grafting) polymer by providing an active species on a polymer compound chain, thereby further polymerizing another monomer that initiates polymerization.
  • graft polymerization is a method of synthesizing a graft (grafting) polymer by providing an active species on a polymer compound chain, thereby further polymerizing another monomer that initiates polymerization.
  • surface graft polymerization when a polymer compound that gives active species forms a solid surface, this is called surface graft polymerization.
  • any known method described in the literature can be used as the surface graft polymerization method applied to the present invention.
  • New Polymer Experimental Science 10, edited by Polymer Society, 1994, published by Kyoritsu Shuppan Co., Ltd., p135 describes a photograft polymerization method and a plasma irradiation graft polymerization method as surface graft polymerization methods.
  • NTS Co., Ltd. supervised by Takeuchi, 1999.2, p203, p695, radiation-induced graft polymerization methods such as ⁇ rays and electron beams are described.
  • methods described in JP-A-63-92658, JP-A-10-296895, and JP-A-11-119413 can be used.
  • reactive functional groups such as trialkoxysilyl groups, isocyanate groups, amino groups, hydroxyl groups, and carboxyl groups are added to the ends of the polymer compound chains.
  • a method of coupling by a coupling reaction between this and a functional group present on the substrate surface can be applied.
  • the “substrate” preferably has a surface capable of forming a state in which a polymer having a functional group that interacts with a plating catalyst or a precursor thereof is directly chemically bonded.
  • the surface layer may have such surface characteristics, or an intermediate layer (for example, a polymerization initiation layer or an adhesion auxiliary layer described later) may be separately provided on the substrate, and the intermediate layer may have such characteristics. It may be. That is, you may form the board
  • the substrate used in the present invention is preferably a dimensionally stable plate, for example, paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), metal plate (for example, , Aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, polyimide) , Epoxy, bismaleimide resin, polyphenylene oxide, liquid crystal polymer, polytetrafluoroethylene, etc.), and paper or plastic film on which a metal as described above is laminated or vapor-deposited.
  • plastic for example, polyethylene, polypropylene, polystyrene, etc.
  • metal plate for example, Aluminum, zinc, copper, etc.
  • plastic film eg, cellulose di
  • an epoxy resin or a polyimide resin is preferable.
  • the base material surface has a function capable of forming a state in which the polymer is directly chemically bonded
  • the base material itself may be used as a substrate.
  • a substrate containing a polyimide having a polymerization initiation site in the skeleton described in paragraphs [0028] to [0088] of JP-A-2005-281350 can also be used.
  • the metal pattern material obtained by the method for producing a metal pattern material 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 (substrate with an insulating resin layer) having a layer) on a base material.
  • a known insulating resin composition When obtaining a substrate made of an insulating resin or a layer made of an insulating resin, a known insulating resin composition is used.
  • various additives can be used in combination with the insulating resin composition depending on the purpose. For example, taking a measure such as adding a polyfunctional acrylate monomer for the purpose of increasing the strength of the insulating layer, or adding inorganic or organic particles for the purpose of increasing the strength of the insulating layer and improving the electrical characteristics. You can also.
  • the “insulating resin” in the present invention means a resin having an insulating property that can be used for a known insulating film or insulating layer, and is not a perfect insulator. In addition, any resin having an insulating property according to the purpose can be applied to the present invention.
  • the insulating resin may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof.
  • examples of the thermosetting resin include an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, and a screw. Maleimide resin, polyolefin resin, isocyanate resin and the like can be mentioned.
  • 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, and alicyclic epoxy resins. These may be used alone or in combination of two or more. Thereby, it will be excellent in heat resistance.
  • polystyrene resin examples include polyethylene, polystyrene, polypropylene, polyisobutylene, polybutadiene, polyisoprene, cycloolefin resin, and copolymers of these resins.
  • thermoplastic resin examples include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide and the like.
  • Other thermoplastic resins include 1,2-bis (vinylphenylene) ethane resin (1,2-Bis (vinylphenyl) ethane) or a modified resin of this with a polyphenylene ether resin (Satoru Amaha et al., Journal of Applied Polymer). Science Vol. 92, 1252-1258 (2004)), liquid crystalline polymers (specifically, Kuraray Bexter, etc.), fluororesin (PTFE), and the like.
  • thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more. This is performed for the purpose of making up for each defect and producing a better effect.
  • thermoplastic resins such as polyphenylene ether (PPE) have a low resistance to heat, and are therefore alloyed with thermosetting resins.
  • PPE polyphenylene ether
  • Cyanate ester is a resin having the most excellent dielectric properties among thermosetting, but it is rarely used alone, and is used as a modified resin such as epoxy resin, maleimide resin, and thermoplastic resin. Details thereof are described in "Electronic Technology" 2002/9, P35.
  • thermosetting resin contains an epoxy resin and / or a phenol resin as a thermosetting resin, and contains a phenoxy resin and / or polyether sulfone (PES) as a thermoplastic resin is also used in order to improve a dielectric characteristic.
  • PES polyether sulfone
  • the substrate used in the present invention has a surface roughness (Rz described later) of preferably 500 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less in consideration of applications to semiconductor packages, various electric wiring boards and the like. Most preferably, it is 20 nm or less.
  • the smaller the surface irregularity of this substrate (the surface irregularity of the layer when an intermediate layer or polymerization initiation layer is provided), the smaller the electrical loss during high-frequency power transmission when the obtained metal pattern material is applied to wiring etc. Is preferable.
  • 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 is a plate-like material, for example, a resin film (plastic film)
  • the polymer layer can be formed on both surfaces of the resin film by performing the (a1) step on both surfaces.
  • the surface metal in which a metal film is formed on both surfaces by further performing steps (a2) and (a3) described later.
  • a membrane material can be obtained.
  • a polymerization initiator is contained on the base material or polymerization is performed when the graft polymer is generated. It is preferable to use a substrate on which a polymerization initiating layer having a functional group capable of initiating is formed. By using this substrate, active sites can be efficiently generated and more graft polymers can be generated.
  • the polymerization initiation layer in the present invention will be described.
  • a base material is a plate-shaped object, you may form a polymerization start layer on both surfaces.
  • Polymerization initiation layer examples include a layer containing a polymer compound and a polymerization initiator, a layer containing a polymerizable compound and a polymerization initiator, and a layer having a functional group capable of initiating polymerization.
  • the polymerization initiating layer in the present invention can be formed by dissolving necessary components in a solvent that can be dissolved, providing the components on the surface of the substrate by a method such as coating, and hardening by heating or light irradiation.
  • the polymerizable compound used in the polymerization initiating layer is particularly limited as long as it has good adhesion to the substrate and produces a surface graft polymer by applying energy such as irradiation with actinic rays.
  • a polyfunctional monomer or the like may be used, but an embodiment using a hydrophobic polymer having a polymerizable group in the molecule is particularly preferable.
  • the content of the polymerizable compound is preferably in the range of 0 to 100% by mass, particularly preferably in the range of 10 to 80% by mass in the solid content in the polymerization initiation layer.
  • the polymerization initiator layer preferably contains a polymerization initiator for expressing the polymerization initiating ability by applying energy.
  • the polymerization initiator used here is described, for example, in paragraph numbers [0043] to [0044] of JP-A No. 2007-154306, and known polymerization initiators represented by these may be used depending on the purpose. It can be appropriately selected and used. Among these, use of photopolymerization is preferable from the viewpoint of production suitability, and therefore, it is preferable to use a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited as long as it is active with respect to irradiated actinic rays and can be surface-grafted, and examples thereof include radical polymerization initiators, anionic polymerization initiators, and cationic polymerization initiators. From the viewpoint of reactivity, a radical polymerization initiator is preferable.
  • the content of the polymerization initiator is preferably in the range of 0.1 to 70% by mass, particularly preferably in the range of 1 to 40% by mass in terms of solid content in the polymerization initiator layer.
  • the solvent used when applying the polymerizable compound and the polymerization initiator is not particularly limited as long as these components can be dissolved. From the viewpoint of ease of drying and workability, a solvent having a boiling point that is not too high is preferable. Specifically, a solvent having a boiling point of about 40 to 150 ° C. may be selected. Specifically, the solvents described in JP 2007-154306 A paragraph number [0045] can be used. These solvents can be used alone or in combination. An appropriate concentration of the solid content in the coating solution is 2 to 50% by mass.
  • the coating amount when the polymerization initiating layer is formed on the substrate is 0.1 g in terms of mass after drying from the viewpoint of sufficient polymerization initiating ability and prevention of film peeling while maintaining film properties.
  • / M 2 to 20 g / m 2 is preferable, and 1 g / m 2 to 15 g / m 2 is more preferable.
  • the graft polymer is generated in the step (a1) using a coupling reaction between the functional group present on the substrate surface and the reactive functional group of the polymer compound at the terminal or side chain.
  • a photograft polymerization method can be used.
  • a substrate having a polymerization initiating layer formed on a base material is used, and a non-dissociative functional group (interactive group) that forms an interaction with the plating catalyst or its precursor on the polymerization initiating layer.
  • a polymer layer containing a polymer directly chemically bonded to the polymerization initiating layer is preferred.
  • the polymer is directly chemically bonded to the substrate surface by applying energy. That is, the composition containing the polymer is directly bonded by the active species generated on the surface of the polymerization initiation layer while being brought into contact with the surface of the polymerization initiation layer.
  • an adhesion auxiliary layer can be provided instead of the polymerization initiation layer.
  • the base material to be described later is made of a known insulating resin that has been used as a material for a multilayer laminate, a build-up substrate, or a flexible substrate, from the viewpoint of adhesion to the base material, an adhesion auxiliary layer
  • An insulating resin composition is preferably used as the resin composition used when forming the film.
  • assistant layer formed from an insulating resin composition suitable when a base material is insulating resin is demonstrated.
  • the insulating resin composition used when forming the adhesion auxiliary layer may contain the same or different electrically insulating resin that constitutes the substrate, but may have a different glass transition point or elastic modulus. It is preferable to use a material having close thermal properties such as a linear expansion coefficient. Specifically, for example, it is preferable in terms of adhesion to use the same type of insulating resin as that constituting the base material. Further, as other components, inorganic or organic particles may be added in order to increase the strength of the adhesion auxiliary layer and improve the electrical characteristics.
  • the insulating resin in the present invention means a resin having an insulating property that can be used for a known insulating film, and even if it is not a complete insulator, it has an insulating property according to the purpose. Any resin can be applied to the present invention.
  • Specific examples of 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, and a bismaleimide resin. , Polyolefin resins, and socyanate resins.
  • thermoplastic resin examples include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide and the like.
  • the thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more.
  • various compounds can be added to the adhesion auxiliary layer in the present invention depending on the purpose.
  • Specific examples include materials such as rubber and SBR latex that can relieve stress during heating, binders for improving film properties, plasticizers, surfactants, viscosity modifiers, and the like.
  • an active species that generates an active site capable of forming an interaction with the polymer in the composition for forming a plated layer, as described above.
  • some energy may be applied, and preferably, light (ultraviolet light, visible light, X-ray, etc.), plasma (oxygen, nitrogen, carbon dioxide, argon, etc.), heat, electricity, Etc. are used.
  • active sites may be generated by chemically decomposing the surface with an oxidizing liquid (potassium permanganate solution) or the like.
  • Preferred examples of the active species include the thermal polymerization initiator and the photopolymerization initiator that are added to the above-described polymerization initiation layer.
  • the amount of the polymerization initiator to be contained in the adhesion auxiliary layer is preferably 0.1 to 50% by mass, more preferably 1.0 to 30% by mass in terms of solid content.
  • the adhesion auxiliary layer has the same function as the above-described polymerization initiation layer.
  • the thickness of the adhesion auxiliary layer in the present invention is generally in the range of 0.1 to 10 ⁇ m, and preferably in the range of 0.2 to 5 ⁇ m.
  • the solvent used when applying the coating solution containing the components constituting the adhesion auxiliary layer is not particularly limited as long as these components can be dissolved. From the viewpoint of ease of drying and workability, a solvent having a boiling point that is not too high is preferable. Specifically, a solvent having a boiling point of about 40 to 150 ° C. may be selected. Specifically, cyclohexanone, methyl ethyl ketone, or the like can be used. The above exemplified solvents can be used alone or in combination.
  • the solid content in the coating solution is suitably 2 to 50% by mass.
  • the coating amount in the case where the adhesion auxiliary layer is formed on the substrate is 0.1 g in terms of the mass after drying from the viewpoints of sufficient polymerization initiating ability and maintaining film properties to prevent film peeling.
  • / M 2 to 20 g / m 2 is preferable, 0.1 g / m 2 to 15 g / m 2 is more preferable, and 0.1 g / m 2 to 2 g / m 2 is still more preferable.
  • the composition for forming an adhesion auxiliary layer is disposed on a base material by coating or the like, and the film is formed by removing the solvent to form the adhesion auxiliary layer.
  • the film is dried by heating and then preliminarily cured by light irradiation, the polymerizable compound is cured to some extent in advance, so that after the graft polymer is formed on the adhesion auxiliary layer, the adhesion auxiliary layer is removed. This is preferable because it is possible to effectively suppress such a situation.
  • the heating temperature and time may be selected as long as the coating solvent can be sufficiently dried.
  • the temperature is preferably 100 ° C. or less, and the drying time is preferably within 30 minutes, and the drying temperature is 40 to 80 ° C. It is more preferable to select heating conditions within a drying time of 10 minutes.
  • the contact between the composition for forming a layer to be plated and the above-described substrate may be performed by immersing the substrate on which the polymerization initiation layer or the adhesion auxiliary layer is formed in the composition for forming a layer to be plated, if desired. From the viewpoint of handleability and production efficiency, as described later, it is preferable to form a layer comprising the composition of the present invention on the substrate surface (polymerization initiation layer or adhesion auxiliary layer surface) by a coating method.
  • the coating amount is 0.1 g / m 2 in terms of solid content from the viewpoint of sufficient interaction formation with the plating catalyst or its precursor. preferably ⁇ 10g / m 2, especially 0.5g / m 2 ⁇ 5g / m 2 preferred.
  • the polymer layer is left between 20 ° C. and 40 ° C. for 0.5 to 2 hours between the coating and drying. The solvent to be removed may be removed.
  • radiation irradiation such as heating or exposure
  • radiation irradiation such as heating or exposure
  • the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
  • radiation include electron beams, X-rays, ion beams, and far infrared rays.
  • g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.
  • Specific examples generally used include direct image-like recording using a thermal recording head, scanning exposure using an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
  • the time required for energy application varies depending on the production amount of the target graft polymer and the light source, but is usually between 10 seconds and 5 hours.
  • the exposure power because to easily proceed the graft polymerization, addition, in order to suppress the decomposition of the produced graft polymer, of 10mJ / cm 2 ⁇ 5000mJ / cm 2 preferably in the range, more preferably in the range of 50mJ / cm 2 ⁇ 3000mJ / cm 2.
  • a polymer having an average molecular weight of 20,000 or more and a polymerization degree of 200 or more is used as the compound having a polymerizable group and a non-dissociative functional group, it is generated because graft polymerization easily proceeds with low energy exposure. Degradation of the graft polymer can be further suppressed.
  • a polymer layer (graft polymer layer) made of a graft polymer having an interactive group can be formed on the substrate.
  • the obtained polymer layer is, for example, added to an alkaline solution having a pH of 12 and stirred for 1 hour and the decomposition of the polymerizable group site is 50% or less, the polymer layer is washed with a highly alkaline solution. It can be carried out.
  • a plating catalyst or a precursor thereof is applied to the polymer layer formed in the step (a1).
  • the non-dissociative functional group (for example, cyano group) of the graft polymer constituting the polymer layer attaches (adsorbs) the applied plating catalyst or its precursor depending on its function.
  • the plating catalyst or a precursor thereof include those that function as a plating catalyst or an electrode in the plating step (a3) described later. Therefore, the plating catalyst or its precursor is determined by the type of plating in the (a3) plating step.
  • the plating catalyst used in this process or its precursor is an electroless plating catalyst or its precursor.
  • Electroless plating catalyst As the electroless plating catalyst used in the present invention, any catalyst can be used as long as it becomes an active nucleus at the time of electroless plating. Examples thereof include metals having catalytic ability for autocatalytic reduction reaction (for example, those known as metals capable of electroless plating having a lower ionization tendency than Ni), and specifically include Pd, Ag, Cu, Ni, Al Fe, Co and the like. Among them, those capable of multidentate coordination are preferable, and Pd is particularly preferable from the viewpoint of the number of types of functional groups capable of coordination and high catalytic ability.
  • This electroless plating catalyst may be used as a metal colloid. Generally, 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 polymer layer and before being immersed in the electroless plating bath by changing it to a zero-valent metal by a reduction reaction.
  • the electroplating 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 precursor is applied onto the polymer layer 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 (OAc) n (M represents an n-valent metal atom, and Ac represents an acetyl group).
  • 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. Pd ions are preferred in terms of the number of types of groups and catalytic ability.
  • a zero-valent metal can be used as a catalyst used for performing electroplating directly on the polymer layer without performing electroless plating.
  • the zero-valent metal include Pd, Ag, Cu, Ni, Al, Fe, and Co. Among them, those capable of multidentate coordination are preferable, and in particular, adsorption to a non-dissociable functional group (cyano group). Pd, Ag, and Cu are preferable from the viewpoint of (adhesion) property and high catalytic ability.
  • a dispersion in which a metal is dispersed in an appropriate dispersion medium, or a metal salt with an appropriate solvent is prepared, and the dispersion or solution is applied on the polymer layer, or the substrate on which the polymer layer is formed is immersed in the dispersion or solution.
  • the step (a1) when the surface graft polymerization method is used, the above-described composition is brought into contact with the substrate, and an electroless plating catalyst or a precursor thereof is added to the composition. Also good.
  • a composition containing the polymer and an electroless plating catalyst or a precursor thereof is brought into contact with a substrate and applied with a surface graft polymerization method, thereby having a non-dissociative functional group (for example, a cyano group).
  • a polymer layer containing a polymer directly chemically bonded to the substrate and a plating catalyst or a precursor thereof can be formed. If this method is used, the steps (a1) and (a2) in the present invention can be performed in one step.
  • the liquid (plating catalyst liquid) containing a plating catalyst or a precursor thereof can contain an organic solvent. By containing this organic solvent, the permeability of the plating catalyst or its precursor to the polymer layer is improved, and the plating catalyst or its precursor can be efficiently adsorbed to the non-dissociative functional group.
  • the solvent used for the preparation of the plating catalyst solution is not particularly limited as long as it is a solvent that can penetrate into the polymer layer. However, since water is generally used as the main solvent (dispersion medium) of the plating catalyst solution, it will be described in detail below. The water-soluble organic solvents described are preferred.
  • the water-soluble organic solvent used in the plating catalyst solution of the present invention is not particularly limited as long as it is a solvent that dissolves 1% by mass or more in water.
  • Examples thereof include water-soluble organic solvents such as ketone solvents, ester solvents, alcohol solvents, ether solvents, amine solvents, thiol solvents, and halogen solvents.
  • the metal concentration in the dispersion, solution, or composition is preferably in the range of 0.001 to 50% by mass, preferably 0.005 to 30% by mass. More preferably, it is in the range.
  • the contact time is preferably about 30 seconds to 24 hours, more preferably about 1 minute to 1 hour.
  • a plating film (metal film) is formed by performing plating on a polymer layer to which a plating catalyst (for example, an electroless plating catalyst) or a precursor thereof is applied.
  • the formed plating film has excellent conductivity and adhesion.
  • Examples of the type of plating (plating treatment) performed in this step include electroless plating and electroplating.
  • the plating catalyst or its precursor that has formed an interaction with the polymer layer. The function can be selected. That is, in this step, electroplating or electroless plating may be performed on the polymer layer provided with the plating catalyst or its precursor.
  • the present invention it is preferable to perform electroless plating from the viewpoint of the formation of a hybrid structure expressed in the polymer layer and the improvement of adhesion.
  • electroplating is further performed after electroless plating.
  • the plating suitably performed in this step 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 immersing the substrate provided with the electroless plating catalyst in water and removing the excess electroless plating catalyst (metal) and then immersing it in an electroless plating bath.
  • the electroless plating bath used a generally known electroless plating bath can be used.
  • the substrate to which the electroless plating catalyst precursor has been applied is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated on the polymer layer, the substrate is washed with excess precursor. After removing the body (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 generally 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 its concentration is 0.1 to 50% by mass, preferably 1 to 30% by mass.
  • a boron-based reducing agent such as sodium borohydride or dimethylamine borane
  • a reducing agent such as formaldehyde or hypophosphorous acid.
  • composition of electroless plating bath is as follows: 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 in this respect, ketones such as acetone and alcohols such as methanol, ethanol, and isopropanol are preferably used.
  • a copper electroless plating bath contains CuSO 4 as a copper salt, HCOH as a reducing agent, a chelating agent such as EDTA or Rochelle salt, which is a stabilizer for copper ions, and a trialkanolamine. .
  • the plating bath used for electroless plating of CoNiP includes cobalt sulfate and nickel sulfate as metal salts, sodium hypophosphite as a reducing agent, sodium malonate, sodium malate, and sodium succinate as complexing agents. It is included.
  • the palladium electroless plating bath contains (Pd (NH 3 ) 4 ) Cl 2 as metal ions, NH 3 and H 2 NNH 2 as reducing agents, and EDTA as a stabilizer. These plating baths may contain components other than the above components.
  • the thickness of the plating 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 0.2 ⁇ m or more, and more preferably 0.5 ⁇ m or more.
  • the immersion time in the plating bath is preferably about 1 minute to 6 hours, and more preferably about 1 minute to 3 hours.
  • the electroless-plated plating film obtained as described above has fine particles of electroless plating catalyst and plating metal dispersed in the polymer layer by cross-sectional observation with SEM, and further, plating is performed on the polymer layer. It was confirmed that metal was deposited. Since the interface between the substrate and the plating film is a hybrid state of polymer and fine particles, the interface between the substrate (organic component) and the inorganic substance (catalyst metal or plating metal) is smooth (for example, the unevenness difference is 500 nm or less). However, the adhesion is good.
  • step (Electroplating) when the plating catalyst or its precursor applied in step (a2) has a function as an electrode, electroplating is performed on the polymer layer to which the catalyst or its precursor is applied. Can do.
  • the formed plating film may be used as an electrode, and electroplating may be further performed. As a result, it is possible to easily form a new plating film (metal film) having an arbitrary thickness on the basis of the electroless plating film having excellent adhesion to the substrate.
  • the metal film can be formed to a thickness according to the purpose, and therefore, the metal film of the present invention is suitable for various applications.
  • a conventionally known method can be used as the electroplating method in the present invention.
  • a metal used for the electroplating of this process copper, chromium, lead, nickel, gold, silver, tin, zinc, etc. are mentioned. From the viewpoint of conductivity, copper, gold, and silver are preferable, and copper is preferable. More preferred.
  • the film thickness of the metal film obtained by electroplating varies depending on the application, and can be controlled by adjusting the concentration of metal contained in the plating bath or the current density.
  • the film thickness in the case of using it for general electric wiring etc. is preferably 0.5 ⁇ m or more, and more preferably 3 ⁇ m or more from the viewpoint of conductivity.
  • the metal or metal salt derived from the above-described plating catalyst, plating catalyst precursor, and / or metal deposited in the polymer layer by electroless plating is used as a fractal microstructure in the layer. By being formed, the adhesion between the metal film and the polymer layer can be further improved.
  • the amount of metal present in the polymer layer is such that when the cross section of the substrate is photographed with a metal microscope, the proportion of metal in the region from the outermost surface of the polymer layer to a depth of 0.5 ⁇ m is 5 to 50 area%, When the arithmetic average roughness Ra (JIS B0633-2001) between the polymer layer and the metal interface is 0.05 ⁇ m to 0.5 ⁇ m, a stronger adhesion is exhibited.
  • the surface metal film material of this invention By passing through each process of the manufacturing method of the surface metal film material of this invention, the surface metal film material of this invention provided with a polymer layer and a metal film (plating film) in order on the said board
  • the surface metal film material obtained by the method for producing a surface metal film material of the present invention has an effect that there is little fluctuation in the adhesion of the metal film even under high temperature and high humidity.
  • the surface metal film material can be applied to various uses such as an electromagnetic wave prevention film, a coating film, a two-layer CCL (Copper Clad Laminate) material, and an electric wiring material.
  • etching step a4 By performing the step of etching the metal film in the surface metal film material in a pattern, a metal pattern material including a polymer layer and a pattern metal film on the substrate in this order can be manufactured. That is, a wiring (metal pattern) can be formed by patterning a metal film (plating film) in the surface metal film material of the present invention. This etching step (step a4) will be described in detail below.
  • the step (a4) is a step of etching the metal film (plating film) formed in the step (a3) into a pattern. That is, in this step, a desired metal pattern can be formed by removing unnecessary portions of the plating film formed on the entire substrate surface by etching. Any method can be used to form the metal pattern, and specifically, a generally known subtractive method or semi-additive method is used.
  • a dry film resist layer is provided on the formed plating film, the same pattern as the metal pattern part is formed by pattern exposure and development, the plating film is removed with an etching solution using the dry film resist pattern as a mask,
  • an etching solution for example, an aqueous solution of cupric chloride, ferric chloride, or the like can be used.
  • the semi-additive method is to provide a dry film resist layer on the formed plating film, form the same pattern as the non-metallic pattern part by pattern exposure and development, and perform electroplating using the dry film resist pattern as a mask,
  • quick etching is performed after the dry film resist pattern is removed, and the plating film is removed in a pattern to form a metal pattern.
  • the dry film resist, the etching solution, etc. can use the same material as the subtractive method.
  • the above-mentioned method can be used as the electroplating method.
  • a metal pattern material can also be produced by forming the polymer layer obtained in the step (a1) in a pattern and performing the steps (a2) and (a3) on the patterned polymer layer (full).
  • Additive method As a method for forming the polymer layer obtained in the step (a1) into a pattern, specifically, the energy applied when forming the polymer layer may be made into a pattern, and the portion to which no energy is applied By removing the film by development, a patterned polymer layer can be formed.
  • the developing method is performed by immersing the material used for forming the polymer layer in a solvent capable of dissolving. The immersion time is preferably 1 to 30 minutes.
  • the steps (a2) and (a3) for forming the plating film on the patterned polymer layer are the same as those described above.
  • the metal pattern material of the present invention is preferably one in which a metal film (plating film) is provided on the entire surface or locally on a substrate having a surface irregularity of 500 nm or less (more preferably 100 nm or less).
  • substrate and a metal pattern is 0.2 kN / m or more. That is, it is characterized in that the substrate surface is smooth and the adhesion between the substrate and the metal pattern is excellent.
  • the unevenness on the substrate surface is a value measured by cutting the substrate perpendicular to the substrate surface and observing the cross section with an SEM. More specifically, Rz measured according to JIS B 0601, that is, “the difference between the average value of the Z data of the peak from the maximum to the fifth in the specified plane and the average value of the valley from the minimum to the fifth. ”Is preferably 500 nm or less. Further, the adhesion value between the substrate and the metal film was determined by attaching a copper plate (thickness: 0.1 mm) to the surface of the metal film (metal pattern) with an epoxy-based adhesive (Araldite, manufactured by Ciba-Geigy).
  • the metal pattern material obtained by the metal pattern material manufacturing method of the present invention is applied to various uses such as semiconductor chips, various electric wiring boards, FPC, COF, TAB, antennas, multilayer wiring boards, motherboards, and the like. be able to.
  • a wiring board having a metal pattern manufactured by the method for manufacturing a metal pattern material of the present invention as a wiring can form a wiring excellent in adhesion to a smooth substrate, has high frequency characteristics, and is fine. Even with a high-density wiring, the insulation reliability between the wirings is excellent.
  • an insulating resin layer may be further laminated on the surface of the metal pattern material, and further wiring (metal pattern) may be formed on the surface.
  • further wiring metal pattern
  • a solder resist may be formed on the surface of the metal pattern material.
  • epoxy resin As an interlayer insulating film that can be used in the present invention, epoxy resin, aramid resin, crystalline polyolefin resin, amorphous polyolefin resin, fluorine-containing resin (polytetrafluoroethylene, perfluorinated polyimide, perfluorinated amorphous resin, etc.), Examples thereof include a polyimide resin, a polyether sulfone resin, a polyphenylene sulfide resin, a polyether ether ketone resin, and a liquid crystal resin.
  • an epoxy resin e.g., ABF GX-13 manufactured by Ajinomoto Fine Techno Co., Ltd.
  • the solder resist used for protecting the wiring on the surface of the metal pattern material is described in detail in, for example, Japanese Patent Application Laid-Open No. 10-204150, Japanese Patent Application Laid-Open No. 2003-222993, and the like. It can be applied to the present invention as desired.
  • a commercially available solder resist may be used, and specific examples include PFR800 manufactured by Taiyo Ink Manufacturing Co., Ltd., PSR4000 (trade name), SR7200G manufactured by Hitachi Chemical Co., Ltd., and the like.
  • the composition for forming a plating layer of the present invention is an epoxy contained in the composition for forming a plating layer when an interlayer insulating resin film or a solder resist film is formed on the surface of the metal pattern material formed using the composition. Due to the function of the polymer having a specific functional group such as a group, these layers also have the effect of exhibiting good adhesion.
  • An epoxy insulating film GX-13 (film thickness 45 ⁇ m) manufactured by Ajinomoto Fine Techno Co., Ltd. is heated and pressurized as an electrical insulating layer on a glass epoxy substrate, and 100 ° C. to 110 ° C. at a pressure of 0.2 MPa using a vacuum laminator.
  • the base material was obtained by bonding under the above conditions.
  • This coating solution was applied to the substrate by a spin coater (rotated at 300 rpm for 5 seconds and then rotated at 1500 rpm for 25 seconds), and then dried and cured at 170 ° C. Thereby, a substrate A1 was obtained.
  • the thickness of the cured adhesion auxiliary layer was 1.3 ⁇ m.
  • the surface roughness (Rz) of this substrate A1 was 0.5 ⁇ m (200 ⁇ m 2 ).
  • This coating solution was applied to the substrate with a spin coater (rotated at 300 rpm for 5 seconds and then rotated at 1500 rpm for 25 seconds), and then cured at 180 ° C. for 30 minutes to be cured. Thereby, a substrate B1 was obtained.
  • the thickness of the cured polymerization initiating layer was 1.8 ⁇ m.
  • the surface unevenness (Rz) of this substrate B1 was 0.2 ⁇ m (200 ⁇ m 2 ).
  • Example 1 Preparation of coating solution (Composition 1 for plating layer formation) 7 parts by mass of polymer A and 93 parts by mass of acetonitrile solution were mixed and stirred to prepare a coating solution for composition 1 for forming a layer to be plated.
  • the prepared coating solution was applied onto the adhesion auxiliary layer of the substrate A1 by a spin coater (rotated at 300 rpm for 5 seconds and then rotated at 750 rpm for 20 seconds) and dried at 80 ° C. for 30 minutes.
  • UV exposure machine model number: UVF-502S, lamp: UXM-501MD
  • irradiation power 10 mW / cm 2 (ultraviolet integrated light meter UIT150-light receiving sensor UVD-S254, manufactured by USHIO)
  • irradiation was performed for 100 seconds to generate a graft polymer on the entire surface of the adhesion auxiliary layer of the substrate A1.
  • the integrated exposure amount was 1000 mJ.
  • the substrate on which the graft polymer was formed was immersed in acetonitrile in a stirred state for 5 minutes, and then washed with distilled water. Thereby, a substrate A2 having a polymer layer containing the polymer was obtained.
  • the thickness of the polymer layer at this time was 0.5 ⁇ m.
  • electroless plating Using the electroless plating bath (1) having the following composition for the substrate A2 having the plating catalyst-accepting cured product layer provided with the plating catalyst as described above, using the Urumura Kogyo Sulcup PGT. The electroless plating was performed at an electroless plating temperature of 26 ° C. for 30 minutes. The thickness of the obtained electroless copper plating film was 0.5 ⁇ m (weight method).
  • the preparation order and raw materials of the electroless plating solution (1) are as follows.
  • electroplating was carried out for 30 minutes under the condition of 3 A / dm 2 using an electroless copper plating film as a power feeding layer and using an electrolytic copper plating bath having the following composition.
  • the thickness of the obtained electrolytic copper plating film was 19.5 ⁇ m.
  • the obtained plated film was baked at 100 ° C. for 30 minutes and at 180 ° C. for 1 hour, and then, using Autograph AGS-J (manufactured by Shimadzu Corporation), the tensile strength was measured for a width of 5 mm. When the 90 ° peel strength was measured at 10 mm / min, it was 0.70 kN / m.
  • Irradiated with energy development was performed by spraying a 1% Na 2 CO 3 aqueous solution onto the exposed substrate at a spray pressure of 0.2 MPa. Thereafter, the substrate was washed with water and dried, and a resist pattern for the subtractive method was formed on the copper plating film. Etching was performed by immersing the substrate on which the resist pattern was formed in an FeCl 3 / HCl aqueous solution (etching solution) at a temperature of 40 ° C. to remove the copper plating layer present in the resist pattern non-formation region.
  • etching solution FeCl 3 / HCl aqueous solution
  • the resist pattern is swollen and peeled off by spraying a 3% NaOH aqueous solution onto the substrate at a spray pressure of 0.2 MPa, neutralized with a 10% sulfuric acid aqueous solution, and washed with water to obtain a comb-shaped wiring. It was.
  • a solder resist (PFR800; manufactured by Taiyo Ink Manufacturing Co., Ltd.) was vacuum laminated on the comb-shaped wiring under the conditions of 70 ° C. and 0.2 MPa, and light energy of 420 mJ was irradiated with an exposure machine having a central wavelength of 365 nm. At this time, a portion to be soldered in a later insulation reliability test was masked with a light shielding tape. Next, the substrate was heat-treated at 80 ° C. for 10 minutes, and then a 1% aqueous solution of Na 2 CO 3 was sprayed onto the substrate surface at a spray pressure of 0.2 MPa, developed, washed with water and dried.
  • PFR800 solder resist
  • the substrate was again irradiated with light energy of 1000 mJ with an exposure machine having a center wavelength of 365 nm.
  • a heat treatment at 150 ° C./1 hr was performed to obtain a comb-shaped wiring (metal pattern material) for measuring the insulating reliability between the wirings covered with the solder resist.
  • the obtained comb-type wiring board was subjected to an insulation reliability test based on the JPCA standard printed wiring board environmental test methods JPCA-ET01 (general rules) and ET07 (high temperature / high humidity / steady unsaturated pressurized steam test). Tested with an ESPEC HAST tester (AMI-150S-25 (EHS-211-MD)) at 130 ° C-85% relative humidity (unsaturated) at an applied voltage of 20 V for 200 hours. During the inspection, the wiring was observed and evaluated according to the following criteria. The results are shown in Table 1. In practice, the following insulation resistance evaluation and dendrite evaluation are preferably “ ⁇ ” or more.
  • Example 2 7 parts by mass of polymer B and 93 parts by mass of acetonitrile solution were mixed and stirred to prepare a coating liquid for composition 2 for plating layer formation.
  • a surface metal film material and a metal pattern material were prepared in the same manner as in Example 1 except that the coating solution for the composition 2 for plating layer formation was used, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.
  • Example 3 7 parts by mass of polymer C and 93 parts by mass of acetonitrile solution were mixed and stirred to prepare a coating solution for composition 3 for forming a layer to be plated.
  • a surface metal film material and a metal pattern material were prepared in the same manner as in Example 1 except that the coating solution for the composition 3 for forming a plated layer was used, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.
  • Example 4 7 parts by mass of polymer D and 93 parts by mass of acetonitrile solution were mixed and stirred to prepare a coating solution for composition 4 for forming a layer to be plated.
  • a surface metal film material and a metal pattern material were prepared in the same manner as in Example 1 except that the coating solution for the composition 4 for forming a plated layer was used, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.
  • Example 5 7 parts by mass of polymer E and 93 parts by mass of acetonitrile solution were mixed and stirred to prepare a coating solution for composition 5 for forming a layer to be plated.
  • a surface metal film material and a metal pattern material were prepared in the same manner as in Example 1 except that the coating solution for the composition 5 for forming a plated layer was used, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.
  • Example 6 Preparation of coating solution 7 parts by mass of polymer C and 93 parts by mass of acetonitrile solution were mixed and stirred to prepare a coating solution for composition 3 for forming a layer to be plated.
  • the prepared coating solution was applied onto the polymerization initiation layer of the substrate B1 by a spin coater (rotated at 300 rpm for 5 seconds and then rotated at 750 rpm for 20 seconds) and dried at 80 ° C. for 30 minutes.
  • UV exposure machine model number: UVF-502S, lamp: UXM-501MD
  • irradiation power 10 mW / cm 2 (Ushio's UV integrated light meter UIT150-light receiving sensor UVD-S254)
  • irradiation was performed for 100 seconds to generate a graft polymer on the entire surface of the polymerization initiation layer of the substrate B1.
  • the integrated exposure amount was 1000 mJ.
  • the substrate on which the graft polymer was formed was immersed in acetonitrile in a stirred state for 5 minutes, and then washed with distilled water.
  • a substrate B2 having a polymer layer containing a polymer directly chemically bonded to the substrate B1 was obtained.
  • the thickness of the polymer layer at this time was 0.5 ⁇ m.
  • a surface metal film material and a metal pattern material were prepared in the same manner as in Example 1 except that the substrate B2 having a polymer layer was used, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.
  • Example 7 Example 1 except that the substrate A2 produced using the composition 1 for forming a layer to be plated used in Example 1 was used, and the catalyst solution B was prepared using the catalyst solution B prepared as follows. Surface metal materials and metal pattern materials were prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.
  • catalyst solution B Pure water: 60% by mass of nitric acid aqueous solution: diethylene glycol diethyl ether (DEGDE, also known as bis (2-ethoxyethyl) ether) at a mass ratio of 2: 1: 2 with respect to 100 parts by mass of a mixed solution of 0.25%
  • DEGDE diethylene glycol diethyl ether
  • a 0.25 mass% palladium catalyst solution (hereinafter referred to as catalyst solution B) in which a part of palladium acetate was dissolved was prepared.
  • the nitric acid (60% by mass aqueous solution) used for the preparation of the catalyst solution B is a nitric acid (1.38) Wako special grade manufactured by Wako Pure Chemical Industries, Ltd.
  • DEGDE is a bis (2 -Ethoxyethyl) ether (Wako grade 1)
  • palladium acetate is a Wako special grade manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 8 A plating catalyst was applied in the same manner as in Example 7 above, using the substrate A2 obtained using the composition 4 for forming a layer to be plated used in Example 4. Thereafter, a surface metal material and a metal pattern material were prepared in the same manner as in Example 1 except that the plating bath and plating conditions used during electroless plating were changed as follows, and the same evaluation as in Example 1 was performed. It was. The results are shown in Table 1.
  • the preparation order and raw materials of the electroless plating solution (2) are as follows.
  • OPC Copper T manufactured by Okuno Pharmaceutical Co., Ltd. was used.
  • [Electroless plating solution (2)] Approximately 60% by volume of distilled water T-1 solution 6.0% by volume T-2 solution 1.2% by volume T-3 solution 10.0% by volume Finally, the liquid level was adjusted with distilled water so that the total amount would be 100% by volume.
  • the substrate A2 was immersed in this electroless plating solution (2) at a temperature of 30 ° C. for 25 minutes to perform electroless plating.
  • the thickness of the obtained electroless copper plating film was 0.7 ⁇ m.
  • the thickness of the obtained electrolytic copper plating film was 20 ⁇ m.
  • Example 9 Using the substrate A2 obtained using the composition 4 for plating layer formation used in Example 4, a catalyst solution B was applied to the catalyst solution B of Example 7 in the same manner as in Example 7. Thereafter, electroless plating was performed in the same manner as in Example 8 using the electroless plating solution (2) of Example 8. Then, after forming a metal pattern under the conditions of Example 1, an insulating film (ABF GX-13, manufactured by Ajinomoto Fine Techno Co., Ltd.) was attached instead of the solder resist (PFR800) under the following conditions. Similar evaluations were made. The thickness of the obtained electroless copper plating film was 0.7 ⁇ m. Moreover, the thickness of the obtained electrolytic copper plating film
  • Comparative Polymer 1 was synthesized as follows. A 1000 ml three-necked flask was charged with 35 g of N, N-dimethylacetamide and heated to 75 ° C. under a nitrogen stream. There, a solution of 6.60 g of 2-hydroxyethyl acrylate (commercially available, Tokyo Kasei), 28.4 g of 2-cyanoethyl acrylate, and 0.65 g of V-601 (manufactured by Wako Pure Chemical Industries), 35 g of N, N-dimethylacetamide Was added dropwise over 2.5 hours. After completion of the dropwise addition, the reaction solution was heated to 80 ° C. and further stirred for 3 hours.
  • 2-hydroxyethyl acrylate commercially available, Tokyo Kasei
  • 2-cyanoethyl acrylate commercially available, Tokyo Kasei
  • V-601 manufactured by Wako Pure Chemical Industries
  • reaction solution was cooled to room temperature.
  • Ditertiary butyl hydroquinone 0.29 g, dibutyltin dilaurate 0.29 g, Karenz AOI (manufactured by Showa Denko KK) 18.56 g, N, N-dimethylacetamide 19 g were added to the above reaction solution, and the mixture was added at 55 ° C. for 4 hours. Reaction was performed. Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours.
  • Example 1 In the composition 1 for forming a plating layer used in Example 1, a surface metal material and a metal pattern material were prepared in the same manner except that the comparative polymer 1 was used instead of the polymer A, and the same as in Example 1 Evaluation was performed. The results are shown in Table 1.
  • Comparative Polymer 2 was synthesized as follows.
  • Synthesis Example: Synthesis of Comparative Polymer 2 In a 300 ml three-necked flask, 16.7 g of dimethyl carbonate was added and heated to 65 ° C. under a nitrogen stream. Thereto was added dropwise a solution of 12.5 g of 2-cyanoethyl acrylate, 7.2 g of acrylic acid, and 0.40 g of V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) in 16.7 g of dimethyl carbonate over 4 hours. After completion of the dropwise addition, the reaction solution was further stirred for 3 hours.
  • composition 1 for forming a plated layer used in Example 1 a surface metal material and a metal pattern material were prepared in the same manner except that the comparative polymer 2 was used instead of the polymer A. Evaluation was performed. The results are shown in Table 1.
  • the solder resist is expressed as “SR”
  • the interlayer insulating film is expressed as “insulating film”.
  • the film thickness means the thickness ( ⁇ m) of the electroless copper plating film.
  • the unit of adhesion is “kN / m”.
  • the surface metal film material and the metal pattern material obtained by the composition for forming a plated layer of the present invention are excellent in the adhesion of the metal film and the insulation reliability between the wirings.
  • each of the above Examples is a surface metal film material (Comparative Example 1, which is obtained by a conventional composition for forming a plated layer having no specific functional group). It was found that the insulation reliability between the wirings was improved even under severe conditions compared to the material (2). In particular, the polymer having a carbonyl group described in Comparative Example 2 is presumed to have deteriorated insulation reliability due to excessive hydrophilicity and increased water absorption.

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  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

La présente invention se rapporte à une composition permettant de former une couche de placage conçue pour pouvoir former une couche polymère qui présente une excellente fiabilité d'isolation et obtient une adhésivité élevée à un film de placage (film métallique) formé sur sa surface. La composition permettant de former une couche de placage comprend un polymère qui contient un groupe radical polymérisable, un groupe fonctionnel non dissociatif pour créer une action mutuelle avec un catalyseur de placage ou un précurseur de ce dernier, et au moins un groupe fonctionnel sélectionné dans les groupes suivants : un groupe époxy, un groupe oxétanyle, un groupe isocyanate, un groupe isocyanate bloqué, un groupe amino primaire et un groupe amino secondaire.
PCT/JP2011/057417 2010-03-26 2011-03-25 Composition permettant de former une couche de placage, matériau de film métallique de surface et procédé de fabrication de ce dernier ainsi que matériau de motif métallique et procédé de fabrication de dernier Ceased WO2011118797A1 (fr)

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JP2010072927A JP2011202109A (ja) 2010-03-26 2010-03-26 被めっき層形成用組成物、表面金属膜材料およびその製造方法、並びに、金属パターン材料およびその製造方法
JP2010-072927 2010-03-26

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
JP2014024322A (ja) * 2012-06-18 2014-02-06 Fujifilm Corp インプリント用下層膜形成組成物およびパターン形成方法
WO2016027843A1 (fr) * 2014-08-21 2016-02-25 富士フイルム株式会社 Composition de résine permettant la formation de film de sous-couche, corps stratifié, procédé de formation de motif et procédé permettant la fabrication d'un kit et/ou d'un dispositif de formation d'empreinte
WO2019172156A1 (fr) * 2018-03-07 2019-09-12 富士フイルム株式会社 Composition de formation de film de sous-couche pour impression, composition durcissable pour impression, et kit
CN114787411A (zh) * 2019-12-06 2022-07-22 Posco公司 弯曲加工性和耐蚀性优异的热浸镀锌钢板及其制造方法

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JP2009164575A (ja) * 2007-12-14 2009-07-23 Fujifilm Corp 表面金属膜材料の作製方法、表面金属膜材料、金属パターン材料の作製方法、金属パターン材料、及びポリマー層形成用組成物
JP2009280904A (ja) * 2008-04-23 2009-12-03 Fujifilm Corp 表面金属膜材料の作製方法、表面金属膜材料、金属パターン材料の作製方法、金属パターン材料、及びポリマー層形成用分散物

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JPS6345379A (ja) * 1986-07-29 1988-02-26 バイエル・アクチエンゲゼルシヤフト 無電気メツキ金属層の結合力改善法
JP2009164575A (ja) * 2007-12-14 2009-07-23 Fujifilm Corp 表面金属膜材料の作製方法、表面金属膜材料、金属パターン材料の作製方法、金属パターン材料、及びポリマー層形成用組成物
JP2009280904A (ja) * 2008-04-23 2009-12-03 Fujifilm Corp 表面金属膜材料の作製方法、表面金属膜材料、金属パターン材料の作製方法、金属パターン材料、及びポリマー層形成用分散物

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014024322A (ja) * 2012-06-18 2014-02-06 Fujifilm Corp インプリント用下層膜形成組成物およびパターン形成方法
US9796803B2 (en) 2012-06-18 2017-10-24 Fujifilm Corporation Under layer film-forming composition for imprints and method of forming pattern
WO2016027843A1 (fr) * 2014-08-21 2016-02-25 富士フイルム株式会社 Composition de résine permettant la formation de film de sous-couche, corps stratifié, procédé de formation de motif et procédé permettant la fabrication d'un kit et/ou d'un dispositif de formation d'empreinte
TWI635365B (zh) * 2014-08-21 2018-09-11 日商富士軟片股份有限公司 Sublayer film forming composition, laminate, pattern forming method, imprint forming kit, and device manufacturing method
WO2019172156A1 (fr) * 2018-03-07 2019-09-12 富士フイルム株式会社 Composition de formation de film de sous-couche pour impression, composition durcissable pour impression, et kit
JPWO2019172156A1 (ja) * 2018-03-07 2021-03-04 富士フイルム株式会社 インプリント用下層膜形成組成物、インプリント用硬化性組成物、キット
JP7017623B2 (ja) 2018-03-07 2022-02-08 富士フイルム株式会社 インプリント用下層膜形成組成物、インプリント用硬化性組成物、キット
CN114787411A (zh) * 2019-12-06 2022-07-22 Posco公司 弯曲加工性和耐蚀性优异的热浸镀锌钢板及其制造方法
CN114787411B (zh) * 2019-12-06 2023-12-12 Posco公司 弯曲加工性和耐蚀性优异的热浸镀锌钢板及其制造方法
US12435405B2 (en) 2019-12-06 2025-10-07 Posco Hot-dipped galvanized steel sheet having excellent bending workability and corrosion resistance and manufacturing method therefor

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