EP2896720B1 - Basismittel für stromlose plattierung - Google Patents

Basismittel für stromlose plattierung Download PDF

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EP2896720B1
EP2896720B1 EP13837102.6A EP13837102A EP2896720B1 EP 2896720 B1 EP2896720 B1 EP 2896720B1 EP 13837102 A EP13837102 A EP 13837102A EP 2896720 B1 EP2896720 B1 EP 2896720B1
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group
metal
primer
film
hyperbranched polymer
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French (fr)
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EP2896720A4 (de
EP2896720A1 (de
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Daigo Saito
Keisuke Kojima
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • 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
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
    • C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
    • 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
    • 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
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
    • C23C18/1882—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
    • 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
    • C23C18/2053—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 only one step pretreatment
    • C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals
    • 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
    • C23C18/2053—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 only one step pretreatment
    • C23C18/2066—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
    • 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

Definitions

  • the present invention relates to a primer for electroless plating comprising a hyperbranched polymer, metal fine particles, and an alkoxysilane.
  • Electroless plating is extensively employed in various fields including decorating applications where a luxurious and aesthetic appearance is imparted to a resin molded body for an automotive part and the like, electromagnetic shielding, and wiring technology for a printed circuit board, a large scale integrated circuit, and the like.
  • the reason is that electroless plating can produce a coating film with a uniform thickness regardless of the kind and shape of the base material only by immersing the base material in a plating solution and can produce a metal plating film also on a nonconductor such as plastic, ceramic, and glass.
  • a pretreatment for electroless plating to increase adhesion between the base material and the metal plating film is carried out.
  • the surface to be treated is roughened and/or hydrophilized by various etching means, followed by sensitization where an adsorbing substance that promotes adsorption of a plating catalyst on the surface to be treated is provided on the surface to be treated and activation where the plating catalyst is allowed to adsorb on the surface to be treated.
  • sensitization involves immersion of the object to be treated in an acidic solution of stannous chloride to allow the metal (Sn 2+ ) capable of acting as a reducing agent to deposit on the surface to be treated.
  • the sensitized surface to be treated is immersed in an acidic solution of palladium chloride for activation.
  • the palladium ion in the solution is reduced by the metal that is a reducing agent (tin ion: Sn 2+ ) and deposited on the surface to be treated as an active palladium catalyst nucleus.
  • the base material is immersed in an electroless plating solution to form a metal plating film on the surface to be treated.
  • JP 2008-007849 A is concerned with a primer composition for electroless plating capable of forming a plating film on a non-conductive base material.
  • the primer composition contains metal colloidal particles, a hardening composition hardenable at a temperature of 120°C or lower and a solvent.
  • An amphiphilic polymer, for example containing carboxy groups, may be used as a dispersant.
  • hyperbranched polymers classified as dendritic polymers have intentionally introduced branches, the most prominent feature of which is a large number of terminal groups. If reactive functional groups are added to the terminal groups, the polymer has reactive functional groups quite densely and is expected to be applied as, for example, a highly sensitive scavenger for functional substances such as catalysts, a sensitive multifunctional cross-linking agent, or a dispersing or coating agent for metals or metal oxides.
  • Patent Document 1 a composition containing a hyperbranched polymer having an ammonium group and metal fine particles is used as a reduction catalyst
  • the conventional electroless plating process needs some improvements in terms of the environmental impact, the costs, and the troublesome operation, including the use of a chromium compound (chromic acid) in the roughening step carried out in the pretreatment and the many steps involved in the pretreatment.
  • a chromium compound chromic acid
  • the present invention focuses on these problems and aims to provide a novel, environmentally friendly primer for use in the pretreatment steps in electroless plating, by which process is easy with fewer steps and which can realize cost reduction.
  • a layer obtained by combining a hyperbranched polymer having an ammonium group at a molecular terminal, metal fine particles, and an alkoxysilane and coating a base material with the combination has excellent platability and adhesion as a priming layer for electroless metal plating and completed the present invention.
  • the present invention relates to a primer for forming a metal plating film on a base material by electroless plating, the primer comprising: (a) a hyperbranched polymer having an ammonium group at a molecular terminal and a weight-average molecular weight of 500 to 5,000,000; (b) a metal fine particle; and (c) an alkoxysilane having an amino group optionally substituted with an aliphatic group, or an epoxy group, or an oligomer of the alkoxysilane.
  • the present invention relates to the primer according to the first aspect, in which the ammonium group of the hyperbranched polymer (a) is attached to the metal fine particle (b) to form a complex.
  • the present invention relates to the primer according to the first aspect or the second aspect, in which the hyperbranched polymer (a) is a hyperbranched polymer of Formula [1]: (where R 1 s are each independently a hydrogen atom or a methyl group; R 2 to R 4 are each independently a hydrogen atom, a linear, branched, or cyclic alkyl group having a carbon atom number of 1 to 20, a C 7-20 arylalkyl group, or -(CH 2 CH 2 ) m R 5 (where R 5 is a hydrogen atom or a methyl group; and m is an integer of 2 to 100) (where the alkyl group and the arylalkyl group are optionally substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxy group, or a cyano group), or two groups of R 2 to R 4 together represent a linear, branched, or cyclic alkylene group, or R 2 to R 4
  • the present invention relates to the primer according to the third aspect, in which the hyperbranched polymer (a) is a hyperbranched polymer of Formula [3]: (where R 1 , R 2 , and n have the same meanings as described above).
  • the present invention relates to the primer according to any one of the first aspect to the fourth aspect, in which the metal fine particle (b) is a fine particle of at least one selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), and gold (Au).
  • the metal fine particle (b) is a fine particle of at least one selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), and gold (Au).
  • the present invention relates to the primer according to the fifth aspect, in which the metal fine particle (b) is a palladium fine particle.
  • the present invention relates to the primer according to the fifth aspect or the sixth aspect, in which the metal fine particle (b) is a fine particle having an average particle diameter of 1 to 100 nm.
  • the present invention relates to the primer according to any one of the first aspect to the seventh aspect, in which the alkoxysilane (c) is a compound of Formula [4]: Z-L-Si(R 6 ) a (OR 7 ) 3-a [4] (where R 6 is a C 1-6 alkyl group or a phenyl group; R 7 are each independently a methyl group or an ethyl group; L is a C 1-6 alkylene group optionally containing an ether bond; Z is an amino group optionally substituted with an aliphatic group, or an epoxy group; and a is 0 or 1).
  • R 6 is a C 1-6 alkyl group or a phenyl group
  • R 7 are each independently a methyl group or an ethyl group
  • L is a C 1-6 alkylene group optionally containing an ether bond
  • Z is an amino group optionally substituted with an aliphatic group, or an epoxy group
  • a is 0 or
  • the present invention relates to a priming layer for electroless plating, obtained by forming a layer of the primer as described in any one of the first aspect to the eighth aspect.
  • the present invention relates to a metal plating film, formed on the priming layer by performing electroless plating on the priming layer for electroless plating as described in the ninth aspect.
  • the present invention relates to a metal-coated base material comprising: a base material; the priming layer for electroless plating as described in the ninth aspect formed on the base material; and the metal plating film as described in the tenth aspect formed on the priming layer for electroless plating.
  • the present invention relates to a method for producing a metal-coated base material, the method comprising: a process A: coating a base material with the primer as described in any one of the first aspect to the eighth aspect to form a priming layer; and a process B: immersing the base material having the priming layer in an electroless plating bath to form a metal plating film.
  • the primer of the present invention can form a priming layer for electroless metal plating easily by only applying on a base material.
  • the primer of the present invention can form a priming layer having excellent adhesion to the base material.
  • the primer of the present invention can provide a fine line having a width in micrometers order, which makes the primer suitable for various wiring technologies.
  • a metal plating film can be easily formed by only immersing a priming layer for electroless metal plating formed from the primer of the present invention in an electroless plating bath, and a metal-coated base material comprising a base material, a priming layer, and a metal plating film can be easily obtained.
  • the metal plating film has excellent adhesion to the underlying priming layer.
  • the primer of the present invention may be used to form a priming layer on a base material, which leads to the formation of a so-called metal plating film having excellent adhesion to the base material.
  • the primer of the present invention comprises (a) a hyperbranched polymer having an ammonium group and a weight-average molecular weight of 500 to 5,000,000, (b) metal fine particles, and (c) an alkoxysilane having an amino group optionally substituted with an aliphatic group, or an epoxy group, or an oligomer of the alkoxysilane.
  • the primer of the present invention is suitably used as a primer for forming a metal plating film on a base material by electroless plating.
  • the hyperbranched polymer for use in the primer of the present invention is a polymer having an ammonium group at a molecular terminal and a weight-average molecular weight of 500 to 5,000,000. Specific examples thereof include a hyperbranched polymer of Formula [1]:
  • R 1 are each independently a hydrogen atom or a methyl group.
  • R 2 to R 4 are each independently a hydrogen atom, a linear, branched, or cyclic alkyl group having a carbon atom number of 1 to 20, a C 7-20 arylalkyl group, or -(CH 2 CH 2 O) m R 5 (where R 5 is a hydrogen atom or a methyl group; and m is an arbitrary integer of 2 to 100).
  • the alkyl group and the arylalkyl group are optionally substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxy group, or a cyano group.
  • two groups of R 2 to R 4 together represent a linear, branched, or cyclic alkylene group, or R 2 to R 4 together with the nitrogen atom to which R 2 to R 4 are bonded may form a ring.
  • X- is an anion
  • n is the number of repeating unit structures and an integer of 5 to 100,000.
  • examples of the linear C 1-20 alkyl group in R 2 to R 4 include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-eicosyl group.
  • a group having eight or more carbon atoms is preferred because the primer with such a group is sparingly soluble in an electroless plating solution and, in particular, an n-octyl group is preferred.
  • the branched alkyl group include an isopropyl group, isobutyl group, sec-butyl group, and tert-butyl group.
  • the cyclic alkyl group include groups having a cyclopentyl ring or cyclohexyl ring structure.
  • Examples of the C 7-20 arylalkyl group in R 2 to R 4 include a benzyl group and phenethyl group.
  • Examples of the linear alkylene group that two groups of R 2 to R 4 together form include a methylene group, ethylene group, n-propylene group, n-butylene group, and n-hexylene group.
  • Examples of the branched alkylene group include an isopropylene group, isobutylene group, and 2-methylpropylene group.
  • Examples of the cyclic alkylene group include monocyclic, multicyclic, bridged cyclic C 3-30 alicyclic aliphatic groups. Specific examples thereof include groups having four or more carbon atoms and monocyclic, bicyclic, tricyclic, tetracyclic, or pentacyclic structures. These alkylene groups may contain a nitrogen atom, a sulfur atom, or an oxygen atom in the groups.
  • the ring that R 2 to R 4 together with the nitrogen atom to which R 2 to R 4 are bonded form in the structure of Formula [1] may contain a nitrogen atom, a sulfur atom, or an oxygen atom in the ring, and examples thereof include a pyridine ring, pyrimidine ring, pyrazine ring, quinoline ring, and bipyridyl ring.
  • R 2 to R 4 include [methyl group, methyl group, methyl group], [methyl group, methyl group, ethyl group], [methyl group, methyl group, n-butyl group], [methyl group, methyl group, n-hexyl group], [methyl group, methyl group, n-octyl group], [methyl group, methyl group, n-decyl group], [methyl group, methyl group, n-dodecyl group], [methyl group, methyl group, n-tetradecyl group], [methyl group, methyl group, n-hexadecyl group], [methyl group, methyl group, n-octadecyl group], [ethyl group, ethyl group, ethyl group], [n-butyl group, n-butyl group, n-butyl group], [n-hexyl group, n-hexyl group, n-hexyl group, n
  • anion X- include a halogen atom, PF 6 - , BF 4 - , or a perfluoroalkane sulfonate.
  • a 1 is a structure of Formula [2]:
  • a 2 is a linear, branched, or cyclic alkylene group having a carbon atom number of 1 to 30 optionally containing an ether bond or an ester bond.
  • Y 1 to Y 4 are each independently a hydrogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, a nitro group, a hydroxy group, an amino group, a carboxy group, or a cyano group.
  • alkylene group of A 2 examples include linear alkylene groups such as a methylene group, ethylene group, n-propylene group, n-butylene group, and n-hexylene group, and branched alkylene groups such as an isopropylene group, isobutylene group, and 2-methylpropylene group.
  • cyclic alkylene group examples include monocyclic, multicyclic, and bridged cyclic C 3-30 alicyclic aliphatic groups. Specific examples thereof include groups having four or more carbon atoms and monocyclic, bicyclic, tricyclic, tetracyclic, pentacyclic structures.
  • structural examples of the alicyclic moieties (a) to (s) in the alicyclic aliphatic groups are shown below:
  • examples of the C 1-20 alkyl group of Y 1 to Y 4 include a methyl group, ethyl group, isopropyl group, cyclohexyl group, and n-pentyl group.
  • examples of the C 1-20 alkoxy group include a methoxy group, ethoxy group, isopropoxy group, cyclohexyloxy group, and n-pentyloxy group.
  • Y 1 to Y 4 are preferably each independently a hydrogen atom or a C 1-20 alkyl group.
  • a 1 is a structure of Formula [5]:
  • R 1 , R 2 , and n have the same meanings as described above.
  • a hyperbranched polymer for use in the present invention having an ammonium group at a molecular terminal can be obtained, for example, by allowing a hyperbranched polymer having a halogen atom at a molecular terminal to react with an amine compound.
  • a hyperbranched polymer having a halogen atom at a molecular terminal can be produced from a hyperbranched polymer having a dithiocarbamate group at a molecular terminal according to the description of WO 2008/029688 Pamphlet.
  • the hyperbranched polymer having a dithiocarbamate group at a molecular terminal is commercially available and HYPERTECH (registered trademark) HPS-200 manufactured by NISSAN CHEMICAL INDUSTRIES, LTD. and the like can be suitably used.
  • Examples of the amine compound that can be used in the reaction include primary amines including aliphatic amines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, and n-eicosylamine;
  • amine compounds such as N-(tert-butoxycarbonyl)-1,2-ethylenediamine, N-(tert-butoxycarbonyl)-1,3-propylenediamine, N-(tert-butoxycarbonyl)-1,4-butylenediamine, N-(tert-butoxycarbonyl)-1,5-pentamethylenediamine, N-(tert-butoxycarbonyl)-1,6-hexamethylenediamine, N-(2-hydroxyethyl)amine, N-(3-hydroxypropyl)amine, N-(2-methoxyethyl)amine, and N-(2-ethoxyethyl)amine.
  • amine compounds such as N-(tert-butoxycarbonyl)-1,2-ethylenediamine, N-(tert-butoxycarbonyl)-1,3-propylenediamine, N-(tert-butoxycarbonyl)-1,4-butylenediamine, N-(tert-butoxycarbon
  • secondary amines include aliphatic amines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-n-pentylamine, ethylmethylamine, methyl-n-propylamine, methyl-n-butylamine, methyl-n-pentylamine, ethylisopropylamine, ethyl-n-butylamine, ethyl-n-pentylamine, methyl-n-octylamine, methyl-n-decylamine, methyl-n-dodecylamine, methyl-n-tetradecylamine, methyl-n-hexadecylamine, methyl-n-octadecylamine, ethylisopropylamine, ethyl-n-n
  • tertiary amines include aliphatic amines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-octylamine, tri-n-dodecylamine, dimethyl(ethyl)amine, dimethyl-n-butylamine, dimethyl-n-hexylamine, dimethyl-n-octylamine, dimethyl-n-decylamine, diethyl-n-decylamine, dimethyl-n-dodecylamine, dimethyl-n-tetradecylamine, dimethyl-n-hexadecylamine, dimethyl-n-octadecylamine, and dimethyl-n-eicosylamine; and nitrogen-containing heterocyclic compounds such as pyridine, pyrazine, pyrimidine, quinoline,
  • the amine compound can be used in the reaction in 0.1 to 20 molar equivalents, preferably 0.5 to 10 molar equivalents, and more preferably 1 to 5 molar equivalents per mole of halogen atom of the hyperbranched polymer having a halogen atom at a molecular terminal.
  • the reaction between the hyperbranched polymer having a halogen atom at a molecular terminal and the amine compound can be carried out in water or an organic solvent in the presence or absence of a base.
  • the solvent used is preferably capable of dissolving the hyperbranched polymer having a halogen atom at a molecular terminal and the amine compound.
  • a solvent capable of dissolving the hyperbranched polymer having a halogen atom at a molecular terminal and the amine compound and incapable of dissolving a hyperbranched polymer having an ammonium group at a molecular terminal would be more suitable for easy isolation.
  • Any solvent may be used in the reaction, provided the solvent does not substantially inhibit the reaction from proceeding, and examples thereof include water; alcohols such as isopropanol; organic acids such as acetic acid; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and 1,2-dichlorobenzene; ethers such as tetrahydrofuran (THF) and diethyl ether; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone; halides such as chloroform, dichloromethane, and 1,2-dichloroethane; aliphatic hydrocarbons such as n-hexane, n-heptane, and cyclohexane; and amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and N-methyl
  • the mass of the solvent used is 0.2 to 1,000 times, preferably 1 to 500 times, more preferably 5 to 100 times, and most preferably 5 to 50 times the mass of the hyperbranched polymer having a halogen atom at a molecular terminal.
  • inorganic compounds including alkali metal hydroxides and alkaline-earth metal hydroxides (for example, sodium hydroxide, potassium hydroxide, calcium hydroxide), alkali metal oxides and alkaline-earth metal oxides (for example, lithium oxide, calcium oxide), alkali metal hydrides and alkaline-earth metal hydrides (for example, sodium hydride, potassium hydride, calcium hydride), alkali metal amides (for example, sodium amide), alkali metal carbonates and alkaline-earth metal carbonates (for example, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate), and alkali metal bicarbonates (for example, sodium bicarbonate), and organometallic compounds including alkali metal alkyls, alkyl magnesium halides, alkali metal alkoxides, alkaline-earth metal alkoxides, and dimethoxymagnesium.
  • organometallic compounds including alkali metal alkyls, alkyl magnesium halides,
  • Potassium carbonate and sodium carbonate are particularly preferable.
  • the base is used in 0.2 to 10 molar equivalents, preferably 0.5 to 10 molar equivalents, and most preferably 1 to 5 molar equivalents per mole of halogen atom of the hyperbranched polymer having a halogen atom at a molecular terminal.
  • Oxygen in the reaction system is preferably thoroughly removed before this reaction is started and inert gases such as nitrogen and argon may be used to purge air from the system.
  • the reaction condition is suitably selected from the reaction time range of 0.01 to 100 hours and the reaction temperature range of 0 to 300°C.
  • the reaction time is 0.1 to 72 hours and the reaction temperature is 20 to 150°C.
  • the hyperbranched polymer of Formula [1] can be obtained whether or not a base is present.
  • a hyperbranched polymer with a terminal ammonium group in which respectively corresponding secondary amine terminal group or tertiary amine terminal group of hyperbranched polymer is protonated can be obtained.
  • the reactants may be mixed with an aqueous solution of an acid such as hydrogen chloride, hydrogen bromide, and hydrogen iodide in an organic solvent to obtain a corresponding hyperbranched polymer with a terminal ammonium group, in which respectively corresponding secondary amine terminal group or tertiary amine terminal group of hyperbranched polymer is protonated.
  • an acid such as hydrogen chloride, hydrogen bromide, and hydrogen iodide
  • the weight-average molecular weight Mw of the hyperbranched polymer measured by gel permeation chromatography in terms of polystyrene is 500 to 5,000,000, preferably 1,000 to 500,000, more preferably 2,000 to 200,000, and most preferably 3,000 to 100,000.
  • the degree of distribution: Mw (weight-average molecular weight)/ Mn (number-average molecular weight) is 1.0 to 7.0, preferably 1.1 to 6.0, and more preferably 1.2 to 5.0.
  • the metal fine particles for use in the primer of the present invention are not specifically limited, and examples of metal species include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), and gold (Au). These metals may be used singly, or an alloy of two or more metals may be used. Among these metals, palladium fine particles are included as suitable metal fine particles. Oxides of the metals may also be used as metal fine particles.
  • the metal fine particles are obtained by reduction of a metal ion, for example, by irradiating an aqueous solution of a metal salt with a high-pressure mercury lamp or adding to the aqueous solution a compound having a reducing action (so-called reducing agent).
  • a metal ion may be reduced by, for example, adding an aqueous solution of a metal salt to a solution in which the hyperbranched polymer is dissolved and irradiating the resultant mixture with ultraviolet light or adding an aqueous solution of a metal salt and a reducing agent to the solution, to form a complex of the hyperbranched polymer and the metal fine particles concurrently with the preparation of a primer comprising the hyperbranched polymer and the metal fine particles.
  • the reducing agent is not specifically limited, and various reducing agents may be used.
  • a reducing agent is preferably selected depending on the metal species added in the intended primer and other factors.
  • the reducing agent that can be used include metal borohydrides such as sodium borohydride and potassium borohydride; aluminum hydrides such as lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, beryllium aluminum hydride, magnesium aluminum hydride, and calcium aluminum hydride; hydrazine compounds; citric acid and salts thereof; succinic acid and salts thereof; ascorbic acid and salts thereof; primary or secondary alcohols such as methanol, ethanol, isopropanol, and polyol; tertiary amines such as trimethylamine, triethylamine, diisopropyl(ethyl)amine, diethylmethylamine, tetramethylethylenediamine [TMEDA], and ethylenediaminetetraacetic acid [EDTA]; hydroxyl
  • the average particle diameter of the metal fine particles is preferably 1 to 100 nm. The reason is that, with an average particle diameter exceeding 100 nm, the surface areas of the metal fine particles decrease, resulting in the decrease in the catalytic activity.
  • the average particle diameter is more preferably 75 nm or less and particularly preferably 1 to 30 nm.
  • the hyperbranched polymer (a) is preferably used for the primer of the present invention in an amount of 50 to 2,000 parts by mass relative to 100 parts by mass of the metal fine particles (b). If the amount is less than 50 parts by mass, the metal fine particles are insufficiently dispersed, and if the amount exceeds 2,000 parts by mass, the organic content becomes high, leading to problems affecting properties and the like.
  • the amount of the hyperbranched polymer is more preferably 100 to 1,000 parts by mass.
  • alkoxy silane or an oligomer thereof for use in the primer of the present invention is any alkoxysilane having an amino group optionally substituted with an aliphatic group or an epoxy group, or an oligomer thereof.
  • alkoxysilane having an amino group optionally substituted with an aliphatic group examples include silane compounds having one or more amino groups optionally substituted with an aliphatic group in one molecule and having an alkoxysilyl group.
  • alkoxysilane having an epoxy group examples include silane compounds having one or more epoxy groups in one molecule and having an alkoxysilyl group.
  • alkoxysilane for use in the primer of the present invention include a compound of Formula [4]: Z - L - Si(R 6 ) a (OR 7 ) 3-a [4]
  • R 6 is a C 1-6 alkyl group or a phenyl group
  • R 7 are each independently a methyl group or an ethyl group
  • L is a C 1-6 alkylene group optionally containing an ether bond
  • Z is an amino group optionally substituted with an aliphatic group, or an epoxy group
  • a is 0 or 1.
  • Examples of the C 1-6 alkyl group in R 6 include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-hexyl group, and cyclohexyl group.
  • a methyl group is preferable.
  • Examples of the C 1-6 alkylene group optionally containing an ether bond in L include a methylene group, ethylene group, trimethylene group, methylethylene group, tetramethylene group, 1-methyltrimethylene group, pentamethylene group, 2,2-dimethyltrimethylene group, hexamethylene group, 2-oxabutane-1,4-diyl group, 2-oxapentane-1,5-diyl group, 3-oxapentane-1,5-diyl group, and 2-oxahexane-1,6-diyl group.
  • an ethylene group, trimethylene group, and 2-oxapentane-1,5-diyl group are preferable.
  • Examples of the amino group optionally substituted with an aliphatic group in Z include an amino group, methylamino group, ethylamino group, 2-aminoethylamino group, diethylamino group, propylamino group, 3-trimethoxysilylpropylamino group, 3-triethoxysilylpropylamino group, and 1-methylpentylideneamino group.
  • an amino group, 2-aminoethylamino group, and 3-trimethoxysilylpropylamino group are preferable.
  • alkoxysilane examples include alkoxysilanes having an amino group such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl(dimethoxy)(methyl)silane, 3-aminopropyl(diethoxy)(methyl)silane, 3-aminopropyl(diethoxy)(ethyl)silane, 3-(1-methylpentylideneamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyl(dimethoxy)(methyl)silane, and bis[3-trimethoxysilylpropyl]amine; alkoxysilanes having an epoxy group such as 3-(glycidyloxy)propyltrimethoxysilane, 3-(glycidyloxy)propyl
  • the alkoxysilane (c) is preferably used for the primer of the present invention in an amount of 1 to 2,000 parts by mass relative to 100 parts by mass of a complex formed of the hyperbranched polymer and the metal fine particles described below. If the amount is 1 part by mass or more, superior base material adhesion can be obtained. If the amount is 2,000 parts or less, superior platability can be obtained. The amount is more preferably 5 to 1,000 parts by mass.
  • the primer of the present invention comprises the hyperbranched polymer (a) having an ammonium group at a molecular terminal, the metal fine particles (b), and the alkoxysilane (c) having an amino group optionally substituted with an aliphatic group or an epoxy group, or an oligomer thereof, in which the hyperbranched polymer and the metal fine particles preferably form a complex.
  • the term complex means a state in which the hyperbranched polymer coexists with the metal fine particles so as to be in contact with or in proximity to the metal fine particles through the action of the ammonium group at the terminal of the hyperbranched polymer to form a particulate form.
  • the complex has a structure in which the ammonium group of the hyperbranched polymer is attached to or coordinates with the metal fine particles.
  • the "complex" in the present invention includes a complex in which the metal fine particles and the hyperbranched polymer are bonded to form a complex as well as a complex in which the metal fine particles and the hyperbranched polymer exist independently without forming bonds.
  • the formation of a complex of the hyperbranched polymer having an ammonium group and the metal fine particles is performed concurrently with the preparation of the primer comprising the hyperbranched polymer and the metal fine particles.
  • the method include a method in which metal fine particles stabilized to a certain degree with a lower ammonium ligand are synthesized and the ligand is exchanged with the hyperbranched polymer and a method in which a metal ion is directly reduced in a solution of the hyperbranched polymer having an ammonium group to form a complex.
  • Examples thereof include a method in which an aqueous solution of a metal salt is added to a solution in which the hyperbranched polymer is dissolved and the resultant mixture is irradiated with ultraviolet light or a method in which an aqueous solution of a metal salt and a reducing agent are added to the solution to reduce the metal ion to form a complex.
  • the raw material that is metal fine particles stabilized to a certain degree with a lower ammonium ligand can be synthesized by the method described in Journal of Organometallic Chemistry 1996, 520, 143 to 162 , etc.
  • a hyperbranched polymer having an ammonium group is dissolved in the resultant reaction mixture of the metal fine particles, and the mixture is stirred at room temperature (approximately 25°C) or stirred with heating to obtain the intended metal fine particle complex.
  • any solvent may be used, provided the solvent is capable of dissolving the metal fine particles and the hyperbranched polymer having an ammonium group at the necessary concentrations or more.
  • Specific examples thereof include alcohols such as ethanol, n-propanol, and isopropanol; halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, and tetrahydropyran; nitriles such as acetonitrile and butyronitrile, and a mixture of these solvents.
  • THF tetrahydrofuran
  • 2-methyltetrahydrofuran 2-methyltetrahydrofuran
  • tetrahydropyran nitriles such as acetonitrile and butyronitrile, and a mixture of these solvents.
  • tetrahydrofuran is used.
  • the temperature at which the reaction mixture of the metal fine particles and the hyperbranched polymer having an ammonium group are mixed may be generally from 0°C to the boiling point of the solvent, and preferably in a range of room temperature (approximately 25°C) to 60°C.
  • a phosphine dispersant (phosphine ligand) may be used instead of the amine dispersant (lower ammonium ligand) to stabilize metal fine particles to a certain degree beforehand.
  • the direct reduction method involves dissolving a metal ion and a hyperbranched polymer having an ammonium group in a solvent and reduction is performed with a primary or secondary alcohol such as methanol, ethanol, isopropanol, and polyols to obtain the intended metal fine particle complex.
  • a primary or secondary alcohol such as methanol, ethanol, isopropanol, and polyols
  • the source of the metal ion used includes the above described metal salts.
  • any solvent may be used, provided the solvent is capable of dissolving the metal ion and the hyperbranched polymer having an ammonium group to the necessary concentrations or more.
  • Specific examples thereof include alcohols such as methanol, ethanol, propanol, and isopropanol; halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; amides such as N,N-dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP); sulfoxides such as dimethylsulfoxide, and mixed solutions of these solvents.
  • alcohols, halogenated hydrocarbons, and cyclic ethers are used. More preferably, ethanol, isopropanol, chloroform, and tetrahydrofur
  • the temperature for the reduction reaction can be generally within the range of 0°C to the boiling point of the solvents and is preferably within the range of room temperature (approximately 25°C) to 60°C.
  • the intended metal fine particle complex can be obtained.
  • the source of the metal ion used includes the above described metal salts and metal carbonyl complexes such as hexacarbonylchromium [Cr(CO) 6 ], pentacarbonyliron [Fe(CO) 5 ], octacarbonyldicobalt [Co 2 (CO) 8 ], and tetracarbonylnickel [Ni(CO) 4 ].
  • metal carbonyl complexes such as hexacarbonylchromium [Cr(CO) 6 ], pentacarbonyliron [Fe(CO) 5 ], octacarbonyldicobalt [Co 2 (CO) 8 ], and tetracarbonylnickel [Ni(CO) 4 ].
  • Zero-valent metal complexes such as metal olefin complexes, metal phosphine complexes, and metal nitrogen complexes may also be used.
  • any solvent may be used, provided the solvent is capable of dissolving the metal ion and the hyperbranched polymer having an ammonium group to the necessary concentrations or more.
  • Specific examples thereof include alcohols such as ethanol and propanol; halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, and tetrahydropyran; nitriles such as acetonitrile and butyronitrile, and a mixture of these solvents.
  • tetrahydrofuran is used.
  • the temperature at which the metal ion and the hyperbranched polymer having an ammonium group are mixed may be generally from 0°C to the boiling point of the solvent.
  • a metal ion and a hyperbranched polymer having an ammonium group may also be dissolved in a solvent and subjected to thermal decomposition to obtain the intended metal fine particle complex.
  • the source of the metal ion used includes the above described metal salts, metal complexes such as metal carbonyl complexes and other zero-valent metal complexes, and metal oxides such as silver oxide.
  • any solvent may be used, provided the solvent is capable of dissolving the metal ion and the hyperbranched polymer having an ammonium group to the necessary concentrations or more.
  • Specific examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, and ethylene glycol; halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; aromatic hydrocarbons such as benzene and toluene, and a mixture of these solvents.
  • toluene is used.
  • the temperature at which the metal ion and the hyperbranched polymer having an ammonium group are mixed may be generally from 0°C to the boiling point of the solvent.
  • the temperature is preferably close to the boiling point of the solvent, for example, 110°C (heating at reflux) in the case of toluene.
  • the complex of the hyperbranched polymer having an ammonium group and the metal fine particles thus obtained can be formed as a solid such as powder after purification such as reprecipitation.
  • the primer of the present invention may be in the form of varnish that comprises the hyperbranched polymer (a) having an ammonium group, the metal fine particles (b) (preferably a complex formed from these ingredients), and the alkoxysilane (c) (or an oligomer of the alkoxysilane) and that is used for forming [a priming layer for electroless plating] as described below.
  • the primer of the present invention may contain thickeners as needed to adjust the viscosity and rheological characteristics of the primer.
  • the addition of the thickeners therefore serves a particularly important role when the primer of the present invention is used as printing ink.
  • thickeners examples include poly(acrylic acid)s (including cross-linked ones) such as carboxyvinyl polymers (carbomers); vinyl polymers such as poly(vinyl pyrrolidone) (PVP), poly(vinyl alcohol) (PVA), poly(vinyl acetate) (PVAc) and polystyrene (PS); poly(ethylene oxide)s; polyesters; polycarbonates; polyamides; polyurethanes; polysaccharides such as dextrin, agar, carrageenan, alginic acid, gum arabic, guar gum, gum traganth, locust bean gum, starch, pectin, carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose; and proteins such as gelatin and casein.
  • the polymers include not only homopolymers but also copolymers. These thickeners may be used singly, or two or more thickeners may be used in combination.
  • the primer of the present invention may further appropriately contain additives such as surfactants and various kinds of surface conditioners as long as the effect of the present invention is not impaired.
  • surfactants examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, and sorbitan trioleate; polyoxyethylene nonionic surfactants such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan trioleate; fluorine-based surfactants such as EFTOP (registered trademark)
  • the surface conditioners include silicone-based leveling agents such as Shin-Etsu Silicone (registered trademark) KP-341 [manufacture by Shin-Etsu Chemical Co., Ltd.]; and silicone-based surface conditioners such as BYK (registered trademark) -302, BYK -307, BYK -322, BYK -323, BYK -330, BYK -333, BYK -370, BYK -375, and BYK -378 [manufactured by BYK Japan KK].
  • silicone-based leveling agents such as Shin-Etsu Silicone (registered trademark) KP-341 [manufacture by Shin-Etsu Chemical Co., Ltd.]
  • silicone-based surface conditioners such as BYK (registered trademark) -302, BYK -307, BYK -322, BYK -323, BYK -330, BYK -333, BYK -370, B
  • additives may be used singly, or two or more additives may be used in combination.
  • the additives are used in an amount of preferably 0.001 to 50 parts by mass, more preferably 0.005 to 10 parts by mass, and even more preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the complex formed of the hyperbranched polymer and the metal fine particles.
  • the primer of the present invention may be applied on a base material to form a priming layer for electroless plating.
  • the present invention is also directed to the priming layer for electroless plating.
  • the base material is not specifically limited, and a nonconducting base material or a conducting base material may be preferably used.
  • nonconducting base material examples include glass, ceramics; polyethylene resin, polypropylene resin, vinyl chloride resin, nylon (polyamide resin), polyimide resin, polycarbonate resin, acrylic resin, PEN (poly(ethylene naphthalate)) resin, PET (poly(ethylene terephthalate)) resin, PEEK (polyetheretherketone) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, epoxy resin, and polyacetal resin; and paper.
  • the nonconducting base material is suitably used in the form of sheet, film, or the like, and the thickness is not specifically limited.
  • the conducting base material examples include metals such as ITO (tin-doped indium oxide), ATO (antimony-doped tin oxide), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), GZO (gallium-doped zinc oxide), various stainless steels, aluminum and aluminum alloys such as duralumin, iron and iron alloys, copper and copper alloys such as brass, phosphor bronze, cupronickel, and beryllium copper, nickel and nickel alloys, and silver and silver alloys such as nickel silver.
  • metals such as ITO (tin-doped indium oxide), ATO (antimony-doped tin oxide), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), GZO (gallium-doped zinc oxide), various stainless steels, aluminum and aluminum alloys such as duralumin, iron and iron alloys, copper and copper alloys such as brass
  • a base material is also usable in which a thin film of any of these conducting base material is formed on the nonconducting base material.
  • the base material may also be a three-dimensional molded body.
  • the specific method to form a priming layer for electroless plating from the primer comprising the hyperbranched polymer having an ammonium group, the metal fine particles, and the alkoxysilane involves dissolving or dispersing the hyperbranched polymer having an ammonium group, the metal fine particles (preferably a complex formed from these ingredients), and the alkoxysilane in a suitable solvent to form a varnish, coating a base material on which a metal plating coating film is to be formed with the varnish by spin coating; blade coating; dip coating; roll coating; bar coating; die coating; spray coating; ink jet method; pen lithography such as fountain-pen nanolithography (FPN) and dip-pen nanolithography (DPN); relief printing such as letterpress printing, flexography, resin relief printing, contact printing, microcontact printing ( ⁇ CP), nanoimprinting lithography (NIL), and nanotransfer printing (nTP); intaglio printing such as gravure printing and engraving; planographic printing; stencil printing such as screen printing and mimeograph; offset printing; or
  • spin coating spin coating, spray coating, ink jet method, pen lithography, contact printing, ⁇ CP, NIL, and nTP are preferred.
  • Spin coating has advantages in that a highly volatile solution can be used because a short time is needed for coating and that a highly uniform coating can be obtained.
  • Spray coating needs only a very small amount of vanish to obtain a highly uniform coating, which is very advantageous for industrial production.
  • Ink jet method, pen lithography, contact printing, ⁇ CP, NIL, and nTP can form (draw), for example, fine patterns such as wiring efficiently, which is very advantageous for industrial production.
  • any solvent can be used, provided the solvent dissolves or disperses the complex and the alkoxysilane, and examples thereof include water; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, and dichlorobenzene; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, n-hexanol, n-octanol, 2-octanol, and 2-ethylhexanol; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and phenyl cellosolve; glycol ethers such as propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, di
  • the concentration of the complex dissolved or dispersed in the solvent is not limited, the concentration of the complex in the varnish is 0.05 to 90% by mass and preferably 0.1 to 80% by mass.
  • the method for drying the solvent is not specifically limited, and, for example, a hotplate or an oven can be used to evaporate the solvent under an appropriate atmosphere, i.e., air, inert gas such as nitrogen, or in vacuum. This can provide a priming layer having a uniformly formed film surface.
  • the heating temperature is not specifically limited, provided the solvent can be evaporated, and a temperature of 40 to 250°C is preferably used.
  • the priming layer for electroless plating formed on the base material thus obtained is subjected to electroless plating to form a metal plating film on the priming layer for electroless plating.
  • the present invention is also directed to the metal plating film thus obtained as well as the metal-coated base material having on a base material a priming layer for electroless plating and a metal plating film in this order.
  • the electroless plating process is not specifically limited, and any commonly known electroless plating process may be used.
  • the common method involves using a conventionally-known electroless plating solution and immersing a priming layer for electroless plating formed on the base material in the plating solution (bath).
  • the electroless plating solution mainly contains a metal ion (a metal salt), a complexing agent, and a reducing agent, and, depending on the application, a pH adjusting agent, a pH buffering agent, a reaction accelerator (a second complexing agent), a stabilizer, a surfactant (used for, for example, giving a luster to the plating film and improving wettability of the surface to be treated), and other agents are contained as appropriate.
  • Examples of the metal for use for the metal plating film formed by electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold, and alloys of these.
  • the metal is suitably selected depending on the purpose.
  • the complexing agent and the reducing agent may be suitably selected depending on the metal ion.
  • electroless nickel plating agent (Melplate (registered trademark) NI series) and electroless copper plating agent (Melplate (registered trademark) CU series) manufactured by Meltex Inc.; electroless nickel plating solution (ICP Nicoron (registered trademark) series), electroless copper plating solution (OPC-700 electroless copper M-K, ATS Addcopper IW), electroless tin plating solution (Substar SN-5), and electroless gold plating solution (Flash Gold 330, Self Gold OTK-IT) manufactured by Okuno Chemical Industries Co., Ltd.; electroless palladium plating solution (Pallet II) and electroless gold plating solution (Dip G series, NC Gold series) manufactured by Kojima Chemicals Co., Ltd.; electroless silver plating solution (S-DIA AG-40) manufactured by SASAKI CHEMICAL CO., LTD.; electroless nickel plating solution (SUMER (registered trademark) series
  • plating bath-related factors including_ temperature, pH, immersion time, concentration of metal ion, the presence or absence of stirring and stirring speed, the presence or absence of feeding of air and oxygen and feeding speed may be adjusted to control the forming speed of a metal coating film and the thickness of the film.
  • the HPS/chloroform solution was added with a feeding pump from the 300 mL reaction flask in which the HPS/ chloroform solution was placed to the sulfuryl chloride/ chloroform solution cooled to 0°C under nitrogen stream over 60 minutes so that the temperature of the reaction liquid was from -5 to 5°C. After the addition was completed, the reaction liquid was stirred for 6 hours while the temperature was kept at -5 to 5°C.
  • the 1 H NMR spectrum of the obtained HPS-Cl is shown in FIG. 1 . Because the peaks derived from the dithiocarbamate group (4.0 ppm, 3.7 ppm) disappeared, it was found that almost all the dithiocarbamate groups at the molecular terminals of the HPS were replaced with chlorine atoms in the obtained HPS-Cl.
  • the weight-average molecular weight Mw of the obtained HPS-Cl measured by GPC in terms of polystyrene was 14,000 and a degree of distribution Mw/Mn was 2.9.
  • the 13 C NMR spectrum of the obtained HPS-NOct 3 Cl is shown in FIG. 2 .
  • the peak of the methylene group bonded to the chlorine atom and the peak of the methylene group bonded to the ammonium group revealed that 71% of the chlorine atoms at the molecular terminals of the HPS-Cl were replaced with the ammonium groups in the obtained HPS-NOct 3 Cl.
  • the weight-average molecular weight Mw of the HPS-NOct 3 Cl calculated from the Mw (14,000) of the HPS-Cl and the degree of introduction (71%) of ammonium group was 37,000.
  • the result of ICP emission spectroscopy showed that the Pd content of the Pd[HPS-NOct 3 Cl] was 11% by mass.
  • the TEM (Transmission Electron Microscope) image showed that the Pd particles had a particle diameter of approximately 2 to 4 nm.
  • the 13 C NMR spectrum of the obtained HPS-N(Me) 2 OctCl is shown in FIG. 3 . From the peak of the benzene ring and the peak of the methyl group of the octyl group at the terminal, it was found that, in the obtained HPS-N(Me) 2 OctCl the chlorine atoms at the molecular terminals of the HPS-Cl molecules were replaced with ammonium groups nearly quantitatively.
  • the weight-average molecular weight of HPS-N(Me) 2 OctCl calculated from Mw (14,000) of HPS-Cl and the degree of introduction of ammonium group (100%) was 28,000.
  • the result of ICP emission spectroscopy showed that the Pd content of the Pd[HPS-N(Me) 2 OctCl] was 61% by mass.
  • the TEM (Transmission Electron Microscepe) image showed that the Pd particles had a particle diameter of approximately 2 to 5 nm.
  • AIL flask was charged with 50 mL of Melplate (registered trademark) NI-6522LF1 [manufactured by Meltex Inc.], 150 mL of Melplate (registered trademark) NI-6522LF2 [manufactured by Meltex Inc.], and 5 mL of Melplate (registered trademark) NI-6522LF Additive [manufactured by Meltex Inc.], and pure water was added to make a total volume of 1 L of solution. To this solution, a 10 vol% sulphuric acid aqueous solution was added to adjust the pH of the solution to 4.6 to obtain the electroless nickel plating solution.
  • a 10 vol% sulphuric acid aqueous solution was added to adjust the pH of the solution to 4.6 to obtain the electroless nickel plating solution.
  • a 100 mL flask was charged with 47 mL of pure water, 25 mL of CUPOSIT (registered trademark) COPPER MIX 328A [manufactured by Dow Chemical], 25 mL of CUPOSIT (registered trademark) COPPER MIX 328L [manufactured by Dow Chemical], and 3 mL of CUPOSIT (registered trademark) COPPER MIX 328C [manufactured by Dow Chemical] in order, and the mixture was stirred to form an electroless copper plating solution.
  • CUPOSIT registered trademark
  • COPPER MIX 328A manufactured by Dow Chemical
  • CUPOSIT registered trademark
  • COPPER MIX 328L manufactured by Dow Chemical
  • 3 mL of CUPOSIT (registered trademark) COPPER MIX 328C manufactured by Dow Chemical
  • the primer was spin-coated (200 rpm ⁇ 5 seconds and then 1,000 rpm ⁇ 30 seconds) on a glass substrate (50 mm ⁇ 50 mm). This substrate was dried on a hot plate at 80°C for 5 minutes to obtain a glass substrate having a priming layer on the whole surface of the substrate.
  • the obtained substrate was immersed in the electroless nickel plating solution prepared in Reference Example 1 heated to 75°C for 180 seconds.
  • the substrate taken out therefrom was washed with water and was dried on a hot plate at 80°C for 5 minutes to obtain a plated substrate.
  • the film uniformity was visually evaluated in accordance with the following criteria.
  • a piece of 18 mm-wide CELLOTAPE (registered trademark) [manufactured by Nichiban Co., Ltd. CT-18S] was applied to the obtained metal plating film area on the plated substrate and was strongly rubbed against the substrate with a finger to securely adhere.
  • the adhered CELLOTAPE (registered trademark) was then peeled off at one go, and the state of the metal plating film was visually evaluated in accordance with the following criteria. Table 1 collectively lists the results.
  • the formed metal plating films had excellent uniformity and had adhesion in terms of the tape test.
  • the metal plating film formed using the primer containing no alkoxysilane (Comparative Example 1) and the metal plating film formed on the primer comprising the alkoxysilane having no amino group had low uniformity and had no adhesion.
  • the primer for plating comprising the alkoxysilane having an amino group of the present invention is advantageous in obtaining a plating film having uniformity and high adhesion.
  • the primer was spin-coated (200 rpm ⁇ 5 seconds and then 1,000 rpm ⁇ 30 seconds) on each of the ITO films on the glass substrates with an ITO film (50 mm ⁇ 50 mm) [manufactured by foresight Co., Ltd].
  • This substrate was dried on a hot plate at 80°C for 5 minutes to obtain a glass substrate with the ITO film having a priming layer on the whole surface of the ITO film.
  • the obtained substrate was immersed for 180 seconds in the electroless nickel plating solution prepared in Reference Example 1 heated to 75°C.
  • the substrate taken out therefrom was washed with water and was dried on a hot plate at 80°C for 5 minutes to obtain a plated substrate.
  • the formed metal plating films had excellent uniformity and had adhesion in terms of the tape test.
  • the metal plating film formed using the primer containing no alkoxysilane (Comparative Example 3) and the metal plating film formed on the primer comprising the alkoxysilane having no amino group had low uniformity and had no adhesion.
  • the primer for plating comprising the alkoxysilane having an amino group of the present invention is advantageous in obtaining a plating film having uniformity and high adhesion also for the ITO films on glass.
  • the primer was spin-coated (200 rpm ⁇ 5 seconds and then 1,000 rpm ⁇ 30 seconds) on each of the PI films (50 mm ⁇ 50 mm) listed in Table 3. This film was dried on a hot plate at 80°C for 5 minutes to obtain a PI film having a priming layer on the whole surface of the film.
  • the obtained film was immersed in the electroless nickel plating solution prepared in Reference Example 1 heated to 75°C for 180 seconds.
  • the film taken out therefrom was washed with water and was dried on a hot plate at 80°C for 5 minutes to obtain a plated film.
  • Example 9 The procedure in Example 9 was repeated to obtain a plated film except that the drying conditions after the primer application and after the washing with water were 150°C and 10 minutes respectively, and that the bath temperature of the electroless nickel plating solution was changed to 80°C.
  • the metal plating film formed using the primer containing no alkoxysilane (Comparative Example 5) and the metal plating film formed on the primer comprising the alkoxysilane having no amino group had excellent uniformity but had no adhesion.
  • the primer for plating comprising the alkoxysilane having an amino group of the present invention is advantageous in obtaining a plating film having uniformity and high adhesion also for the PI films.
  • the primer was dip-coated on a nylon substrate N66 (10 ⁇ 50 ⁇ 1 mm) whose surface had been hydrophilized by being immersed in a 40°C, 8% by mass hydrochloric acid for 10 minutes.
  • This substrate was dried in a drier at 80°C for 10 minutes to obtain a nylon substrate having a priming layer on the whole surface of the substrate.
  • the obtained substrate was immersed in the electroless nickel plating solution prepared in Reference Example 1 heated to 70°C for 180 seconds.
  • the substrate taken out therefrom was washed with water and was dried in a drier at 80°C for 10 minutes to obtain a plated substrate.
  • Example 14 The procedure in Example 14 was repeated to obtain a plated substrate except that the above primer was used.
  • Example 15 The procedure in Example 15 was repeated to obtain a plated substrate except that IPA and the nylon substrate were changed to MEK and N6, respectively.
  • the formed metal plating films had excellent uniformity and had adhesion in terms of the tape test. For the different kind of nylon substrate, a similar effect was revealed (Example 16).
  • the metal plating film formed using the primer containing no alkoxysilane (Comparative Example 7) and the metal plating film formed on the primer comprising the alkoxysilane having no epoxy group had low uniformity and had no adhesion.
  • the primer for plating comprising the alkoxysilane having an epoxy group of the present invention is advantageous in obtaining a plating film having uniformity and high adhesion.
  • the primer was spin-coated (200 rpm ⁇ 5 seconds and then 1,000 rpm ⁇ 30 seconds) on a PEEK film (30 mm ⁇ 30 mm) whose surface had been hydrophilized using a UV ozone cleaning apparatus beforehand. This film was dried on a hot plate at 80°C for 10 minutes to obtain a PEEK film having a priming layer on the whole surface of the film.
  • the obtained film was immersed in the electroless nickel plating solution prepared in Reference Example 1 heated to 75°C for 180 seconds.
  • the film taken out therefrom was washed with water and was dried on a hot plate at 80°C for 10 minutes to obtain a plated film.
  • Example 17 The procedure in Example 17 was repeated to obtain a plated film except that the PEEK film was changed to PET-1 (40 mm ⁇ 40 mm) whose surface had been hydrophilized using a UV ozone cleaning apparatus beforehand.
  • Example 17 The procedure in Example 17 was repeated to obtain a plated film except that the PEEK film was changed to PET-2 (40 mm ⁇ 40 mm).
  • the plating films formed using the primer of the present invention comprising the alkoxysilane having an amino group had excellent uniformity and had adhesion in terms of the tape test for all the films.
  • inkjet coating was performed on the PI film PI-1. Specifically, using the fine droplet ejecting apparatus having 85 droplet ejecting nozzles in a row at intervals of 423 ⁇ m, the primer was ejected onto the PI film 571 times per second while moving the fine droplet ejecting apparatus by 10 cm at 40 mm/second relatively while keeping a gap of 0.5 mm relative to the PI film.
  • the primer is applied onto the PI film at intervals of 423 ⁇ m in an X-axial direction (the direction in which the nozzles are arranged) and at intervals of 70 ⁇ m in a Y-axial direction (the travel direction of the fine droplet ejecting apparatus).
  • the amount of liquid of the primer per droplet calculated from an obtained film thickness was approximately 20 to 40 pL.
  • the film to which the primer had been applied was left as it was (approximately 25°C) for 1 minute and was dried on a hot plate at 160°C for 5 minutes to obtain a PI film having 85 linear priming layers on the film.
  • FIG. 4 shows an electron microscope image of the obtained metal plating film on the film
  • FIG. 5 shows a sectional SEM image of one linear metal plating film.
  • the obtained metal plating film on the film was observed to find that the metal plating film having metallic luster was precipitated on the whole surface of the priming layers formed linearly without non-uniformity and the metal plating film was uniformly formed.
  • the film adhesion of the metal plating film was evaluated by the above method to find that the metal plating film was not separated and remained adhering to the film regardless of whether the direction of peeling off CELLOTAPE (registered trademark) was the X-axial direction or the Y-axial direction.
  • a solution obtained by further diluting the primer six times with ethanol was spin-coated (200 rpm ⁇ 5 seconds and then 1,000 rpm ⁇ 30 seconds) on the PI film PI-1 (40 mm ⁇ 40 mm) whose surface had been hydrophilized using a UV ozone cleaning apparatus beforehand.
  • This film was dried on a hot plate at 150°C for 5 minutes to obtain a PI film having a priming layer on the whole surface of the film.
  • the obtained film was immersed for 180 seconds in the electroless nickel plating solution prepared in Reference Example 1 heated to 75°C.
  • the film taken out therefrom was washed with water and was dried on a hot plate at 150°C for 5 minutes to obtain a plated film.
  • a PI film having a priming layer on the whole surface of the film produced by the same method as Example 21 was immersed for 300 seconds in the electroless copper plating solution prepared in Reference Example 2 temperature-regulated at 25°C. The film taken out therefrom was washed with water and was dried on a hot plate at 150°C for 5 minutes to obtain a plated film.
  • Patent Document 1 WO 2010/021386 Pamphlet

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Claims (11)

  1. Primer zum Bilden eines Metallplattierungsfilms auf einem Basismaterial durch stromloses Plattieren, wobei der Primer umfasst:
    (a) ein hyperverzweigtes Polymer mit einer Ammoniumgruppe an einem Molekülende und einem gewichtsmittleren Molekulargewicht von 500 bis 5.000.000;
    (b) einen Metallfeinpartikel; und
    (c) ein Alkoxysilan mit einer Aminogruppe, optional substituiert mit einer aliphatischen Gruppe oder einer Epoxygruppe, oder ein Oligomer des Alkoxysilans.
  2. Primer gemäß Anspruch 1, wobei
    die Ammoniumgruppe des hyperverzweigten Polymers (a) an den Metallfeinpartikel (b) gebunden ist, um einen Komplex zu bilden.
  3. Primer gemäß Anspruch 1 oder 2, wobei
    das hyperverzweigte Polymer (a) ein hyperverzweigtes Polymer der Formel [1] ist:
    Figure imgb0019
     (worin R1 jeweils unabhängig voneinander ein Wasserstoffatom oder eine Methylgruppe sind, R2 bis R4 jeweils unabhängig voneinander ein Wasserstoffatom, eine lineare, verzweigte oder cyclische Alkylgruppe mit einer Kohlenstoffatomzahl von 1 bis 20, eine C7-20-Arylalkylgruppe oder -(CH2CH2O)mR5 sind (worin R5 ein Wasserstoffatom oder eine Methylgruppe ist; und m eine ganze Zahl von 2 bis 100 ist) (wobei die Alkylgruppe und die Arylalkylgruppe optional mit einer Alkoxygruppe, einer Hydroxygruppe, einer Ammoniumgruppe, einer Carboxylgruppe oder einer Cyanogruppe substituiert sind), oder zwei Gruppen von R2 bis R4 zusammen für eine lineare, verzweigte oder cyclische Alkylengruppe stehen, oder R2 bis R4 zusammen mit einem Stickstoffatom, an das R2 bis R4 gebunden sind, optional einen Ring bilden; X-ein Anion ist; n die Anzahl der sich wiederholenden Struktureinheiten und eine ganze Zahl von 5 bis 100.000 ist; und A1 eine Struktur der Formel [2] ist:
    Figure imgb0020
     (worin A2 eine lineare, verzweigte oder cyclische Alkylengruppe mit einer Kohlenstoffatomzahl von 1 bis 30 ist, die optional eine Etherbindung oder eine Esterbindung enthält; und Y1 bis Y4 jeweils unabhängig voneinander ein Wasserstoffatom, eine C1-20-Alkylgruppe, eine C1-20-Alkoxygruppe, eine Nitrogruppe, eine Hydroxygruppe, eine Aminogruppe, eine Carboxylgruppe oder eine Cyanogruppe sind)).
  4. Primer gemäß Anspruch 3, wobei
    das hyperverzweigte Polymer (a) ein hyperverzweigtes Polymer der Formel [3] ist:
    Figure imgb0021
     (worin R1, R2 und n die gleichen Bedeutungen haben, wie oben beschrieben).
  5. Primer gemäß einem der Ansprüche 1 bis 4, wobei
    der Metallfeinpartikel (b) ein Feinpartikel von mindestens einem Vertreter ist, der aus der Gruppe ausgewählt ist, die aus Eisen (Fe), Cobalt (Co), Nickel (Ni), Kupfer (Cu), Palladium (Pd), Silber (Ag), Zinn (Sn), Platin (Pt) und Gold (Au) besteht.
  6. Primer gemäß Anspruch 5, wobei
    der Metallfeinpartikel (b) ein Palladium-Feinpartikel ist.
  7. Primer gemäß Anspruch 5 oder 6, wobei
    der Metallfeinpartikel (b) ein Feinpartikel mit einem mittleren Partikeldurchmesser von 1 bis 100 nm ist.
  8. Primer gemäß einem der Ansprüche 1 bis 7, wobei
    das Alkoxysilan (c) eine Verbindung der Formel [4] ist:

            Z-L-Si(R6)a(OR7)3-a      [4]

    (worin R6 eine C1-6-Alkylgruppe oder eine Phenylgruppe ist; R7 jeweils unabhängig voneinander eine Methylgruppe oder eine Ethylgruppe sind; L eine C1-6-Alkylengruppe ist, die optional eine Etherbindung enthält; Z eine Aminogruppe ist, die optional mit einer aliphatischen Gruppe oder einer Epoxygruppe substituiert ist; und a = 0 oder 1 ist).
  9. Primer-Schicht zum stromlosen Plattieren, erhalten durch Bilden einer Schicht des Primers, wie in einem der Ansprüche 1 bis 8 beansprucht.
  10. Metallbeschichtetes Basismaterial, umfassend:
    ein Basismaterial;
    die Primer-Schicht zum stromlosen Plattieren gemäß Anspruch 9, die auf dem Basismaterial ausgebildet ist; und
    ein stromloser Metallplattierungsfilm, der auf der Primer-Schicht zum stromlosen Plattieren ausgebildet ist.
  11. Verfahren zur Herstellung eines metallbeschichteten Basismaterials, wobei das Verfahren umfasst:
    einen Prozess A: das Beschichten eines Basismaterials mit dem Primer, wie in einem der Ansprüche 1 bis 8 beansprucht, um eine Primer-Schicht zu bilden; und
    einen Prozess B: das Eintauchen des Basismaterials mit der Primer-Schicht in ein Bad zum stromlosen Plattieren, um einen Metallplattierungsfilm zu bilden.
EP13837102.6A 2012-09-13 2013-09-12 Basismittel für stromlose plattierung Active EP2896720B1 (de)

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TW201920306A (zh) * 2017-07-25 2019-06-01 日商日產化學股份有限公司 金屬微粒子複合物之製造方法
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