WO2014042215A1 - Agent de base pour dépôt autocatalytique - Google Patents

Agent de base pour dépôt autocatalytique Download PDF

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Publication number
WO2014042215A1
WO2014042215A1 PCT/JP2013/074714 JP2013074714W WO2014042215A1 WO 2014042215 A1 WO2014042215 A1 WO 2014042215A1 JP 2013074714 W JP2013074714 W JP 2013074714W WO 2014042215 A1 WO2014042215 A1 WO 2014042215A1
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group
metal
film
plating
hyperbranched polymer
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PCT/JP2013/074714
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English (en)
Japanese (ja)
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大吾 齊藤
小島　圭介
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日産化学工業株式会社
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Priority to KR1020207003144A priority Critical patent/KR102157192B1/ko
Priority to JP2014535588A priority patent/JP6354950B2/ja
Priority to US14/428,189 priority patent/US20160010215A1/en
Priority to EP13837102.6A priority patent/EP2896720B1/fr
Priority to CN201380047242.XA priority patent/CN104641017B/zh
Priority to KR1020157007380A priority patent/KR20150054851A/ko
Publication of WO2014042215A1 publication Critical patent/WO2014042215A1/fr

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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 an electroless plating base material containing a hyperbranched polymer, metal fine particles and alkoxysilane.
  • a film with a uniform thickness can be obtained by simply immersing the substrate in the plating solution, regardless of the type or shape of the substrate.
  • Metal plating films can also be applied to non-conductive materials such as plastic, ceramic, and glass. For example, it is widely used in various fields such as decorative applications such as imparting a sense of quality and aesthetics to resin moldings such as automobile parts, and wiring technologies such as electromagnetic shielding, printed circuit boards, and large-scale integrated circuits. ing.
  • decorative applications such as imparting a sense of quality and aesthetics to resin moldings such as automobile parts
  • wiring technologies such as electromagnetic shielding, printed circuit boards, and large-scale integrated circuits. ing.
  • the pre-processing for improving the adhesiveness of a base material and a metal plating film is performed.
  • the surface to be treated is roughened and / or made hydrophilic by various etching means, and then the sensitization of supplying an adsorbing substance that promotes adsorption of the plating catalyst onto the surface to be treated is performed.
  • a treatment (sensitization) and an activation treatment (activation) for adsorbing the plating catalyst on the surface to be treated are performed.
  • the sensitizing treatment immerses the object to be treated in an acidic solution of stannous chloride, so that a metal (Sn 2+ ) that can act as a reducing agent adheres to the surface to be treated.
  • the object to be treated is immersed in an acidic solution of palladium chloride as an activation treatment for the sensitized surface to be treated.
  • the palladium ions in the solution are reduced by the metal (tin ion: Sn 2+ ) as a reducing agent, and adhere to the surface to be processed as active palladium catalyst nuclei.
  • it is immersed in an electroless plating solution to form a metal plating film on the surface to be treated.
  • hyperbranched polymers classified as dendritic (dendritic) polymers actively introduce branching, and the most remarkable feature is the large number of terminal groups.
  • a reactive functional group is added to this end group, the polymer has a reactive functional group at a very high density.
  • a high-sensitivity capture agent for functional substances such as catalysts, a high-sensitivity multifunctional Application as a crosslinking agent, a dispersing agent or a coating agent of a metal or a metal oxide is expected.
  • Patent Document 1 an example in which a composition containing a hyperbranched polymer having an ammonium group and metal fine particles is used as a reduction catalyst has been reported (Patent Document 1).
  • the roughening process performed in the pretreatment process uses a chromium compound (chromic acid), and the number of pretreatment processes is very large.
  • the molding technology for resin casings has been improved, and a method that enables plating of a clean casing surface as it is, especially with the miniaturization of electronic circuit formation and the speeding up of electrical signals, is highly electroless.
  • the present invention pays attention to such problems, and aims to provide a new base material used as a pretreatment process of electroless plating that can be easily processed with a small number of processes and can realize cost reduction in consideration of the environment.
  • the present inventors have combined a hyperbranched polymer having an ammonium group at the molecular end with metal fine particles and an alkoxysilane, and a layer obtained by applying this to a substrate. Was found to be excellent in plating properties and adhesion as an underlayer for electroless metal plating, and completed the present invention.
  • the present invention is a base agent for forming a metal plating film on a substrate by electroless plating, and (a) has an ammonium group at the molecular end and a weight average molecular weight of 500.
  • Substrates comprising a hyperbranched polymer of ⁇ 5,000,000, (b) fine metal particles, and (c) an alkoxy group having an amino group optionally substituted with an aliphatic group or an epoxy group, or an oligomer thereof It relates to the agent.
  • the present invention relates to the base agent according to the first aspect, in which the ammonium group of the hyperbranched polymer (a) is attached to the metal fine particles (b) to form a complex.
  • each R 1 independently represents a hydrogen atom or a methyl group
  • R 2 to R 4 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
  • the alkyl group and arylalkyl group may be substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxyl group, or a cyano group), or two groups of R 2 to R 4 may be bonded together.
  • a number of structures an integer of 5 ⁇ 100,000, A 1 represents a structure represented by the formula [2].)
  • a 2 represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, and Y 1 to Y 4 each independently represents hydrogen.
  • the said (a) hyperbranched polymer is related with the base agent as described in a 3rd viewpoint which is a hyperbranched polymer represented by Formula [3].
  • the metal fine particles (b) are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (
  • the present invention relates to the base material according to the fifth aspect, wherein the metal fine particles (b) are palladium fine particles.
  • the present invention relates to the base agent according to the fifth aspect or the sixth aspect, wherein the metal fine particles (b) are fine particles having an average particle diameter of 1 to 100 nm.
  • the present invention relates to the base agent according to any one of the first to seventh aspects, wherein (c) the alkoxysilane is a compound represented by the formula [4]. (Wherein R 6 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, R 7 independently represents a methyl group or an ethyl group, and L represents the number of carbon atoms optionally containing an ether bond.
  • the present invention relates to an electroless plating base layer obtained by layering the base agent according to any one of the first aspect to the eighth aspect.
  • a 10th viewpoint it is related with the metal plating film formed on this base layer by electroless-plating to the electroless plating base layer as described in a 9th viewpoint.
  • the base material, the electroless plating base layer according to the ninth aspect formed on the base material, and the metal plating film according to the tenth aspect formed on the electroless plating base layer And a metal-coated substrate.
  • Step A Applying the base agent according to any one of the first aspect to the eighth aspect on the base material and providing the base layer
  • Step B Electroless plating bath for the base material provided with the base layer A step of forming a metal plating film by dipping in a metal.
  • the base agent of the present invention can easily form a base layer of electroless metal plating simply by coating on a substrate. Moreover, the base agent of this invention can form the base layer which is excellent in adhesiveness with a base material. Furthermore, the base material of the present invention can draw fine lines on the order of ⁇ m and can be suitably used for various wiring techniques.
  • the electroless metal plating base layer formed from the base agent of the present invention can be easily formed by simply immersing it in an electroless plating bath, and the substrate, the base layer, and the metal plating film can be formed. The provided metal-coated substrate can be easily obtained. And the said metal plating film is excellent in adhesiveness with a lower base layer. That is, by forming the base layer on the base material using the base material of the present invention, it is possible to form a metal plating film having excellent adhesion to the base material.
  • FIG. 1 is a diagram showing a 1 H NMR spectrum of a hyperbranched polymer (HPS-Cl) having a chlorine atom at the molecular end obtained in Synthesis Example 1.
  • FIG. 2 is a diagram showing a 13 C NMR spectrum of a hyperbranched polymer (HPS-NOct 3 Cl) having a trioctylammonium group at the molecular end obtained in Synthesis Example 2.
  • FIG. 3 is a diagram showing a 13 C NMR spectrum of a hyperbranched polymer (HPS—N (Me) 2 OctCl) having a dimethyloctylammonium group at the molecular end obtained in Synthesis Example 4.
  • FIG. 4 is a view showing an electron microscope image of a metal plating film on the PI film obtained in Example 20.
  • FIG. 5 is a view showing a cross-sectional SEM (scanning electron microscope) image of the metal plating film on the PI film obtained in Example 20.
  • FIG. 4 is a view showing an electron microscope image of a metal plating film on the PI film obtained in Example 20.
  • FIG. 5 is a view showing a cross-sectional SEM (scanning electron microscope) image of the metal plating film on the PI film obtained in Example 20.
  • the base agent of the present invention is substituted with (a) a hyperbranched polymer containing an ammonium group and having a weight average molecular weight of 500 to 5,000,000, (b) metal fine particles, and (c) an aliphatic group. It is a base agent containing an alkoxysilane having an amino group or an epoxy group, or an oligomer thereof.
  • the base agent of the present invention is suitably used as a base agent for forming a metal plating film on a substrate by electroless plating.
  • the hyperbranched polymer used in the base material of the present invention is a polymer having an ammonium group at the molecular end and a weight average molecular weight of 500 to 5,000,000, specifically represented by the following formula [1]. And hyperbranched polymers.
  • R 1 represents a hydrogen atom or a methyl group independently.
  • R 2 to R 4 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or — ( CH 2 CH 2 O) m R 5 (wherein R 5 represents a hydrogen atom or a methyl group, and m represents an arbitrary integer of 2 to 100).
  • the alkyl group and arylalkyl group may be substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxyl group, or a cyano group.
  • R 2 to R 4 together represent a linear, branched or cyclic alkylene group, or R 2 to R 4 and the nitrogen atom to which they are bonded together To form a ring.
  • X ⁇ represents an anion
  • n represents the number of repeating unit structures, which represents an integer of 5 to 100,000.
  • Examples of the linear alkyl group having 1 to 20 carbon atoms in R 2 to R 4 include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n -Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc., and a group having 8 or more carbon atoms is preferred in that the base agent is difficult to elute into the electroless plating solution.
  • Octyl groups are preferred.
  • Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and the like.
  • Examples of the cyclic alkyl group include a cyclopentyl ring and a group having a cyclohexyl ring structure.
  • Examples of the arylalkyl group having 7 to 20 carbon atoms in R 2 to R 4 include a benzyl group and a phenethyl group.
  • examples of the linear alkylene group in which two of R 2 to R 4 are combined include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, and an n-hexylene group. It is done.
  • examples of the branched alkylene group include an isopropylene group, an isobutylene group, and a 2-methylpropylene group.
  • examples of the cyclic alkylene group include alicyclic aliphatic groups having a monocyclic, polycyclic or bridged cyclic structure having 3 to 30 carbon atoms. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, or pentacyclo structure having 4 or more carbon atoms.
  • alkylene groups may contain a nitrogen atom, a sulfur atom or an oxygen atom in the group.
  • the ring formed by combining R 2 to R 4 and the nitrogen atom bonded thereto may contain a nitrogen atom, a sulfur atom or an oxygen atom in the ring. Examples thereof include a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, and a bipyridyl ring.
  • R 2 to R 4 examples include [methyl group, methyl group, methyl group], [methyl group, methyl group, ethyl group], [methyl group, methyl group, n-butyl group], [methyl group] 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-buty
  • a 1 represents a structure represented by the following formula [2].
  • a 2 represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
  • Y 1 to Y 4 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxyl group, or a cyano group.
  • alkylene group of A 2 examples include linear alkylene groups such as methylene group, ethylene group, n-propylene group, n-butylene group and n-hexylene group, isopropylene group, isobutylene group, 2-methyl group.
  • examples include branched alkylene groups such as propylene groups.
  • the cyclic alkylene group include alicyclic aliphatic groups having a monocyclic, polycyclic and bridged cyclic structure having 3 to 30 carbon atoms. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, or pentacyclo structure having 4 or more carbon atoms.
  • structural examples (a) to (s) of the alicyclic portion of the alicyclic aliphatic group are shown below.
  • Examples of the alkyl group having 1 to 20 carbon atoms of Y 1 to Y 4 in the above formula [2] include a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, and an n-pentyl group.
  • Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, isopropoxy group, cyclohexyloxy group, n-pentyloxy group and the like.
  • Y 1 to Y 4 are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • the A 1 is a structure represented by the following formula [5].
  • the hyperbranched polymer used in the present invention includes a hyperbranched polymer represented by the following formula [3].
  • R ⁇ 1 >, R ⁇ 2 > and n represent the same meaning as the above.
  • the hyperbranched polymer having an ammonium group at the molecular end used in the present invention can be obtained, for example, by reacting an amine compound with a hyperbranched polymer having a halogen atom at the molecular end.
  • a hyperbranched polymer having a halogen atom at the molecular end can be produced from a hyperbranched polymer having a dithiocarbamate group at the molecular end in accordance with the description in WO 2008/029688.
  • As the hyperbranched polymer having a dithiocarbamate group at the molecular end a commercially available product can be used, and Hypertech (registered trademark) HPS-200 manufactured by Nissan Chemical Industries, Ltd. can be preferably used.
  • the amine compounds that can be used in this reaction are, as primary amines, 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, n-eicosylamine and other aliphatic amines;
  • Secondary amines include 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-octylamine, di
  • Tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-octylamine, tri-n-dodecyl.
  • Amine dimethylethylamine, dimethyl-n-butylamine, dimethyl-n-hexylamine, dimethyl-n-octylamine, dimethyl-n-decylamine, diethyl-n-decylamine, dimethyl-n-dodecylamine, dimethyl-n-tetradecyl Aliphatic amines such as amine, dimethyl-n-hexadecylamine, dimethyl-n-octadecylamine, dimethyl-n-eicosylamine; pyridine, pyrazine, pyrimidine, quinoline, 1-methylimidazole, 4,4′-bipyridyl, 4-methyl-4,4 - Nitrogen-containing heterocyclic compounds such as bipyridyl and the like.
  • the amount of the amine compound that can be used in these reactions is 0.1 to 20 molar equivalents, preferably 0.5 to 10 molar equivalents, based on 1 mol of the halogen atom of the hyperbranched polymer having a halogen atom at the molecular end. Preferably, it is 1 to 5 molar equivalents.
  • the reaction between the hyperbranched polymer having a halogen atom at the molecular end and the amine compound can be carried out in water or an organic solvent in the presence or absence of a base.
  • the solvent to be used is preferably a solvent capable of dissolving a hyperbranched polymer having a halogen atom at the molecular end and an amine compound.
  • a hyperbranched polymer having a halogen atom at the molecular end and an amine compound can be dissolved, but a solvent that does not dissolve the hyperbranched polymer having an ammonium group at the molecular end is more preferable because it can be easily isolated.
  • the solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction.
  • the amides can be used. These solvents may be used alone or in combination of two or more.
  • the amount used is 0.2 to 1,000 times, preferably 1 to 500 times, more preferably 5 to 100 times, most preferably the mass of the hyperbranched polymer having a halogen atom at the molecular end. It is preferable to use a solvent having a mass of 5 to 50 times.
  • Suitable bases generally include alkali metal hydroxides and alkaline earth metal hydroxides (eg sodium hydroxide, potassium hydroxide, calcium hydroxide), alkali metal oxides and alkaline earth metal oxides (eg lithium oxide). Calcium oxide), alkali metal hydrides and alkaline earth metal hydrides (eg sodium hydride, potassium hydride, calcium hydride), alkali metal amides (eg sodium amide), alkali metal carbonates and alkaline earth metal carbonates Inorganic compounds such as salts (eg lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate), alkali metal bicarbonates (eg sodium bicarbonate), and alkali metal alkyls, alkylmagnesium halides, alkali metal alkoxides, alkaline earth metals Alkoki De, organometallic compounds such as dimethoxy magnesium was used.
  • alkali metal hydroxides and alkaline earth metal hydroxides eg sodium hydroxide, potassium hydroxide,
  • potassium carbonate and sodium carbonate are particularly preferred.
  • the amount used is 0.2 to 10 molar equivalents, preferably 0.5 to 10 molar equivalents, most preferably 1 to 5 molar equivalents per mole of halogen atoms of the hyperbranched polymer having a halogen atom at the molecular end. It is preferable to use the base.
  • reaction conditions are appropriately selected from a reaction time of 0.01 to 100 hours and a reaction temperature of 0 to 300 ° C.
  • the reaction time is 0.1 to 72 hours, and the reaction temperature is 20 to 150 ° C.
  • a hyperbranched polymer represented by the formula [1] can be obtained regardless of the presence / absence of a base.
  • a hyperbranched polymer having a halogen atom at the molecular end is reacted with a primary amine or secondary amine compound in the absence of a base, the terminal secondary amine and tertiary tertiary of the corresponding hyperbranched polymer are respectively reacted.
  • a hyperbranched polymer having ammonium groups terminated with protonated primary amines is obtained.
  • the terminal secondary amine of the corresponding hyperbranched polymer can be obtained by mixing with an aqueous solution of an acid such as hydrogen chloride, hydrogen bromide, or hydrogen iodide in an organic solvent. And a hyperbranched polymer having an ammonium group terminated with a tertiary amine protonated.
  • the hyperbranched polymer has a weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography of 500 to 5,000,000, preferably 1,000 to 500,000, more preferably 2,000. ⁇ 200,000, most preferably 3,000 ⁇ 100,000. Further, the dispersity 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 used in the base material of the present invention are not particularly limited, and the metal species are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag). , Tin (Sn), platinum (Pt), and gold (Au).
  • the metal species are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag). , Tin (Sn), platinum (Pt), and gold (Au).
  • the metal species are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag). , Tin (Sn), platinum (Pt), and gold (Au).
  • the metal species are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag). , Tin (Sn), platinum (Pt), and gold (Au).
  • the metal fine particles can be obtained by reducing metal ions by, for example, a method of irradiating an aqueous solution of a metal salt with a high-pressure mercury lamp or a method of adding a compound having a reducing action (so-called reducing agent) to the aqueous solution.
  • a compound having a reducing action for example, an aqueous solution of a metal salt is added to a solution in which the hyperbranched polymer is dissolved and irradiated with ultraviolet light, or an aqueous solution of a metal salt and a reducing agent are added to the solution to reduce metal ions.
  • the base agent containing the hyperbranched polymer and the metal fine particles can be prepared while forming a complex of the hyperbranched polymer and the metal fine particles.
  • the reducing agent is not particularly limited, and various reducing agents can be used, and it is preferable to select the reducing agent according to the metal species to be contained in the obtained base material.
  • the reducing agent that can be used include metal borohydrides such as sodium borohydride and potassium borohydride; lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, aluminum beryllium hydride, hydrogenation
  • Aluminum hydride salts such as aluminum magnesium and calcium aluminum hydride; hydrazine compounds; citric acid and salts thereof; succinic acid and salts thereof; ascorbic acid and salts thereof; primary or secondary such as methanol, ethanol, isopropanol and polyol Tertiary alcohols; tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine [TMEDA], ethylenediaminetetraacetic acid [EDTA];
  • the average particle size of the metal fine particles is preferably 1 to 100 nm. The reason is that when the average particle diameter of the metal fine particles exceeds 100 nm, the surface area decreases and the catalytic activity decreases.
  • the average particle size is more preferably 75 nm or less, and particularly preferably 1 to 30 nm.
  • the amount of the (a) hyperbranched polymer added to the base material of the present invention is preferably 50 to 2,000 parts by mass with respect to 100 parts by mass of the (b) metal fine particles.
  • the amount is less than 50 parts by mass, the dispersibility of the metal fine particles is insufficient, and when the amount exceeds 2,000 parts by mass, the organic matter content increases, and problems such as physical properties tend to occur. More preferably, it is 100 to 1,000 parts by mass.
  • alkoxysilane or oligomer thereof used for the base material of the present invention has an amino group or an epoxy group which may be substituted with an aliphatic group. If it is alkoxysilane or its oligomer, it will not specifically limit.
  • alkoxysilane having an amino group optionally substituted with an aliphatic group a silane compound having one or more amino groups optionally substituted with an aliphatic group in one molecule and having an alkoxysilyl group Is mentioned.
  • alkoxysilane having an epoxy group include silane compounds having one or more epoxy groups in one molecule and having an alkoxysilyl group.
  • the alkoxysilane used in the base agent of the present invention includes a compound represented by the following formula [4].
  • R 6 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group
  • R 7 each independently represents a methyl group or an ethyl group
  • L may contain an ether bond.
  • Z represents an amino group which may be substituted with an aliphatic group, or an epoxy group
  • a represents 0 or 1;
  • alkyl group having 1 to 6 carbon atoms in R 6 examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-hexyl. Group, cyclohexyl group and the like. Among these, a methyl group is preferable.
  • Examples of the alkylene group having 1 to 6 carbon atoms which may contain an ether bond in L include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, a 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, 2- Examples include oxahexane-1,6-diyl group. Of these, an ethylene group, a trimethylene group, and a 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, a methylamino group, an ethylamino group, a 2-aminoethylamino group, a diethylamino group, a propylamino group, and a 3-trimethoxysilylpropylamino group. , 3-triethoxysilylpropylamino group, 1-methylpentylideneamino group and the like. Of these, an amino group, 2-aminoethylamino group, and 3-trimethoxysilylpropylamino group are preferable.
  • alkoxysilane examples include 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) Alkoxysilanes having an amino group such as propyl (dimethoxy) (methyl) silane and bis [3-trimethoxysilylpropyl] amine; 3- (glycidyloxy) propyltrimethoxysilane, 3- (glycidyloxy) propyltriethoxysilane , Dimethoxy (3 (Gly),
  • the amount of (c) alkoxysilane added to the base material of the present invention is preferably 1 to 2,000 parts by mass with respect to 100 parts by mass of the composite formed from the hyperbranched polymer and metal fine particles described later. By setting it as 1 mass part or more, the more superior base-material adhesiveness can be obtained, and more excellent plating property can be obtained by setting it as 2,000 mass parts or less. More preferred is 5 to 1,000 parts by mass.
  • the base agent of the present invention comprises (a) a hyperbranched polymer having an ammonium group at the molecular end, (b) an amino group optionally substituted with fine metal particles and (c) an aliphatic group, or an alkoxy having an epoxy group. Silane or an oligomer thereof is included, and at this time, it is preferable that the hyperbranched polymer and the metal fine particles form a complex.
  • the composite is a particle that is in contact with or close to the metal fine particles due to the action of the ammonium group at the end of the hyperbranched polymer to form a particulate form. It is expressed as a composite having a structure in which the ammonium group of the polymer is attached or coordinated to the metal fine particles.
  • the metal fine particles and the hyperbranched polymer are combined to form one composite as described above, but also the metal fine particles and the hyperbranched polymer have bonding portions. Those that are present independently without being formed may also be included.
  • Formation of a complex of a hyperbranched polymer having an ammonium group and metal fine particles is performed simultaneously with the preparation of a base material containing the hyperbranched polymer and metal fine particles, and the method includes a metal stabilized to some extent by a lower ammonium ligand.
  • an aqueous solution of a metal salt is added to a solution in which the hyperbranched polymer is dissolved and irradiated with ultraviolet light, or an aqueous solution of a metal salt and a reducing agent are added to the solution to reduce metal ions.
  • a complex can also be formed.
  • the metal fine particles stabilized to some extent by the lower ammonium ligand used as a raw material can be synthesized by the method described in Journal of Organometallic Chemistry 1996, 520, 143-162 and the like.
  • the target metal fine particle composite can be obtained by dissolving the hyperbranched polymer having an ammonium group in the obtained reaction mixture solution of metal fine particles and stirring at room temperature (approximately 25 ° C.) or with heating.
  • the solvent to be used is not particularly limited as long as it is a solvent capable of dissolving the metal fine particles and the hyperbranched polymer having an ammonium group at a required concentration or more.
  • alcohols such as ethanol, n-propanol, and isopropanol are used.
  • 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 mixtures of these solvents.
  • THF tetrahydrofuran
  • 2-methyltetrahydrofuran and tetrahydropyran nitriles such as acetonitrile and butyronitrile
  • mixtures of these solvents Preferably, 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 usually ranges from 0 ° C.
  • the metal fine particles can be stabilized to some extent in advance by using a phosphine dispersant (phosphine ligand) in addition to the amine dispersant (lower ammonium ligand).
  • phosphine dispersant phosphine ligand
  • amine dispersant lower ammonium ligand
  • the direct reduction method involves dissolving a hyperbranched polymer having a metal ion and an ammonium group in a solvent and reducing it with a primary or secondary alcohol such as methanol, ethanol, isopropanol, polyol, etc.
  • a primary or secondary alcohol such as methanol, ethanol, isopropanol, polyol, etc.
  • a fine particle composite can be obtained.
  • the metal ion source used here the above-mentioned metal salts can be used.
  • the solvent to be used is not particularly limited as long as it is a solvent capable of dissolving the hyperbranched polymer having a metal ion and an ammonium group at a required concentration or more, and specifically, alcohols such as methanol, ethanol, propanol, 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; N, N-dimethylformamide (DMF), N- Amides such as methyl-2-pyrrolidone (NMP); Sulfoxides such as dimethyl sulfoxide and the like, and mixtures of these solvents are preferable.
  • alcohols such as methanol, ethanol, propanol, isopropanol
  • Halogenated hydrocarbons such as methylene chloride and chloroform
  • Mashiku are ethanol, isopropanol, chloroform, tetrahydrofuran, and the like.
  • the temperature of the reduction reaction can usually be in the range of 0 ° C. to the boiling point of the solvent, and is preferably in the range of room temperature (approximately 25 ° C.) to 60 ° C.
  • a target metal fine particle composite can be obtained by dissolving a hyperbranched polymer having a metal ion and an ammonium group in a solvent and reacting them in a hydrogen gas atmosphere.
  • a metal ion source used here the above-mentioned metal salt, hexacarbonyl chromium [Cr (CO) 6 ], pentacarbonyl iron [Fe (Co) 5 ], octacarbonyl dicobalt [Co 2 (CO) 8 ].
  • a metal carbonyl complex such as tetracarbonyl nickel [Ni (CO) 4 ] can be used.
  • zero-valent metal complexes such as metal olefin complexes, metal phosphine complexes, and metal nitrogen complexes can also be used.
  • the solvent to be used is not particularly limited as long as it can dissolve a hyperbranched polymer having a metal ion and an ammonium group at a required concentration or higher.
  • alcohols such as ethanol and propanol
  • methylene chloride, chloroform Halogenated hydrocarbons such as tetrahydrofuran
  • cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and tetrahydropyran
  • nitriles such as acetonitrile and butyronitrile
  • a mixture of these solvents preferably tetrahydrofuran.
  • a range of usually 0 ° C. to the boiling point of the solvent can be used.
  • a target metal fine particle composite can be obtained by dissolving a hyperbranched polymer having a metal ion and an ammonium group in a solvent and causing a thermal decomposition reaction.
  • a metal ion source used here the above metal salts, metal carbonyl complexes, other zero-valent metal complexes, and metal oxides such as silver oxide can be used.
  • the solvent to be used is not particularly limited as long as it can dissolve the hyperbranched polymer having a metal ion and an ammonium group at a required concentration or more.
  • methanol, ethanol, n-propanol, isopropanol, ethylene glycol Alcohols such as: Halogenated hydrocarbons such as methylene chloride and chloroform; Cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; Nitriles such as acetonitrile and butyronitrile; Aromatics such as benzene and toluene Examples thereof include hydrocarbons and a mixture of these solvents, and preferably toluene.
  • the temperature at which the metal ion and the hyperbranched polymer having an ammonium group are mixed is usually 0 ° C. to the boiling point of the solvent, preferably around the boiling point of the solvent, for example, 110 ° C. (heating reflux) in the case of toluene. It is.
  • the thus obtained complex of the hyperbranched polymer having ammonium groups and the metal fine particles can be made into a solid form such as a powder through a purification treatment such as reprecipitation.
  • the base agent of the present invention comprises (a) a hyperbranched polymer having an ammonium group, (b) metal fine particles (preferably a composite comprising these), and (c) an alkoxysilane (or an oligomer thereof). It may be in the form of a varnish used when forming the [electroless plating base layer] described later.
  • the base agent of the present invention can adjust the viscosity and rheological properties of the base agent by blending a thickener as necessary. Therefore, the addition of the thickener plays an especially important role when the base agent of the present invention is used as a printing ink.
  • the thickener examples include polyacrylic acids such as carboxyvinyl polymer (carbomer) (including crosslinked ones); polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), polystyrene (PS) Polyethylene oxides; Polyester; Polycarbonate; Polyamide; Polyurethane; Dextrin, agar, carrageenan, alginic acid, gum arabic, guar gum, tragacanth gum, locust bean gum, starch, pectin, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose And other polysaccharides; and proteins such as gelatin and casein.
  • Each of the above polymers includes not only a homopolymer but also a copolymer. These thickeners may be used individually by 1 type, and may use 2 or more types together.
  • additives such as surfactants and various surface conditioners may be added as appropriate to the base material of the present invention.
  • surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxy Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, Sorbitan fatty acid esters such as sorbitan trioleate; polyoxyethylene sorbitan monolaurate, polyoxyethylene Polyoxyethylene nonionic surfactants such as sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate; EFTOP (registered trademark) EF-301, EF-303, EF-
  • the surface conditioner examples include silicone-based leveling agents such as Shin-Etsu Silicone (registered trademark) KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK (registered trademark) -302, 307, 322, and 323. , 330, 333, 370, 375, 378 [above, manufactured by Big Chemie Japan Co., Ltd.] and the like.
  • silicone-based leveling agents such as Shin-Etsu Silicone (registered trademark) KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK (registered trademark) -302, 307, 322, and 323. , 330, 333, 370, 375, 378 [above, manufactured by Big Chemie Japan Co., Ltd.] and the like.
  • additives may be used alone or in combination of two or more.
  • the amount of the additive used is preferably 0.001 to 50 parts by weight, more preferably 0.005 to 10 parts by weight, based on 100 parts by weight of the composite formed from the hyperbranched polymer and metal fine particles. 01-5 parts by mass is even more preferable.
  • Electroless plating underlayer The base agent of the present invention described above can form an electroless plating base layer by coating on a substrate. This electroless plating underlayer is also an object of the present invention.
  • a nonelectroconductive base material or a conductive base material can be used preferably.
  • the non-conductive substrate include glass, ceramic, etc .; polyethylene resin, polypropylene resin, vinyl chloride resin, nylon (polyamide resin), polyimide resin, polycarbonate resin, acrylic resin, PEN (polyethylene naphthalate) resin, PET (polyethylene) Terephthalate) resin, PEEK (polyetheretherketone) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, epoxy resin, polyacetal resin, etc .; paper and the like. These are preferably used in the form of a sheet or a film, and the thickness in this case is not particularly limited.
  • the conductive substrate examples include 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, white copper and beryllium copper, metals such as nickel and nickel alloys, and silver alloys such as silver and western silver Etc. Furthermore, the base material in which the thin film was formed with these electroconductive base materials on the said nonelectroconductive base material can also be used. Further, the base material may be a three-dimensional molded body.
  • the hyperbranched polymer having metal groups and metal fine particles (preferably A composite comprising these) and alkoxysilane are dissolved or dispersed in an appropriate solvent to form a varnish, and the varnish is formed on a substrate on which a metal plating film is formed by spin coating; blade coating; dip coating; Roll coating method; Bar coating method; Die coating method; Spray coating method; Ink jet method; Pen lithography such as fountain pen nano lithography (FPN), dip pen nano lithography (DPN); Letterpress printing, flexographic printing, resin letterpress printing, contact printing , Letterpress printing methods such as micro-contact printing ( ⁇ CP), nanoimprinting lithography (NIL), nanotransfer printing (nTP); intaglio printing methods such as gravure printing and engraving; lithographic printing methods; A thin layer is formed by applying a
  • spin coating spin coating, spray coating, ink jet, pen lithography, contact printing, ⁇ CP, NIL, and nTP are preferable.
  • spin coating method since it can be applied in a single time, even a highly volatile solution can be used, and there is an advantage that highly uniform application can be performed.
  • spray coating method highly uniform coating can be performed with a very small amount of varnish, which is industrially very advantageous.
  • ink jet method, pen lithography, contact printing, ⁇ CP, NIL, or nTP is used, a fine pattern such as a wiring can be efficiently formed (drawn), which is very advantageous industrially.
  • the solvent used here is not particularly limited as long as it dissolves or disperses the complex and the alkoxysilane.
  • water aromatic carbonization such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene, etc.
  • Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, n-hexanol, n-octanol, 2-octanol, 2-ethylhexanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, Cellosolves such as phenyl cellosolve; propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl Ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethylene glyco
  • solvents may be used alone, or two or more kinds of solvents may be mixed.
  • glycols such as ethylene glycol, propylene glycol and butylene glycol may be added.
  • concentration for dissolving or dispersing in the solvent is arbitrary, but the concentration of the complex in the varnish is 0.05 to 90% by mass, preferably 0.1 to 80% by mass.
  • the method for drying the solvent is not particularly limited.
  • the solvent may be evaporated using a hot plate or an oven in an appropriate atmosphere, that is, in an inert gas such as air or nitrogen, or in a vacuum. Thereby, it is possible to obtain an underlayer having a uniform film formation surface.
  • the firing temperature is not particularly limited as long as the solvent can be evaporated, but it is preferably performed at 40 to 250 ° C.
  • electroless plating treatment By electrolessly plating the electroless plating base layer formed on the substrate obtained as described above, a metal plating film is formed on the electroless plating base layer.
  • the metal plating film thus obtained, and the metal-coated base material provided in the order of the electroless plating base layer and the metal plating film on the base material are also objects of the present invention.
  • the electroless plating treatment (process) is not particularly limited, and can be performed by any generally known electroless plating treatment.
  • the plating is performed using a conventionally known electroless plating solution.
  • a method of immersing an electroless plating base layer formed on a substrate in a liquid (bath) is common.
  • the electroless plating solution mainly contains a metal ion (metal salt), a complexing agent, and a reducing agent, and a pH adjuster, a pH buffering agent, a reaction accelerator (second complexing agent) according to other uses.
  • a metal ion metal salt
  • a complexing agent complexing agent
  • a reducing agent a pH adjuster
  • a pH buffering agent pH buffering agent
  • a reaction accelerator second complexing agent
  • Stabilizers surfactants (use for imparting gloss to the plating film, use for improving wettability of the surface to be treated, etc.) and the like are appropriately included.
  • the metal used in the metal plating film formed by electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold, and alloys thereof, and are appropriately selected according to the purpose. Is done.
  • the complexing agent and the reducing agent may be appropriately selected according to the metal ion.
  • the electroless plating solution may be a commercially available plating solution.
  • an electroless nickel plating chemical (Melplate (registered trademark) NI series) manufactured by Meltex Co., Ltd., an electroless copper plating chemical (Melplate ( (Registered trademark) CU series); Electroless nickel plating solution (ICP Nicolon (registered trademark) series) manufactured by Okuno Pharmaceutical Industry Co., Ltd., Electroless copper plating solution (OPC-700 Electroless copper MK, ATS Addcopper IW) ), Electroless tin plating solution (Substar SN-5), electroless gold plating solution (flash gold 330, self gold OTK-IT); electroless palladium plating solution (pallet II) manufactured by Kojima Chemical Co., Ltd.
  • Electroless gold plating solution (Dip G series, NC gold series); Electroless silver plating solution manufactured by Sasaki Chemical Co., Ltd. ); Electroless nickel plating solution (Schumer (registered trademark) series, Schumer (registered trademark) crab black (registered trademark) series), Electroless palladium plating solution (S-KPD) manufactured by Nippon Kanisen Co., Ltd .; Dow Chemical Company Electroless copper plating solution (Cuposit (registered trademark) Coppermix series, Circuposit (registered trademark) series), Electroless palladium plating solution (Paramars (registered trademark) series), Electroless nickel plating solution (Duraposit ( (Registered trademark) series), electroless gold plating solution (Aurolectroles (registered trademark) series), electroless tin plating solution (Tinposit (registered trademark) series) and the like can be suitably used.
  • the electroless plating process adjusts the temperature, pH, immersion time, metal ion concentration, presence / absence of stirring, stirring speed, presence / absence of supply of air / oxygen, supply speed, etc. And the film thickness can be controlled.
  • HPS Hyperbranched polystyrene [Hypertech (registered trademark) HPS-200 manufactured by Nissan Chemical Industries, Ltd.]
  • AEAPM 3- (2-aminoethylamino) propyl (dimethoxy) (methyl) silane [manufactured by Tokyo Chemical Industry Co., Ltd.]
  • AEAP 3- (2-aminoethylamino) propyltrimethoxysilane [Tokyo Chemical Industry Co., Ltd.]
  • APMES 3-aminopropyl (diethoxy) (methyl) silane [manufactured by Tokyo Chemical Industry Co., Ltd.]
  • APES 3-aminopropyltriethoxysilane [Shin-Etsu Silicone (registered trademark) KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.]
  • APMS 3-aminopropyltrimethoxysilane [manufactured by Tokyo Chemical Industry Co.,
  • the white powder obtained by filtering this precipitate was dissolved in 100 g of chloroform and added to 500 g of IPA to reprecipitate the polymer. This precipitate was filtered under reduced pressure and vacuum dried to obtain 8.5 g of a hyperbranched polymer (HPS-Cl) having a chlorine atom at the molecular end as a white powder (yield 99%).
  • the 1 H NMR spectrum of the obtained HPS-Cl is shown in FIG. Since the peak (4.0 ppm, 3.7 ppm) derived from the dithiocarbamate group disappeared, it was confirmed that the obtained HPS-Cl had almost all the dithiocarbamate groups at the HPS molecule terminals substituted with chlorine atoms. It became clear.
  • the weight average molecular weight Mw measured by polystyrene conversion by GPC of the obtained HPS-Cl was 14,000, and the dispersity Mw / Mn was 2.9.
  • the precipitated polymer was filtered under reduced pressure and vacuum dried at 40 ° C. to obtain 9.6 g of a hyperbranched polymer (HPS-NOct 3 Cl) having a trioctylammonium group at the molecular end as a pale yellow powder.
  • the 13 C NMR spectrum of the obtained HPS-NOct 3 Cl is shown in FIG. From the peak of the methylene group to which the chlorine atom is bonded and the peak of the methylene group to which the ammonium group is bonded, the obtained HPS-NOct 3 Cl has 71% of the chlorine atom at the end of the HPS-Cl molecule replaced by the ammonium group Became clear.
  • the weight average molecular weight Mw of HPS-NOct 3 Cl calculated from Mw (14,000) of HPS-Cl and ammonium group introduction rate (71%) was 37,000.
  • the obtained residue was dissolved in 300 g of THF and cooled to 0 ° C. This solution was added to 6,000 g of IPE at 0 ° C. for reprecipitation purification.
  • the precipitated polymer was filtered under reduced pressure and vacuum dried at 60 ° C. to obtain 19.9 g of a complex of a hyperbranched polymer having an ammonium group at the molecular end and Pd particles (Pd [HPS-NOct 3 Cl]) as a black powder. It was. From the result of ICP emission analysis, the Pd content of the obtained Pd [HPS-NOct 3 Cl] was 11% by mass. Further, from the TEM (transmission electron microscope) image, the Pd particle diameter was about 2 to 4 nm.
  • HPS-N (Me) 2 OctCl obtained from the peak of the benzene ring and the peak of the methyl group at the end of the octyl group shows that the chlorine atom at the end of the HPS-Cl molecule is almost quantitatively substituted with an ammonium group. Became clear.
  • the weight average molecular weight Mw of HPS-N (Me) 2 OctCl calculated from Mw (14,000) of HPS-Cl and ammonium group introduction rate (100%) was 28,000.
  • An electroless plating base material having a solid content concentration of 4.5 mass% was prepared by dissolving in 2.55 g.
  • the base agent was spin-coated (200 rpm ⁇ 5 seconds followed by 1,000 rpm ⁇ 30 seconds) on a glass substrate (50 ⁇ 50 mm). This substrate was dried for 5 minutes on a hot plate at 80 ° C. to obtain a glass substrate having an underlayer on the entire surface of the substrate.
  • the obtained substrate was immersed in an electroless nickel plating solution prepared in Reference Example 1 heated to 75 ° C. for 180 seconds. Then, the taken-out board
  • Example 1 when the plating film was formed using the base material of the present invention containing an alkoxysilane having an amino group (Examples 1 to 4), the uniformity of the formed metal plating film was excellent. All had adhesion to the tape test. In contrast, a metal plating film (Comparative Example 1) formed using a base material to which no alkoxysilane was added, or a metal plating film formed from a base material containing alkoxysilane having no amino group (Comparison) In Example 2), the uniformity was low, and no adhesion was obtained. From the above results, it became clear that the plating base material containing an alkoxysilane having an amino group of the present invention is advantageous in obtaining a plating film having uniform and high adhesion.
  • the base material was spin-coated (200 rpm ⁇ 5 seconds followed by 1,000 rpm ⁇ 30 seconds) on the ITO film of a glass substrate with ITO film (50 ⁇ 50 mm) [manufactured by Foresight Co., Ltd.]. This substrate was dried on a hot plate at 80 ° C.
  • the obtained substrate was immersed in an electroless nickel plating solution prepared in Reference Example 1 heated to 75 ° C. for 180 seconds. Then, the taken-out board
  • Electroless plating on PI film 20 mg of Pd [HPS-NOct 3 Cl] produced in Synthesis Example 3 and 100 mg of alkoxysilane described in Table 3 were mixed with n-propanol.
  • An electroless plating base material having a solid content concentration of 4.5 mass% was prepared by dissolving in 2.55 g.
  • the base agent was spin-coated (200 rpm ⁇ 5 seconds followed by 1,000 rpm ⁇ 30 seconds) on a PI film (50 ⁇ 50 mm) described in Table 3. This film was dried on an 80 ° C. hot plate for 5 minutes to obtain a PI film having an underlayer on the entire 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. Then, the taken-out film was washed with water, and the plated film was obtained by drying for 5 minutes with an 80 degreeC hotplate.
  • Electroless plating on PI film The drying conditions after applying the base agent and washing with water were 150 ° C. and 10 minutes, respectively, and the bath temperature of the electroless nickel plating solution was changed to 80 ° C. By operating in the same manner as in Example 9, a plated film was obtained.
  • Example 14 Electroless plating on nylon 6,6 substrate-1 100 mg of Pd [HPS-NOct 3 Cl] produced in Synthesis Example 3, 10 mg of alkoxysilane described in Table 4, and 1 mg of fluorosurfactant F554 were dissolved in 39.89 g of IPA, and the solid content concentration was 0.28% by mass.
  • An electroless plating base material was prepared. The above base agent was dip coated on a nylon substrate N66 (10 ⁇ 50 ⁇ 1 mm) whose surface was hydrophilically treated by immersion in 8% by mass hydrochloric acid at 40 ° C. for 10 minutes. This substrate was dried for 10 minutes in an oven at 80 ° C.
  • the obtained substrate was immersed in the electroless nickel plating solution prepared in Reference Example 1 heated to 70 ° C. for 180 seconds. Then, the taken-out board
  • Example 15 Electroless Plating on Nylon 6,6 Substrate-2 50 mg of Pd [HPS-NOct 3 Cl] produced in Synthesis Example 3 and 5 mg of EMSO as an alkoxysilane were dissolved in 7.95 g of IPA to prepare an electroless plating base material having a solid content concentration of 0.69% by mass. Except having used the said base agent, it operated similarly to Example 14 and obtained the plating board
  • Example 16 Electroless plating on nylon 6 substrate A plating substrate was obtained in the same manner as in Example 15 except that IPA was changed to MEK and the nylon substrate was changed to N6.
  • Electroless plating on PEEK film 20 mg of Pd [HPS-NOct 3 Cl] prepared in Synthesis Example 3 and 100 mg of APMS were dissolved in 2.55 g of n-propanol, and the solid content concentration was 4.5% by mass.
  • An electroless plating base material was prepared.
  • the above base agent was spin-coated (200 rpm ⁇ 5 seconds followed by 1,000 rpm ⁇ 30 seconds) on a PEEK film (30 ⁇ 30 mm) whose surface was hydrophilically treated in advance using a UV ozone cleaning device. This film was dried on a hot plate at 80 ° C. for 10 minutes to obtain a PEEK film having an underlayer on the entire 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. Then, the taken-out film was washed with water, and the plating film was obtained by drying for 10 minutes with an 80 degreeC hotplate.
  • Example 18 Electroless plating on PET film-1 A plated film was obtained in the same manner as in Example 17 except that the PEEK film was changed to PET-1 (40 ⁇ 40 mm) whose surface was hydrophilically treated in advance using a UV ozone cleaning device.
  • Example 19 Electroless Plating on PET Film-2 A plated film was obtained in the same manner as in Example 17 except that the PEEK film was changed to PET-2 (40 ⁇ 40 mm).
  • the plating film formed using the base agent of the present invention containing an alkoxysilane having an amino group is excellent in uniformity in any film, and has an adhesion property to a tape test. Had.
  • Electroless plating on PI film-2 1.0 g of Pd [HPS-NOct 3 Cl] produced in Synthesis Example 3 and 4.0 g of APMS were dissolved in 95 g of a butyl cellosolve / n-hexanol mixed solution (mass ratio 4: 1), and the solid content concentration was 5% by mass. An electroless plating base material was prepared. Next, inkjet coating was performed on the PI film PI-1 using a microdroplet ejecting apparatus filled with the base material.
  • the micro droplet ejecting apparatus uses 85 nozzles for ejecting droplets arranged in a horizontal row at intervals of 423 ⁇ m, and is relative to the PI film while maintaining an interval of 0.5 mm.
  • the base agent was injected 571 times per second while moving 10 cm at 40 mm / second. That is, the base material is presumed to be applied on the PI film at intervals of 423 ⁇ m in the X-axis direction (the direction in which the nozzles are arranged) and at intervals of 70 ⁇ m in the Y-axis direction (advancing direction of the micro droplet ejection device). Is done.
  • the liquid volume per drop of the base agent calculated from the obtained film thickness was about 20 to 40 pL.
  • the coated film is allowed to stand for 1 minute in the state as it is (approximately 25 ° C.), dried on a hot plate at 160 ° C. for 5 minutes, and a PI film having 85 linear base layers on the film is obtained. Obtained.
  • the obtained film was immersed in the electroless nickel plating solution prepared in Reference Example 1 heated to 90 ° C. for 300 seconds. Then, the taken-out film was washed with water, and the plating film was obtained by drying for 5 minutes with a 100 degreeC hotplate.
  • FIG. 4 shows an electron microscope image of the metal plating film on the obtained film
  • FIG. 5 shows a cross-sectional SEM image of one linear metal plating film.
  • the metal plating film on the obtained film was observed, it was confirmed that the metal plating film with a metallic luster was uniformly deposited on the entire surface of the linear base layer, and the metal plating film was formed uniformly. It was done.
  • the peeling of the metal plating film could be confirmed regardless of whether the cello tape (registered trademark) peeling direction was the X-axis direction or the Y-axis direction. The metal plating film remained adhered on the film.
  • Example 22 Electroless copper plating on PI film Electroless electrode prepared in Reference Example 2 in which a PI film having a base layer on the entire surface produced by the same method as in Example 21 was controlled at 25 ° C. It was immersed in a copper plating solution for 300 seconds. Then, the taken-out film was washed with water, and the plated film was obtained by drying for 5 minutes with a 150 degreeC hotplate. About the metal plating film

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Abstract

Le problème posé par l'invention consiste à fournir un agent de base innovant, utilisé pour une étape de pré-traitement de dépôt autocatalytique et qui permette de réaliser le pré-traitement grâce à un petit nombre d'étapes, tout en étant écologique et obtenu à faible coût. La solution de l'invention porte sur un agent de base, destiné à la formation d'un film de dépôt métallique sur un substrat par dépôt autocatalytique, qui contient de fines particules métalliques, un alkoxy silane et un polymère hyper-ramifié qui présente un groupe ammonium à une extrémité moléculaire et un poids moléculaire moyen compris entre 500 et 5 000 000.
PCT/JP2013/074714 2012-09-13 2013-09-12 Agent de base pour dépôt autocatalytique WO2014042215A1 (fr)

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KR1020207003144A KR102157192B1 (ko) 2012-09-13 2013-09-12 무전해 도금 하지제
JP2014535588A JP6354950B2 (ja) 2012-09-13 2013-09-12 無電解めっき下地剤
US14/428,189 US20160010215A1 (en) 2012-09-13 2013-09-12 Primer for electroless plating
EP13837102.6A EP2896720B1 (fr) 2012-09-13 2013-09-12 Agent de base pour dépôt autocatalytique
CN201380047242.XA CN104641017B (zh) 2012-09-13 2013-09-12 无电解镀基底剂
KR1020157007380A KR20150054851A (ko) 2012-09-13 2013-09-12 무전해 도금 하지제

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JP2015229788A (ja) * 2014-06-05 2015-12-21 奥野製薬工業株式会社 無電解めっき下地層形成用組成物
WO2016017625A1 (fr) * 2014-07-30 2016-02-04 日産化学工業株式会社 Polymère hyper-ramifié, microparticules de métal, et agent de base de dépôt autocatalytique contenant un apprêt de résine
WO2016035897A1 (fr) * 2014-09-05 2016-03-10 日産化学工業株式会社 Agent de sous-couche de placage autocatalytique photosensible
WO2016035896A1 (fr) * 2014-09-05 2016-03-10 日産化学工業株式会社 Couche primaire pour dépôt autocatalytique photodurcissable
WO2016102473A1 (fr) * 2014-12-23 2016-06-30 Metalor Technologies International Sa Procédé de dépôt autocatalytique d'un métal précieux
WO2017142022A1 (fr) * 2016-02-19 2017-08-24 日産化学工業株式会社 Primaire pour placage autocatalytique contenant des particules de polymère ramifié et de métal
WO2017154913A1 (fr) * 2016-03-09 2017-09-14 日産化学工業株式会社 Agent de sous-couche de placage autocatalytique photosensible
JPWO2016158949A1 (ja) * 2015-03-31 2018-01-25 日産化学工業株式会社 感光性無電解めっき下地剤
JPWO2017154919A1 (ja) * 2016-03-09 2019-01-10 日産化学株式会社 高分岐高分子及び金属微粒子を含む無電解めっき下地剤
WO2019022151A1 (fr) * 2017-07-25 2019-01-31 日産化学株式会社 Procédé pour la production d'un corps composite de fines particules métalliques
WO2020179821A1 (fr) * 2019-03-05 2020-09-10 マクセルホールディングス株式会社 Composition de suppression de placage autocatalytique et procédé de fabrication de composant plaqué

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JP6607811B2 (ja) * 2016-03-11 2019-11-20 マクセルホールディングス株式会社 メッキ部品の製造方法、メッキ部品、触媒活性妨害剤及び無電解メッキ用複合材料
JP7401856B2 (ja) * 2018-12-21 2023-12-20 日産化学株式会社 高分子及び金属微粒子を含む無電解めっき下地剤
KR20220143007A (ko) * 2020-02-19 2022-10-24 닛산 가가쿠 가부시키가이샤 고분자 및 금속미립자를 포함하는 무전해 도금 하지제

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JP2015229788A (ja) * 2014-06-05 2015-12-21 奥野製薬工業株式会社 無電解めっき下地層形成用組成物
EP3187622A4 (fr) * 2014-07-30 2018-02-07 Nissan Chemical Industries, Ltd. Polymère hyper-ramifié, microparticules de métal, et agent de base de dépôt autocatalytique contenant un apprêt de résine
JPWO2016017625A1 (ja) * 2014-07-30 2017-04-27 日産化学工業株式会社 ハイパーブランチポリマー、金属微粒子及び樹脂プライマーを含む無電解めっき下地剤
WO2016017625A1 (fr) * 2014-07-30 2016-02-04 日産化学工業株式会社 Polymère hyper-ramifié, microparticules de métal, et agent de base de dépôt autocatalytique contenant un apprêt de résine
WO2016035897A1 (fr) * 2014-09-05 2016-03-10 日産化学工業株式会社 Agent de sous-couche de placage autocatalytique photosensible
JPWO2016035896A1 (ja) * 2014-09-05 2017-06-29 日産化学工業株式会社 光硬化性無電解めっき下地剤
WO2016035896A1 (fr) * 2014-09-05 2016-03-10 日産化学工業株式会社 Couche primaire pour dépôt autocatalytique photodurcissable
WO2016102473A1 (fr) * 2014-12-23 2016-06-30 Metalor Technologies International Sa Procédé de dépôt autocatalytique d'un métal précieux
JPWO2016158949A1 (ja) * 2015-03-31 2018-01-25 日産化学工業株式会社 感光性無電解めっき下地剤
WO2017142022A1 (fr) * 2016-02-19 2017-08-24 日産化学工業株式会社 Primaire pour placage autocatalytique contenant des particules de polymère ramifié et de métal
JPWO2017142022A1 (ja) * 2016-02-19 2018-12-13 日産化学株式会社 高分岐高分子及び金属微粒子を含む無電解めっき下地剤
WO2017154913A1 (fr) * 2016-03-09 2017-09-14 日産化学工業株式会社 Agent de sous-couche de placage autocatalytique photosensible
JPWO2017154913A1 (ja) * 2016-03-09 2019-01-10 日産化学株式会社 感光性無電解めっき下地剤
JPWO2017154919A1 (ja) * 2016-03-09 2019-01-10 日産化学株式会社 高分岐高分子及び金属微粒子を含む無電解めっき下地剤
WO2019022151A1 (fr) * 2017-07-25 2019-01-31 日産化学株式会社 Procédé pour la production d'un corps composite de fines particules métalliques
JPWO2019022151A1 (ja) * 2017-07-25 2020-07-09 日産化学株式会社 金属微粒子複合体の製造方法
WO2020179821A1 (fr) * 2019-03-05 2020-09-10 マクセルホールディングス株式会社 Composition de suppression de placage autocatalytique et procédé de fabrication de composant plaqué
JP6817502B1 (ja) * 2019-03-05 2021-01-20 マクセルホールディングス株式会社 無電解メッキ抑制組成物及びメッキ部品の製造方法
JP2021046614A (ja) * 2019-03-05 2021-03-25 マクセルホールディングス株式会社 無電解メッキ抑制組成物及びメッキ部品の製造方法
JP7438929B2 (ja) 2019-03-05 2024-02-27 マクセル株式会社 無電解メッキ抑制組成物及びメッキ部品の製造方法

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CN104641017B (zh) 2018-06-15
EP2896720B1 (fr) 2017-11-22
EP2896720A4 (fr) 2016-06-22
KR102157192B1 (ko) 2020-09-18
TW201418299A (zh) 2014-05-16
US20160010215A1 (en) 2016-01-14
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