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WO2012141216A1 - Primaire pour dépôt autocatalytique comprenant un polymère hyperramifié, des microparticules métalliques et un acide organique - Google Patents

Primaire pour dépôt autocatalytique comprenant un polymère hyperramifié, des microparticules métalliques et un acide organique Download PDF

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Publication number
WO2012141216A1
WO2012141216A1 PCT/JP2012/059907 JP2012059907W WO2012141216A1 WO 2012141216 A1 WO2012141216 A1 WO 2012141216A1 JP 2012059907 W JP2012059907 W JP 2012059907W WO 2012141216 A1 WO2012141216 A1 WO 2012141216A1
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acid
group
metal
substrate
base material
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Japanese (ja)
Inventor
永島　英夫
孝司 西形
小島　圭介
大悟 齊藤
啓祐 大土井
近間　克己
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Kyushu University NUC
Nissan Chemical Corp
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Kyushu University NUC
Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/26—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/30—Sulfur
    • 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
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

  • the present invention relates to an electroless plating base material containing a hyperbranched polymer, metal fine particles and an organic acid.
  • 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 treated 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 organic acid, 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 treatment, having an ammonium group at a molecular end and a weight average molecular weight of 500 to 5
  • the present invention relates to a base agent containing a hyperbranched polymer, metal fine particles and an organic acid.
  • the ammonium group of the said hyperbranched polymer adheres to the said metal microparticle, It is related with the base material as described in a 1st viewpoint.
  • the organic acid is acetic acid, propionic acid, (meth) acrylic acid, butyric acid, lactic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid.
  • Citric acid Citric acid, poly (meth) acrylic acid, benzoic acid, salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, phthalic acid, isophthalic acid,
  • the base material according to the first aspect or the second aspect which is selected from the group consisting of terephthalic acid, trimellitic acid and pyromellitic acid.
  • the present invention relates to the base agent according to the third aspect, in which the organic acid is succinic acid, maleic acid, citric acid or poly (meth) acrylic acid.
  • the present invention relates to the base agent according to any one of the first aspect to the fourth aspect, in which the hyperbranched polymer is a hyperbranched polymer represented by the formula [1].
  • R 1 independently represents a hydrogen atom or a methyl group
  • R 2 , R 3 and R 4 each independently represent a hydrogen atom, a straight chain having 1 to 20 carbon atoms, A branched or cyclic alkyl group, an arylalkyl group having 7 to 20 carbon atoms, or — (CH 2 CH 2 O) m
  • R 5 represents a hydrogen atom or a methyl group; Represents an 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 , R Two of 3 and R 4 together represent a linear, branched or cyclic alkylene group
  • the present invention relates to the base agent according to the fifth aspect, in which the hyperbranched polymer is a hyperbranched polymer represented by the formula [3].
  • the metal fine particles include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt) and It is related with the base material as described in any one of the 1st viewpoint thru
  • the present invention relates to the base agent according to the seventh aspect, wherein the metal fine particles are palladium fine particles.
  • the present invention relates to the base agent according to the seventh aspect or the eighth aspect, in which the metal fine particles are fine particles having an average particle diameter of 1 to 100 nm.
  • the base agent as described in any one of the 1st viewpoint thru
  • it is related with the base agent as described in any one of the 1st viewpoint thru
  • the base material, the electroless plating base layer according to the twelfth aspect formed on the base material, and the metal plating film according to the thirteenth aspect formed on the electroless plating base layer And a metal-coated substrate.
  • the present invention relates to the metal-coated substrate according to the fourteenth aspect, in which the substrate is a non-conductive substrate.
  • the present invention relates to the metal-coated substrate according to the fourteenth aspect, in which the substrate is a conductive substrate.
  • it is related with the manufacturing method of a metal film base material containing the following A process and B process.
  • Step A Step of applying the base agent according to any one of the first aspect to the eleventh aspect on the base material to form a 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 said base material is related with the manufacturing method as described in a 17th viewpoint which is a nonelectroconductive base material.
  • the present invention relates to the manufacturing method according to the seventeenth aspect, wherein the base material is a conductive base material.
  • 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-NBu 3 Cl) having a tributylammonium 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-NOct 3 Cl) having a trioctylammonium group at the molecular end obtained in Synthesis Example 4.
  • the base agent of the present invention is a base agent containing a hyperbranched polymer containing an ammonium group and having a weight average molecular weight of 500 to 5,000,000, fine metal particles and an organic acid.
  • 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 agent 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 , R 3 and 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 , R 3 and R 4 together represent a linear, branched or cyclic alkylene group, or R 2 , R 3 and R 4 and they are bonded
  • the nitrogen atoms to be bonded together may form a ring.
  • X ⁇ represents an anion
  • n is the number of repeating unit structures, and represents an integer of 2 to 100,000.
  • Examples of the linear alkyl group having 1 to 20 carbon atoms in R 2 , R 3 and R 4 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group.
  • n-octyl group is particularly preferred.
  • the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and the like.
  • the cyclic alkyl group include a cyclopentyl ring and a group having a cyclohexyl ring structure.
  • the arylalkyl group having 7 to 20 carbon atoms in R 2 , R 3 and R 4 include a benzyl group and a phenethyl group.
  • the linear alkylene group in which two groups out of R 2 , R 3 and R 4 are combined includes a methylene group, an ethylene group, an n-propylene group, an n-butylene group and an n-hexylene group.
  • 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.
  • alkylene groups may contain a nitrogen atom, a sulfur atom or an oxygen atom in the group.
  • the ring formed by combining R 2 , R 3 and R 4 and the nitrogen atom bonded thereto contains 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.
  • the anion of X ⁇ is preferably a halogen atom, PF 6 ⁇ , BF 4 ⁇ or perfluoroalkanesulfonate.
  • 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 , Y 2 , Y 3 and Y 4 are each independently 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, Represents a carboxyl group or a cyano group.
  • alkylene group represented by 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 , Y 2 , Y 3 and 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. Can be mentioned.
  • 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 , Y 2 , Y 3 and Y 4 are each independently 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 [4].
  • 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; cyclopen
  • 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-octylamine, tri-n-dodecylamine, dimethyl-n-octyl.
  • Amine diethyl-n-decylamine, dimethyl-n-dodecylamine, dimethyl-n-tetradecylamine, dimethyl-n-hexadecylamine, dimethyl-n-octadecylamine, dimethyl-n-eicosylamine, dimethyl-n- Aliphatic amines such as dodecylamine; nitrogen-containing heterocyclic compounds such as pyridine, pyrazine, pyrimidine, quinoline, 1-methylimidazole, 4,4′-bipyridyl, 4-methyl-4,4′-bipyridyl.
  • the amount of amine compound that can be used in these reactions is 0.1 to 20 molar equivalents, preferably 0.5 to 10 molar equivalents per mole of halogen atoms of the hyperbranched polymer having a halogen atom at the molecular end. Preferably, it may be 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.
  • Alcohols such as isopropanol
  • organic acids such as acetic acid
  • Aromatic hydrocarbons such as chlorobenzene
  • ethers such as tetrahydrofuran and diethyl ether
  • ketones such as acetone, ethyl methyl ketone, isobutyl methyl ketone and cyclohexanone
  • halides such as chloroform, dichloromethane and 1,2-dichloroethane
  • n- Aliphatic hydrocarbons such as hexane, n-heptane and cyclohexane
  • Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone can be used.
  • 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 10 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 1,000,000, more preferably 2. 3,000 to 500,000, most preferably 3,000 to 200,000.
  • the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) is 1.0 to 7.0, preferably 1.1 to 6.0, more preferably 1.2 to 5. .0.
  • the organic acid used in the base material of the present invention is not particularly limited, and examples thereof include aliphatic monocarboxylic acids such as acetic acid, propionic acid, (meth) acrylic acid, butyric acid, and lactic acid; oxalic acid, malonic acid, succinic acid, and glutar Aliphatic polycarboxylic acids such as acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid, poly (meth) acrylic acid; benzoic acid, salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid Aromatic monocarboxylic acids such as 2,6-dihydroxybenzoic acid and 3,5-dihydroxybenzoic acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid Can be mentioned.
  • aliphatic monocarboxylic acids such as acetic acid, propionic acid, (meth) acrylic
  • organic acids may be used alone or in combination of two or more.
  • an aliphatic polycarboxylic acid is preferable as the organic acid. More preferred are succinic acid, maleic acid, citric acid and poly (meth) acrylic acid, and more preferred are citric acid and poly (meth) acrylic acid.
  • the poly (meth) acrylic acid is composed of (meth) acrylic acid esters such as methyl (meth) acrylate; (meth) acrylic acid amides; (meth) acrylic acid salts such as sodium (meth) acrylate; It may be a copolymer with a polymerizable monomer such as maleic acid such as acid or maleic anhydride; an aromatic vinyl compound such as styrene; or a diene compound such as butadiene.
  • (meth) acrylic acid refers to both acrylic acid and methacrylic acid.
  • the addition amount of the organic acid in the base material of the present invention is preferably 0.01 to 50 parts by mass with respect to 1 part by mass of the composite formed from the hyperbranched polymer and metal fine particles described later. By setting it as 0.01 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 50 mass parts or less. More preferably, it is 0.03 to 50 parts by mass.
  • 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). These metals may be one kind or two or more kinds of alloys. Among these, preferable metal fine particles include palladium fine particles.
  • the metal oxide may be an oxide of the metal.
  • 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]; Rox
  • 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 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 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.
  • the base agent of the present invention includes a hyperbranched polymer having an ammonium group at a molecular end, metal fine particles, and an organic acid, and at this time, 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 the solution in which the hyperbranched polymer is dissolved and irradiated with ultraviolet rays, or an aqueous solution of a metal salt and a reducing agent are added to the solution.
  • a complex can also be formed by reducing metal ions.
  • 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 higher.
  • alcohols such as ethanol, propanol, and isopropanol
  • halogenated hydrocarbons such as methylene and chloroform
  • cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and tetrahydropyran
  • nitriles such as acetonitrile and butyronitrile
  • 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
  • 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.
  • the metal ion source used here include the above metal salts, hexacarbonyl chromium [Cr (CO) 6 ], pentacarbonyl iron [Fe (Co) 5 ], and 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, 2-methyltetrahydrofuran and tetrahydropyran; Nitriles such as acetonitrile and butyronitrile; Aromatic hydrocarbons such as benzene and toluene And a mixed solution of these solvents, 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 includes the hyperbranched polymer having an ammonium group, metal fine particles (preferably a composite made of these), and the organic acid, and forms an [electroless plating base layer] described later. It may be in the form of a varnish used sometimes.
  • 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, ABS (acrylonitrile-butadiene-styrene copolymer) resin, epoxy resin, polyacetal resin and the like; and paper. 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 (indium tin oxide), various stainless steels, aluminum alloys such as aluminum and duralumin, iron and iron alloys, copper and copper alloys such as brass, phosphor bronze, white copper and beryllium copper, Examples thereof include metals such as nickel and nickel alloys, and silver alloys such as silver and foreign silver.
  • the base material may be a three-dimensional molded body.
  • the hyperbranched polymer having metal groups and metal fine particles (preferably from these) The composite) is dissolved or dispersed in a suitable solvent to form a varnish, and the varnish is applied onto a substrate on which a metal plating film is formed; spin coating method; blade coating method; dip coating method; roll coating method; Die coating method; spray coating method; ink jet method; pen lithography such as fountain pen nanolithography (FPN), dip pen nanolithography (DPN); letterpress printing, flexographic printing, resin letterpress printing, contact printing, microcontact printing ( Intaglio printing methods such as CP), nanoimprinting lithography (NIL), and nanotransfer printing (nTP); intaglio printing methods such as gravure and engraving; lithographic printing methods; stencil printing methods such as screen printing and engraving printing; offset A thin layer is formed by applying by a printing method or the like and then e
  • 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 above complex.
  • water aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene; Alcohols such as methanol, ethanol and isopropanol; ethers such as tetrahydrofuran, methyltetrahydrofuran, 1,4-dioxane, diethyl ether, diethylene glycol dimethyl ether and propylene glycol methyl ether; esters such as ethyl acetate; acetone, ethyl methyl ketone and isobutyl Ketones such as methyl ketone, cyclopentanone, cyclohexanone; aliphatic hydrocarbons such as n-heptane, n-hexane, cyclohexane; 1,2-dichloroethane, chloroform
  • 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 in which the solvent is dissolved or dispersed is arbitrary, but the complex concentration 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 the electroless plating base layer formed on the 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.
  • electroless nickel plating chemicals (Melplate NI series), electroless copper plating chemicals (Melplate CU series) manufactured by Meltex Co., Ltd., Okuno Electroless nickel plating solution (ICP Nicolon series), electroless copper plating solution (OPC-700 electroless copper MK, ATS add copper 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 (Esdia AG-40) manufactured by Sasaki Chemical Co., Ltd. Kell plating solution (Schumer (registered trademark) series, Schumer (R) Crab Black (registered trademark) series), electroless palladium plating solution (S-KPD) and the
  • 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.]
  • PAA polyacrylic acid [manufactured by Aldrich Co., Ltd., average molecular weight ⁇ 450,000]
  • IPA Isopropanol IPE: Diisopropyl ether
  • THF Tetrahydrofuran ABS: Acrylonitrile-butadiene-styrene copolymer
  • PET Polyethylene terephthalate
  • PI Polyimide
  • PC Polycarbonate ITO: Indium tin oxide
  • 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.
  • the precipitate was filtered under reduced pressure and vacuum dried to obtain 8.5 g of 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 5.8 g of a hyperbranched polymer (HPS-NBu 3 Cl) having a tributylammonium group at the molecular end as a light brown powder.
  • the 13 C NMR spectrum of the obtained HPS-NBu 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-NBu 3 Cl has 80% of the chlorine atom at the end of the HPS-Cl molecule replaced with an ammonium group. Became clear.
  • the weight average molecular weight Mw of HPS-NBu 3 Cl calculated from Mw (14,000) of HPS-Cl and ammonium group introduction rate (80%) was 28,000.
  • Synthesis Example 4 Production of HPS-NOct 3 Cl
  • a 1 L reaction flask equipped with a reflux tower was charged with 30.4 g (0.2 mol) of HPS-Cl prepared according to Synthesis Example 1 and 100 g of chloroform, and stirred until uniform.
  • a solution prepared by dissolving 77.8 g (0.22 mol) of trioctylamine [manufactured by Guangei Chemical Industry Co., Ltd.] in 50 g of chloroform was added using a dropping funnel.
  • the dropping funnel was washed into the reaction flask using 50 g of chloroform and then 50 g of IPA. The mixture was stirred at 60 ° C. for 48 hours.
  • HPS-NOct 3 Cl 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 with 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 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 results 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.
  • Example 1 Electroless plating on an ABS substrate using a base material containing citric acid 10 mg of Pd [HPS-NBu 3 Cl] produced in Synthesis Example 3 and 200 mg of citric acid [manufactured by Tokyo Chemical Industry Co., Ltd.] Was dissolved in 4.0 g of IPA to prepare an electroless plating base material having a solid content concentration of 5 mass%.
  • a 25 ⁇ 25 mm ABS substrate [Mitsubishi Resin Co., Ltd.] washed in advance with ethanol, the above base material 0.3 mL was dropped on the center of the substrate, and spin coated for 5 seconds, 1,500 rpm ⁇ 30 seconds, and 5 seconds of slope. . This substrate was dried on an 80 ° C.
  • the adhered cellophane (registered trademark) was peeled off at once, and the substrate adhesion of the metal plating film was evaluated.
  • the state of the metal plating film was confirmed by visual observation, the metal plating film remained in close contact with the substrate without peeling off from the substrate.
  • the roughnesses of the substrate surface before coating of the base agent, the surface of the base layer (base agent coating film) and the surface of the metal plating film were measured by AFM and found to be 4.1 nm, 3.3 nm and 2.9 nm, respectively.
  • Example 2 Electroless plating on an ABS substrate using a base material containing succinic acid
  • succinic acid manufactured by Tokyo Chemical Industry Co., Ltd.
  • 200 mg was used instead of citric acid.
  • a metal plating film having a metallic luster was formed on the entire surface of the substrate on which the base layer was formed by the electroless plating treatment.
  • the substrate adhesion of the plating film was evaluated in the same manner as in Example 1, the metal plating film remained adhered to the substrate without peeling off from the substrate.
  • Example 3 Electroless plating on an ABS substrate using a base material containing maleic acid
  • maleic acid manufactured by Wako Pure Chemical Industries, Ltd.
  • 200 mg was used instead of citric acid.
  • a metal plating film having a metallic luster was formed on the entire surface of the substrate on which the underlayer was formed.
  • the substrate adhesion of the plating film was evaluated in the same manner as in Example 1, the metal plating film remained adhered to the substrate without peeling off from the substrate.
  • Example 1 Electroless plating on an ABS substrate using a base material containing no organic acid-1
  • Example 1 the same operation was performed except that citric acid was not added.
  • an electroless plating treatment resulted in a metal plating film having a metallic luster on the entire surface on which the base layer was formed.
  • the adhesion of the metal plating film to the substrate was evaluated in the same manner as in Example 1, most of the metal plating film was peeled off from the substrate and adhered to the cello tape (registered trademark).
  • Example 4 Electroless plating on an ABS substrate using a base material containing PAA 100 mg of Pd [HPS-NOct 3 Cl] produced in Synthesis Example 5 and 7 mg of PAA were dissolved in 3.46 g of propanol to obtain a solid content. An electroless plating base material having a concentration of 3% by mass was prepared. The above base agent was impregnated into Bencot (registered trademark) M-1 (manufactured by Asahi Kasei Fibers) and applied to the entire surface of a 25 ⁇ 25 mm ABS substrate (manufactured by Mitsubishi Plastics).
  • Bencot registered trademark
  • M-1 manufactured by Asahi Kasei Fibers
  • This substrate was dried at room temperature (approximately 25 ° C.) for 1 hour to obtain an ABS substrate having a base layer on the entire surface of the substrate.
  • the obtained substrate was immersed in the electroless plating solution B at 80 ° C. prepared in Reference Example 2 for 60 seconds. Thereafter, the substrate taken out was washed with water and dried on a hot plate at 80 ° C. for 5 minutes.
  • the electroless plating treatment resulted in a metallic plating film having a metallic luster on the entire surface of the substrate on which the base layer was formed.
  • substrate adhesiveness of the obtained metal plating film was evaluated by the method similar to Example 1, the metal plating film remained on the board
  • Example 5 Electroless plating on a PET substrate using a base material containing PAA
  • a PET substrate [manufactured by Nippon Polypenco Co., Ltd.] was used instead of the ABS substrate.
  • a metallic plating film having a metallic luster was formed on the entire surface of the substrate on which the underlayer was formed.
  • the substrate adhesion of the plating film was evaluated in the same manner as in Example 1, the metal plating film remained adhered to the substrate without peeling off from the substrate.
  • Example 6 Electroless Plating on PI Film Using Base Material Containing PAA-1
  • a PI film [Kapton (registered trademark) 200EN manufactured by Toray DuPont Co., Ltd.] was used instead of the ABS substrate, and a film in which an underlayer was formed by electroless plating treatment A metallic plating film having a metallic luster was formed on the entire upper surface.
  • the metal plating film remained adhered to the film without peeling off from the film.
  • Example 7 Electroless plating on a PVC substrate using a base material containing PAA
  • a PVC substrate [thin plate hard vinyl chloride plate manufactured by Kasai Sangyo Co., Ltd.] was used instead of the ABS substrate.
  • a metal plating film having a metallic luster was formed on the entire surface of the substrate on which the base layer was formed by the electroless plating treatment.
  • the substrate adhesion of the plating film was evaluated in the same manner as in Example 1, the metal plating film remained adhered to the substrate without peeling off from the substrate.
  • Example 8 Electroless plating on 6,6-nylon substrate using base material containing PAA
  • a 6,6-nylon substrate [Asahi Kasei Co., Ltd.] was used instead of the ABS substrate.
  • an electroless plating treatment resulted in a metal plating film having a metallic luster on the entire surface of the substrate on which the base layer was formed.
  • the substrate adhesion of the plating film was evaluated in the same manner as in Example 1, the metal plating film remained adhered to the substrate without peeling off from the substrate.
  • Example 9 Electroless plating on a PC board using a base material containing PAA
  • a PC board manufactured by Takiron Co., Ltd.
  • the electroless plating treatment resulted in a metallic plating film having a metallic luster on the entire surface of the substrate on which the base layer was formed.
  • the substrate adhesion of the plating film was evaluated in the same manner as in Example 1, the metal plating film remained adhered to the substrate without peeling off from the substrate.
  • Example 2 Electroless plating on an ABS substrate using a base material containing no organic acid-2
  • Example 4 the same operation was performed except that PAA was not added.
  • an electroless plating treatment resulted in a metal plating film having a metallic luster on the entire surface on which the base layer was formed.
  • the adhesion of the metal plating film to the substrate was evaluated in the same manner as in Example 1, most of the metal plating film was peeled off from the substrate and adhered to the cello tape (registered trademark).
  • Example 3 Electroless plating on a PET substrate using a base material containing no organic acid
  • a PA substrate manufactured by Nippon Polypenco Co., Ltd.
  • an electroless plating treatment resulted in a metal plating film having a metallic luster on the entire surface of the substrate on which the base layer was formed.
  • the adhesion of the metal plating film to the substrate was evaluated in the same manner as in Example 1, most of the metal plating film was peeled off from the substrate and adhered to the cello tape (registered trademark).
  • Example 4 Electroless plating on PI film using a base material containing no organic acid-1
  • the PI film [Kapton (registered trademark) 200EN manufactured by Toray DuPont Co., Ltd.] was used instead of the ABS substrate, the same operation was performed.
  • a metallic plating film having a metallic luster was formed on the entire surface of the film on which the underlayer was formed.
  • the film adhesion of the metal plating film was evaluated in the same manner as in Example 1, most of the metal plating film was peeled off from the film and adhered to the cello tape (registered trademark).
  • Example 5 Electroless plating on a PVC substrate using a base material that does not contain an organic acid
  • PAA was not added, and instead of an ABS substrate, a PVC substrate [thin plate hard chloride manufactured by Kasai Sangyo Co., Ltd.
  • a PVC substrate [thin plate hard chloride manufactured by Kasai Sangyo Co., Ltd.
  • an electroless plating process resulted in a metallic plating film having a metallic luster on the entire surface of the substrate on which the base layer was formed.
  • the adhesion of the metal plating film to the substrate was evaluated in the same manner as in Example 1, most of the metal plating film was peeled off from the substrate and adhered to the cello tape (registered trademark).
  • Example 7 Electroless plating on a PC board using a base material containing no organic acid
  • a PA board manufactured by Takiron Co., Ltd.
  • an electroless plating treatment resulted in a metal plating film having a metallic luster on the entire surface of the substrate on which the base layer was formed.
  • the adhesion of the metal plating film to the substrate was evaluated in the same manner as in Example 1, most of the metal plating film was peeled off from the substrate and adhered to the cello tape (registered trademark).
  • Example 10 Electroless plating-2 on a PI film using a base material containing PAA-2 100 mg of Pd [HPS-NOct 3 Cl] produced in Synthesis Example 5 and 50 mg of PAA were dissolved in 4.85 g of propanol to prepare an electroless plating base material having a solid content concentration of 3% by mass.
  • the above base agent was impregnated into Bencot (registered trademark) M-1 (Asahi Kasei Fibers Co., Ltd.) and applied to the entire surface of a 25 ⁇ 25 mm PI film (Kapton (registered trademark) 200EN manufactured by Toray DuPont). .
  • This film was dried at room temperature (approximately 25 ° C.) for 1 hour to obtain a PI film having an underlayer on the entire surface of the film.
  • the obtained film was immersed in the electroless plating solution C at 80 ° C. prepared in Reference Example 3 for 60 seconds. Thereafter, the film taken out was washed with water and dried on a hot plate at 80 ° C. for 5 minutes.
  • the electroless plating treatment resulted in a metallic plating film having a metallic luster on the entire surface of the film on which the underlayer was formed.
  • the film adhesion of the obtained metal plating film was evaluated by the same method as in Example 1, the metal plating film remained adhered to the film without peeling off from the film.
  • Example 8 Electroless plating-2 on a PI film using a base material containing no organic acid-2
  • Example 10 the same operation was performed except that PAA was not added.
  • an electroless plating treatment resulted in a metal plating film having a metallic luster on the entire surface on which the underlayer was formed.
  • the film adhesion of the metal plating film was evaluated in the same manner as in Example 1, most of the metal plating film was peeled off from the film and adhered to the cello tape (registered trademark).
  • Example 11 Electroless plating on an ITO-attached PET substrate using a base material containing PAA
  • electroless plating was performed in the same manner except that an PET substrate with ITO was used instead of the ABS substrate.
  • a metallic plating film having a metallic luster was formed on the entire surface of the ITO film on which the underlayer was formed.
  • Table 1 shows the uniformity and substrate (or film) adhesion of each metal plating film obtained in Examples 1 to 10 and Comparative Examples 1 to 8.
  • the addition amount of organic acid represents the addition amount [parts by mass] with respect to 1 part by mass of the complex of hyperbranched polymer and metal fine particles, and the uniformity and adhesion were visually evaluated according to the following criteria.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemically Coating (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un nouveau primaire respectueux de l'environnement utilisé dans une étape de prétraitement d'un dépôt autocatalytique, le primaire permettant d'effectuer le traitement facilement avec un petit nombre d'étapes tout en minimisant les coûts. Ledit primaire, destiné à former un film de placage métallique sur un substrat par dépôt autocatalytique, comprend un acide organique, des microparticules métalliques, et un polymère hyperramifié portant un groupe ammonium sur une extrémité moléculaire et ayant un poids moléculaire moyen en poids de 500 à 5 000 000.
PCT/JP2012/059907 2011-04-12 2012-04-11 Primaire pour dépôt autocatalytique comprenant un polymère hyperramifié, des microparticules métalliques et un acide organique Ceased WO2012141216A1 (fr)

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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
WO2016158949A1 (fr) * 2015-03-31 2016-10-06 日産化学工業株式会社 Agent de sous-couche de placage autocatalytique photosensible
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
WO2017154919A1 (fr) * 2016-03-09 2017-09-14 日産化学工業株式会社 Agent de sous-couche de dépôt autocatalytique comprenant des microparticules métalliques et un polymère hyper-ramifié
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

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JP2008007849A (ja) * 2006-06-01 2008-01-17 Nippon Paint Co Ltd 無電解めっき用プライマー組成物及び無電解めっき方法
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WO2013157420A1 (fr) * 2012-04-18 2013-10-24 コニカミノルタ株式会社 Elément à motif conducteur translucide et blindage électromagnétique translucide ou élément d'antenne l'utilisant
JP2014159620A (ja) * 2013-02-20 2014-09-04 Nissan Chem Ind Ltd スクリーン印刷用触媒インク
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
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
CN107532301A (zh) * 2014-07-30 2018-01-02 日产化学工业株式会社 包含超支化聚合物、金属微粒和树脂底涂剂的非电解镀基底剂
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
CN106687619A (zh) * 2014-09-05 2017-05-17 日产化学工业株式会社 光固化性非电解镀基底剂
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
KR20170132804A (ko) * 2015-03-31 2017-12-04 닛산 가가쿠 고교 가부시키 가이샤 감광성 무전해도금 하지제
CN107532302A (zh) * 2015-03-31 2018-01-02 日产化学工业株式会社 感光性非电解镀基底剂
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
WO2016158949A1 (fr) * 2015-03-31 2016-10-06 日産化学工業株式会社 Agent de sous-couche de placage autocatalytique photosensible
CN107532302B (zh) * 2015-03-31 2019-10-08 日产化学工业株式会社 感光性非电解镀基底剂
KR102558400B1 (ko) 2015-03-31 2023-07-24 닛산 가가쿠 가부시키가이샤 감광성 무전해도금 하지제
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
CN108699694A (zh) * 2016-02-19 2018-10-23 日产化学株式会社 包含高支化高分子和金属微粒的非电解镀基底剂
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
WO2017154919A1 (fr) * 2016-03-09 2017-09-14 日産化学工業株式会社 Agent de sous-couche de dépôt autocatalytique comprenant des microparticules métalliques et un polymère hyper-ramifié
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
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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

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