WO2021166726A1 - Agent de base de dépôt autocatalytique contenant un polymère et des microparticules métalliques - Google Patents

Agent de base de dépôt autocatalytique contenant un polymère et des microparticules métalliques Download PDF

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Publication number
WO2021166726A1
WO2021166726A1 PCT/JP2021/004682 JP2021004682W WO2021166726A1 WO 2021166726 A1 WO2021166726 A1 WO 2021166726A1 JP 2021004682 W JP2021004682 W JP 2021004682W WO 2021166726 A1 WO2021166726 A1 WO 2021166726A1
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group
base material
metal
monomer
copolymer
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PCT/JP2021/004682
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English (en)
Japanese (ja)
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有輝 星野
雄大 森元
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日産化学株式会社
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Priority to CN202180015302.4A priority Critical patent/CN115135803B/zh
Priority to JP2022501817A priority patent/JPWO2021166726A1/ja
Priority to KR1020227024956A priority patent/KR20220143007A/ko
Publication of WO2021166726A1 publication Critical patent/WO2021166726A1/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
    • C23C18/18—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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • C23C18/28—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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents

Definitions

  • the present invention relates to an electroless plating base material containing polymers and metal fine particles.
  • a uniform thickness film can be obtained regardless of the type and shape of the substrate simply by immersing the substrate in the plating solution, and the metal plating film can be applied to non-conductor materials such as plastics, ceramics, and glass. It is widely used in various fields such as decorative applications such as giving a sense of quality and aesthetics to resin molded bodies such as automobile parts, and wiring technology for electromagnetic shielding, printed circuit boards, large-scale integrated circuits, etc. ing. Usually, when a metal plating film is formed on a base material (object to be plated) by electroless plating, a pretreatment for improving the adhesion between the base material and the metal plating film is performed.
  • the surface to be treated is first roughened and / or made hydrophilic by various etching means, and then an adsorbent that promotes adsorption of the plating catalyst on the surface to be treated is supplied onto the surface to be treated for sensitization.
  • a treatment (sensitization) and an activation treatment (activation) in which the plating catalyst is adsorbed on the surface to be treated are performed.
  • the sensitization treatment immerses the object to be treated in an acidic solution of stannous chloride, which causes a metal (Sn 2+ ) that can act as a reducing agent to adhere to the surface to be treated. Then, the sensitized surface to be treated is immersed in an acidic solution of palladium chloride as an activation treatment.
  • the palladium ions in the solution are reduced by the metal (tin ion: Sn 2+ ) which is a reducing agent and adhere to the surface to be treated as an active palladium catalyst nucleus.
  • the metal tin ion: Sn 2+
  • it is immersed in an electroless plating solution to form a metal plating film on the surface to be treated.
  • the composition containing various highly branched polymers and metal fine particles proposed as a base material for electroless plating described above other functions on the substrate (for example, adhesion, heat resistance, photosensitivity, dielectric property, etc.) ) Is required to be added to other base resins having their respective functions, but the above-mentioned base resin is contained because it contains other base resins that do not exhibit the function as a plating base agent.
  • the agent may significantly impair the precipitation property of the plating. That is, the electroless plating base material containing the highly branched polymer and metal fine particles proposed so far has a problem that the plating precipitation property may decrease when another base resin having no function of the plating base material is added. was there.
  • the present invention has been made to solve this conventional problem, and even if a plating base material having a composition containing a base resin that imparts adhesion is used, a plating base that exhibits excellent plating precipitation property is exhibited.
  • An object of the present invention is to provide a base material capable of forming a stratum. Furthermore, an object of the present invention is to provide a new base material used as a pretreatment step of electroless plating, which can realize cost reduction in its production.
  • a polymer containing a fluorine atom specifically, a polymer having a trifluoromethyl group and a metal dispersibility group in the molecule has excellent metal dispersibility.
  • the present invention was completed by finding that a layer obtained by combining the polymer and metal fine particles and applying the polymer onto a base material has excellent plating properties as an underlayer for electroless metal plating.
  • the present invention is, as a first aspect, an electroless plating base material for forming a metal plating film on a base material by an electroless plating treatment.
  • a copolymer containing a structural unit derived from a monomer b having a double bond The present invention relates to (B) metal fine particles and (C) a base material containing a solvent.
  • a second aspect of the present invention relates to the base material according to the first aspect, which comprises a complex in which the (B) metal fine particles are adhered or coordinated to the metal dispersible group in the (A) copolymer.
  • the base material according to the first aspect or the second aspect wherein the monomer a is a compound having either a vinyl group or a (meth) acryloyl group.
  • the base material according to the third aspect wherein the monomer a is a compound represented by the following formula (1).
  • M represents a single bond, a carbonyloxy group, an amide group or a phenylene group
  • J is a linear or branched group having 1 to 10 carbon atoms having at least one trifluoromethyl group.
  • R 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the monomer b has either a vinyl group or a (meth) acryloyl group.
  • the base material according to the first aspect or the second aspect which is a compound.
  • the base material according to the fifth aspect, wherein the monomer b is a compound represented by the following formula (2) or (3).
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • L represents O or N
  • R 2 exists only when L represents N. Representing a hydrogen atom, or R 1 and R 2 may be combined with the atom to which they are attached to form a 4- to 6-membered cyclic amide.
  • R 3 represents a hydrogen atom or a methyl group.
  • R 4 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or an alkoxyl having 1 to 10 carbon atoms.
  • the base material according to any one of the viewpoints As a ninth aspect, the first to eighth aspects, wherein the copolymer (A) further contains a structural unit derived from a monomer c having a crosslinkable group and one radically polymerizable double bond in the molecule. Regarding the base material described in any one of the items. As a tenth aspect, the base material according to the ninth aspect, wherein the monomer c is a compound having either a vinyl group or a (meth) acryloyl group. As an eleventh aspect, the base material according to the tenth aspect, wherein the monomer c is a compound represented by the following formula (4).
  • X represents a single bond, a carbonyloxy group, an amide group or a phenylene group
  • Y is an alkylene group having 1 to 6 carbon atoms and an oxyalkylene group having 1 to 6 carbon atoms, which are branched.
  • the monomer mixture giving the (A) copolymer contains the monomer c in an amount which is 5 to 300% of the number of moles of the monomer b, and the ninth aspect to the eleventh aspect.
  • the base material according to any one of the viewpoints.
  • the metal fine particles (B) are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (
  • the base material according to any one of the first to twelfth viewpoints which is a fine particle of at least one kind of metal selected from the group consisting of Pt) and gold (Au).
  • the base material according to the thirteenth aspect wherein the metal fine particles (B) are palladium fine particles.
  • the base material according to any one of the first to fifteenth aspects which contains (D) a base resin further having a non-radical polymerizable crosslinkable group.
  • a 17th viewpoint it relates to the base material according to any one of the 1st to 16th viewpoints, which further contains (E) a cross-linking agent.
  • the present invention relates to an electroless metal plating base layer composed of a film containing the electroless plating base agent according to any one of the first to seventeenth viewpoints.
  • the nineteenth aspect relates to the metal plating film formed on the base layer of the electroless metal plating according to the eighteenth aspect.
  • the present invention relates to a metal coating substrate.
  • the present invention relates to a method for producing a metal coating base material, which comprises the following steps (1) and (2).
  • the base material of the present invention can easily form a base layer for non-electrostatic plating simply by applying it on a base material. Further, according to the present invention, it is possible to form a base layer for plating which is excellent in adhesion to a substrate and does not affect the precipitation property of plating. Moreover, the base material of the present invention can be easily varnished with various compositions, and can have high metal fine particle dispersion stability. Further, since the polymer used for the base material of the present invention can be easily prepared with a small number of processes, it is possible to simplify the manufacturing process of the plating base material and reduce the manufacturing cost.
  • the electroless metal plating base layer formed from the electroless plating base agent of the present invention can easily form a metal plating film simply by immersing it in an electroless plating bath, and can easily form a base material, a base layer, and a metal.
  • a metal film base material provided with a plating film can be easily obtained. That is, even if a plating base agent containing a base resin that imparts adhesion of the present invention is used, a base layer that exhibits excellent plating precipitation can be formed on the base material.
  • the base material of the present invention is a base material containing (A) a copolymer having the above-mentioned specific structural unit, (B) metal fine particles, and (C) a solvent, and if necessary, containing other components.
  • the base material of the present invention is suitably used as a catalyst for forming a metal plating film on a substrate by electroless plating.
  • each component will be described.
  • the component (A) has a structural unit derived from a monomer a having a crosslinkable group and one radically polymerizable double bond in the molecule, and a metal dispersible group and one radically polymerizable double bond in the molecule. It is a copolymer containing a structural unit derived from the monomer b having.
  • Monomer a is a monomer having at least one trifluoromethyl group and one radically polymerizable double bond in the molecule.
  • the monomer a include a compound represented by the following formula (1).
  • M represents a single bond, a carbonyloxy group, an amide group or a phenylene group
  • J is a linear or branched group having 1 to 10 carbon atoms having at least one trifluoromethyl group.
  • R 6 represents an alkyl group having a hydrogen atom or 1 to 4 carbon atoms.
  • M represents a carbonyloxy group or an amide group
  • it can take the structures of the following formulas (1-1) to (1-3), but the structure of the formula (1-1) is preferable.
  • J is a perfluoromethyl group (that is, a trifluoromethyl group), a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2,2-pentafluoroethyl group, 2,2.
  • J is preferably a 2,2,2-trifluoroethyl group, a hexafluoroisopropyl group or a 2- (perfluorohexyl) ethyl group.
  • Such a monomer a are not limited, but include the following.
  • 2,2,2-trifluoroethyl acrylate, hexafluoro-2-propyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate and the like can be mentioned.
  • the monomer b is a compound having a metal dispersible group and one radically polymerizable double bond in the molecule.
  • the metal dispersible group improves the dispersibility in the composition of the metal fine particles by interacting with the metal fine particles of the component (B) such as adhesion and / or coordination, thereby forming the metal fine particles in the composition. It is a basis for stable existence.
  • a group selected from the group consisting of a group having an amide bond and a group having an imide bond is preferable.
  • the radically polymerizable double bond is preferably a compound having one of either a vinyl group or a (meth) acryloyl group.
  • the monomer b include compounds represented by the following formula (2) or formula (3).
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • L represents O or N
  • R 2 exists only when L represents N. Representing a hydrogen atom, or R 1 and R 2 may be combined with the atom to which they are attached to form a 4- to 6-membered cyclic amide.
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or a branch having 1 to 10 carbon atoms.
  • alkoxyl group or represents an alkoxyl alkyl group branched having 1 to 10 carbon atoms
  • L represents an O or N
  • R 5 is present only when L represents N
  • R 4 and R 5 may be combined with the atoms to which they are attached to form a 4- to 6-membered cyclic amide, or a 4- to 6-membered cyclic imide.
  • Examples of such a monomer b include N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-propyl (meth).
  • the monomer b the monomer represented by the formula (2) is preferable from the viewpoint of the coordinating ability of the monomer to the metal, the monomer having an N-vinylamide group is more preferable, and N- Vinylpyrrolidone, N-vinylformamide, and N-vinylacetamide are more preferable.
  • One of these monomers b may be used alone, or two or more thereof may be used in combination.
  • the component (A) is also a copolymer containing, in addition to the monomer a and the monomer b, a structural unit derived from the monomer c having a crosslinkable group and one radically polymerizable double bond in the molecule.
  • the crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an epoxy group which may have a substituent Q, an alicyclic epoxy group which may have a substituent Q, and a substituent Q.
  • examples thereof include an oxetane group which may be used.
  • the substituent Q include an alkyl group having 1 to 4 carbon atoms and a phenyl group which may be substituted with a halogen.
  • the monomer c include a compound represented by the following formula (4).
  • X represents a single bond, a carbonyloxy group, an amide group or a phenylene group
  • Y is an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, and a carbon atom.
  • Z is the number of carbon atoms having at least one trifluoromethyl group.
  • 1 to 10 represents an alkyl group having a linear or branched structure
  • R 7 represents an alkyl group having a hydrogen atom or 1 to 4 carbon atoms.
  • the alkylene group having 1 to 6 carbon atoms represented by Y may be linear or branched, and specific examples thereof are not limited, but are methylene group and ethane-1,1-diyl.
  • Oxyalkylene group having from 1 to 6 carbon atoms is, on linear, may be either branched, -O-R 8 - and an alkylene group having 1 described above as specific examples of a group which satisfies the R 8 6 It is the same.
  • Alkyl ether group having from 1 to 6 carbon atoms is, on linear, may be either branched, -R 9 -O-R 9 - is a group satisfying, the invention is not limited to specific examples of R 9 Not, but independently of each other, methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2, Examples thereof include 2-diyl group, butane-1,4-diyl group and pentane-1,5-diyl group. However the total number of carbon atoms of the two R 9 is a 6.
  • Thioalkylene groups having from 1 to 6 carbon atoms is, on linear, may be either branched, -S-R 8 - a group that satisfies R 8 are as described above.
  • the thioalkyl ether group having 1 to 6 carbon atoms may be linear or branched, and is a group satisfying —R 9 ⁇ SR 9 ⁇ , and R 9 is as described above.
  • Such a monomer c are not limited, but include the following.
  • Examples of the monomer having one radically polymerizable double bond and further having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, and N-methoxymethylmethacrylamide. , N-methylol acrylamide and the like.
  • Examples of the monomer having one radically polymerizable double bond and further having an N-hydroxymethyl group include, but are not limited to, N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide. Be done.
  • the monomer having one radically polymerizable double bond and further having an epoxy group is not limited, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethylacrylate, ⁇ -n-propyl.
  • Glycidyl acrylate, ⁇ -n-butyl glycidyl acrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylate-6,7-epoxyheptyl, methacrylic acid-6,7- Epoxide heptyl, ⁇ -ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate and the like can be mentioned. ..
  • glycidyl methacrylate -6,7-epoxyheptyl methacrylate
  • o-vinylbenzyl glycidyl ether o-vinylbenzyl glycidyl ether
  • m-vinylbenzyl glycidyl ether p-vinylbenzyl glycidyl ether
  • 3,4-epoxycyclohexyl methacrylate preferably used. These may be used alone or in combination.
  • the monomer having one radically polymerizable double bond and further having an oxetane group is not limited, and examples thereof include (meth) acrylic acid ester having an oxetane group.
  • monomers 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetan, 3- (acryloyloxymethyl) -3- Ethyl-oxetan, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetan, 3- (Acryloyloxymethyl) -2-phenyl-oxetan, 2- (methacryloyloxymethyl) oxe
  • other monomers can be used together with the above-mentioned monomer a, the above-mentioned monomer b, and the above-mentioned monomer c when producing the copolymer of the component (A).
  • Such other monomers include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, and 2 -Ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, ⁇ -butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclode
  • the resistance of the obtained copolymer of the component (A) to a plating solution or the like can be imparted by using the above-mentioned other monomers. ..
  • the method for obtaining the specific copolymer used in the present invention is not particularly limited, but for example, in a solvent in which the above-mentioned monomer a, the above-mentioned monomer b, the above-mentioned monomer c, and if desired, another monomer and a polymerization initiator or the like coexist, 50 It is obtained by carrying out a polymerization reaction at a temperature of about 110 ° C.
  • the solvent used is not particularly limited as long as it dissolves a monomer having a specific functional group, a monomer having no specific functional group used if desired, a polymerization initiator and the like. Specific examples will be described in ⁇ (C) Solvent> described later.
  • the specific copolymer obtained by the above method is usually in the state of a solution dissolved in a solvent.
  • the solution of the specific copolymer obtained by the above method is put into diethyl ether or water under stirring to precipitate, and the generated precipitate is filtered and washed, and then at room temperature under normal pressure or reduced pressure. It can be dried or heat-dried to obtain a powder of a specific copolymer.
  • the polymerization initiator and the unreacted monomer coexisting with the specific copolymer can be removed, and as a result, the purified powder of the specific copolymer can be obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
  • the specific copolymer may be used in the form of a powder or in the form of a solution in which the purified powder is redissolved in a solvent described later.
  • the specific copolymer of the component (A) may be a mixture of a plurality of types of specific copolymers.
  • the ratio of copolymerizing the monomer a and the monomer b is preferably 0.05 mol to 5 mol of the monomer a with respect to 1 mol of the monomer b, particularly from the viewpoint of reactivity and plating property. It is preferably 0.1 mol to 3 mol.
  • the ratio of copolymerizing the monomer b and the monomer c is preferably 0.05 mol to 3 mol, particularly, 0.05 mol to 3 mol of the monomer c with respect to 1 mol of the monomer b from the viewpoint of reactivity and plating property. It is preferably 0.1 mol to 1 mol.
  • the total number of moles of the monomer a and the monomer b, or the monomer a, the monomer b and the monomer are used.
  • the amount of moles is 1 to 200%, more preferably 10 to 100% of the total number of moles of c.
  • the (B) metal fine particles used in the base material of the present invention are not particularly limited, and the metal species include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), and silver. Examples thereof include (Ag), tin (Sn), platinum (Pt) and gold (Au), and alloys thereof, and one kind of these metals may be used, or two or more kinds of alloys may be used. Among them, palladium fine particles are mentioned as preferable metal fine particles.
  • the metal oxide may be used as the metal fine particles.
  • the metal fine particles are obtained by reducing metal ions by, for example, a method of irradiating a solution of a metal salt with light with a high-pressure mercury lamp, a method of adding a compound having a reducing action (so-called reducing agent) to the solution, or the like.
  • a metal salt solution is added to a solution in which the component polymer (A) is dissolved and irradiated with ultraviolet rays, or a metal salt solution and a reducing agent are added to the solution to obtain metal ions.
  • a base material containing the component polymer (A) and the metal fine particles can be prepared while forming a complex of the component polymer (A) 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 and the like contained in the obtained base material.
  • Examples of the reducing agent that can be used include boron hydride metal salts such as sodium boron hydride and potassium boron hydride; aluminum lithium hydride, potassium aluminum hydride, aluminum cesium hydride, aluminum berylium hydride, and hydrogenation.
  • Aluminum hydride salts such as aluminum magnesium and aluminum hydride calcium; hydrazine compounds; citric acid and its salts; succinic acid and its salts; ascorbic acid and its salts; primary or secondary such as methanol, ethanol, isopropanol and polyols.
  • tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine [TMEDA], ethylenediaminetetraacetic acid [EDTA]; hydroxylamine; tri-n-propylphosphine, tri-n- Butylphosphine, tricyclohexylphosphine, tribenzylphosphine, triphenylphosphine, triethoxyphosphine, 1,2-bis (diphenylphosphino) ethane [DPPE], 1,3-bis (diphenylphosphino) propane [DPPP], 1 , 1'-bis (diphenylphosphino) ferrocene [DPPF], 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl [BINAP] and the like.
  • DPPE 1,2-bis (diphenylpho
  • the average particle size of the primary particles of the metal fine particles is preferably 1 to 100 nm. By setting the average particle size of the primary particles of the metal fine particles to 100 nm or less, the surface area is not reduced and sufficient catalytic activity can be obtained.
  • the average particle size of the primary particles is more preferably 75 nm or less, and particularly preferably 1 to 30 nm.
  • the average particle size of the primary particles can be measured by the following method. [Measurement of average particle size of primary particles] After dispersing the metal fine particles in ethanol, they are dropped onto a carbon support membrane and dried to prepare a sample, and then the obtained sample is microscopically subjected to a TEM device (Hitachi, Ltd .: H-8000 acceleration voltage 200 kV). The average particle size can be determined.
  • the amount of the copolymer, which is the component (A), added to the base material of the present invention is preferably 20 parts by mass or more and 10,000 parts by mass or less with respect to 100 parts by mass of the metal fine particles (B).
  • the amount of the (A) copolymer added to 100 parts by mass of the (B) metal fine particles is 20 parts by mass or more, the metal fine particles can be sufficiently dispersed, and when it is 20 parts by mass or less, the metal fine particles can be sufficiently dispersed.
  • the dispersibility of the metal fine particles is insufficient, and precipitates and agglomerates are likely to be formed. More preferably, it is 30 parts by mass or more.
  • 10,000 parts by mass or more of the (A) copolymer is added to 100 parts by mass of (B) metal fine particles, the amount of Pd per unit area after coating becomes insufficient, so that the precipitation property of plating becomes poor. It may decrease.
  • the electroless plating base material of the present invention contains the above-mentioned (A) copolymer, (B) metal fine particles, and (C) solvent, and further contains other components if necessary.
  • the copolymer which is the component (A) and the metal fine particles (B) form a composite, that is, the base material is the component (A). It is preferable to contain a composite formed by a certain copolymer and the metal fine particles (B).
  • the composite is a composite in which both of them coexist in contact with or in close contact with the metal fine particles due to the action of the metal dispersible group of the side chain of the copolymer which is the component (A), and form a particulate form.
  • it is expressed as a composite having a structure in which metal fine particles are attached or coordinated to the metal dispersible group of the copolymer which is the component (A).
  • the "adhered or coordinated structure” refers to a state in which a part or all of the metal dispersible groups of the copolymer which is the component (A) interacts with the metal fine particles, thereby forming a complex-like structure. Is considered to form. Therefore, when palladium fine particles are used as the metal fine particles, it is considered that the Pd atom on the surface layer interacts with the metal dispersible group to form a structure in which the component polymer (A) surrounds the metal fine particles.
  • the "complex" in the present invention includes not only those in which the metal fine particles and the copolymer (A) are bonded to form one complex as described above, but also the metal fine particles ( A) Copolymers as components may be included in which they exist independently without forming a bonding portion (those that appear to form one particle). ..
  • the formation of the composite of the copolymer (A) component and the (B) metal fine particles is carried out at the same time as the preparation of the base material containing the copolymer (A) component and the metal fine particles, and the method is as follows. , A method of exchanging a ligand with a polymer which is a component (A) after synthesizing metal fine particles stabilized to some extent by a metal dispersible group, or a metal ion in a solution of a polymer which is a component (A). There is a method of forming a complex by directly reducing.
  • a metal salt solution is added to a solution in which the copolymer which is the component (A) is dissolved and irradiated with ultraviolet rays, or a metal salt solution and a reducing agent are added to the solution.
  • a complex can also be formed by reducing metal ions, such as by adding them.
  • the metal ion and the copolymer (A) component are dissolved in a solvent and reduced with primary or secondary alcohols such as methanol, ethanol, 2-propanol and polyol.
  • the desired metal fine particle composite can be obtained.
  • the metal ion source used here the above-mentioned metal salt can be used.
  • the solvent to be used is not particularly limited as long as it can dissolve a polymer having a metal ion and a metal dispersible group in a required concentration or more, but specifically, methanol, ethanol, n-propanol, 2-propanol and the like.
  • Alcohols 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-methyl-2-pyrrolidone (NMP) and the like; sulfoxides such as dimethyl sulfoxide and the like and a mixed solution of these solvents are mentioned, and alcohols, halogenated hydrocarbons, cyclic ethers and the like are preferable.
  • halogenated hydrocarbons such as methylene chloride and chloroform
  • cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran
  • nitriles such as acetonitrile and butyronitrile
  • 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 room temperature (about 25 ° C.) to 100 ° C. Is the range of.
  • the desired metal fine particle composite can be obtained by dissolving the metal ion and the copolymer (A) component in a solvent and reacting them in a hydrogen gas atmosphere.
  • the metal ion source used here include the above-mentioned metal salts, hexacarbonyl chrome [Cr (CO) 6 ], pentacarbonyl iron [Fe (Co) 5 ], and octacarbonyl dicobalt [Co 2 (CO) 8 ]. , Tetracarbonyl nickel [Ni (CO) 4 ] and other metal carbonyl complexes can be used.
  • the desired metal fine particle composite can be obtained by dissolving the metal ion and the copolymer (A) component in a solvent and causing a thermal decomposition reaction.
  • the metal ion source used here the above-mentioned metal salt, metal carbonyl complex, other zero-valent metal complex, and metal oxide such as silver oxide can be used.
  • the solvent used is not particularly limited as long as it can dissolve the metal ion and the copolymer (A) component in a required concentration or more, but specifically, methanol, ethanol, n-propanol, isopropanol, etc.
  • Alcohols such as ethylene glycol; halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; benzene, toluene and the like Examples thereof include aromatic hydrocarbons and a mixed solution of these solvents, and toluene is preferable.
  • the temperature at which the metal ion and the copolymer which is the component (A) having a metal dispersible group are mixed can usually be in the range of 0 ° C. to the boiling point of the solvent, and is preferably near the boiling point of the solvent, for example, toluene. In the case, it is 110 ° C. (heating reflux).
  • the composite of the copolymer and the metal fine particles, which is the component (A) thus obtained, can be in the form of a solid substance such as powder through a purification treatment such as reprecipitation.
  • the base material of the present invention contains the copolymer (A) component, (B) metal fine particles (preferably a composite composed of these), and (C) solvent, and further, if necessary.
  • the base material contains other components, and the base material may be in the form of a varnish used when forming the [base layer of electroless metal plating] described later.
  • the electroless plating base material of the present invention can contain the base resin which is the component (D), if desired.
  • the component (D) a component having a non-radical polymerizable crosslinkable group, which is a group that undergoes a crosslink reaction with the crosslinkable group in the component (A) by heat, is preferable. The one described as is preferable. By adding such a component (D), it may be possible to further improve other functions (for example, adhesion, heat resistance, photosensitivity, dielectric property, etc.) of the obtained base layer.
  • the content is 0 parts by mass based on a total of 100 parts by mass of the copolymer of the component (A) and the metal fine particles of the component (B). It is preferably from 0 part by mass to 200 parts by mass, and more preferably from 0 part by mass to 150 parts by mass. If the content of the component (D) is excessive, the plating precipitation property may decrease.
  • the electroless plating base material of the present invention can contain a cross-linking agent which is the component (E), if desired.
  • Examples of the cross-linking agent as the component (E) include an epoxy compound, a methylol compound, a blocked isocyanate compound, a phenoplast compound, a compound having two or more trialkoxysilyl groups, a compound such as an alkoxysilane compound having an amino group, an alkoxy group, and the like.
  • epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-Hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N', N', -tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane, and N, N, N', N'-tetraglycidyl-4, 4'-diaminodiphen
  • methylol compound examples include compounds such as alkoxymethylated glycol uryl, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
  • alkoxymethylated glycol uryl examples include 1,3,4,6-tetrax (methoxymethyl) glycol uryl, 1,3,4,6-tetrax (butoxymethyl) glycol uryl, 1,3,4. , 6-Tetrax (hydroxymethyl) glycoluryl, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples thereof include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.
  • alkoxymethylated benzoguanamine examples include tetramethoxymethylbenzoguanamine and the like.
  • Mitsui Cytec Co., Ltd. trade name: Cymel (registered trademark) 1123
  • Sanwa Chemical Co., Ltd. trade name: Nicarac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.
  • alkoxymethylated melamine examples include hexamethoxymethylmelamine and the like.
  • Commercially available products include methoxymethyl type melamine compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine compound (trade name: Mycoat (registered trademark)).
  • Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercial products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.) and the like.
  • the above-mentioned blocked isocyanate compound has two or more isocyanate groups in one molecule in which the isocyanate group is blocked by an appropriate protective group, and when exposed to a high temperature during thermosetting, the protective group (block portion) becomes hot. It dissociates and comes off, and the generated isocyanate group causes a cross-linking reaction with the resin.
  • Such a polyfunctional blocked isocyanate compound can be obtained, for example, by reacting a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule with an appropriate blocking agent.
  • polyfunctional isocyanate compound examples include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 2,2,4-trimethyl-1,6-hexamethylene diisocyanate.
  • isocyanurate body biuret body, ethylene glycol adduct body, propylene glycol adduct body, trimethylpropane adduct body, ethanolamine adduct body, polyester polyol adduct body, polyether polyol adduct body, polyamide adduct body, polyami (Adduct body) can be mentioned.
  • the blocking agent examples include methanol, ethanol, isopropanol, n-butanol, heptanol, hexanol, 2-ethoxyhexanol, cyclohexanol, octanol, isononyl alcohol, stearyl alcohol, benzyl alcohol, 2-ethoxyethanol, methyl lactate, and the like.
  • Examples thereof include acidimides such as amides, succinateimide, maleateimide and phthalateimide, and urea compounds such as urea, thiourea and ethyleneurea. Further, it may be an internal block type due to a uretdione bond (dimerization of isocyanate groups).
  • VESTANAT [registered trademark] B1358A, B1358 / 100, B1370, VESTAGON [registered trademark] B1065, B1400, B1530, BF1320, BF1540 (all manufactured by Evonik Industries).
  • examples of the polyfunctional blocked isocyanate compound include homopolymers or copolymers obtained by radical polymerization of (meth) acrylate having a blocked isocyanate group.
  • the copolymer means a polymer obtained by polymerizing two or more kinds of monomers.
  • the copolymer may be a copolymer obtained by polymerizing two or more kinds of (meth) acrylates having a blocked isocyanate group, or polymerizing a (meth) acrylate having a blocked isocyanate group and another (meth) acrylate. It may be the obtained copolymer.
  • (meth) acrylates having such a blocked isocyanate group include, for example, Showa Denko KK Karens [registered trademark] MOI-BM, AOI-BM, MOI-BP, AOI-BP, and the like. Examples thereof include the MOI-DEM, the MOI-CP, the MOI-MP, the MOI-OEt, the MOI-OBu, and the MOI-OiPr.
  • These polyfunctional blocked isocyanate compounds may be used alone or in combination of two or more.
  • phenoplast compound examples include the following compounds, but the phenoplast compound is not limited to the following compound examples.
  • the compound having two or more trialkoxysilyl groups include 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, and 4,4'-bis (tri). Methoxysilyl) biphenyl, 4,4'-bis (triethoxysilyl) biphenyl, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, Bis (trimethoxysilyl) ethylene, bis (triethoxysilyl) ethylene, 1,3-bis (trimethoxysilylethyl) tetramethyldisiloxane, 1,3-bis (triethoxysilylethyl) tetramethyldisiloxane, bis ( Triethoxysilylmethyl) amine, bis (trimethoxysilylmethyl
  • alkoxysilane compound having an amino group examples include, for example, N, N'-bis [3- (trimethoxysilyl) propyl] -1,2-ethanediamine, N, N'-bis [3- (tri). Ethoxysilyl) propyl] -1,2-ethanediamine, N- [3- (trimethoxysilyl) propyl] -1,2-ethanediamine, N- [3- (triethoxysilyl) propyl] -1,2- Ethandiamine, bis- ⁇ 3- (trimethoxysilyl) propyl ⁇ amine, bis- ⁇ 3- (triethoxysilyl) propyl ⁇ amine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, trimethoxy ⁇ 3 -(Methylamino) propylsilane, 3- (N-allylamino) propyltrimethoxysilane,
  • organic metal compound having an alkoxy group and / or a chelating ligand include, for example, diisopropoxyethylacetoneacetate aluminum, diisopropoxyacetylacetonealuminum, triacetylacetonealuminum, tetrakisisopropoxytitanium, and tetrakis.
  • N-alkoxymethylacrylamide polymer examples include N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth).
  • examples thereof include polymers produced by using an acrylamide compound or a methacrylicamide compound substituted with a hydroxymethyl group such as acrylamide or an alkoxymethyl group.
  • polymers include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N.
  • examples thereof include a copolymer of -ethoxymethylmethacrylamide and benzylmethacrylate, and a copolymer of N-butoxymethylacrylamide, benzylmethacrylate and 2-hydroxypropylmethacrylate.
  • the weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.
  • Examples of the polymer of the compound having an epoxy group include a polymer produced by using a compound having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethylmethacrylate, and 3,4-epoxycyclohexylmethylmethacrylate. Be done.
  • polymers include poly (3,4-epoxycyclohexylmethylmethacrylate), poly (glycidylmethacrylate), copolymers of glycidylmethacrylate and methylmethacrylate, and 3,4-epoxycyclohexylmethylmethacrylate.
  • examples thereof include a copolymer with methyl methacrylate and a copolymer with glycidyl methacrylate and styrene.
  • the weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.
  • Examples of the polymer of the compound having an alkoxysilyl group described above include a polymer produced by using a compound having an alkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane.
  • polymers include poly (3-methacryloxypropyltrimethoxysilane), a copolymer of 3-methacryloxypropyltrimethoxysilane and styrene, and 3-methacryloxypropyltrimethoxysilane and methyl.
  • examples thereof include a copolymer with methacrylate.
  • the weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.
  • poly ((meth) acryloxypropyltrimethoxysilane) means a poly (meth) acrylate having an alkoxysilyl group.
  • the content is 0 parts by mass based on a total of 100 parts by mass of the copolymer of the component (A) and the metal fine particles of the component (B). It is preferably from 0 parts by mass to 100 parts by mass, and more preferably from 0 parts by mass to 50 parts by mass.
  • additives such as a surfactant, various surface conditioners, and thickeners may be appropriately added as long as the effects of the present invention are not impaired.
  • surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether and polyoxy.
  • Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, Solbitan fatty acid esters such as sorbitan trioleate; polyoxyethylene nonionic surfactants such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan trioleate.
  • EF Top (registered trademark) EF-301, EF-303, EF-352 [above, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.], Megafuck (registered trademark) F-171, F-173, R -08, R-30 [above, manufactured by DIC Co., Ltd.], Novec (registered trademark) FC-430, FC-431 [above, manufactured by Sumitomo 3M Co., Ltd.], Asahi Guard (registered trademark) AG-710 Fluorine-based surfactants such as [manufactured by Asahi Glass Co., Ltd.] and Surflon (registered trademark) S-382 [manufactured by AGC Seimi Chemical Co., Ltd.] can be mentioned.
  • a silicone-based leveling agent such as Shin-Etsu Silicone (registered trademark) KP-341 [manufactured by Shin-Etsu Chemical Co., Ltd.]; BYK (registered trademark) -302, 307, 322, 323. , 330, 333, 370, 375, 378 [above, manufactured by Big Chemie Japan Co., Ltd.] and the like.
  • thickener examples include polyacrylic acids (including crosslinked ones) such as carboxyvinyl polymer (carbomer); polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), and polystyrene (PS). ) And other vinyl polymers; polyethylene oxides; polyester; polycarbonate; polyamide; polyurethane; dextrin, agar, caraginan, alginic acid, Arabic gum, guar gum, tragant gum, locust bean gum, starch, pectin, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose Polysaccharides such as, and proteins such as gelatin and casein.
  • polyacrylic acids including crosslinked ones
  • carboxyvinyl polymer carboxyvinyl polymer
  • PVP polyvinylpyrrolidone
  • PVA polyvinyl alcohol
  • PVAc polyvinyl acetate
  • PS polyst
  • each of the above polymers includes not only homopolymers but also copolymers. These thickeners may be used alone or in combination of two or more.
  • the viscosity and rheological characteristics of the base material can be adjusted by adding a thickener as necessary, and the base material can be appropriately applied according to the application method, application location, and the like. Can be adopted / selected.
  • 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 mass, preferably 0.005 parts by mass, based on 100 parts by mass of the complex formed of the polymer as the component (A) and the metal fine particles as the component (B). To 10 parts by mass is more preferable, and 0.01 to 5 parts by mass is even more preferable.
  • the electroless plating base material of the present invention described above can be applied onto a base material to form an electroless metal plating base layer.
  • the base layer of this electroless metal plating is also an object of the present invention.
  • the base material is not particularly limited, but a non-conductive base material or a conductive base material can be preferably used.
  • the non-conductive base material 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).
  • examples thereof include terephthalate) resin, PEEK (polyether ether ketone) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, epoxy resin, polyacetal resin, LCP (liquid crystal polymer) resin, and the like.
  • the conductive substrate examples include ITO (tin-doped indium oxide), ATO (antimon-doped tin oxide), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), GZO (gallium-doped zinc oxide), and the like.
  • a base material in which a thin film is formed of these conductive base materials on the non-conductive base material can also be used. Further, the base material may be a three-dimensional molded product.
  • the component polymer (A) and fine metal particles (B) preferably a composite composed of these
  • the component polymer (A) and fine metal particles (B) are used.
  • (And, if necessary, (D) base resin, (E) cross-linking agent and other components) are dissolved or dispersed in (C) solvent to form a varnish, and the varnish is used as a group to form a metal plating film.
  • bar coating method, flexographic printing, gravure printing, spin coating method, spray coating method, inkjet method, pen lithography, contact printing, ⁇ CP, NIL and nTP are preferable.
  • spin coating method since it can be applied in a single time, there is an advantage that even a highly volatile solution can be used and a highly uniform application can be performed.
  • spray coating method a highly uniform coating can be performed with a very small amount of varnish, which is industrially very advantageous.
  • the inkjet method, pen lithography, contact printing, ⁇ CP, NIL, or nTP is used, fine patterns such as wiring can be efficiently formed (drawn), which is industrially very advantageous.
  • the solvent used here the polymer which is the component (A), (B) fine metal particles (preferably a composite composed of these), and optionally the component (D), the component (E) and other components are dissolved.
  • the solvent used here it is not particularly limited as long as it disperses, but for example, water; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene and dichlorobenzene; methanol, ethanol, n-propanol, isopropanol, n-butanol, and the like.
  • Alcohols such as 2-butanol, n-hexanol, n-octanol, 2-octanol, 2-ethylhexanol; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, 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, Glycol ethers such as diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol
  • solvents may be used alone or may be a mixture of two or more kinds of solvents.
  • glycols such as ethylene glycol, propylene glycol and butylene glycol may be added for the purpose of adjusting the viscosity of the varnish.
  • concentration to be dissolved or dispersed in the solvent is arbitrary, but the concentration of the non-solvent component in the varnish [the polymer which is the component ((A)) and the metal fine particles (B) (preferably) of all the components except the solvent contained in the base material. Concentration of (complex composed of these), optionally (D) base polymer, (E) cross-linking agent, other components, etc.)] is 0.05 to 90% by mass, preferably 0.1 to 80% by mass. be.
  • the method for drying the solvent is not particularly limited, and for example, it may be evaporated in an appropriate atmosphere, that is, in an atmosphere, an inert gas such as nitrogen, or in a vacuum, using a hot plate or an oven. This makes it possible to obtain a base layer having a uniform film-forming 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, metal plating film, metal film base material By electroless plating the base layer of the electroless metal plating formed on the base material obtained as described above, a metal plating film is formed on the base layer.
  • the metal plating film thus obtained, and the metal coating base material provided on the base material in the order of the electroless metal plating base layer and the metal plating film are also the 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 general method is to immerse the base layer of electroless metal plating formed on the base material in a liquid (bath).
  • the electroless plating solution mainly contains a metal ion (metal salt), a complexing agent, and a reducing agent, and is a pH adjuster, a pH buffer, and a reaction accelerator (second complexing agent) according to other uses.
  • a metal ion metal salt
  • a complexing agent for improving the wettability of the surface to be treated, etc.
  • second complexing agent for imparting gloss to the plating film, for improving the wettability of the surface to be treated, etc.
  • the metal used for the metal plating film formed by electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold and alloys thereof, which are appropriately selected according to the purpose. Will be done.
  • the complexing agent and the reducing agent may be appropriately selected according to the metal ions.
  • a commercially available electroless plating solution may be used as the electroless plating solution.
  • an electroless nickel plating chemical (Melplate (registered trademark) NI series) manufactured by Meltex Co., Ltd. and an electroless copper plating chemical (Melplate (Melplate)) may be used.
  • Electroless nickel plating solution (ICP Nicolon (registered trademark) series, Top Piena 650) manufactured by Okuno Pharmaceutical Co., Ltd., electroless copper plating solution (OPC-700 electroless copper MK, ATS Ad Copper IW, CT, OPC Copper (registered trademark) AF series, HFS, NCA), electroless tin plating solution (Substar SN-5), electroless gold plating solution (flash gold 330, self gold OTK) -IT), electroless silver plating solution (Muden Silver); electroless palladium plating solution (pallet II) manufactured by Kojima Chemical Co., Ltd., electroless gold plating solution (Dip G series, NC gold series); Sasaki Chemical Electroless silver plating solution manufactured by Yakuhin Co., Ltd.
  • ICP Nicolon (registered trademark) series, Top Piena 650) manufactured by Okuno Pharmaceutical Co., Ltd. electroless copper plating solution (OPC-700 electroless copper MK, ATS Ad Copper IW, CT
  • Electroless copper plating solution (Print Gant (registered trademark) PV, PVE) manufactured by Atotech Japan Co., Ltd. can be preferably used.
  • the formation speed of the metal film is adjusted by adjusting the temperature, pH, immersion time, metal ion concentration, presence / absence of stirring and stirring speed, presence / absence of supply of air / oxygen, supply speed, and the like. And the film thickness can be controlled.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • HEA 2-Hydroxyethyl acrylate
  • NVA N-Vinylacetamide
  • GMA Glycidyl methacrylate cyclomer
  • M100 3,4-Epoxycyclohexylmethylmethacrylate (manufactured by Daicel)
  • Viscoat 3F 2,2,2-trifluoroethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
  • HFIP-M Hexafluoro-2-propyl methacrylate (manufactured by Central Glass)
  • FAMAC-6 2- (Perfluorohexyl) Ethyl Methacrylate (manufactured by Unimatec)
  • AMBN 2,2'-azobis-2-methylbutyronitrile
  • PGME propylene glycol monomethyl ether
  • IPE diisopropyl ether
  • BL-10 polyvinyl acetal resin
  • ⁇ Synthesis example 1> A polymer solution (solid content concentration: 30 mass) obtained by dissolving 2.03 g of styrene, 1.63 g of NVA, 2.23 g of HEA, and 0.29 g of AMBN in 14.37 g of PGME and reacting at 80 ° C. for 20 hours. %) was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P1). The obtained polymer had Mn of 6,806 and Mw of 11,797.
  • the solution (solid content concentration: 30% by mass) was added to 500 mL of diethyl ether with stirring to precipitate a polymer.
  • the precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P4).
  • the obtained copolymer had Mn of 7,669 and Mw of 16,610.
  • the coalesced solution (solid content concentration: 30% by mass) was added to 500 mL of diethyl ether with stirring to precipitate a polymer.
  • the precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P5).
  • the obtained copolymer had Mn of 6,146 and Mw of 13,143.
  • the coalesced solution (solid content concentration: 30% by mass) was added to 500 mL of diethyl ether with stirring to precipitate a polymer.
  • the precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P7).
  • the obtained copolymer had Mn of 5,257 and Mw of 9,324.
  • this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite.
  • the precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M1) as a black powder.
  • this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite.
  • the precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M2) as a black powder.
  • this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite.
  • the precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M3) as a black powder.
  • this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite.
  • the precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M4) as a black powder.
  • this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite.
  • the precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M5) as a black powder.
  • this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite.
  • the precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M6) as a black powder.
  • this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite.
  • the precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M7) as a black powder.
  • this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite.
  • the precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M8) as a black powder.
  • this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite.
  • the precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M9) as a black powder.
  • this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite.
  • the precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M10) as a black powder.
  • this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite.
  • the precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M11) as a black powder.
  • this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite.
  • the precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M12) as a black powder.
  • this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite.
  • the precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M13) as a black powder.
  • the components (C) and (D) were added to the complexes M1 to M13 of the Pd particles at the ratios shown in Table 1 below to prepare an electroless plating base material.
  • the electroless plating base material containing M1 to M3 is used as a comparative example.
  • Examples include electroless plating base materials containing M4 to M13, respectively.
  • Preparation of plating solution ⁇ Preparation Example 1> 200 mL Beaker with 100 mL of pure water, Basic Print Gantt V (Atotech) 17 mL, Copper Solution Print Gantt V (Atotech) 9 mL, Starter Print Gantt PV (Atotech) 1.6 mL, Stabilizer Print Gantt PV (Atotech) 0. 24 mL, reducer Cu (manufactured by Atotech) 3.2 mL, 18.5 mass% NaOH aqueous solution 4 mL were charged, and pure water was further added to bring the total volume of the solution to 200 mL. This solution was stirred to obtain an electroless copper plating solution.
  • Plating is uniformly deposited on the entire surface of the coating film.
  • X Plating is not uniformly deposited on the entire surface of the coating film.

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Abstract

L'invention fournit un agent de base de dépôt autocatalytique contenant un polymère et des microparticules métalliques. Plus précisément, l'invention concerne un agent de base de dépôt autocatalytique qui est destiné à former un film de dépôt métallique par traitement de dépôt autocatalytique sur un substrat. L'agent de base de l'invention contient : (A) un copolymère qui contient à son tour une unité structurale dérivée d'un monomère (a) possédant dans chaque molécule au moins un groupe trifluorométhyle et une double liaison polymérisable par voie radicalaire, et une unité structurale dérivée d'un monomère (b) possédant dans chaque molécule un groupe métallique capable de se disperser et une double liaison polymérisable par voie radicalaire ; (B) des microparticules métalliques ; et (C) un solvant.
PCT/JP2021/004682 2020-02-19 2021-02-08 Agent de base de dépôt autocatalytique contenant un polymère et des microparticules métalliques WO2021166726A1 (fr)

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JP2013155437A (ja) * 2011-12-31 2013-08-15 Rohm & Haas Electronic Materials Llc めっき触媒および方法
WO2018151073A1 (fr) * 2017-02-14 2018-08-23 日産化学工業株式会社 Procédé de formation de câblage
WO2019171985A1 (fr) * 2018-03-06 2019-09-12 日産化学株式会社 Agent primaire pour dépôt autocatalytique comprenant un polymère et de fines particules métalliques

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