WO2015045056A1 - Composition de revêtement pour dépôt autocatalytique - Google Patents

Composition de revêtement pour dépôt autocatalytique Download PDF

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Publication number
WO2015045056A1
WO2015045056A1 PCT/JP2013/076040 JP2013076040W WO2015045056A1 WO 2015045056 A1 WO2015045056 A1 WO 2015045056A1 JP 2013076040 W JP2013076040 W JP 2013076040W WO 2015045056 A1 WO2015045056 A1 WO 2015045056A1
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Prior art keywords
electroless plating
coating composition
resin
group
dispersant
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PCT/JP2013/076040
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English (en)
Japanese (ja)
Inventor
達也 中辻
梶原　康一
克弘 中村
博 落合
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株式会社イオックス
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Priority to JP2015538698A priority Critical patent/JP6284536B2/ja
Priority to PCT/JP2013/076040 priority patent/WO2015045056A1/fr
Publication of WO2015045056A1 publication Critical patent/WO2015045056A1/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
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • 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
    • 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
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides

Definitions

  • the present invention relates to a coating composition for electroless plating.
  • plating metal plating
  • non-conductive substrates such as polyethylene terephthalate (PET) and polycarbonate (PC)
  • PET polyethylene terephthalate
  • PC polycarbonate
  • Decorative plating for the purpose of: Electronic components such as integrated circuits and resistors;
  • a technique for forming the plating is used when forming a conductive wiring pattern on a non-conductive substrate.
  • Non-conductive substrate cannot obtain metal bond at the interface with plating. Therefore, in order to obtain excellent adhesion between the nonconductive substrate and the plating, by performing etching (roughening) to form fine irregularities on the surface of the nonconductive substrate, It is necessary to give an anchor effect (throwing effect). This etching has a problem that the process is complicated and a chemical having a high environmental load such as chromic acid has to be used.
  • Patent Documents 1 to 4 describe techniques for forming a plating on a non-conductive substrate by performing a treatment aiming at the same effect as etching without using chromic acid. .
  • Patent Documents 1 and 2 there is a method in which a chemical bond is generated between the base material, the adhesive layer, and the catalyst by forming an adhesive layer having a binding property with the catalyst on the base material.
  • Patent Document 3 describes a technique for imparting an anchor effect by etching a substrate with UV or ozone.
  • Patent Document 4 describes a method for forming an underlayer for electroless plating by applying an ink having an electroless plating catalyst onto a substrate.
  • Patent Documents 1 to 3 a step of applying a catalyst between the pretreatment step for imparting adhesion and the electroless plating step (for example, palladium ions are attached to the substrate).
  • a process of activating the catalytic metal and a process of converting the palladium ion into a metal by later metallizing the palladium ion is required. That is, there is a problem that the number of steps is not different from the conventional etching with chromic acid, and the steps are complicated.
  • patent document 4 before performing electroless plating, it calls an activation process, and the reduction process by a boron type compound and the washing
  • the present invention is a coating composition having excellent dispersibility that enables easy electroless plating treatment, has less adverse effects on the environment, has high safety, and has excellent plating adhesion and appearance coating. It aims at providing the coating composition which can provide.
  • the present invention has found that a coating composition capable of achieving the above object can be obtained by using specific components, and the present invention is completed here. It came.
  • this invention relates to the following coating composition, its manufacturing method, its use, its usage, and to-be-plated object.
  • a coating composition for electroless plating comprising: 2. Item 2. The coating composition according to Item 1, wherein the complex (1) is obtained by reducing palladium ions in the presence of a dispersant. 3. Item 3.
  • Item 4 The coating composition according to any one of Items 1 to 3, wherein the resin (3) is at least one selected from the group consisting of a polyamide resin, a polyamideimide resin, and a polyimide resin. 5.
  • the dispersant is a block copolymer type polymer dispersant having at least one group selected from the group consisting of a hydroxyl group and a carboxyl group. 6).
  • the manufacturing method of the coating composition for electroless plating characterized by the above-mentioned. 7).
  • the electroless plating coating composition according to any one of the above items 1 to 5 is applied on a substrate to form a coating film, and then contacted with an electroless plating solution to form an electroless plating film how to. 8).
  • Item 8 The method according to Item 7, wherein the application is application by a gravure offset printing method or a flexographic printing method.
  • An object to be plated obtained by applying the electroless plating coating composition according to any one of the above items 1 to 5 to a substrate and then applying electroless plating. 10.
  • Item 10 The plated object according to Item 9, wherein the application is an application by a gravure offset printing method or a flexographic printing method.
  • this invention also includes the invention of the manufacturing method of a coating composition, the invention of the use of a coating composition, the invention of the usage method of a coating composition, and the invention of a to-be-plated object.
  • the coating composition of the present invention includes the following (1) to (3): (1) a composite of palladium particles and a dispersant, (2) at least one selected from the group consisting of water and an aprotic polar solvent, and (3) Resin, It is characterized by containing.
  • the coating composition of the present invention can form a coating film for electroless plating more easily and efficiently than conventional methods. Yes, there are few adverse effects on the environment and safety is high.
  • the coating composition of this invention is excellent in the dispersibility.
  • the coating film for electroless plating formed by the coating composition can form an electroless plating film excellent in adhesion and appearance film, and is excellent in the deposition rate of the electroless plating film.
  • a coating composition comprising (1) a composite of palladium particles and a dispersant, (2) at least one selected from the group consisting of water and an aprotic polar solvent, and (3) a resin is provided in the present invention. It is one of the preferable aspects as a coating composition for electroless plating. And (1) a composite of palladium particles and a dispersant, (2) at least one selected from the group consisting of water and an aprotic polar solvent, (3) a resin, and (4) the above (2) A coating composition comprising a solvent other than) is also one of the preferred embodiments as the coating composition for electroless plating of the present invention. In the present invention, indications such as parts and% are used, and unless otherwise specified, parts by mass or mass% (wt%) are expressed.
  • the coating composition for electroless plating of the present invention contains a composite of palladium particles (Pd particles) and a dispersant (hereinafter, this composite is referred to as a Pd composite). Also called body).
  • the Pd complex can be obtained, for example, by allowing a dispersant and palladium ions (Pd ions) to exist in a solvent and then reducing the palladium ions.
  • the shape of the Pd composite satisfies the condition that (i) the dispersants are intertwined with each other and (ii) at least some of the dispersants are in contact with each other.
  • polycarboxylic acid polymer dispersants such as polycarboxylic acid ammonium salt, polycarboxylic acid sodium salt, polycarboxylic acid triethylamine salt, polycarboxylic acid triethanolamine salt; polyoxyethylene alkyl ether carboxylate, alkyl hydroxy ether Block copolymer type polymer dispersant having hydroxyl group such as carboxylate; Block having carboxyl group such as acrylic acid-maleic acid copolymer, styrene-maleic acid copolymer, acrylic acid-sulfonic acid copolymer Copolymer type polymer dispersants; and the like can be used.
  • a dispersing agent can be used 1 type or in combination of 2 or more types.
  • a block copolymer type polymer dispersant having at least one group selected from the group consisting of a hydroxyl group and a carboxyl group is preferable.
  • a commercially available product can be used as the dispersant.
  • Polycarboxylic acid-based polymer dispersants are Nopco Santo K, R, RFA manufactured by San Nopco Co., Ltd., Nop Cosperth 44-C, SN Dispersant 5020, 5027, 5029, 5034, 5045, 5468, Kao Co., Ltd. Demall P, It is sold as EP, Poise 520, 521, 530, 532A, etc.
  • Block copolymer type polymer dispersants having a carboxyl group are marketed as Big Chemie Japan Co., Ltd. DISPERBYK 180, 187, 191, 194, Nippon Shokubai Co., Ltd. Aquaric TL, GL, LS.
  • a block copolymer type polymer dispersing agent having a hydroxyl group it is sold as DISPERBYK190, 2010, etc. manufactured by BYK Japan Japan Co., Ltd.
  • Examples of the compound that supplies palladium ions include palladium chloride, palladium sulfate, palladium nitrate, palladium acetate, palladium benzoate, palladium salicylate, palladium paratoluenesulfonate, palladium perchlorate, palladium benzenesulfonate, and the like.
  • the compound which supplies palladium ion can be used 1 type or in combination of 2 or more types.
  • a method for reducing Pd ions there may be mentioned a method in which a dispersant and Pd ions are present in a solvent and then a reducing agent is added to the solvent. Thereby, Pd ion and a reducing agent contact and react.
  • the reducing agent include secondary or tertiary amines such as hydrazine hydrate (hydrazine monohydrate), sodium borohydride, N, N dimethylethanolamine and diethanolamine.
  • the solvent used for the reduction is at least one selected from the group consisting of water and an aprotic polar solvent described in (2) below (Hereinafter also referred to as the solvent (2)) can be used.
  • a solvent can be used 1 type or in combination of 2 or more types.
  • the shape of the Pd composite is such that (i) the dispersants are intertwined with each other, and (ii) at least some of the dispersants are in contact with each other. (iii) It is considered that the Pd particles are attached to the dispersant.
  • the shape of the Pd complex may be a random coil shape, a dense spherical shape, or a spherical structure.
  • Pd particles are considered to be attached to the outside of the dispersant.
  • the shape of the Pd composite (the shape of the entire dispersant) is a dense sphere, it is considered that most of the Pd particles are attached to the spherical surface side (outside).
  • the average particle size of the Pd particles alone is not particularly limited, but is preferably 2 to 10 nm.
  • the particle diameter of the Pd particles is measured by a transmission electron microscope described later. Further, in this specification, the average particle diameter of Pd particles is calculated by randomly selecting 10 Pd particles, measuring the particle diameter of the Pd particles with the transmission electron microscope, and averaging the number. (Number-based average diameter).
  • the average particle diameter of the Pd complex is not particularly limited, but preferably has a spherical structure (FIG. 2 in the present specification) having an average particle diameter of about 20 to 300 nm as a whole.
  • the average particle diameter of the Pd complex is measured by a particle size analyzer (Otsuka Electronics Co., Ltd., FPAR-1000) (mass standard average diameter).
  • the reason why the coating film for electroless plating of the present invention can form an electroless plating film excellent in adhesion and appearance film, and is excellent in the deposition rate of the electroless plating film is based on the following principle. It is considered a thing. (Principle)
  • the inside of the structure formed by the Pd complex is included so as to adsorb the solvent of (2).
  • the solvent (2) inside the Pd composite has a lower drying rate than the solvent (2) in the coating composition of the present invention. Therefore, when the coating composition of the present invention is applied to the substrate, the solvent of (2) in the coating composition is first dried to form the entire coating film, and then the inside of the Pd complex present in the coating film When the solvent (2) is dried, crater-like irregularities are formed on the surface of the coating film.
  • a coating film for electroless plating (hereinafter also simply referred to as a coating film) is formed.
  • a coating film for electroless plating (hereinafter also simply referred to as a coating film) is formed.
  • the coating film is formed on such a principle, the following (a) and (b): (a) Since there are many Pd particles so as to be concentrated on the coating film surface, the reactivity between the coating film surface and the electroless plating solution is excellent, (b) Since the unevenness is formed on the coating film surface, the anchor effect between the plating film and the coating film is excellent, (c) Since the unevenness is very fine and the smoothness of the coating film surface is maintained (example: FIG. 7 in the present specification), a plating film having a high glossiness (excellent film appearance) can be obtained. , It is thought that the effect is played.
  • coating composition of at least one present invention selected from the group consisting of water and an aprotic polar solvent is at least one selected from the group consisting of water and an aprotic polar solvent (2) Contains solvent (solvent (2)).
  • the solvent of (2) has excellent affinity with the Pd complex of (1) and the resin of (3), and (1) a solvent (or dispersion medium) for dispersing the Pd complex and (3) resin. As a function.
  • an atomic group of> NC ( ⁇ O) — such as N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc) ( Or an aprotic polar solvent having a group or a bond; dimethyl sulfoxide; ⁇ -butyrolactone, and the like.
  • NMP N-methylpyrrolidone
  • DMF N-dimethylformamide
  • DMAc N-dimethylacetamide
  • an aprotic polar solvent having a group or a bond dimethyl sulfoxide; ⁇ -butyrolactone, and the like.
  • aprotic polar solvents aprotic polar solvents having> N—C ( ⁇ O) —atomic groups are preferred, and at least one selected from the group consisting of NMP, DMF and DMAc is more preferred.
  • the solvent of (2) can be used 1 type or in combination of 2 or more types.
  • the solvent of (2) can be converted after the reduction reaction of palladium ions (for example, the solvent is converted from water to NMP).
  • the content of the solvent is not particularly limited, but is preferably about 10 2 to 10 6 parts by mass with respect to 100 parts by mass of the aforementioned Pd complex.
  • the solvent of (2) is only water, (1) 5 ⁇ 10 3 to 3 ⁇ 10 5 parts by mass is preferable with respect to 100 parts by mass of Pd complex, and 10 4 to 2 ⁇ 10 5 parts by mass is more preferable. preferable.
  • the solvent of (2) is only an aprotic polar solvent, (1) 5 ⁇ 10 2 to 5 ⁇ 10 3 parts by mass is preferable with respect to 100 parts by mass of the Pd complex, and 10 3 to 2 ⁇ 10 3 Part by mass is more preferable.
  • the coating composition of the present invention contains a resin.
  • resin in this invention the coating film for electroless plating can be more firmly adhered to a base material on a base material.
  • the resin becomes a polymer base material (matrix resin) constituting the coating film for electroless plating.
  • a resin that is dispersed or dissolved in the solvent of the above (2) can be used.
  • the resin include epoxy resin, polyester resin, acrylic resin, polyurethane resin, polyamide resin, polyimide resin, polyamideimide resin (PAI), shellac resin, melamine resin, urea resin, and the like.
  • an acrylic resin means a polymer of an acrylate ester or a polymer of a methacrylic ester, or a copolymer using these as a comonomer.
  • polymethyl methacrylate resin, polyacrylic resin examples thereof include methyl acid resin, ethylene-methyl acrylate copolymer, and ethylene-methyl methacrylate copolymer.
  • the polyamideimide resin is a resin in which an amide bond is introduced into the polyimide main chain, and is obtained by a reaction between trimellitic anhydride and diisocyanate, a reaction between trimellitic anhydride chloride and diamine, or the like. Resin.
  • the resins at least one selected from the group consisting of polyimide resin, polyamideimide resin, polyamide resin, polyurethane resin, polyester resin and acrylic resin is preferable, and the group consisting of polyamide resin, polyamideimide resin and polyimide resin Is more preferable, and at least one selected from the group consisting of a polyimide resin and a polyamideimide resin is more preferable.
  • Resin components can be used alone or in combination of two or more. In addition, when using 2 or more types of resin components as (3) resin, it is preferable to use it so that content of one type of resin component in it may become 90 wt% or more in (3) resin components.
  • the 4-alkyl-3-carboxylic acid ester polypyrrole is preferably not contained as the resin component (3) from the viewpoints of lowering adhesion of the plating film, lowering water resistance, lowering weather resistance, and the like.
  • the content of the resin, relative to Pd complexes 100 parts by weight, preferably 10 to 104 parts by mass, and more preferably 50-1500 parts by weight.
  • Diluting solvents include alcohols such as methanol, ethanol and isopropyl alcohol (IPA); ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone and diacetone alcohol; ethylene glycol monomethyl ether, ethylene glycol monobutyl ether (butyl cellosolve), tert -Glycol ethers such as butyl cellosolve; Aromatic carboxylic acid esters such as methyl benzoate, ethyl benzoate and methyl salicylate; Aromatic hydrocarbons such as toluene and xylene; Methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl Glycol ether esters such as carbitol acetate, butyl carbitol acetate, propy
  • the content thereof is preferably (0) to 2 ⁇ 10 4 parts by mass with respect to 100 parts by mass of (1) Pd complex, and 20 to 2 ⁇ 10 4 parts by mass. More preferably.
  • a dilution solvent can be used 1 type or in combination of 2 or more types.
  • the method for producing the coating composition of the present invention is not particularly limited, but includes (2) at least one selected from the group consisting of water and an aprotic polar solvent, and (3) a resin.
  • the method for producing the coating composition of the present invention is not particularly limited, but includes (2) at least one selected from the group consisting of water and an aprotic polar solvent, and (3) a resin.
  • Step 1 in which palladium ions and a dispersant are present in at least one selected from the group consisting of water and an aprotic polar solvent
  • Step 2 of reducing the palladium ions by reacting the palladium ions with a reducing agent It is preferable to manufacture by the manufacturing method which contains these in order.
  • the coating composition for electroless plating which can form the coating film for electroless plating can manufacture easily and efficiently with little bad influence with respect to an environment.
  • the coating composition for electroless plating is excellent in dispersibility, can form a coating film for electroless plating more easily and efficiently than conventional methods, and has less adverse effects on the environment and is safe. High nature.
  • the coating film for electroless plating can form an electroless plating film excellent in adhesion and appearance film, and is excellent in the deposition rate of the electroless plating film.
  • step 1 palladium ions and a dispersant are present in a solvent.
  • the palladium ion the above-mentioned compound supplying the palladium ion can be used as a supply source.
  • the dispersant the above-described dispersants can be used.
  • the use ratio (mass ratio) of palladium ions and dispersant in Step 1 is usually about 10 to 200 parts by mass with respect to 100 parts by mass of palladium ions.
  • the dispersing agent is preferably 30 to 150 parts by mass, more preferably 50 to 100 parts by mass with respect to 100 parts by mass of palladium ions.
  • the above solvent (2) can be used.
  • the amount of the solvent used is not particularly limited as long as palladium ions and a dispersing agent can be uniformly present, but is preferably 10 4 to 3 ⁇ 10 5 parts by mass with respect to 100 parts by mass of palladium ions, and 10 4 to 10 5. Part by mass is more preferable.
  • step 2 palladium ions are reduced by the reducing agent by reacting the palladium ions with the reducing agent. That is, in Step 2, a palladium ion reduction reaction occurs, and as a result, the above-mentioned Pd complex (1) can be obtained.
  • the reducing agent in step 2 the reducing agent used for preparing the Pd complex of (1) described above can be used.
  • the amount of the reducing agent to be used is not particularly limited, but is about 100 to 800 parts by mass, preferably 200 to 600 parts by mass with respect to 100 parts by mass of palladium ions.
  • the reaction temperature is about 35 to 45 ° C, and the temperature is raised to about 50 to 60 ° C.
  • the reaction time is not particularly limited, but may be about 1 to 5 hours.
  • the pressure and atmosphere during the reaction are not particularly limited, and may be carried out under atmospheric pressure and air (air) atmosphere.
  • the reaction can be carried out in an open system such as a beaker.
  • a solution containing palladium ions, a dispersing agent and a reducing agent may be stirred with a bladed stirring rod.
  • the coating composition for electroless plating of the present invention can also be obtained by the procedure of only step 1 and step 2, but after step 2, for example, containing (2) solvent, (3) resin, and other components ( Other operations such as addition); separation of the Pd complex-containing liquid; This point will be described below.
  • Step 2 it may contain at least one selected from the group consisting of (2) solvent and (3) resin described above.
  • the solvent is converted after the reduction reaction of palladium ions (for example, water is used as the solvent in Step 1 and the water is converted into NMP after Step 2 so that the electroless plating paint composition using NMP as the solvent is used. It is also possible that
  • the Pd complex-containing liquid obtained in step 2 can be separated by ultrafiltration. By this operation, it is possible to remove inorganic salts, excess dispersants, and the like contained in the Pd complex-containing liquid. More specifically, filtration operation and water, solvent, etc. (especially water) supplementation operations can be repeated for the Pd complex-containing liquid.
  • the coating composition of the present invention can be used for a substrate on which electroless plating is desired.
  • a coating film suitable for electroless plating can be formed on the substrate.
  • the shape of the substrate is not particularly limited.
  • it may be any of a plate shape (or film shape), a nonwoven fabric shape (or woven fabric shape), a thread shape, various shapes formed by a mold, and the like.
  • the component of the substrate is not particularly limited, and examples thereof include resins and ceramics.
  • resins include: polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polylactic acid esters; acrylic resins such as polymethyl methacrylate (PMMA); polycarbonate resins (PC); polystyrene resins; Polyamide resin; Polyimide resin; Polyetherimide resin; Polyacetal resin; Polyether ether ketone resin; Cyclic polyolefin resin; Polyethylene resin; Polyphenylene sulfide resin; Liquid crystal polymer; Modified polyphenyl ether resin; And polyphthalamide resin (PPA); polyarylate resin; and the like.
  • Specific ceramics include glass and alumina.
  • nonwoven fabrics such as a wood fiber, glass fiber, asbestos, polyester fiber, vinylon fiber, rayon fiber, polyolefin fiber, are mentioned.
  • the method for using the coating composition on the substrate is not particularly limited, and examples thereof include application.
  • a coating method a bar coater, a gravure printing machine (gravure offset), a flexographic printing machine, an ink jet printing machine, dipping, spraying, a spin coater, a roll coater, a reverse coater, a screen printing machine, etc. can be used for coating. .
  • gravure offset printing or flexographic printing is preferable.
  • a drying treatment can be performed.
  • the drying step can efficiently remove an unnecessary solvent when performing electroless plating, and can improve the adhesion between the coating film and the substrate and the surface strength of the coating film.
  • the temperature of the drying treatment is preferably about 60 to 400 ° C. More preferably, it is 80 to 150 ° C.
  • the drying time is usually about 0.1 minute (6 seconds) to 60 minutes, depending on the drying temperature. More preferably, it is about 10 to 30 minutes.
  • the coating film for electroless plating contains a Pd composite.
  • the Pd complex exists in a state of being uniformly dispersed in the coating film. Therefore, electroless plating can be more efficiently performed on the coating film.
  • the thickness of the coating film before drying can be appropriately selected depending on the intended use. Before drying, it is usually about 1 to 30 ⁇ m, preferably 2 to 20 ⁇ m.
  • the thickness of the coating after drying is usually about 0.05 to 3 ⁇ m, preferably 0.1 to 1 ⁇ m. If the thickness of the coating film after drying is within the above range, the adhesion between the substrate and the coating film and the adhesion between the electroless plating film (metal film) and the coating film are particularly excellent.
  • An electroless plating film can be formed by performing electroless plating after forming the coating film for electroless plating of the present invention by using the coating composition of the present invention as a substrate.
  • the object to be plated of the present invention on which the electroless plating film is formed is excellent in the adhesion of the plating film.
  • the base material on which the coating film is formed by the above method comes into contact with a plating solution for depositing metal, thereby forming an electroless plating film.
  • Electroless plating has good reactivity, and the obtained electroless plating film has no unevenness and is excellent in adhesion and appearance film.
  • the plating solution is not particularly limited as long as it is usually a plating solution used for electroless plating, and examples thereof include copper, gold, silver, nickel, and chromium.
  • copper or nickel is preferable from the relationship with the coating film formed by the coating composition of the present invention.
  • the electroless copper plating bath is usually about 25 to 45 ° C.
  • the processing time is about 10 to 20 minutes
  • the deposited film thickness is about 0.3 to 0.4 ⁇ m.
  • the treatment temperature is about 55 to 70 ° C.
  • the deposition rate is usually about 5 ⁇ m / hr (60 ° C.).
  • it is usually about 85 to 95 ° C.
  • the deposition rate is usually about 20 ⁇ m / hr (90 ° C.).
  • the plated object of the present invention can be used for electronic components such as integrated circuits and resistors; electromagnetic wave shields; Moreover, when the said to-be-plated object is a thread-like electroconductive fiber, it can be used for clothing or an electric wire.
  • the coating composition of the present invention When the coating composition of the present invention is used for a specific application for electroless plating, the coating composition can form a coating film for electroless plating more easily and efficiently than conventional methods. Yes, there are few adverse effects on the environment and safety is high. Moreover, the coating composition of this invention is excellent in the dispersibility. Furthermore, the coating film for electroless plating formed by the coating composition can form an electroless plating film excellent in adhesion and appearance film, and is excellent in the deposition rate of the electroless plating film.
  • Production Example 1 Preparation of Pd complex-containing liquid A 944.5 g of ion-exchanged water was placed in a 3 liter flask, and 5.0 g of palladium nitrate was added to the ion-exchanged water, followed by stirring. Thereby, palladium nitrate was dissolved in water. To the aqueous solution, 3.8 g of a block copolymer type polymer dispersant having a carboxyl group (DISPERBYK194, manufactured by Big Chemie Japan, nonvolatile content 53 wt%) was further added and dissolved in the aqueous solution.
  • DISPERBYK194 a block copolymer type polymer dispersant having a carboxyl group
  • This solution was heated to 42 ° C., and 10.0 g of hydrazine monohydrate was added with stirring. Thereafter, the solution was stirred at room temperature (23 ° C.) for 1 hour. The temperature of the solution rose to 53 ° C. after the addition of hydrazine monohydrate, but the temperature of the solution after stirring for 1 hour was 40 ° C. By this operation, palladium ions in the aqueous solution were reduced.
  • This solution was subjected to ultrafiltration filter AHP-1010 (manufactured by Asahi Kasei Corporation) to separate the reduced Pd complex-containing liquid and the inorganic salt-containing liquid.
  • the Pd complex content was found to be 1.2 wt%. all right.
  • Production Example 2 Preparation of Pd complex-containing liquid B
  • DISPERBYK2010 BIC Chemie Japan Co., Ltd., nonvolatile content 40 wt%) having a hydroxyl group
  • a Pd complex-containing liquid B was obtained.
  • the Pd complex content rate of the Pd complex containing liquid B was 1.4 wt%.
  • Pd complex containing A Pd complex-containing liquid C (dispersion medium: N-methylpyrrolidone (NMP)) having a rate of 8 wt% was obtained.
  • Production Example 5 Preparation of Pd complex-containing liquid E Pd complex having a Pd complex content of 8 wt% was prepared in the same manner as in Production Example 3, except that N, N-dimethylformamide was used instead of N-methylpyrrolidone.
  • Body-containing liquid E (dispersion medium: N, N-dimethylformamide (DMF)) was obtained.
  • Production Example 6 Preparation of Pd complex-containing liquid F A Pd complex-containing liquid F (with a Pd complex content of 8 wt%) was prepared in the same manner as in Production Example 3, except that ethanol was used instead of N-methylpyrrolidone. Dispersion medium: ethanol) was obtained.
  • Production Example 7 Preparation of Pd complex-containing liquid G Pd complex was prepared in the same manner as in Production Example 3, except that a solvent having a mass ratio of ethanol and IPA of 1: 1 was used instead of N-methylpyrrolidone.
  • a Pd complex-containing liquid G (dispersion medium: ethanol and IPA) having a body content of 8 wt% was obtained.
  • Production Example 8 Preparation of Pd complex-containing liquid H Pd complex-containing liquid H (with a Pd complex content of 8 wt%) was prepared in the same manner as in Production Example 3 except that cyclohexanone was used instead of N-methylpyrrolidone. Dispersion medium: cyclohexanone) was obtained.
  • Production Example 9 Preparation of Pd complex-containing liquid I
  • a Pd complex-containing liquid I (with a Pd complex content of 8 wt%) was prepared in the same manner as in Production Example 3 except that butyl cellosolve was used instead of N-methylpyrrolidone.
  • Production Example 10 Preparation of Pd complex-containing liquid J Pd complex-containing liquid J having a Pd complex content of 8 wt% was prepared in the same manner as in Production Example 3, except that butyl acetate was used instead of N-methylpyrrolidone. (Dispersion medium: butyl acetate) was obtained.
  • Production Example 11 Preparation of Pd complex-containing liquid K A Pd complex-containing liquid K having a Pd complex content of 8 wt% was prepared in the same manner as in Production Example 3, except that ethylene glycol was used instead of N-methylpyrrolidone. (Dispersion medium: ethylene glycol) was obtained.
  • Example 1 was prepared by mixing Pd complex-containing liquid A 8.3 wt%, polyester resin aqueous solution (RZ-570, solid content 25 wt%, manufactured by Kyoyo Chemical Co., Ltd.) 4.0 wt%, and ion-exchanged water 87.7 wt%.
  • a coating composition for electroless plating was prepared. The coating composition was applied onto a polyethylene terephthalate (PET) film (SL-50, manufactured by Teijin DuPont Films Ltd.) using a bar coater # 4 and dried in an oven for drying at 105 ° C. for 5 minutes. This obtained the film in which the coating film for electroless plating of Example 1 was formed.
  • PET polyethylene terephthalate
  • Examples 2 to 36 and Comparative Examples 1 to 16 As shown in Tables 1 to 3, except that the type or content of (1) Pd complex-containing liquid or Pd ion-containing liquid, (3) resin component, (2) solvent, other solvent, etc. is appropriately changed. Each coating composition for electroless plating was produced in the same manner as in Example 1.
  • each electroless plating coating film was formed in the same manner as in Example 1 except that the type of substrate, coating method, drying conditions, coating film thickness, etc. were appropriately changed.
  • the obtained base material (hereinafter also referred to as a coating film-containing article) was obtained.
  • Examples 1 to 4, 21, 22, and 31 and Comparative Examples 1 and 2 Polyester resin aqueous solution (RZ-570, solid content 25 wt%, manufactured by Kyoyo Chemical Co., Ltd.)
  • Examples 5 and 6 and Comparative Examples 13 to 16 Polyester resin solution (Pesresin S-250, solid content 30 wt%, manufactured by Takamatsu Yushi Co., Ltd.) Examples 7, 8, 23 to 26, 33 and 34, and Comparative Examples 9 to 12: polyimide resin solution (Q-IP-X0897, solid content 32 wt%, manufactured by PI Engineering Laboratory Co., Ltd.)
  • Examples 9 and 10 Polyamideimide resin solution (HPC-6000, solid content 26 wt%, manufactured by Hitachi Chemical Co., Ltd.) Examples 11, 12, 17 to 20, 27 to 30, 32, 35 and 36, and Comparative Examples 3 to 8: Polyamide resin solution (Aronmite FS175SV10, solid content 10 wt
  • Evaluation Test 1 Dispersibility Test of Coating Composition
  • Each coating composition obtained in Examples 1 to 36 and Comparative Examples 1 to 16 was evaluated for dispersibility. Specifically, after preparing each coating composition, the coating composition was allowed to stand for 24 hours, and each coating composition after the standing was visually evaluated.
  • the evaluation criteria for dispersibility were as follows. Only A is accepted as a product. A: (1) Pd complex and (3) resin were uniformly dispersed. B: (1) Pd complex (or palladium particles) or (3) resin was not uniformly dispersed but partially or completely precipitated.
  • Electroless plating property (electroless copper plating) is obtained by immersing each of the coating film-containing articles obtained in Examples 1 to 36 and Comparative Examples 1 to 16 in an electroless plating bath. And electroless nickel plating property).
  • the electroless copper plating bath uses Sulcup PSY made by Uemura Kogyo Co., Ltd. (initial Cu concentration 2.5 g / l, bath volume 500 ml 30 ° C), and the electroless nickel plating bath is BEL801 made by Uemura Kogyo Co., Ltd. 6 g / l, bath volume 500 ml 65 ° C.) was used. Immersion in the electroless plating bath was performed for 15 minutes.
  • the evaluation criteria for electroless plating were as follows. A to C are acceptable as products. A: The plating deposition reaction started immediately after immersion of the plating solution, a glossy plating film was obtained immediately, and no peeling was observed. B: Although not immediately after immersion of the plating solution, a glossy plating film was obtained within 15 minutes, and no peeling was observed. C: Although it was not as glossy as the above-mentioned B evaluation, a plating film that was glossy enough to be acceptable as a product was obtained, and peeling was not observed. D: Although a plating film was obtained, peeling of the plating film was observed. E: A plating film was not obtained.
  • Evaluation test 3 Adhesion test (cross-cut test evaluation) In order to confirm the adhesion of the electroless plating film, the following test was performed. Copper or nickel plating films were obtained in the same manner as in Evaluation Test 2 for the coating film-containing articles of Examples 1 to 36 and Comparative Examples 1 to 16. On the copper or nickel plating film, 25 squares were cut at 1 mm intervals based on JIS K 5600 (cross cut method). A cellophane tape (cello tape (registered trademark), manufactured by Nichiban Co., Ltd.) was applied thereon, and the number of squares peeled when the tape was peeled was measured. Only A is accepted as a product. A: The number of squares peeled off was zero. B: The number of squares peeled off was 1 or more.
  • test results are shown in Tables 1 to 3 below.
  • the parts by mass (% by mass) of each component used for preparing each coating composition are also shown.
  • the mass part of each component is displayed to the second decimal place.
  • the total mass part (mass%) of each electroless plating coating composition is 100 mass parts (mass%).
  • NMP represents N-methylpyrrolidone
  • DMF represents N, N-dimethylformamide
  • DMAc represents N, N-dimethylacetamide
  • MEK represents methyl ethyl ketone
  • ⁇ is a polyethylene terephthalate (PET) film (KEL-86W, manufactured by Teijin Limited), ⁇ is a polyimide film (Kapton EN100, manufactured by Toray DuPont Co., Ltd.), and ⁇ is a PET film. (SL-50, manufactured by Teijin Ltd.), ⁇ indicates a polyester fiber (Uniecolo, manufactured by Unitika Ltd.), and ⁇ indicates an aramid fiber (Kevlar 29, manufactured by Toray DuPont Co., Ltd.).
  • b represents a bar coater
  • i represents an inkjet
  • g represents a gravure offset
  • r represents a roll coat
  • d represents a coating by dipping (dipping).
  • the bar coater used was Select-Roller L60 made by Matsuo Sangyo Co., Ltd., and the PX-A550 made by Seiko Epson Corporation was used for the inkjet.
  • the gravure offset the coating composition was filled into the pores of a gravure intaglio plate made of a round dot mesh formed at a pitch of 100 ⁇ m using a doctor blade.
  • a transfer blanket rubber roll (A (0.6) SP11-1, manufactured by Kinyo Co., Ltd.) was brought into close contact with the portion filled with the coating composition, and the coating composition was transferred onto the roll. Thereafter, the coating composition was transferred onto each film by bringing the blanket rubber roll into close contact with each film.
  • Pd complex 2. at least one selected from the group consisting of water and aprotic polar solvents, and resin; Pd particles4. 4. Dispersant Base material 6. 6. Electroless plating coating film Electroless plating film

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Abstract

La présente invention porte sur une composition de revêtement qui permet d'effectuer facilement un procédé de dépôt autocatalytique, qui a une excellente dispersibilité, qui a moins d'impact négatif sur l'environnement, qui est sans danger et qui peut conférer une bonne adhérence du dépôt et un bon aspect du revêtement. Cette composition de revêtement pour dépôt électrolytique comprend (1) un composite de particules de palladium et d'un dispersant, (2) au moins un type de composant choisi entre l'eau et un solvant polaire aprotique et (3) une résine.
PCT/JP2013/076040 2013-09-26 2013-09-26 Composition de revêtement pour dépôt autocatalytique WO2015045056A1 (fr)

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JP2007197798A (ja) * 2006-01-27 2007-08-09 Taiyo Ink Mfg Ltd 無電解めっきプライマー用熱硬化性樹脂組成物及びそれを用いた無電解めっき処理方法
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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