WO2007138795A1 - Agent catalytiseur pour dÉpÔt autocatalytique - Google Patents

Agent catalytiseur pour dÉpÔt autocatalytique Download PDF

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Publication number
WO2007138795A1
WO2007138795A1 PCT/JP2007/058313 JP2007058313W WO2007138795A1 WO 2007138795 A1 WO2007138795 A1 WO 2007138795A1 JP 2007058313 W JP2007058313 W JP 2007058313W WO 2007138795 A1 WO2007138795 A1 WO 2007138795A1
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Prior art keywords
water
catalyst
group
acid
plating
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PCT/JP2007/058313
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English (en)
Japanese (ja)
Inventor
Keiko Takagi
Masaru Seita
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Technic Japan Inc.
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Publication of WO2007138795A1 publication Critical patent/WO2007138795A1/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
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment

Definitions

  • the present invention relates to a metal compound, an alkali metal hydroxide, a water-soluble silane coupling agent,
  • the present invention also relates to a catalyst agent for electroless plating using a mixture of at least one of an inorganic acid and an organic acid.
  • Non-catalytic chemical reduction plating is a method of forming a metal film by chemical reduction that is controlled without using a deposited metal or alloy as a catalyst. Has been used.
  • the reducing agent reduces the metal ions in the bath and deposits as a metal on the substrate.
  • electroless nickel plating is a plating that deposits copper on a catalytic surface, and has been widely used as a printed wiring board formation technology such as through-hole plating, semi-additive method, additive method, and plastic plating.
  • Electroless nickel plating is used for decorative purposes and electronic parts because nickel is deposited on the catalytic surface.
  • nickel phosphorus alloy plating, nickel boron alloy plating, and ternary alloy plating baths to which tantasten and molybdenum are added have been developed to improve the characteristics.
  • the method of plating deposited on these catalytic surfaces is a catalyst on the surface of a non-conductive material.
  • a catalyst nucleus serving as an initiator for electroless plating such as palladium colloid or palladium ion is formed on a non-conductive material, and then a metal film is formed by a reduction reaction around the catalyst nucleus. It is the method of making it precipitate.
  • the conventionally used palladium-tin colloidal catalyst has very good activity and colloidal stability, and the bath management is poor.
  • a highly hydrochloric acid solution pH 1 or less
  • a palladium-tin colloidal catalyst remains between the circuits, causing a decrease in insulation.
  • a stripping agent has been developed to completely remove this residue, but it has not been fully effective.
  • a treatment with a silane coupling agent is generally performed as a pretreatment.
  • a silane coupling agent is adsorbed after irradiating a resin with far-ultraviolet rays having a wavelength of 350 ⁇ m or less, application of a palladium-tin catalyst is promoted, and electroless plating with stronger adhesion is obtained.
  • the step of immersing a polyimide film in a 0.05 to 10 wt% aqueous solution of a water-soluble aminosilane coupling agent and washing the film surface with water at least once in the next step, and a palladium-tin colloid catalyst solution Dipping in metal, removing tin and removing metal It consists of a step of immersing in a catalytically active solution that changes into a volume, and a step of forming an electroless plating layer by performing electroless metal plating.
  • Patent Document 6 after the surface treatment with a silane coupling agent obtained by the reaction of an azole compound and an epoxy silane compound is treated with a solution containing a noble metal ion such as palladium. , Copper or nickel electroless plating.
  • Patent Document 7 after pretreatment of a covering material with an alkali metal salt, a silane coupling agent having a substituent having a metal-capturing ability in one molecule is converted into a nitrogen-containing heterocyclic azole compound and an epoxy group.
  • Surface treatment is applied to the coating agent with a pre-mixed or reacted pre-metal compound (palladium chloride), which is a reaction product of the silane compound, and the electroless plating Has been given.
  • a metal vapor deposition method As other methods for forming a conductive film on a non-conductive material, a metal vapor deposition method, a laminating method, a casting method, or the like is generally used.
  • a laminating method is a method in which a double-sided adhesive layer is applied to a polyimide film and a copper foil is laminated. Since an adhesive layer is required on both sides, there is a limit to reducing the thickness.
  • the casting method is a method in which a polyimide raw material is applied to an electrolytic copper foil, heat-treated, and then the copper foil is further bonded. Since copper foil with a large number of processes is used, there is a limit to reducing the thickness of the film.
  • the sputtering method has a force of forming nickel-chromium sputter 0 ⁇ 003 to 0.03 / im and copper sputter 0 ⁇ 2 / im on a 25 ⁇ polyimide film.
  • Equipment and running costs are expensive. Therefore, it is necessary to balance film tension avoidance, the conveyance tension, and the sputter output, which are difficult during sputtering, and there is a problem in low mass productivity.
  • Patent Document 1 Japanese Patent No. 2622016
  • Patent Document 2 JP 63-259083 A
  • Patent Document 3 Japanese Patent Laid-Open No. 2005-116745
  • Patent Document 4 JP-A-10-310873
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2005-116745
  • Patent Document 6 Japanese Patent No. 3277463
  • Patent Document 7 JP 2002-226972 A
  • a palladium-seed colloid catalyst has been widely used for hitting through-holes in printed wiring boards, but the catalyst remains between the lines during circuit formation by the semi-additive method, and later electroless nickel In other words, the problem is that the substitutional gold plating is deposited between the lines and deteriorates the insulation.
  • a catalyzing method that can be easily removed by acid treatment or the like, and an inexpensive catalyzing method that replaces the palladiumose colloidal catalyst solution.
  • the present invention has been made in view of such circumstances, and includes a resin substrate and a conductive thin film.
  • the purpose is to provide a new method for catalyzing on non-conductive surfaces, replacing the conventional electroless plating pre-treatment for obtaining high adhesion strength, and a relatively simple treatment by the wet method. It is an object of the present invention to provide a catalytic method for forming a conductive thin film on the surface of the non-conductive material that does not pollute the work environment or the global environment.
  • the electroless plating catalyst of the present invention comprises a mixture of a metal compound, an alkali metal hydroxide, a water-soluble silane coupling agent, and at least one of an inorganic acid and an organic acid.
  • the electroless plating catalyst of the present invention is a new catalyst on a non-conductive surface, replacing the conventional electroless plating pretreatment for obtaining high adhesion strength between a resin substrate and a conductive thin film.
  • the agent is provided.
  • the non-conductive substrate that can be used in the electroless plating catalyst of the present embodiment is a resin substrate having appropriate physical properties according to the purpose of use, such as strength, insulation, and corrosion resistance. It is not particularly limited. Further, the non-conductive substrate that can be used in the electroless plating catalyst of the present embodiment is not limited to a resin molded product, but may be a composite in which the resin is reinforced. It is also possible to use a base material made of various materials such as ceramics, glass, metal, etc., or a film formed from these with a resin.
  • Arbitrary resins can be used for the non-conductive substrate, such as epoxy resin, polyimide resin, polyphenylene ether resin, fluorine resin, ABS resin, epoxy resin, and poly An imide resin is exemplified.
  • the resin substrate may be composed of a single resin or a plurality of resins.
  • the treatment process using the electroless plating catalyst of the present embodiment includes (1) a surface modification treatment of a non-conductive substrate, and (2) a non-electrolytic plating catalyst on the non-conductive substrate. It comprises the steps of forming nuclei, (3) a step of forming a metal conductive thin film layer by electroless plating, and (4) a step of heat treatment after electroless plating. ) Can be adjusted appropriately by changing each condition. In the case of a composite resin substrate with a metal, a metal etching treatment step and an acid activation step can be added as necessary. In addition, if necessary, the electroless reaction can be accelerated before the electroless connection.
  • the electroless plating film may be subjected to degreasing treatment, descaling treatment, acid activation treatment, etc., and then electroplating. Heat treatment after electroplating can be applied as needed.
  • the above-mentioned (1) surface modification treatment of the non-conductive substrate can be applied by a dry method such as general-purpose plasma treatment or a wet method using chemicals.
  • the optimum method can be selected considering the chemical characteristics of the non-conductive substrate to be treated.
  • the non-conductive substrate is subjected to surface roughening by etching, desorption of the resin constituent elements by high-energy active species, branch cross-linking and desaturation, and introduction of a group having ion exchange ability. Occurs and can impart hydrophilicity.
  • the plasma processing apparatus include a room temperature plasma processing apparatus and a microwave low temperature oxygen plasma processing apparatus.
  • An acidic solution such as sulfuric acid or an alkaline solution such as sodium hydroxide or potassium hydroxide can be used for surface modification of a non-conductive substrate by a wet method.
  • an alkaline solution such as sodium hydroxide or potassium hydroxide
  • 0.1 mol / L to 10 mol / L-NaOH solution or 0.1 mol / L to 10 mol / L-KOH solution can be used.
  • the temperature is preferably in the range of 20 to 90 ° C, and the treatment time is preferably in the range of 10 seconds to 10 minutes.
  • the step of forming a catalyst nucleus with electroless plating on a non-conductive substrate includes the step of forming a metal compound, an alkali metal hydroxide, a water-soluble silane coupling agent on the non-conductive substrate, This is a step of treating with the electroless plating catalyst of the present embodiment comprising a mixture of at least one of an inorganic acid and an organic acid. Metallization to be reacted depending on the type of electroless plating A compound can be selected.
  • metal compounds of metals such as palladium, gold, silver and platinum can be used for electroless copper plating, and palladium, titanium, cobalt, tungsten, gold, Metal compounds of metals such as silver and platinum can be used. Concentration is 5 X 10 5 X 10 1 molZL, 3 X 10 5 X 10 2 molZL is preferred.
  • the electroless plating catalyst according to the present embodiment develops the catalytic ability of metal compounds by metals such as titanium, cobalt, tungsten, etc. that have not been used as a catalyst as well as palladium, gold, silver, platinum. It becomes possible.
  • an optimal water-soluble silane coupling agent can be selected depending on the type of non-conductive substrate.
  • the epoxy resin polyimide resin, phenol resin, polyethylene resin, polypropylene resin, polystyrene resin, PET resin, acrylic resin
  • the trialkoxysilane is trimethoxysilane, triethoxysilane, tripropoxysilane, triplicate.
  • Toxisilane Diethoxymonomethoxysilane, Monomethoxydimethoxysilane, Monomethoxydipropoxysilane, Ptoxhetoxypropoxysilane, Dimethoxymonopropoxysilane, Diethoxymonopropoxysilane, Monobutoxydimethoxysilane, Tetraalkoxysilane Are tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraethoxymonomethoxysilane, dimethoxydioxydipropoxysilane, Toximopropoxysilane, dibutoxydimethoxysilane, and monoalkyltrialkoxysilane include monomethyltrimethoxysilane, monoethyltrimethoxysilane, monopropyltriethoxysilane, monomethyltryptoxysilane, monoethyltribut
  • the water-soluble silane coupling agent of this embodiment includes a vinyl group, an epoxy group, an amino group, a methacryloxy group, a mercapto group, a methoxy group chemically bonded to an inorganic material, and an ethoxy group. One or a plurality selected from a group having a group.
  • Examples of the bur group possessed by the water-soluble silane coupling agent of the present embodiment include butyl trimethoxy silane, butyl triethoxy silane, butyl trichloro silane, butyl triacetoxy silane, burtris (methoxy ethoxy) silane, butyl triisopropoxy silane,
  • the epoxy group possessed by the water-soluble silane coupling agent of the embodiment includes 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyljetoxysilane, and 3-glycidoxy.
  • Propylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the amino group of the water-soluble silane coupling agent of this embodiment include N- (2-aminoethyl) 3 —Aminopropi
  • Examples of mercapto groups possessed by 3-methacryloxypropylmethylmethoxysilane and the water-soluble silane coupling agent of this embodiment include 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrisilane.
  • the concentration of the inorganic acid used in the electroless plated catalyst agent of the present embodiment 3 is X 10 5mol / L, 2 10- 1 ⁇ 2111017 Mr. Shi favored I.
  • the concentration of the alkali metal hydroxide used in the electroless plated catalyst agent of the present embodiment 2 10- 2-311101 / Shideari, IX 10 1 ⁇ 2 mol / L is preferred.
  • the concentration of the organic acid used in the electroless plating catalyst of the present embodiment is 2 ⁇ 10 ⁇ 2 to 2 mol / L, preferably 3 ⁇ 10 ⁇ 1 to 1 mol / L.
  • the alkali metal hydroxide used for the electroless plating catalyst of this embodiment is sodium hydroxide. Any alkali metal hydroxide selected from the group consisting of thorium and potassium hydroxide may be used.
  • the inorganic acid used in the electroless plating catalyst of the present embodiment may be an inorganic acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and carbonic acid.
  • the organic acid used in the electroless plating catalyst of this embodiment is an organic acid selected from the group consisting of carboxylic acids, hydroxycarboxylic acids, and amino acids.
  • the step (3) of forming a metal conductive thin film layer by electroless plating can be selected according to the purpose as long as it is an electroless plating having catalytic activity.
  • electroless nickel plating, electroless copper plating, electroless cobalt plating, electroless palladium plating, electroless silver plating, electroless gold plating, electroless platinum plating, electroless ruthenium plating examples include electroless openings such as zinc plating, electroless indium plating, electroless tin plating, electroless lead plating, electroless antimony plating, and electroless bismuth plating.
  • the heat treatment method is also related to the heat resistance of the resin. It is preferable that the heat treatment is performed within a range where the resin does not deteriorate or excessively oxidize. For example, in the case of an epoxy resin-based resin substrate, it is preferable to heat at about 80 to 150 ° C. In the case of a polyimide-based resin substrate, it is preferable to heat at about 80 to 180 ° C. The heating time is usually preferably about 30 to about 120 minutes.
  • the heating atmosphere may be heat-treated in air with no particular limitation, but heating may be performed in a reducing atmosphere such as a nitrogen atmosphere or a hydrogen atmosphere so that oxidation of the formed conductive thin film does not proceed excessively.
  • a heating atmosphere may be appropriately set according to the properties of the target component.
  • the electroless plating catalyst of the present embodiment is a new alternative to the conventional electroless plating pretreatment for obtaining high adhesion strength between the resin substrate and the conductive thin film.
  • the catalyst agent is provided on the surface of the non-conductor.
  • a palladium-tin colloidal catalyst has been widely used to mate through holes in printed wiring boards, but this catalyst remains between lines during circuit formation by the semi-additive method, and later electroless nickel, substitutional gold A problem arises in that the metal deposits are deposited between the lines and the insulation is deteriorated.
  • the electroless plating catalyst of the present embodiment solves this problem, It is possible to provide a catalytic method that can be easily removed by acid treatment or the like and a catalyst agent that replaces the palladiumose colloidal catalyst solution.
  • the metal ion having catalytic ability to be mixed or reacted with the silane coupling agent is alone from the group consisting of cobalt ion, tungsten ion, titanium ion, silver ion, gold ion, platinum ion, Alternatively, since a plurality of options can be selected, it is possible to provide a low-cost electroless plating catalyst.
  • the adhesion between the metal element-containing component and the resin substrate is improved.
  • the adhesion can be judged by the peel strength of the film and the tape peeling test.
  • a copper film of 10 to 20 ⁇ is formed on the electrolytic copper. It is formed by eye contact. After heat treatment at 200 ° C for 10 minutes, the film was cut into a lcm width and measured by a vertical peeling test (90 ° peel strength) at a rate of 5 OmmZ using a tensile tester.
  • a 15 cm X 15 cm polyimide film (UPILEX-25R manufactured by Ube Industries) was placed in an atmospheric pressure plasma apparatus (manufactured by Nippon Paint Co., Ltd.) and treated at 80 kV for a distance of 2 cm between electrodes for 10 minutes.
  • This sample was immersed in a degreasing agent (Techni FPD Cleaner 20mL / L, 60 ° C) for 1 minute, washed with water, and then in an activator (Technique ACT9600 50g / L) solution at room temperature for 30 seconds. Soak After washing with water, use a copper sulfate plating bath (Techni TECH2 CU2300) to perform copper plating at 15 / m, wash with water, and prevent oxidation of the copper film surface (Technics Corp. And then washed with water and dried for 20 seconds at room temperature. After that, when observed with a metallographic microscope, cracks did not occur and a uniform film was obtained. After heat treatment at 250 ° C. for 1 minute, the peel strength of the obtained film was measured to be 0.85 kN / m.
  • a degreasing agent Techni FPD Cleaner 20mL / L, 60 ° C
  • an activator Technique ACT9600 50g / L
  • This sample was immersed in a degreasing agent (Techni FPD Cleaner 20mL / L 60 ° C) for 1 minute, washed with water, and then in an activating agent (Technique: ACT9600 50mL / L) solution at room temperature for 30 seconds. After soaking, washing with water, using a commercially available copper sulfate bath, wash the copper with 15 zm, wash with water, and prevent oxidation of the copper film surface (Technique: Tech. And then washed with water and dried for 20 seconds. After that, when observed with a metallurgical microscope, no cracks occurred, a uniform film was obtained, and heat treatment at 150 ° C for 5 minutes Later, when the peel strength of the obtained film was measured, it was 0.60 kN / m.
  • a degreasing agent Techni FPD Cleaner 20mL / L 60 ° C
  • an activating agent Technique: ACT9600 50mL / L
  • This sample was immersed in a degreasing agent (Techni FPD Cleaner 20mL / L 60 ° C) for 1 minute, washed with water, and then immersed in an activator (Technique 50g / L ACT9600 solution, room temperature) for 30 seconds.
  • a degreasing agent Techni FPD Cleaner 20mL / L 60 ° C
  • an activator Technique 50g / L ACT9600 solution, room temperature
  • This sample is immersed in a degreasing agent (Techni FPD Cleaner 20mL / L, 60 ° C) for 1 minute, washed with water, and then immersed in an activating agent (Technique: ACT9600 50mL / L, room temperature) for 30 seconds. After washing with water, use a copper sulfate bath (Technique: Cuprochic 84 A: 40mL / L, B: 30m LZL, additive: 30mLZL, F: 100mL / L 50 ° C).
  • a degreasing agent Techni FPD Cleaner 20mL / L, 60 ° C
  • an activating agent Technique: ACT9600 50mL / L, room temperature
  • An epoxy resin (manufactured by Matsushita Electric Works Co., Ltd.) 100 / m was applied as an insulating layer to a 5cm x 10cm (plate thickness 1.6mm) substrate, cured at 150 ° C for 1 hour, and then micro vias with a carbon dioxide laser Formed.
  • This sample was treated with an atmospheric pressure plasma apparatus at 80 kV for 10 minutes with an electrode distance of 2 cm.
  • This sample was palladium acetate 3 X 10 _3 mol / L, diethoxymonomethoxysilane 0 3 mol / L, hydrochloric acid 3 X 10 _2 mol / L, sodium hydroxide 1 X 10 _2 mol / L, glycolic acid 0
  • an electroless plating catalyst consisting of a 5 mol / L mixed solution at room temperature for 5 minutes, wash with water, and then wash this sample with an electroless copper plating bath (Technic Co., Ltd .: Cuprosic 84 A: 40 mL / L, B: 30 mL / L, additive: 30 mL / L, F: 100 mL / L 50 ° C) for 5 minutes to obtain a copper conductive thin film.
  • Example 6 Preparation of electroless copper thin film on glass
  • 6cm X 7.6cm slide glass Iwaki Glass Co., Ltd.
  • 80g / L sodium hydroxide solution 80 ° C for 5 minutes
  • washed with water washed with water, and activated (Techni ACT3500 lOOmL / L chamber) after immersion in temperature)
  • the sample palladium sulfate 5 X 10- 3 mol / L, Jefferies chill dimethoxy silane-0.
  • This sample is immersed in a degreasing agent (Techni FPD cleaner 20mL / L, 60 ° C) for 1 minute, washed with water, and then immersed in an activator (Technique: ACT9600 50mL / L, room temperature) for 30 seconds.
  • a degreasing agent Techni FPD cleaner 20mL / L, 60 ° C
  • an activator Technique: ACT9600 50mL / L, room temperature
  • the surface was washed with water, washed with water, treated with a discoloration inhibitor (Technique: Techni Anti-Turnish) for 20 seconds at room temperature to prevent oxidation of the copper film surface, washed with water and dried. After that, when the surface was observed with a metallographic microscope, a uniform film with no cracks or scratches on the material was obtained. After heat treatment at 150 ° C for 1 minute, the peel strength of the obtained film was measured to be 0.65 kN / m.
  • a discoloration inhibitor Technique: Techni Anti-Turnish
  • This sample was immersed in a degreasing agent (Techni FPD Cleaner 20mL / L, 60 ° C) for 1 minute, washed with water, and then immersed in an activator (Technique: ACT9600 50mL / L, room temperature) for 30 seconds.
  • a degreasing agent Techni FPD Cleaner 20mL / L, 60 ° C
  • an activator Technique: ACT9600 50mL / L, room temperature
  • Prosic 84 A 40 mL / L, B: 30 mL / L, additive: 30 mL / L, F: 100 mL / L) Dipped at 50 ° C for 5 minutes to obtain a copper plating film. Thereafter, heat treatment was performed at 200 ° C. for 10 minutes.
  • 5cm X 10cm polyimide film (Ube Industries Upilex 25R) is immersed in 80g / L sodium hydroxide solution at 80 ° C for 5 minutes, washed with water, and then activated (Techni ACT350 0 lOOmL / L room temperature) after, the sample, palladium chloride 5 X 10 _3 mol / L, salts of cobalt 5 X 10 _3 mol / L, triethoxy silane 0 ⁇ 5 mol / L, hydrochloric 6 X 10 "2 mol / L , sodium hydroxide Soak in water for 10 minutes at room temperature in a non-electrolytic agent consisting of a mixture of 2 X 10 _2 mol / L and lmol / L maleic acid, rinse with water, and electroless nickel plating bath (Techni AT-5000 A: A uniform nickel film was obtained when immersed in 60 mL / L, B: 150 mL / L 80
  • 5 cm X 1 Ocm polyimide film (Ube Industries Upilex 25R) is immersed in 80 g / L sodium hydroxide solution at 80 ° C for 5 minutes, washed with water, and activator (Techni ACT350 0 lOOmL / L room temperature) It immersed 5 minutes at after immersion silver nitrate 5 X 10- 3 mol / L, Jechi dimethoxysilane 0.
  • This sample was immersed in a degreasing agent (Techni FPD Cleaner 20mL / L 60 ° C) for 1 minute, washed with water, and then in an activator (Technique: ACT9600 50mL / L) solution at room temperature for 30 seconds. After soaking, rinsing with water, use a commercially available copper sulfate messenger bath to perform copper plating at 15 / m, wash with water, and prevent oxidation of the copper film surface (anti-discoloration made by Technic Co., Ltd.). And room temperature) for 20 seconds, washed with water and dried. After that, when observed with a metallographic microscope, no cracks occurred and a uniform film was obtained. After heat treatment at 150 ° C for 10 minutes, the peel strength of the obtained film was measured to be 0.65 kN / m. showed that.
  • 5cm X 10cm polyimide film (Ube Industries Upilex 25R) is immersed in 80g / L sodium hydroxide solution at 80 ° C for 5 minutes, washed with water, and then activated (Techni ACT350 0 lOOmL / L room temperature) after, the sample, cobalt chloride l X 10_ 2 molZL, tetramethylene Tokishishiran 0.
  • This sample was immersed in a degreasing agent (Techni FPD Cleaner 20mL / L 60 ° C) for 1 minute, After washing, immerse in an activating agent (Technique: ACT9600 50mL / L) solution at room temperature for 30 seconds, wash with water, and then use a commercially available copper sulfate bath to perform copper plating at 15 / m. Then, in order to prevent oxidation of the copper film surface, it was treated with a discoloration inhibitor (manufactured by Technic Co., Ltd .: Techni Anti-Tanisch, room temperature) for 20 seconds, washed with water and dried. Thereafter, when observed with a metallurgical microscope, cracks did not occur and a uniform film was obtained. After heat treatment at 250 ° C for 1 minute, the peel strength of the obtained film was measured to show 0.70 kNZm. It was.
  • a degreasing agent Techni FPD Cleaner 20mL / L 60
  • Conductive copper thin film by electroless copper plating (ATS Ad Power Par IW process manufactured by Okuno Seiyaku Co., Ltd.) using commercially available palladium-tin colloid on 5cm X 1 Ocm polyimide film (UPILEX-25R manufactured by Ube Industries) Formed.
  • UPILEX-25R manufactured by Ube Industries
  • the copper plating is washed at 15 zm, washed with water, and used to prevent oxidation of the copper film surface (Technic Co., Ltd.).
  • Manufactured by Techni Anti-Turnish, room temperature washed for 20 seconds and dried. After heat treatment at 200 ° C for 10 minutes, when measuring the peel strength of the copper plating film, it showed 0.1 kN / m, and good adhesion could not be obtained.
  • 5 cm x 1 Ocm polyimide film (UPILEX-25R manufactured by Ube Industries, Ltd.) is immersed in 80 g / L sodium hydroxide solution at 80 ° C for 5 minutes, washed with water, and then a commercially available electroless copper plating pretreatment agent (Okuno) 100mL / L3 aminosilane (Torayda And immersing it at room temperature for 5 minutes to give a palladium-tin colloidal catalyst. After washing with water, immersed in an electroless nickel plating bath at 80 ° C for 5 minutes.After film formation, the surface was observed with a metallurgical microscope, and numerous cracks were formed on the nickel surface, and then at 200 ° C for 10 minutes. As a result of this heat treatment, the nickel film peeled off from the polyimide substrate. Further, the adhesion strength was not measurable.
  • a 5cm x 10cm polyimide film (UPILEX-25R made by Ube Industries) is immersed in 80g / L sodium hydroxide solution at 80 ° C for 5 minutes, washed with water, and then added to 0.05g / L stannous chloride solution at room temperature. After immersion for 5 minutes, it was immersed in 0.05 g ZL palladium chloride solution at room temperature for 5 minutes to give a palladium catalyst. After washing with water, a nickel thin film was formed by immersing in an electroless nickel plating bath (Techni AT-500 00 A: 60 mL / LB: 150 L / L 80 ° C) for 5 minutes, and then the surface was observed with a metallurgical microscope. However, innumerable cracks occurred, and when heat treatment was performed at 200 ° C. for 10 minutes, the nickel thin film peeled off from the polyimide base material. Further, the adhesion strength was not measurable.
  • a 5cm x 10cm polyimide film (UPILEX 25R manufactured by Ube Industries) is immersed in 80g / L sodium hydroxide solution at 80 ° C for 5 minutes, washed with water, and then a commercially available electroless copper plating pre-treatment agent (Okuno Pharmaceutical Co., Ltd.) 100 mL / L3 aminosilane (Toray Duco Co., Ltd. Z-6050) was added to OPC-80 KYATARISTO M), and immersed for 5 minutes at room temperature to give a palladium-tin colloid catalyst.
  • UPILEX 25R manufactured by Ube Industries
  • Tungstic acid paste sodium monomonoxide ⁇ 7X10 L 0, 70k / m actual fiber 8 sodium 1X10-1 ⁇ 2I / L methoxysilane maleic acid IX 10 "'
  • Comparative example 1 S-free plating process using commercially available palladium-tin colloids Innumerable elephant cracks 0.1 k N / m Comparative example 2 Commercially available «Unwrapping pre-treatment agent Countless cracks; Impossible Comparative Example 3 Commercially available s »Pre-treatment agent for countless cracks; 3 ⁇ 4 Not determined Comparable example 4 0.05 s / L fermented * Sousse 3 ⁇ 4 solution at room temperature for 5 min, 0.05 s count & crack iJU Indefinite
  • Tables 2 and 3 are tables showing the observation results and measurement results of the films obtained from the above Examples:! -12 and Comparative Examples 1-5. As can be seen from Tables 2 and 3, the film obtained with the electroless plating catalyst of this example has sufficient peel strength and surface properties, and is superior to the electroless plating catalyst of this example. Sex was confirmed.

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Abstract

L'invention concerne un agent catalyseur pour dépôt autocatalytique économique permettant d'obtenir une adhérence élevée, constitué d'un mélange d'un composé métallique, d'un hydroxyde de métal alcalin, d'un agent de couplage de silane hydrosoluble, et d'un acide inorganique et/ou d'un acide organique.
PCT/JP2007/058313 2006-05-31 2007-04-17 Agent catalytiseur pour dÉpÔt autocatalytique WO2007138795A1 (fr)

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US11155924B2 (en) 2017-03-31 2021-10-26 Toyoda Gosei Co., Ltd. Silver mirror film, decorative article, silver mirror film-forming liquid, and method for producing reducing liquid therefor

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JP2009173999A (ja) * 2008-01-24 2009-08-06 Nippon Mining & Metals Co Ltd 耐熱エージング特性に優れた金属被覆ポリイミド樹脂基板の製造方法
JP5694265B2 (ja) * 2012-10-02 2015-04-01 学校法人関東学院 無電解めっき方法及び無電解めっき膜
JP6912773B2 (ja) * 2017-07-03 2021-08-04 大日本印刷株式会社 成膜基板、基板、およびそれらの製造方法

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JP2003105550A (ja) * 2001-09-26 2003-04-09 Kyocera Corp 無電解めっき用触媒液
JP2003193245A (ja) * 2001-12-21 2003-07-09 Nikko Materials Co Ltd めっき前処理剤、及びそれを用いた無電解めっき方法
JP2004315895A (ja) * 2003-04-16 2004-11-11 Hitachi Chem Co Ltd 無電解めっき用前処理液及びこれを用いた無電解めっき方法
JP2005146372A (ja) * 2003-11-18 2005-06-09 Meltex Inc 無電解めっき用の触媒付与液

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JP2513270B2 (ja) * 1988-05-06 1996-07-03 日立化成工業株式会社 無電解めっき用触媒溶液
JP3758532B2 (ja) * 2001-06-28 2006-03-22 株式会社日鉱マテリアルズ 銅あるいは銅合金上への無電解ニッケルめっき用前処理液及び無電解ニッケルめっき方法

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JP2003105550A (ja) * 2001-09-26 2003-04-09 Kyocera Corp 無電解めっき用触媒液
JP2003193245A (ja) * 2001-12-21 2003-07-09 Nikko Materials Co Ltd めっき前処理剤、及びそれを用いた無電解めっき方法
JP2004315895A (ja) * 2003-04-16 2004-11-11 Hitachi Chem Co Ltd 無電解めっき用前処理液及びこれを用いた無電解めっき方法
JP2005146372A (ja) * 2003-11-18 2005-06-09 Meltex Inc 無電解めっき用の触媒付与液

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11155924B2 (en) 2017-03-31 2021-10-26 Toyoda Gosei Co., Ltd. Silver mirror film, decorative article, silver mirror film-forming liquid, and method for producing reducing liquid therefor

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