WO2013157574A1 - Agent de traitement de surface du type à dépôt automatique pour du cuivre et procédé de fabrication d'un substrat contenant du cuivre pourvu d'un film de revêtement résineux - Google Patents

Agent de traitement de surface du type à dépôt automatique pour du cuivre et procédé de fabrication d'un substrat contenant du cuivre pourvu d'un film de revêtement résineux Download PDF

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WO2013157574A1
WO2013157574A1 PCT/JP2013/061389 JP2013061389W WO2013157574A1 WO 2013157574 A1 WO2013157574 A1 WO 2013157574A1 JP 2013061389 W JP2013061389 W JP 2013061389W WO 2013157574 A1 WO2013157574 A1 WO 2013157574A1
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Prior art keywords
copper
group
parts
treatment agent
mass
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PCT/JP2013/061389
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English (en)
Japanese (ja)
Inventor
森　和彦
宏志 清水
雅矢 宮崎
淳一 南
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日本パーカライジング株式会社
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Application filed by 日本パーカライジング株式会社 filed Critical 日本パーカライジング株式会社
Priority to KR1020147027063A priority Critical patent/KR101611783B1/ko
Priority to CN201380020600.8A priority patent/CN104246011A/zh
Priority to JP2014511233A priority patent/JP5809351B2/ja
Publication of WO2013157574A1 publication Critical patent/WO2013157574A1/fr

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    • 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
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/086—Organic or non-macromolecular compounds
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment

Definitions

  • the present invention relates to a self-depositing surface treatment agent for copper used to selectively form a self-depositing resin film on the surface of a copper member, and a copper coating with a resin film using the surface treatment agent for self-depositing copper.
  • the present invention relates to a method for manufacturing a substrate.
  • the self-depositing water-based resin composition can deposit an organic polymer film (adhesive resin film) on a metal surface by an electroless chemical reaction with the metal surface.
  • an organic polymer film adheresive resin film
  • compositions are acidic having a pH value in the range of about 1 to about 4.
  • Such compositions and methods of forming films on metal surfaces using such compositions have been commonly described in the art and herein, as “auto-deposition (auto-deposition). deposition) "or" self-depositing "compositions, dispersions, emulsions, suspensions, baths, solutions, processes, methods or similar terms.
  • Self-depositing compositions are generally in liquid form, and more specifically in the form of aqueous solutions, emulsions or dispersions, and the liquid composition is polymer free of contact with active metals. Spontaneous precipitation or agglomeration is suppressed, and it is stable for a long time.
  • the surface of the object to be processed is covered with a polymer film having adhesiveness. Since the film deposited on the workpiece is not redispersed or re-dissolved in water, it can be dried and baked and cured after being washed with water.
  • active metal refers to a metal that is more active than hydrogen in the electrochemical series, ie, when introduced into a liquid self-depositing solution, emulsion or dispersion at a substantial rate.
  • active metal refers to a metal that is more active than hydrogen in the electrochemical series, ie, when introduced into a liquid self-depositing solution, emulsion or dispersion at a substantial rate.
  • iron, zinc, aluminum, etc. are defined as metals that begin to dissolve in (with generation of hydrogen gas).
  • the deposition reaction mechanism of self-deposition resin is different from electrodeposition coating, and metal ion elution reaction from the surface of the metal to be treated is the starting point. Therefore, if a strong oxidizing agent such as hydrogen peroxide is used to apply to a metal surface that is more inert (noble) than hydrogen in the electrochemical series, metal ions can be eluted, but the resin component is oxidatively decomposed. Therefore, it has been difficult to apply to noble metal materials such as copper.
  • Patent Document 1 discloses a metal material ground treatment agent containing a thiourea derivative and an elastomer.
  • Patent Document 1 when a strong oxidizing agent such as thiourea and vanadate is mixed and the acid precipitation is such that the polymer precipitation amount is in a practical range, the thiourea is oxidized and decomposed. There was a problem that it was inferior in stability and not practical.
  • a strong oxidizing agent such as thiourea and vanadate
  • the present invention provides a self-deposition type copper surface treatment agent with excellent liquid stability, which can form a film having excellent adhesion, corrosion resistance, and electrical properties on a copper material by autodeposition.
  • the purpose is to do.
  • Another object of the present invention is to provide a method for producing a copper-containing substrate with a resin film using this autodeposition-type copper surface treatment agent.
  • the present inventors have confirmed that the elution of copper ions from the copper-containing substrate is not sufficient in the known auto-precipitation type surface treatment agent. .
  • the present inventors have found that the above problem can be solved by using a copper complexing agent and adjusting the oxidation-reduction potential of the surface treatment agent to a predetermined range. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • a surface treatment agent for autodeposition type copper characterized in that the oxidation-reduction potential at pH 3.0 is in the range of -500 to +200 mV (vs. SHE).
  • the copper complexing agent has at least one bond selected from the group consisting of C ⁇ S, C—S, N—N and C ⁇ N in its molecular structure.
  • Surface treatment agent for copper is the group consisting of C ⁇ S, C—S, N—N and C ⁇ N in its molecular structure.
  • the polymer is selected from the group consisting of acrylic resin, polyvinyl chloride, epoxy resin, polyurethane, polyamide, polyimide, phenol-formaldehyde condensation resin, silicone resin, fluororesin, conductive resin, and epoxy-acrylic hybrid polymer.
  • the self-depositing surface treatment agent for copper according to any one of (1) to (5), which is at least one selected from the group consisting of:
  • the surface treatment agent for autodeposition type copper according to any one of (1) to (6), further comprising 0.1 to 100 parts by mass of insoluble inorganic particles.
  • the copper-containing base material is composed of motor parts, power storage device parts, sensor parts, antennas, copper wiring boards, copper wires, copper alloy coated wires, coils, automobile parts, bearings, heat dissipation parts, and piping parts.
  • the surface treatment agent for self-precipitation type copper of the present invention allows adhesion on a base material containing copper or a copper alloy, which is a noble metal, than a base metal such as iron or zinc contained in a conventional object to be treated. ⁇ It is possible to form a coating with excellent corrosion resistance and electrical characteristics with high productivity, and as a result, electromagnetic coils, batteries / capacitor current collectors, sensors, antennas, copper wiring, wire harnesses, bearings, which could not be applied conventionally. It can be applied to a wide range of applications such as heat dissipation parts and gas / water pipe parts. Effects obtained by coating the surface of the copper-containing substrate with the resin of the present invention include insulation, conductivity, corrosion resistance, adhesion, adhesion, heat insulation, strain stress relaxation, vibration / sound absorption And so on.
  • a mechanism for depositing a film on the surface of a copper-containing substrate that is a metal to be treated of the self-deposition type surface treatment agent first, when the copper-containing substrate is brought into contact with the surface treatment agent containing a polymer, the surface of the copper-containing substrate From which copper ions (preferably Cu (I) ions) are eluted, and then the eluted copper ions are quickly bonded to the polymer and gelled and deposited to adhere to the surface of the copper-containing substrate. Yes.
  • elution of copper ions from the substrate surface is essential for the precipitation and fixation of the polymer in the surface treatment agent.
  • the conventional self-precipitation type surface treatment agents have sufficient elution of copper ions in the first place. It was not.
  • the present invention it has been found that if the oxidation-reduction potential is within a predetermined range, elution of copper ions proceeds sufficiently and a film having desired characteristics can be obtained.
  • the surface treatment agent for self-deposited copper includes 1 to 60 parts by mass of a water-soluble or water-dispersible polymer, 30 to 99 parts by mass of a water-based solvent, and 0.01 to 5 parts by mass of a copper complex. And an agent. Below, each component is explained in full detail.
  • a water-soluble or water-dispersible polymer refers to a polymer that can be completely dissolved or finely dispersed in water at room temperature.
  • the polymer is the main component of the film formed on the copper-containing substrate.
  • water is mainly used as a solvent in the autodeposition-type copper surface treatment agent, and the polymer dispersed in water is also called polymer fine particles or latex.
  • the polymer fine particles or latex can be produced by a known emulsion polymerization method.
  • the surfactants, polymerization initiators, etc. used there may be those used in conventional methods.
  • the type of water-soluble or water-dispersible polymer is not particularly limited.
  • acrylic resin polyvinyl chloride, epoxy resin, polyurethane, polyamide, polyimide, phenol-formaldehyde condensation resin, silicone resin, fluorine resin, conductive resin, epoxy -Acrylic hybrid polymers.
  • the polymer may be a homopolymer of the above polymer or a copolymer containing two or more of the above polymers in the main chain. In the case of a copolymer, it may be a random copolymer or a block copolymer.
  • an epoxy resin an acrylic resin, a conductive resin, or a mixture thereof is preferable from the viewpoint of easy precipitation, and an epoxy-acrylic copolymer is more preferable.
  • a kind of conductive resin polythiophene-based conductive polymers such as polyaniline, polypyrrole, and polyethylenedioxythiophene are preferable.
  • Preferred resin types and combinations thereof include polyamideimide, polyimide, phenol-formaldehyde condensation resin, silicone resin, or fluororesin when heat resistance is important. Adhesion, strain stress relaxation, vibration When it is desired to impart sound absorption, it is preferable to include polyurethane or other soft resin, and for applications requiring conductivity, it is preferable to include a conductive resin as a main component.
  • the polymer preferably has an anionic group.
  • anionic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and the sulfonic acid group or the carboxyl group is preferable in that the characteristics of the resulting film (adhesion, corrosion resistance, voltage resistance, etc.) are more excellent. preferable.
  • the conductive resin used in the present invention is preferably one in which anionicity is imparted to the resin by doping with anions such as sulfonic acid, polysulfonic acid, phosphoric acid, and polyphosphoric acid.
  • the surfactant used when producing the polymer fine particles or latex easily interacts with copper ions eluted from the copper-containing base material, and the film formability is further improved. It is preferable that it is an ionic surfactant.
  • the polymer is contained in an amount of 1 to 60 parts by mass, and preferably 3 to 30 parts by mass. If the amount is less than 1 part by mass, the film thickness of the deposited film is not sufficient, and if it exceeds 60 parts by mass, the polymer is liable to aggregate in the surface treatment agent for autodeposition type copper and the liquid stability is poor.
  • the solvent is mainly water.
  • the main component means that water is a main component, more specifically, the content of water in the solvent means 25% by mass or more, and preferably 70% by mass or more.
  • an organic solvent may be used together with water, and a water-soluble organic solvent is preferable as the organic solvent.
  • the water-soluble organic solvent include alcohol solvents, ketone solvents, ethylene glycol solvents (cellosolve) and the like.
  • the solvent is contained in an amount of 30 to 99 parts by mass, and more preferably 60 to 95 parts by mass.
  • the amount is less than 30 parts by mass, the viscosity becomes too high and washing becomes difficult, which is not preferable.
  • the amount exceeds 99 parts by mass the amount of polymer deposited is insufficient and the corrosion resistance and electrical characteristics of the resin film are deteriorated. It is not preferable.
  • the copper complexing agent is not particularly limited as long as it is a compound that can form a complex with copper ions. By adding a copper complexing agent, elution of copper ions from the copper-containing base material is further promoted, and as a result, the depositability of a film having desired characteristics is further improved.
  • the copper complexing agent include thiourea or a derivative thereof, a thiol compound (SH group-containing compound), an azo compound (azo group-containing compound), and a pyridine compound.
  • a copper complexing agent having at least one bond selected from the group consisting of C ⁇ S, C—S, N—N and C ⁇ N in the molecular structure in terms of more excellent film properties Is more preferable.
  • a strong oxidizing agent such as hydrogen peroxide or nitric acid.
  • organic additives such as polymers and surfactants that form a film are easily oxidized and altered.
  • Examples of the copper complexing agent having a predetermined bond include thiourea, alkylthiourea (for example, methylthiourea, ethylthiourea), acetylthiourea, alkenylthiourea (for example, 1-allyl-2-thiourea), arylthiourea (For example, 1-phenyl-2-thiourea), thioacetamide, thioglycolic acid, 2,2′-bipyridyl, diphenylcarbazide, thiosulfuric acid, thiocyanic acid and the like.
  • alkylthiourea for example, methylthiourea, ethylthiourea
  • acetylthiourea alkenylthiourea
  • alkenylthiourea for example, 1-allyl-2-thiourea
  • arylthiourea for example, 1-phenyl-2-thiourea
  • a compound represented by the following formula (1) is preferable in that the properties of the resulting film are more excellent.
  • Z 1 and Z 2 are each independently an alkyl group (preferably having 1 to 3 carbon atoms. Specific examples include a methyl group and an ethyl group), an aryl group (preferably 6 to 10 carbon atoms, specifically phenyl group, naphthyl group, etc.), alkoxycarbonyl group, alkenyl group (preferably 1 to 3 carbon atoms.
  • allyl group, vinyl group Groups amino groups, alkenylamino groups (eg, allylamino groups, 1-propenylamino groups, 3-butenylamino groups, etc.), alkylamino groups, arylamino groups, acetylamino groups, hydroxyethylamino groups, N-benzoylamino group, cyclohexylamino group, phenylamino group, tolylamino group, naphthylamino group, phenylazo group, guanylami Represents a cyano group, a nicotine group, a hydrazino group, a phenyl hydrazino group, a thiocarbamoyl group, or a thiocarbamoylamino group.
  • an alkylamino group, an arylamino group, an alkenylamino group, and a hydroxyethylamino group are preferable.
  • R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or a hydroxyalkyl group.
  • the alkyl group is not particularly limited and preferably has 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, and a propyl group.
  • the alkenyl group is not particularly limited and preferably has 2 to 3 carbon atoms. Specific examples include a vinyl group and an allyl group.
  • the hydroxyalkyl group is not particularly limited and preferably has 1 to 3 carbon atoms. Specific examples include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
  • the copper complexing agent is contained in an amount of 0.01 to 5.0 parts by mass, and preferably 0.2 to 3.0 parts by mass. If it is less than 0.01 parts by mass, the elution of Cu ions is small, so that the film thickness is not sufficient and the voltage resistance is poor, and if it exceeds 5.0 parts by mass, precipitation is likely to occur and the liquid stability is poor.
  • the self-deposited copper surface treatment agent preferably further contains Fe (III) ions and / or Cu (II) ions, and particularly preferably contains Fe (III) ions. These ions pull out electrons from the surface of the copper-containing substrate and cause rapid dissolution of the copper ions, which has the effect of further promoting the precipitation of the polymer, resulting in a film with better adhesion, corrosion resistance, and electrical properties. .
  • the total content of these ions in the autodeposition-type copper surface treatment agent is preferably 0.1 to 10 parts by mass.
  • the self-depositing copper surface treatment agent preferably further contains insoluble inorganic particles.
  • insoluble inorganic particles various functionalities of the coating can be improved.
  • the type and particle size of the insoluble inorganic particles are not particularly limited. However, when used for the purpose of imparting lubricity, molybdenum disulfide, graphite, boron nitride, PTFE particles, etc. are preferable, and it is desired to improve insulation. Alumina, silica, mica, zirconia, magnesia, mullite particles and the like are preferable.
  • For the purpose of imparting conductivity graphite, nanocarbon, aluminum, copper, silver, zinc oxide, tin oxide, ITO, ATO, FTO Etc. are preferable. In addition to these, it is also preferable to use conventionally known color pigments and rust preventive pigments.
  • the content of insoluble inorganic particles in the self-depositing copper surface treatment agent is preferably 0.1 to 100 parts by mass.
  • paint additives such as an antifoamer, a dispersing agent, a leveling agent, are mentioned, for example.
  • pigments for coloring and soluble colorants can be used as additive components. Examples thereof include carbon black, phthalocyanine blue, phthalocyanine green, Prussian blue, and titanium white pigment.
  • the oxidation-reduction potential (hereinafter also referred to as ORP as appropriate) of the surface treatment agent for self-deposited copper is in the range of ⁇ 500 to +200 mV (vs. SHE) at pH 3.0. Among these, ⁇ 450 to +150 mV (vs. SHE) is preferable, and ⁇ 300 to +100 mV (vs. SHE) is more preferable. If the oxidation-reduction potential is within this range, a film having desired characteristics can be obtained and the liquid stability of the treatment agent is excellent. On the other hand, when the oxidation-reduction potential is less than ⁇ 500 mV (vs.
  • ORP control method when the ORP is too high, it is preferably lowered by adding a copper complexing agent or an ORP adjusting agent. When the ORP is too low, addition of ferric salt, air blowing, etc. It is preferable to raise by.
  • the ORP adjuster include a reducing agent such as sodium sulfite and an oxidizing agent such as ammonium persulfate.
  • the oxidation-reduction potential of the surface treatment agent for autodeposition type copper adjusted to pH 3.0 is measured using a known measuring device (for example, ORP composite electrode manufactured by Toa DKK Corporation). it can.
  • the numerical value of the measured oxidation-reduction potential is converted into the numerical value of the standard hydrogen electrode (SHE).
  • the method in particular of adjusting the pH of the surface treatment agent for autodeposition type copper to 3.0 is not restrict
  • the pH of the self-depositing copper surface treatment agent is not particularly limited, but is preferably 1.0 to 5.0, and more preferably 2.0 to 3.3. If it is in the said range, while the depositability of a polymer is more excellent and a thick film can be obtained, the corrosivity of the processing agent with respect to a container or a jig
  • a well-known acid for example, hydrofluoric acid
  • a well-known alkali for example, aqueous ammonia
  • the method for producing a copper-containing substrate with a resin film using the self-depositing copper surface treatment agent comprises bringing the surface treatment agent for self-depositing copper into contact with the copper-containing substrate, and A first step of forming a porous coating; a second step of cleaning the porous coating formed with a solvent containing water; and sealing and curing by dehydrating and heating the cleaned porous coating; And a third step of forming a resin film on the copper-containing substrate.
  • a 1st process is a process of making the said surface treatment agent for autoprecipitation type copper and a copper containing base material contact, and forming a porous membrane
  • the copper containing base material used at this process is explained in full detail, and the procedure of the post process is explained in full detail.
  • the copper-containing substrate is not particularly limited as long as it is a substrate containing copper as a component.
  • a substrate containing copper for example, pure copper, deoxidized copper, brass, bronze, white copper, western white, cupronickel, beryllium copper and the like can be mentioned.
  • a copper containing base material contains other metal components other than copper, nickel, zinc, tin, iron etc. are mentioned as another metal component, for example.
  • the copper-containing substrate may contain phosphorus as another component.
  • the copper-containing base material only needs to have copper on the surface that comes into contact with the surface treatment agent for self-precipitation type copper, such as an electrolytic copper plating material, an electroless copper plating material, a vapor deposition material or a clad material, a copper paste cured material, and a copper powder firing. If the surface layer is copper like a knot, it can be applied without problems.
  • the surface treatment agent for self-precipitation type copper such as an electrolytic copper plating material, an electroless copper plating material, a vapor deposition material or a clad material, a copper paste cured material, and a copper powder firing. If the surface layer is copper like a knot, it can be applied without problems.
  • the type of copper-containing base material is not particularly limited, but for example, motor parts, power storage device parts, sensor parts, antennas, copper wiring boards, copper wires, copper alloy coated wires, coils, automobile parts, bearings, heat dissipation parts, piping parts Etc.
  • a copper containing base material is cleaned in advance with a cleaning agent (for example, an alkaline cleaning agent or an acidic cleaning agent) before contacting with the surface treatment agent for autodeposition type copper.
  • a cleaning agent for example, an alkaline cleaning agent or an acidic cleaning agent
  • the type of cleaning agent is not particularly limited, and examples include weak alkaline cleaning agents for non-ferrous metals: Fine Cleaner 315, Fine Cleaner E3019L (Nippon Parkerizing Co., Ltd., acidic cleaning agents: 182A, 7310 Cleaner (Henkel Corporation), and the like. .
  • the method for bringing the surface treatment agent for autodeposition type copper into contact with the copper-containing substrate is not particularly limited, and a known method can be adopted. For example, a method of immersing a copper-containing base material in a self-depositing copper surface treatment agent (dipping), a method of pouring, spraying, or roller-applying a self-precipitating copper surface treatment agent onto a copper-containing base material, etc. Is mentioned.
  • the time for contacting the self-depositing copper surface treatment agent with the copper-containing substrate is not particularly limited, and optimal conditions are appropriately selected according to the component composition of the self-depositing copper surface treatment agent used. From the viewpoint of achieving both productivity and obtained film properties, it is preferably from several seconds to several minutes, and more specifically from 5 to 180 seconds.
  • the thickness of the porous film to be formed is not particularly limited, but is preferably 10 to 100 ⁇ m and more preferably 20 to 80 ⁇ m from the viewpoint of obtaining a resin film with a desired thickness.
  • the porous film is rendered nonporous by heat treatment in the curing step described later, and the film thickness of the finally obtained resin film is reduced to a fraction of that of the porous film.
  • the second step is a step of washing the porous film formed in the first step with a solvent containing water. By carrying out this step, excess components can be removed from the film, and as a result, a resin film having better properties can be obtained.
  • the solvent (washing solvent) used is a solvent containing water.
  • water is contained as a main component.
  • the main component means that the content of water in the solvent is 80% by mass or more.
  • an organic solvent may be used in combination with water, and the organic solvent is preferably a water-soluble organic solvent.
  • the water-soluble organic solvent include alcohol solvents, ketone solvents, ethylene glycol solvents (for example, cellosolve), amine solvents (for example, N-methylpyrrolidone, morpholine) and the like.
  • the method for cleaning the porous film with the solvent is not particularly limited, and a known cleaning method can be employed.
  • a known cleaning method can be employed.
  • coat in the said solvent, etc. are mentioned.
  • the third step is a step in which the porous film washed in the second step is subjected to heat treatment to form a resin film on the copper-containing substrate.
  • the porous film is dehydrated, sealed and cured, and a dense resin film without pinholes can be obtained.
  • the conditions for the heat treatment can be appropriately selected according to the glass transition temperature of the polymer used and the temperature at which the uncured polymer is crosslinked. For example, it is preferable to perform heat treatment at 140 to 280 ° C. for 1 to 30 minutes. Further, the heat treatment may be performed stepwise at different temperatures. For example, in the case of using an uncured polymer, there is a method in which the heat treatment is performed at a temperature lower than the temperature at which the crosslinking reaction proceeds, and then the heat treatment is performed at a temperature equal to or higher than the temperature at which the crosslinking reaction proceeds. More specifically, first, dehydration is performed at a temperature in the range of 90 to 160 ° C. for 1 to 10 minutes, preferably at least 100 ° C., and sealing and curing are performed by baking at 180 to 220 ° C. for 20 minutes. Do.
  • the thickness of the resin film formed through the above steps is not particularly limited, but is preferably 10 to 50 ⁇ m, more preferably 15 to 40 ⁇ m, from the viewpoint of better adhesion, corrosion resistance, and voltage resistance.
  • the copper-containing substrate with a resin film formed through the above steps can be applied to various uses. For example, it can be used for electric wires, wire harnesses, bearings, copper tubes, copper meshes, battery components, printed wiring boards, and the like.
  • Electroless copper plating polyimide resin film 50x20mm Thickness 0.2mm h. Copper paste coated alumina plate 30 ⁇ 20mm Thickness 1mm a1. Oxygen-free copper wire coil (Material: C1020) ⁇ 1mm a2. Glass copper clad laminate (Material: Electrolytic copper foil affixed glass-epoxy resin composite) c1. Copper tube for heat exchanger (Material: C1220) d1. Brass plated wire (Material: Brass plated steel cord) f1. Water meter (Material: Bismuth bronze) g1. Sintered copper alloy bearing (Material: Cu-Sn alloy)
  • Pretreatment process of substrate to be treated As the pretreatment process of the substrate to be treated, the following processes (1) to (4) were performed in order. (1) Degreasing (60 ° C., 10 minutes, immersion method, 5% by mass aqueous solution prepared using Fine Cleaner 315 manufactured by Nihon Parkerizing Co., Ltd.) (2) Washing with water (room temperature, 30 seconds, immersion method) (3) Pickling (using a 10% aqueous solution prepared using room temperature, 30 seconds, immersion method, commercially available sulfuric acid) (4) Washing with water (room temperature, 30 seconds, immersion method)
  • Example 1 Polyvinylidene chloride dispersion (Asahi Kasei Chemical Co., Ltd. Saran Latex L232A: containing an anionic group, solid content 48%) as a polymer is 20 parts by mass in terms of solids and hydrofluoric acid (40% by mass) is 0. .2 parts by mass, 3 parts by mass of thiourea as a copper complexing agent, 0.2 parts by mass of sodium sulfite as an ORP regulator, and 95 parts by mass of deionized water A surface treatment agent was prepared. It was pH 2.8 when pH of the obtained processing agent was measured with the pH meter.
  • the oxidation-reduction potential (ORP) of the obtained treatment agent at pH 3.0 was measured with an ORP electrode (Ag / AgCl) and converted into a potential based on SHE, and the ORP was -420 mV. .
  • the oxidation-reduction potential of the obtained treatment agent was measured after adjusting the pH of the treatment agent to 3.0 using aqueous ammonia.
  • the copper alloy f and the copper alloy member f1 were immersed in the obtained autodeposition-type copper surface treatment agent for 120 seconds at room temperature. After the immersion treatment, the obtained copper alloy f and copper alloy member f1 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy f and the copper alloy member f1 were dehydrated and dried at 40 ° C. for 10 minutes and subjected to heat treatment at 120 ° C. for 5 minutes. The film formed on the copper alloy f and the copper alloy member f1 after dehydration and drying was porous, but a dense resin film without pinholes was obtained by heat curing. In addition, the surface treatment agent for autodeposition type copper after the above treatment was stable and no abnormality was observed even after 24 hours.
  • Example 2 8 parts by mass of an epoxy-acrylic resin (containing an anionic group, solid content concentration: 47%) as a polymer, 0.2 parts by mass of hydrofluoric acid (40% by mass), and copper complexation
  • 0.1 parts by mass of thioacetamide and 90 parts by mass of deionized water were mixed to prepare an autodeposition type surface treatment agent for copper. It was pH 4.0 when pH of the obtained processing agent was measured with the pH meter. Further, the oxidation-reduction potential (ORP) of the obtained treatment agent at pH 3.0 was measured with an ORP electrode (Ag / AgCl) and converted into a potential based on SHE, and the ORP was ⁇ 80 mV. . In addition, the oxidation-reduction potential of the obtained processing agent was measured after adjusting the pH of the processing agent to 3.0 using 5% hydrofluoric acid.
  • ORP oxidation-reduction potential
  • Copper alloy c and copper alloy member a2 were immersed in the obtained autodeposition-type copper surface treatment agent for 120 seconds at room temperature. After the immersion treatment, the obtained copper alloy c and copper alloy member a2 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy c and the copper alloy member a2 were dehydrated and dried at 40 ° C. for 10 minutes, and subjected to heat treatment at 120 ° C. for 5 minutes. The film formed on the copper alloy c and the copper alloy member a2 after dehydration and drying was porous, but a dense resin film without pinholes was obtained by heat curing. In addition, the surface treatment agent for autodeposition type copper after the above treatment was stable and no abnormality was observed even after 24 hours.
  • Example 3 25 parts by mass of an epoxy-acrylic resin (containing an anionic group, solid content concentration: 47%) as a polymer as a polymer, 0.5 parts by mass of thiourea as a copper complexing agent, and hydrofluoric acid
  • a surface treatment agent for self-precipitation type copper was prepared by mixing 0.1 parts by mass of a cupric fluoride solution prepared by dissolving CuO in terms of CuF 2 and 60 parts by mass of water. It was pH 3.0 when pH of the obtained processing agent was measured with the pH meter.
  • the oxidation-reduction potential (ORP) of the obtained treatment agent at pH 3.0 was measured with an ORP electrode (Ag / AgCl) and converted into a potential based on SHE, and the ORP was -70 mV. .
  • the copper alloy b and the copper alloy member d1 were immersed in the obtained autodeposition-type copper surface treatment agent for 120 seconds at room temperature. After the immersion treatment, the obtained copper alloy b and copper alloy member d1 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy b and the copper alloy member d1 were dehydrated and dried at 40 ° C. for 10 minutes, and heat treatment was performed at 160 ° C. for 10 minutes. The film formed on the copper alloy b and the copper alloy member d1 after dehydration and drying was porous, but a dense resin film without pinholes was obtained by heat curing. In addition, the surface treatment agent for autodeposition type copper after the above treatment was stable and no abnormality was observed even after 24 hours.
  • Example 4 15 parts by mass of epoxy-acrylic resin (anionic group content, solid content concentration: 47%) as a polymer, 0.5 parts by mass of ethylthiourea as a copper complexing agent, ferric fluoride 2 parts by weight, a cupric fluoride solution prepared by dissolving CuO in hydrofluoric acid, 0.1 parts by weight in terms of CuF 2 , 5 parts by weight of 2-propanol, and 60 parts by weight of water Were mixed to prepare a self-depositing surface treatment agent for copper. It was pH 3.0 when pH of the obtained processing agent was measured with the pH meter.
  • ORP oxidation-reduction potential
  • the copper alloy e and the copper alloy member a2 were immersed in the obtained surface treating agent for autodeposition type copper at room temperature for 120 seconds. After the immersion treatment, the obtained copper alloy e and copper alloy member a2 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy e and the copper alloy member a2 were dehydrated and dried at 40 ° C. for 10 minutes and subjected to heat treatment at 160 ° C. for 10 minutes. The film formed on the copper alloy e and the copper alloy member a2 after the dehydration drying was porous, but a dense resin film without pinholes was obtained by heat curing. In addition, the surface treatment agent for autodeposition type copper after the above treatment was stable and no abnormality was observed even after 24 hours.
  • Example 5 As the polymer, a phenol resin shown in Examples of Japanese Patent Publication No. 2009-293101 was synthesized and used. Specifically, using dimethylaminobenzene as an alkali catalyst, 60 g of phenol (reagent: F) and 135 g of 37% by mass formaldehyde (reagent: P) were mixed and stirred at 70 ° C., and the F / P ratio was 2.6. A water-soluble resol resin having a solid content of 55% by mass was obtained.
  • a solution obtained by adding 40 g of 2,3-dihydroxynaphthalene-6-sulfonic acid sodium salt (reagent), 35 g of catechol (reagent), and 50 g of water to 200 g of this water-soluble resol resin is heated to 90 ° C. Stir for 3 hours. After stirring, 200 g of water to which 210 g of resorcinol (reagent) and 5 g of 85% by mass phosphoric acid (reagent) were added was added and stirred for 1 hour while maintaining the temperature at 90 ° C. After stirring, 70 g of 37 mass% formaldehyde (reagent) is added little by little, and it is visually confirmed that the viscosity of the synthesized product increases.
  • An anionic novolac type having an F / P ratio of 0.84 and a solid content concentration of 53% A phenolic resin was obtained.
  • As a crosslinking agent 87 g of 2-butanone oxime was cooled from the outside so that the reaction temperature did not exceed 40 ° C. in 174 g of toluene diisocyanate (Coronate T80: manufactured by Nippon Polyurethane Industry Co., Ltd.) under a dry nitrogen atmosphere. Added while. After holding at 40 ° C. for 1 hour, the reaction vessel was warmed to 70 ° C.
  • ORP oxidation-reduction potential
  • the copper alloy b and the copper alloy member a2 were immersed in the obtained autodeposition-type copper surface treatment agent at 40 ° C. for 60 seconds. After the immersion treatment, the obtained copper alloy b and copper alloy member a2 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy b and the copper alloy member a2 were dehydrated and dried at 40 ° C. for 10 minutes, and heat treatment was performed at 160 ° C. for 10 minutes. The film formed on the copper alloy b and the copper alloy member a2 after dehydration and drying was porous, but a dense resin film without pinholes was obtained by heat curing. In addition, the surface treatment agent for autodeposition type copper after the above treatment was stable and no abnormality was observed even after 24 hours.
  • Example 6 With reference to Japanese Patent No. 3089195, 64.44 g of 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 42.72 g of bis- [4- (3-aminophenoxy) phenyl] sulfone, valerolactone 3 g, 4.8 g of pyridine, 400 g of N-methylpyrrolidone and 90 g of toluene were added and stirred at room temperature for 30 minutes. Thereafter, the reaction solution was heated and reacted at 180 ° with stirring for 1 hour (200 rpm) to prepare a polyimide resin raw material.
  • a self-deposition type copper surface treating agent was prepared by stirring 1 part by mass of 2-thiourea, 0.5 part by mass of ethylenediamine, and 25 parts by mass of water. It was pH 4.5 when pH of the obtained processing agent was measured with the pH meter.
  • the oxidation-reduction potential (ORP) at the time of pH3.0 of the obtained processing agent was measured with the ORP electrode (Ag / AgCl) and converted into a potential based on SHE, it was ORP: +150 mV.
  • the oxidation-reduction potential of the obtained processing agent was measured after adjusting the pH of the processing agent to 3.0 using 5% hydrofluoric acid.
  • Copper alloy a and copper alloy member a1 were immersed in the obtained autodeposition-type copper surface treatment agent for 120 seconds at room temperature. After the immersion treatment, the obtained copper alloy a and copper alloy member a1 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy a and the copper alloy member a1 were dehydrated and dried at 40 ° C. for 10 minutes, and heat-treated at 180 ° C. for 5 minutes. The film formed on the copper alloy a and the copper alloy member a1 after the dehydration drying was porous, but a dense resin film without pinholes was obtained by heat curing. In addition, the surface treatment agent for autodeposition type copper after the above treatment was stable and no abnormality was observed even after 24 hours.
  • Example 7 10 parts by mass of epoxy-acrylic resin (anionic group content, solid content concentration: 47%) as a polymer, 0.1 parts by mass of hydrofluoric acid (40% by mass) as a polymer, and copper complexation
  • a self-precipitating copper surface treatment agent was prepared by mixing 0.2 parts by mass of 2,2′-bipyridyl and 90 parts by mass of deionized water. It was pH 4.2 when pH of the obtained processing agent was measured with the pH meter. Further, the oxidation-reduction potential (ORP) of the obtained treatment agent at pH 3.0 was measured with an ORP electrode (Ag / AgCl) and converted into a potential based on SHE, and the ORP was ⁇ 120 mV. . In addition, the oxidation-reduction potential of the obtained processing agent was measured after adjusting the pH of the processing agent to 3.0 using 5% hydrofluoric acid.
  • Copper alloy c and copper alloy member a2 were immersed in the obtained autodeposition-type copper surface treatment agent for 120 seconds at room temperature. After the immersion treatment, the obtained copper alloy c and copper alloy member a2 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy c and the copper alloy member a2 were dehydrated and dried at 40 ° C. for 10 minutes, and subjected to heat treatment at 120 ° C. for 5 minutes. The film formed on the copper alloy c and the copper alloy member a2 after dehydration and drying was porous, but a dense resin film without pinholes was obtained by heat curing. In addition, the surface treatment agent for autodeposition type copper after the above treatment was stable and no abnormality was observed even after 24 hours.
  • Example 8 15 parts by mass of an epoxy-acrylic resin (containing an anionic group, solid content concentration: 47%) as a polymer, 0.2 parts by mass of hydrofluoric acid (40% by mass) as a polymer, and copper complexation
  • a self-deposition type surface treatment agent for copper was prepared by mixing 0.5 parts by mass of diphenylcarbazide and 98 parts by mass of deionized water as an agent. It was pH 3.5 when pH of the obtained processing agent was measured with the pH meter. Further, the oxidation-reduction potential (ORP) of the obtained treatment agent at pH 3.0 was measured with an ORP electrode (Ag / AgCl), and converted into a potential based on SHE, which was ORP: ⁇ 160 mV. . In addition, the oxidation-reduction potential of the obtained processing agent was measured after adjusting the pH of the processing agent to 3.0 using 5% hydrofluoric acid.
  • the copper alloy c and the copper alloy member a1 were immersed in the obtained autodeposition-type copper surface treatment agent for 120 seconds at room temperature. After the immersion treatment, the obtained copper alloy c and copper alloy member a1 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy c and the copper alloy member a1 were dehydrated and dried at 40 ° C. for 10 minutes, and heat treatment was performed at 150 ° C. for 5 minutes. The film formed on the copper alloy c and the copper alloy member a1 after dehydration and drying was porous, but a dense resin film without pinholes was obtained by heat curing. In addition, the surface treatment agent for autodeposition type copper after the above treatment was stable and no abnormality was observed even after 24 hours.
  • Example 9 20 parts by mass of the following polyaniline dispersion (concentration 5%) as a polymer, 0.2 parts by mass of hydrofluoric acid (40% by mass), and 2 parts by mass of thiourea as a copper complexing agent And 95 mass parts of deionized water was mixed, and the surface treatment agent for autodeposition type copper was prepared. It was pH 2.4 when pH of the obtained processing agent was measured with the pH meter. Moreover, when the oxidation-reduction potential (ORP) at the time of pH3.0 of the obtained processing agent was measured with the ORP electrode (Ag / AgCl) and converted into a potential based on SHE, it was ORP: 60 mV. The oxidation-reduction potential of the obtained treatment agent was measured after adjusting the pH of the treatment agent to 3.0 using aqueous ammonia.
  • ORP oxidation-reduction potential
  • Copper alloys a and g were immersed in the obtained surface treatment agent for autodeposition type copper at room temperature for 120 seconds. After the immersion treatment, the obtained copper alloys a and g were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloys a and g were dehydrated and dried at 40 ° C. for 10 minutes, and heat treatment was performed at 120 ° C. for 5 minutes. The film formed on the copper alloys a and g after dehydration drying was porous, but a dense resin film without pinholes was obtained by heat curing. In addition, the surface treatment agent for autodeposition type copper after the above treatment was stable and no abnormality was observed even after 24 hours.
  • Example 10 20 parts by mass of the following polypyrrole dispersion (concentration 5%) as a polymer, 0.5 part by mass of sulfuric acid (10% by mass), and 1-allyl-2-thiourea as a copper complexing agent
  • a surface treatment agent for autodeposition type copper was prepared. It was pH 1.9 when pH of the obtained processing agent was measured with the pH meter. Further, the oxidation-reduction potential (ORP) of the obtained treatment agent at pH 3.0 was measured with an ORP electrode (Ag / AgCl), and converted into a potential based on SHE, and ORP was ⁇ 30 mV. .
  • the oxidation-reduction potential of the obtained treatment agent was measured after adjusting the pH of the treatment agent to 3.0 using aqueous ammonia.
  • polypyrrole dispersion liquid 50 parts by mass of a 30% aqueous solution of polystyrene sulfonic acid (molecular weight of about 50,000) and 10 parts by mass of pyrrole monomer were added to 500 parts by mass of deionized water and stirred. After thorough mixing, 60 parts by mass of a 15% aqueous solution of ammonium persulfate was added to this solution at room temperature. After completion of the addition, the mixture was further stirred for 2 hours to obtain a polypyrrole dispersion. The synthesized polypyrrole dispersion was put in a dialysis tube and desalted for 24 hours, and then diluted to a solid content concentration of 5% for use in the experiment.
  • Copper alloys c and g were immersed in the obtained surface treatment agent for autodeposition type copper at room temperature for 120 seconds. After the immersion treatment, the obtained copper alloys c and g were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy c and the copper alloy member g were dehydrated and dried at 40 ° C. for 10 minutes, and subjected to heat treatment at 120 ° C. for 5 minutes. The film formed on the copper alloys c and g after dehydration and drying was porous, but a dense resin film without pinholes was obtained by heat curing. In addition, the surface treatment agent for autodeposition type copper after the above treatment was stable and no abnormality was observed even after 24 hours.
  • Example 11 10 parts by mass of the following PEDOT (polyethylenedioxythiophene) dispersion as a polymer, 0.2 part by mass of 2,2′-bipyridyl as a copper complexing agent, and 90 parts by mass of deionized water was mixed to prepare a self-deposition type surface treating agent for copper. It was pH 3.1 when pH of the obtained processing agent was measured with the pH meter. Moreover, when the oxidation-reduction potential (ORP) at the time of pH3.0 of the obtained processing agent was measured with the ORP electrode (Ag / AgCl) and converted into a potential based on SHE, it was ORP: 80 mV. In addition, the oxidation-reduction potential of the obtained processing agent was measured after adjusting the pH of the processing agent to 3.0 using 5% sulfuric acid.
  • PEDOT polyethylenedioxythiophene
  • PEDOT dispersion 50 parts by mass of 30% aqueous polystyrene sulfonic acid (molecular weight of about 50,000), 10 parts by mass of 3,4-ethylenedioxythiophene, 0.3 parts by mass of ferric sulfate, 500 parts by mass of deionized water To the part and stirred. After thorough mixing, 60 parts by mass of a 15% aqueous solution of ammonium persulfate was added to this solution at room temperature. After completion of the addition, the mixture was further stirred for 2 hours to obtain a polythiophene dispersion. The synthesized polythiophene dispersion was put into a dialysis tube and desalted for 24 hours, and then diluted to a solid content concentration of 5% for use in the experiment.
  • Copper alloys a and h were immersed in the obtained autodeposition-type surface treatment agent for copper at room temperature for 120 seconds. After the immersion treatment, the obtained copper alloys a and h were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloys a and h were dehydrated and dried at 40 ° C. for 10 minutes, and heat-treated at 120 ° C. for 5 minutes. The film formed on the copper alloys a and h after dehydration drying was porous, but a dense resin film without pinholes was obtained by heat curing. In addition, the surface treatment agent for autodeposition type copper after the above treatment was stable and no abnormality was observed even after 24 hours.
  • Example 12 10 parts by mass of the following PEDOT (polyethylenedioxythiophene) dispersion as a polymer in terms of solid content and an anionic urethane resin emulsion (trade name “Euprene UX-306”: solid content concentration 45%, manufactured by Sanyo Chemical Industries, Ltd.) Is mixed with 5 parts by mass in terms of solid content, and 0.5 parts by mass of thiourea and 90 parts by mass of deionized water are further mixed as a copper complexing agent.
  • PEDOT polyethylenedioxythiophene
  • anionic urethane resin emulsion trade name “Euprene UX-306”: solid content concentration 45%, manufactured by Sanyo Chemical Industries, Ltd.
  • ORP oxidation-reduction potential
  • PEDOT Dispersion A polystyrenesulfonic acid 30% aqueous solution (molecular weight of about 50,000) 50 parts by mass and 3,4-ethylenedioxythiophene 10 parts by mass were added to deionized water 500 parts by mass and stirred. After thorough mixing, 60 parts by mass of a 15% aqueous solution of ammonium persulfate was added to this solution at room temperature. After completion of the addition, the mixture was further stirred for 6 hours to obtain a polythiophene dispersion. The synthesized polythiophene dispersion was put into a dialysis tube and desalted for 24 hours, and then diluted to a solid content concentration of 5% for use in the experiment.
  • Copper alloys c and h were immersed in the obtained autodeposition-type copper surface treatment agent for 120 seconds at room temperature. After the immersion treatment, the obtained copper alloys c and h were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloys c and h were dehydrated and dried at 40 ° C. for 10 minutes, and heat-treated at 120 ° C. for 5 minutes. The film formed on the copper alloys c and h after dehydration drying was porous, but a dense resin film without pinholes was obtained by heat curing. In addition, the surface treatment agent for autodeposition type copper after the above treatment was stable and no abnormality was observed even after 24 hours.
  • Example 13 10 parts by mass of the PEDOT (polyethylenedioxythiophene) dispersion used in Example 12 as a polymer in terms of solid content and an epoxy-acrylic resin (containing an anionic group, solid content concentration: 47%) in terms of solid content. 3 parts by mass was mixed, and 0.2 parts by mass of thioacetamide as a copper complexing agent and 90 parts by mass of deionized water were mixed to prepare a self-deposition type copper surface treatment agent. It was pH1.8 when pH of the obtained processing agent was measured with the pH meter.
  • PEDOT polyethylenedioxythiophene
  • ORP oxidation-reduction potential
  • Copper alloys a and g were immersed in the obtained surface treatment agent for autodeposition type copper at room temperature for 120 seconds. After the immersion treatment, the obtained copper alloys a and g were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloys a and g were dehydrated and dried at 40 ° C. for 10 minutes, and heat treatment was performed at 120 ° C. for 5 minutes. The film formed on the copper alloys a and g after dehydration drying was porous, but a dense resin film without pinholes was obtained by heat curing. In addition, the surface treatment agent for autodeposition type copper after the above treatment was stable and no abnormality was observed even after 24 hours.
  • ORP oxidation-reduction potential
  • the copper alloy f and the copper alloy member f1 were immersed in the obtained autodeposition-type copper surface treatment agent for 120 seconds at room temperature. After the immersion treatment, the obtained copper alloy f and copper alloy member f1 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy f and the copper alloy member f1 were dehydrated and dried at 40 ° C. for 10 minutes, and subjected to heat treatment at 120 ° C. for 10 minutes. As a result of microscopic observation, the deposited film was uneven and partially peeled. Defects such as pinholes were also observed in the resin film obtained after heat curing. Further, the treatment agent aggregated within a few hours and gelled, making the treatment impossible.
  • Comparative Example 2 30 parts by mass of an aqueous dispersion of acrylonitrile butadiene styrene rubber having a carboxyl group and a methylol group as a polymer (solid content concentration: 47%, pH: 2.5) in terms of solid content, and 2 parts by mass of ferric fluoride And 1 part by mass of hydrogen peroxide as an ORP regulator (oxidant), 0.001 part by mass of thiourea as a copper complexing agent, and 90 parts by mass of deionized water A surface treating agent for copper was prepared. The pH of the obtained treatment agent was measured with a pH meter and found to be pH 3.0.
  • ORP oxidation-reduction potential
  • the copper alloy c and the copper alloy member a2 were immersed in the surface treatment agent for autodeposition type copper obtained for 120 seconds at room temperature. After the immersion treatment, the obtained copper alloy c and copper alloy member a2 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy c and the copper alloy member a2 were dehydrated and dried at 40 ° C. for 10 minutes, and heat treatment was performed at 160 ° C. for 10 minutes. As a result of microscopic observation, the resin deposition was incomplete and non-uniform. In addition, defects such as pinholes were also observed in the resin film obtained after heat curing.
  • the copper alloy b and the copper alloy member c1 were immersed in the obtained autodeposition-type copper surface treatment agent for 120 seconds at room temperature. After the immersion treatment, the obtained copper alloy b and copper alloy member c1 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy b and the copper alloy member c1 were dehydrated and dried at 40 ° C. for 10 minutes, and heat treatment was performed at 160 ° C. for 10 minutes. As a result of microscopic observation, the deposited film was uneven and partially peeled. Defects such as pinholes were also observed in the resin film obtained after heat curing. Further, the treatment agent had a tendency to thicken after 24 hours and was inferior in stability.
  • the oxidation-reduction potential (ORP) of the obtained treatment agent at pH 3.0 was measured with an ORP electrode (Ag / AgCl) and converted into a potential based on SHE, and the ORP was ⁇ 580 mV. .
  • the oxidation-reduction potential of the obtained processing agent was measured after adjusting the pH of the processing agent to 3.0 using 5% hydrofluoric acid.
  • ORP is out of the scope of the present invention.
  • the copper alloy a and the copper alloy member c1 were soaked at 40 ° C. for 120 seconds in the obtained autodeposition-type copper surface treatment agent. After the immersion treatment, the obtained copper alloy a and copper alloy member c1 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy a and the copper alloy member c1 were dehydrated and dried at 40 ° C. for 10 minutes, and subjected to heat treatment at 120 ° C. for 10 minutes. As a result of microscopic observation, almost no precipitation of resin was observed on the copper alloy a and the copper alloy member c1, and there were many undeposited portions.
  • the copper alloy b and the copper alloy member c1 were immersed in the obtained surface treatment agent for autodeposition type copper at room temperature for 120 seconds. After the immersion treatment, the obtained copper alloy b and copper alloy member c1 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy b and the copper alloy member c1 were dehydrated and dried at 40 ° C. for 10 minutes, and heat treatment was performed at 160 ° C. for 10 minutes. As a result of microscopic observation, almost no resin was deposited on the copper alloy b and the copper alloy member c1.
  • Example 6 As shown in Example 29 of International Publication No. 2009/066665, 0.5% by mass of thiourea, 30% by mass of acrylonitrile butadiene styrene rubber as an elastomer, and 0.5% by mass of ammonium metavanadate (V) as an oxidizing agent
  • the processing agent containing these was prepared.
  • the pH of the obtained treatment agent was measured with a pH meter and found to be 8.1.
  • ORP oxidation-reduction potential
  • the ORP electrode Ag / AgCl
  • the oxidation-reduction potential of the obtained processing agent was measured after adjusting the pH of the processing agent to 3.0 using 5% hydrofluoric acid.
  • the copper alloy b and the copper alloy member c1 were immersed for 120 seconds at room temperature. After the immersion treatment, the obtained copper alloy b and copper alloy member c1 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy b and the copper alloy member c1 were dehydrated and dried at 40 ° C. for 10 minutes, and heat treatment was performed at 100 ° C. for 10 minutes. As a result of microscopic observation, almost no resin was deposited on the copper alloy b and the copper alloy member c1.
  • the copper alloy b and the copper alloy member c1 were immersed for 120 seconds at room temperature. After the immersion treatment, the obtained copper alloy b and copper alloy member c1 were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloy b and the copper alloy member c1 were dehydrated and dried at 40 ° C. for 10 minutes, and heat treatment was performed at 100 ° C. for 10 minutes. As a result of microscopic observation, resin deposition on the copper alloy b and the copper alloy member c1 was not uniform. Moreover, the processing agent turned yellow within 1 hour after the treatment, resulting in precipitation, resulting in poor liquid stability.
  • Example 8 As a polymer, the polyaniline dispersion (concentration 5%) used in Example 9 was 20 parts by mass in terms of solid content, 0.2 parts by mass of hydrofluoric acid (40% by mass), and 2 parts by mass of hydrogen peroxide.
  • the surface treatment agent for autodeposition type copper was prepared by mixing 95 parts by mass with deionized water. It was pH 2.4 when pH of the obtained processing agent was measured with the pH meter.
  • ORP oxidation-reduction potential
  • ORP oxidation-reduction potential at the time of pH3.0 of the obtained processing agent was measured with the ORP electrode (Ag / AgCl) and converted into a potential based on SHE, it was ORP: 360 mV.
  • the oxidation-reduction potential of the obtained treatment agent was measured after adjusting the pH of the treatment agent to 3.0 using aqueous ammonia.
  • ORP is out of the scope of the present invention.
  • Copper alloys a and g were immersed in the obtained autodeposition-type copper surface treatment agent for 120 seconds at room temperature. After the immersion treatment, the obtained copper alloys a and g were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloys a and g were dehydrated and dried at 40 ° C. for 10 minutes and subjected to heat treatment at 120 ° C. for 10 minutes. As a result of microscopic observation, the deposited film was uneven and partially peeled. Defects such as pinholes were also observed in the resin film obtained after heat curing. Further, the treatment agent aggregated within several tens of minutes to form a gel, making the treatment impossible.
  • Example 9 30 parts by mass of PEDOT (polyethylenedioxythiophene) dispersion used in Example 12 as a polymer, 2 parts by mass of ferric fluoride, and 3 parts of ammonium persulfate as an ORP regulator (oxidant).
  • a self-precipitation type copper surface treatment agent was prepared by mixing mass parts and 90 parts by weight of deionized water. The pH of the obtained treatment agent was measured with a pH meter and found to be pH 3.0. Moreover, when the oxidation-reduction potential (ORP) at the time of pH3.0 of the obtained processing agent was measured with the ORP electrode (Ag / AgCl) and converted into a potential based on SHE, it was ORP: +420 mV. In the treatment agent, ORP is out of the scope of the present invention.
  • the copper alloys c and h were immersed at room temperature for 120 seconds. After the immersion treatment, the obtained copper alloys c and h were immersed in water (room temperature) for 30 seconds and washed with water. Thereafter, the copper alloys c and h were dehydrated and dried at 40 ° C. for 10 minutes, and heat treatment was performed at 160 ° C. for 10 minutes. As a result of microscopic observation, resin deposition was incomplete and non-uniform. In addition, defective portions such as pinholes were also observed in the resin film obtained after heat curing, and precipitates were observed in the treatment liquid.
  • Table 1 shows the test results. From these results, according to the surface treatment agent for autodeposition type copper and the method for producing a copper-containing substrate with a resin film according to the present invention, for copper (or copper alloy) and copper alloy members, which were difficult with the prior art, However, it is possible to obtain a film having a sufficient film thickness, and the obtained film has an excellent adhesive and corrosion resistance. In the insulation applications shown in Examples 1 to 8, excellent voltage resistance is obtained. It was confirmed that the conductive uses shown in Examples 9 to 13 have characteristics applicable to various uses because low electrical resistance is obtained. Moreover, the surface treatment agent for autodeposition type copper was also excellent in liquid stability. Furthermore, the treatment agents described in Examples 3 to 5 contain Fe (III) ions or Cu (II) ions, and it was confirmed that the corrosion resistance of the formed film showed a more excellent effect.
  • the film when a treatment agent that does not satisfy the predetermined requirements is used, the film is hardly formed, or the adhesive, corrosion resistance, or electrical characteristics (voltage resistance or electrical properties) of the formed film are formed. It was confirmed that the resistance was inferior.
  • the treatment agents described in Comparative Examples 6 and 7 are treatment agents described in the Examples column of Patent Document 1, and only a thin film is formed. The formed film itself is also an adhesive, corrosion resistance, and electrical characteristics. Was confirmed to be inferior.

Abstract

L'objet de la présente invention est de résoudre le problème consistant à fournir un agent de traitement de surface du type à dépôt automatique pour du cuivre, ledit agent de traitement de surface du type à dépôt automatique présentant une stabilité à l'état liquide élevée, un film de revêtement présentant une adhésivité élevée, une résistance à la corrosion élevée et d'excellentes caractéristiques électriques pouvant être formé sur un matériau de cuivre par dépôt automatique. L'agent de traitement de surface du type à dépôt automatique pour du cuivre selon la présente invention comprend 1-60 parties en masse d'un polymère soluble dans l'eau ou dispersible dans l'eau, 30-99 parties en masse d'un solvant à base d'eau et 0,01-5 parties en masse d'un agent complexant du cuivre, et présente un potentiel d'oxydoréduction dans une plage allant de -500 à +200 mV (vs. SHE) à un pH de 3,0.
PCT/JP2013/061389 2012-04-19 2013-04-17 Agent de traitement de surface du type à dépôt automatique pour du cuivre et procédé de fabrication d'un substrat contenant du cuivre pourvu d'un film de revêtement résineux WO2013157574A1 (fr)

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