Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
  • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
  • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
  • C23C18/1879—Use of metal, e.g. activation, sensitisation with noble 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
  • C23C18/31—Coating with metals
  • C23C18/38—Coating with copper
  • C23C18/40—Coating with copper using reducing agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/72—Copper
• • 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
• • 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
  • C23C18/1635—Composition of the substrate
  • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
• • 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
  • C23C18/1635—Composition of the substrate
  • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
  • C23C18/1641—Organic substrates, e.g. resin, plastic
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
  • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
• • 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
  • C23C18/2006—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
  • C23C18/2073—Multistep pretreatment
  • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/31—Coating with metals
  • C23C18/38—Coating with copper

Definitions

• the present invention relates to an aqueous copper colloidal catalyst solution for applying a catalyst as a pretreatment when electroless copper plating is applied to a non-conductive substrate, and the electroless copper plating method. It is possible to provide a copper film having a good uniformity and a uniform appearance.
• a noble metal such as palladium, silver, or platinum is adsorbed on the substrate and used as a catalyst nucleus, and then electroless copper is passed through the catalyst nucleus.
• a copper film is deposited on a substrate by a plating solution.
• a catalyst application method that uses a specific metal such as copper, nickel, cobalt, etc., which is inexpensive, without using a precious metal catalyst.
• a specific metal such as copper, nickel, cobalt, etc.
• a soluble metal salt is treated with a reducing agent to form a metal.
• the basic principle is to produce colloidal particles of this and use them as catalyst nuclei.
• the prior art of the aqueous copper colloid catalyst solution is as follows.
• Patent Document 1 Japanese Patent Laid-Open No. 2-093076, Mitsumata Special Metal
• a soluble copper salt, a dispersant, and a complexing agent are added, and after reducing with a reducing agent, a stabilizer is added to produce a fine copper catalyst solution for electroless copper plating.
• the dispersant is gelatin or a nonionic surfactant
• the complexing agent is dicarboxylic acid, oxycarboxylic acid or the like
• the reducing agent is sodium borohydride, dimethylamine borane or the like.
• Stabilizers include sodium hypophosphite and dimethylamine borane.
• Example 4 (upper left column on page 4), an object to be plated was immersed in a catalyst solution containing copper sulfate, gelatin, sodium borohydride, and hypophosphite, and then electroless copper plating was performed. Yes.
• Patent Document 2 Japanese Patent Laid-Open No. 10-229280, Okuno Pharmaceutical
• An electroless plating catalyst comprising a copper salt, an anionic surfactant, and a reducing agent is applied to an object to be plated, and after electroless copper plating, electrolytic copper plating is performed (claims 1 and 2, paragraph 42).
• the catalyst solution contains a copper ammine complex of copper sulfate and ammonia, an anionic surfactant, and sodium borohydride (reducing agent).
• Patent Document 3 Japanese Patent Laid-Open No. 7-197266, Nippon Leonal
• a catalyst with a copper (I) oxide colloidal catalyst solution After applying a catalyst with a copper (I) oxide colloidal catalyst solution to a substrate, copper is directly plated on the substrate by immersion in a solution containing a copper salt, a reducing agent, and a complexing agent.
• the solution contains a complexing agent and a reducing agent, but the composition of the catalyst solution is unknown.
• Patent Document 4 Japanese Patent Laid-Open No. 2011-225929, Kanto Gakuin University
• Items 1 to 3) and the object to be plated are pretreated with a conditioning agent containing a surfactant (cationic, anionic, amphoteric, nonionic; paragraph 56), treated with a catalyst solution, and electroless plating is performed.
• a method (claims 8-9) is disclosed.
• the types of electroless plating are copper, nickel, gold, etc., and electroless copper plating is preferred (paragraph 70).
• the conditioning agent particularly when a cationic surfactant is used, the hydrophilic group of the surfactant adsorbed on the object to be plated is negatively charged, the first copper ion is easily adsorbed, and the copper is uniformly distributed. It is described that a catalyzed plating object on which ions are adsorbed is obtained (paragraph 58).
• Patent Document 5 Japanese Patent Publication No. 2013-522476; Enson Incorporated Treating the non-conductive substrate with an activator solution containing a noble metal / metal-colloid (eg, a colloidal solution of palladium / tin), and then a metal salt solution such as a copper salt and a complexing agent and reducing agent of the metal ion
• a direct metallization method of a non-conductive substrate is described (paragraphs 1 and 13), in which electroless plating and electroplating are performed after contact with a conductive solution containing.
• the metal salt of the conductor solution is reduced with the metal of the activator solution.
• divalent tin (oxidizing cation) of the activator solution acts on the divalent copper ion (reducing cation) of the conductor solution.
• divalent copper ion reducing cation
• divalent copper ions are reduced to metallic copper (paragraphs 24 and 29).
• Example 1 after activation treatment of an ABS plastic substrate with an activator dispersion containing a palladium-tin colloid, tartaric acid (complexing agent) and hypophosphite (or hypophosphite and hydroxy) Treatment with a conductor solution containing methyl sulfonate (reducing agent), copper salt, lithium salt, and the like is described (Table 1 in paragraphs 65 and 66).
• the above-mentioned aqueous catalyst solution is based on the basic principle of producing a fine metal particle by treating a soluble metal salt with a reducing agent.
• a problem in stability over time including the catalyst solution of the above-mentioned patent document.
• deposition is difficult, plating defects that do not partially deposit on the film, or uneven plating occurs. Or inferior uniformity.
• the present invention has a technical problem of improving the aging stability of the aqueous copper catalyst solution and performing electroless copper plating on the non-conductive substrate provided with the catalyst to obtain a uniform and non-uniform copper film.
• the inventors of the present invention use a stabilizer in order to maintain the reduced state of copper in Patent Document 1, and therefore, first, a component having a complexing function with respect to the copper salt is contained in the catalyst solution.
• the idea was to stabilize colloidal particles.
• colloidal stabilizers such as oxycarboxylic acids and aminocarboxylic acids that stabilize the copper salt in the copper catalyst solution, it is possible to improve the temporal stability by adjusting the mixing ratio of the copper salt and the stabilizer,
• the presence of the surfactant has an adverse effect on the stability over time, and even if it is added, its content should be kept to a very small amount, and the presence of the predetermined water-soluble polymer greatly contributes to the stability over time. I got the knowledge.
• the catalyst activity is increased when applying the catalyst.
• the present invention has been completed by newly finding out that it is excellent in the uniformity of the deposited film obtained by electroless copper plating and the prevention of uneven appearance of the film.
• the present invention 1 is an aqueous copper colloid catalyst solution for applying a catalyst by bringing it into contact with a non-conductive substrate on which electroless copper plating is performed.
• A a soluble copper salt
• B a reducing agent
• An aqueous copper colloidal catalyst solution for electroless copper plating characterized by not containing a surfactant or having a surfactant content of 950 mg / L or less.
• Invention 3 is characterized in that, in the Invention 2, the synthetic water-soluble polymer is at least one selected from polyethylene glycol, polypropylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, polyacrylamide, and polyethyleneimine.
• An aqueous copper colloid catalyst solution for copper plating is provided.
• Invention 4 relates to any one of Inventions 1 to 3, wherein the reducing agent (B) is a borohydride compound, amine boranes, hypophosphorous acids, aldehydes, ascorbic acids, hydrazines, polyhydric phenols, An aqueous copper colloid catalyst solution for electroless copper plating, which is at least one selected from the group consisting of polyvalent naphthols, phenolsulfonic acids, naphtholsulfonic acids, and sulfinic acids.
• the reducing agent (B) is a borohydride compound, amine boranes, hypophosphorous acids, aldehydes, ascorbic acids, hydrazines, polyhydric phenols,
• An aqueous copper colloid catalyst solution for electroless copper plating which is at least one selected from the group consisting of polyvalent naphthols, phenolsulfonic acids, naphtholsulfonic acids, and sulfinic acids.
• the present invention 5 provides the method according to any one of the present inventions 1 to 4, wherein the monocarboxylic acid (C) is formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid.
• An aqueous copper colloid catalyst solution for electroless copper plating which is at least one selected from the group consisting of palmitic acid, stearic acid, and salts thereof.
• the present invention 6 relates to any one of the present inventions 1 to 5, wherein the oxycarboxylic acid (C) is citric acid, tartaric acid, malic acid, gluconic acid, golcoheptonic acid, glycolic acid, lactic acid, trioxybutyric acid, ascorbic acid, isocitrate
• An aqueous copper colloidal catalyst solution for electroless copper plating characterized in that it is at least one selected from the group consisting of acids, tartronic acid, glyceric acid, hydroxybutyric acid, leucine acid, citramalic acid, and salts thereof .
• the present invention 7 relates to the above inventions 1 to 6, wherein the aminocarboxylic acid (C) is hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, Nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, iminodipropionic acid, 1,3-propanediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol etherdiaminetetraacetic acid, metaphenylenediaminetetraacetate Acetic acid, 1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid, diaminopropionic acid, glutamic acid, dicarboxymethylglutamic acid, ornithine
• Invention 8 relates to any one of Inventions 1 to 7, wherein the polycarboxylic acid (C) is succinic acid, glutaric acid, malonic acid, adipic acid, oxalic acid, maleic acid, citraconic acid, itaconic acid, mesaconic acid And an aqueous copper colloid catalyst solution for electroless copper plating, which is at least one selected from the group consisting of these salts.
• the polycarboxylic acid (C) is succinic acid, glutaric acid, malonic acid, adipic acid, oxalic acid, maleic acid, citraconic acid, itaconic acid, mesaconic acid
• an aqueous copper colloid catalyst solution for electroless copper plating which is at least one selected from the group consisting of these salts.
• the present invention 9 is (a) non-conductive in a liquid containing at least one adsorption accelerator selected from the group consisting of a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.
• Adsorption promotion process for immersing the substrate;
• C an electroless plating step of forming a copper film using an electroless copper plating solution on the adsorption-treated substrate.
• the present invention 10 is the electroless copper plating method, wherein the adsorption accelerator in the step (a) is a cationic surfactant and / or an amphoteric surfactant.
• the copper colloidal catalyst solution of the present invention contains a colloidal stabilizer that has a complexing action on a copper salt, specifies the ratio of the stabilizer and the copper salt, and specifies predetermined ratios such as polyethylene glycol, polyvinylpyrrolidone, and polyvinyl alcohol.
• a colloidal stabilizer that has a complexing action on a copper salt
• specifies the ratio of the stabilizer and the copper salt and specifies predetermined ratios such as polyethylene glycol, polyvinylpyrrolidone, and polyvinyl alcohol.
• the catalyst solution of Example 4 of Patent Document 1 (upper left column to upper right column on page 4) contains 1000 mg / L of gelatin as a dispersant, or Production Example 2 of Patent Document 2 (paragraph 52).
• This catalyst solution contains 1000 mg / L of an anionic surfactant, and both exceed the upper limit of the specified amount of the surfactant in the catalyst solution of the present invention 1.
• the basic principle is to apply electroless copper plating after applying the copper colloid catalyst to the non-conductive substrate.
• the non-conductive substrate is used as an interface.
• the catalyst activity at the time of catalyst application is enhanced by electroless plating.
• the uniformity of the deposited copper film can be improved and unevenness of the film can be prevented well.
• the present invention is, firstly, an aqueous copper colloid catalyst solution for bringing a catalyst into contact with a non-conductive substrate, comprising (A) a soluble copper salt, (B) a reducing agent, and (C) a colloid stabilizer.
• An aqueous copper colloidal catalyst solution for electroless copper plating that contains the above components (A) and (C), specifies the molar ratio of the components (A) and (C), does not contain a surfactant, or contains only a small amount
• a second aspect is an aqueous copper colloid catalyst solution containing a synthetic water-soluble polymer in place of the first invention which excludes or suppresses the surfactant content to a predetermined amount or less.
• the non-conductive substrate is preliminarily adsorbed with a surfactant-containing solution and then electrolessly plated with the catalyst after applying the catalyst with the catalyst solution. It is a method to do.
• the non-conductive substrate include glass substrates, ceramic substrates, and the like including resin substrates such as glass / epoxy resin, glass / polyimide resin, epoxy resin, polyimide resin, polycarbonate resin, ABS resin, and PET resin.
• the basic composition of the aqueous copper colloid catalyst solution of the first invention is (A) a soluble copper salt, (B) a reducing agent, and (C) a colloid stabilizer.
• Any soluble salt (A) may be used as long as it is a soluble salt that generates cuprous or cupric ions in an aqueous solution, and there is no particular limitation, and hardly soluble salts are not excluded.
• copper sulfate, copper oxide, copper chloride, copper pyrophosphate, copper carbonate, or carboxylic acid copper salts such as copper acetate, copper oxalate and copper citrate, or copper methanesulfonate and copper hydroxyethanesulfonate And the like, and copper sulfate, copper citrate, and copper methanesulfonate are preferable.
• Examples of the reducing agent (B) include borohydride compounds, amine boranes, hypophosphorous acids, aldehydes, ascorbic acids, hydrazines, polyhydric phenols, polyhydric naphthols, phenolsulfonic acids, naphtholsulfonic acids, sulfines.
• Examples include acids.
• Aldehydes are formaldehyde, glyoxylic acid or salts thereof
• polyhydric phenols are catechol, hydroquinone, resorcin, pyrogallol, phloroglucin, gallic acid, etc.
• phenol sulfonic acids are phenol sulfonic acid, cresol sulfonic acid or salts thereof, etc. It is.
• the colloid stabilizer (C) is a compound that forms a copper complex in the plating bath, and fulfills the function of ensuring the temporal stability of the catalyst solution.
• the colloid stabilizer (C) is selected from the group consisting of monocarboxylic acids, oxycarboxylic acids, aminocarboxylic acids, and polycarboxylic acids.
• Examples of the monocarboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and salts thereof.
• oxycarboxylic acids examples include citric acid, tartaric acid, malic acid, gluconic acid, golcoheptonic acid, glycolic acid, lactic acid, trioxybutyric acid, ascorbic acid, isocitric acid, tartronic acid, glyceric acid, hydroxybutyric acid, leucine acid, citramalic acid, And salts thereof.
• aminocarboxylic acids examples include ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), triethylenetetraminehexaacetic acid (TTHA), ethylenediaminetetrapropionic acid, nitrilotriacetic acid (NTA).
• EDTA ethylenediaminetetraacetic acid
• HEDTA hydroxyethylethylenediaminetriacetic acid
• DTPA diethylenetriaminepentaacetic acid
• TTHA triethylenetetraminehexaacetic acid
• NTA nitrilotriacetic acid
• Iminodiacetic acid IDA
• iminodipropionic acid Iminodiacetic acid
• IDP iminodipropionic acid
• hydroxyethyliminodiacetic acid 1,3-propanediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol etherdiaminetetraacetic acid, meta Phenylenediaminetetraacetic acid, 1,2-diaminocyclohexane-N, N, N ', N'-tetraacetic acid, diaminopropionic acid, glutamic acid, dicarboxymethylglutamic acid, ornithine, cysteine, N, N-bis (2-hydroxyethyl) )glycine, S, S) - ethylenediamine succinic acid and salts thereof.
• IDA Iminodiacetic acid
• IDP iminodipropionic acid
• polycarboxylic acids examples include succinic acid, glutaric acid, malonic acid, adipic acid, oxalic acid, maleic acid, citraconic acid, itaconic acid, mesaconic acid, and salts thereof.
• the solvent of the solution is limited to water and / or hydrophilic alcohol, and the use of organic solvents (including lipophilic alcohol) alone is excluded.
• the pH of the solution is preferably on the acid side or alkali side excluding the neutral range, and specifically, pH 1 to 6 and 8 to 12 are suitable.
• the pH is preferably 2 to 5 and 8 to 11.
• the soluble copper salt (A) can be used singly or in combination, and its content is 0.005 to 1 mol / L, preferably 0.05 to 0.5 mol / L, more preferably 0.04 to 0.2 mol / L.
• the reducing agent (B) can be used alone or in combination, and its content is 0.005 to 1 mol / L, preferably 0.05 to 0.5 mol / L. If the content of the reducing agent is less than the appropriate amount, the reducing action of the copper salt is lowered. Conversely, if the content is too large, the homogeneity of the copper film deposited by electroless plating may be lowered.
• the colloidal stabilizer (C) can be used alone or in combination, and its content is 0.005 to 2 mol / L, preferably 0.05 to 1.5 mol / L.
• the reducing agent solution is slowly dropped over the solution containing the soluble copper salt (and colloid stabilizer) over time. Basically to do.
• a reducing agent solution of 5 to 50 ° C.
• the copper colloid particles generated from the soluble copper salt by the action of the reducing agent are fine particles having a suitable average particle size of 1 to 250 nm, preferably 1 to 120 nm, more preferably 1 to 100 nm.
• the average particle size of the copper colloidal particles is 250 nm or less, when the non-conductive substrate is immersed in the catalyst solution, the colloidal particles enter into the dents on the fine uneven surface of the substrate, and are closely adsorbed or caught. It can be presumed that the application of copper colloid nuclei to the surface of the substrate is promoted. Conversely, when the average particle size is larger than 250 nm, it is difficult to obtain a stable copper colloid due to agglomeration, precipitation, or separation, and the anchor effect cannot be expected. Therefore, the copper colloid particles can only be partially applied to the substrate surface. There is a risk that it may not be applied or it may become defective.
• aqueous copper colloid catalyst solution of the present invention it is necessary not to contain a surfactant or to suppress the content of the surfactant to 950 mg / L or less. If a surfactant is contained in the catalyst solution, the catalyst activity may decrease, and it is preferable not to add a surfactant. However, in the case of a very small content of 950 mg / L or less, there is not much adverse effect on the decrease in catalyst activity, and preferably 700 mg / L or less.
• the above-mentioned surfactant means various nonionic, amphoteric, cationic, or anionic surfactants. In particular, amphoteric, cationic, anionic, or low-molecular nonionic surfactants are not preferable.
• Nonionic surfactants include C1-C20 alkanols, phenols, naphthols, bisphenols, (poly) C1-C25 alkylphenols, (poly) arylalkylphenols, C1-C25 alkylnaphthols, C1-C25 alkoxylated phosphoric acids (salts). ), Sorbitan esters, polyalkylene glycols, C1 to C22 aliphatic amines, C1 to C22 aliphatic amides, and the like obtained by addition condensation of 2 to 300 moles of ethylene oxide (EO) and / or propylene oxide (PO), And C25 alkoxylated phosphoric acid (salt).
• EO ethylene oxide
• PO propylene oxide
• Examples of the cationic surfactant include quaternary ammonium salts, pyridinium salts, and the like. Specific examples include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, lauryl dimethyl ethyl ammonium salt, octadecyl dimethyl ethyl ammonium salt.
• anionic surfactant examples include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonates, ⁇ (mono, di, tri) alkyl ⁇ naphthalene sulfonates, etc. Is mentioned.
• amphoteric surfactant examples include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid.
• sulfation of a condensation product of ethylene oxide and / or propylene oxide and an alkylamine or diamine, or a sulfonated adduct can also be used.
• the aqueous copper colloid catalyst solution of the present invention 2 has the same basic composition as the catalyst solution of the present invention 1, and comprises (A) a soluble copper salt, (B) a reducing agent, and (C) a colloid stabilizer as essential components.
• the requirements for the mixing ratio of components (A) and (C) are also the same as in the first invention.
• the catalyst solution of the present invention 2 is characterized by containing a synthetic water-soluble polymer in place of the requirement of the present invention 1 to eliminate the surfactant content to zero or suppress it to a very small amount. When the synthetic water-soluble polymer is contained in the catalyst solution, the dispersibility of the colloidal particles is improved, thereby contributing to excellent uniformity and uniform copper film deposition during electroless copper plating.
• the above-mentioned synthetic water-soluble polymer means to exclude naturally derived water-soluble polymers such as gelatin and starch, and does not exclude semi-synthetic carboxymethyl cellulose (CMC) and cellulose derivatives such as methyl cellulose (MC).
• CMC carboxymethyl cellulose
• MC methyl cellulose
• the synthetic water-soluble polymer that is the target of the catalyst liquid of the present invention 2 partially overlaps with the component to which it belongs in relation to the surfactant that is the target of the exclusion or suppression of the catalyst liquid of the present invention 1
• the possibility is also considered, in the present invention, both are different concepts.
• the catalyst solution of the present invention 2 since it is not a requirement for the inclusion of components other than the water-soluble polymer, for example, it may or may not be contained regardless of whether or not a surfactant is contained.
• the synthetic water-soluble polymer examples include polyethylene glycol (PEG), polypropylene glycol (PPG), polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylamide (PAM), polyethylene imine, as shown in the present invention 3. (PEI), polyacrylate, and the like, and high molecular weight PEG, PVP, PVA, and the like are particularly preferable.
• the synthetic water-soluble polymer can be used singly or in combination, and its content relative to the catalyst solution is 0.05 to 100 g / L, preferably 0.5 to 50 g / L, more preferably 1.0 to 30 g / L. It is.
• the present invention 9 is an electroless plating method using the above aqueous copper colloid catalyst solution, which is formed by sequentially combining the following three steps.
• the adsorption promotion step (a) is, in other words, a pretreatment (pretreatment) step of catalyst application of (b), and is a nonionic surfactant.
• This is a step of immersing a non-conductive substrate in a liquid containing at least one adsorption accelerator selected from the group consisting of an agent, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.
• the wettability of the substrate surface is increased to enhance the catalytic activity, and the adsorption of the copper colloid catalyst in the next step is promoted.
• the adsorption promotion step it is necessary to bring the non-conductive substrate into contact with the surfactant-containing liquid, so it is basically immersed in the liquid, but the containing liquid is sprayed on the substrate or applied with a brush. There is no problem.
• a positively charged cationic or amphoteric surfactant is preferred from the viewpoint of promoting adsorption, and a cationic surfactant is particularly preferred.
• the adsorption promoting effect is further increased.
• the colloidal copper particles produced by allowing a reducing agent to act on a soluble copper salt have a negative zeta potential, for example, when a non-conductive substrate is contact-treated with a cationic surfactant, The substrate tends to be positively charged, and the adsorption efficiency of the copper colloid particles on the substrate in the next step is increased.
• Specific examples of the surfactant are as described for the surfactant described as an object to be excluded or suppressed in the catalyst solution of the first invention.
• the content of the surfactant is 0.05 to 100 g / L, preferably 0.5 to 50 g / L.
• the temperature of the surfactant-containing liquid is preferably about 15 to 70 ° C., and the immersion time is preferably about 0.5 to 20 minutes.
• the non-conductive substrate that has finished the adsorption promoting process is washed with pure water and then dried or transferred to the next catalyst application step (b) without drying.
• the non-conductive substrate is immersed in the aqueous copper colloid catalyst solution to adsorb the copper colloid particles on the substrate surface.
• the liquid temperature of the catalyst solution is 10 to 70 ° C., and the immersion time is about 0.1 to 20 minutes. In the immersion treatment, it is sufficient to immerse the substrate in the catalyst solution in a stationary state. You may move.
• the nonconductive substrate immersed in the catalyst solution is washed with pure water and then dried or transferred to the electroless copper plating step (c) without drying.
• the electroless copper plating may be processed in the same manner as in the past, and there are no particular restrictions.
• the temperature of the electroless copper plating solution is generally 15 to 70 ° C., preferably 20 to 60 ° C.
• air stirring, rapid liquid flow stirring, mechanical stirring using a stirring blade, or the like can be used.
• the electroless copper plating solution basically contains a soluble copper salt, a reducing agent, and a complexing agent, or may further contain various additives such as a surfactant and a pH adjusting agent, or an acid.
• the soluble copper salt is as described in the copper colloid catalyst solution.
• the reducing agent contained in the electroless copper plating solution is also as described in the copper colloid catalyst solution, including formaldehyde (formalin water), hypophosphorous acid, phosphorous acid, amine borane, borohydride. And glyoxylic acid, and formalin water is preferred.
• the complexing agent contained in the electroless copper plating solution has a part in common with the colloidal stabilizer described in the copper colloid catalyst solution, specifically, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA).
• EDTA ethylenediaminetetraacetic acid
• DTPA diethylenetriaminepentaacetic acid
• Aminocarboxylic acids such as triethylenetetramine hexaacetic acid (TTHA), hydroxyethylethylenediamine triacetic acid (HEDTA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), ethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, Polyamines such as tetraethylenepentamine and pentaethylenehexamine, aminoalcohols such as monoethanolamine, diethanolamine and triethanolamine, oxycarbones such as citric acid, tartaric acid, lactic acid and malic acid Acids, thioglycolic acid, glycine and the like.
• TTHA triethylenetetramine hexaacetic acid
• HEDTA hydroxyethylethylenediamine triacetic acid
• NTA nitrilotriacetic acid
• IDA iminodiacetic acid
• ethylenediamine tetra
• the electroless copper plating solution may contain an organic acid and an inorganic acid or a salt thereof as a base component of the solution.
• the inorganic acid include sulfuric acid, pyrophosphoric acid, and borofluoric acid.
• the organic acid include oxycarboxylic acids such as glycolic acid and tartaric acid, and organic sulfonic acids such as methanesulfonic acid and 2-hydroxyethanesulfonic acid.
• the examples of the electroless copper plating method including the preparation of the adsorption promoter of the present invention, the copper colloid catalyst solution, and the electroless copper plating solution will be described, and the temporal stability test example of the copper colloid catalyst solution, Examples of appearance evaluation tests of the deposited copper film obtained in the above examples will be sequentially described.
• the present invention is not limited to the following examples and test examples, and it is needless to say that arbitrary modifications can be made within the scope of the technical idea of the present invention.
• Example 7 is an example in which a copper colloid catalyst solution contains a very small amount of a surfactant
• Examples 1 to 4 are surfactants to the catalyst solution.
• Examples containing no agent, Examples 5 to 6, Example 9 and Examples 13 to 17 are examples in which the catalyst solution contains a synthetic water-soluble polymer.
• Example 1 is an example in which citric acid was used as the colloid stabilizer in the catalyst solution and sodium borohydride was used as the reducing agent.
• Example 2 is an example in which the content of colloidal stabilizer is reduced
• Example 3 is an example in which the content of colloidal stabilizer is increased
• Example 4 is in which the content of reducing agent is reduced.
• Example 8 is an example in which the type and content of the colloidal stabilizer are changed
• Example 9 is an example in which the type of the reducing agent and the liquid temperature of the catalyst solution are changed.
• Examples 10 to 11 and 15 are examples in which the soluble copper salt is changed
• Example 12 is an example in which the colloid stabilizer is changed.
• Example 7 is an example in which a very small amount of nonionic surfactant is contained on the basis of Example 1, and the kind of colloidal stabilizer and the pH of the catalyst solution are changed.
• Example 5 is an example in which polyvinylpyrrolidone (PVP) is contained in the catalyst solution
• Example 6 is an example in which polyethylene glycol (PEG) is also contained
• Examples 9 and 14 are PVP.
• Example 13 was an example containing polyethyleneimine (PEI)
• Example 15 was an example containing polyacrylamide (PAM).
• Examples 1 to 15 are examples in which the pH of the catalyst solution is acidic
• Examples 16 to 18 are examples in which the pH of the catalyst solution is on the alkali side. Incidentally, about 10 to 20% sulfuric acid or sodium hydroxide was used for pH adjustment.
• Comparative Example 1 is a blank example in which no colloid stabilizer is contained in the catalyst solution
• Comparative Example 2 is a catalyst solution in which the relative content of the colloid stabilizer to the copper salt is 1 to Example 2 is lower than the lower limit of the prescribed amount of 2
• Comparative Example 3 is an example in which the content ratio exceeds the upper limit of the prescribed amount of the present invention 1-2
• Comparative Example 4 is a surfactant prescribed amount of the present invention 1 in the catalyst solution
• the catalyst solution contains more surfactant than Comparative Example 4
• Comparative Example 6 the electroless plating process was immediately performed from the catalyst application process without the adsorption promotion process. This is a blank example.
• Example 4 of Patent Document 1 described above gelatin is contained as a dispersant in the catalyst solution, but Comparative Example 7 is not a synthetic system defined in the present invention 2 but a water-soluble polymer derived from nature. It contains a certain gelatin, which is a conforming example of Patent Document 1 mentioned above.
• Example 1 Preparation of Adsorption Accelerator-Containing Liquid An adsorption accelerator-containing liquid was prepared with the following composition.
• Reducing agent solution Sodium borohydride 0.2 mol / L A reducing agent solution was dropped into the copper solution at 25 ° C.
• the sample substrate was immersed in the adsorption accelerator-containing liquid at 50 ° C. for 2 minutes and washed with pure water.
• the sample substrate subjected to the adsorption promotion treatment was immersed in the copper colloid catalyst solution at 25 ° C. for 10 minutes and washed with pure water.
• the sample substrate to which the catalyst is applied is immersed in the electroless copper plating solution, subjected to electroless plating at 50 ° C. for 10 minutes, and a copper film is formed on the sample substrate. Washed with and dried.
• Example 2 Example in which the colloidal stabilizer of Example 1 is lowered
• the preparation method of the copper colloid catalyst solution and the electroless copper plating solution and the processing conditions of each step were carried out except that the adsorption accelerator containing liquid and the copper colloid catalyst liquid were prepared with the following composition. Same as Example 1.
• the molar ratio of each component of the catalyst solution is as follows.
• A) Preparation of adsorption accelerator-containing liquid [Adsorption accelerator-containing liquid] Lauryldimethylbenzylammonium chloride 5g / L
• Reducing agent solution Sodium borohydride 0.2 mol / L
• the reducing agent solution was dropped into a copper solution at 25 ° C. adjusted to pH 4.0 and stirred for 45 minutes. The average particle diameter of the produced copper colloid particles was about 15 nm.
• Example 3 (Example in which the colloidal stabilizer of Example 1 was raised) Based on the above Example 1, the preparation method of the copper colloid catalyst solution and the electroless copper plating solution and the processing conditions of each step were carried out except that the adsorption accelerator containing liquid and the copper colloid catalyst liquid were prepared with the following composition. Same as Example 1. In addition, the molar ratio of each component of the catalyst solution is as follows.
• Example 4 (Example in which the reducing agent of Example 1 is lowered) Based on the above Example 1, the preparation method of the copper colloid catalyst solution and the electroless copper plating solution and the processing conditions of each step were carried out except that the adsorption accelerator containing liquid and the copper colloid catalyst liquid were prepared with the following composition. Same as Example 1. In addition, the molar ratio of each component of the catalyst solution is as follows.
• Reducing agent solution Sodium borohydride 0.01 mol / L
• the reducing agent solution was dropped into a copper solution at 25 ° C. adjusted to pH 4.0 and stirred for 45 minutes.
• the produced copper colloid particles had an average particle size of about 25 nm.
• Example 5 Example of raising the reducing agent of Example 1 Based on the above Example 1, the preparation method of the copper colloid catalyst solution and the electroless copper plating solution and the processing conditions of each step were carried out except that the adsorption accelerator containing liquid and the copper colloid catalyst liquid were prepared with the following composition. Same as Example 1. In addition, the molar ratio of each component of the catalyst solution is as follows.
• Example 6 Example in which the colloidal stabilizer and reducing agent in Example 1 are lowered, and the stirring time is increased
• a preparation method of a copper colloid catalyst solution (excluding the stirring time) and an electroless copper plating solution, except that the adsorption accelerator containing solution and the copper colloid catalyst solution were prepared with the following composition on the basis of Example 1 above.
• the processing conditions for each step were the same as those in Example 1.
• the molar ratio of each component of the catalyst solution is as follows.
• Copper salt: colloidal stabilizer 1: 3
• copper salt: reducing agent 1: 0.5
• A) Preparation of adsorption accelerator-containing liquid [Adsorption accelerator-containing liquid] Lauryldimethylbenzylammonium chloride 5g / L
• B) Preparation of copper colloid catalyst solution [Copper solution] Copper sulfate (as Cu2 +) 0.2 mol / L Citric acid 0.6 mol / L
• Reducing agent solution Sodium borohydride 0.1 mol / L
• the reducing agent solution is added dropwise to a copper solution at 25 ° C. adjusted to pH 4.0 and stirred for 60 minutes.
• the produced copper colloid particles had an average particle size of about 30 nm.
• Example 7 (change of colloidal stabilizer of Example 1, change of amount, change of pH, addition of surfactant to catalyst solution)
• a preparation method of a copper colloid catalyst solution (excluding pH conditions) and an electroless copper plating solution, except that the adsorption accelerator containing solution and the copper colloid catalyst solution were prepared with the following composition on the basis of Example 1 above.
• the processing conditions for each step were the same as those in Example 1.
• the ratio of each component of the said catalyst liquid is as follows.
• A) Preparation of adsorption accelerator-containing liquid [Adsorption accelerator-containing liquid] Lauryldimethylaminoacetic acid betaine 5g / L
• Reducing agent solution Sodium borohydride 0.2 mol / L
• the reducing agent solution was added dropwise to a 25 ° C. copper solution adjusted to pH 3.0 and stirred for 45 minutes. The average particle diameter of the produced copper colloidal particles was about 17 nm.
• Example 8 Example of changing the amount of colloidal stabilizer in Example 1
• a preparation method of a copper colloid catalyst solution (except for stirring conditions) and an electroless copper plating solution, except that the adsorption accelerator containing solution and the copper colloid catalyst solution were prepared with the following composition on the basis of Example 1 above.
• the processing conditions for each step were the same as those in Example 1.
• the molar ratio of each component of the catalyst solution is as follows.
• Example 9 Example of changing the reducing agent of Example 1 and changing the bath temperature
• the copper colloid catalyst solution except for the temperature condition of the copper solution
• electroless copper plating except that the liquid containing the adsorption accelerator and the copper colloid catalyst solution were prepared with the following composition:
• the liquid preparation method and the treatment conditions for each step were the same as in Example 1.
• the molar ratio of each component of the catalyst solution is as follows.
• Copper salt: colloidal stabilizer 1: 3
• copper salt: reducing agent 1: 0.5
• A) Preparation of adsorption accelerator-containing liquid [Adsorption accelerator-containing liquid] Quaternary ammonium salt of diallylamine polymer 5g / L Polyoxyalkylene branched decyl ether 1g / L
• the reducing agent solution was added dropwise to a 35 ° C. copper solution adjusted to pH 4.0 and stirred for 45 minutes.
• the produced copper colloid particles had an average particle size of about 45 nm.
• Example 10 (example of changing the soluble copper salt of Example 9) Based on Example 1 above, a copper colloid catalyst solution (except for pH and temperature conditions of the copper solution) and electroless, except that the liquid containing the adsorption accelerator and the copper colloid catalyst solution were prepared with the following composition: The method for preparing the copper plating solution and the processing conditions for each step were the same as in Example 1. In addition, the molar ratio of each component of the catalyst solution is as follows.
• Copper salt: colloidal stabilizer 1: 4
• copper salt: reducing agent 1: 0.5
• A) Preparation of adsorption accelerator-containing liquid [Adsorption accelerator-containing liquid] Lauryldimethylbenzylammonium chloride 5g / L
• B) Preparation of copper colloid catalyst solution [Copper solution] Copper methanesulfonate (as Cu2 +) 0.2 mol / L Citric acid 0.8 mol / L
• Reducing agent solution Dimethylamine borane 0.1 mol / L
• the reducing agent solution was added dropwise to a 35 ° C. copper solution adjusted to pH 3.0 and stirred for 45 minutes.
• the produced copper colloid particles had an average particle size of about 16 nm.
• Example 11 (example in which the soluble copper salt of Example 9 was changed) Based on Example 1 above, a copper colloid catalyst solution (except for pH and temperature conditions of the copper solution) and electroless, except that the liquid containing the adsorption accelerator and the copper colloid catalyst solution were prepared with the following composition: The method for preparing the copper plating solution and the processing conditions for each step were the same as in Example 1. In addition, the molar ratio of each component of the catalyst solution is as follows.
• Example 12 Example of changing the colloidal stabilizer of Example 9 Based on Example 1 above, the copper colloid catalyst solution (except for the temperature condition of the copper solution) or electroless copper plating, except that the liquid containing the adsorption accelerator and the copper colloid catalyst solution were prepared with the following composition: The liquid preparation method and the treatment conditions for each step were the same as in Example 1. In addition, the molar ratio of each component of the catalyst solution is as follows.
• Example 13 (when water-soluble polymer is added) Based on the above Example 1, the preparation method of the copper colloid catalyst solution and the electroless copper plating solution and the processing conditions of each step were carried out except that the adsorption accelerator containing liquid and the copper colloid catalyst liquid were prepared with the following composition. Same as Example 1. In addition, the molar ratio of each component of the catalyst solution is as follows.
• Example 14 (when water-soluble polymer is added) Based on the above Example 1, the preparation method of the copper colloid catalyst solution and the electroless copper plating solution and the processing conditions of each step were carried out except that the adsorption accelerator containing liquid and the copper colloid catalyst liquid were prepared with the following composition. Same as Example 1. In addition, the molar ratio of each component of the catalyst solution is as follows.
• Example 15 (when soluble copper salt is changed and water-soluble polymer is added) Based on the above Example 1, the preparation method of the copper colloid catalyst solution and the electroless copper plating solution and the processing conditions of each step were carried out except that the adsorption accelerator containing liquid and the copper colloid catalyst liquid were prepared with the following composition. Same as Example 1. In addition, the molar ratio of each component of the catalyst solution is as follows.
• Example 16 (example in which the pH of Example 1 was raised) A preparation method of a copper colloid catalyst solution (excluding pH conditions) and an electroless copper plating solution, except that the adsorption accelerator containing solution and the copper colloid catalyst solution were prepared with the following composition on the basis of Example 1 above.
• the processing conditions for each step were the same as those in Example 1.
• the molar ratio of each component of the catalyst solution is as follows.
• Copper salt: colloidal stabilizer 1: 3
• copper salt: reducing agent 1: 0.5
• A) Preparation of adsorption accelerator-containing liquid [Adsorption accelerator-containing liquid] Quaternary ammonium salt of diallylamine polymer 5g / L Polyoxyalkylene branched decyl ether 1g / L
• B) Preparation of copper colloid catalyst solution [Copper solution] Copper sulfate (as Cu2 +) 0.2 mol / L Ethylenediaminetetraacetic acid 0.6 mol / L Polyvinylpyrrolidone (Molecular weight 300,000) 1.0 g / L [Reducing agent solution] Sodium borohydride 0.1 mol / L The reducing agent solution was added dropwise to a 25 ° C. copper solution adjusted to pH 9.0 and stirred for 45 minutes. The produced copper colloid particles had an average particle size of about 18 nm.
• Example 17 (Example in which pH of Example 1 was increased) A preparation method of a copper colloid catalyst solution (excluding pH conditions) and an electroless copper plating solution, except that the adsorption accelerator containing solution and the copper colloid catalyst solution were prepared with the following composition on the basis of Example 1 above.
• the processing conditions for each step were the same as those in Example 1.
• the molar ratio of each component of the catalyst solution is as follows.
• Example 18 (Example in which pH of Example 1 was raised) A preparation method of a copper colloid catalyst solution (excluding pH conditions) and an electroless copper plating solution, except that the adsorption accelerator containing solution and the copper colloid catalyst solution were prepared with the following composition on the basis of Example 1 above.
• the processing conditions for each step were the same as those in Example 1.
• the molar ratio of each component of the catalyst solution is as follows.
• Copper salt: colloidal stabilizer 1: 3
• copper salt: reducing agent 1: 0.5
• A) Preparation of adsorption accelerator-containing liquid [Adsorption accelerator-containing liquid] Quaternary ammonium salt of diallylamine polymer 5g / L
• Reducing agent solution Sodium borohydride 0.1 mol / L
• the reducing agent solution was added dropwise to a 25 ° C. copper solution adjusted to pH 10.0 and stirred for 45 minutes.
• the produced copper colloid particles had an average particle size of about 20 nm.
• A) Preparation of adsorption accelerator-containing liquid [Adsorption accelerator-containing liquid] Quaternary ammonium salt of diallylamine polymer 5g / L
• B) Preparation of copper colloid catalyst solution [Copper solution] Copper sulfate (as Cu2 +) 0.2 mol / L
• Reducing agent solution Sodium borohydride 0.2 mol / L
• the reducing agent solution was dropped into a copper solution at 25 ° C. adjusted to pH 4.0 and stirred for 45 minutes. Copper colloidal particles were formed, but agglomerated and precipitated.
• Comparative Example 2 (when the ratio of copper and stabilizer is outside the minimum limit) Based on the above Example 1, the preparation method of the copper colloid catalyst solution and the electroless copper plating solution and the processing conditions of each step were carried out except that the adsorption accelerator containing liquid and the copper colloid catalyst liquid were prepared with the following composition. Same as Example 1. In addition, the molar ratio of each component of the catalyst solution is as follows.
• A) Preparation of adsorption accelerator-containing liquid [Adsorption accelerator-containing liquid] Quaternary ammonium salt of diallylamine polymer 5g / L
• Reducing agent solution Sodium borohydride 0.2 mol / L
• the reducing agent solution was dropped into a copper solution at 25 ° C. adjusted to pH 4.0 and stirred for 45 minutes. Copper colloidal particles were formed, but agglomerated and precipitated.
• Example 4 Example in which the catalyst solution of Example 1 contains a surfactant in excess of the specified value in the present application
• the preparation method of the copper colloid catalyst solution and the electroless copper plating solution and the processing conditions of each step were carried out except that the adsorption accelerator containing liquid and the copper colloid catalyst liquid were prepared with the following composition. Same as Example 1.
• the molar ratio of each component of the catalyst solution is as follows.
• Example of stability of catalyst solution over time >> Therefore, for each of the copper colloid catalyst solutions prepared in Examples 1 to 18 and Comparative Examples 1 to 7, The superiority or inferiority of colloidal stability was evaluated according to the following criteria. ⁇ : No precipitation or decomposition occurred for 1 month after bathing. X: Sedimented or decomposed immediately after bathing.
• the catalyst solution was inferior in stability over time, and no copper film was deposited in electroless plating.
• Comparative Example 6 in which the catalyst was applied to the non-conductive substrate without adsorption promoting treatment and electroless copper plating was performed, the temporal stability of the catalyst solution was the same as that of the example.
• the copper film to be applied was generally uniform and excellent in uniformity. Comparing Examples 1 to 18 with Comparative Example 1 above, in order to obtain a copper film having no unevenness and excellent uniformity, the catalyst solution contains not only a copper salt and a reducing agent but also a colloidal stabilizer. It turns out to be essential. Further, when Examples 1 to 18 are compared with Comparative Examples 2 to 3, it is not sufficient to contain a colloidal stabilizer in order to obtain a copper film having excellent uniformity and no unevenness. It can be judged that optimization of the content ratio is important.
• Example 4 in which the surfactant was contained in the catalyst solution in excess of the suppression regulation amount of the present invention 1, “plating failure” in which non-deposition occurred in a part of the copper film deposited in electroless plating was observed.
• the comparative example 5 which made the catalyst solution contain more surfactant than the comparative example 4, the copper membrane
• Example 7 in which the surfactant was suppressed to a very small amount equal to or less than the specified amount of the present invention 1, the copper film was smoothly deposited without any plating defects or the like in electroless plating (however, the film Was found to be uneven).
• Example 8 to 12 and Example 18 in which the catalyst solution did not contain a surfactant naturally there was no unevenness and an excellent uniform copper film was deposited. That is, if a surfactant is added to the catalyst solution exceeding the specified value of the present invention, the catalyst activity of the copper colloid catalyst solution is reduced, and the copper film obtained by electroless plating is not plated, and the surfactant is further removed. When the content of the catalyst is increased, the catalytic activity of the liquid is lost and the copper film does not precipitate. Therefore, the copper film is deposited smoothly only when the content of the surfactant is suppressed to a very small amount.
• Example 1 a non-conductive substrate is pretreated with an adsorption accelerator containing a quaternary ammonium salt of diallylamine polymer which is a cationic surfactant, copper sulfate is used as a copper salt, and sodium borohydride is used as a reducing agent.
• an adsorption accelerator containing a quaternary ammonium salt of diallylamine polymer which is a cationic surfactant copper sulfate is used as a copper salt
• sodium borohydride is used as a reducing agent.
• Example 2 is an example in which the content ratio of the colloidal stabilizer to the copper salt is lowered with respect to Example 1
• Example 4 is an example in which the content of the reducing agent is lowered with respect to Example 1
• Example 5 is a reducing agent.
• Example 8 is an example in which the colloidal stabilizer is changed from citric acid to glycolic acid of Example 1, but the stability of the catalyst solution over time and the appearance of the plating film are shown in Examples. The evaluation was the same as 1.
• Example 9 is an example in which the reducing agent was changed from sodium borohydride of Example 1 to dimethylamine borane in Example 1 and the temperature of the catalyst solution was raised. The appearance of was the same as in Example 1.
• Example 10 is an example in which methanesulfonic acid is a copper salt
• Example 11 is an example in which copper chloride is a copper salt, but the stability over time of the catalyst solution and the appearance of the plating film are evaluated in the same manner as in Example 1. there were.
• Example 7 where the surfactant is present in a very small amount not more than the specified amount of the present invention 1, the copper film was smoothly deposited without any plating defects in the electroless plating, but uneven deposition was observed in the film. It was.
• Example 5 containing PVP (average molecular weight 40,000) as a water-soluble polymer in the catalyst solution
• Example 6 also containing PEG
• Example 13 containing PEI
• Example 15 and 9 and PAM containing PAM the stability over time of the catalyst solution and the appearance of the plating film were evaluated in the same manner as in Example 1.
• Example 10 at pH 3
• Example 11 at pH 5
• Example 16 at pH 9, and Examples 17 to 18 at pH 10
• the appearance of the plating film was evaluated in the same manner as in Example 1.

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