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
  • C23C18/20—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
  • C23C18/18—Pretreatment of the material to be coated
• • 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
  • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
  • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
  • C23C18/1837—Multistep pretreatment
  • C23C18/1841—Multistep pretreatment with use of metal 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
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
  • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
  • C23C18/1837—Multistep pretreatment
  • C23C18/1844—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
  • C23C18/18—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
  • C23C18/208—Multistep pretreatment with use of metal 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
  • C23C18/40—Coating with copper using reducing agents

Definitions

• the present invention provides a copper colloid catalyst solution for applying a catalyst as a pretreatment when electroless copper plating is applied to a non-conductive substrate, an electroless copper plating method using the catalyst solution, and a copper film formed by the method.
• the present invention relates to a method for manufacturing a formed copper plated substrate.
• the present invention relates to a copper colloid catalyst solution that has remarkably improved stability over time and sustainability of catalytic activity and can impart an excellent appearance to a copper film.
• Electroless copper plating is applied on non-conductive substrates such as glass substrates and ceramic substrates, including glass / epoxy resins, glass / polyimide resins, epoxy resins, polyimide resins, polycarbonate resins, ABS resins, and PET resins.
• a noble metal such as palladium, silver, or platinum is adsorbed on the substrate to make it a catalyst nucleus, and then a copper film is deposited on the substrate by an electroless copper plating solution through the catalyst nucleus. Is common.
• Patent Document 1 Add soluble copper salt, dispersant (gelatin, nonionic surfactant) and complexing agent (dicarboxylic acid, oxycarboxylic acid, etc.) and reduce with reducing agent (sodium borohydride, dimethylamine borane, etc.) It is disclosed that a stabilizer (sodium hypophosphite, dimethylamine borane, etc.) is added after the treatment to produce a fine copper catalyst solution for electroless copper plating.
• reducing agent sodium borohydride, dimethylamine borane, etc.
• Patent Document 2 An electroless plating catalyst comprising a copper salt (in Production Example 2, a copper ammine complex), an anionic surfactant, and a reducing agent is applied to the object to be plated, and after electroless copper plating is performed, electrolytic copper plating is performed. (Claims 1 and 2, paragraph 42).
• Patent Document 3 It is disclosed that after a catalyst is applied to a substrate with a copper (I) oxide colloidal catalyst solution, copper is directly plated on the substrate by immersion in a solution containing a copper salt, a reducing agent, and a complexing agent. .
• Patent Document 4 The object to be plated is pretreated with a conditioning agent containing a surfactant (cationic, amphoteric, nonionic, etc .; paragraph 56), and cuprous salt, hypophosphite and chloride ions, or further a reducing agent.
• a conditioning agent containing a surfactant (cationic, amphoteric, nonionic, etc .; paragraph 56), and cuprous salt, hypophosphite and chloride ions, or further a reducing agent.
• a method (Claim 8 to 9, Paragraph 70) in which electroless copper plating is performed by catalytic treatment with a catalyst solution containing (amine boranes, borohydrides, etc.).
• a cationic surfactant is used in particular, the hydrophilic group of the surfactant adsorbed on the object to be plated is negatively charged and the cuprous ions are easily adsorbed.
• Patent Document 5 Treating a non-conductive substrate with a dispersion of an activator comprising a noble metal / metal-colloid (eg, a colloidal solution of palladium / tin) and then into a conductor solution comprising a copper salt solution, a complexing agent and a reducing agent.
• an activator comprising a noble metal / metal-colloid (eg, a colloidal solution of palladium / tin) and then into a conductor solution comprising a copper salt solution, a complexing agent and a reducing agent.
• the catalyst solution is based on the basic principle of producing a fine metal particle by treating a soluble metal salt with a reducing agent.
• the catalyst solution based on this principle includes those described in Patent Documents 1 to 5,
• there is a particular problem in terms of stability over time and there is a situation that it is not easy to ensure the continuity of the catalyst application work and the electroless plating work smoothly over a long period of time. If the stability over time decreases, the catalyst is applied, and even when electroless copper plating is applied, the film does not deposit well, partial plating that does not deposit the film occurs, unevenness occurs in the plating film, and uniformity There are problems such as inferiority.
• the present inventors include a colloidal stabilizer such as oxycarboxylic acids and aminocarboxylic acids that stabilize the copper salt in the copper catalyst solution as shown in JP-A-2015-147987 (hereinafter referred to as Prior Invention 1).
• a colloidal stabilizer such as oxycarboxylic acids and aminocarboxylic acids that stabilize the copper salt in the copper catalyst solution as shown in JP-A-2015-147987 (hereinafter referred to as Prior Invention 1).
• Prior Invention 1 a colloidal stabilizer such as oxycarboxylic acids and aminocarboxylic acids that stabilize the copper salt in the copper catalyst solution as shown in JP-A-2015-147987
• Patent Document 6 In this method, a metal salt is reduced on a non-conductive substrate and subjected to a catalyst application treatment, and then an electroless copper plating treatment is performed (Claim 1, paragraph 1). , Reducing sugars such as galactose, maltose (maltose), fructose (fructose) and wood sugar (xylose) are included (claims 1, 10, paragraphs 1 and 24). Moreover, the said composition can contain buffer agents, such as a citric acid, tartaric acid, and malic acid (paragraph 19). Japanese Laid-Open Patent Publication No. 2012-127002 (Rohm & Haas) is a similar prior document.
• Patent Document 7 In this method, a metal salt (such as a copper salt) is reduced on a non-conductive substrate, a catalyst is applied, and an electroless copper plating process is performed (Claims 1 and 3, paragraph 29, Table 1). Glucose is mentioned (paragraph 25). Further, by dissolving carboxylic acids such as tartaric acid, citric acid and succinic acid, and saccharides such as sucrose and fructose in the catalyst solution, the amount of catalyst metal attached to the substrate surface can be increased (paragraph 31).
• carboxylic acids such as tartaric acid, citric acid and succinic acid
• saccharides such as sucrose and fructose
• Patent Document 8 In this method, electroless copper plating is performed after a catalyst application treatment is performed using a silver colloid catalyst solution (pretreatment solution) instead of a copper catalyst solution (Claims 1 and 35).
• pretreatment solution a silver colloid catalyst solution
• the catalyst solution includes known colloidal dispersions such as cellulose and its derivatives, monosaccharides, polysaccharides and its derivatives.
• An agent can be added (paragraph 46). Monosaccharides, polysaccharides and derivatives thereof are sucrose, mannitol, sorbitol, glycerol, dextrin, etc. (paragraph 50).
• Patent Document 9 Etching is performed on a non-conductive substrate made of a resin molded product, and then contacted with a colloidal solution containing a precious metal compound (gold, silver, etc.) and stannous salt, and then contacted with an aqueous solution of a palladium compound to give a catalyst.
• This is a method of performing an electroless copper plating process (claims 1 and 2). Reducing sugars such as glucose, sorbit, cellulose, sucrose, mannitol, gluconolactone can be contained in the electroless copper plating solution instead of the catalyst solution (paragraph 73).
• Patent Document 10 Etching is performed on non-conductive substrates such as resin, ceramics, glass, etc., tin salt (such as stannous chloride) is attached, and then sensitized, soaked in a silver nitrate solution to replace silver on the tin.
• tin salt such as stannous chloride
• This is a method of growing a tin-silver composite, immersing it in a reducing solution and activating it, followed by electroless copper plating (claims 1 to 6, paragraphs 10 and 22).
• Glucose can be used.
• Japanese Patent Laid-Open No. 02-093076 JP-A-10-229280 Japanese Patent Application Laid-Open No. 07-197266 JP 2011-225929 A Special table 2013-522476 gazette JP 2012-130910 A JP 2003-313670 A JP 2004-190042 A JP 2006-299366 A JP 2005-146330 A
• Patent Documents 6 to 10 sugars such as glucose, fructose, maltose and cellulose, or sugar alcohols such as mannitol and sorbitol are used in the catalyst solution as a pretreatment agent.
• sugars such as glucose, fructose, maltose and cellulose, or sugar alcohols such as mannitol and sorbitol are used in the catalyst solution as a pretreatment agent.
• sugar alcohols such as mannitol and sorbitol
• saccharides and sugar alcohols are used for the electroless copper plating solution, not for the catalyst solution. It is a technical object of the present invention to further improve the temporal stability of a copper colloid catalyst solution by developing its characteristic component structure based on the above-mentioned Prior Invention 1.
• the present inventors have earnestly studied the relationship between the copper colloid catalyst solution to which a saccharide or a sugar alcohol is added and its stability over time, starting from Patent Documents 6 to 10 described above.
• a specific saccharide such as glucose, maltose, sorbitol, xylitol
• the stability of the catalyst solution over time is further increased than when no saccharide is contained.
• a copper film having a good appearance can be formed by electroless plating, and a proposal as shown in Japanese Patent Application Laid-Open No. 2016-151056 (hereinafter referred to as Prior Invention 2) has been made.
• the present inventors have found that a saccharide that is included in a saccharide in a broad sense but deviates from the range defined in the preceding invention 2 and the temporal stability of the copper colloid catalyst solution. Researched the relationship eagerly. As a result, when the non-reducing oligosaccharide is used as a saccharide deviating from this rule, the inventors of the prior invention 2 described above can improve the temporal stability of the copper colloid catalyst solution and the durability of the catalytic activity. As a result, it has been found that a further excellent effect can be expected as compared with the case of using the specified carbohydrate.
• the present invention 1 is a copper colloid catalyst solution for applying a catalyst by bringing it into contact with a non-conductive substrate to be electrolessly plated with copper, (A) a soluble copper salt; (B) a reducing agent; (C) at least one colloid stabilizer selected from the group consisting of oxycarboxylic acids, aminocarboxylic acids, and polycarboxylic acids; (D) A copper colloid catalyst solution for electroless copper plating, comprising a non-reducing oligosaccharide.
• the present invention 2 is the copper colloid catalyst solution for electroless copper plating according to the present invention 1, which further contains a reducing saccharide.
• Invention 3 is the electroless copper plating according to Invention 1 or 2, wherein the non-reducing oligosaccharide (D) is at least one selected from sucrose, trehalose, raffinose, and cyclodextrin. This is a copper colloid catalyst solution.
• Invention 4 relates to any one of Inventions 1 to 3, wherein the reducing agent (B) is a borohydride compound, amine boranes, hypophosphorous acid, aldehydes, ascorbic acids, hydrazines, polyhydric phenols.
• a 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 colloid stabilizer (C) according to any one of the present inventions 1 to 4, wherein
• the oxycarboxylic acids are citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic acid, glycolic acid, lactic acid, trioxybutyric acid, ascorbic acid, isocitric acid, tartronic acid, glyceric acid, hydroxybutyric acid, leucine acid, citramalic acid, and Is at least one selected from the group consisting of these salts,
• the above aminocarboxylic acids are ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, ethylenediaminetetrapropionic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, iminodipropionic acid, 1
• the present invention 6 A non-conductive substrate is brought into contact with 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 promoting step (pretreatment step)
• a non-conductive substrate that has been subjected to adsorption promotion treatment is brought into contact with the copper colloid catalyst solution for electroless copper plating according to any of the first to fifth aspects of the present invention, and copper is deposited on the surface of the non-conductive substrate A catalyst application step for adsorbing colloidal particles;
• An electroless copper plating method comprising: an electroless plating step of forming a copper film using an electroless copper plating solution on a non-conductive substrate subjected to a catalyst application treatment.
• the present invention 7 is the electroless copper plating method according to the present invention 6, wherein the adsorption accelerator used in the adsorption promoting step (a) includes at least a cationic surfactant.
• the present invention 8 is a method for producing a copper-plated substrate, wherein a copper film is formed on a non-conductive substrate by the electroless copper plating method of the present invention 6 or 7.
• non-reducing oligosaccharides such as sucrose and trehalose are selectively used in place of the specific carbohydrate defined in the above-mentioned prior invention 2, so that the temporal stability of the catalyst solution is higher than that of the above-mentioned prior invention 2.
• the color tone and denseness of the copper film obtained by electroless plating are also improved.
• the stability over time of the colloidal catalyst solution after the building bath can be improved. As will be described later, even if the catalyst is applied using the catalyst solution at the time when 3 months have passed after the building bath, the catalyst immediately after the building bath A copper film having the same properties as when a liquid is used can be formed, and the catalyst activity is excellent.
• the maintenance of the catalyst solution can be further reduced as compared with the prior inventions 1 and 2, and the productivity of the electroless copper plating can be further improved.
• the adsorption promotion treatment is performed with a surfactant before applying the catalyst to the non-conductive substrate, the effect of the copper colloid catalyst solution can be improved.
• treatment with a cationic surfactant significantly improves the effect of the copper colloid catalyst solution.
• Patent Document 8 discloses that sucrose (sucrose) is contained in the catalyst solution in order to stabilize the colloid of the catalyst solution ([0046] [0050]).
• Example 19 which is a specific silver catalyst solution containing no sugar, and sucrose is contained, oxycarboxylic acids and aminocarboxylic acids are not contained. This is different from the present invention.
• prior literatures that are not included in the above-mentioned patent documents but have descriptions relating to carbohydrates classified as non-reducing oligosaccharides used in the present invention, JP-A-2014-180666 and JP-T-2016-539244 There is. Among them, Japanese Patent Application Laid-Open No.
• 2014-180666 discloses a metal catalyst solution for electroless copper plating (Claims 1 and 7), and the catalyst solution is a noble metal such as gold, silver or palladium ([0024 ], A reducing agent ([0023]), and a flavonoid glycoside to which a saccharide (trehalose, glucose, mannose, etc.) is bound ([0021]).
• the metal contained in the catalyst solution is a noble metal and not copper, and saccharides such as trehalose are blended as specific organic compounds incorporated in the flavonoid skeleton, and are not blended directly as independent saccharide components This is different from the present invention.
• JP-T-2016-539244 discloses an electroless copper plating solution containing a copper salt, a reducing agent, and a complexing agent for forming a copper seed layer on the barrier layer.
• sucrose is exemplified as the reducing agent (Claim 5, [0040]).
• the liquid containing the reducing agent is a plating liquid and not a catalyst liquid, and that there is a misconception that non-reducing sucrose is classified as a reducing agent. .
• the present invention is primarily a copper colloid catalyst liquid 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. And (D) a copper colloid catalyst solution for electroless copper plating, which further contains a non-reducing oligosaccharide (the present invention 1).
• the non-conductive substrate is preliminarily promoted (pretreated) with a surfactant (adsorption accelerator) -containing liquid, and then the catalyst is applied using the first copper colloid catalyst liquid.
• This is an electroless copper plating method in which a copper film is formed by performing electroless copper plating later (present invention 6).
• the present invention is a method for producing a copper-plated substrate, wherein a copper film is formed on a non-conductive substrate by the second electroless copper plating method (the present invention 8).
• the non-conductive substrate refers to a glass substrate, a ceramic substrate, and the like including a resin substrate such as glass / epoxy resin, glass / polyimide resin, epoxy resin, polyimide resin, polycarbonate resin, ABS resin, and PET resin.
• the essential components of the copper colloid catalyst solution of the present invention 1 are (A) a soluble copper salt, (B) a reducing agent, (C) a colloid stabilizer, and (D) a non-reducing oligosaccharide.
• Any soluble copper salt (A) can be used as long as it is a soluble salt that generates cuprous ions or cupric ions in an aqueous solution.
• soluble salts are not excluded.
• examples thereof include organic sulfonic acid copper salts such as acid copper, 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 a salt thereof. Polyhydric phenols are catechol, hydroquinone, resorcin, pyrogallol, phloroglucin, gallic acid and the like. The phenol sulfonic acids include phenol sulfonic acid, cresol sulfonic acid, or a salt thereof.
• the colloid stabilizer (C) is a compound that forms a copper complex in the plating bath, and fulfills a function of ensuring the stability of the catalyst solution over time.
• the colloid stabilizer (C) is selected from the group consisting of oxycarboxylic acids, aminocarboxylic acids, and polycarboxylic acids.
• oxycarboxylic acids examples include citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic 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
• hydroxyethyliminodiacetic acid iminodipropionic acid
• IDP 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 their salts.
• IDA Iminodiacetic acid
• IDP iminodipropionic acid
• 1,3-propanediaminetetraacetic acid 1,3-diamino-2-hydroxypropa
• 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 feature of the copper colloid catalyst solution of the present invention 1 is that the non-reducing oligosaccharide (D) is selected and added.
• oligosaccharide means a saccharide condensed with about 2 to 10 monosaccharides.
• the non-reducing oligosaccharide (D) is selected from sucrose, trehalose, raffinose, cyclodextrin and the like, and these can be used alone or in combination, but sucrose and trehalose are preferred.
• cyclodextrin is a non-reducing oligosaccharide having a reducing end in a cyclic shape.
• the solubility decreases when the number of bonds of monosaccharide units is large, so that the number of bonds is preferably small.
• the pH of the copper colloid catalyst solution of the present invention is preferably a value in the alkaline region or acidic region excluding neutrality, but the copper colloid catalyst solution of the present invention containing the non-reducing oligosaccharide (D) is The alkaline region tends to promote the catalytic function more easily than the acidic region.
• a reducing saccharide in the said prior invention 2, when specific saccharides, such as glucose and maltose, are mix
• a reducing saccharide also in the copper colloid catalyst liquid of this invention characterized by containing the said non-reducing oligosaccharide (D), a reducing saccharide can be further contained.
• the reducing sugar include monosaccharides such as glucose (glucose), galactose, mannose, fructose (fructose), and wood sugar (xylose), maltose (maltose), isomaltose, lactose (lactose), isomaltulose and the like.
• the specific carbohydrate defined in the preceding invention 2 includes a specific sugar alcohol
• the copper colloid catalyst solution of the present invention may contain the specific sugar alcohol defined in the prior invention 2. it can.
• the sugar alcohol include sorbitol, xylitol, mannitol, maltitol, erythritol, lactitol and the like.
• the copper colloid catalyst solution of the present invention 1 is aqueous, its solvent is water and / or hydrophilic alcohol, and organic solvents (including lipophilic alcohols) are usually not used.
• the pH is preferably in the acidic region or alkaline region excluding the neutral region.
• pH 1 to 6 and 8 to 12 are suitable, preferably pH 2 to 5 and 8 to 11. If adjusted to this appropriate range, the copper colloid particles are easily stabilized.
• the copper colloid catalyst solution of the present invention containing the non-reducing oligosaccharide (D) tends to promote the catalytic function more easily in the alkaline region than in the acidic region.
• an aminocarboxylic acid such as EDTA or NTA as the colloid stabilizer (C) is slightly different from using an oxycarboxylic acid such as tartaric acid or citric acid in order to bring out the catalytic function.
• an aminocarboxylic acid such as EDTA or NTA
• an oxycarboxylic acid such as tartaric acid or citric acid
• the soluble copper salt (A) can be used alone or in combination, and the content thereof is preferably 0.005 mol / L to 3 mol / L, more preferably 0.05 mol / L to 2. Mol / L, more preferably 0.04 mol / L to 1.2 mol / L.
• the reducing agent (B) can be used alone or in combination, and the content thereof is preferably 0.005 mol / L to 4 mol / L, more preferably 0.01 mol / L to 3 mol. / L, more preferably 0.02 mol / L to 2.2 mol / L.
• the colloid stabilizer (C) can be used alone or in combination, and the content thereof is preferably 0.005 mol / L to 4 mol / L, more preferably 0.01 mol / L to 2 Mol / L, more preferably 0.05 mol / L to 1.6 mol / L.
• the non-reducing oligosaccharide (D) can be used alone or in combination, and the content thereof is preferably 0.001 mol / L to 4 mol / L, more preferably 0.01 mol / L. -3 mol / L, more preferably 0.05 mol / L to 2.2 mol / L.
• the above-mentioned specific example is mentioned as a reducing saccharide
• the total content of the catalyst solution is preferably 0.001 mol / L to 2.0 mol / L, more preferably 0.01 mol / L to 1.5 mol / L, and still more preferably 0.05. Mol / L to 1.0 mol / L.
• the relative content of the non-reducing oligosaccharide (D) is too low, the stability of the copper colloid catalyst solution over time and the sustainability of the catalyst activity may be reduced.
• the relative content of the non-reducing oligosaccharide (D) is too high, there is a possibility that the formation of a film having a good appearance may be hindered by imparting catalyst nuclei to the non-conductive substrate.
• the catalyst solution is prepared by containing a solution of the reducing agent (B) with a soluble copper salt (A) (and a colloid stabilizer (C)). Basically, it is performed by slowly dropping the solution over time.
• a reducing agent (B) solution preferably 5 ° C. to 50 ° C., more preferably 10 ° C. to 40 ° C., is dropped into the soluble copper salt (A) solution, preferably 20 minutes to 1200 minutes, more preferably Is stirred for 30 to 300 minutes to prepare a catalyst solution.
• the copper colloid particles generated from the soluble copper salt (A) by the action of the reducing agent (B) have a suitable average particle size of 1 nm to 250 nm, preferably 1 nm to 120 nm, more preferably 1 nm to 100 nm. Of fine particles.
• the average particle size of the copper colloid particles is 250 nm or less, when the non-conductive substrate is brought into contact with the catalyst solution, the copper colloid particles enter the dents on the fine uneven surface of the substrate, and are adsorbed densely or caught.
• the anchor effect of this promotes the application of copper colloid nuclei to the substrate surface.
• the average particle diameter is larger than 250 nm, it is difficult to obtain a stable copper colloid due to aggregation, precipitation, or separation, and it is difficult to expect an anchor effect. There is a risk that it may be applied only to the surface, or a poor application.
• the copper colloid catalyst solution of the present invention 1 can contain a surfactant, since the catalyst activity may be lowered, the content is preferably suppressed to a small amount of 950 mg / L or less.
• the above-mentioned surfactant means various nonionic, cationic, anionic or amphoteric surfactants. In particular, amphoteric, cationic, anionic or low molecular nonionic surfactants are preferred. Absent.
• nonionic surfactant examples include C1 to C20 alkanol, phenol, naphthol, bisphenol, (poly) C1 to C25 alkylphenol, (poly) arylalkylphenol, C1 to C25 alkylnaphthol, C1 to C25 alkoxylated phosphoric acid (salt) ), Sorbitan ester, polyalkylene glycol, polyoxyalkylene alkyl ether, C1-C22 aliphatic amine, C1-C22 aliphatic amide, etc. are subjected to addition condensation of 2-300 moles of ethylene oxide (EO) and / or propylene oxide (PO). Etc.
• EO ethylene oxide
• PO propylene oxide
• Examples of the cationic surfactant include quaternary ammonium salts and pyridinium salts. Specifically, diallylamine polymer ammonium salt, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, lauryl dimethyl ethyl ammonium salt, octadecyl dimethyl ethyl ammonium salt, lauryl dimethyl benzyl ammonium salt, cetyl dimethyl benzyl ammonium salt, octadecyl dimethyl benzyl ammonium salt , Trimethylbenzylammonium salt, triethylbenzylammonium salt, dimethyldiphenylammonium salt, benzyldimethylphenylammonium salt, hexadecylpyridinium salt, laurylpyridinium salt, dodecylpyridinium salt, stearylamine acetate, laurylamine acetate, octade
• anionic surfactant examples include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonates, ⁇ (mono, di, tri) alkyl ⁇ naphthalene sulfonates, and the like. Is mentioned.
• amphoteric surfactant examples include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid betaine.
• sulfated adducts or sulfonated adducts of condensation products of ethylene oxide (EO) and / or propylene oxide (PO) with alkylamines or diamines can also be used.
• the present invention 6 is an electroless copper plating method using the above-described copper colloid catalyst solution, which is formed by sequentially combining the following three steps.
• Adsorption promotion step (b) Catalyst application step (c) Electroless plating step
• the adsorption promotion step (a) is a pretreatment step of the catalyst application step (b), which is a nonionic surfactant, a cationic system.
• a adsorption accelerator selected from the group consisting of a surfactant, an anionic surfactant, and an amphoteric surfactant;
• the wettability of the substrate surface is enhanced to enhance the catalytic activity, and the adsorption of the copper colloid particles in the next step is promoted.
• the adsorption promoting step (a) since it is necessary to bring the non-conductive substrate into contact with the surfactant-containing liquid, it is fundamental to immerse the substrate in the containing liquid.
• the contained liquid may be applied to the substrate with a brush.
• the colloidal copper particles produced by allowing the reducing agent (B) to act on the soluble copper salt (A) have a negative zeta potential.
• a non-conductive substrate is treated with a cationic surfactant.
• the substrate When the treatment is performed in contact with the containing liquid, the substrate tends to be positively charged, and the adsorption efficiency of the copper colloid particles on the substrate in the next step increases.
• Specific examples of the surfactant are the same as those described as the suppression target in the catalyst solution of the first invention.
• the surfactant content is preferably 0.05 g / L to 100 g / L, and more preferably 0.5 g / L to 50 g / L.
• the temperature of the surfactant-containing liquid is preferably about 15 to 70 ° C., and the contact time of the substrate with the surfactant-containing liquid is preferably about 0.5 to 20 minutes.
• the process proceeds to the next catalyst application step (b) without drying or drying.
• the non-conductive substrate is brought into contact with the copper colloid catalyst solution, and the copper colloid particles are adsorbed on the surface of the non-conductive substrate.
• the catalyst solution may be applied to the substrate with a brush.
• the temperature of the catalyst solution is preferably 5 ° C to 70 ° C, more preferably 15 ° C to 60 ° C.
• the contact time of the substrate with the catalyst solution is preferably 0.1 minutes to 20 minutes, more preferably 0.2 minutes to 10 minutes.
• an acid washing step may be added after the catalyst application step (b) and before the next electroless plating step (c).
• the acid cleaning process is added, the activity of the catalytic activity can be further increased compared to the case without the acid cleaning treatment, and even if the substrate has a complicated shape with vias and through holes, plating unevenness and disconnection are prevented. It is possible to prevent harmful effects and improve the adhesion of the copper film.
• the acid concentration is preferably 10 g / L to 200 g / L, more preferably 20 g / L to 100 g / L.
• the acid include inorganic acids such as sulfuric acid and hydrochloric acid, and organic sulfonic acids.
• Organic acids such as carboxylic acids such as acetic acid, tartaric acid and citric acid can be used.
• the treatment temperature for acid washing is preferably 5 ° C. to 70 ° C., more preferably 15 ° C. to 60 ° C., and the treatment time is preferably 0.1 minutes to 20 minutes, more preferably 0.2 minutes to 10 minutes. It is.
• the electroless plating step (c) is performed without drying or drying.
• the electroless copper plating in the electroless plating step (c) may be performed in the same manner as in the past, and there are no particular restrictions.
• the liquid temperature of the electroless copper plating solution is generally 15 ° C. to 70 ° C., preferably 20 ° C. to 60 ° C.
• air stirring, rapid liquid flow stirring, mechanical stirring using stirring blades, or the like can be employed.
• This invention 8 is a manufacturing method of a copper plating board
• the non-conductive substrate refers to a resin substrate such as glass / epoxy resin, glass / polyimide resin, epoxy resin, polyimide resin, polycarbonate resin, ABS resin, and PET resin, or a glass substrate or a ceramic substrate.
• the electroless copper plating solution basically contains a soluble copper salt, a reducing agent, and a complexing agent, and can further contain various additives such as a surfactant and a pH adjusting agent, and 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 may be the same as that of the colloid stabilizer described in the above copper colloid catalyst solution. Specifically, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), triethylenetetraminehexaacetic acid (TTHA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), etc.
• EDTA ethylenediaminetetraacetic acid
• DTPA diethylenetriaminepentaacetic acid
• TTHA triethylenetetraminehexaacetic acid
• HEDTA hydroxyethylethylenediaminetriacetic acid
• NTA nitrilotriacetic acid
• IDA iminodiacetic acid
• Aminocarboxylic acids ethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine and other polyamines, monoethanolamine, diethanolamine, triethanolamine and other amino alcohols, citric acid, tartaric acid, Examples thereof include oxycarboxylic acids such as lactic acid and malic acid, thioglycolic acid, and glycine.
• 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 tetrafluoroboric acid.
• organic acids include oxycarboxylic acids such as glycolic acid and tartaric acid, and organic sulfonic acids such as methanesulfonic acid and 2-hydroxyethanesulfonic acid.
• the adsorption accelerator containing liquid and the copper colloid catalyst liquid of Example 1 each contain the following components.
• Cationic surfactant quaternary ammonium salt nonionic surfactant of diallylamine polymer: polyoxyalkylene branched decyl ether (copper colloid catalyst solution)
• Soluble copper salt A: Copper sulfate reducing agent
• B Sodium borohydride colloid stabilizer
• C Tetrasodium ethylenediaminetetraacetate (EDTA ⁇ 4Na)
• Non-reducing oligosaccharide D): sucrose
• Examples 2 to 5, 7, 9, 11, and 13 are examples based on Example 1.
• Example 2 Non-reducing oligosaccharide (D) is changed to trehalose
• Example 3 Non-reducing oligosaccharide (D) is used in combination with sucrose and trehalose
• Example 4 Non-reducing oligosaccharide (D) is changed to raffinose Modified
• Example 5 Non-reducing oligosaccharide (D) (sucrose) and reducing sugar (fructose) are used in combination.
• Example 7 Colloidal stabilizer (C) is changed to iminodiacetic acid.
• Example 9 Colloidal stabilizer (C ) was changed to citrate
• Example 11 the reducing agent (B) was changed to dimethylamine borane
• Example 13 the adsorption accelerator was changed to lauryldimethylbenzylammonium chloride and polyoxyalkylene branched decyl ether
• Examples 6, 8, 10, 12, and 14 are examples based on the second embodiment.
• Example 6 Combination of non-reducing oligosaccharide (D) (trehalose) and reducing sugar (maltose)
• Example 8 Changing colloidal stabilizer (C) to nitrilotriacetate
• Example 10 Colloidal stabilizer ( C) was changed to citrate
• Example 12 Reductant (B) was changed to dimethylamine borane
• Example 14 Adsorption accelerator was changed to lauryldimethylbenzylammonium chloride and polyoxyalkylene branched decyl ether
• Reference Examples 1 to 3 are examples in which the copper colloid catalyst solution contains a specific carbohydrate defined in the Prior Invention 2 in accordance with the Prior Invention 2 described above.
• the specific carbohydrate is as follows.
• Reference Example 1 Reducing disaccharide (maltose)
• Reference Example 2 Reducing monosaccharide (glucose)
• Reference example 3 sugar alcohol (xylitol)
• the following Comparative Examples 1 to 3 are blank examples as follows.
• Comparative Example 1 Example in which the copper colloid catalyst liquid does not contain the non-reducing oligosaccharide (D) Comparative example 2: The copper colloid catalyst liquid is specified in the above-mentioned prior invention 2 instead of the non-reducing oligosaccharide (D) Example 3 containing saccharides other than saccharides (starch) Comparative Example 3: Example of Immediately Performing Electroless Plating Process (c) From Catalyst Application Process (b) Without Adsorption Promotion Process (a)
• Example 1 Providedure for adsorption promotion, catalyst application, and electroless plating ⁇
• a glass / epoxy resin substrate (FR-4 manufactured by Panasonic Electric Works Co., Ltd., plate thickness: 1.0 mm) without a copper foil was used as a non-conductive sample substrate.
• the sample substrate is subjected to an adsorption promotion treatment using the following (a) adsorption accelerator-containing liquid, and then immersed in a copper colloid catalyst solution (b) below, followed by a catalyst application treatment, and then the following (c) ) Was subjected to electroless plating treatment.
• the sample substrate was immersed in a solution containing the following adsorption accelerator under conditions of 50 ° C.
• (B) Preparation of copper colloid catalyst solution [copper solution] Copper sulfate (as Cu 2+ ) 0.1 mol / L EDTA ⁇ 4Na 0.4mol / L Sucrose 0.5 mol / L
• a reducing agent solution was added dropwise to the above copper solution at 25 ° C. adjusted to pH 9.0 and stirred for 45 minutes to prepare a copper colloid catalyst solution.
• the molar ratio of each component of the catalyst solution is as follows.
• Example 2 Based on the above Example 1, except that the copper colloid catalyst solution was prepared with the following composition, the composition of the adsorption promoter-containing liquid and the composition of the electroless copper plating solution, as well as adsorption promotion, catalyst application, and electroless plating
• the processing conditions for each step were the same as in Example 1.
• Example 3 Based on the above Example 1, except that the copper colloid catalyst solution was prepared with the following composition, the composition of the adsorption promoter-containing liquid and the composition of the electroless copper plating solution, as well as adsorption promotion, catalyst application, and electroless plating
• the processing conditions for each step were the same as in Example 1.
• Example 4 Based on the above Example 1, except that the copper colloid catalyst solution was prepared with the following composition, the composition of the adsorption promoter-containing liquid and the composition of the electroless copper plating solution, as well as adsorption promotion, catalyst application, and electroless plating
• the processing conditions for each step were the same as in Example 1.
• Example 5 Based on the above Example 1, except that the copper colloid catalyst solution was prepared with the following composition, the composition of the adsorption promoter-containing liquid and the composition of the electroless copper plating solution, as well as adsorption promotion, catalyst application, and electroless plating The processing conditions for each step were the same as in Example 1.
• Example 6 Based on Example 2 above, except that the copper colloid catalyst solution was prepared with the following composition, the composition of the adsorption promoter-containing liquid and the composition of the electroless copper plating solution, as well as adsorption promotion, catalyst application, and electroless plating
• the processing conditions for each step were the same as in Example 2.
• Example 7 Based on the above Example 1, except that the copper colloid catalyst solution was prepared with the following composition, the composition of the adsorption promoter-containing liquid and the composition of the electroless copper plating solution, as well as adsorption promotion, catalyst application, and electroless plating
• the processing conditions for each step were the same as in Example 1.
• Example 8 Based on Example 2 above, except that the copper colloid catalyst solution was prepared with the following composition, the composition of the adsorption promoter-containing liquid and the composition of the electroless copper plating solution, as well as adsorption promotion, catalyst application, and electroless plating
• the processing conditions for each step were the same as in Example 2.
• Example 9 Based on the above Example 1, except that the copper colloid catalyst solution was prepared with the following composition, the composition of the adsorption promoter-containing liquid and the composition of the electroless copper plating solution, as well as adsorption promotion, catalyst application, and electroless plating
• the processing conditions for each step were the same as in Example 1.
• Example 10 Based on Example 2 above, except that the copper colloid catalyst solution was prepared with the following composition, the composition of the adsorption promoter-containing liquid and the composition of the electroless copper plating solution, as well as adsorption promotion, catalyst application, and electroless plating
• the processing conditions for each step were the same as in Example 2.
• Example 11 Based on the above Example 1, except that the copper colloid catalyst solution was prepared with the following composition, the composition of the adsorption promoter-containing liquid and the composition of the electroless copper plating solution, as well as adsorption promotion, catalyst application, and electroless plating
• the processing conditions for each step were the same as in Example 1.
• Example 12 Based on Example 2 above, except that the copper colloid catalyst solution was prepared with the following composition, the composition of the adsorption promoter-containing liquid and the composition of the electroless copper plating solution, as well as adsorption promotion, catalyst application, and electroless plating
• the processing conditions for each step were the same as in Example 2.
• Example 13 Based on Example 1 above, the composition of the electroless copper plating solution, and the promotion of adsorption, catalyst application, and electroless plating, except that the adsorption promoter containing liquid and the copper colloid catalyst liquid were prepared with the following compositions, respectively. The processing conditions for each step were the same as in Example 1.
• Copper solution Copper sulfate (as Cu 2+ ) 0.1 mol / L EDTA ⁇ 4Na 0.4mol / L Sucrose 0.5 mol / L
• Reducing agent solution Sodium borohydride 0.02 mol / L
• a reducing agent solution was dropped into the copper solution at 25 ° C. adjusted to pH 9.5 and stirred for 45 minutes to prepare a copper colloid catalyst solution.
• the molar ratio of each component of the catalyst solution is as follows.
• Example 14 Based on Example 2 above, the composition of the electroless copper plating solution, and the promotion of adsorption, catalyst application, and electroless plating, except that the adsorption promoter containing liquid and the copper colloid catalyst liquid were prepared with the following compositions, respectively. The processing conditions for each step were the same as in Example 2.
• Copper solution Copper sulfate (as Cu 2+ ) 0.1 mol / L EDTA ⁇ 4Na 0.4mol / L
• Reducing agent solution Sodium borohydride 0.02 mol / L
• a reducing agent solution was dropped into the copper solution at 25 ° C. adjusted to pH 9.5 and stirred for 45 minutes to prepare a copper colloid catalyst solution.
• the molar ratio of each component of the catalyst solution is as follows.
• Reference example 1 It is an example based on the preceding invention 2 described above, and the copper colloid catalyst solution contains a reducing disaccharide (maltose) which is a specific carbohydrate defined in the preceding invention 2, and is a non-reducing oligosaccharide used in the present invention. (D) is not included. That is, on the basis of Example 1 above, except that the copper colloid catalyst solution was prepared with the following composition, the composition of the adsorption promoter-containing liquid and the composition of the electroless copper plating solution, as well as adsorption promotion, catalyst application, and no The processing conditions for each step of electrolytic plating were the same as those in Example 1.
• a reducing disaccharide maltose
• D is not included. That is, on the basis of Example 1 above, except that the copper colloid catalyst solution was prepared with the following composition, the composition of the adsorption promoter-containing liquid and the composition of the electroless copper plating solution, as well as adsorption promotion, catalyst application, and no The processing
• the copper colloid catalyst solution is an example based on the preceding invention 2 described above, and contains a sugar alcohol (xylitol) which is a specific carbohydrate defined in the preceding invention 2, and is a non-reducing oligosaccharide (D ) Is not included. That is, on the basis of Example 1 above, except that the copper colloid catalyst solution was prepared with the following composition, the composition of the adsorption promoter-containing liquid and the composition of the electroless copper plating solution, as well as adsorption promotion, catalyst application, and no The processing conditions for each step of electrolytic plating were the same as those in Example 1.
• Example 3 This is an example in which the adsorption promotion step is omitted based on the first embodiment. That is, the sample substrate was immediately immersed in the copper colloid catalyst solution (b) of Example 1 without being subjected to adsorption promotion treatment, and the catalyst was applied, and further, the sample substrate was coated with the electroless copper plating solution (c) of Example 1. Electrolytic plating was performed. The treatment conditions for the steps of catalyst application and electroless plating, and the preparation conditions for the copper colloid catalyst solution and the electroless copper plating solution are the same as in Example 1.
• Example of stability test of copper colloid catalyst solution over time With respect to each of the copper colloid catalyst solutions constructed in Examples 1 to 14, Reference Examples 1 to 3, and Comparative Examples 1 to 3, the temporal stability of the colloid was evaluated based on the following evaluation criteria.
• evaluation criteria for the stability over time, in the preceding invention 2, the point of time “2 months after the bathing” was set as the branching point of the evaluation. The point of “3 months after bathing” was taken as the branch point for evaluation.
• evaluation criteria Double-circle: Even if three months or more passed after the bathing, it did not precipitate or decompose.
• ⁇ No precipitation or decomposition for 1 to 2 months after bathing.
• ⁇ Precipitation or decomposition within 1 month after bathing.
• X Colloidal particles were not formed, or precipitated or decomposed immediately after the bath.
• Example of sustainability test of catalytic activity of copper colloid catalyst solution For each of the copper colloid catalyst liquids bathed in Examples 1 to 14, Reference Examples 1 to 3, and Comparative Examples 1 to 3, the sustainability of the catalyst activity was evaluated based on the following evaluation criteria.
• the “stable stability of the catalyst solution” in the test example is mainly intended for observing the properties of the catalyst solution itself, and the “sustainability of catalyst activity” in the test example is that the function of imparting the catalyst is maintained. The main objective is to observe the effectiveness of the function.
• evaluation criteria A: A uniform and uniform copper film was obtained when the catalyst was applied with a catalyst solution that had passed 3 months after the bathing.
• the non-reducing oligosaccharide (D) defined in the present invention is necessary (shift from ⁇ evaluation to ⁇ evaluation).
• the non-reducing oligosaccharide (D) defined in the present invention is contained in the catalyst solution instead of the specific carbohydrate defined in the prior invention 2, the sustainability of the catalytic activity is remarkably improved. (Transition from ⁇ evaluation to ⁇ evaluation). From the above, the superiority of the catalyst solutions of Examples 1 to 14 over the catalyst solutions of Reference Examples 1 to 3 in terms of stability over time and sustainability of catalyst activity is clear, and the present invention is used as a saccharide.
• the non-reducing oligosaccharide (D) defined in (1) is selected, the maintenance of the copper colloid catalyst solution can be greatly simplified as compared with the reference example, and there is an advantage that the plating processing cost can be reduced.
• Example 1 a non-conductive substrate is subjected to adsorption promotion treatment (pretreatment) with an adsorption accelerator containing a quaternary ammonium salt of diallylamine polymer which is a cationic surfactant, and copper sulfate is dissolved into a soluble copper salt (A). And a catalyst with a copper colloid catalyst solution containing sodium borohydride as a reducing agent (B), ethylenediaminetetraacetate as a colloid stabilizer (C), and sucrose as a non-reducing oligosaccharide (D), This is an example of electroless copper plating.
• Example 1 both the stability of the catalyst solution over time and the sustainability of the catalyst activity are both good, and both obtained by electroless plating when using the catalyst solution immediately after the building bath or at the time when 3 months have passed since the building bath.
• the obtained copper film showed no appearance irregularities and lack of plating and showed an excellent appearance.
• Example 2 is an example in which the non-reducing oligosaccharide (D) in Example 1 was changed to trehalose.
• Example 2 as with Example 1, the stability of the catalyst solution with time and the sustainability of the catalyst activity were good, and the obtained copper film exhibited an excellent appearance.
• Example 3 is an example in which sucrose and trehalose are used in combination as the non-reducing oligosaccharide (D)
• Example 4 is an example in which raffinose is used as the non-reducing oligosaccharide (D).
• Examples 3 to 4 similar to Example 1, high stability over time, long-lasting catalytic activity, and excellent film appearance were exhibited.
• Examples 5 to 6 are examples in which the non-reducing oligosaccharide (D) defined in the present invention and the reducing sugar (fructose, maltose), which are specific carbohydrates defined in the prior invention 2, are used in combination. Again, in Examples 5 to 6, as in Example 1 or 2, high aging stability and sustained catalytic activity and excellent film appearance were exhibited.
• Examples 7 to 10 are examples in which the colloidal stabilizer (C) was changed in the catalyst solution of Example 1 or 2, and Examples 11 to 12 were the reducing agent (B) in the catalyst solution of Example 1 or 2. This is an example in which is changed.
• Examples 7 to 12 similar to these basic examples 1 and 2, high stability with time, long-lasting catalytic activity, and excellent film appearance were exhibited.
• Examples 13 to 14 are examples in which the adsorption accelerator used in the adsorption promotion step (a) in Example 1 or 2 was changed. Again, in Examples 13 to 14, as with the basic Example 1 or 2, high stability over time, sustained catalytic activity, and excellent film appearance were exhibited.
• Examples 9 to 10 are examples in which citrate was used as the colloid stabilizer (C) and the pH of the catalyst solution was set in the acidic region. As in Examples 1 to 8 and 11 to 14, in which EDTA ⁇ 4Na or iminodiacetic acid was used as the colloid stabilizer (C) and the pH of the catalyst solution was set in the alkaline region, There was no change in the evaluation of the stability over time, the sustainability of the catalytic activity, and the appearance of the film.
• the copper colloid catalyst solution of the present invention has significantly improved temporal stability and sustainability of catalytic activity.
• electroless copper plating is performed using the copper colloid catalyst solution, the resulting copper film is excellent. Appearance is given.

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