JP2009046761A - Surface treatment agent - Google Patents
Surface treatment agent Download PDFInfo
- Publication number
- JP2009046761A JP2009046761A JP2008177891A JP2008177891A JP2009046761A JP 2009046761 A JP2009046761 A JP 2009046761A JP 2008177891 A JP2008177891 A JP 2008177891A JP 2008177891 A JP2008177891 A JP 2008177891A JP 2009046761 A JP2009046761 A JP 2009046761A
- Authority
- JP
- Japan
- Prior art keywords
- surface treatment
- treatment agent
- mass
- acid
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/08—Radicals containing only hydrogen and carbon atoms
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax, thiol
- H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
本発明は、表面処理剤に関する。さらに詳しくは、銅又はその合金からなる表面を有する基材の表面を処理するための表面処理剤に関する。 The present invention relates to a surface treatment agent. More specifically, the present invention relates to a surface treatment agent for treating the surface of a substrate having a surface made of copper or an alloy thereof.
従来、銅又はその合金からなる配線回路の防錆やはんだ付け性の向上のための表面処理剤として、ベンズイミダゾールなどのイミダゾール化合物を含む水溶性プリフラックス（ＯＳＰ）が知られている（例えば、特許文献１〜４参照）。 Conventionally, water-soluble preflux (OSP) containing an imidazole compound such as benzimidazole is known as a surface treatment agent for improving rust prevention and solderability of a wiring circuit made of copper or an alloy thereof (for example, (See Patent Documents 1 to 4).
近年、環境への配慮から、鉛フリーはんだが多く使用されている。鉛フリーはんだは、従来の共晶はんだと比べて融点が高いことから、高温下ではんだ付けを行う必要がある。従って、鉛フリーはんだを用いてはんだ付けを行う際に使用される表面処理剤によって形成される皮膜には、耐熱性が要求される。耐熱性に優れた皮膜を形成する表面処理剤として、亜鉛化合物を含有する表面処理剤が知られている（例えば、特許文献５参照）。しかし、この表面処理剤によって形成された皮膜は、未だ耐熱性が十分であるとはいえない。 In recent years, a lot of lead-free solder has been used in consideration of the environment. Since lead-free solder has a higher melting point than conventional eutectic solder, it must be soldered at a high temperature. Therefore, heat resistance is required for the film formed by the surface treatment agent used when soldering using lead-free solder. As a surface treatment agent that forms a film having excellent heat resistance, a surface treatment agent containing a zinc compound is known (see, for example, Patent Document 5). However, it cannot be said that the film formed by this surface treatment agent has sufficient heat resistance.
本発明は、前記従来技術に鑑みなされたものであり、従来の共晶はんだのみならず、鉛フリーはんだを用いてはんだ付けを行なう際に使用することができ、耐熱性に優れた皮膜を形成する表面処理剤を提供することを課題とする。 The present invention has been made in view of the above prior art, and can be used when soldering using not only conventional eutectic solder but also lead-free solder, forming a film having excellent heat resistance. It is an object of the present invention to provide a surface treatment agent.
本発明は、銅又はその合金からなる基材の表面を処理するための表面処理剤であって、イミダゾール化合物及び糖アルコールの溶液からなり、亜鉛イオンを含有してなる表面処理剤に関する。 The present invention relates to a surface treatment agent for treating the surface of a substrate made of copper or an alloy thereof, which is made of a solution of an imidazole compound and a sugar alcohol and contains zinc ions.
本発明の表面処理剤は、従来の共晶はんだのみならず、鉛フリーはんだを用いてはんだ付けを行なう際に使用することができ、耐熱性に優れた皮膜を形成するという効果を奏する。 The surface treating agent of the present invention can be used when soldering using not only conventional eutectic solder but also lead-free solder, and has an effect of forming a film having excellent heat resistance.
本発明の表面処理剤は、イミダゾール化合物及び糖アルコールの溶液からなり、亜鉛イオンを含有する。 The surface treatment agent of the present invention comprises a solution of an imidazole compound and a sugar alcohol and contains zinc ions.
イミダゾール化合物としては、例えば、２−プロピルベンズイミダゾール、２−シクロヘキシルベンズイミダゾール、２−フェニルベンズイミダゾール、２−ベンジルベンズイミダゾール、２−（３−フェニルプロピル）−５−メチルベンズイミダゾール、２−（メルカプトメチル）ベンズイミダゾール、２−（１−ナフチルメチル）ベンズイミダゾール、２−（５’−フェニル）ペンチルベンズイミダゾール、２−フェニルエチルベンズイミダゾール、５−クロロ−２−オクチルベンズイミダゾールなどのベンズイミダゾール化合物；２，４−ジフェニル−５−メチルイミダゾール、２−ペンチルイミダゾール、２−ウンデシル−４−メチルイミダゾール、２，４−ジメチルイミダゾール、２，４−ジフェニルイミダゾール、２，４，５−トリフェニルイミダゾール、２−ベンジルイミダゾール、２−ベンジル−４−メチルイミダゾールなどのその他のイミダゾール化合物などが挙げられる。これらのイミダゾール化合物は、それぞれ単独で用いてもよく、２種以上を併用してもよい。 Examples of the imidazole compound include 2-propylbenzimidazole, 2-cyclohexylbenzimidazole, 2-phenylbenzimidazole, 2-benzylbenzimidazole, 2- (3-phenylpropyl) -5-methylbenzimidazole, and 2- (mercapto). Benzimidazole compounds such as methyl) benzimidazole, 2- (1-naphthylmethyl) benzimidazole, 2- (5′-phenyl) pentylbenzimidazole, 2-phenylethylbenzimidazole, 5-chloro-2-octylbenzimidazole; 2,4-diphenyl-5-methylimidazole, 2-pentylimidazole, 2-undecyl-4-methylimidazole, 2,4-dimethylimidazole, 2,4-diphenylimidazole, 2,4,5- Li phenylimidazole, 2-benzyl imidazole, and other imidazole compounds such as 2-benzyl-4-methylimidazole. These imidazole compounds may be used alone or in combination of two or more.
本発明の表面処理剤におけるイミダゾール化合物の濃度は、皮膜形成性を向上させる観点から、好ましくは０．０１質量％以上、より好ましくは０．０５質量％以上であり、イミダゾール化合物を本発明の表面処理剤に十分に溶解させ、本発明の表面処理剤の均一性を向上させる観点から、好ましくは５質量％以下、より好ましくは１質量％以下である。前述の観点から、本発明の表面処理剤におけるイミダゾール化合物の濃度は、好ましくは０．０１〜５質量％、より好ましくは０．０５〜１質量％である。 The concentration of the imidazole compound in the surface treatment agent of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of improving film-forming properties. From the viewpoint of sufficiently dissolving in the treatment agent and improving the uniformity of the surface treatment agent of the present invention, it is preferably 5% by mass or less, more preferably 1% by mass or less. From the above viewpoint, the concentration of the imidazole compound in the surface treatment agent of the present invention is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass.
本発明においては、糖アルコールが本発明の表面処理剤に用いられている点に、１つの大きな特徴がある。糖アルコールは、本発明の表面処理剤中に溶出した銅イオンと結合するので、銅又はその合金からなる基材上での本発明の表面処理剤の皮膜形成性が高められるとともに、異種金属上への皮膜形成を抑制することができる。 The present invention has one major feature in that sugar alcohol is used in the surface treatment agent of the present invention. Since the sugar alcohol binds to the copper ions eluted in the surface treatment agent of the present invention, the film-forming property of the surface treatment agent of the present invention on the substrate made of copper or an alloy thereof is enhanced, and on the dissimilar metal It is possible to suppress film formation on the surface.
本発明の表面処理剤をプリント配線板の製造に使用した場合、銅または銅合金からなる配線回路の防錆やはんだ付け性向上のために使用することができる。 When the surface treating agent of the present invention is used for the production of a printed wiring board, it can be used for rust prevention and solderability improvement of a wiring circuit made of copper or a copper alloy.
プリント配線板上の銅からなる配線には、金、銀、アルミニウム、スズなどの銅以外の金属が共存している場合がある。このような場合、従来のイミダゾール化合物を含む表面処理剤を用いたとき、異種金属表面にも皮膜が形成されるため、表面処理剤の皮膜に変色が生じるおそれがある。これに対して、本発明の表面処理剤を用いた場合には、表面処理剤の皮膜の変色を抑制することができる。 Metals other than copper, such as gold, silver, aluminum, and tin, may coexist in the wiring made of copper on the printed wiring board. In such a case, when a conventional surface treatment agent containing an imidazole compound is used, a film is also formed on the surface of the dissimilar metal, which may cause discoloration of the film of the surface treatment agent. On the other hand, when the surface treatment agent of the present invention is used, discoloration of the film of the surface treatment agent can be suppressed.
さらに、本願発明の表面処理剤では、このような異種金属への皮膜形成を抑制する添加剤として従来の銅イオンキレート剤ではなく、糖アルコールが用いられているので、本願発明の表面処理剤は、皮膜を形成させる際に得られた廃液の処理が容易であり、環境負荷を低減するという利点を有する。 Furthermore, in the surface treatment agent of the present invention, a sugar alcohol is used instead of a conventional copper ion chelating agent as an additive for suppressing film formation on such different metals. The treatment of the waste liquid obtained when the film is formed is easy and has the advantage of reducing the environmental load.
糖アルコールとしては、例えば、マンニトール、ソルビトール、キシリトール、エリスリトール、マルチトール、ラクチトールなどの単糖アルコール、スクロースなどの二糖アルコール、オリゴ糖アルコールなどの多糖アルコールなどが挙げられる。これらの糖アルコールは、それぞれ単独で用いてもよく、２種以上を併用してもよい。糖アルコールのなかでは、金などの異種金属上への皮膜の形成を抑制することができる観点から、マンニトール、ソルビトール及びキシリトールからなる群より選ばれた少なくとも１種が好ましい。 Examples of the sugar alcohol include monosaccharide alcohols such as mannitol, sorbitol, xylitol, erythritol, maltitol, and lactitol, disaccharide alcohols such as sucrose, polysaccharide alcohols such as oligosaccharide alcohol, and the like. These sugar alcohols may be used alone or in combination of two or more. Among sugar alcohols, at least one selected from the group consisting of mannitol, sorbitol, and xylitol is preferable from the viewpoint of suppressing the formation of a film on a different metal such as gold.
本発明の表面処理剤における糖アルコールの濃度は、本発明の表面処理剤からなる皮膜の耐熱性を向上させる観点から、好ましくは０．０１質量％以上、より好ましくは０．０５質量％以上、さらに好ましくは０．１質量％以上であり、経済性の観点から、好ましくは７質量％以下、より好ましくは４質量％以下、さらに好ましくは１質量％以下である。前述の観点から、本発明の表面処理剤における糖アルコールの濃度は、好ましくは０．０１〜７質量％、より好ましくは０．０５〜４質量％、さらに好ましくは０．１〜１質量％である。 The concentration of the sugar alcohol in the surface treatment agent of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of improving the heat resistance of the film comprising the surface treatment agent of the present invention. More preferably, it is 0.1% by mass or more, and from the viewpoint of economy, it is preferably 7% by mass or less, more preferably 4% by mass or less, and further preferably 1% by mass or less. From the above viewpoint, the concentration of the sugar alcohol in the surface treatment agent of the present invention is preferably 0.01 to 7% by mass, more preferably 0.05 to 4% by mass, and still more preferably 0.1 to 1% by mass. is there.
イミダゾール化合物及び糖アルコールの溶液は、イミダゾール化合物及び糖アルコールを溶媒に溶解させることによって調製される。 The solution of imidazole compound and sugar alcohol is prepared by dissolving the imidazole compound and sugar alcohol in a solvent.
溶媒としては、例えば、イオン交換水、純水、超純水などの水；有機酸、無機酸などの酸；水溶性有機溶媒などが挙げられる。これらの溶媒のなかでは、イミダゾール化合物の溶解を促進させる観点から、酸及び水溶性有機溶媒が好ましい。 Examples of the solvent include water such as ion-exchanged water, pure water, and ultrapure water; acids such as organic acids and inorganic acids; and water-soluble organic solvents. Among these solvents, acids and water-soluble organic solvents are preferable from the viewpoint of promoting dissolution of the imidazole compound.
酸としては、有機酸及び無機酸が挙げられる。有機酸及び無機酸は、それぞれ単独で用いてもよく、併用してもよい。 Examples of the acid include organic acids and inorganic acids. The organic acid and the inorganic acid may be used alone or in combination.
有機酸としては、例えば、ギ酸、酢酸、プロピオン酸、グリコール酸、ｎ−酪酸、イソ酪酸、アクリル酸、クロトン酸、イソクロトン酸、シュウ酸、マロン酸、コハク酸、アジピン酸、マレイン酸、アセチレンジカルボン酸、モノクロロ酢酸、トリクロロ酢酸、モノブロモ酢酸、乳酸、オキシ酪酸、グリセリン酸、酒石酸、リンゴ酸、クエン酸、エナント酸、カプロン酸などが挙げられる。これらの有機酸は、それぞれ単独で用いてもよく、２種以上を併用してもよい。 Examples of organic acids include formic acid, acetic acid, propionic acid, glycolic acid, n-butyric acid, isobutyric acid, acrylic acid, crotonic acid, isocrotonic acid, oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, acetylenedicarboxyl Examples include acids, monochloroacetic acid, trichloroacetic acid, monobromoacetic acid, lactic acid, oxybutyric acid, glyceric acid, tartaric acid, malic acid, citric acid, enanthic acid, and caproic acid. These organic acids may be used alone or in combination of two or more.
無機酸としては、例えば、塩酸、硫酸、硝酸、リン酸などが挙げられる。これらの無機酸は、それぞれ単独で用いてもよく、２種以上を併用してもよい。 Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like. These inorganic acids may be used alone or in combination of two or more.
なお、イミダゾール化合物の酸に対する溶解度は、イミダゾール化合物及び酸の種類によって異なるので、イミダゾール化合物の種類に応じて酸の種類及びその量を選択することが好ましい。 In addition, since the solubility with respect to the acid of an imidazole compound changes with kinds of an imidazole compound and an acid, it is preferable to select the kind and amount of an acid according to the kind of imidazole compound.
本発明の表面処理剤における酸の濃度は、イミダゾール化合物を十分に溶解させる観点から、好ましくは１質量％以上、より好ましくは１．５質量％以上、さらに好ましくは３質量％であり、本発明の表面処理剤の皮膜形成性を向上させる観点から、好ましくは８０質量％以下、より好ましくは５０質量％以下、さらに好ましくは３０質量％以下である。前述の観点から、本発明の表面処理剤における酸の濃度は、好ましくは１〜８０質量％、より好ましくは１．５〜５０質量％、さらに好ましくは３〜３０質量％である。 The concentration of the acid in the surface treatment agent of the present invention is preferably 1% by mass or more, more preferably 1.5% by mass or more, and further preferably 3% by mass from the viewpoint of sufficiently dissolving the imidazole compound. From the viewpoint of improving the film-forming property of the surface treatment agent, it is preferably 80% by mass or less, more preferably 50% by mass or less, and still more preferably 30% by mass or less. From the above viewpoint, the acid concentration in the surface treatment agent of the present invention is preferably 1 to 80% by mass, more preferably 1.5 to 50% by mass, and further preferably 3 to 30% by mass.
水溶性有機溶媒としては、例えば、メタノール、エタノール、イソプロピルアルコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテルなどが挙げられる。 Examples of the water-soluble organic solvent include methanol, ethanol, isopropyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like.
本発明の表面処理剤における水溶性有機溶媒の濃度は、イミダゾール化合物を十分に溶解させる観点から、好ましくは１質量％以上、より好ましくは１．５質量％以上、さらに好ましくは３質量％以上であり、本発明の表面処理剤の皮膜形成性を向上させる観点から、好ましくは８０質量％以下、より好ましくは３０質量％以下、さらに好ましくは１５質量％以下である。前述の観点から、本発明の表面処理剤における水溶性有機溶媒の濃度は、好ましくは１〜８０質量％、より好ましくは１．５〜３０質量％、さらに好ましくは３〜１５質量％である。 From the viewpoint of sufficiently dissolving the imidazole compound, the concentration of the water-soluble organic solvent in the surface treatment agent of the present invention is preferably 1% by mass or more, more preferably 1.5% by mass or more, and further preferably 3% by mass or more. From the viewpoint of improving the film-forming property of the surface treatment agent of the present invention, it is preferably 80% by mass or less, more preferably 30% by mass or less, and further preferably 15% by mass or less. From the above viewpoint, the concentration of the water-soluble organic solvent in the surface treatment agent of the present invention is preferably 1 to 80% by mass, more preferably 1.5 to 30% by mass, and further preferably 3 to 15% by mass.
本発明の表面処理剤における溶媒の濃度は、本発明の表面処理剤にイミダゾール化合物、糖アルコール及び亜鉛イオンが所望の量で含有されるように調整される。 The concentration of the solvent in the surface treatment agent of the present invention is adjusted so that the surface treatment agent of the present invention contains imidazole compound, sugar alcohol and zinc ions in desired amounts.
亜鉛イオンは、例えば、本発明の表面処理剤に用いられる成分に溶解したときに亜鉛イオンを生じる化合物を用いることにより、本発明の表面処理剤に含有させることができる。前記「表面処理剤に用いられる成分に溶解したときに亜鉛イオンを生じる化合物」を以下、「亜鉛イオンを生じる化合物」という。亜鉛イオンを生じる化合物は、本発明の表面処理剤に用いられる成分によって溶解しやすい亜鉛化合物であることが好ましい。例えば、本発明の表面処理剤に酢酸が含まれている場合には、亜鉛イオンを生じる化合物として、酢酸亜鉛は、酢酸に容易に溶解することから好ましい。 Zinc ions can be contained in the surface treatment agent of the present invention by using, for example, a compound that generates zinc ions when dissolved in the components used in the surface treatment agent of the present invention. The “compound that generates zinc ions when dissolved in the components used for the surface treatment agent” is hereinafter referred to as “compound that generates zinc ions”. The compound that generates zinc ions is preferably a zinc compound that is easily dissolved by the components used in the surface treatment agent of the present invention. For example, when acetic acid is contained in the surface treatment agent of the present invention, zinc acetate is preferable because it easily dissolves in acetic acid as a compound that generates zinc ions.
亜鉛イオンを生じる化合物としては、例えば、酸化亜鉛、酢酸亜鉛、ギ酸亜鉛、硫化亜鉛、硫酸亜鉛、リン酸亜鉛、塩化亜鉛などが挙げられる。これらの亜鉛イオンを生じる化合物は、それぞれ単独で用いてもよく、２種以上を併用してもよい。亜鉛イオンを生じる化合物のなかでは、溶解性が良好であり、液中に安定的に存在させることができる観点から、酸化亜鉛、酢酸亜鉛及びギ酸亜鉛からなる群より選ばれた少なくとも１種が好ましい。 Examples of the compound that generates zinc ions include zinc oxide, zinc acetate, zinc formate, zinc sulfide, zinc sulfate, zinc phosphate, and zinc chloride. These compounds that generate zinc ions may be used alone or in combination of two or more. Among the compounds that generate zinc ions, at least one selected from the group consisting of zinc oxide, zinc acetate, and zinc formate is preferable from the viewpoint of good solubility and stable presence in the liquid. .
亜鉛イオンは、前記溶媒に亜鉛イオンを生じる化合物を溶解させることにより、生成することができる。 Zinc ions can be generated by dissolving a compound that generates zinc ions in the solvent.
本発明の表面処理剤における亜鉛イオンの濃度は、本発明の表面処理剤によって形成される皮膜の耐熱性を向上させる観点から、好ましくは０．０３質量％以上、より好ましくは０．１質量％以上、さらに好ましくは０．２質量％以上であり、イミダゾール化合物の溶解性を向上させる観点から、好ましくは０．５質量％以下である。前述の観点から、本発明の表面処理剤における亜鉛イオンの濃度は、好ましくは０．０３〜０．５質量％、より好ましくは０．１〜０．５質量％、さらに好ましくは０．２〜０．５質量％である。 The concentration of zinc ions in the surface treatment agent of the present invention is preferably 0.03% by mass or more, more preferably 0.1% by mass from the viewpoint of improving the heat resistance of the film formed by the surface treatment agent of the present invention. As mentioned above, More preferably, it is 0.2 mass% or more, From a viewpoint of improving the solubility of an imidazole compound, Preferably it is 0.5 mass% or less. From the above viewpoint, the concentration of zinc ions in the surface treatment agent of the present invention is preferably 0.03 to 0.5% by mass, more preferably 0.1 to 0.5% by mass, and still more preferably 0.2 to 0.5% by mass.
なお、本発明の表面処理剤における亜鉛イオンの濃度は、本発明の表面処理剤における亜鉛イオンを生じる化合物の溶解量における亜鉛の量を求め、この亜鉛の量を表面処理剤の全体の量で除することによって求められた値を意味する。 The concentration of zinc ions in the surface treatment agent of the present invention is determined by determining the amount of zinc in the dissolved amount of the compound that generates zinc ions in the surface treatment agent of the present invention, and the amount of zinc is the total amount of the surface treatment agent. The value obtained by dividing.
本発明の表面処理剤は、イミダゾール化合物、糖アルコール及び亜鉛イオンを生じる化合物を所定量で溶媒に溶解させることにより、容易に調製することができる。イミダゾール化合物、糖アルコール及び亜鉛化合物を溶媒に溶解させるときの溶媒の温度は、特に限定されず、通常、常温であればよい。 The surface treating agent of the present invention can be easily prepared by dissolving imidazole compound, sugar alcohol and a compound that generates zinc ions in a solvent in a predetermined amount. The temperature of the solvent when the imidazole compound, sugar alcohol, and zinc compound are dissolved in the solvent is not particularly limited, and may usually be room temperature.
なお、本発明の表面処理剤には、銅又はその合金からなる基材の表面で、本発明の表面処理剤の皮膜形成性を向上させるために、銅イオンが含有されていてもよい。 In addition, in order to improve the film formation property of the surface treatment agent of this invention on the surface of the base material which consists of copper or its alloy, the surface treatment agent of this invention may contain the copper ion.
また、本発明の表面処理剤には、さらに、必要に応じて皮膜形成補助剤、溶解安定剤などの添加剤が含有されていてもよい。 In addition, the surface treatment agent of the present invention may further contain additives such as a film formation auxiliary agent and a dissolution stabilizer, if necessary.
本発明の表面処理剤を適用することができる基材としては、例えば、銅又はその合金で導体パターンが形成されたプリント配線板などが例示される。プリント配線板としては、例えば、硬質プリント配線板、フレキシブルプリント配線板などが挙げられる。本発明の表面処理剤は、プリント配線板の銅回路部に好適に適用することができる。銅の合金は、好ましくは、銅５０質量％以上と錫、金、銀、アルミニウムなどの銅以外の金属５０質量％以下とを含む。 Examples of the substrate to which the surface treating agent of the present invention can be applied include a printed wiring board in which a conductor pattern is formed of copper or an alloy thereof. Examples of the printed wiring board include a hard printed wiring board and a flexible printed wiring board. The surface treating agent of the present invention can be suitably applied to the copper circuit portion of a printed wiring board. The copper alloy preferably contains 50% by mass or more of copper and 50% by mass or less of a metal other than copper, such as tin, gold, silver, and aluminum.
本発明の表面処理剤を基材に適用するときの表面処理剤の温度は、通常、２５〜３５℃程度であればよい。本発明の表面処理剤は、例えば、浸漬法、スプレー法などにより、基材に適用することができる。浸漬法を採用する場合、基材を本発明の表面処理剤に浸漬する時間は、例えば、１５〜１２０秒間程度であればよい。 The temperature of the surface treatment agent when the surface treatment agent of the present invention is applied to a substrate may be usually about 25 to 35 ° C. The surface treating agent of the present invention can be applied to a substrate by, for example, a dipping method, a spray method or the like. When the immersion method is employed, the time for immersing the substrate in the surface treatment agent of the present invention may be, for example, about 15 to 120 seconds.
本発明の表面処理剤を例えば自動処理装置等の装置を用いて基材に使用する場合には、例えば、前記表面処理剤の全成分を所定の組成になるように混合した後に装置に供給する方法や、各成分を個別に装置に供給し、装置内で前記各成分を混合して所定の組成とする方法などを採用することができる。後者の方法を採用する場合、各成分の濃度は、特に限定されない。例えば、高濃度の各成分を装置に供給し、装置内で酸や水を用いて所定の濃度となるように希釈してもよい。 When the surface treatment agent of the present invention is used as a base material using an apparatus such as an automatic treatment apparatus, for example, all components of the surface treatment agent are mixed so as to have a predetermined composition and then supplied to the apparatus. A method, a method of individually supplying each component to the apparatus, and mixing the respective components in the apparatus to obtain a predetermined composition can be employed. When the latter method is employed, the concentration of each component is not particularly limited. For example, each component having a high concentration may be supplied to the apparatus and diluted to a predetermined concentration using acid or water in the apparatus.
次に、本発明を実施例に基づいてさらに詳細に説明するが、本発明は、かかる実施例のみに限定されるものではない。 Next, the present invention will be described in more detail based on examples. However, the present invention is not limited to such examples.
実施例１〜７及び比較例１〜９
表１に示すイミダゾール化合物、糖アルコールおよび亜鉛イオンを生成する化合物として亜鉛化合物を表１に示す組成となるように、２５℃の酸とイオン交換水との混合溶液に溶解させ、表面処理剤を得た。
Examples 1-7 and Comparative Examples 1-9
As a compound that produces imidazole compounds, sugar alcohols, and zinc ions shown in Table 1, a zinc compound is dissolved in a mixed solution of acid at 25 ° C. and ion-exchanged water so as to have the composition shown in Table 1, and a surface treatment agent is used. Obtained.
一方、ガラスエポキシ基材〔日立化成工業（株）製、品番：ＧＥＡ−６７Ｎ、厚さ：１．６ｍｍ〕の片面に厚さ１８μｍの銅箔が貼付された片面銅張の基材を用意し、これに縦：０．３ｍｍ、横：８ｍｍの矩形状の導体パターン４０個を形成し、処理用基材を作製した。該処理用基材をマイクロエッチング剤〔メック（株）製、商品名：メックブライトＣＢ−８０１〕に浸漬し、銅箔表面を１μｍだけエッチングして水洗した。次に、この基材を１枚ずつ前記で得られた液温が３０℃の表面処理剤にそれぞれ６０秒間浸漬し、水洗し、乾燥させた。 On the other hand, a single-sided copper-clad base material in which a 18 μm-thick copper foil is attached to one side of a glass epoxy base material (manufactured by Hitachi Chemical Co., Ltd., product number: GEA-67N, thickness: 1.6 mm) is prepared. Then, 40 rectangular conductor patterns having a length of 0.3 mm and a width of 8 mm were formed thereon, and a substrate for processing was produced. The substrate for treatment was dipped in a microetching agent (trade name: MEC BRITE CB-801, manufactured by MEC Co., Ltd.), and the copper foil surface was etched by 1 μm and washed with water. Next, each of the substrates was immersed in a surface treatment agent having a liquid temperature of 30 ° C. obtained above for 60 seconds, washed with water, and dried.
前記基材の各導体パターン上の中央部分に、直径０．４ｍｍ、厚さ１００μｍの円形状の印刷パターンとなるように、ソルダーペースト（ソルダーコート（株）製、品番：ＴＡＳ６５０ Ｓ１０／０１１／Ｍ９．５）を印刷した後、熱風循環型リフロー炉に入れ、基材の表面温度が２２５〜２３０℃となるように印刷された基材を４０秒間加熱した。該基材の熱処理の後、各基材の拡がったソルダーペーストの最も長い径の長さを光学顕微鏡で計測し、その平均値を算出した。その結果を表１に示す。 Solder paste (manufactured by Solder Coat Co., Ltd., product number: TAS650 S10 / 011 / M9) is formed so that a circular printed pattern having a diameter of 0.4 mm and a thickness of 100 μm is formed in the central portion on each conductor pattern of the substrate. After printing 5), the substrate was placed in a hot-air circulating reflow furnace, and the substrate printed so that the surface temperature of the substrate was 225 to 230 ° C. was heated for 40 seconds. After the heat treatment of the base material, the length of the longest diameter of the solder paste in which each base material spread was measured with an optical microscope, and the average value was calculated. The results are shown in Table 1.
表１に示された結果から、実施例１〜７で得られた表面処理剤を用いた場合には、比較例１〜９と対比して、はんだが広がりやすいことがわかる。このことから、実施例１〜７で得られた表面処理剤は、はんだ濡れ拡がり性に優れていることがわかる。 From the results shown in Table 1, it can be seen that when the surface treating agent obtained in Examples 1 to 7 is used, the solder is likely to spread as compared with Comparative Examples 1 to 9. From this, it can be seen that the surface treatment agents obtained in Examples 1 to 7 are excellent in solder wettability.
実施例８〜１２及び比較例１０
ガラスエポキシ基材〔日立化成工業（株）製、品番：ＧＥＡ−６７Ｎ、厚さ：１．６ｍｍ〕の両面に厚さ１８μｍの銅箔を貼付し、両面銅張積層板（縦：７．８ｃｍ、横：４．８ｃｍ）を得た。この積層板に直径が０．８ｍｍのスルーホール６００個を形成して処理用基材を作製した。
Examples 8-12 and Comparative Example 10
A 18 μm thick copper foil was pasted on both sides of a glass epoxy substrate (manufactured by Hitachi Chemical Co., Ltd., product number: GEA-67N, thickness: 1.6 mm), and double-sided copper-clad laminate (length: 7.8 cm) , Width: 4.8 cm). 600 through-holes having a diameter of 0.8 mm were formed on this laminated plate to produce a processing substrate.
この処理用基材をマイクロエッチング剤〔メック（株）製、商品名：メックブライトＣＢ−８０１）に浸漬し、銅箔表面を１μｍだけエッチングして水洗した後、各実施例及び比較例10で得られた温度が３０℃の表面処理剤に、該処理用基材をそれぞれ１枚ずつ６０秒間浸漬し、水洗し、乾燥させた。 The substrate for this treatment was immersed in a micro-etching agent [MEC Co., Ltd., trade name: MEC BRITE CB-801], and the copper foil surface was etched by 1 μm and washed with water. Each of the substrates for treatment was immersed in a surface treatment agent having a temperature of 30 ° C. for 60 seconds, washed with water, and dried.
次に、乾燥後の各処理用基材にリフロー処理を１〜５回施した。リフロー処理には、熱風循環型リフロー炉を用い、１回のリフロー処理につき、処理用基材の表面温度を２４０〜２４５℃に調節し、処理用基材を４０秒間加熱した。 Next, the reflow treatment was performed 1 to 5 times on each substrate for treatment after drying. For the reflow treatment, a hot air circulation type reflow furnace was used, and the surface temperature of the treatment base material was adjusted to 240 to 245 ° C. for one reflow treatment, and the treatment base material was heated for 40 seconds.
リフロー処理の後、ポストフラックス剤〔（株）アサヒ化学研究所製、品番：ＡＧＦ−８８０〕を用いて、スプレーにより各処理用基材にポストフラックス処理を施した。 After the reflow treatment, post-flux treatment was applied to each treatment substrate by spraying using a post-flux agent [manufactured by Asahi Chemical Laboratory, product number: AGF-880].
ポストフラックス処理の後、各処理用基材にフロー処理を施した。フロー処理では、処理用基材の表面温度を１００℃に調節し、８０秒間加熱することにより、プレヒート処理を施した後、錫９６．５質量％、銀３質量％及び銅０．５質量％からなるはんだの温度を２５５℃に調節してダブルウェーブ処理を処理用基材に施すことにより行った。なお、ダブルウェーブ処理では、処理用基材とはんだとを２．５秒間接触させた後、２．５秒間処理用基材とはんだとを非接触にし、再度処理用基材とはんだとを３秒間接触させる処理を施した。 After the post flux treatment, each treatment substrate was subjected to a flow treatment. In the flow treatment, the surface temperature of the substrate for treatment is adjusted to 100 ° C. and heated for 80 seconds to give a preheat treatment, and then 96.5% by mass of tin, 3% by mass of silver and 0.5% by mass of copper. The temperature of the solder consisting of was adjusted to 255 ° C. and subjected to double wave treatment on the substrate for treatment. In the double wave treatment, after the treatment base material and the solder are brought into contact with each other for 2.5 seconds, the treatment base material and the solder are brought into non-contact for 2.5 seconds, and the treatment base material and the solder are again connected to each other. The contact process was performed for 2 seconds.
次に、各処理用基材のはんだ付けの状態を目視にて確認した。その結果を表２に示す。なお、表２において、「はんだ揚がり合格率」は、全スルーホール６００個に対するはんだ揚がりが合格したスルーホールの割合である。はんだ揚がりが合格のスルーホールとは、目視にて観察したとき、はんだがスルーホール内に完全に充填されていることを意味する。 Next, the soldering state of each processing substrate was visually confirmed. The results are shown in Table 2. In Table 2, “Solder Lift Pass Rate” is the ratio of through holes that passed the solder lift to all 600 through holes. A through-hole having passed the solder lifting means that the solder is completely filled in the through-hole when visually observed.
表２に示された結果から、実施例８〜１２では、比較例１０と比べて、はんだ揚がりの合格率が高いことがわかる。これは、皮膜中に含まれている亜鉛が、銅よりも先に酸化されるので、はんだ付けの際の加熱による銅表面の酸化が抑制されることに基づくものと考えられる。このことから、実施例８〜１２によれば、高温処理後にも高いはんだ揚がり性を維持することができることがわかる。 From the results shown in Table 2, it can be seen that in Examples 8 to 12, the passing rate of solder lifting is higher than that in Comparative Example 10. This is presumably based on the fact that the zinc contained in the film is oxidized prior to copper, so that the oxidation of the copper surface by heating during soldering is suppressed. From this, according to Examples 8-12, it turns out that high solder liftability can be maintained even after high temperature processing.
以上の結果から、本発明の表面処理剤を用いて銅又はその合金からなる基材の表面を処理した場合には、その皮膜に含まれている亜鉛が銅よりも先に酸化されることから、皮膜が形成された基材を長期保管している間や、はんだ付けを行う際の加熱によって銅又はその合金が酸化することを抑制することができ、高温処理後であっても、高いはんだ濡れ性を維持することができる。 From the above results, when the surface of the base material made of copper or an alloy thereof is treated using the surface treating agent of the present invention, zinc contained in the film is oxidized before copper. It is possible to suppress the oxidation of copper or its alloy during the long-term storage of the substrate on which the film is formed, or by heating when performing soldering. The wettability can be maintained.
また、皮膜中では、イミダゾール化合物と亜鉛との錯体が形成されるので、はんだ付け性が相乗的に向上するという効果が奏される。 Moreover, since the complex of an imidazole compound and zinc is formed in a film | membrane, the effect that solderability improves synergistically is show | played.
したがって、本発明の表面処理剤を用いれば、高温加熱処理後であっても、高いはんだ濡れ性を有する防錆皮膜を銅又はその合金からなる基材上に形成することができる。 Therefore, if the surface treating agent of the present invention is used, a rust preventive film having high solder wettability can be formed on a substrate made of copper or an alloy thereof even after high-temperature heat treatment.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008177891A JP2009046761A (en) | 2007-07-20 | 2008-07-08 | Surface treatment agent |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007189950 | 2007-07-20 | ||
| JP2008177891A JP2009046761A (en) | 2007-07-20 | 2008-07-08 | Surface treatment agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2009046761A true JP2009046761A (en) | 2009-03-05 |
Family
ID=40149312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008177891A Pending JP2009046761A (en) | 2007-07-20 | 2008-07-08 | Surface treatment agent |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2009046761A (en) |
| KR (1) | KR20090009734A (en) |
| CN (1) | CN101348913B (en) |
| DE (1) | DE102008033348A1 (en) |
| TW (1) | TW200907107A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106460188A (en) * | 2014-06-24 | 2017-02-22 | 奥野制药工业株式会社 | Composition for blackening copper-based or silver-based metals |
| JP2017203194A (en) * | 2016-05-12 | 2017-11-16 | 株式会社タムラ製作所 | Water-soluble preflux, electronic substrate using the same, and surface processing method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105750354A (en) * | 2016-03-31 | 2016-07-13 | 常州易藤电气有限公司 | Method for manufacturing copper-magnesium alloy stranded wire for cold tinned railway |
| CN105880432A (en) * | 2016-03-31 | 2016-08-24 | 常州易藤电气有限公司 | Preparation method of copper-magnesium alloy stranded wire used for hot-tinned railway |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0313584A (en) * | 1989-06-09 | 1991-01-22 | Shikoku Chem Corp | Surface treatment of copper and copper alloy |
| JPH0499285A (en) * | 1990-08-10 | 1992-03-31 | Shikoku Chem Corp | Surface treatment of copper and copper alloy |
| JPH04165083A (en) * | 1990-10-29 | 1992-06-10 | Shikoku Chem Corp | Surface treatment of copper and copper alloy |
| JPH05163585A (en) * | 1991-12-12 | 1993-06-29 | Shikoku Chem Corp | Surface treatment of copper and copper alloy |
| JPH09316649A (en) * | 1996-05-27 | 1997-12-09 | Matsushita Electric Ind Co Ltd | Electroless plating solution |
| JPH10251867A (en) * | 1997-03-07 | 1998-09-22 | Shikoku Chem Corp | Surface treating agent for copper and copper alloy |
| JP2005349439A (en) * | 2004-06-10 | 2005-12-22 | Shikoku Chem Corp | Surface treating agent for copper or copper alloy and soldering method |
| JP2007115497A (en) * | 2005-10-20 | 2007-05-10 | Mitsubishi Materials Corp | Nickel-coated copper fine particle, manufacturing method of the same, conductive paste, and manufacturing method of conductive film |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4772645A (en) * | 1986-05-07 | 1988-09-20 | Minnesota Mining And Manufacturing Company | Epoxy resin composition |
| JPH05237688A (en) | 1992-02-28 | 1993-09-17 | Shikoku Chem Corp | Flux composition for soldering |
| JP2923596B2 (en) | 1993-08-11 | 1999-07-26 | メック株式会社 | Surface treatment agent for copper and copper alloys using imidazole compounds |
| US5747623A (en) * | 1994-10-14 | 1998-05-05 | Tonen Corporation | Method and composition for forming ceramics and article coated with the ceramics |
| JPH11177218A (en) | 1997-12-12 | 1999-07-02 | Tamura Kaken Co Ltd | Component equipped with metal surface for electronic circuit, and surface protecting agent therefor |
-
2008
- 2008-07-01 TW TW097124748A patent/TW200907107A/en unknown
- 2008-07-08 JP JP2008177891A patent/JP2009046761A/en active Pending
- 2008-07-16 DE DE102008033348A patent/DE102008033348A1/en not_active Withdrawn
- 2008-07-17 CN CN2008101335670A patent/CN101348913B/en not_active Expired - Fee Related
- 2008-07-18 KR KR1020080069864A patent/KR20090009734A/en not_active Application Discontinuation
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0313584A (en) * | 1989-06-09 | 1991-01-22 | Shikoku Chem Corp | Surface treatment of copper and copper alloy |
| JPH0499285A (en) * | 1990-08-10 | 1992-03-31 | Shikoku Chem Corp | Surface treatment of copper and copper alloy |
| JPH04165083A (en) * | 1990-10-29 | 1992-06-10 | Shikoku Chem Corp | Surface treatment of copper and copper alloy |
| JPH05163585A (en) * | 1991-12-12 | 1993-06-29 | Shikoku Chem Corp | Surface treatment of copper and copper alloy |
| JPH09316649A (en) * | 1996-05-27 | 1997-12-09 | Matsushita Electric Ind Co Ltd | Electroless plating solution |
| JPH10251867A (en) * | 1997-03-07 | 1998-09-22 | Shikoku Chem Corp | Surface treating agent for copper and copper alloy |
| JP2005349439A (en) * | 2004-06-10 | 2005-12-22 | Shikoku Chem Corp | Surface treating agent for copper or copper alloy and soldering method |
| JP2007115497A (en) * | 2005-10-20 | 2007-05-10 | Mitsubishi Materials Corp | Nickel-coated copper fine particle, manufacturing method of the same, conductive paste, and manufacturing method of conductive film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106460188A (en) * | 2014-06-24 | 2017-02-22 | 奥野制药工业株式会社 | Composition for blackening copper-based or silver-based metals |
| US10184186B2 (en) | 2014-06-24 | 2019-01-22 | Okuno Chemical Industries Co., Ltd. | Composition for blackening copper-based or silver-based metals |
| JP2017203194A (en) * | 2016-05-12 | 2017-11-16 | 株式会社タムラ製作所 | Water-soluble preflux, electronic substrate using the same, and surface processing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101348913B (en) | 2011-09-07 |
| DE102008033348A1 (en) | 2009-01-22 |
| TW200907107A (en) | 2009-02-16 |
| KR20090009734A (en) | 2009-01-23 |
| CN101348913A (en) | 2009-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4063475B2 (en) | Copper or copper alloy etchant | |
| US9932678B2 (en) | Microetching solution for copper, replenishment solution therefor and method for production of wiring board | |
| US5439783A (en) | Composition for treating copper or copper alloys | |
| JP6338232B1 (en) | Copper surface roughening method and wiring board manufacturing method | |
| JP6243792B2 (en) | Manufacturing method of circuit board on which solder is solidified, manufacturing method of circuit board on which electronic parts are mounted, and cleaning composition for flux | |
| JP3952410B2 (en) | Metal surface treatment agent, printed circuit board, and metal surface treatment method for printed circuit board | |
| JP2006022400A (en) | Surface treating agent for copper or copper alloy and its utilization | |
| JP2010070838A (en) | Aqueous solution for surface treatment of metal and method for reducing whisker on metal surface | |
| JP2009046761A (en) | Surface treatment agent | |
| KR20070090808A (en) | Surface treating agent and method for manufacturing coating using the same | |
| JP2005068530A (en) | Surface-treating agent, printed circuit board, and method for surface-treating metal on printed circuit board | |
| JP5985368B2 (en) | Surface treatment solution for copper or copper alloy and use thereof | |
| JP5321878B2 (en) | Surface treatment agent for copper or copper alloy and use thereof | |
| JP6598917B2 (en) | Copper micro-etchant | |
| JP4968909B2 (en) | Surface treatment agent | |
| KR102298998B1 (en) | Organic coating agent for surface treatment of plating layer containing copper and surface treatment of plating layer using the same | |
| KR20090046513A (en) | Pre-flux performing selective coating for pwb | |
| JP2009057596A (en) | Sealing agent for gold-plated film, and its use | |
| JP2022054426A (en) | Surface treatment method of printed wiring board and manufacturing method of printed wiring board | |
| JPH07118880A (en) | Metal surface protective agent and treatment using the same | |
| KR19990014550A (en) | Surface treatment method of copper and copper alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090909 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20100901 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20100903 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20111227 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120120 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20120928 |