JP2006328494A - Control method of copper plating bath and producing method of copper plating coat - Google Patents
Control method of copper plating bath and producing method of copper plating coat Download PDFInfo
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Abstract
Description
本発明は、銅めっき浴の管理方法及びこの管理方法により管理された銅めっき浴を用い、特に、グラビア印刷等に使用されるグラビア版及び電鋳法により作成される金型等に施す銅めっき被膜の製造方法に関するものである。 The present invention uses a copper plating bath management method and a copper plating bath managed by this management method, and in particular, copper plating applied to gravure plates used for gravure printing, etc., and dies created by electroforming The present invention relates to a method for producing a coating.
電析により銅めっき皮膜を形成するための銅めっき浴として、例えば硫酸銅浴、シアン化銅浴、ホウフッ化銅浴、ピロ燐酸銅浴等があるが、グラビア印刷やグラビアコート等に用いられるグラビア版のように機械的加工適性が要求される用途においては硫酸銅浴を基本とし、それに他成分を添加して機械的加工適性のある銅めっき皮膜を得るのが一般的である。 Examples of copper plating baths for forming a copper plating film by electrodeposition include a copper sulfate bath, a copper cyanide bath, a copper borofluoride bath, a copper pyrophosphate bath, etc., but gravure used for gravure printing, gravure coating, etc. In applications where mechanical workability is required, such as a plate, it is common to use a copper sulfate bath as a base and to add a copper plating film having mechanical workability by adding other components thereto.
上記機械的加工適性を得るための添加成分（添加剤）として、表面の光沢と均一電着性の向上を目的としたレベラー、ブライトナー、キャリアーと呼ばれる添加剤のほかに、機械的彫刻（バイトによる切削）に適した物理的性質を確保するためのハードナーと呼ばれる添加剤の添加が行われている。 In addition to additives called levelers, brighteners, and carriers for the purpose of improving surface gloss and uniform electrodeposition, mechanical engraving (bite) Addition of an additive called a hardener has been carried out to ensure physical properties suitable for cutting.
このように、グラビア版の機械的彫刻適正に関する物理的性質として、従来から皮膜のビッカース硬さ等の押込み硬さによる評価が行われており、この評価方法による判定はおおむね妥当なものとされている。このビッカース硬さによる評価では彫刻される銅めっき皮膜の適正な物性範囲は約１８０〜２３０とされているが、上記の添加剤即ちハードナーなしの硫酸銅浴ではこの硬さを実現することは困難であった。そのためハードナーの添加により実現されるビッカース硬さの増加を測定して、ハードナーの浴中濃度を推定し、それによって添加量を管理する方法が行われている。 Thus, as a physical property related to the mechanical engraving of a gravure plate, it has been conventionally evaluated by indentation hardness such as Vickers hardness of the film, and the determination by this evaluation method is generally appropriate. Yes. According to the evaluation based on the Vickers hardness, the appropriate physical property range of the copper plating film to be engraved is about 180 to 230, but it is difficult to realize this hardness with the above-described additive, that is, a copper sulfate bath without a hardener. Met. Therefore, a method of measuring the increase in the Vickers hardness realized by the addition of the hardener to estimate the concentration of the hardener in the bath and thereby controlling the amount added is performed.
これらの添加剤の管理のための手段として、理想的には浴中濃度の直接定量が挙げられるが、工業的にはレベラー、ブライトナー成分の一部についてのみサイクリックボルタンメトリックストリッピング法、高速液体クロマトグラフィー法、イオンクロマログラフィー法、キャピラリー電気泳動法で浴中濃度の定量が可能であるというのが現状である（例えば、非特許文献１参照。）。 As a means for controlling these additives, ideally direct quantification of the concentration in the bath can be mentioned, but industrially, only a part of the leveler and brightener components are cyclic voltammetric stripping, high-speed At present, the concentration in a bath can be determined by liquid chromatography, ion chromatography, or capillary electrophoresis (see, for example, Non-Patent Document 1).
しかしながら、機械彫刻適性のための添加剤としてのハードナーのビッカース硬さによる上記のような管理方法では、特に浴中濃度の増加にともなうビッカース硬さの増加が飽和する高濃度域での判定が測定精度の問題からも困難で、適正値以上の添加により起こる光沢異常やキズ状欠陥の発生といっためっき皮膜外観の欠陥と彫刻適性の変動といういわば「過剰添加」を防止することが困難であった。 However, the management method as described above based on the Vickers hardness of the hardener as an additive for machine engraving suitability, particularly in the high concentration range where the increase in Vickers hardness with increasing concentration in the bath is measured. It was difficult due to the problem of accuracy, and it was difficult to prevent so-called “excessive addition” in terms of defects in the appearance of the plating film such as abnormal luster and flaw-like defects caused by addition of more than the appropriate value, and fluctuations in engraving suitability.
また、銅めっき浴に用いられる添加剤の効果の発現機構、特に、硬さを増大させる効果の機構についてはまだ完全には解明されていない。しかし、ハードナーの添加の増加にともない銅めっき皮膜の硬さが増大することと、ハードナーの種類と添加量によって銅めっき皮膜の硬さの経時低下の程度が異なることはすでに報告されている（例えば、非特許文献２参照。）。 Further, the mechanism of the effect of the additive used in the copper plating bath, particularly the mechanism of the effect of increasing the hardness, has not been completely elucidated. However, it has already been reported that the hardness of the copper plating film increases with the addition of the hardener, and that the degree of temporal decrease in the hardness of the copper plating film varies depending on the type and amount of the hardener (for example, Non-patent document 2).
また、先に本発明者等はハードナーの添加の増加にともなう銅めっき皮膜の硬さの増大は、結晶粒の微細化によってもたらされることを定量的に解明したが、未知濃度であるめっき液に対しての分析、管理方法の確立には至っていない（例えば、非特許文献３参照。）。 In addition, the present inventors quantitatively elucidated that the increase in the hardness of the copper plating film accompanying the increase in the addition of the hardener is caused by the refinement of the crystal grains. However, analysis and management methods have not been established (for example, see Non-Patent Document 3).
さらにまた、特にハードナーの添加量が低濃度の場合、著しい銅めっき皮膜の硬さの経時低下となるため、銅めっき皮膜の形成後、機械彫刻までの経時により機械彫刻適正が劣化し、彫刻の安定性に欠けるという問題点があった。 Furthermore, especially when the amount of hardener added is low, the hardness of the copper plating film decreases significantly with time, so the mechanical engraving suitability deteriorates over time until the machine engraving after the formation of the copper plating film. There was a problem of lack of stability.
以下に、上記先行技術文献を示す。
本発明は、かかる従来技術の問題点等に鑑みなされたものであり、その課題とするところは、たとえ添加量が低濃度の場合でも添加剤としてのハードナーの効果の変動を抑制し、特にグラビア版の製造工程における機械彫刻に適した銅めっき皮膜を安定的に製造するために、銅めっき浴中に添加するハードナーの添加濃度を管理する銅めっき浴の管理方法を提供することにある。 The present invention has been made in view of such problems of the prior art, and the object of the present invention is to suppress fluctuations in the effect of the hardener as an additive even when the addition amount is low, and in particular, gravure. In order to stably produce a copper plating film suitable for machine engraving in the plate production process, it is an object of the present invention to provide a copper plating bath management method for managing the addition concentration of a hardener added to a copper plating bath.
本発明に於いて上記課題を達成するために、まず請求項１の発明では、銅めっき浴の添加剤の濃度を管理する銅めっき浴の管理方法において、前記添加剤を含むめっき浴から析出した銅めっき皮膜の引張試験物性と、前記銅めっき皮膜を加温したものの引張試験物性から添加剤濃度を定量し、管理することを特徴とする銅めっき浴の管理方法としたものである。 In order to achieve the above object in the present invention, first, in the invention of claim 1, in the copper plating bath management method for managing the concentration of the additive of the copper plating bath, it is deposited from the plating bath containing the additive. The copper plating bath management method is characterized in that the additive concentration is quantified and managed from the tensile test physical properties of the copper plating film and the tensile test physical properties of the heated copper plating film.
また、請求項２の発明では、前記何れの引張試験物性も、公称歪み量、引張強さ、破断強さの少なくとも一つであることを特徴とする請求項１記載の銅めっき浴の管理方法としたものである。 In the invention of claim 2, the tensile test physical property is at least one of a nominal strain amount, a tensile strength, and a breaking strength. It is what.
さらにまた、請求項３の発明では、請求項１または２記載の銅めっき浴の管理方法で管理されためっき浴を用いて、電気めっきまたは電鋳法にてめっきすることを特徴とする銅めっき被膜の製造方法としたものである。 Furthermore, in the invention of claim 3, copper plating is performed by electroplating or electroforming using the plating bath managed by the copper plating bath management method of claim 1 or 2. This is a method for producing a coating film.
本発明は以上の構成であるから、下記に示す如き効果がある。 Since this invention is the above structure, there exist the following effects.
即ち、上記請求項に係る発明によれば、めっき皮膜の引張試験物性と、それを加温したものの引張試験物性物性から添加剤濃度を定量し、管理することによって、この銅めっき皮膜の物理的性質の評価を、従来のビッカース硬さ等の押し込み硬さに代え、引張変形における応力−歪み曲線の特性値から求められる公称歪み量、引張り強さ、破断強さのいずれかとしたので、押込み硬さでは認識出来なかったより詳細な情報を得ることができ、さらにその情報と添加剤濃度との相関を把握することによって、上記請求項３に係る銅めっき皮膜の製造方法を完成するに至った。即ち、上記のような銅めっき浴中の添加剤の濃度を管理することによって、たとえ添加量が低濃度の場合でも添加剤の効果の変動を抑制し、特に、グラビア版の製造工程における機械彫刻に適した銅めっき皮膜を安定的に製造することが出来るようになった。 That is, according to the invention according to the above claim, the physical properties of the copper plating film are determined by quantifying and managing the additive concentration from the tensile test physical properties of the plating film and the tensile test physical properties of the heated film. Instead of the indentation hardness such as the conventional Vickers hardness, the evaluation of the property is any one of the nominal strain amount, tensile strength, and breaking strength obtained from the characteristic value of the stress-strain curve in tensile deformation. Thus, more detailed information that could not be recognized could be obtained, and further, by grasping the correlation between the information and the additive concentration, the method for producing a copper plating film according to claim 3 was completed. That is, by controlling the concentration of the additive in the copper plating bath as described above, even if the addition amount is low, fluctuations in the effect of the additive are suppressed, and in particular, mechanical engraving in the gravure plate manufacturing process. It is now possible to stably produce a copper plating film suitable for the above.
さらに具体的には、添加剤としてのハードナーの銅めっき浴中の濃度低下によって起こる銅めっき皮膜表面の光沢異常と硬さの低下を制御するための濃度定量が可能になり、かつ室温での経時による銅皮膜物性低下の定量的予測が可能になる。また、ハードナーの銅めっき浴中濃度の過多によって起こる銅めっき皮膜表面のキズ状欠陥の防止と適正硬さを超えることによる彫刻刃の破損を防止することができる効果がある。 More specifically, it is possible to determine the concentration of the hardener as an additive in order to control the abnormality of gloss and hardness of the surface of the copper plating film caused by the decrease in the concentration in the copper plating bath. This makes it possible to quantitatively predict the deterioration of the physical properties of the copper film. In addition, there are effects of preventing scratch defects on the surface of the copper plating film caused by excessive concentration of the hardener in the copper plating bath and preventing the engraving blade from being damaged due to exceeding the appropriate hardness.
以下本発明を実施するための最良の形態を説明する。 The best mode for carrying out the present invention will be described below.
まず、例えば、グラビア版の銅めっき皮膜の製造の銅めっき浴としては、硫酸銅浴を用い、特に断りのない限り、その銅めっき浴の組成としては、硫酸銅５水和物２００〜２４０ｋｇ／ｍ3 、硫酸４０〜８０ｋｇ／ｍ3 、塩化ナトリウム１８０〜２４０ｋｇ／ｍ3 をイオン交換水に溶解したものに添加剤を加えたものが用いられる。 First, for example, a copper sulfate bath is used as a copper plating bath for the production of a copper plating film of a gravure plate. Unless otherwise specified, the composition of the copper plating bath is copper sulfate pentahydrate 200-240 kg / m 3, sulfuric acid 40 to 80 kg / m 3, which the sodium chloride 180~240kg / m 3 plus additive is dissolved in a deionized water is used.
また、表１には、本発明の銅めっき浴の管理方法及び銅めっき被膜の製造方法に用いられる銅めっき浴添加剤の一覧を示した。 Table 1 shows a list of copper plating bath additives used in the copper plating bath management method and the copper plating film manufacturing method of the present invention.
以下に、本発明の具体的実施例について説明する。 Specific examples of the present invention will be described below.
上記表２に示すハードナーとして、コスモＧ１（大和特殊社製）を用い、その濃度を変えた硫酸銅浴を作成し、長さ４００ｍｍ、直径２００ｍｍの回転するシリンダーに前記条件でそれぞれの濃度の硫酸銅浴を用いて銅めっきを行い銅めっき皮膜を作成した。 As a hardener shown in Table 2 above, Cosmo G1 (manufactured by Daiwa Special Co., Ltd.) was used, and copper sulfate baths having different concentrations were prepared. Copper plating was performed using a copper bath to prepare a copper plating film.
上記で得られた銅めっき皮膜を剥離後、一定形状に裁断して厚み測定し、前記の条件で引張試験を行い応力−歪み曲線を得た。そこから引張強さを読み取り添加剤の濃度を変えた時の引張強さと添加剤（ハードナー）濃度との関係式を得た。その結果を図１に示した。この図１に示す引張強さと添加剤濃度の矢印内が、得られた銅めっき皮膜を加温しない場合の銅めっき浴の管理方法に於ける管理範囲である。 The copper plating film obtained above was peeled, then cut into a fixed shape, measured for thickness, and subjected to a tensile test under the above conditions to obtain a stress-strain curve. From that, the tensile strength was read and the relational expression between the tensile strength and the additive (hardener) concentration when the concentration of the additive was changed was obtained. The results are shown in FIG. The inside of the arrows of tensile strength and additive concentration shown in FIG. 1 is the management range in the copper plating bath management method when the obtained copper plating film is not heated.
また、上記で得られた銅めっき皮膜を隔離後、一定形状に裁断して厚み測定し、その後オイルバス中で一定温度（約１００℃）で３０分間加温してから水冷し、それを上記の条件で引張試験を行い応力−歪み曲線を得た。そこから引張強さを読み取り添加剤の濃度を変えた時の銅めっき皮膜の加温後の引張強さと添加剤（ハードナー）濃度との関係式を得た。その結果を図２に示した。この図２に示す引張強さと添加剤濃度の矢印内が、得られた銅めっき皮膜を加温した場合の銅めっき浴の管理方法に於ける管理範囲である。 In addition, after isolating the copper plating film obtained above, it was cut into a certain shape and measured for thickness, and then heated in an oil bath at a constant temperature (about 100 ° C.) for 30 minutes and then water-cooled. A tensile test was performed under the conditions described above to obtain a stress-strain curve. From this, the tensile strength was read, and the relational expression between the tensile strength after heating of the copper plating film and the additive (hardener) concentration when the concentration of the additive was changed was obtained. The results are shown in FIG. The inside of the arrows of tensile strength and additive concentration shown in FIG. 2 is the management range in the copper plating bath management method when the obtained copper plating film is heated.
さらにまた、上記で得られた銅めっき皮膜を隔離後、室温で３ケ月間放置した後一定形状に裁断して厚み測定し、その後前記の条件で引張試験を行い応力−歪み曲線を得た。そ
こから引張強さを読み取り添加剤の濃度を変えた時の銅めっき皮膜の室温経時後の引張強さと添加剤（ハードナー）濃度との関係式を得た。その結果を図３に示した。この図３に示す引張強さと添加剤濃度の矢印内が、得られた銅めっき皮膜を加温せず、室温で３ケ月間放置した場合の銅めっき浴の管理方法に於ける管理範囲である。
Furthermore, the copper plating film obtained above was isolated, allowed to stand at room temperature for 3 months, then cut into a fixed shape, measured for thickness, and then subjected to a tensile test under the above conditions to obtain a stress-strain curve. From that, the tensile strength was read, and the relational expression between the tensile strength of the copper plating film after room temperature aging and the additive (hardener) concentration when the concentration of the additive was changed was obtained. The results are shown in FIG. The inside of the arrow of the tensile strength and additive concentration shown in FIG. 3 is the management range in the management method of the copper plating bath when the obtained copper plating film is left unheated for 3 months at room temperature. .
図１、図２および図３より、得られた銅めっき皮膜の剥離直後と加温後及び室温経時後の銅めっき皮膜の引張強さと添加剤濃度の関係を整理すると、添加剤濃度の増加にともなって加温後及び室温経時後の引張強さと、その低下するまでの期間が変化していく相関が定量的に捉えられた。また、加温条件と室温経時との相関も得られた。よって、本発明の銅めっき浴の管理方法および銅めっき皮膜の製造方法によって、従来の銅めっき浴の管理方法では管理し得なかったハードナーの過剰な添加を抑えられることが確認できた。 From FIG. 1, FIG. 2 and FIG. 3, when the relationship between the tensile strength of the copper plating film and the additive concentration immediately after peeling of the obtained copper plating film, after heating, and after aging at room temperature is arranged, the additive concentration increases. At the same time, the correlation between the tensile strength after heating and after aging at room temperature and the period until the strength decreased was quantitatively captured. In addition, a correlation between heating conditions and room temperature was also obtained. Therefore, it was confirmed that the excessive addition of the hardener that could not be managed by the conventional copper plating bath management method can be suppressed by the copper plating bath management method and the copper plating film manufacturing method of the present invention.
本発明は、出版・包装・建材分野をはじめとして広く用いられているグラビア印刷用シリンダーの銅めっき皮膜の表面外観及び機械彫刻適性の安定化に用いられる。さらには電鋳法により作成される金型及び一般的には銅箔の製造工程の安定化にも有用である。 INDUSTRIAL APPLICABILITY The present invention is used for stabilizing the surface appearance and machine engraving suitability of a copper plating film of a gravure cylinder widely used in the fields of publishing, packaging and building materials. Furthermore, it is useful for stabilization of the manufacturing process of the metal mold | die produced by an electroforming method, and generally copper foil.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09241882A (en) * | 1996-03-11 | 1997-09-16 | Mitsui Mining & Smelting Co Ltd | Production of copper foil for printed circuit board |
| JP2000273684A (en) * | 1999-03-26 | 2000-10-03 | Ishihara Chem Co Ltd | Electrolytic copper plating bath and semiconductor device forming copper wiring by the plating bath |
| JP2001247994A (en) * | 1990-05-30 | 2001-09-14 | Ga Tek Inc | Electrodeposited copper foil and method for manufacturing the foil by using electrolyte solution with low chlorine ion |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247994A (en) * | 1990-05-30 | 2001-09-14 | Ga Tek Inc | Electrodeposited copper foil and method for manufacturing the foil by using electrolyte solution with low chlorine ion |
| JPH09241882A (en) * | 1996-03-11 | 1997-09-16 | Mitsui Mining & Smelting Co Ltd | Production of copper foil for printed circuit board |
| JP2000273684A (en) * | 1999-03-26 | 2000-10-03 | Ishihara Chem Co Ltd | Electrolytic copper plating bath and semiconductor device forming copper wiring by the plating bath |
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