JP2005097676A - Plated copper film, photogravure using it and mold for lens - Google Patents
Plated copper film, photogravure using it and mold for lens Download PDFInfo
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Abstract
Description
本発明は、銅めっき技術に関し、さらに詳細には、硬度、光沢性、レベリング性に優れるとともに、切削性に優れ加工安定性の良い銅めっき皮膜及びその銅めっき皮膜を設けて作製されるグラビア版並びにレンズ金型に関する。 The present invention relates to copper plating technology, and more specifically, a copper plating film having excellent hardness, glossiness, and leveling properties, and having excellent machinability and processing stability, and a gravure plate produced by providing the copper plating film And a lens mold.
以下に特許文献を示す。
例えば、スルホールを有するプリント基板の銅めっきを良好な均一電着性を実現し、めっき液の寿命を長期に安定させるために添加剤濃度の測定はCVS法(Cyclic Voltammetric Stripping)により行なわれている例がある。(特許文献1参照)
グラビア版、これを利用したレンズ金型、または平型板を切削して作製するフレネル金型は切削性を良好にするため硬化剤を添加して、ビッカース硬度Hv190〜220範囲に保っている。硬度を上げるために、硬化剤としてチオ尿素誘導体が単独で添加される場合もある。
For example, the additive concentration is measured by the CVS method (Cyclic Voltammetric Stripping) in order to achieve good throwing power of copper plating on printed circuit boards having through holes and to stabilize the plating solution life for a long period of time. There is an example. (See Patent Document 1)
A gravure plate, a lens mold using the gravure plate, or a Fresnel mold manufactured by cutting a flat mold plate has a Vickers hardness Hv of 190 to 220 by adding a curing agent in order to improve the machinability. In order to increase the hardness, a thiourea derivative may be added alone as a curing agent.
しかしながら、硬化剤を光沢剤、抑制剤、レベリング剤と併用してめっき液中に添加する場合、CVS法では他の成分の影響を無くすことができず、これらの成分の分析管理ができない。ハルセルなどの目視試験でのみ可能であるが、数値管理によるきめ細かい管理ができなかった。 However, when a curing agent is added to a plating solution in combination with a brightener, an inhibitor, and a leveling agent, the CVS method cannot eliminate the influence of other components, and analysis and management of these components cannot be performed. Although it is possible only by a visual test such as a hull cell, detailed control by numerical control was not possible.
そこで、たとえばめっき液中のイオウ化合物濃度をICP発光分析装置を用いて、20〜60mg/Lに維持管理してめっきすると、良好な銅めっき層が得られる例がある。(特許文献2参照)
しかしながら、特に銅めっき方法を用いてグラビア版やレンズ金型を作製する場合、めっき液中のイオウ化合物濃度の管理だけでは不十分であって、グラビア版の硬度が経時変化を起こしたり、スタイラス針の欠損が発生したり、めっき後の加工が安定しなかった。レンズ金型を切削する場合、レンチキュラーレンズの形状が設計値と異なるなど良好に切削できない場合が生じた。さらに、フレネルレンズ金型作製においては、添加剤管理が適正に添加されていないとバリ発生とか、バイトの切削途中での欠損等の不具合が発生するという問題があった。
Thus, for example, when the plating is performed while maintaining the sulfur compound concentration in the plating solution at 20 to 60 mg / L using an ICP emission analyzer, there is an example in which a good copper plating layer is obtained. (See Patent Document 2)
However, especially when producing a gravure plate or lens mold using a copper plating method, it is not sufficient to control the concentration of the sulfur compound in the plating solution, and the hardness of the gravure plate may change over time, or a stylus needle Deficiency occurred or the processing after plating was not stable. When cutting a lens mold, there were cases where cutting was not possible because the shape of the lenticular lens was different from the design value. Furthermore, in the manufacture of a Fresnel lens mold, there are problems such as occurrence of burrs and defects such as chipping during cutting of the tool unless the additive management is properly added.
本発明は、上記の課題を解決するためになされたものであって、硬度、光沢性、レベリ
ング性に優れるとともに、切削性に優れ加工安定性の良い銅めっき皮膜及びその銅めっき皮膜を設けて作製されるグラビア版及びレンズ金型を提供することを目的とする。
The present invention has been made in order to solve the above-described problems, and has a copper plating film having excellent hardness, glossiness, and leveling properties, and excellent in machinability and processing stability, and the copper plating film. An object is to provide a gravure plate and a lens mold to be manufactured.
発明者等は、有機イオウ化合物濃度管理だけでは十分ではなく、硬化剤になりうる有機窒素含有ポリマーの添加濃度に着目してこれを適正に管理し、硬度、光沢性、レベリング性を良好にして加工安定性の良い銅めっき皮膜を形成できることを発見し、本発明に至ったものである。 The inventors have not only managed the organic sulfur compound concentration alone, but focused on the addition concentration of the organic nitrogen-containing polymer that can be a curing agent, and appropriately managed this to improve the hardness, glossiness, and leveling properties. The present inventors have found that a copper plating film with good processing stability can be formed, and have reached the present invention.
すなわち、請求項1に係る発明は、銅の結晶配向性が無配向であることを特徴とする銅めっき皮膜である。 That is, the invention according to claim 1 is a copper plating film characterized in that the crystal orientation of copper is non-oriented.
また、請求項2に係る発明は、請求項1記載の銅めっき皮膜を、金属シリンダー上に設け、グラビア印刷用セルを形成したことを特徴とするグラビア版である。 The invention according to claim 2 is a gravure plate in which the copper plating film according to claim 1 is provided on a metal cylinder to form a gravure printing cell.
また、請求項3に係る発明は、金属板上に請求項1記載の銅めっき皮膜を設け、該銅めっき皮膜にレンズパターン形状と逆形状の型を切削形成してなることを特徴とするレンズ金型である。 According to a third aspect of the present invention, a lens is obtained by providing the copper plating film according to the first aspect on a metal plate, and cutting and forming a mold having a shape opposite to the lens pattern shape on the copper plating film. It is a mold.
また、請求項4に係る発明は、前記レンズパターンが、レンチキュラーレンズ、フレネルレンズ、マイクロレンズ、もしくはプリズムレンズのいずれかのパターンであることを特徴とする請求項3記載のレンズ金型である。 The invention according to claim 4 is the lens mold according to claim 3, wherein the lens pattern is a pattern of any one of a lenticular lens, a Fresnel lens, a micro lens, and a prism lens.
また、請求項5に係る発明は、前記レンズ金型の表面に、極薄のクロムめっき、無電解ニッケルめっき、もしくは電解ニッケルめっきのいずれかのめっきを施したことを特徴とする請求項3又は4記載のレンズ金型である。 The invention according to claim 5 is characterized in that any one of ultra-thin chrome plating, electroless nickel plating, or electrolytic nickel plating is applied to the surface of the lens mold. 4. The lens mold according to 4.
本発明により、窒素含有ポリマー添加濃度が20〜80ppm、より好ましくは60〜80ppmの範囲のめっき液を用いてその濃度を管理することで、硬度、光沢性、レベリング性に優れるとともに、切削性に優れ加工安定性の良い、結晶配向が無配向となる銅めっき皮膜層を提供することが可能となった。また、切削性に優れ加工安定性の良い銅めっき皮膜層が得られることから、切削工具の寿命も延ばすことができるようになり製版工程の原価低減に貢献することができる。さらに、本発明の銅めっき皮膜を設けて作製される、高精度のグラビア版及びレンズ金型を提供できる。 According to the present invention, the concentration of nitrogen-containing polymer added is 20 to 80 ppm, more preferably 60 to 80 ppm. By controlling the concentration using a plating solution, the hardness, gloss, and leveling properties are excellent, and the machinability is improved. It has become possible to provide a copper plating film layer having excellent processing stability and having no crystal orientation. Moreover, since a copper plating film layer having excellent machinability and good process stability can be obtained, the life of the cutting tool can be extended, which can contribute to cost reduction in the plate making process. Furthermore, it is possible to provide a high-precision gravure plate and a lens mold which are produced by providing the copper plating film of the present invention.
まず、本発明のめっき方法について説明する。めっき液組成は硫酸銅を150〜270g/L望ましくは200〜240g/L、硫酸を40〜100g/L望ましくは40〜80g/L、塩素イオンを50〜150ppm望ましくは80〜120ppmを含まれる液に被めっき対象物をアルカリ脱脂、酸による活性化を行い添加剤を分析管理し安定的に切削に適するめっきを行なって作製することを特徴とする。塩素イオンの供給は塩酸、塩化ナトリウムなどの塩素が含まれる化合物の何れで供給しても良い。 First, the plating method of the present invention will be described. The plating solution composition is copper sulfate containing 150 to 270 g / L, preferably 200 to 240 g / L, sulfuric acid 40 to 100 g / L, preferably 40 to 80 g / L, and chlorine ions 50 to 150 ppm, preferably 80 to 120 ppm. The object to be plated is manufactured by subjecting an object to be plated to alkaline degreasing and activation with an acid, analyzing and managing the additive, and performing stable plating suitable for cutting. Chlorine ions may be supplied by any of compounds containing chlorine such as hydrochloric acid and sodium chloride.
被めっき対象物はグラビア版シリンダー、レンチキュラー用金型、フレネルレンズ成形金型、マイクロレンズ成形金型の何れでもにも適応が可能である。めっき条件はグラビア版シリンダー、レンチキュラー用金型、マイクロレンズ成形金型は陰極電流密度Dk=20〜30A/dm2で行なわれ、フレネルレンズ金型用のめっきは陰極電流密度Dk=3〜8A/dm2で行なうのが良い。特に平板状の金属板にめっきする場合は電着応力により歪みが発生するため、このような低い電流密度でめっきを行なった方が良い。めっき温
度は25〜45℃の範囲であればいずれでも良いが、高電流密度でめっきを行なう場合は温度を高くした方が表面の焼けの発生を押さえることができる。
The object to be plated can be applied to any of a gravure cylinder, a lenticular mold, a Fresnel lens mold, and a microlens mold. The plating conditions are a gravure cylinder, a lenticular mold, a microlens mold with a cathode current density Dk = 20-30 A / dm 2 , and a plating for a Fresnel lens mold with a cathode current density Dk = 3-8 A / It is better to perform at dm 2 . In particular, when plating on a flat metal plate, distortion occurs due to electrodeposition stress, so it is better to perform plating at such a low current density. The plating temperature may be any as long as it is in the range of 25 to 45 ° C. However, when plating is performed at a high current density, it is possible to suppress the occurrence of surface burning by increasing the temperature.
何れの被めっき対象物に銅めっきを電着させた後、表面を砥石で研磨し最終的にはバフで研磨して下地を作製する。何れもダイヤモンド製の切削工具を用いて所望のパターンに切削を行なう。この切削を行なう場合、被切削物の硬度管理が重要であり、これを一定範囲に収めないとバリなどの発生があり、形状が設計値を異なることさえ発生する。グラビア用シリンダーではヘリオ彫刻機で作製する場合、硬度が低いとセルにバリが発生しやすく形状が所望のものが得られず、望むグラデーションカーブを描く版の作製が困難である。レンチキュラー金型またはフレネル用金型の作製においては、切削条件として周速、切込み深さなどが重要であり、また素材である銅めっきの硬度を所定の範囲で管理する必要がある。硬度としてビッカース硬度を測定し、硬度範囲はHv180〜240望ましくはHv190〜210程度の範囲に収めると良い。 After electrodepositing copper plating on any object to be plated, the surface is polished with a grindstone and finally polished with a buff to prepare a base. In either case, a desired pattern is cut using a diamond cutting tool. When performing this cutting, it is important to control the hardness of the workpiece, and if this is not kept within a certain range, burrs or the like may occur, and the shape may even differ from the design value. When a gravure cylinder is manufactured by a helio engraving machine, if the hardness is low, burrs are likely to occur in the cell, and a desired shape cannot be obtained, and it is difficult to prepare a plate that draws a desired gradation curve. In the production of a lenticular mold or a Fresnel mold, peripheral speed, depth of cut, and the like are important as cutting conditions, and the hardness of copper plating as a material must be controlled within a predetermined range. Vickers hardness is measured as the hardness, and the hardness range is preferably in the range of Hv 180 to 240, preferably Hv 190 to 210.
これらの添加剤の管理方法とし、従来から有るCVS(Cyclic Voltammetric Stripping)法では切削に用いる硬化剤を含むめっき液中の添加剤は分析管理することが困難とされ、ハルセル試験により目視試験の結果で管理してきた。一方、プリント配線基板などに用いられている添加剤は光沢剤、抑制剤、レベリング剤から構成されており、硬化剤が含まれていないためCVS法で容易に分析管理が行なわれている。本発明の銅めっき皮膜はハルセル試験によらず、有機窒素含有化合物、有機イオウ化合物を分析機器を用いて分析管理することができる。すなわち、有機窒素含有化合物は高速液体クロマトグラフ分析装置(HPLC)を用いて、有機イオウ化合物はキャピラリー電気泳動/質量分析装置(CE/MS)を用いて分析管理することが可能である。 With the conventional CVS (Cyclic Voltammetric Stripping) method as a management method for these additives, it is difficult to analyze and manage the additives in the plating solution containing the hardener used for cutting. I have managed with. On the other hand, additives used for printed wiring boards and the like are composed of brighteners, inhibitors, and leveling agents, and since they do not contain curing agents, they are easily analyzed and managed by the CVS method. The copper plating film of the present invention can analyze and manage an organic nitrogen-containing compound and an organic sulfur compound using an analytical instrument regardless of the hull cell test. That is, the organic nitrogen-containing compound can be analyzed and managed using a high performance liquid chromatograph analyzer (HPLC), and the organic sulfur compound can be analyzed and managed using a capillary electrophoresis / mass spectrometer (CE / MS).
グラビア版シリンダーは、彫刻後表面の酸化防止と硬度上昇のためクロムめっきを行なう。レンチキュラー金型、フレネル金型、マイクロレンズ金型は切削後、同様な目的のため無電解ニッケルめっきまたは電解ニッケルめっきを数μm以下のめっき厚でレンズパターン表面へ形成させる。 Gravure cylinders are plated with chromium to prevent oxidation and increase hardness after engraving. After cutting the lenticular mold, the Fresnel mold, and the microlens mold, an electroless nickel plating or an electrolytic nickel plating is formed on the lens pattern surface with a plating thickness of several μm or less for the same purpose.
以下に、本発明の実施例を更に詳しく説明する。しかし、本発明は以下の実施例に限定されるものではない。
<実施例1>
硫酸銅濃度210g/L、硫酸濃度60g/L、塩素イオン濃度100ppmの溶液に、有機窒素含有化合物を含む添加剤(大和特殊製コスモG―1)を2.5ml/L、有機イオウ化合物を含む添加剤(大和特殊製コスモG―MU)を8ml/L添加し、浴温度を35℃に保ちグラビア版シリンダーをめっきした。添加剤の補充は、特に光沢剤はCE/MS装置を用いて数本めっきする毎に分析し、硬化剤も同様にHPLC装置を用いて分析し、減少した量を補充を行ない初期添加量±10ppmの範囲で補充管理するようにした。以上の方法によりめっきされた層のビッカース硬度はHv210であった。
In the following, embodiments of the present invention will be described in more detail. However, the present invention is not limited to the following examples.
<Example 1>
Additive containing organic nitrogen containing compound (Daiwa Cosmo G-1) 2.5ml / L, organic sulfur compound in solution with copper sulfate concentration 210g / L, sulfuric acid concentration 60g / L, chloride ion concentration 100ppm An additive (Cosmo G-MU manufactured by Daiwa Special Co., Ltd.) was added at 8 ml / L, and the gravure cylinder was plated while maintaining the bath temperature at 35 ° C. Replenishment of the additive is analyzed every time several brighteners are plated using a CE / MS apparatus, and the curing agent is similarly analyzed using an HPLC apparatus. Replenishment management was performed in the range of 10 ppm. The Vickers hardness of the layer plated by the above method was Hv210.
次に、得られたグラビア版シリンダーをヘリオ彫刻機で彫ると、良好なセル形状が形成され、切削途中でスタイラス針の欠損が起こることなく良好なグラビア版を作製することができた。添加剤を管理して数百本のグラビア版を作製すると、スタイラス針の欠損がほとんど起こらずにヘリオ切削工程での損版率が0.1〜0.3%と押さえることができた。
<実施例2>
硫酸銅濃度210g/L、硫酸濃度60g/L、塩素イオン濃度100ppmの溶液に
、有機窒素含有化合物を含む添加剤(大和特殊製コスモG―1)を2.5ml/L、有機イオウ化合物を含む添加剤(大和特殊製コスモG―MU)を8ml/L添加し、浴温度を35℃に保ちフレネルレンズ用シリンダーまたはフレネルレンズ用真鍮板をめっきした。添加剤の補充は、特に光沢剤はCE/MS装置を用いて1本または1枚めっきする毎に分析し、硬化剤も同様にHPLC装置を用いて分析し、減少した量の補充を行ない初期添加量±10ppmの範囲で補充管理するようにした。以上の方法によりめっきされた層のビッカース硬度はHv210であった。
Next, when the obtained gravure plate cylinder was carved with a helio engraving machine, a good cell shape was formed, and a good gravure plate could be produced without any loss of stylus needles during cutting. When hundreds of gravure plates were produced by controlling the additive, the loss of stylus needles hardly occurred, and the plate loss rate in the helio cutting process could be suppressed to 0.1 to 0.3%.
<Example 2>
Additive containing organic nitrogen containing compound (Daiwa Cosmo G-1) 2.5ml / L, organic sulfur compound in solution with copper sulfate concentration 210g / L, sulfuric acid concentration 60g / L, chloride ion concentration 100ppm An additive (Cosmo G-MU manufactured by Daiwa Special Co., Ltd.) was added at 8 ml / L, and the bath temperature was maintained at 35 ° C., and a Fresnel lens cylinder or a brass plate for Fresnel lens was plated. Additives are replenished, especially when the brightener is plated one or one plate using a CE / MS device, and the curing agent is analyzed using a HPLC device as well, and a reduced amount is replenished. Replenishment management was made within the range of the added amount ± 10 ppm. The Vickers hardness of the layer plated by the above method was Hv210.
次に、得られたフレネルレンズ用シリンダーまたはフレネルレンズ用真鍮板を専用彫刻機で彫ると、切削途中でダイヤモンドバイトの欠損が起こることなく良好な形状の金型を作製することができた。 Next, when the obtained cylinder for the Fresnel lens or the brass plate for the Fresnel lens was carved with a dedicated engraving machine, a mold having a good shape could be produced without any loss of diamond bite during the cutting.
以下に、本発明の比較例について説明する。
<比較例1>
めっき液組成は実施例1と同様にして、有機窒素含有化合物を含む添加剤(大和特殊製コスモG―1)を1.5ml/L、有機イオウ化合物を含む添加剤(大和特殊製コスモG―MU)を8ml/Lを添加し、浴温度を35℃に保ちグラビア版シリンダーをめっきした。得られた銅めっき層は光沢良好でレベリング性も良好であったが、ビッカース硬度がHv170であった。得られたグラビア版シリンダーをヘリオ彫刻機で彫ると、セル形状の変形が見られバリが発生しやすく、グラビア版として使用できるような品質ではなかった。
<比較例2>
めっき液組成は実施例1と同様にして、有機窒素含有化合物を含む添加剤(大和特殊製コスモG―1)を5.0ml/L、有機イオウ化合物を含む添加剤(大和特殊製コスモG―MU)を8ml/L添加し、浴温度を35℃に保ちグラビア版シリンダーをめっきした。得られた銅めっき層の光沢は良好であったが、ビッカース硬度はHv240であった。得られたグラビア版シリンダーをヘリオ彫刻機で彫ると、セル形状は良好であったが、セル内にスジが目立ちスタイラス針が切削途中で欠損が起こる場合が見られた。
Below, the comparative example of this invention is demonstrated.
<Comparative Example 1>
The plating solution composition was the same as in Example 1, 1.5 ml / L of an additive containing an organic nitrogen-containing compound (Daiwa Special Cosmo G-1), and an additive containing an organic sulfur compound (Daiwa Special Cosmo G- 8 ml / L of MU) was added, and the gravure cylinder was plated while maintaining the bath temperature at 35 ° C. The obtained copper plating layer had good gloss and leveling properties, but had a Vickers hardness of Hv170. When the obtained gravure plate cylinder was carved with a helio engraving machine, the cell shape was deformed and burrs were likely to occur, and the quality could not be used as a gravure plate.
<Comparative example 2>
The plating solution composition was the same as in Example 1, 5.0 ml / L of an additive containing an organic nitrogen-containing compound (Daiwa Special Cosmo G-1), and an additive containing an organic sulfur compound (Daiwa Special Cosmo G- MU) was added at 8 ml / L, and the gravure cylinder was plated while maintaining the bath temperature at 35 ° C. The resulting copper plating layer had good gloss, but the Vickers hardness was Hv240. When the obtained gravure plate cylinder was carved with a helio engraving machine, the cell shape was good, but streaks were conspicuous in the cell, and the stylus needle was sometimes broken during cutting.
次に、以上の実施例とは別に、硬化剤となる窒素含有化合物として、窒素含有水溶性ポリマー(窒素含有ポリマー)を単独に添加し、この添加量を変えた場合の銅めっき硬度の経時変化を起こす機構を考察した。
<実験1>
まず、めっき液組成として、次のように作成した。
Next, apart from the above examples, as a nitrogen-containing compound serving as a curing agent, a nitrogen-containing water-soluble polymer (nitrogen-containing polymer) was added alone, and the change over time in the copper plating hardness when this addition amount was changed The mechanism that causes the problem is considered.
<Experiment 1>
First, the plating solution composition was prepared as follows.
・硫酸銅・5水塩 0.9M
・硫酸 0.6M
を基本浴として、この液に更に
・塩素イオン 120ppm
・SPS(Bis(3−sulfopropyl)disulfide disodium salt) 50ppm
・PEG(polyethylene glycohol)
200ppm
を添加し、これに窒素含有ポリマーを5,15,20,40,60,80,100ppmになるようにそれぞれ添加したものをめっき液として用いた。
・ Copper sulfate ・ pentahydrate 0.9M
・ Sulfuric acid 0.6M
As a basic bath, further to this solution ・ Chlorine ion 120ppm
-SPS (Bis (3-sulfopropyl) disulphide disodium salt) 50ppm
・ PEG (Polyethylene Glycohol)
200ppm
A nitrogen-containing polymer was added to this to have a concentration of 5, 15, 20, 40, 60, 80, and 100 ppm, respectively, and was used as a plating solution.
次に、各めっき液でめっきを行い、室温で放置してビッカース硬度を測定した。 Next, plating was performed with each plating solution, and the mixture was left at room temperature to measure the Vickers hardness.
更に、銅めっき硬度の経時変化の機構を考察する為、銅めっき皮膜中の硫黄元素、炭素
元素、水素元素の分析を行った。
Furthermore, in order to consider the mechanism of the time-dependent change of the copper plating hardness, sulfur element, carbon element and hydrogen element in the copper plating film were analyzed.
図1に、窒素含有ポリマー添加量の違いによる銅めっき硬度の経時変化を示す。図面上、ppmがmg/L表記になっているが、これは同じ意味である。これによると、窒素含有ポリマーの添加量が20ppmであると、めっき後約30日で急速な低下が見られ、ビッカース硬度も180より下がってしまった。これが40ppmでは、めっき後、徐々に硬度が低下していることが判り、40日後でもビッカース硬度が180以上を維持している。また、60ppm以上の添加量では、測定期間内での硬度低下がほとんど見られず、ビッカース硬度も220〜240を維持している。 In FIG. 1, the time-dependent change of the copper plating hardness by the difference in nitrogen-containing polymer addition amount is shown. In the figure, ppm is expressed in mg / L, which has the same meaning. According to this, when the addition amount of the nitrogen-containing polymer was 20 ppm, a rapid decrease was observed about 30 days after plating, and the Vickers hardness was also lowered from 180. At 40 ppm, it can be seen that the hardness gradually decreases after plating, and the Vickers hardness is maintained at 180 or more even after 40 days. Moreover, when the addition amount is 60 ppm or more, almost no decrease in hardness is observed within the measurement period, and the Vickers hardness is maintained at 220 to 240.
また、銅めっき皮膜を燃焼法によって元素分析を行った。その結果を図2に示す。図面上、ppmがmg/L表記になっているが、これは同じ意味である。窒素含有ポリマー添加量が0〜60ppmの添加までは、窒素含有ポリマー添加量の増大に伴って、硫黄原子、炭素原子の皮膜中の含有率は増大するが、窒素含有ポリマー添加量が60ppmを越えた領域では、これらの元素の増加傾向が若干鈍っている。一方、水素原子はこの窒素含有ポリマーの添加量が0〜100ppmの添加までは、窒素含有ポリマー添加量の増大に伴って、含有率は増大するが、その後は増加が鈍っている。
<実験2>
次に、窒素含有ポリマーの添加量を5,10,20ppmとした以外は、実験1と同一の組成のめっき液を用意した。そして、各めっき液でめっきを行い、室温で放置してビッカース硬度を測定した。この測定に関連しては、それぞれの銅めっきに対して、FIB(Focuced Ion Beam System,収束イオンビーム装置)によって結晶面をエッチングし、SIM(Scanning Ion Microscope,走査イオン顕微鏡)により結晶組織を観察した。
The copper plating film was subjected to elemental analysis by a combustion method. The result is shown in FIG. In the figure, ppm is expressed in mg / L, which has the same meaning. Until the addition of the nitrogen-containing polymer is 0 to 60 ppm, the content of sulfur atoms and carbon atoms in the film increases as the nitrogen-containing polymer addition increases, but the nitrogen-containing polymer addition exceeds 60 ppm. In these regions, the increasing trend of these elements has been slightly slowed. On the other hand, the content of hydrogen atoms increases with an increase in the amount of addition of the nitrogen-containing polymer until the addition amount of this nitrogen-containing polymer is 0 to 100 ppm, but the increase is slow thereafter.
<Experiment 2>
Next, a plating solution having the same composition as in Experiment 1 was prepared, except that the addition amount of the nitrogen-containing polymer was changed to 5, 10, 20 ppm. Then, plating was performed with each plating solution, and the mixture was left at room temperature to measure the Vickers hardness. In connection with this measurement, for each copper plating, the crystal surface is etched by FIB (Focused Ion Beam System), and the crystal structure is observed by SIM (Scanning Ion Microscope, Scanning Ion Microscope). did.
この時の銅めっき硬度の経時変化を図3に示す。図面上、ppmがmg/L表記になっているが、これは同じ意味である。また、図3に示した窒素含有ポリマーの添加量が20ppmの時の結晶組織のSIM像を図4に示した。図4の撮影条件は、いずれも倍率が7500倍で行った。 The change with time of the copper plating hardness at this time is shown in FIG. In the figure, ppm is expressed in mg / L, which has the same meaning. FIG. 4 shows a SIM image of the crystal structure when the addition amount of the nitrogen-containing polymer shown in FIG. 3 is 20 ppm. The shooting conditions in FIG. 4 were all performed at a magnification of 7500 times.
その結果、窒素含有ポリマー添加量20ppmにおいては、めっき後30日までは、ビッカース硬度が240近辺を維持しており、その時の結晶粒径は0.3〜0.5μmと小さいが、これが30日を越えると、ビッカース硬度が急激に落ち込んで180を割り込むようになった。そこで、36日時点のSIM像を見ると、急激に粒径の増大が見られ約4〜10μm以上に成長していることが判った。これらの結果から、硬度低下の原因は結晶粒径の粗大化にあることが示唆された。 As a result, when the nitrogen-containing polymer addition amount is 20 ppm, the Vickers hardness is maintained around 240 until 30 days after plating, and the crystal grain size at that time is as small as 0.3 to 0.5 μm, but this is 30 days. After exceeding Vickers hardness, it fell sharply to 180. Thus, looking at the SIM image as of the 36th, it was found that the particle diameter increased rapidly and grew to about 4 to 10 μm or more. From these results, it was suggested that the cause of the decrease in hardness is the coarsening of the crystal grain size.
以上の実験1及び実験2の結果を見ると、銅めっき皮膜の硬度は窒素含有ポリマー添加量が60ppmより少ない添加では経時により低下するが、60ppm以上では硬度の経時変化が見られず、また、硫黄元素と炭素元素のめっき膜中の含有率の増加が鈍るといった現象を示している。これらのことから、銅めっき硬度は、これらの硫黄元素と炭素原子が結晶粒界に偏析し、ピン止め効果により結晶成長を抑制しているものと推察される。従って、銅めっき硬度の経時による低下(時効軟化現象)機構は、硫黄元素と炭素原子の含有量が不十分なために、結晶成長が進んでしまうことによるものと推察される。このことより、窒素含有ポリマーが60ppm以上の添加では硬度の経時変化が見られないものと思われる。 Looking at the results of Experiment 1 and Experiment 2 above, the hardness of the copper plating film decreases with time when the addition amount of the nitrogen-containing polymer is less than 60 ppm, but no change in hardness with time is seen at 60 ppm or more. It shows a phenomenon that the increase in the content of sulfur element and carbon element in the plating film is dull. From these facts, it is presumed that the copper plating hardness is such that these sulfur elements and carbon atoms are segregated at the grain boundaries and the crystal growth is suppressed by the pinning effect. Therefore, it is presumed that the mechanism of aging (aging softening phenomenon) of the copper plating hardness is due to the progress of crystal growth due to insufficient content of elemental sulfur and carbon atoms. From this, it is considered that when the nitrogen-containing polymer is added in an amount of 60 ppm or more, the change in hardness with time is not observed.
次に、本発明の結晶配向性が無配向であることを特徴とする銅めっき皮膜について、結晶成長と配向性との相関に基づいて以下に説明する。ここで、無配向とは、JCPDS(
Joint Committee on Powder Diffraction Standards)に掲載されている銅の標準試料のX線回折ピーク強度パターンに近いものである。図5に、時効前と時効後の窒素含有ポリマーの添加による銅めっき皮膜の結晶配向を示した。図5(a)には時効前のX線回折図形(XRD)を示し、同(b)には時効後(めっき後200日)のXRDを示した。時効前は、窒素含有ポリマーを添加していないものは200面すなわち方向性は100配向が極めて強くなっているが、窒素含有ポリマーの添加により急激に200ピークの強度を下げ、添加量の増大に伴って更に弱くなり、逆に111配向を強めている。時効後は、窒素含有ポリマーを添加していない場合は配向性の変化は見られない。しかし、添加量が20,40mg/Lの添加では結晶成長して時効軟化を起すと、100配向を強くしている。添加量が60mg/L以上で時効軟化は見られず、配向性の変化も見られない。以上の事から、軟化したものは<100>方向を膜面に垂直にした結晶が成長することが分った。
Next, the copper plating film characterized in that the crystal orientation of the present invention is non-oriented will be described below based on the correlation between crystal growth and orientation. Here, non-oriented means JCPDS (
This is close to the X-ray diffraction peak intensity pattern of a copper standard sample published in Joint Committee on Powder Diffraction Standards). In FIG. 5, the crystal orientation of the copper plating film by the addition of the nitrogen-containing polymer before and after aging is shown. FIG. 5A shows an X-ray diffraction pattern (XRD) before aging, and FIG. 5B shows an XRD after aging (200 days after plating). Before aging, those with no nitrogen-containing polymer added have 200 planes, that is, the orientation of 100 is extremely strong, but the addition of the nitrogen-containing polymer drastically reduces the strength of the 200 peak and increases the amount added. Along with this, it becomes weaker, and conversely, the 111 orientation is strengthened. After aging, no change in orientation is observed when no nitrogen-containing polymer is added. However, when the addition amount is 20, 40 mg / L, when crystal growth occurs and aging softening occurs, 100 orientation is strengthened. When the addition amount is 60 mg / L or more, no aging softening is observed, and no change in orientation is observed. From the above, it was found that the softened crystal grew with the <100> direction perpendicular to the film surface.
この現象について、図6に、銅めっき皮膜における結晶成長と配向性との相関モデルの模式図を示した。即ち、(a)時効前ではめっき膜の結晶は何れも小さく、窒素含有ポリマー添加無しの場合はほとんどが100配向(黒く塗られた結晶)をしている。窒素含有ポリマーの添加量が20,40,60mg/Lと増加すると100配向結晶は少なくなっている。そして、(b)時効により窒素含有ポリマーが60mg/Lより少ない場合は、100配向の結晶(黒く塗られた結晶)のみが粗大化している。 About this phenomenon, the schematic diagram of the correlation model of the crystal growth and orientation in a copper plating film was shown in FIG. That is, (a) before aging, the crystals of the plating film are all small, and in the absence of addition of the nitrogen-containing polymer, most of them have 100 orientation (crystals painted black). When the addition amount of the nitrogen-containing polymer is increased to 20, 40, 60 mg / L, the number of 100-oriented crystals decreases. When (b) the nitrogen-containing polymer is less than 60 mg / L due to aging, only 100-oriented crystals (crystals painted black) are coarsened.
以上のように、結晶成長と配向は密接な関係があることが分り、膜面に100配向した結晶が多いほど、結晶成長しやすいことが分かる。しかし、図4に示したSIM像から分かるように、結晶は膜面に垂直方向ばかり成長するのではなく、膜面に平行方向も成長させる。 As described above, it can be seen that there is a close relationship between crystal growth and orientation, and it can be seen that the more crystals with 100 orientation on the film surface, the easier the crystal growth. However, as can be seen from the SIM image shown in FIG. 4, the crystal grows not only in the direction perpendicular to the film surface but also in the direction parallel to the film surface.
以上、ビッカース硬度の観点から、窒素含有ポリマーの分量を論じてきたが、この窒素含有ポリマーが60ppm以上であると経時変化が無くなることがわかったが、実験1での窒素含有ポリマーを100ppm入れためっき液での銅めっき皮膜は、脆くなる傾向が出ていた。従って、窒素含有ポリマーは60〜80ppmが好ましい値であることがわかった。また、30日程度の短期間であれば、20〜60ppmの濃度でも、必要な銅めっき硬度が保てることがわかった。 As mentioned above, from the viewpoint of Vickers hardness, the amount of the nitrogen-containing polymer has been discussed, but it was found that the change with time was eliminated when the nitrogen-containing polymer was 60 ppm or more, but 100 ppm of the nitrogen-containing polymer in Experiment 1 was added. The copper plating film with the plating solution tended to be brittle. Therefore, it was found that the nitrogen-containing polymer has a preferable value of 60 to 80 ppm. It was also found that the required copper plating hardness could be maintained even at a concentration of 20 to 60 ppm for a short period of about 30 days.
本発明は、硬度、光沢性、レベリング性に優れるとともに、切削性に優れ加工安定性の良い銅めっき皮膜及びその銅めっき皮膜を設けて作製されるグラビア版及びレンズ金型を作製する銅めっき技術として広い分野で用いられる。 The present invention provides a copper plating film having excellent hardness, glossiness, leveling property, excellent machinability and good process stability, and a copper plating technique for producing a gravure plate and a lens mold produced by providing the copper plating film. Used in a wide range of fields.
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JP2009093171A (en) * | 2007-09-20 | 2009-04-30 | Think Laboratory Co Ltd | Method of manufacturing photogravure plate having cushion property |
JP2009090662A (en) * | 2007-09-20 | 2009-04-30 | Think Laboratory Co Ltd | Gravure printing equipment |
JP2009093170A (en) * | 2007-09-20 | 2009-04-30 | Think Laboratory Co Ltd | Photogravure plate having cushion property and method of manufacturing it |
WO2011136061A1 (en) * | 2010-04-30 | 2011-11-03 | Jx日鉱日石金属株式会社 | Laminate for flexible wiring |
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JP2009093171A (en) * | 2007-09-20 | 2009-04-30 | Think Laboratory Co Ltd | Method of manufacturing photogravure plate having cushion property |
JP2009090662A (en) * | 2007-09-20 | 2009-04-30 | Think Laboratory Co Ltd | Gravure printing equipment |
JP2009093170A (en) * | 2007-09-20 | 2009-04-30 | Think Laboratory Co Ltd | Photogravure plate having cushion property and method of manufacturing it |
WO2011136061A1 (en) * | 2010-04-30 | 2011-11-03 | Jx日鉱日石金属株式会社 | Laminate for flexible wiring |
JPWO2011136061A1 (en) * | 2010-04-30 | 2013-07-18 | Jx日鉱日石金属株式会社 | Laminate for flexible wiring |
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