JP2020186962A - Method of analyzing and controlling nano diamond particle concentration in composite plating solution - Google Patents
Method of analyzing and controlling nano diamond particle concentration in composite plating solution Download PDFInfo
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- 238000007747 plating Methods 0.000 title claims abstract description 114
- 239000002245 particle Substances 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 239000002113 nanodiamond Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000002835 absorbance Methods 0.000 claims abstract description 27
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- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
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- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
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- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 229910000889 permalloy Inorganic materials 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
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- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- SIGUVTURIMRFDD-UHFFFAOYSA-M sodium dioxidophosphanium Chemical compound [Na+].[O-][PH2]=O SIGUVTURIMRFDD-UHFFFAOYSA-M 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- YPPQYORGOMWNMX-UHFFFAOYSA-L sodium phosphonate pentahydrate Chemical compound [Na+].[Na+].[O-]P([O-])=O YPPQYORGOMWNMX-UHFFFAOYSA-L 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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- Investigating Or Analysing Materials By Optical Means (AREA)
- Chemically Coating (AREA)
Abstract
Description
本発明は、複合めっき液中のナノダイヤモンド粒子濃度の分析方法及び管理方法に関する。 The present invention relates to a method for analyzing and controlling the concentration of nanodiamond particles in a composite plating solution.
本明細書において、ナノダイヤモンドを「ＮＤ」と記載する場合がある。 In the present specification, nanodiamond may be referred to as "ND".
通常のめっき液にナノダイヤモンド粒子を混合分散させた複合めっき液が知られている（特許文献１）。ナノダイヤモンド粒子を含有する複合めっき液を使用することで、ナノダイヤモンド粒子が均一に分散しためっき皮膜が形成され、めっき皮膜の意匠性や機械的特性、機能性を高めることができる。 A composite plating solution in which nanodiamond particles are mixed and dispersed in a normal plating solution is known (Patent Document 1). By using a composite plating solution containing nanodiamond particles, a plating film in which nanodiamond particles are uniformly dispersed is formed, and the design, mechanical properties, and functionality of the plating film can be enhanced.
このような複合めっき液を用いて所望の特性を有するめっき皮膜を再現性良く形成するためには、複合めっき液中のナノダイヤモンド粒子の濃度を管理し、この濃度が所定濃度となるように適宜複合めっき液中にナノダイヤモンド粒子を添加し、ナノダイヤモンド粒子濃度を維持管理する必要がある。 In order to form a plating film having desired characteristics with good reproducibility using such a composite plating solution, the concentration of nanodiamond particles in the composite plating solution is controlled, and the concentration is appropriately adjusted to a predetermined concentration. It is necessary to add nanodiamond particles to the composite plating solution to maintain and manage the concentration of nanodiamond particles.
複合めっき液中のナノダイヤモンド粒子濃度は、例えばめっき皮膜中のナノダイヤモンド粒子量を定量することで推定できるが、この方法は煩雑な操作が必要になる。 The concentration of nanodiamond particles in the composite plating solution can be estimated, for example, by quantifying the amount of nanodiamond particles in the plating film, but this method requires complicated operations.
本発明の目的は、複合めっき液中のナノダイヤモンド粒子の濃度を簡易な方法で迅速かつ的確に分析し、複合めっき液を適切に管理することにある。 An object of the present invention is to analyze the concentration of nanodiamond particles in a composite plating solution quickly and accurately by a simple method, and to appropriately manage the composite plating solution.
本発明は、以下の複合めっき液中のナノダイヤモンド粒子濃度の分析方法及び管理方法を提供するものである。
〔１〕 ナノダイヤモンド粒子を含む複合めっき液の吸光度を測定し、吸光度の測定値に基づきナノダイヤモンド粒子の濃度を求める工程を含み、前記吸光度は２５０〜６３０ｎｍ の範囲から選択される波長で測定される、複合めっき液中のナノダイヤモンド粒子濃度の分析方法。
〔２〕 〔１〕の方法で複合めっき液中のナノダイヤモンド粒子濃度を分析し、前記濃度が所定濃度となるように、必要に応じて複合めっき液にナノダイヤモンド粒子を添加する、複合めっき液中のナノダイヤモンド粒子濃度の管理方法。
The present invention provides a method for analyzing and controlling the concentration of nanodiamond particles in the following composite plating solution.
[1] Including a step of measuring the absorbance of a composite plating solution containing nanodiamond particles and determining the concentration of nanodiamond particles based on the measured absorbance, the absorbance is measured at a wavelength selected from the range of 250 to 630 nm. A method for analyzing the concentration of nanodiamond particles in a composite plating solution.
[2] A composite plating solution in which the concentration of nanodiamond particles in the composite plating solution is analyzed by the method of [1], and nanodiamond particles are added to the composite plating solution as necessary so that the concentration becomes a predetermined concentration. How to control the concentration of nanodiamond particles inside.
本発明によれば、複合めっき液中のナノダイヤモンド粒子濃度を、簡易かつ迅速に分析することができ、この分析方法を利用する本発明の複合めっき液の管理方法によれば、ナノダイヤモンド粒子の濃度の分析値をリアルタイムでナノダイヤモンド粒子の添加制御に反映させて、良好なめっき工程の維持管理のもとに、所望の特性を有する複合めっき皮膜を容易に得ることが可能になる。 According to the present invention, the concentration of nanodiamond particles in the composite plating solution can be easily and quickly analyzed, and according to the method for managing the composite plating solution of the present invention using this analysis method, the nanodiamond particles By reflecting the analysis value of the concentration in the addition control of nanodiamond particles in real time, it becomes possible to easily obtain a composite plating film having desired characteristics under good maintenance of the plating process.
本明細書において、複合めっき浴は卑金属めっき液とナノダイヤモンド粒子（ＮＤ粒子）とを含む。前記卑金属めっき浴中におけるＮＤ粒子の濃度は、例えば０．００１〜１．０ｇ／Ｌ（下限は、好ましくは０．００３ｇ／Ｌ、より好ましくは０．００６ｇ／Ｌ、さらに好ましくは０．０１ｇ／Ｌ、特に好ましくは０．０３ｇ／Ｌである。ＮＤ粒子の濃度の上限は、好ましくは０．８ｇ／Ｌ、さらに好ましくは０．６ｇ／Ｌ、特に好ましくは０．５ｇ／Ｌである）の範囲であり、好ましくは０．０１〜０．５ｇ／Ｌである。 In the present specification, the composite plating bath contains a base metal plating solution and nanodiamond particles (ND particles). The concentration of ND particles in the base metal plating bath is, for example, 0.001 to 1.0 g / L (the lower limit is preferably 0.003 g / L, more preferably 0.006 g / L, still more preferably 0.01 g / L). L, particularly preferably 0.03 g / L. The upper limit of the concentration of ND particles is preferably 0.8 g / L, more preferably 0.6 g / L, and particularly preferably 0.5 g / L). It is in the range, preferably 0.01 to 0.5 g / L.
卑金属としては、鉄、ニッケル、亜鉛、銅、スズ、アルミニウム、タングステン、モリブデン、タンタル、マグネシウム、コバルト、ビスマス、カドミウム、チタニウム、ジルコニウム、アンチモン、マンガン、ベリリウム、クロム、ゲルマニウム、バナジウム、ガリウム、ハフニウム、インジウム、ニオブ、レニウム及びタリウムからなる群から選ばれる少なくとも１種であり、好ましくは銅、ニッケル、亜鉛、スズ、クロム、パーマロイからなる群から選ばれる少なくとも１種であり、より好ましくは銅、ニッケル、亜鉛、スズからなる群から選ばれる少なくとも１種であり、特に好ましくは銅、ニッケルである。 Base metals include iron, nickel, zinc, copper, tin, aluminum, tungsten, molybdenum, tantalum, magnesium, cobalt, bismuth, cadmium, titanium, zirconium, antimony, manganese, beryllium, chromium, germanium, vanadium, gallium, hafnium, At least one selected from the group consisting of indium, niobium, renium and tallium, preferably at least one selected from the group consisting of copper, nickel, zinc, tin, chromium and permalloy, more preferably copper and nickel. , Zinc, at least one selected from the group consisting of tin, particularly preferably copper and nickel.
複合めっき液中のＮＤ粒子の粒径（Ｄ５０）は、例えば９５ｎｍ以下、好ましくは７０ｎｍ以下、特に好ましくは６０ｎｍ以下、最も好ましくは５０ｎｍ以下である。ＮＤ粒子の粒径（Ｄ５０）の下限は、例えば２０ｎｍである。 The particle size (D50) of the ND particles in the composite plating solution is, for example, 95 nm or less, preferably 70 nm or less, particularly preferably 60 nm or less, and most preferably 50 nm or less. The lower limit of the particle size (D50) of the ND particles is, for example, 20 nm.
卑金属めっき液は公知であり、公知の卑金属めっき液にＮＤ粒子又はその分散液を添加することで、複合めっき浴が得られる。ＮＤ粒子の分散液は、水溶液が好ましい。複合めっき浴は電解複合めっき浴と無電解複合めっき浴のいずれであってもよい。複合めっき浴は、水溶性卑金属塩、ＮＤ粒子を必須成分として含み、電導度塩、錯化剤、還元剤（無電解めっき浴）、アノード溶解促進剤(複合電解めっき浴の場合)、リン供給源(無電解ニッケル‐リン合金めっきの場合)、ｐＨ緩衝剤、界面活性剤、安定剤、皮膜の外観と物性を調整する添加剤（光沢化剤、平滑化剤、応力減少剤など）などから選択されるその他の成分をさらに含むことができる。前記水溶性卑金属塩は、卑金属めっき浴中においては卑金属イオンとして存在する。その他、卑金属の酸素酸イオンや、錯化剤と結合した卑金属錯イオンとして存在する場合もある。 複合めっき浴における水溶性卑金属塩の濃度は、複合めっき液に供給される卑金属イオン濃度換算で、例えば０．０１〜０．５ｍｏｌ／Ｌであり、好ましくは０．０５〜０．２ｍｏｌ／Ｌである。 Base metal plating solutions are known, and a composite plating bath can be obtained by adding ND particles or a dispersion thereof to the known base metal plating solutions. The dispersion liquid of the ND particles is preferably an aqueous solution. The composite plating bath may be either an electrolytic composite plating bath or an electroless composite plating bath. The composite plating bath contains a water-soluble base metal salt and ND particles as essential components, and supplies a conductivity salt, a complexing agent, a reducing agent (electroless plating bath), an anode dissolution accelerator (in the case of a composite electrolytic plating bath), and phosphorus. From sources (in the case of electroless nickel-phosphorus alloy plating), pH buffers, surfactants, stabilizers, additives that adjust the appearance and physical properties of the film (brightening agents, smoothing agents, stress reducing agents, etc.) Other components of choice may be further included. The water-soluble base metal salt exists as a base metal ion in the base metal plating bath. In addition, it may exist as a base metal oxygenate ion or a base metal complex ion bonded to a complexing agent. The concentration of the water-soluble base metal salt in the composite plating bath is, for example, 0.01 to 0.5 mol / L, preferably 0.05 to 0.2 mol / L, in terms of the concentration of base metal ions supplied to the composite plating solution. is there.
無電解複合めっき液に含有される還元剤としては、ホスホン酸又はホスホン酸塩（例えばホスホン酸ナトリウムなどのホスホン酸アルカリ金属塩）、ホスフィン酸又はホスフィン酸塩（例えばホスフィン酸ナトリウムなどのホスフィン酸アルカリ金属塩）などが挙げられる。還元剤としてホスフィン酸塩、ホスホン酸塩を採用する場合、無電解複合めっき液におけるホスフィン酸塩、ホスホン酸塩の濃度は、例えば０．０２〜０．５ｍｏｌ／Ｌであり、好ましくは０．１〜０．２ｍｏｌ／Ｌである。 Examples of the reducing agent contained in the electroless composite plating solution include phosphonic acid or phosphonate (for example, an alkali metal phosphonate such as sodium phosphonate), phosphinic acid or phosphinate (for example, alkali phosphinate such as sodium phosphinate). Metal salt) and the like. When phosphinate or phosphonate is used as the reducing agent, the concentration of phosphinate or phosphonate in the electroless composite plating solution is, for example, 0.02 to 0.5 mol / L, preferably 0.1. It is ~ 0.2 mol / L.
電解及び無電解卑金属めっき浴に含有される錯化剤としては、例えば、クエン酸、乳酸、リンゴ酸、グリコール酸、およびこれらの塩が挙げられる。クエン酸としては、クエン酸ナトリウムやクエン酸カリウムなどのクエン酸アルカリ金属塩が挙げられる。クエン酸および／またはその塩を採用する場合、電解及び無電解卑金属めっき浴におけるクエン酸および／またはその塩の濃度は、例えば０．０２〜１．０ｍｏｌ／Ｌであり、好ましくは０．１〜０．５ｍｏｌ／Ｌである。 Examples of the complexing agent contained in the electrolytic and electroless base metal plating bath include citric acid, lactic acid, malic acid, glycolic acid, and salts thereof. Examples of citric acid include alkali metal citrate salts such as sodium citrate and potassium citrate. When citric acid and / or a salt thereof is adopted, the concentration of citric acid and / or a salt thereof in the electrolytic and electroless base metal plating bath is, for example, 0.02 to 1.0 mol / L, preferably 0.1 to 0.1. It is 0.5 mol / L.
卑金属めっき浴のｐＨは、例えば５〜１１である。 The pH of the base metal plating bath is, for example, 5 to 11.
本発明では、これらの複合めっき液の成分のうち、ＮＤ粒子の管理を行うものである。ＮＤ粒子以外の成分の管理は、常法に従い行うことができる。 In the present invention, among the components of these composite plating solutions, ND particles are controlled. The components other than the ND particles can be managed according to a conventional method.
本発明の好ましい１つの実施形態において、ＮＤ粒子以外の卑金属めっき用のめっき液としては、ＮＤ粒子、卑金属の硫酸塩、硫酸、塩化物イオンなどからなる硫酸卑金属めっき液；卑金属シアン化物、シアン化ナトリウム、炭酸アルカリ、ロッシェル塩などからなるシアン化卑金属めっき液；卑金属ピロリン酸塩、ピロリン酸カリウム、アンモニア水、硝酸カリウムなどからなるピロリン酸卑金属めっき液などが挙げられる。 In one preferred embodiment of the present invention, the plating solution for base metal plating other than ND particles is a base metal sulfate plating solution composed of ND particles, base metal sulfate, sulfuric acid, chloride ion, etc .; base metal cyanide, cyanation. Base metal cyanide plating solution composed of sodium, alkali carbonate, Rochelle salt and the like; base metal pyrophosphate plating solution composed of base metal pyrophosphate, potassium pyrophosphate, aqueous ammonia, potassium nitrate and the like can be mentioned.
ＮＤ粒子の表面は、ＯＨ、ＣＯＯＨ、ＮＨ２などの親水性官能基を有していてもよい。また、これらの官能基を介して、親水性基を導入したＮＤ粒子を用いてもよい。親水性基としては、グリセリン、ポリグリセリン（PG）、エチレングリコール、プロピレングリコール、ブチレングリコールなどのＣ２−４アルキレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコールなどのポリ（Ｃ２−４アルキレングリコール）などが挙げられる。これらの親水性ＮＤ粒子は公知であるか、公知に方法により製造することができる。 The surface of the ND particles may have hydrophilic functional groups such as OH, COOH and NH 2 . Further, ND particles into which a hydrophilic group has been introduced via these functional groups may be used. Examples of the hydrophilic group include C 2-4 alkylene glycol such as glycerin, polyglycerin (PG), ethylene glycol, propylene glycol and butylene glycol, and poly (C 2-4 alkylene glycol) such as polyethylene glycol, polypropylene glycol and polybutylene glycol. ) And so on. These hydrophilic ND particles are known or can be produced by a known method.
ＮＤ粒子は、固体を(複合)めっき浴に配合してもよく、ＮＤ粒子分散液を(複合)めっき浴に配合してもよい。ＮＤ粒子分散液中のＮＤ粒子濃度は、例えば１〜１００ｇ／Ｌ程度である。 For the ND particles, the solid may be blended in the (composite) plating bath, or the ND particle dispersion may be blended in the (composite) plating bath. The ND particle concentration in the ND particle dispersion is, for example, about 1 to 100 g / L.
前記ＮＤ粒子としては、分散性に優れる点において、親水性高分子でコーティングもしくは修飾された親水性ＮＤ粒子が好ましく、特に好ましくはポリグリセリン鎖を含む水溶性高分子を有する親水性ＮＤ粒子である。 The ND particles are preferably hydrophilic ND particles coated or modified with a hydrophilic polymer in terms of excellent dispersibility, and particularly preferably hydrophilic ND particles having a water-soluble polymer containing a polyglycerin chain. ..
本発明の複合めっき液中のＮＤ粒子濃度の分析は、以下のようにして行うことができる。
(i)先ず、ＮＤ粒子の濃度を分析すべき複合めっき液に対して、ＮＤ粒子濃度を管理すべき範囲において、様々な配合量でＮＤ粒子を配合したＮＤ粒子濃度の既知の複数種類の複合めっき液を調製する。
(ii）次に、上記(i)で調製した複合めっき液について、各々、吸光度を測定する。
(iii）上記（ii）の結果をもとに、図４に示すように如く、複合めっき液の吸光度とＮＤ粒子濃度の関係を示す検量線を作成する。
The analysis of the ND particle concentration in the composite plating solution of the present invention can be performed as follows.
(i) First, with respect to the composite plating solution for which the concentration of ND particles should be analyzed, a plurality of known composites having ND particle concentrations in which ND particles are blended in various blending amounts within a range in which the ND particle concentration should be controlled. Prepare the plating solution.
(ii) Next, the absorbance of each of the composite plating solutions prepared in (i) above is measured.
(iii) Based on the result of (ii) above, as shown in FIG. 4, a calibration curve showing the relationship between the absorbance of the composite plating solution and the ND particle concentration is prepared.
複合めっき液の吸光度を測定する波長は、２５０〜６３０ｎｍの範囲から選択され、この範囲内であれば、任意の波長で検量線を作成し、複合めっき液中のＮＤ粒子濃度を分析することができる。検量線を作成する波長は、NDを含まないめっき液を基準として、ND粒子の濃度を高めていったときの吸光度変化の大きい波長が好ましい。例えば、図１〜３に示す銅めっき液の場合、好ましくは280nm〜630nm、より好ましくは300nm〜600nm、さらに好ましくは310nm〜500nmである。また、図５〜６に示すニッケルめっき液の場合、好ましくは300nm〜370nmと430nm〜580nm、より好ましくは305nm〜360nmと440nm〜560nm、さらに好ましくは310nm〜350nmと440nm〜550nmである。銅めっき液とニッケルめっき液であったとしても、めっき液に含まれる成分や濃度が変化すれば、検量線作成の好ましい波長は変化し得る。また、卑金属めっき液の卑金属の種類が銅、ニッケルから鉄、亜鉛、スズ、アルミニウム、タングステン、モリブデン、タンタル、マグネシウム、コバルト、ビスマス、カドミウム、チタニウム、ジルコニウム、アンチモン、マンガン、ベリリウム、クロム、ゲルマニウム、バナジウム、ガリウム、ハフニウム、インジウム、ニオブ、レニウム、タリウムなどの他の卑金属に変わった場合にも、検量線作成の好ましい波長は変化し得る。検量線作成の好ましい波長の決定は、銅めっき液とニッケルめっき液の結果を参考にして容易に行うことができる。検量線は、１つの波長のみで作成してもよく、複数の波長（好ましくが２つの波長もしくは３つの波長）で作成してもよい。図３に示すように、ＮＤ粒子の水分散液の吸光度は、ＮＤ粒子の濃度によっても大きく影響を受けるので、このことを考慮して、検量線を作成する波長を決定することが好ましい。ＮＤ粒子濃度の管理すべき範囲内で、ＮＤ粒子濃度の決定に有利な吸光度の測定波長を検量線により決定する。複合めっき液のＮＤ粒子の濃度は、予め作製された検量線を用いて、吸光度の測定値により分析することができる。ＮＤ粒子濃度の分析は、ＮＤ粒子の濃度を特定するように行ってもよく、ＮＤ粒子濃度が許容範囲を逸脱する可能性が生じ、ＮＤ粒子を例えば水分散液の形態で複合めっき液に添加するべきか否かを判断できるように濃度ゾーンで分析してもよい。 The wavelength for measuring the absorbance of the composite plating solution is selected from the range of 250 to 630 nm, and within this range, a calibration curve can be created at any wavelength and the ND particle concentration in the composite plating solution can be analyzed. it can. The wavelength at which the calibration curve is created is preferably a wavelength having a large change in absorbance when the concentration of ND particles is increased, based on a plating solution containing no ND. For example, in the case of the copper plating solution shown in FIGS. 1 to 3, it is preferably 280 nm to 630 nm, more preferably 300 nm to 600 nm, and further preferably 310 nm to 500 nm. Further, in the case of the nickel plating solution shown in FIGS. 5 to 6, it is preferably 300 nm to 370 nm and 430 nm to 580 nm, more preferably 305 nm to 360 nm and 440 nm to 560 nm, and further preferably 310 nm to 350 nm and 440 nm to 550 nm. Even if the copper plating solution and the nickel plating solution are used, the preferable wavelength for preparing the calibration curve can change if the components and concentrations contained in the plating solution change. In addition, the types of base metals in the base metal plating solution are copper, nickel, iron, zinc, tin, aluminum, tungsten, molybdenum, tantalum, magnesium, cobalt, bismuth, cadmium, titanium, zirconium, antimony, manganese, beryllium, chromium, germanium, etc. The preferred wavelength of calibration line preparation can also change when changing to other base metals such as vanadium, gallium, hafnium, indium, niobium, renium, tantalum. The preferred wavelength for preparing the calibration curve can be easily determined by referring to the results of the copper plating solution and the nickel plating solution. The calibration curve may be produced with only one wavelength, or may be produced with a plurality of wavelengths (preferably two wavelengths or three wavelengths). As shown in FIG. 3, the absorbance of the aqueous dispersion of ND particles is greatly affected by the concentration of ND particles, and it is preferable to determine the wavelength at which the calibration curve is prepared in consideration of this. Within the range to be controlled of the ND particle concentration, the measurement wavelength of the absorbance which is advantageous for determining the ND particle concentration is determined by the calibration curve. The concentration of ND particles in the composite plating solution can be analyzed by measuring the absorbance using a calibration curve prepared in advance. The analysis of the ND particle concentration may be performed so as to specify the concentration of the ND particles, and the ND particle concentration may deviate from the permissible range, and the ND particles are added to the composite plating solution in the form of an aqueous dispersion, for example. It may be analyzed in the concentration zone so that it can be determined whether or not it should be done.
本発明の複合めっき液のＮＤ粒子濃度の管理方法では、めっき槽から複合めっき液をサンプリングし、上述のような方法で複合めっき液中のＮＤ粒子の濃度を分析し、分析結果に基づきＮＤ粒子濃度が次のサンプリングまで許容範囲内にとどまると判断されればＮＤ粒子の添加は行わず、分析結果に基づきＮＤ粒子濃度が次のサンプリング時には許容範囲外になる可能性があると判断される場合には、必要に応じてめっき槽中の複合めっき液にＮＤ粒子を例えば水分散液の形態で添加し、ＮＤ粒子濃度が許容範囲内でめっきが行われるようにする。 In the method for controlling the ND particle concentration of the composite plating solution of the present invention, the composite plating solution is sampled from the plating tank, the concentration of the ND particles in the composite plating solution is analyzed by the method as described above, and the ND particles are based on the analysis result. If it is judged that the concentration remains within the permissible range until the next sampling, ND particles are not added, and based on the analysis results, it is judged that the ND particle concentration may be out of the permissible range at the time of the next sampling. If necessary, ND particles are added to the composite plating solution in the plating tank in the form of, for example, an aqueous dispersion so that the plating is performed within an allowable range of the ND particle concentration.
本発明のＮＤ濃度の管理方法について、例えば複合めっき液からめっき液をポンプなどでサンプリングするサンプリング手段、サンプリングした試料の吸光度を測定する分析手段、分析手段の結果の信号を受け取り、ＮＤ粒子を複合めっき液に添加するか否かと添加量を決定する制御手段、前記制御手段によりＮＤ粒子の添加を制御されるＮＤ粒子添加手段を備えたシステムにより自動的にＮＤ粒子の濃度管理を行ってもよく、管理者がめっきの状況を見ながら適切なタイミングで複合めっき液のサンプリング及び吸光度測定を手動で行い、その結果から、複合めっき液へのＮＤ粒子の添加の要否、添加する場合にはその添加量を管理者が判断して実施してもよい。 Regarding the method for controlling the ND concentration of the present invention, for example, a sampling means for sampling a plating solution from a composite plating solution with a pump or the like, an analysis means for measuring the absorbance of the sampled sample, and a signal of the result of the analysis means are received to combine ND particles. The concentration of ND particles may be automatically controlled by a system provided with a control means for determining whether or not to add to the plating solution and an addition amount, and an ND particle addition means for which the addition of ND particles is controlled by the control means. , The administrator manually samples the composite plating solution and measures the absorbance at an appropriate timing while observing the plating status, and based on the results, whether or not to add ND particles to the composite plating solution, and if so, The manager may determine the amount of addition and carry out the process.
以下、本発明を実施例を挙げてより詳細に説明する。
実施例１
銅めっき液（商品名「電解めっき液」、清川めっき工業（株）製）に、ポリグリセリン（ＰＧ）で修飾することで親水化処理されたＮＤ粒子水分散液（ＰＧ−ＮＤ粒子水分散液（(株)ダイセル製）を、銅めっき液中のＰＧ−ＮＤ濃度が０、５０、１００、２００、３００、４００、５００、１０００ppmとなるように添加して、各種ＮＤ濃度の複合めっき液を調製した。
Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1
ND particle water dispersion (PG-ND particle water dispersion) that has been hydrophilized by modifying copper plating solution (trade name "electroplating solution", manufactured by Kiyokawa Plating Industry Co., Ltd.) with polyglycerin (PG). (Manufactured by Daicel Co., Ltd.) is added so that the PG-ND concentration in the copper plating solution is 0, 50, 100, 200, 300, 400, 500, 1000 ppm to add composite plating solutions having various ND concentrations. Prepared.
得られた複合銅めっき液について、分光光度計（（株）日立ハイテクフィールディング社製「U-3900H Spectrophotometer）を用い、波長300nm、310nm、320nm、330nm、340nm、350nm、355nm、360nmで吸光度測定を行い、検量線を作成した(図4)。図１は、ＰＧ−ＮＤを添加していない銅めっき液の吸光度測定結果を示し、図２は、ＰＧ−ＮＤを５０ｐｐｍ、１００ｐｐｍ、２００ｐｐｍ、３００ｐｐｍ、４００ｐｐｍ、５００ｐｐｍ、１０００ｐｐｍを各々添加した銅めっき液の吸光度測定結果を示す。また、図３は、ＰＧ−ＮＤ濃度が５０ｐｐｍと５００ｐｐｍのときのＰＧ−ＮＤ水分散液の吸光度を示す。 Absorbance measurement of the obtained composite copper plating solution was performed at wavelengths of 300 nm, 310 nm, 320 nm, 330 nm, 340 nm, 350 nm, 355 nm, and 360 nm using a spectrophotometer (U-3900H Spectrophotometer manufactured by Hitachi High-Tech Fielding Co., Ltd.). A calibration curve was prepared (FIG. 4). FIG. 1 shows the absorbance measurement results of the copper plating solution to which PG-ND was not added, and FIG. 2 shows PG-ND at 50 ppm, 100 ppm, 200 ppm, and 300 ppm. The absorbance measurement results of the copper plating solution to which 400 ppm, 500 ppm, and 1000 ppm are added are shown. FIG. 3 shows the absorbance of the PG-ND aqueous dispersion when the PG-ND concentrations are 50 ppm and 500 ppm, respectively.
図４の結果から、ＮＤ粒子の濃度は吸光度により決定でき、複合めっき液中のＮＤ粒子濃度を適切に管理できることが明らかになった。 From the results of FIG. 4, it was clarified that the concentration of ND particles can be determined by the absorbance, and the concentration of ND particles in the composite plating solution can be appropriately controlled.
実施例２
ニッケルめっき液（商品名「電解ニッケルめっき液」、清川めっき工業（株）製）に、ポリエチレングリコール（ＰＧ）で修飾することで親水化処理されたＮＤ粒子水分散液（ＰＧ−ＮＤ粒子水分散液（(株)ダイセル製）を、銅めっき液中のＰＧ−ＮＤ濃度が０、５０、１００、２００、３００、４００、５００、１０００ppmとなるように添加して、各種ＮＤ濃度の複合めっき液を調製した。
Example 2
ND particle water dispersion (PG-ND particle water dispersion) that has been hydrophilized by modifying nickel plating solution (trade name "electrolytic nickel plating solution", manufactured by Kiyokawa Plating Industry Co., Ltd.) with polyethylene glycol (PG). A liquid (manufactured by Daicel Co., Ltd.) is added so that the PG-ND concentration in the copper plating liquid becomes 0, 50, 100, 200, 300, 400, 500, 1000 ppm, and a composite plating liquid having various ND concentrations is added. Was prepared.
得られた複合銅めっき液について、分光光度計を用いて吸光度測定を行った。図５は、ＰＧ−ＮＤを添加していない銅めっき液の吸光度測定結果を示し、図６は、ＰＧ−ＮＤを５０ｐｐｍ、１００ｐｐｍ、２００ｐｐｍ、３００ｐｐｍ、４００ｐｐｍ、５００ｐｐｍ、１０００ｐｐｍを各々添加した銅めっき液の吸光度測定結果を示す。 The absorbance of the obtained composite copper plating solution was measured using a spectrophotometer. FIG. 5 shows the absorbance measurement results of the copper plating solution to which PG-ND was not added, and FIG. 6 shows the copper plating solution to which PG-ND was added at 50 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, and 1000 ppm, respectively. The results of the absorbance measurement of.
図５，６の結果から、ＮＤ粒子の濃度は吸光度により決定でき、銅めっき液中のＮＤ粒子濃度を適切に管理できることが明らかになった。 From the results of FIGS. 5 and 6, it was clarified that the concentration of ND particles can be determined by the absorbance and the concentration of ND particles in the copper plating solution can be appropriately controlled.
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| JP2002047575A (en) * | 2000-05-22 | 2002-02-15 | C Uyemura & Co Ltd | Automatic analyser and controller of electroless composite plating liquid |
| CN1786686A (en) * | 2005-11-11 | 2006-06-14 | 哈尔滨工业大学 | Method for measuring nano particle content in electroplate liquid or layer by spectrophotometer |
| US20190044185A1 (en) * | 2017-08-01 | 2019-02-07 | Drexel University | Additives for suppressing dendritic growth in batteries |
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| JP2002047575A (en) * | 2000-05-22 | 2002-02-15 | C Uyemura & Co Ltd | Automatic analyser and controller of electroless composite plating liquid |
| CN1786686A (en) * | 2005-11-11 | 2006-06-14 | 哈尔滨工业大学 | Method for measuring nano particle content in electroplate liquid or layer by spectrophotometer |
| US20190044185A1 (en) * | 2017-08-01 | 2019-02-07 | Drexel University | Additives for suppressing dendritic growth in batteries |
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| MEIHUA LIU ET AL.: "Effect of Nanodiamond Concentration and the Current Density of the Electrolyte on the Texture and Me", MATERIALS, vol. Vol.12, No.7, 1105, JPN6022050004, 3 April 2019 (2019-04-03), ISSN: 0004994912 * |
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