WO2019117230A1 - Trivalent chromium plating solution and trivalent chromium plating method using same - Google Patents
Trivalent chromium plating solution and trivalent chromium plating method using same Download PDFInfo
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- WO2019117230A1 WO2019117230A1 PCT/JP2018/045799 JP2018045799W WO2019117230A1 WO 2019117230 A1 WO2019117230 A1 WO 2019117230A1 JP 2018045799 W JP2018045799 W JP 2018045799W WO 2019117230 A1 WO2019117230 A1 WO 2019117230A1
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- trivalent chromium
- plating solution
- chromium plating
- chloride
- plating
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used
Abstract
Description
更に、以下の一般式(1)
で表される不飽和スルホン酸化合物を含有することを特徴とする3価クロムメッキ液である。 That is, the present invention is a trivalent chromium plating solution containing a trivalent chromium compound, a chloride as a conductive salt, a pH buffer, and a complexing agent,
Furthermore, the following general formula (1)
It is a trivalent chromium plating solution characterized by containing the unsaturated sulfonic acid compound represented by these.
で表される不飽和スルホン酸化合物を含有させ、前記3価クロムメッキ液が金属不純物を含有した際の耐性を向上させる方法である。 Furthermore, the present invention is further directed to a trivalent chromium plating solution containing a trivalent chromium compound, a chloride as a conductive salt, a pH buffer, and a complexing agent, further comprising the following general formula (1)
It is the method of containing the unsaturated sulfonic acid compound represented by these, and improving the tolerance when the said trivalent chromium plating liquid contains a metal impurity.
で表される不飽和スルホン酸化合物とニッケルを含有させ、前記3価クロムメッキ液を用いてメッキした際の高電流密度におけるこげを防止する方法である。 Still further, the present invention is further directed to a trivalent chromium plating solution containing a trivalent chromium compound, a chloride as a conductive salt, a pH buffer, a complexing agent, and a compound represented by the following general formula (1)
And the nickel is contained, and it is the method of preventing the burn in the high current density at the time of plating using said trivalent chromium plating liquid.
更に、以下の一般式(1)
Furthermore, the following general formula (1)
クロムメッキ:
以下の基本組成と表1に記載の化合物をそれぞれ水に溶解して、3価クロムメッキ液を調製した。これらの3価クロムメッキ液について、ニッケルメッキを施した真鍮板を用いてハルセル試験を行った。ハルセル試験の条件は電流5A、メッキ時間3分である。メッキ後、真鍮板の左端からメッキ被膜が析出している距離を図1のように測定し、これから、以下のようにしてつきまわり減少率を算出した。また、以下のようにして色調評価と外観評価をした。更に、メッキ後の色調は色彩色差計(コニカミノルタ社製)を用いてL*値により評価した。これらの結果も表1に示した。 Example 1
Chrome-plated:
The following basic compositions and the compounds described in Table 1 were respectively dissolved in water to prepare a trivalent chromium plating solution. A Hull cell test was performed using a nickel-plated brass plate for these trivalent chromium plating solutions. The conditions for the Hull cell test are a current of 5 A and a plating time of 3 minutes. After plating, the distance at which the plating film was deposited from the left end of the brass plate was measured as shown in FIG. 1, and from this, the reduction rate was calculated as follows. Moreover, color tone evaluation and appearance evaluation were performed as follows. Furthermore, the color tone after plating was evaluated by L * value using a colorimeter (manufactured by Konica Minolta Co., Ltd.). These results are also shown in Table 1.
塩基性硫酸クロム 64g/L
ギ酸アンモニウム 16g/L
塩化カリウム 165g/L
塩化アンモニウム 100g/L
臭化アンモニウム 6g/L
ほう酸 67g/L <Basic composition 1>
Basic chromium sulfate 64g / L
Ammonium formate 16 g / L
Potassium chloride 165 g / L
Ammonium chloride 100 g / L
Ammonium bromide 6g / L
67 g / L boric acid
塩基性硫酸クロム 64g/L
ギ酸アンモニウム 16g/L
塩化ナトリウム 75g/L
塩化カリウム 165g/L
塩化アンモニウム 100g/L
臭化アンモニウム 6g/L
ほう酸 67g/L <Basic composition 2>
Basic chromium sulfate 64g / L
Ammonium formate 16 g / L
Sodium chloride 75g / L
Potassium chloride 165 g / L
Ammonium chloride 100 g / L
Ammonium bromide 6g / L
67 g / L boric acid
塩基性硫酸クロム 64g/L
酒石酸アンモニウム 30g/L
硫酸カリウム 150g/L
硫酸アンモニウム 20g/L
ほう酸 80g/L <
Basic chromium sulfate 64g / L
Ammonium tartrate 30g / L
Potassium sulfate 150 g / L
Ammonium sulfate 20 g / L
Boric acid 80 g / L
[数1]
(減少率[%])=((標準値-試験値))/(標準値)×100 <Calculating method of percentage reduction rate>
[Equation 1]
(Decrease rate [%]) = ((standard value-test value)) / (standard value) x 100
(評価)(内容)
○:L*が78以上
×:L*が78未満 <Color tone evaluation>
(Evaluation) (Contents)
○: L * is 78 or more ×: L * is less than 78
○:外観が均一であり、かつムラ模様がない
×:外観が不均一、あるいはムラ模様がある <Appearance evaluation>
○: uniform appearance and no unevenness pattern ×: uneven appearance or uneven pattern
不純物存在下のクロムメッキ:
金属不純物として、ニッケルが100ppmとなるような量のワット浴を添加した以外は実施例1と同様にして3価クロムメッキ液を調製した。これらの3価クロムメッキ液について、実施例1と同様の試験を行った。その結果を表2に示した。 Example 2
Chrome plating in the presence of impurities:
A trivalent chromium plating solution was prepared in the same manner as in Example 1 except that a watt bath containing 100 ppm of nickel was added as a metal impurity. The same tests as in Example 1 were conducted on these trivalent chromium plating solutions. The results are shown in Table 2.
不純物存在下のクロムメッキ:
実施例1で用いた基本組成1と表3に記載の化合物と、金属不純物として、銅が20ppmとなるような量の塩化銅水溶液を含有する3価クロムメッキ液を調製した。この3価クロムメッキ液について、実施例1と同様の試験を行った。その結果を表3に示した。また、比較として特定の構造の不飽和スルホン酸化合物を含有しない3価クロムメッキ液で同様の試験を行った。その結果も表3に示した。 Example 3
Chrome plating in the presence of impurities:
A trivalent chromium plating solution was prepared containing the compounds described in Basic Composition 1 and Table 3 used in Example 1 and an aqueous solution of copper chloride as a metal impurity in such an amount that copper becomes 20 ppm. The same test as in Example 1 was conducted on this trivalent chromium plating solution. The results are shown in Table 3. In addition, as a comparison, the same test was conducted with a trivalent chromium plating solution containing no unsaturated sulfonic acid compound having a specific structure. The results are also shown in Table 3.
クロムメッキ:
以下の基本組成4とビニルスルホン酸ナトリウム25%水溶液とニッケル(塩化ニッケルとして添加)を表4に記載の濃度でそれぞれ水に溶解して、3価クロムメッキ液を調製した。これらの3価クロムメッキ液について、ニッケルメッキを施した真鍮板を用いてハルセル試験を行った。ハルセル試験の条件は電流5A、メッキ時間3分である。この3価クロムメッキ液について、実施例1と同様の試験を行った。また、高電流密度(図1の左端部分)のこげの有無を目視で評価した。その結果も表4に示した。こげの有無の例を示すため、ニッケル無添加のメッキ液でメッキ後の真鍮板(こげあり)を図2に、ニッケル10ppm添加したメッキ液でメッキ後の真鍮板(こげなし)の外観を図3に示した。 Example 4
Chrome-plated:
The following basic composition 4, a 25% aqueous solution of sodium vinyl sulfonate and nickel (added as nickel chloride) were dissolved in water at the concentrations shown in Table 4 to prepare a trivalent chromium plating solution. A Hull cell test was performed using a nickel-plated brass plate for these trivalent chromium plating solutions. The conditions for the Hull cell test are a current of 5 A and a plating time of 3 minutes. The same test as in Example 1 was conducted on this trivalent chromium plating solution. Further, the presence or absence of burnt at high current density (left end in FIG. 1) was visually evaluated. The results are also shown in Table 4. To show an example of the presence or absence of burnt, Figure 2 shows the appearance of a brass plate (without burnt) after plating with a plating solution containing 10 ppm of nickel. It showed to 3.
塩基性硫酸クロム 64g/L
ギ酸アンモニウム 16g/L
塩化ナトリウム 70g/L
塩化カリウム 140g/L
塩化アンモニウム 85g/L
臭化アンモニウム 6g/L
ほう酸 67g/L <Basic composition 4>
Basic chromium sulfate 64g / L
Ammonium formate 16 g / L
Sodium chloride 70g / L
Potassium chloride 140 g / L
Ammonium chloride 85 g / L
Ammonium bromide 6g / L
67 g / L boric acid
クロムメッキ:
基本組成4のメッキ液に、ビニルスルホン酸ナトリウム25%水溶液を添加せず、ニッケルを0、10、30、50ppm添加して3価クロムメッキ液を調製した。これらの3価クロムメッキ液について、ニッケルメッキを施した真鍮板を用いてハルセル試験を行った。ハルセル試験の条件は電流5A、メッキ時間3分である。この3価クロムメッキ液について、実施例1と同様の試験と、実施例4と同様の高電流密度のこげの有無を評価した。 Reference Example 1
Chrome-plated:
A trivalent chromium plating solution was prepared by adding 0, 10, 30, 50 ppm of nickel to the plating solution of the basic composition 4 without adding a 25% aqueous solution of sodium vinyl sulfonate. A Hull cell test was performed using a nickel-plated brass plate for these trivalent chromium plating solutions. The conditions for the Hull cell test are a current of 5 A and a plating time of 3 minutes. With respect to this trivalent chromium plating solution, the same test as in Example 1 and the presence or absence of a high current density burnout as in Example 4 were evaluated.
以 上 The trivalent chromium plating solution of the present invention can be used in various applications as the plating using hexavalent chromium.
that's all
Claims (11)
- 3価クロム化合物、伝導性塩として塩化物、pH緩衝剤、錯化剤を含有する3価クロムメッキ液であって、
更に、以下の一般式(1)
で表される不飽和スルホン酸化合物を含有することを特徴とする3価クロムメッキ液。 A trivalent chromium plating solution containing a trivalent chromium compound, a chloride as a conductive salt, a pH buffer, and a complexing agent,
Furthermore, the following general formula (1)
A trivalent chromium plating solution comprising the unsaturated sulfonic acid compound represented by - 不飽和スルホン酸化合物が、ビニルスルホン酸ナトリウム、アリルスルホン酸ナトリウムおよびp-スチレンスルホン酸ナトリウム、β-スチレンスルホン酸ナトリウムからなる群から選ばれる1種または2種以上である請求項1記載の3価クロムメッキ液。 The unsaturated sulfonic acid compound is one or more selected from the group consisting of sodium vinyl sulfonate, sodium allyl sulfonate, sodium p-styrene sulfonate, and sodium β-styrene sulfonate according to claim 1. Chromium plating solution.
- 塩化物が、塩化カリウム、塩化アンモニウム、塩化ナトリウムからなる群から選ばれる1種または2種以上である請求項1記載の3価クロムメッキ液。 The trivalent chromium plating solution according to claim 1, wherein the chloride is one or more selected from the group consisting of potassium chloride, ammonium chloride and sodium chloride.
- 更に、金属不純物を含有する請求項1~3の何れかに記載の3価クロムメッキ液。 The trivalent chromium plating solution according to any one of claims 1 to 3, further comprising a metal impurity.
- 更に、ニッケルを含有する請求項1~4の何れかに記載の3価クロムメッキ液。 The trivalent chromium plating solution according to any one of claims 1 to 4, further comprising nickel.
- 鉄および/またはコバルトを実質的に含有しないものである請求項1~5の何れかに記載の3価クロムメッキ液。 The trivalent chromium plating solution according to any one of claims 1 to 5, which is substantially free of iron and / or cobalt.
- 被メッキ物を、請求項1~6の何れかに記載の3価クロムメッキ液で電気メッキすることを特徴とする被メッキ物への3価クロムメッキ方法。 A method for trivalent chromium plating on an object to be plated, which comprises electroplating the object to be plated with the trivalent chromium plating solution according to any one of claims 1 to 6.
- 3価クロム化合物、伝導性塩として塩化物、pH緩衝剤、錯化剤を含有する3価クロムメッキ液に、更に、以下の一般式(1)
で表される不飽和スルホン酸化合物を含有させ、前記3価クロムメッキ液が金属不純物を含有した際の耐性を向上させる方法。 In addition to the trivalent chromium plating solution containing a trivalent chromium compound, a chloride as a conductive salt, a pH buffer, and a complexing agent, the following general formula (1)
And a method of improving resistance when the trivalent chromium plating solution contains a metal impurity. - 3価クロム化合物、伝導性塩として塩化物、pH緩衝剤、錯化剤を含有する3価クロムメッキ液に、更に、以下の一般式(1)
で表される不飽和スルホン酸化合物とニッケルを含有させ、前記3価クロムメッキ液を用いてメッキした際の高電流密度におけるこげを防止する方法。 In addition to the trivalent chromium plating solution containing a trivalent chromium compound, a chloride as a conductive salt, a pH buffer, and a complexing agent, the following general formula (1)
A method for preventing the dark current at high current density when plating using the above-mentioned trivalent chromium plating solution, containing the unsaturated sulfonic acid compound represented by and nickel. - 被メッキ物を、請求項1~6の何れかに記載の3価クロムメッキ液で電気メッキして得られるクロムメッキ製品。 A chromium plated product obtained by electroplating a material to be plated with the trivalent chromium plating solution according to any one of claims 1 to 6.
- クロムメッキが鉄および/またはコバルトを実質的に含有しないものである請求項10記載のクロムメッキ製品。 The chromium plated product according to claim 10, wherein the chromium plating is substantially free of iron and / or cobalt.
Priority Applications (5)
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EP18888525.5A EP3725919A4 (en) | 2017-12-14 | 2018-12-13 | Trivalent chromium plating solution and trivalent chromium plating method using same |
CN201880080667.3A CN111479956A (en) | 2017-12-14 | 2018-12-13 | Trivalent chromium plating solution and trivalent chromium plating method using the same |
US16/771,066 US20210198797A1 (en) | 2017-12-14 | 2018-12-13 | Trivalent chromium plating solution and trivalent chromium plating method using same |
JP2019559193A JPWO2019117230A1 (en) | 2017-12-14 | 2018-12-13 | Trivalent chromium plating solution and trivalent chromium plating method using this |
KR1020207017355A KR20200096932A (en) | 2017-12-14 | 2018-12-13 | Trivalent chromium plating solution and trivalent chromium plating method using the same |
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EP (1) | EP3725919A4 (en) |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS57152483A (en) * | 1981-02-09 | 1982-09-20 | W Kiyaningu Materiaruzu Ltd | Chromium electrodeposition |
JP2009074170A (en) | 2007-08-30 | 2009-04-09 | Nissan Motor Co Ltd | Chrome-plated part and manufacturing method of the same |
JP2016172933A (en) * | 2011-05-03 | 2016-09-29 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングAtotech Deutschland GmbH | Electroplating bath and method for producing dark chromium layers |
Family Cites Families (7)
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US4167460A (en) * | 1978-04-03 | 1979-09-11 | Oxy Metal Industries Corporation | Trivalent chromium plating bath composition and process |
US4450052A (en) * | 1982-07-28 | 1984-05-22 | M&T Chemicals Inc. | Zinc and nickel tolerant trivalent chromium plating baths |
CA1223547A (en) * | 1983-07-27 | 1987-06-30 | Louis Gianelos | Electrodeposition from trivalent chromium bath |
GB8503019D0 (en) * | 1985-02-06 | 1985-03-06 | Canning W Materials Ltd | Electroplating |
US9765437B2 (en) * | 2009-03-24 | 2017-09-19 | Roderick D. Herdman | Chromium alloy coating with enhanced resistance to corrosion in calcium chloride environments |
CN101792917A (en) * | 2010-03-31 | 2010-08-04 | 哈尔滨工业大学 | Preparation method and electroplating method of normal-temperature environment-friendly sulfate trivalent chromium electroplating liquid |
CN105671599A (en) * | 2016-04-11 | 2016-06-15 | 济南德锡科技有限公司 | Sulfate trivalent chromium electroplating solution and preparation method thereof |
-
2018
- 2018-12-13 JP JP2019559193A patent/JPWO2019117230A1/en active Pending
- 2018-12-13 WO PCT/JP2018/045799 patent/WO2019117230A1/en unknown
- 2018-12-13 US US16/771,066 patent/US20210198797A1/en not_active Abandoned
- 2018-12-13 EP EP18888525.5A patent/EP3725919A4/en not_active Withdrawn
- 2018-12-13 CN CN201880080667.3A patent/CN111479956A/en active Pending
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57152483A (en) * | 1981-02-09 | 1982-09-20 | W Kiyaningu Materiaruzu Ltd | Chromium electrodeposition |
JP2009074170A (en) | 2007-08-30 | 2009-04-09 | Nissan Motor Co Ltd | Chrome-plated part and manufacturing method of the same |
JP2016172933A (en) * | 2011-05-03 | 2016-09-29 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングAtotech Deutschland GmbH | Electroplating bath and method for producing dark chromium layers |
Non-Patent Citations (1)
Title |
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See also references of EP3725919A4 * |
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KR20200096932A (en) | 2020-08-14 |
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EP3725919A4 (en) | 2021-09-01 |
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