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 PDF

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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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PCT/JP2018/045799
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French (fr)
Japanese (ja)
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雄斗 森川
真雄 堀
まどか 中上
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株式会社Jcu
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Priority to EP18888525.5A priority Critical patent/EP3725919A4/en
Priority to CN201880080667.3A priority patent/CN111479956A/en
Priority to US16/771,066 priority patent/US20210198797A1/en
Priority to JP2019559193A priority patent/JPWO2019117230A1/en
Priority to KR1020207017355A priority patent/KR20200096932A/en
Publication of WO2019117230A1 publication Critical patent/WO2019117230A1/en

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/04Electroplating: Baths therefor from solutions of chromium
    • C25D3/06Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/04Electroplating: Baths therefor from solutions of chromium
    • C25D3/10Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used

Abstract

Provided are: a trivalent chromium plating solution which contains a trivalent chromium compound, a chloride that serves as a conductive salt, a pH buffering agent and a complexing agent, and which is characterized by additionally containing an unsaturated sulfonic acid represented by general formula (1) (in general formula (1), R1 represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1-10 carbon atoms; R2 is absent or represents a hydrocarbon group having 1-10 carbon atoms; and X represents a hydrogen atom or an alkali metal atom); and a trivalent chromium plating method which uses this trivalent chromium plating solution. The trivalent chromium plating solution and the trivalent chromium plating method according to the present invention are consequently free from problems such as deposition failure of a plating and generation of color unevenness such as brown stripes in a plating even if a metal impurity is contained in the plating solution.

Description

3価クロムメッキ液およびこれを用いた3価クロムメッキ方法Trivalent chromium plating solution and trivalent chromium plating method using the same
 本発明は、3価クロムメッキ液およびこれを用いた3価クロムメッキ方法に関する。 The present invention relates to a trivalent chromium plating solution and a trivalent chromium plating method using the same.
 クロムメッキは、銀白色の外観を有するため装飾用のコーティング膜として用いられている。このクロムメッキには6価のクロムが用いられていたが、近年ではこの6価のクロムが環境に影響を及ぼすため、その使用が制限されてきていて、3価のクロムを用いる技術へシフトしてきている。 Chrome plating is used as a coating film for decoration because it has a silver-white appearance. Although hexavalent chromium was used for this chromium plating, since this hexavalent chromium affects the environment in recent years, its use has been limited, and the technology has shifted to the technique using trivalent chromium. ing.
 このような3価のクロムを用いる技術は種々のメーカーから多数報告されている(例えば、特許文献1参照)。 Many techniques using such trivalent chromium have been reported by various manufacturers (see, for example, Patent Document 1).
 しかしながら、3価のクロムメッキ液の場合、下地にされるメッキやその他メッキに付随する薬品等に由来する金属不純物が入ることにより、メッキの未析出やメッキに茶色の縞模様等の色むらが発生する等の問題があった。 However, in the case of a trivalent chromium plating solution, metal impurities derived from the plating used as the substrate and other chemicals that accompany the plating are included, resulting in non-deposition of plating and color unevenness such as brown stripes in plating. There were problems such as occurrence.
特開2009-74170号公報JP, 2009-74170, A
 本発明の課題は、メッキ液に金属不純物が入ったとしても、メッキの未析出やメッキに茶色の縞模様等の色むらが発生する等の問題が生じない3価のクロムメッキ液を提供することである。 An object of the present invention is to provide a trivalent chromium plating solution which does not cause problems such as non-deposition of plating and occurrence of color unevenness such as brown stripes in plating even if metal impurities enter the plating solution. It is.
 本発明者らは、上記課題を解決するために鋭意研究した結果、伝導性塩として塩化物を含有する3価クロムメッキ液に、特定の構造の不飽和スルホン酸化合物を含有させることにより、メッキ液に金属不純物が入ったとしても、メッキの未析出やメッキに茶色の縞模様等の色むらが発生する等の問題が生じないことを見出し、本発明を完成させた。また、金属不純物としてニッケルを3価クロムメッキ液に積極的に含有させることにより、前記問題だけではなく、メッキした際の高電流密度におけるこげを防止できることも見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have found that a trivalent chromium plating solution containing a chloride as a conductive salt contains an unsaturated sulfonic acid compound having a specific structure, thereby achieving plating. It was found that even if metal impurities were contained in the solution, problems such as non-deposition of plating and occurrence of color unevenness such as brown streaks did not occur in plating, and the present invention was completed. In addition to the above problems, it has been found that by actively incorporating nickel as a metal impurity in a trivalent chromium plating solution, it is possible to prevent burnout at a high current density when plating, and the present invention has been completed.
 すなわち、本発明は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)
Figure JPOXMLDOC01-appb-C000004
(ただし、式(1)中、Rは炭素数1~10の炭化水素基、水素またはハロゲンを示し、Rはなしまたは炭素数1~10の炭化水素基を示し、Xは水素またはアルカリ金属を示す。)
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)
Figure JPOXMLDOC01-appb-C000004
(Wherein, in the formula (1), R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, hydrogen or a halogen, R 2 represents none or a hydrocarbon group having 1 to 10 carbon atoms, and X represents a hydrogen or an alkali metal Indicate
It is a trivalent chromium plating solution characterized by containing the unsaturated sulfonic acid compound represented by these.
 また、本発明は、被メッキ物を、上記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である。 Further, the present invention is a method of trivalent chromium plating on an object to be plated, characterized in that the object to be plated is electroplated with the above-mentioned trivalent chromium plating solution.
 更に、本発明は、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)
Figure JPOXMLDOC01-appb-C000005
(ただし、式(1)中、Rは炭素数1~10の炭化水素基、水素またはハロゲンを示し、Rはなしまたは炭素数1~10の炭化水素基を示し、Xは水素またはアルカリ金属を示す。)
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)
Figure JPOXMLDOC01-appb-C000005
(Wherein, in the formula (1), R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, hydrogen or a halogen, R 2 represents none or a hydrocarbon group having 1 to 10 carbon atoms, and X represents a hydrogen or an alkali metal Indicate
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.
 また更に、本発明は、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)
Figure JPOXMLDOC01-appb-C000006
(ただし、式(1)中、Rは炭素数1~10の炭化水素基、水素またはハロゲンを示し、Rはなしまたは炭素数1~10の炭化水素基を示し、Xは水素またはアルカリ金属を示す。)
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)
Figure JPOXMLDOC01-appb-C000006
(Wherein, in the formula (1), R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, hydrogen or a halogen, R 2 represents none or a hydrocarbon group having 1 to 10 carbon atoms, and X represents a hydrogen or an alkali metal Indicate
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.
 更にまた、本発明は、被メッキ物を、上記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である。 Furthermore, the present invention is a chromium plated product obtained by electroplating a material to be plated with the above trivalent chromium plating solution.
 本発明の3価のクロムメッキ液は、金属不純物が入ったとしても、メッキの未析出やメッキに茶色の縞模様等の色むらが発生する等の問題が生じない優れたものである。 The trivalent chromium plating solution of the present invention is an excellent one that does not cause problems such as non-deposition of plating and occurrence of color unevenness such as brown stripes in plating even if metal impurities are contained.
 また、本発明の3価のクロムメッキ液に、金属不純物としてニッケルを積極的に含有させることにより、前記問題だけではなく、メッキした際の高電流密度におけるこげを防止できる。 Further, not only the above-mentioned problems but also the darkening at high current density when plating can be prevented by positively containing nickel as a metal impurity in the trivalent chromium plating solution of the present invention.
実施例1のハルセル試験において付きまわりの距離を測定した位置を示す図である。FIG. 7 is a view showing the position at which the distance around the stick was measured in the Hull cell test of Example 1; 実施例4において、ニッケル無添加のメッキ液でメッキ後のニッケルメッキを施した真鍮板(こげあり)のハルセル外観を示す図である。In Example 4, it is a figure which shows the Hull cell external appearance of the brass plate (with a koge) which performed nickel plating after plating by the plating solution without nickel addition. 実施例4において、ニッケル10ppm添加したメッキ液でメッキ後のニッケルメッキを施した真鍮板(こげなし)のハルセル外観を示す図である。In Example 4, it is a figure which shows the Hull cell external appearance of the brass plate (it is not shown) which plated nickel by plating liquid which added nickel 10 ppm.
 本発明の3価クロムメッキ液(以下、「本発明メッキ液」という)は、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)
Figure JPOXMLDOC01-appb-C000007
で表される不飽和スルホン酸化合物を含有するものである。
The trivalent chromium plating solution of the present invention (hereinafter referred to as "the plating solution of 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)
Figure JPOXMLDOC01-appb-C000007
It contains the unsaturated sulfonic acid compound represented by these.
 上記式(1)中、Rは炭素数1~10の炭化水素基、水素またはハロゲンを示し、Rはなしまたは炭素数1~10の炭化水素基を示し、Xは水素またはアルカリ金属を示し、好ましくはRは炭素数1~6の炭化水素基または水素を示し、Rはなしまたは炭素数1~6の炭化水素基を示し、Xは水素、ナトリウムまたはカリウムを示す。上記式(1)が示す具体的な不飽和スルホン酸化合物としては、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等が挙げられる。これら不飽和スルホン酸化合物は1種または2種以上を組み合わせてもよい。本発明メッキ液における不飽和スルホン酸化合物の含有量は特に限定されないが、例えば、0.01~20g/Lであり、好ましくは0.1~5g/Lである。 In the above formula (1), R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, hydrogen or halogen, R 2 represents no or a hydrocarbon group having 1 to 10 carbon atoms, and X represents hydrogen or an alkali metal. Preferably, R 1 represents a hydrocarbon group having 1 to 6 carbon atoms or hydrogen, R 2 represents no or a hydrocarbon group having 1 to 6 carbon atoms, and X represents hydrogen, sodium or potassium. Specific unsaturated sulfonic acid compounds represented by the above formula (1) include sodium vinylsulfonate, sodium allylsulfonate, sodium p-styrenesulfonate, sodium β-styrenesulfonate and the like. These unsaturated sulfonic acid compounds may be used alone or in combination of two or more. The content of the unsaturated sulfonic acid compound in the plating solution of the present invention is not particularly limited, and is, for example, 0.01 to 20 g / L, and preferably 0.1 to 5 g / L.
 本発明メッキ液に用いられる3価クロム化合物は、特に限定されないが、例えば、塩基性硫酸クロム、硫酸クロム、塩化クロム、スルファミン酸クロム、酢酸クロムであり、好ましくは塩基性硫酸クロム、硫酸クロム、塩化クロムである。これら3価クロム化合物は1種または2種以上を組み合わせてもよい。本発明メッキ液における3価クロム化合物の含有量は特に限定されないが、例えば金属クロムとして1~20g/Lであり、好ましくは5~15g/Lである。 The trivalent chromium compound used in the plating solution of the present invention is not particularly limited, and is, for example, basic chromium sulfate, chromium sulfate, chromium chloride, chromium sulfamate, chromium acetate, preferably basic chromium sulfate, chromium sulfate, It is chromium chloride. These trivalent chromium compounds may be used alone or in combination of two or more. Although the content of the trivalent chromium compound in the plating solution of the present invention is not particularly limited, it is, for example, 1 to 20 g / L as metal chromium, preferably 5 to 15 g / L.
 本発明メッキ液に用いられる伝導性塩は、塩化物である。塩化物の種類は特に限定されないが、例えば、塩化カリウム、塩化アンモニウム、塩化ナトリウム等が挙げられる。これら塩化物は1種または2種以上を組み合わせてもよい。本発明メッキ液における塩化物の含有量は特に限定されないが、例えば、150~400g/Lであり、好ましくは200~350g/Lである。 The conductive salt used in the plating solution of the present invention is a chloride. The type of chloride is not particularly limited, and examples include potassium chloride, ammonium chloride, sodium chloride and the like. These chlorides may be used alone or in combination of two or more. The content of chloride in the plating solution of the present invention is not particularly limited, and is, for example, 150 to 400 g / L, preferably 200 to 350 g / L.
 本発明メッキ液に用いられるpH緩衝剤は、特に限定されないが、例えば、ホウ酸、ホウ酸ナトリウム、ホウ酸カリウム、リン酸、リン酸水素2カリウム等であり、好ましくはホウ酸、ホウ酸ナトリウムである。これらpH緩衝剤は1種または2種以上を組み合わせてもよい。本発明メッキ液におけるpH緩衝剤の含有量は特に限定されないが、例えば、10~150g/Lであり、好ましくは50~100g/Lである。 The pH buffer used in the plating solution of the present invention is not particularly limited, and examples thereof include boric acid, sodium borate, potassium borate, phosphoric acid, and dipotassium hydrogen phosphate, preferably boric acid and sodium borate. It is. These pH buffers may be used alone or in combination of two or more. The content of the pH buffer in the plating solution of the present invention is not particularly limited, and is, for example, 10 to 150 g / L, preferably 50 to 100 g / L.
 本発明メッキ液に用いられる錯化剤は、特に限定されないが、例えば、ギ酸、ギ酸アンモニウム、ギ酸カリウム、クエン酸、クエン酸三アンモニウム等が挙げられる。これらの中でも、ギ酸アンモニウム、クエン酸三アンモニウムが好ましい。これら錯化剤は1種または2種以上を組み合わせて用いることができる。本発明メッキ液における錯化剤の含有量は特に限定されないが、例えば、金属クロム濃度に対して0.3~2倍モル濃度、好ましくは0.8~1.5倍モル濃度である。 The complexing agent used in the plating solution of the present invention is not particularly limited, and examples thereof include formic acid, ammonium formate, potassium formate, citric acid, triammonium citrate and the like. Among these, ammonium formate and triammonium citrate are preferable. These complexing agents can be used alone or in combination of two or more. Although the content of the complexing agent in the plating solution of the present invention is not particularly limited, it is, for example, 0.3 to 2 times by mole, preferably 0.8 to 1.5 times by mole, the metal chromium concentration.
 本発明メッキ液には、更に、臭化アンモニウム、臭化カリウム等を含有させてもよい。 The plating solution of the present invention may further contain ammonium bromide, potassium bromide and the like.
 本発明メッキ液のpHは酸性であれば特に限定されず、例えば、2~4が好ましく、2.5~3.5がより好ましい。 The pH of the plating solution of the present invention is not particularly limited as long as it is acidic, and is preferably, for example, 2 to 4, and more preferably 2.5 to 3.5.
 本発明メッキ液の調製法は特に限定されず、例えば、40~50℃の水に3価クロム化合物、塩化物塩、pH緩衝剤、錯化剤、不飽和スルホン酸化合物を添加、混合したり、必要によりその他の成分を添加、混合したり、pHを調整することにより調製することができる。 The preparation method of the plating solution of the present invention is not particularly limited. For example, trivalent chromium compound, chloride salt, pH buffer, complexing agent and unsaturated sulfonic acid compound are added to water at 40 to 50 ° C. If necessary, it can be prepared by adding and mixing other components and adjusting the pH.
 なお、本発明メッキ液は、金属不純物が含有されたとしても、メッキの未析出やメッキに茶色の縞模様等の色むらが発生する等の問題がない(つまり、金属不純物への耐性がある)。特に本発明メッキ液は、長期間の使用や突発的に、金属不純物が数百ppm程度の濃度で多量に含有されたとしても、上記問題がない。ここで金属不純物は、下地にされるメッキやその他メッキに付随する薬品等に由来する金属である。具体的な金属としては、例えば、ニッケル、亜鉛、銅、6価のクロム等が挙げられ、好ましくは下地メッキに用いられることが多いニッケルまたは銅である。 In the plating solution of the present invention, even if metal impurities are contained, there is no problem such as non-deposition of plating or occurrence of color unevenness such as brown stripes in plating (that is, resistance to metal impurities) ). In particular, the plating solution of the present invention does not have the above problems even if the metal impurity is contained in a large amount at a concentration of about several hundreds ppm for long-term use or suddenly. Here, the metal impurities are metals derived from the plating used as the base and other chemicals accompanying the plating. Specific metals include, for example, nickel, zinc, copper, hexavalent chromium and the like, preferably nickel or copper which is often used for base plating.
 また、本発明メッキ液の場合、金属不純物として、ニッケルを積極的に含有させた場合、メッキした際の高電流密度におけるこげを防止することができる。ここで高電流密度とは、品物の角部や先端部など、電流が集中しやすい箇所のことをいう。本発明メッキ液に用いることのできるニッケルは、特に限定されないが、例えば、塩化ニッケル、硫酸ニッケル等のニッケル塩等が挙げられる。本発明メッキ液におけるニッケルの含有量は特に限定されないが、例えば、10~500ppm、好ましくは15~200ppmであり、より好ましくは20~100ppmである。 In addition, in the case of the plating solution of the present invention, when nickel is positively contained as a metal impurity, it is possible to prevent burnout at a high current density when plating. Here, the high current density means a portion where current tends to be concentrated, such as a corner or a tip of an item. The nickel that can be used in the plating solution of the present invention is not particularly limited, and examples thereof include nickel salts such as nickel chloride and nickel sulfate. The content of nickel in the plating solution of the present invention is not particularly limited, but is, for example, 10 to 500 ppm, preferably 15 to 200 ppm, and more preferably 20 to 100 ppm.
 なお、ニッケルは本発明メッキ液から一般式(1)で表される不飽和スルホン酸化合物を除いた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も同様の濃度でメッキした際の高電流密度におけるこげを防止する。3価クロム化合物、塩化物、pH緩衝剤、錯化剤については、本発明メッキ液と同様の種類、濃度である。 Nickel is a trivalent chromium compound obtained by removing the unsaturated sulfonic acid compound represented by the general formula (1) from the plating solution of the present invention, a chloride as a conductive salt, a pH buffer, and a complexing agent. Even with a chromium plating solution, it prevents burnout at high current density when plating at the same concentration. The trivalent chromium compound, the chloride, the pH buffer, and the complexing agent are the same kind and concentration as the plating solution of the present invention.
 更に、通常の3価クロムメッキ液には、低電流密度へのつきまわりを向上させるために、鉄やコバルトを含有させるが、上記した本発明メッキ液は、鉄および/またはコバルトを含有させなくてもつきまわりが向上する。なお、鉄やコバルトを含有するメッキ液の場合、メッキ皮膜中に鉄やコバルトの共析により耐食性が低下する傾向にある。そのため、本発明メッキ液には鉄および/またはコバルトを実質的に含有させないことが好ましい。本発明メッキ液が鉄および/またはコバルトを実質的に含有しないとは、鉄および/またはコバルトが2ppm以下、好ましくは1ppm以下、より好ましくは 0.5ppm以下であることを言う。この鉄および/またはコバルトの量はICP-MS法や原子吸光光度法等で分析することができる。 Furthermore, although the normal trivalent chromium plating solution contains iron and cobalt in order to improve the low current density, the above-mentioned plating solution of the present invention does not contain iron and / or cobalt. Even so, the enthusiasm improves. In the case of a plating solution containing iron or cobalt, the corrosion resistance tends to decrease due to the co-precipitation of iron or cobalt in the plating film. Therefore, it is preferable that the plating solution of the present invention does not substantially contain iron and / or cobalt. When the plating solution of the present invention contains substantially no iron and / or cobalt, it means that iron and / or cobalt is 2 ppm or less, preferably 1 ppm or less, more preferably 0.5 ppm or less. The amount of iron and / or cobalt can be analyzed by ICP-MS, atomic absorption spectrophotometry, or the like.
 本発明メッキ液は、従来のクロムメッキ液と同様に、被メッキ物を本発明メッキ液で電気メッキすることにより被メッキ物へクロムメッキをすることができる。 The plating solution of the present invention can be plated with chromium on a material to be plated by electroplating the material to be plated with the plating solution of the present invention, as in the conventional chromium plating solution.
 電気メッキの条件は特に限定されないが、例えば、浴温が25~45℃、アノードがカーボンあるいは酸化イリジウム、陰極電流密度が4~20A/dm、で1~15分間電気メッキを行えばよい。 The conditions for electroplating are not particularly limited. For example, electroplating may be performed for 1 to 15 minutes at a bath temperature of 25 to 45 ° C., an anode of carbon or iridium oxide, and a cathode current density of 4 to 20 A / dm 2 .
 電気メッキすることのできる被メッキ物としては、例えば、鉄、ステンレス、真鍮等の金属、ABS、PC/ABS等の樹脂が挙げられる。なお、この被メッキ部材は本発明のメッキ液で処理する前に予め銅メッキ、ニッケルメッキ等の処理をしておいてもよい。 As a thing to be plated which can be electroplated, metals, such as iron, stainless steel, and brass, resin, such as ABS and PC / ABS, are mentioned, for example. The member to be plated may be treated beforehand with copper plating, nickel plating or the like before being treated with the plating solution of the present invention.
 斯くして得られるクロムメッキは、6価のクロムを用いたのと同程度の外観、つきまわり性、析出速度を有するクロムメッキとなる。また、式(1)で表される不飽和スルホン酸化合物は、その他の不飽和スルホン酸化合物と比較して、得られるクロムメッキの色調の暗色化も抑えられる。そのため、このクロムめっき製品は、ドアハンドルやエンブレムなどの自動車外装部品、アクセサリー、水洗金具、工具等の部品にするのに好適である。 The chromium plating thus obtained is a chromium plating having the same appearance, throwing power and deposition rate as hexavalent chromium. In addition, the unsaturated sulfonic acid compound represented by the formula (1) can suppress the darkening of the color tone of the obtained chromium plating as compared with other unsaturated sulfonic acid compounds. Therefore, this chrome-plated product is suitable for use as parts such as automobile exterior parts such as door handles and emblems, accessories, flush fittings, tools and the like.
 また、本発明メッキ液が鉄および/またはコバルトを実質的に含有しない場合には、得られるクロムメッキ製品も鉄および/またはコバルトを実質的に含有しない。本発明のクロムメッキ製品が鉄および/またはコバルトを実質的に含有しないとは、クロムメッキ中に鉄および/またはコバルトが0.5at%未満、好ましくは0.3at%以下であることを言う。この鉄および/またはコバルトの量はEDSやXPS等で分析することができる。 Moreover, when the plating solution of the present invention contains substantially no iron and / or cobalt, the resulting chromium plated product also contains substantially no iron and / or cobalt. When the chromium plating product of the present invention contains substantially no iron and / or cobalt, it means that iron and / or cobalt is less than 0.5 at%, preferably 0.3 at% or less during chromium plating. The amount of iron and / or cobalt can be analyzed by EDS, XPS or the like.
 以下、本発明を実施例を挙げて詳細に説明するが、本発明はこれら実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.
実 施 例 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.
<基本組成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
<基本組成2>
 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
<基本組成3>
 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 composition 3>
Basic chromium sulfate 64g / L
Ammonium tartrate 30g / L
Potassium sulfate 150 g / L
Ammonium sulfate 20 g / L
Boric acid 80 g / L
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
<つきまわり減少率算出方法>
[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
 上記式において、標準値は無添加時のつきまわりの値であり、試験値は各条件で試験した際のつきまわり実測値である。標準値の値はそれぞれ、基本組成1:71mm、基本組成2:73mm、基本組成3:74mmである。 In the above equation, the standard value is the value at the time of no addition, and the test value is the actually measured value at the time of testing under each condition. The standard values are, respectively, a base composition 1:71 mm, a base composition 2:73 mm, and a base composition 3:74 mm.
<色調評価>
(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
<外観評価>
  ○: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
 これらの結果から、本発明メッキ液に含有される不飽和スルホン酸化合物は、これの使用によってクロムメッキの色調や外観、つきまわりを損なう物質ではないことがわかった。 From these results, it has been found that the unsaturated sulfonic acid compound contained in the plating solution of the present invention is not a material that impairs the color tone, appearance, and throwing power of chromium plating due to its use.
 なお、上記した3価クロムメッキ液中の鉄およびコバルトをICP-MS法で測定した結果、それぞれ0.5ppm未満であった。また、得られたクロムメッキ中の鉄およびコバルトをEDSによる元素分析で測定した結果、それぞれ0.3at%未満であった。 As a result of measuring iron and cobalt in the above-described trivalent chromium plating solution by the ICP-MS method, they were less than 0.5 ppm respectively. Moreover, as a result of measuring iron and cobalt in the obtained chromium plating by the elemental analysis by EDS, they were each less than 0.3 at%.
実 施 例 2
   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.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
 塩化物浴であり、特定の構造の不飽和スルホン酸化合物を含有する本発明の3価クロムメッキ液(実施品)は、メッキ液中に金属不純物としてニッケルを100ppm含有する場合であっても、メッキの性能に影響がないことがわかった。一方、同じ3価クロムメッキ液であっても硫酸浴の場合(比較品の基本組成3のもの)には、特定の構造の不飽和スルホン酸化合物を含有していても金属不純物耐性がないことがわかった。また、塩化物浴であっても、特定の構造でない場合には、メッキ液中に金属不純物としてニッケルを100ppm含有する場合にメッキの性能に影響があることもわかった。 The trivalent chromium plating solution (implementation article) of the present invention, which is a chloride bath and contains an unsaturated sulfonic acid compound having a specific structure, has 100 ppm of nickel as a metal impurity in the plating solution, It was found that the performance of the plating was not affected. On the other hand, even in the case of the sulfuric acid bath (the basic composition 3 of the comparative product), even if it is the same trivalent chromium plating solution, there is no metal impurity resistance even if it contains the unsaturated sulfonic acid compound of a specific structure I understand. In addition, it was also found that the plating performance is affected when the plating solution contains 100 ppm of nickel as a metal impurity unless it has a specific structure, even in a chloride bath.
 なお、上記した3価クロムメッキ液中の鉄およびコバルトをICP-MS法で測定した結果、それぞれ0.5ppm未満であった。また、得られたクロムメッキ中の鉄およびコバルトをEDSによる元素分析で測定した結果、それぞれ0.3at%未満であった。 As a result of measuring iron and cobalt in the above-described trivalent chromium plating solution by the ICP-MS method, they were less than 0.5 ppm respectively. Moreover, as a result of measuring iron and cobalt in the obtained chromium plating by the elemental analysis by EDS, they were each less than 0.3 at%.
実 施 例 3
   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.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
 本発明の3価クロムメッキ液(実施品)は、メッキ液中に金属不純物として銅を20ppm含有する場合であっても、メッキの性能に影響がないことがわかった。 It was found that the trivalent chromium plating solution (implemented product) of the present invention did not affect the plating performance even when 20 ppm of copper was contained as a metal impurity in the plating solution.
 なお、上記した3価クロムメッキ液中の鉄およびコバルトをICP-MS法で測定した結果、それぞれ0.5ppm未満であった。また、得られたクロムメッキ中の鉄およびコバルトをEDSによる元素分析で測定した結果、それぞれ0.3at%未満であった。 As a result of measuring iron and cobalt in the above-described trivalent chromium plating solution by the ICP-MS method, they were less than 0.5 ppm respectively. Moreover, as a result of measuring iron and cobalt in the obtained chromium plating by the elemental analysis by EDS, they were each less than 0.3 at%.
実 施 例 4
   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.
<基本組成4>
 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
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
 本発明の3価クロムメッキ液(実施品)は、メッキ液中に金属不純物としてニッケルを積極的に含有させることによりメッキした際の高電流密度におけるこげを防止できることがわかった。 It has been found that the trivalent chromium plating solution (implemented product) of the present invention can prevent darkening at high current density when plating by positively containing nickel as a metal impurity in the plating solution.
 なお、上記した3価クロムメッキ液中の鉄およびコバルトをICP-MS法で測定した結果、それぞれ0.5ppm未満であった。また、得られたクロムメッキ中の鉄およびコバルトをEDSによる元素分析で測定した結果、それぞれ0.3at%未満であった。 As a result of measuring iron and cobalt in the above-described trivalent chromium plating solution by the ICP-MS method, they were less than 0.5 ppm respectively. Moreover, as a result of measuring iron and cobalt in the obtained chromium plating by the elemental analysis by EDS, they were each less than 0.3 at%.
参 考 例 1
   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.
 本発明の3価クロムメッキ液は、メッキ液中に金属不純物としてニッケルを積極的に含有させることにより、得られるメッキの色調や外観は実施例1~3のビニルスルホン酸ナトリウム25%水溶液を添加したものでメッキした際と同等で、メッキした際に高電流密度におけるこげを防止できることがわかった。なお、ニッケルを無添加の場合にはメッキした際に高電流密度におけるこげが発生した。 The color tone and appearance of the plating obtained by positively containing nickel as a metal impurity in the plating solution of the trivalent chromium plating solution of the present invention were obtained by adding a 25% aqueous solution of sodium vinyl sulfonate of Examples 1 to 3. It was found that it is possible to prevent darkening at high current density when plating, which is the same as when plating with copper. In the case of no addition of nickel, burnt occurred at high current density when plating.
 本発明の3価のクロムメッキ液は、6価のクロムを用いたメッキと同様に各種用途に用いることができる。
                         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)

  1.  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)
    Figure JPOXMLDOC01-appb-C000001
    (ただし、式(1)中、Rは炭素数1~10の炭化水素基、水素またはハロゲンを示し、Rはなしまたは炭素数1~10の炭化水素基を示し、Xは水素またはアルカリ金属を示す。)
    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)
    Figure JPOXMLDOC01-appb-C000001
    (Wherein, in the formula (1), R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, hydrogen or a halogen, R 2 represents none or a hydrocarbon group having 1 to 10 carbon atoms, and X represents a hydrogen or an alkali metal Indicate
    A trivalent chromium plating solution comprising the unsaturated sulfonic acid compound represented by
  2.  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.
  3.  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.
  4.  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.
  5.  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.
  6.  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.
  7.  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.
  8.  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)
    Figure JPOXMLDOC01-appb-C000002
    (ただし、式(1)中、Rは炭素数1~10の炭化水素基、水素またはハロゲンを示し、Rはなしまたは炭素数1~10の炭化水素基を示し、Xは水素またはアルカリ金属を示す。)
    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)
    Figure JPOXMLDOC01-appb-C000002
    (Wherein, in the formula (1), R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, hydrogen or a halogen, R 2 represents none or a hydrocarbon group having 1 to 10 carbon atoms, and X represents a hydrogen or an alkali metal Indicate
    And a method of improving resistance when the trivalent chromium plating solution contains a metal impurity.
  9.  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)
    Figure JPOXMLDOC01-appb-C000003
    (ただし、式(1)中、Rは炭素数1~10の炭化水素基、水素またはハロゲンを示し、Rはなしまたは炭素数1~10の炭化水素基を示し、Xは水素またはアルカリ金属を示す。)
    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)
    Figure JPOXMLDOC01-appb-C000003
    (Wherein, in the formula (1), R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, hydrogen or a halogen, R 2 represents none or a hydrocarbon group having 1 to 10 carbon atoms, and X represents a hydrogen or an alkali metal Indicate
    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.
  10.  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.
  11.  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.
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