KR100419658B1 - An additive for chloride zn-fe alloy electrodeposite and chloride zn-fe alloy electrodeposite solution containg the same - Google Patents
An additive for chloride zn-fe alloy electrodeposite and chloride zn-fe alloy electrodeposite solution containg the same Download PDFInfo
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- KR100419658B1 KR100419658B1 KR10-1999-0059213A KR19990059213A KR100419658B1 KR 100419658 B1 KR100419658 B1 KR 100419658B1 KR 19990059213 A KR19990059213 A KR 19990059213A KR 100419658 B1 KR100419658 B1 KR 100419658B1
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- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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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
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Abstract
염화물계 아연-철 도금욕에 사용되는 첨가제 및 이를 함유하는 염화물계 아연-철 도금용액 조성물에 관한 것으로,An additive used in a chloride-based zinc-iron plating bath and a chloride-based zinc-iron plating solution composition containing the same,
중합도가 10-20인 폴리에틸렌글리콜(H(OCH2CH2)nOH)과 중합도가 20-30인 폴리에틸렌글리콜(H(OCH2CH2)nOH)이 1:2-1:5중량비로 혼합된 수용액중의 농도가 5-15중량%인 폴리에틸렌혼합물; 오바닐린 0.02-0.2g/ℓ; 오바닐린과 동일한 농도의 안식향산; 및 구연산 0.5-30g/ℓ로된 염화물계 아연-철 도금용액용 첨가제 및 염화아연의 아연이온 몰농도 0.5-2.5몰/ℓ, 염화철의 철이온 몰농도 0.1-0.5몰/ℓ, 염화이온의 몰농도 4.0-9.0몰/ℓ 그리고 철이온:(철이온+아연이온)의 비가 0.05-0.3:1로된 염화물계 아연-철 합금전기도금액에 상기 첨가제가 0.2-8.0㎖/ℓ로 첨가된 염화물계 아연-철 합금전기도금액 조성물이 제공된다.A polyethylene glycol polymerization degree of 10-20 (H (OCH 2 CH 2 ) n OH) and polyethylene glycol (H (OCH 2 CH 2) n OH) a degree of polymerization of 20 to 30 is 1: 2-1: 5 mixture by weight Polyethylene mixture having a concentration of 5-15% by weight in the aqueous solution; Obaniline 0.02-0.2 g / l; Benzoic acid at the same concentration as obaniline; And additives for chloride-based zinc-iron plating solution with 0.5-30 g / l citric acid, 0.5-2.5 mol / l zinc ion molarity, 0.1-0.5 mol / l iron ion molarity of iron chloride, and mol of chloride ion. Chloride with the additive added in an amount of 0.2-8.0 mL / L in a chloride-based zinc-iron alloy electroplating solution having a concentration of 4.0-9.0 mol / L and an iron ion: (iron ion + zinc ion) ratio of 0.05-0.3: 1. A zinc-iron alloy electroplating solution composition is provided.
본 발명의 조성으로된 첨가제가 첨가된 산성 염화물계 아연-철 도금액 조성물을 사용하여 도금함으로써 도금 결정립이 미세하고 균일하여 조도가 개선되며, 광택도 및 백색도등의 도표면외관 및 철 석출율이 우수한 도금층을 제조할 수 있다.By plating using the acid chloride-based zinc-iron plating solution composition to which the additive of the composition of the present invention is added, plating grains are fine and uniform, improving roughness, and having excellent surface appearance and gloss precipitation rate such as gloss and whiteness. A plating layer can be manufactured.
Description
본 발명은 염화물계 아연-철 도금욕에 사용되는 첨가제 및 이를 함유하는 염화물계 아연-철 도금용액 조성물에 관한 것이며, 보다 상세하게는 염화물계 아연-철 도금시 도금층의 조도, 표면외관 및 철 석출률을 개선하기 위해 염화물계 아연-철 도금욕에 사용되는 첨가제 및 이를 함유하는 염화물계 아연-철 도금용액 조성물에 관한 것이다.The present invention relates to an additive used in a chloride-based zinc-iron plating bath and a chloride-based zinc-iron plating solution composition containing the same, and more particularly, roughness, surface appearance, and iron precipitation of the plating layer during chloride-based zinc-iron plating. The present invention relates to an additive used in a chloride-based zinc-iron plating bath and a chloride-based zinc-iron plating solution composition containing the same to improve the rate.
강판의 내식성을 향상시키기 위해 일반적으로 아연을 소재로한 도금이 실시되고 있으며, 그중 전기적인 힘으로 도금하여 제조되는 전기도금 강판은 가전, 자동차, 건설등의 분야에 널리 사용되고 있다. 그러나 가혹한 분위기에서 내식성을 확보하기 위해 아연 도금층의 두께를 증가시켜야 하며 이로 인하여 비용이 증가하고 도금밀착성, 가공성, 용접성, 도장성등의 품질특성도 저하된다.In order to improve the corrosion resistance of the steel sheet is generally plated with zinc, and electroplated steel sheet manufactured by plating with electric force is widely used in the fields of home appliances, automobiles, construction, and the like. However, in order to secure corrosion resistance in a harsh atmosphere, the thickness of the galvanized layer should be increased, thereby increasing the cost and degrading the quality characteristics such as plating adhesion, processability, weldability, and paintability.
이러한 문제점을 개선하기 위해서 자동차용 강판을 중심으로 아연계 합금전기도금이 개발되었다. 그 중 아연-철 합금전기도금재는 내식성, 가공성, 도장성등이 우수한 도금재로 알려져 있다. 아연-철 도금방법은 도금욕의 성분에 따라서 여러 가지 방법이 제안되어 있으나, 그 중 산성욕을 기본으로한 도금액은 황화물욕과 염화물욕으로 구분된다.In order to improve this problem, zinc-based alloy electroplating has been developed, mainly for automotive steel plates. Among them, zinc-iron alloy electroplating material is known as a plating material excellent in corrosion resistance, workability, coating properties. The zinc-iron plating method has been proposed in various ways depending on the components of the plating bath, but the plating solution based on the acid bath is divided into sulfide bath and chloride bath.
염화물욕은 황화물욕에 비하여 전기전도도가 우수하여 고전류밀도 도금이 가능하고 용해성 양극을 사용함으로 불용성 양극을 사용하는 황화물에 비하여 용액의 관리가 용이하고 비용이 적게든다.Chloride baths have better electrical conductivity than sulfide baths, which enables high current density plating and the use of soluble anodes makes solution management easier and less expensive than sulfides using insoluble anodes.
그러나 용해성 양극을 사용하는 염화물욕의 아연-철 합금전기도금 제품은 양호한 전도도에 부분적인 우선 석출로 인하여 조도가 불량해지고 도금액에 슬러지가 발생되어 백색도 및 광택도등의 표면외관이 불량하고, 전류밀도에 따른 철의 석출물이 급격히 변화되는 경향이 있다.However, zinc-iron alloy electroplating products of chloride baths using soluble anodes have poor conductivity due to partial preferential precipitation and good sludge, resulting in sludge in the plating solution, resulting in poor surface appearance such as whiteness and glossiness. The precipitation of iron tends to change rapidly.
종래 아연-철 합금도금의 표면외관 개선을 위해 일본특허 소57-114686은 아연을 주성분으로한 철족금속(Fe, Ni, Co등)과의 합금도금시 폴리아민이나 폴리비닐 알콜등을 첨가하여 금속공침으로 작업성, 경제성 및 광택성을 개선하는 것이나, 도금부착성 및 표면거칠기는 개선하지 못하는 것이다.In order to improve the surface appearance of conventional zinc-iron alloy plating, Japanese Patent No. 57-114686 discloses metal coprecipitation by adding polyamine or polyvinyl alcohol when alloy plating with iron group metal (Fe, Ni, Co, etc.) mainly composed of zinc. In order to improve workability, economics and glossiness, plating adhesion and surface roughness are not improved.
일본특허 소 64-47893은 첨가제로서 치환 폴리에테르류등을 첨가하여 표면균일 및 외관 색조등을 개선하고 있으나, 도금층의 표면이 거칠어지고 철 석출률이 저조한 문제가 있는 것이다.Japanese Patent No. 64-47893 improves the surface uniformity and appearance color tone by adding substituted polyethers as an additive, but there is a problem that the surface of the plating layer is rough and the iron precipitation rate is low.
또한 일본특허 소 64-47892는 비이온성 계면활성제인 폴리에틸렌 글리콜을 첨가함으로써 도금층의 내수밀착성, 화성처리성, 상층 철 함유율등을 개선하는 것이나, 표면외관이 불량해지는 문제가 있다.In addition, Japanese Patent No. 64-47892 improves the water-tightness of the plating layer, the chemical conversion treatment, the upper iron content, etc. by adding polyethylene glycol, which is a nonionic surfactant, and has a problem of poor surface appearance.
이에 본 발명의 목적은 개선된 도금층 조도, 표면외관 및 철 석출률을 제공하는 염화물계 아연-철 도금액용 첨가제를 제공하는 것이다.It is therefore an object of the present invention to provide an additive for a chloride-based zinc-iron plating solution that provides improved plating roughness, surface appearance and iron deposition rate.
본 발명의 또 다른 목적은 본 발명의 첨가제를 함유하는 염화물계 아연-철 도금액 조성물을 제공하는 것이다.Another object of the present invention is to provide a chloride-based zinc-iron plating solution composition containing the additive of the present invention.
본 발명의 일견지에 의하면,According to one aspect of the invention,
중합도가 10-20인 폴리에틸렌글리콜(H(OCH2CH2)nOH)과 중합도가 20-30인 폴리에틸렌글리콜(H(OCH2CH2)nOH)이 1:2-1:5중량비로 혼합된 수용액중의 농도가 5-15중량%인 폴리에틸렌혼합물;A polyethylene glycol polymerization degree of 10-20 (H (OCH 2 CH 2 ) n OH) and polyethylene glycol (H (OCH 2 CH 2) n OH) a degree of polymerization of 20 to 30 is 1: 2-1: 5 mixture by weight Polyethylene mixture having a concentration of 5-15% by weight in the aqueous solution;
오바닐린 0.02-0.2g/ℓ;Obaniline 0.02-0.2 g / l;
오바닐린과 동일한 농도의 안식향산;및Benzoic acid at the same concentration as obaniline; and
구연산 0.5-30g/ℓ로된,0.5-30 g / l citric acid,
염화물계 아연-철 도금용액용 첨가제가 제공된다.An additive for a chloride-based zinc-iron plating solution is provided.
본 발명의 다른 견지에 의하면,According to another aspect of the present invention,
염화아연의 아연이온 몰농도 0.5-2.5몰/ℓ, 염화철의 철이온 몰농도 0.1-0.5몰/ℓ, 염화이온의 몰농도 4.0-9.0몰/ℓ 그리고 철이온:(철이온+아연이온)의 비가 0.05-0.3:1로된 염화물계 아연-철 합금전기도금액에 본 발명의 첨가제가 0.2-8.0㎖/ℓ로 첨가된 염화물계 아연-철 합금전기도금액 조성물이 제공된다.The zinc ion molar concentration of zinc chloride is 0.5-2.5 mol / l, the iron ion molar concentration of iron chloride 0.1-0.5 mol / l, the molar concentration of chloride chloride 4.0-9.0 mol / l and the iron ion: (iron + zinc ion) A chloride-based zinc-iron alloy electroplating solution composition in which the additive of the present invention is added in an amount of 0.2-8.0 ml / L to a chloride-based zinc-iron alloy electroplating solution having a ratio of 0.05-0.3: 1 is provided.
이하, 본 발명에 대하여 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명의 폴리에틸렌글리콜혼합물, 안식향산, 오바닐린 및 구연산으로 구성된 아연-철 합금전기도금액용 첨가제는 도금액에 이를 첨가하여 사용함으로써 도금층의 조도, 광택도 및 백색도등과 같은 표면외관 및 철 석출율이 개선된다.The additive for zinc-iron alloy electroplating solution composed of the polyethylene glycol mixture, benzoic acid, obaniline, and citric acid of the present invention is used by adding it to the plating solution, thereby improving surface appearance and iron deposition rate such as roughness, glossiness and whiteness of the plating layer. Is improved.
본 발명의 아연-철 합금전기도금액용 첨가제를 구성하는 각 성분의 작용 및 그 함량을 한정한 이유는 다음과 같다.The reason for limiting the action and the content of each component constituting the additive for zinc-iron alloy electroplating solution of the present invention is as follows.
폴리에틸렌글리콜로는 중합도가 10-20인 폴리에틸렌글리콜(H(OCH2CH2)nOH)과 중합도가 20-30인 폴리에틸렌글리콜(H(OCH2CH2)nOH)이 1:2-1:5중량비로 혼합된 폴리에틸렌글리콜 혼합물이 사용된다.Polyethylene is a polyethylene glycol polymerization degree of 10 to 20 as a glycol (H (OCH 2 CH 2) n OH) and having a degree of polymerization of 20 to 30 polyethylene glycol (H (OCH 2 CH 2) n OH) is 1: 2-1: Polyethylene glycol mixtures mixed in a 5 weight ratio are used.
폴리에틸렌글리콜의 중합도(식중 n값)가 10이하인 폴리에틸렌글리콜을 사용하면 도금이 거칠게되고 철 석출률이 미미하며, n의 수가 30이상인 폴리에틸렌글리콜을 사용하면 도금층의 표면외관 향상 효과가 감소된다. 중합도가 10-20인 폴리에틸렌글리콜과 중합도가 20-30인 폴리에틸렌글리콜을 상기 중량비로 혼합하여 사용하는 이유는 상기 n값을 한정한 이유와 같다. n수가 클수록 표면조도는 개선되지만 광택도 및 백색도와 같은 표면외관 향상효과는 저하된다. 상기 첨가제를 구성하는 폴리에틸렌글리콜 혼합물로 수용액중의 농도 5-15중량%인 것을 사용한다. 농도가 5중량%이하인 경우에는 도금결정의 미세화효과가 적어서 밀착성이 떨어지고, 15중량%이상인 경우에는 도금층의 표면외관 향상 효과가 감소된다.When polyethylene glycol having a degree of polymerization (n value) of polyethylene glycol is 10 or less, the plating becomes rough and the iron precipitation rate is insignificant, and when polyethylene glycol having a number of n or more is used, the effect of improving the surface appearance of the plating layer is reduced. The reason why the polyethylene glycol having a degree of polymerization of 10-20 and the polyethylene glycol having a degree of polymerization of 20-30 is mixed and used is the same as the reason for limiting the n value. The larger the n number, the better the surface roughness, but the lower the surface appearance improvement effect such as glossiness and whiteness. The polyethylene glycol mixture constituting the additive is used in a concentration of 5-15% by weight in an aqueous solution. When the concentration is 5% by weight or less, the microcrystallization effect of the plating crystals is small, and the adhesion is inferior. When the concentration is 15% by weight or more, the surface appearance improvement effect of the plating layer is reduced.
오바닐린은 각각 0.02-0.2g/ℓ의 양으로 혼합된다. 오바닐린의 양이 0.02g/ℓ이하인 경우에는 도금전류효율과 광택성을 개선하지 못하며, 0.2g/ℓ이상에서는 도금층의 밀착성이 떨어지고 표면이 검게된다.Ovanillin is mixed in an amount of 0.02-0.2 g / l, respectively. When the amount of ovaniline is 0.02 g / l or less, the plating current efficiency and glossiness cannot be improved. At 0.2 g / l or more, the adhesion of the plating layer is reduced and the surface becomes black.
나아가, 안식향산과 오바닐린이 1:1농도비를 벗어나면 표면외관이 좋지 않으며, 1:1 농도비로 첨가될 때 우수한 조도를 나타낸다. 따라서, 안식향산은 오바닐린과 동일한 농도비로 첨가된다.Furthermore, when the benzoic acid and the obaniline deviate from the 1: 1 concentration ratio, the surface appearance is not good, and when added in a 1: 1 concentration ratio, it shows excellent roughness. Therefore, benzoic acid is added in the same concentration ratio as the obaniline.
첨가제에 대하여 구연산은 0.5-30g/ℓ의 양으로 첨가된다. 구연산의 양이 0.5g/ℓ이하인 경우에는 표면외관 개선효과가 없으며 0.5g/ℓ이상이 되어야 도금액의 슬러지 감소로 인하여 표면외관이 개선된다. 그러나 구연산의 함량이 30g/ℓ이상인 경우에는 도금 전류효율이 떨어지고 표면이 황변함으로 바람직하지 않다.For the additives citric acid is added in an amount of 0.5-30 g / l. If the amount of citric acid is less than 0.5g / ℓ does not improve the surface appearance and should be more than 0.5g / ℓ to improve the surface appearance due to the reduction of sludge in the plating solution. However, when the content of citric acid is more than 30g / ℓ plating current efficiency is deteriorated and the surface yellowing is not preferable.
상기한 바와 같이 조성된 염화물계 아연-철 도금액 첨가제는 다음과 같이 조성된 염화물계 아연-철 도금액에서 첨가되는 경우 원하는 물성을 나타낸다.The chloride-based zinc-iron plating solution additive prepared as described above has the desired physical properties when added in the chloride-based zinc-iron plating solution.
즉, 상기 첨가제는 염화아연의 아연이온 몰농도 0.5-2.5몰/ℓ, 염화철의 철이온 몰농도 0.1-0.5몰/ℓ, 염화이온의 몰농도 4.0-9.0몰/ℓ 그리고 철이온:(철이온+아연이온)의 비가 0.05-0.3:1로 조성된 염화물계 아연-철 도금액에 첨가된다.In other words, the additive is a zinc chloride molar concentration of 0.5-2.5 mol / l, iron chloride molar concentration of 0.1-0.5 mol / l, chloride chloride molar concentration of 4.0-9.0 mol / l and iron ion: (iron ion: + Zinc ion) is added to the chloride-based zinc-iron plating solution having a ratio of 0.05-0.3: 1.
도금용액의 아연이온의 몰농도가 0.5 몰/ℓ이하에서는 피복될 이온의 농도부족에 의하여 도금에 검게 그을리는 자국(burning)이 생기며, 2.5몰/ℓ이상에서는 도금층의 분말형태의 도금이 되어서 밀착성이 떨어지고 도금층의 철함량이 저하되어 내식성이 떨어진다.If the molar concentration of zinc ions in the plating solution is 0.5 mol / l or less, burning may be blackened due to the lack of concentration of the ions to be coated, and in the case of 2.5 mol / l or more, the plating layer is powder-plated. Adhesion is inferior, iron content of a plating layer falls, and corrosion resistance is inferior.
철이온의 몰농도가 0.1몰/ℓ이하에서는 도금층의 철함량이 감소하여 용접성 및 도장성이 열화되며, 0.5몰/ℓ이상에서는 도금층의 철함량이 너무 높아 가공성이 저하되고 갈바닉 부식에 의한 내식성이 저하된다.If the molar concentration of iron ions is less than 0.1 mol / l, the iron content of the plating layer is decreased, and weldability and paintability are deteriorated. Degrades.
염소이온이 몰농도가 4.0몰/ℓ이하인 경우에는 전기전도도의 감소로 인하여 버닝이 다량 발생하고, 9.0몰/ℓ이상에서는 염소이온이 석출되어 도금작업성이 저하되고 도금액의 농도관리가 어렵게 된다.When the chlorine ion has a molar concentration of 4.0 mol / l or less, a large amount of burning occurs due to a decrease in electrical conductivity, and at 9.0 mol / l or more, chlorine ions are precipitated, resulting in poor plating workability and difficulty in managing the concentration of the plating solution.
아연-철 합금전기도금은 도금층의 철함량이 4-30퍼센트 범위에서 내식성 및 가공성이 우수하며 10-20퍼센트 범위에서 보다 바람직한 것이다.Zinc-iron alloy electroplating is excellent in corrosion resistance and workability in the iron content of the plated layer in the 4-30% range, and more preferable in the 10-20% range.
따라서, 철이온:(철이온+아연이온)비가 0.05이하인 경우에는 도금층에서 철함량이 4퍼센트 이하로 낮아지고 0.3이상에서는 철함량이 30퍼센트 이상으로 내식성 및 가공성이 저하된다.Therefore, when the iron ion: (iron ion + zinc ion) ratio is 0.05 or less, the iron content is lowered to 4% or less in the plating layer, and at 0.3 or more, the iron content is lowered to 30% or more and the corrosion resistance and workability are lowered.
본 발명의 첨가제는 상기한 바와 같이 조성된 총 아연-철 도금액에 대하여 0.2-8.0㎖/ℓ, 바람직하게는 1.0-4.0㎖/ℓ의 양으로 첨가된다.The additive of the present invention is added in an amount of 0.2-8.0 ml / l, preferably 1.0-4.0 ml / l, relative to the total zinc-iron plating solution formulated as described above.
첨가되는 첨가제의 함량이 0.2㎖/ℓ이하인 경우에는 도금결정립 미세화에 의한 조도 및 표면외관 향상 효과를 기대할 수 없으며, 8.0㎖/ℓ이상인 경우에는 전류효율이 떨어지고 표면이 오히려 어두워지며 도금밀착성이 저하됨으로 도금욕에 첨가제는 0.2∼8.0㎖/ℓ의 양으로 첨가하는 것이 좋으며, 특히 1.0-4.0㎖/ℓ의 양으로 첨가한 경우 가장 우수한 특성을 나타낸다.When the content of the added additive is 0.2ml / l or less, it is not expected to improve the roughness and surface appearance by the refinement of the plating grains, and when it is more than 8.0ml / l, the current efficiency is lowered, the surface becomes darker, and the plating adhesion is deteriorated. The additive is preferably added to the plating bath in an amount of 0.2 to 8.0 ml / l, and particularly when added in an amount of 1.0 to 4.0 ml / l.
본 발명의 첨가제가 첨가된 염화물계 아연-철 도금액은 강판에 예를들어 pH 1.0-5.0, 도금액의 온도를 40-70℃, 전류밀도를 20-200A/dm2그리고 도금액과 음극의 상대유속을 0.1-2.5m/sec로 하여 강판에 적용할 수 있다.The chloride-based zinc-iron plating solution to which the additive of the present invention is added is, for example, pH 1.0-5.0 on a steel sheet, the temperature of the plating liquid is 40-70 ° C, the current density is 20-200 A / dm 2, and 0.1-2.5m / sec can be applied to the steel sheet.
본 발명의 첨가제를 함유하는 염화물계 아연-철 도금용액은 피도금체인 금속의 종류, 형상등에 관계없이 적용될 수 있으며, 특히 고전류밀도 도금이 필요한 강판의 연속전기아연도금시 우수한 도금품질을 용이하게 얻을 수 있다.The chloride-based zinc-iron plating solution containing the additive of the present invention can be applied regardless of the type, shape, etc. of the metal to be plated, and particularly, excellent plating quality can be easily obtained when continuous electric zinc plating is required for high current density plating. Can be.
이하, 실시예를 통하여 본 발명에 대하여 상세히 설명한다.실시예Hereinafter, the present invention will be described in detail with reference to Examples.
냉연강판을 소지금속으로 하여 하기 표 1에 나타낸 조성으로된 도금액을 도금량이 40g/㎠dl이 되도록 도금하고 이때 도금층과 소지층과의 조도차이, 도금층의 백색도, 광택도, 철이온의 석출률을 나타내었다.Using a cold-rolled steel sheet as a base metal, the plating solution having the composition shown in Table 1 was plated so that the plating amount was 40 g / cm 2 dl. At this time, the roughness difference between the plating layer and the base layer, the whiteness, glossiness, and precipitation rate of iron ions of the plating layer were measured. Indicated.
본 실시예에서 사용된 도금조건을 pH=2, 온도 =60℃, 상대유속=1.5m/sec, 전류밀도=60A/㎠였다.The plating conditions used in this example were pH = 2, temperature = 60 ° C., relative flow rate = 1.5 m / sec and current density = 60 A / cm 2.
* 도금층 조도: 도금층조도>원판조도:불량, 도금층조도≤원판조도:양호* Plating layer roughness: Plating layer roughness> Disc roughness: Poor, Plating layer roughness≤ disc roughness: Good
** 철 석출률: 도금층 Fe함량/도금액에서 Fe함량=98%이상 양호, 이하 불량** Iron deposition rate: Fe content = 98% or more good in the plating layer Fe content / plating solution, or less
*** 백색도: 색차수기(Color Difference Meter)의 L값*** Whiteness: L value of Color Difference Meter
(양호:69이상, 불량:68이하)(Good: 69 or more, poor: 68 or less)
**** 광택도: 광택기(양호:66이상, 불량:65이하)**** Glossiness: Polisher (good: more than 66, poor: less than 65)
상기 표 1에 나타낸 바와 같이, 본 발명에 부합되는 조건에서는 도금밀착성, 도금층의 철 석출률, 표면외관(광택도 및 백색도)은 양호하지만, 발명의 범위를 벗어난 도금용액조건에서 실시된 도금층은 그 상태가 불량하였다.As shown in Table 1, the plating adhesion, the iron deposition rate of the plating layer, the surface appearance (glossiness and whiteness) is good under the conditions in accordance with the present invention, but the plating layer carried out in the plating solution conditions outside the scope of the invention The condition was bad.
상기한 바와 같이, 본 발명의 조성으로된 첨가제가 첨가된 산성 염화물계 아연-철 도금액 조성물을 사용하여 도금함으로써 도금 결정립이 미세하고 균일하여 조도가 개선되며, 광택도 및 백색도등의 도표면외관 및 철 석출율이 우수한 도금층을 얻을 수 있다.As described above, by plating using an acid chloride-based zinc-iron plating solution composition to which the additive of the composition of the present invention is added, the plating grains are fine and uniform to improve roughness, and the surface appearance of glossiness and whiteness, etc. A plating layer excellent in iron deposition rate can be obtained.
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