KR100429153B1 - the blackening method of electrogalvanized steel sheet by Cu-flash treatment - Google Patents
the blackening method of electrogalvanized steel sheet by Cu-flash treatment Download PDFInfo
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- KR100429153B1 KR100429153B1 KR10-1999-0060596A KR19990060596A KR100429153B1 KR 100429153 B1 KR100429153 B1 KR 100429153B1 KR 19990060596 A KR19990060596 A KR 19990060596A KR 100429153 B1 KR100429153 B1 KR 100429153B1
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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Abstract
본 발명은 구리 플래시(flash)처리를 통한 흑색처리강판의 제조방법에 관한 것으로, 특히 기존의 흑색처리강판 제조방법인 흑색 크로메이트처리법이나 전해 에칭처리법 등에 비해 제조원가가 저렴하고 환경친화적인 제품을 생산할 수 있는 새로운 흑색처리강판의 제조방법에 관한 것이다.The present invention relates to a method for manufacturing a black-treated steel sheet through a copper flash treatment, and in particular, it is possible to produce an environment-friendly product having a lower manufacturing cost and an environment-friendly product than a black chromate treatment method or an electrolytic etching treatment method, which is a conventional method for manufacturing a black-treated steel sheet. The present invention relates to a method for manufacturing a new black steel sheet.
본 발명은 강판에 연속으로 전기 아연 및 아연계 합금도금을 실시하는 전기아연도금강판에서, 상기 강판의 표면에 구리를 3.0∼100mg/m2의 부착량으로 피복시키는 단계와; 상기 피복된 강판에 인산염 처리를 실시하는 단계와; 상기 인산염 처리된 강판에 투명한 계통의 수지를 피복하는 단계와; 로 이루어진 Cu 플래시 처리에 의한 흑색처리강판의 제조방법을 제공한다.The present invention comprises the steps of coating the surface of the steel sheet with an adhesion amount of 3.0 to 100mg / m 2 in an electrogalvanized steel sheet which is subjected to electro-zinc and zinc-based alloy plating on the steel sheet continuously; Phosphating the coated steel sheet; Coating a resin of a transparent system on the phosphate-treated steel sheet; Provided is a method of manufacturing a black-treated steel sheet by Cu flash treatment.
본 발명에 의하면, 경제적이면서 또한 기존 생산제품 및 공정을 크게 변화시키지 않고도 흑색처리 강판 제조할 수 있으며, 특히 보다 환경친화적이고 기존의 인산염처리 용액을 사용하면서 간단하게 흑색처리 강판을 제조할 수 있는 효과를 있다.Advantageous Effects of Invention According to the present invention, it is possible to manufacture black-treated steel sheet economically and without significantly changing existing products and processes, and in particular, it is more environmentally friendly and the effect of simply manufacturing black-treated steel sheet using existing phosphate treatment solution. There is.
Description
본 발명은 Cu 플래시(flash) 처리를 통한 흑색처리강판의 제조방법에 관한 것으로, 특히 기존의 흑색처리강판 제조방법인 흑색 크로메이트처리법이나 전해 에칭처리법 등에 비해 제조원가가 저렴하면서 환경친화적인 제품을 생산할 수 있는 새로운 흑색처리강판의 제조방법에 관한 것이다.The present invention relates to a method for manufacturing black-treated steel sheet through Cu flash treatment, and in particular, it is possible to produce environmentally friendly products with low manufacturing cost compared to the conventional black chromate treatment method or electrolytic etching treatment method. The present invention relates to a method for producing a new black steel sheet.
일반적으로 흑색처리된 전기아연도금 강판은 오디오, 복사기, 카메라, 자동차 와이퍼 등과 같이 장식용의 목적이나 빛을 흡수하는 성질이 필요한 경우에 사용되고 있다. 이와 같은 흑색처리된 전기아연 도금강판은 기존의 전기아연 도금강판에 흑색의 페인트를 피복하는 방법이 있었으나, 이 방법은 연속전기도금라인에서 제조된 아연도금강판을 도장하는 업체에서 탈지 및 화성처리를 거쳐 페인트 피복을 하는 공정을 거치기 때문에 많은 폐수가 발생되어 환경측면에서 많은 어려움이 있으며, 제조원가도 많이 드는 문제가 있다.In general, black zinc-plated electro galvanized steel sheet is used for decorative purposes and light absorbing properties such as audio, photocopiers, cameras, and car wipers. Such black galvanized steel sheet had a method of coating black paint on the existing galvanized steel sheet, but this method was subjected to degreasing and chemical conversion treatment by a company coating a galvanized steel sheet manufactured in a continuous electroplating line. Since the process of coating the paint through a lot of waste water is generated, there are a lot of difficulties in terms of the environment, there is also a problem that costs a lot of manufacturing.
이에 강판에 연속으로 전기도금을 실시하는 방법으로서 대표적인 것으로서, 다음과 같이 흑색처리 강판을 생산하여 도장 단계를 생략하는 방향으로 제품이 개발되어 왔다. 먼저, 크로메이트 처리용액에 은성분을 첨가하여 흑색화시키는 방법으로 연속으로 강판에 전기아연도금을 하고 흑색을 내는 특수한 크로메이트 용액을 이용하여 흑색 전기아연도금을 하고, 수지를 연속으로 피복하는 방법이 있다.As a representative method for continuously electroplating the steel sheet, the product has been developed in the direction of producing a black-treated steel sheet to omit the coating step as follows. First, there is a method of adding a silver component to a chromate treatment solution to blacken it, followed by electrogalvanization of the steel sheet continuously, and black electrozinc plating using a special chromate solution that produces black color, and then coating the resin continuously.
이 방법은 6가 크롬을 함유한 크로메이트 용액으로 처리를 해야하며 이는 전세계적으로 환경규제가 되고 있는 6가 크롬이 사용되어 강판에 잔류하는 문제가 있으며, 흑색을 얻기 위해 사용하는 특수한 크로메이트 용액의 가격이 높고 공정이 추가되는 문제로 생산비가 증가하는 단점이 있다.This method has to be treated with chromate solution containing hexavalent chromium, which is a problem that the hexavalent chromium, which is environmentally regulated around the world, remains on the steel sheet and the price of the special chromate solution used to obtain black color. This high and additional process has the disadvantage of increasing production costs.
또한, 아연-니켈 합금전기도금강판을 특수한 용액에서 양극 에칭시켜 흑색을 얻은 후 수지를 피복하는 방법이 있다. 그러나, 이 방법도 도금층을 다시 전해에칭시키는 단계가 필요하므로 폐수 발생과 공정 증가에 의한 생산비 증가라는 문제가 있다.In addition, there is a method of coating the resin after anodizing zinc-nickel alloy electroplated steel sheet in a special solution to obtain a black color. However, this method also requires a step of electroetching the plating layer again, which leads to a problem of increased production cost due to wastewater generation and process increase.
마지막으로 인산염처리 용액에 니켈이온 농도를 3.5∼7.0g/l 첨가시켜 인산염피막을 흑색화시키는 방법으로서, 일본 공개특허 공보 (특개평:8-218181)에 제안된 방법이 있으나, 이 방법은 연속으로 강판에 전기 도금을 하는 공정에서 일반 인산염처리된 아연도금강판을 생산할 때와 흑색화 인산염처리 강판을 생산할 때 사용되는 인산염철 용액이 달라 제품에 따라 용액교체 및 설비 청소작업을 해주어야 하는 문제로 작업성을 저해하는 문제점을 안고 있다.Finally, as a method of blackening the phosphate coating by adding nickel ion concentration of 3.5 to 7.0 g / l to the phosphate treatment solution, there is a method proposed in Japanese Unexamined Patent Publication (Japanese Patent Application Laid-Open No. 8-218181). In the process of electroplating steel plate, iron phosphate solution used in producing phosphated galvanized steel sheet and blackening phosphated steel sheet is different, so it is necessary to replace solution and clean equipment according to products. It has a problem that hinders.
본 발명은 상기와 같은 문제점등을 해결하기 위하여 안출된 것으로서, 먼저, 본 발명자들은 환경친화적이고 기존의 인산염처리 용액을 사용하면서도 간단하게 흑색처리 강판을 제조하는 방법을 제공하는 것을 목적으로 한다.The present invention has been made in order to solve the above problems, the first object of the present invention is to provide a method for producing a black steel sheet simply while using an environmentally friendly and conventional phosphate treatment solution.
본 발명은 상기 목적을 달성하기 위하여, 연구한 결과 도금층 표면에 구리를 미량 피복시킨 후 기존 방법으로 인산염처리를 함으로써 우수한 흑색처리 강판을 제공하는 것을 특징으로 한다.In order to achieve the above object, the present invention is characterized by providing a fine black-treated steel sheet by performing a phosphate treatment in a conventional method after coating a small amount of copper on the plating layer surface.
이하 본 발명을 더욱 상세히 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
본 발명은 강판에 연속으로 전기아연 및 아연계 합금도금을 하는 공정에서, 그 표면에 구리를 3.0∼100mg/m㎡의 부착량으로 피복시킨 후 인산염 처리를 한 후 투명한 계통의 수지를 피복하는 흑색처리 강판의 제조방법을 제공한다.According to the present invention, in the process of continuous electro-zinc and zinc-based alloy plating on a steel sheet, the surface is coated with copper at an adhesion amount of 3.0 to 100 mg / m 2, followed by a phosphate treatment, followed by a black treatment of coating a transparent resin. It provides a method for producing a steel sheet.
여기서 구리 부착량을 3.0∼100mg/㎡으로 규정하는 이유는 3.0mg/㎡ 이하에서는 흑색화 현상이 충분하지 않고, 100mg/㎡ 이상에서는 구리 석출물의 양이 너무 많아 밀착력 열화 및 구리 고유의 붉은색이 나타나서 본 발명의 목적인 순수한 흑색으로만 된 도금 강판을 얻을 수 없기 때문이다.The reason why the copper adhesion amount is defined as 3.0 to 100 mg / m 2 is that the blackening phenomenon is not sufficient at 3.0 mg / m 2 or less, and the amount of copper precipitates is too high at 100 mg / m 2 or more, resulting in deterioration of adhesion and red color inherent in copper. This is because a plated steel sheet made of pure black, which is the object of the present invention, cannot be obtained.
상기 구리의 부착방법은 전기도금, 진공증착도금, 환원제를 이용한 무전해 도금, 치환도금법 등이 모두 가능하고, 동일한 효과를 얻을 수 있으나, 구리와 아연 및 아연계 합금도금층 간의 전기화학적 이온화 경향이 크므로 기존의 설비에 설치가 간단하고 관리가 용이하여 상태적으로 설비 및 생산비가 저렴한 치환 도금법이 가장 적당하다.The method of attaching copper is possible by electroplating, vacuum deposition plating, electroless plating using a reducing agent, substitution plating, etc., and the same effect can be obtained, but the electrochemical ionization tendency between copper, zinc, and zinc-based alloy plating layers is large. As it is simple to install in existing equipment and easy to manage, substitution plating method which is cheap in equipment and production cost is most suitable.
이하 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다,Hereinafter, the present invention will be described in detail with reference to Examples.
아연도금 부착량 20g/㎡인 아연도금강판, 아연도금 부착량 20g/㎡이고 철함량 17wt%인 아연-철 합금도금강판 및 아연도금 부착량 20g/㎡이고 니켈함량 11wt%인 아연-니켈 합금도금강판에 대하여 다음과 같은 방법으로 구리도금, 인산염처리를 한 후 실리카변성 에틸렌-아크릴/에폭시 수지를 롤코팅방법으로 피복처리를 하여 시편을 제조하였다.For galvanized steel sheets with a zinc coating weight of 20 g / m2, zinc-iron alloy coated steel sheets with a zinc coating weight of 20 g / m2 and iron content of 17 wt%, and zinc-nickel alloy coated steel sheets with a zinc coating weight of 20 g / m2 and nickel content of 11 wt%. After copper plating and phosphate treatment in the following manner, the specimen was prepared by coating the silica-modified ethylene-acrylic / epoxy resin with a roll coating method.
가. 구리도금end. Copper plating
도금욕 조건 : Cu2+;0.1∼2.0g/1, pH 1.5, 상온Plating bath conditions: Cu 2+ ; 0.1-2.0 g / 1, pH 1.5, room temperature
도금방법 : 치환도금Plating Method: Substitution Plating
수세 : 상온의 수돗물 2초간 분사Water washing: spraying tap water for 2 seconds at room temperature
나. 인산염처리 작업I. Phosphating Process
(1) 표면조정(1) surface adjustment
용액 : PREPALENE-ZJ(Nippon Parkerizing(주))Solution: PREPALENE-ZJ (Nippon Parkerizing)
방법 : 40℃ 용액에서 2초간 분무Method: spray for 2 seconds in a 40 ° C solution
(2) 인산염처리(2) phosphate treatment
용액 : PALBOND 3312J(Nippon Parkerizing(주))Solution: PALBOND 3312J (Nippon Parkerizing Co., Ltd.)
방법 : 60℃ 용액에서 8초간 침지Method: Soak for 8 seconds in a 60 ° C solution
(3)수세 : 상온의 수돗물 2초간 분사(3) washing with water: spraying tap water for 2 seconds at room temperature
(4) Cr-실링(sealing) 처리(4) Cr-sealing treatment
용액 : PALEENE 62J(Nippon Parkerizing(주))Solution: PALEENE 62J (Nippon Parkerizing)
방법 : 45℃ 용액으로 롤 코팅Method: roll coating with 45 ℃ solution
도금 강판의 백색도는 일본 SUGA사의 멀티스텍트로 칼라 미터(Multispectro Colour Meter)를 사용하여 측정하였다.The whiteness of the plated steel sheet was measured using a multispectro color meter manufactured by SUGA, Japan.
상기에 제조된 시편의 피막밀착성은 시편 위에 일반 스카치를 붙인후 테이프 붙인 방향으로 60°각도로 강판을 꺽는다. 그 후 테이프를 박리시켰을 때 피막이 테이프에 묻어나는지 여부를 육안관찰하였다.The film adhesion of the prepared specimen was attached to the scotch on the specimen and then bent the steel sheet at an angle of 60 ° in the taped direction. After that, when the tape was peeled off, it was visually observed whether the film was buried on the tape.
내흑변성 평가로는 습윤성(60℃, 상대습도 85%) 조건에서 110시간 경과 전후의 강판의 백색도로서 평가하였으며 평가 기준은 다음과 같다.The blackening resistance evaluation was evaluated as the whiteness of the steel sheet before and after 110 hours under the wettability (60 ℃, 85% relative humidity) conditions are as follows.
1 : 습윤상에서 평가면과 평가전의 면과의 백색도 차이 ΔL 2.0 이하1: difference in whiteness between the evaluation surface and the surface before evaluation in the wet phase ΔL 2.0 or less
2 : 습윤상에서 평가면과 평가전의 면과의 백색도 차이 ΔL 2.0∼4.02: difference in whiteness between the evaluation surface and the surface before evaluation in the wet phase ΔL 2.0 to 4.0
3 : 습윤상에서 평가면과 평가전의 면과의 백색도 차이 ΔL 4.0∼6.03: Difference in whiteness between the evaluation surface and the surface before evaluation in the wet phase ΔL 4.0 to 6.0
4 : 습윤상에서 평가면과 평가전의 면과의 백색도 차이 ΔL 6.0∼8.04: Whiteness difference between the evaluation surface and the surface before evaluation in a wet phase ΔL 6.0-8.0
5 : 습윤상에서 평가면과 평가전의 면과의 백색도 차이 ΔL 8.0 이상5: Whiteness difference between the evaluation surface and the surface before evaluation in a wet phase ΔL 8.0 or more
내화학성 평가는 MEK로 도막을 문질렀을 경우, 수지도막의 박리 및 변색되는 정도를 5단계로 나누어 평가하였으며, 평가기준은 다음과 같다.Chemical resistance was evaluated by dividing the degree of peeling and discoloration of the resin coating film in five stages when rubbing the coating film with MEK, and the evaluation criteria are as follows.
1 : 수지도막의 박리가 없고 색차(처리 전,후)ΔE 1이하1: No peeling of resin film and color difference (before and after treatment) ΔE 1 or less
2 : 수지도막의 박리가 없고 색차(처리 전,후)ΔE 2∼32: Color difference (before and after treatment) ΔE 2-3 with no peeling of resin coating film
3 : 수지도막의 박리가 없고 색차(처리 전,후)ΔE 5 이상3: No peeling of resin film and color difference (before and after treatment) ΔE 5 or more
4 : 수지도막이 부분박리(박리부분이 수지 전도포면의 30% 이하)4: partial peeling of resin coating film
5 : 수지도막이 완전박리(박리부분이 수지 전도포면의 50% 이상)5: Complete peeling of resin coating film (The peeling part is more than 50% of the resin conductive cloth surface)
내식성은 염수분무 시험기를 이용하여 평판부와 가공부를 나누어 평가하였는데 가공부의 경우 직경 30mm와 6mm 높이의 돔을 만들었다. 이러한 시편을 염수분무 시험기에 장입하여 144 시간이 경과한 후 반출하여 순수로 세척하고 건조한 다음 발생한 백청율로서 내식성을 평가하였다.Corrosion resistance was evaluated by using a salt spray tester, and the flat part and the processed part were evaluated. For the processed part, a dome having a diameter of 30 mm and a height of 6 mm was made. These specimens were charged into the salt spray tester, and after 144 hours, they were taken out, washed with pure water, dried, and evaluated for corrosion resistance as white bleaching rate.
1 : 5% 이하1: less than 5%
2 : 5∼10%2: 5-10%
3 : 10∼20%3: 10 to 20%
4 : 20∼30%4: 20-30%
5 : 30% 이상5: 30% or more
표 1은 아연 및 아연계 합금도금강판에 대한 구리 부착량에 따른 백색도 및 품질특성 평가결과를 도시한 것이다.Table 1 shows the results of evaluation of whiteness and quality characteristics according to the amount of copper adhesion to zinc and zinc-based alloy plated steel sheet.
비교예 1∼3은 구리부착량이 적은 경우로 백색도가 원하는 만큼 낮지 않아 충분한 흑색표면을 얻을 수 없었다. 반면에 비교예 4∼6은 구리 부착량이 너무 많은 경우로 백색도는 낮게 유지할 수 있으나 석출된 구리의 양이 과다하여 피막 밀착력 및 내식성이 나쁜 문제가 있었다.In Comparative Examples 1 to 3, when the amount of copper deposition was small, the whiteness was not as low as desired and a sufficient black surface could not be obtained. On the other hand, Comparative Examples 4 to 6 have too much copper adhesion, but the whiteness can be kept low, but the amount of precipitated copper is excessive, resulting in poor film adhesion and corrosion resistance.
따라서 발명예와 같이 구리 부착량을 3.0∼100mg/㎡으로 유지해 주는 것이 가장 우수한 특성을 나타내는 것을 알 수 있다.Therefore, it can be seen that maintaining the copper adhesion amount at 3.0 to 100 mg / m 2 as in the invention example shows the most excellent characteristics.
열세)Thirteen)
상술한 바와 같이, 본 발명에 의하면, 경제적이면서 또한 기존 생산제품 및 공정을 크게 변화시키지 않고도 흑색처리 강판 제조할 수 있으며, 특히 보다 환경친화적이고 기존의 인산염처리 용액을 사용하면서 간단하게 흑색처리 강판을 제조할 수 있는 효과를 있다.As described above, according to the present invention, it is possible to manufacture black-treated steel sheet economically and without significantly changing existing products and processes. Has the effect of being manufactured.
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
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| KR10-1999-0060596A KR100429153B1 (en) | 1999-12-22 | 1999-12-22 | the blackening method of electrogalvanized steel sheet by Cu-flash treatment |
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| KR10-1999-0060596A KR100429153B1 (en) | 1999-12-22 | 1999-12-22 | the blackening method of electrogalvanized steel sheet by Cu-flash treatment |
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| KR100429153B1 true KR100429153B1 (en) | 2004-04-28 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101277940B1 (en) * | 2011-03-28 | 2013-06-27 | 주식회사 포스코 | Blackened steel stheet with high adhesion property of blackened layer and surface appearance, and method for manufacturing the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6270583A (en) * | 1986-09-16 | 1987-04-01 | Nippon Steel Corp | Production of black zinc alloy plated steel sheet |
| JPS6277482A (en) * | 1985-09-30 | 1987-04-09 | Nippon Steel Corp | Manufacture of corrosion resistant black zinc alloy plated steel sheet |
| US4861441A (en) * | 1986-08-18 | 1989-08-29 | Nippon Steel Corporation | Method of making a black surface treated steel sheet |
| KR960009198A (en) * | 1994-08-30 | 1996-03-22 | 기다오까 다까시 | Memory Cell Layout for Semiconductor Memory Devices |
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1999
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6277482A (en) * | 1985-09-30 | 1987-04-09 | Nippon Steel Corp | Manufacture of corrosion resistant black zinc alloy plated steel sheet |
| US4861441A (en) * | 1986-08-18 | 1989-08-29 | Nippon Steel Corporation | Method of making a black surface treated steel sheet |
| JPS6270583A (en) * | 1986-09-16 | 1987-04-01 | Nippon Steel Corp | Production of black zinc alloy plated steel sheet |
| KR960009198A (en) * | 1994-08-30 | 1996-03-22 | 기다오까 다까시 | Memory Cell Layout for Semiconductor Memory Devices |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101277940B1 (en) * | 2011-03-28 | 2013-06-27 | 주식회사 포스코 | Blackened steel stheet with high adhesion property of blackened layer and surface appearance, and method for manufacturing the same |
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| KR20010060422A (en) | 2001-07-07 |
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