KR0125318B1 - MANUFACTURING METHOD FOR PYRO-BLACK Zn-Cu ALLOY COATED STEEL SHEET - Google Patents

MANUFACTURING METHOD FOR PYRO-BLACK Zn-Cu ALLOY COATED STEEL SHEET

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KR0125318B1
KR0125318B1 KR1019940027834A KR19940027834A KR0125318B1 KR 0125318 B1 KR0125318 B1 KR 0125318B1 KR 1019940027834 A KR1019940027834 A KR 1019940027834A KR 19940027834 A KR19940027834 A KR 19940027834A KR 0125318 B1 KR0125318 B1 KR 0125318B1
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steel sheet
black
plated steel
zinc
copper
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KR1019940027834A
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Korean (ko)
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KR960014402A (en
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전재호
조준형
신정철
임병문
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신찬식
한국신철강기술연구조합
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50Multilayers
    • B05D7/52Two layers
    • B05D7/53Base coat plus clear coat type
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic material, boron or silicon
    • C23C14/16Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24Vacuum evaporation
    • C23C14/26Vacuum evaporation by resistance or inductive heating of the source
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58After-treatment
    • C23C14/5846Reactive treatment
    • C23C14/5853Oxidation
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00Coating not provided for in groups C23C2/00 - C23C24/00
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The fabrication method for the black coated steel sheet includes the steps of: vacuum depositing a Zn-Cu coated layer having the copper content of 5-50 wt.% on a steel sheet, subjecting the Zn-Cu alloy coated steel sheet at 500-600 degrees centigrade in air for 1 minute, and coating the surface of the black Zn-Cu alloy coated steel sheet with a 0.5-30M of a transparent pigment.

Description

건식 흑색 아연-구리 합금도금강판의 제조방법Manufacturing method of dry black zinc-copper alloy plated steel sheet

본 발명은 진공증착 방법으로 아연-구리 합금도금강판을 만든 후 아연-구리 합금도금강판을 대기중의 노내에서 산화시켜 외관이 미려한 흑색 도금 강판을 건식(乾式) 방법에 의해 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a zinc-copper alloy plated steel sheet by vacuum deposition and then oxidizing the zinc-copper alloy plated steel sheet in an air furnace to produce a black-coated steel sheet having a beautiful appearance by a dry method. .

흑색 강판은 금속표면에 미려한 검은 색상을 띄어 상품의 외관을 고급스럽게 하거나, 중후한 느낌으로 상품의 가치를 더해주는 효과를 주기 때문에 음향기기의 외판재 및 내부 부품, 영상 기기의 내부 부품, 가전기기의 외판재, 사무용 기기, 건재용의 내외판재 및 조명기고, 장식품 등에 널리 사용되고 있으며, 최근에는 흑색 강판의 용도가 더욱 확대되고 있다.The black steel plate has a beautiful black color on the metal surface to enhance the appearance of the product or to add value to the product with a heavy impression. It is widely used for interior and exterior boards for lighting materials, office equipment, building materials, lighting cabinets, ornaments, and the like, and recently, the use of black steel sheets has been further expanded.

기존의 흑색강판의 제조방법으로는 ① 용액중에 침지하거나 용액의 스프레이에 의해 수지 기판과의 화학반응을 일으켜 검은색의 금속산화물을 형성하는 방법 ② 금속표면에 양극전해처리를 통해 산화물을 형성하는 방법 등이 있다. 일본특허공보 소 63-161176호 및 62-290880호에는 아연 또는 아연 합금도금 강판에 Ag2+, Sb2+, Cu2+, Bi2+중 2종 이상의 금속이온을 0.18~20g/L 함유하고 또한 Ni2+, Fe2+, Co2+중 2종 이상의 금속이온을 1~100g/L 함유된 수용액을 50~60℃의 온도에서 스프레이시켜 흑색화 처리하는 방법에 대하여 기재하고 있다. 그리고 후처리로서 크로메이트 처리를 실시한다. 한편 일본특허공보 소 61-291981호에는 아연-니켈 합금도금강판을 PO4 2-/NO3 -이온의 비를 0.01~1이 되도록 함유된 pH가 3이하의 산성용액속에서 전류밀도를 20~40A/dm2로 하는 양극 전해처리를 하여 흑색화 처리하는 방법에 대하여 기재하고 있다.Existing methods for manufacturing black steel sheet include: ① Method of forming black metal oxide by immersing in solution or chemical reaction with resin substrate by spraying solution. ② Method of forming oxide on metal surface through anodization. Etc. Japanese Patent Laid-Open Nos. 63-161176 and 62-290880 contain 0.18-20 g / L of two or more metal ions of Ag 2+ , Sb 2+ , Cu 2+ , Bi 2+ in a zinc or zinc alloy plated steel sheet. Moreover, it describes the method of blackening by spraying the aqueous solution containing 1-100 g / L of 2 or more types of metal ions among Ni2 + , Fe2 + , and Co2 + at the temperature of 50-60 degreeC. Then, chromate treatment is performed as a post treatment. On the other hand, Japanese Patent Publication No. 61-291981 discloses a zinc-nickel alloy plated steel sheet having a current density of 20 to 20 in an acidic solution having a pH of 3 or less containing a ratio of PO 4 2- / NO 3 - ions to 0.01 to 1. It describes about the method of blackening by performing the anodic electrolytic treatment to 40A / dm <2> .

그러나 기존의 흑색 강판에는 공해문제 및 작업성 측면에서 몇가지 단점을 가지고 있다. 일본특허공보 소 63-161176호 및 62-290080호에서 제시된 방법은 여러종의 중금속을 함유한 용액을 사용하기 때문에 폐수처리시설을 별도로 마련해야 하고, 연속작업시 금속이온의 농도를 일정하게 유지해야만 하는 어려움이 있다. 또한 내판재로 사용되는 경우는 후처리로 실시된 크로메이트 처리 때문에 사람의 지문이나 물(Water)등과의 접촉에 의해 6가의 Cr 이온이 용출될 수 있기 때문에 사용범위에 제한을 받는다. 그리고 일본 특허공보 소 61-291981호에서 제시된 방법은 pH가 3이하의 강산성에서 작업을 해야 하기 때문에 작업환경이 나쁘고 공해문제를 유발하기 쉬우며, 별도의 폐수처리가 필요하게 된다. 그리고 강산욕에 도금강판을 침지하기 때문에 도금층의 일부원소가 녹아나오기 쉽고, 전해처리시의 전류밀도도 비교적 고전류를 사용하여야 한다.However, the existing black steel sheet has some disadvantages in terms of pollution and workability. In the Japanese Patent Laid-Open Publication Nos. 63-161176 and 62-290080, the waste water treatment facility must be separately prepared because the solution containing various heavy metals is used, and the concentration of metal ions must be kept constant during continuous operation. There is difficulty. In addition, when used as an inner plate material, the use range is limited because hexavalent Cr ions can be eluted by contact with human fingerprints or water due to chromate treatment performed by post treatment. In addition, the method proposed in Japanese Patent Application Laid-Open No. 61-291981 has a bad working environment, it is easy to cause pollution problem, and requires separate wastewater treatment because it has to work in strong acidity with pH less than 3. In addition, since the plated steel sheet is immersed in the strong acid bath, some elements of the plated layer are easily melted, and the current density during the electrolytic treatment should be relatively high.

본 발명에서는 상술한 방법들에서 용액을 사용함에 따른 공해분제 및 폐수처리의 단점을 개선하고, 기존의 공지기술보다 작업이 용이하고 작업공정이 비교적 간단한 방법으로 흑색화 강판을 제조하고자 하는데 주안점을 두었다. 즉 우선 진공증착 방법으로 아연-구리 합금 도금강판을 만든 후, 이를 수용액을 사용하지 않고 대기중의 노내에서 열처리를 하여 표면에 흑색의 색상을 띄는 산화막을 형성시키는 흑색 강판의 제조방법을 개발하게 되었다.The present invention focuses on improving the disadvantages of pollutants and wastewater treatment by using the solution in the above-described methods, and to produce blackened steel sheet in a manner that is easier to work than the conventional known technology and the work process is relatively simple. . That is, first, a zinc-copper alloy-coated steel sheet was made by vacuum deposition, and then a black steel sheet was manufactured by heat-treating it in an air furnace without using an aqueous solution to form an oxide film having a black color on its surface. .

본 발명의 제조공정을 상세히 설명하면 다음과 같다.Hereinafter, the manufacturing process of the present invention will be described in detail.

먼저 소지기판인 일반 냉연강판을 알칼리 용액세서 탈지한 후 아세톤 및 알콜 용액에서 초음파 세척하여 전처리를 실시하였다. 이렇게 전처리를 거친 강판을 진공조에 장입하여 10-4torr까지 진공배기 하였다. 진공배기 후 강판을 진공중에서 200℃ 온도까지 가열한 후 각기 다른 증발원에 아연 금속 낱알(grain)과 구리금속 낱알을 각각 넣고 증발원에 전원을 공급하여 저항가열 방식으로 아연-구리 합금도금강판을 각가 제조하였다. 여기서 구리를 아연과 합금상태로 처가한 이유는 다음에 설명될 열처리공정에서 도금층의 구리성분이 흑색의 산화물로 변화하기 쉽기 때문이다. 한편 첨가되는 구리의 양은 5~50wt% 사이에서 실시하여야 한다. 왜냐하면 구리의 첨가량이 적으면 흑색의 발색이 일어나지 않으며, 구리의 양이 많으면 내식성 및 밀착성이 떨어지기 때문이다.First, the cold rolled steel sheet, which is a base plate, was degreased under alkaline solution, and then pretreated by ultrasonic cleaning in acetone and alcohol solution. The pretreated steel sheet was charged into a vacuum chamber and evacuated to 10 -4 torr. After vacuum evacuation, the steel sheet is heated to a temperature of 200 ° C. in vacuum, and then zinc grains and copper metal grains are put in different evaporation sources, and power is supplied to the evaporation sources to produce zinc-copper alloy plated steel sheets by resistance heating. It was. The reason why copper is disposed in an alloy state with zinc is that the copper component of the plating layer is likely to change into a black oxide in the heat treatment process described later. Meanwhile, the amount of copper added should be between 5 and 50wt%. This is because if the amount of copper added is small, black color development does not occur, and if the amount of copper is large, corrosion resistance and adhesion are inferior.

진공증착법에 의해 제조된 아연-구리 합금도금강판은 흑색의 표면 산화막을 형성시키기 위해 열처리 공정을 거치게 된다. 즉 아연-구리 합금도금 강판을공기중의 노내에서 가열시키는데, 온도는 500℃ 이상 600℃에서 1분동안 가열시켰다. 여기서 하한온도를 500℃로 한 이유는 이 온도 이하에서는 강판표면에 산화가 충분하게 일어나지 않기 때문에 표면색상이 원하는 흑색을 얻지 못하기 때문이다. 그리고 상한온도를 600℃로 한 이유는 열처리온도가 600℃가 넘으면 소지강판의 기계적 성질에 영향을 줄 뿐 아니라 소지금속에 있는 철 성분이 도금층까지 확산하여 도금층 조직을 변화시켜 내식성 및 밀착성을 나쁘게하기 때문이다.The zinc-copper alloy plated steel sheet produced by vacuum deposition is subjected to a heat treatment process to form a black surface oxide film. That is, the zinc-copper alloy plated steel sheet was heated in an air furnace, and the temperature was heated at 500 ° C. to 600 ° C. for 1 minute. The reason why the lower limit temperature is 500 deg. C is because the oxidation of the surface of the steel sheet does not occur sufficiently below this temperature, so that the surface color does not obtain the desired black color. And the upper limit temperature is 600 ℃ because the heat treatment temperature exceeds 600 ℃ not only affects the mechanical properties of the steel sheet, but also the iron component of the metal spreads to the plating layer to change the structure of the plating layer, thus deteriorating corrosion resistance and adhesion. Because.

마지막으로 상기와 같은 제조된 흑색처리 강판은 비록 표면에 흑색의 색상을 나타내지만, 열악한 환경분위기에서도 사용할 수 있도록 내식성 및 내후성을 증가시키기 위해 아크릴계 투명도료를 두께 0.5~30μm의 범위로 도포하였다. 도포의 두께의 하한치를 0.5μm로 한 이유는 이 이하의 두께에서는 내식성 및 내후성을 뚜렷하게 증가시키지 못하기 때문이다. 왜냐하면 도포되는 도료의 두께가 작으면 피막자체가 가지는 조도를 완전하고 유일하게 막아주지 못하기 때문에 외부 환경에 의한 부식을 방어해주지 못하기 때문이다. 투명도료는 밑바탕이 되는 흑색 산화막층에 영향을 주지않고 생상을 그대로 유지해주기 때문에 환경조건이 열악한 경우에는 투명도료를 도포하는 것이 유리하다. 그리고 이경우에는 도료가 부분적으로 박리되었다 하더라도 도금층 표면에 흑색의 산화막이 존재하므로 흑색 처리 강판자체의 미관은 손상되지 않는다.Lastly, the manufactured black-treated steel sheet, although showing a black color on its surface, was coated with an acrylic transparent paint in a range of 0.5 to 30 μm in order to increase corrosion resistance and weather resistance so that it may be used even in a harsh environmental atmosphere. The reason why the lower limit of the thickness of the coating is set to 0.5 µm is that the corrosion resistance and the weather resistance are not significantly increased at the thickness below this. This is because the small thickness of the applied coating does not prevent the roughness of the film itself completely and solely, so it does not protect against corrosion caused by the external environment. Since the transparent paint maintains the raw material without affecting the underlying black oxide layer, it is advantageous to apply the transparent paint when the environmental conditions are poor. In this case, even if the paint is partially peeled off, since a black oxide film exists on the surface of the plating layer, the aesthetics of the black-treated steel sheet itself are not damaged.

본 발명의 구체적인 실시예를 설명하면 다음과 같다.Hereinafter, specific embodiments of the present invention will be described.

실시예 1-2Example 1-2

우선일반 냉연강판을 탈지한 후, 진공조에 장입하여 10-4torr 까지 진공배기하였다. 진공배기 후, 기판을 200℃ 온도까지 가열하고 저항가열 방식으로 아연과 구리를 동시에 증발시켜서 구리의 농도가 5wt%가 되도록 증발속도를 조절하여 아연도금강판을 제조하였다. 이때 도금층의 도금량은 20g/m2이었다. 그리고 마지막으로 공기중의 노내에서 도금강판을 550~600℃ 사이의 적당한 온도에서 각각 1분간 열처리 하였다.First, the general cold rolled steel sheet was degreased, charged into a vacuum chamber, and evacuated to 10 −4 torr. After vacuum evacuation, the substrate was heated to a temperature of 200 ° C. and zinc and copper were simultaneously evaporated by a resistance heating method to adjust the evaporation rate so that the concentration of copper was 5 wt% to prepare a galvanized steel sheet. At this time, the plating amount of the plating layer was 20g / m 2 . Finally, the plated steel sheet was heat-treated in an air furnace at a suitable temperature between 550 and 600 ° C. for 1 minute.

실시예 3-4Example 3-4

실시예 1과같은 방법으로 아연-구리 합금도금강판을 제조하는데 있어, 구리의 농도가 10wt%가 되도록 증발속도를 조절하여 합금도금강판을 제조하였다. 그리고 마지막으로 공기중의 노내에서 도금강판을 550~600℃ 사이의 적당한 온도에서 각각 1분간 열처리 하였다.In preparing a zinc-copper alloy plated steel sheet in the same manner as in Example 1, an alloy plated steel sheet was manufactured by adjusting the evaporation rate so that the concentration of copper was 10wt%. Finally, the plated steel sheet was heat-treated in an air furnace at a suitable temperature between 550 and 600 ° C. for 1 minute.

실시예5-7Example 5-7

실시예 1과같은 방법으로 아연-구리 합금도금강판을 제조하는데 있어, 구리의 농도가 30wt%가 되도록 증발속도를 조절하여 합금도금강판을 제조하였다. 그리고 마지막으로 공기중의 노내에서 도금강판을 500~600℃의 적당한 온도에서 각각 1분간 열처리 하였다.In preparing a zinc-copper alloy plated steel sheet in the same manner as in Example 1, an alloy plated steel sheet was manufactured by adjusting the evaporation rate so that the copper concentration was 30 wt%. Finally, the plated steel sheet was heat-treated in an air furnace at a suitable temperature of 500 to 600 ° C. for 1 minute.

실시예 8-10Example 8-10

실시예 1과같은 방법으로 아연-구리 합금도금강판을 제조하는데 있어, 구리의 농도가 50wt%가 되도록 증발속도를 조절하여 합금도금강판을 제조하였다. 그리고 마지막으로 공기중의 노내에서 도금강판을 550~600℃의 적당한 온도에서 각각 1분간 열처리 하였다.In preparing a zinc-copper alloy plated steel sheet in the same manner as in Example 1, an alloy plated steel sheet was manufactured by adjusting the evaporation rate so that the copper concentration was 50 wt%. Finally, the plated steel sheet was heat-treated in an air furnace at a suitable temperature of 550-600 ° C. for 1 minute.

실시예 11-15Example 11-15

실시예 3과 같은 방법으로 흑색처리 아연도금강판을 제조한 후, 표면에 투명도료를 가지고 도포하였다. 투명도료는 아크릴계 알키드 수지(Acrylicalkyd resting)를 0.5~30μm 두께로 바른 후, 상온에서 건조하였다.After the black-treated galvanized steel sheet was prepared in the same manner as in Example 3, the surface was coated with a transparent paint. The transparent paint was coated with an acrylic alkyd resin (Acrylicalkyd resting) to a thickness of 0.5 ~ 30μm, and dried at room temperature.

실시예 16-20Example 16-20

실시예 9과 같은 방법으로 흑색처리 아연도금강판을 제조한 후, 토명도료를 가지고 도포하였다. 투명도료는 아크릴계 알키드 수지(Acrylicalkyd resting)를 0.5~30μm 두께로 바른 후, 상온에서 건조하였다.After the black-treated galvanized steel sheet was prepared in the same manner as in Example 9, it was applied with a clear paint. The transparent paint was coated with an acrylic alkyd resin (Acrylicalkyd resting) to a thickness of 0.5 ~ 30μm, and dried at room temperature.

비교예 1Comparative Example 1

실시예 1과 같은 방법으로 아연-구리 합금도금강판을 제조하는데 있어, 구리의 농도가 1wt%가 되도록 증발속도를 조절하여 합금도금강판을 제조하였다. 그리고 공기중에서 열처리 온도는 550℃에서 1분간 열처리를 하였다.In preparing the zinc-copper alloy plated steel sheet in the same manner as in Example 1, an alloy plated steel sheet was manufactured by adjusting the evaporation rate so that the copper concentration was 1 wt%. And heat treatment temperature in air was heat-treated for 1 minute at 550 ℃.

비교예 2-3Comparative Example 2-3

실시예 1과 같은 방법으로 아연-구리 합금도금강판을 제조하는데 있어, 구리의 농도가 5wt%가 되도록 증발속도를 조절하여 합금도금강판을 제조하였다. 그리고 공기중에서 열처리 온도는 550℃ 및 650℃에서 1분간 열처리를 하였다.In preparing the zinc-copper alloy plated steel sheet in the same manner as in Example 1, an alloy plated steel sheet was manufactured by adjusting the evaporation rate so that the concentration of copper was 5wt%. And heat treatment temperature in air was heat-treated for 1 minute at 550 ℃ and 650 ℃.

비교예 4-5Comparative Example 4-5

실시예 1과 같은 방법으로 아연-구리 합금도금강판을 제조하는데 있어, 구리의 농도가 각각 60,90wt%가 되도록 증발속도를 조절하여 합금도금강판을 제조하였다. 그리고 공기중에서 열처리 온도는 550℃에서 각각 1분간 열처리를 하였다.In preparing a zinc-copper alloy plated steel sheet in the same manner as in Example 1, an alloy plated steel sheet was prepared by adjusting the evaporation rate so that the concentration of copper was 60,90 wt%. In the air, the heat treatment temperature was performed at 550 ° C. for 1 minute.

비교예 6Comparative Example 6

실시예 3과 같은 방법으로 흑색처리 아연도금강판을 제조한 후, 표면에 투명도료를 가지고 도장을 추가로 실시하였다. 토명도료는 아크릴계 알키드수지(Acrylic Alkyd resin)를 0.1μm 두께로 바른 후 상온에서 건조하였다.After producing a black-treated galvanized steel sheet in the same manner as in Example 3, the coating was further performed with a transparent coating on the surface. The clear paint was coated with acrylic Alkyd resin (0.15 m thick) and dried at room temperature.

비교예 7Comparative Example 7

실시예 9와 같은 방법으로 흑색처리 아연도금강판을 제조한 후, 표면에 투명도료를 가지고 도장을 추가로 실시하였다. 토명도료는 아크릴계 알키드수지(Acrylic Alkyd resin)를 0.1μm 두께로 바른 후 상온에서 건조하였다.After the black-treated galvanized steel sheet was manufactured in the same manner as in Example 9, the surface was further coated with a transparent coating. The clear paint was coated with acrylic Alkyd resin (0.15 m thick) and dried at room temperature.

상기와 같은 제조된 시편의 품질특성평가는 표 1에 나타내었다. 이때 도금층 표면에 색상은 목측 및 색차계를 가지고 관찰하였고, 도금층의 밀착성을 평가하기 위해 시편을 180°Ot 굴곡 후 접착테이프를 이용하여 도금층의 박리정도를 비교 평가하였다(○ : 박리가 발생하지 않음 △ : 박리가 부분적으로 발생 × : 박리가 전반적으로 발생) 그리고 내식성을 평가하기 위해 10cm×15cm의 크기로 시편을 제조한 후 각 시편을 ASTM B3317-73에 의거 염수분무장치에서 적청발생시간을 기록하였다. (◎ : 98시간 이상, ○ : 24~98시간, △ : ~24시간 × : 6시간 이하) 도금 표면층의 내지문성은 백색 바세린을 바르기 전후의 △E 값을 색차계를 이용하여 경량화 하였다. (○ : 3이하 △ : 3~10 × : 10이상)마지막으로 시편의 내후성은 6개월간 옥외폭로를 실시한 후 표면색상의 변색여부를 평가하였다. (○ : 변색이 일어나지 않음 × : 변색됨)Evaluation of the quality characteristics of the prepared specimens are shown in Table 1. At this time, the color was observed on the surface of the plating layer with the neck side and the color difference meter. In order to evaluate the adhesion of the plating layer, the specimen was bent 180 ° Ot, and then the degree of peeling of the plating layer was evaluated using adhesive tape (○: no peeling occurred). △: peeling partly occurred ×: peeling partly)) And to evaluate the corrosion resistance, the specimens were prepared in the size of 10cm × 15cm, and each specimen was recorded in the salt spray device according to ASTM B3317-73. It was. (◎: 98 hours or more, (circle): 24-98 hours, (triangle | delta):-24 hours x: 6 hours or less) The anti-fingerprint of the plating surface layer reduced the value of (DELTA) E before and after applying white petrolatum using a color difference meter. Finally, the weather resistance of the specimens was evaluated for the change of surface color after 6 months of outdoor exposure. (○: discoloration does not occur ×: discoloration)

표 1에서 나타난 것처럼 본 발명은 진공증착법으로 구리의 첨가량이5~50wt%가 되도록 구리-아연 합금도금강판을 제조한 후, 대기중의 500~600℃ 온도범위에서 산화시키면 흑색화 아연 도금강판의 제조가 가능함을 보여준다. 그리고 추가로 그 후에 투명도료를 0.5μm 이상 도포하면 내식성 및 내후성이 요구되는 열악한 환경분위기에서도 사용할 수 있다.As shown in Table 1, the present invention manufactures a copper-zinc alloy plated steel sheet so that the amount of copper is added in an amount of 5 to 50 wt% by vacuum evaporation, and then oxidizes it at 500 to 600 ° C. in the air. It shows that manufacturing is possible. In addition, if the transparent paint is applied after 0.5μm or more, it can be used even in a harsh environment where corrosion resistance and weather resistance are required.

결국 본 발명은 기존의 수용액을 사용하여 측색 처리강판을 제조하는 방법보다 공해유방이나 폐수처리의 설비없이 간단하게 흑색 처리강판을 제조할 수 있으며 각종 가전기기의 내외판제, 건재용의 내외판제 및 장식품 등 넓은 적용이 가능하다.As a result, the present invention can produce a simple black treated steel sheet without the facilities of pollution oil or waste water treatment than the method of manufacturing the color-treated steel sheet using a conventional aqueous solution, the interior and exterior panels of various home appliances, interior and exterior panels for building materials and ornaments Wide application is possible.

표 1. 제조조건에 다른 흑색처리 아연도금강판의 품질특성 평가결과Table 1. Evaluation results of quality characteristics of black-treated galvanized steel sheet according to manufacturing conditions

Claims (2)

흑색 도금강판의 제조방법에 있어서, 구리 함량이 5~50wt%인 아연-구리(Zn-Cu) 도금층을 진공증착시킨 아연-구리 합금도금강판을 공기중에서 500~600℃의 온도로 약 1분간 열처리 하여서 된 흑색 아연-구리 합금도금강판 표면에 투명도료를 0.5~30μm 도포하는 건식 흑색 아연-구리 합금도금강판의 제조방법.In the manufacturing method of black plated steel sheet, the zinc-copper alloy plated steel sheet vacuum-deposited the zinc-copper (Zn-Cu) plating layer having a copper content of 5 to 50wt% is heat-treated at a temperature of 500 to 600 ° C. in air for about 1 minute. Method for producing a dry black zinc-copper alloy plated steel sheet by applying a 0.5-30μm transparent coating on the surface of the black zinc-copper alloy plated steel sheet. 제1항에 있어서, 토명도료가 아크릴계 알키드 수지인 건식 흑색 아연-구리 합금도금강판의 제조방법.The method for producing a dry black zinc-copper alloy plated steel sheet according to claim 1, wherein the transparent paint is an acrylic alkyd resin.
KR1019940027834A 1994-10-28 1994-10-28 MANUFACTURING METHOD FOR PYRO-BLACK Zn-Cu ALLOY COATED STEEL SHEET KR0125318B1 (en)

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WO2018190474A1 (en) * 2017-04-12 2018-10-18 이홍규 Nonferrous metal coating-dry plating method, and nonferrous metal coating-dry plated product

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018190474A1 (en) * 2017-04-12 2018-10-18 이홍규 Nonferrous metal coating-dry plating method, and nonferrous metal coating-dry plated product

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