KR101277940B1 - Blackened steel stheet with high adhesion property of blackened layer and surface appearance, and method for manufacturing the same - Google Patents
Blackened steel stheet with high adhesion property of blackened layer and surface appearance, and method for manufacturing the same Download PDFInfo
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- KR101277940B1 KR101277940B1 KR1020110027731A KR20110027731A KR101277940B1 KR 101277940 B1 KR101277940 B1 KR 101277940B1 KR 1020110027731 A KR1020110027731 A KR 1020110027731A KR 20110027731 A KR20110027731 A KR 20110027731A KR 101277940 B1 KR101277940 B1 KR 101277940B1
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 63
- 239000010959 steel Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 39
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 32
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- -1 organic acid ions Chemical class 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 71
- 239000000243 solution Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000227 grinding Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 8
- 229910001297 Zn alloy Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
- C23C22/26—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also organic compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C28/00—Coating 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
본 발명은 흑화층 밀착성이 개선되고, 표면외관이 우수한 흑색강판을 제공하고, 이를 용이하고, 친환경적으로 제조하는 방법을 제공하고자 하는 것이다.
이를 위해, 본 발명은 아연 또는 아연계 합금도금강판;
상기 아연 또는 아연계 합금도금강판의 표면에 형성된 Ni층; 및
상기 Ni층 위에 형성된 흑화층을 포함하는 흑화층 밀착성이 우수한 흑색강판과 이를 제조하는 방법을 제공한다.The present invention is to provide a black steel sheet with improved blackening layer adhesion, excellent surface appearance, and to provide a method for easily and eco-friendly manufacturing.
To this end, the present invention is a zinc or zinc-based alloy plated steel sheet;
Ni layer formed on the surface of the zinc or zinc-based alloy plated steel sheet; And
It provides a black steel sheet excellent in blackening layer adhesion including a blackening layer formed on the Ni layer and a method of manufacturing the same.
Description
본 발명은 영상가전용 전자제품, 가전제품, 음향기기, OA기기 등에 적용되는 흑색강판 및 그 제조방법에 관한 것으로서, 보다 상세하게는 흑화층의 밀착성 및 표면외관을 향상시킨 흑색강판과 이를 용이하고 친환경적으로 제조할 수 있는 제조방법에 관한 것이다.The present invention relates to a black steel sheet and a method for manufacturing the same, which are applied to electronic appliances, home appliances, sound equipment, OA devices, and the like, and more particularly, a black steel sheet having improved adhesion and surface appearance of a blackening layer and an easy and eco-friendly method. It relates to a manufacturing method that can be prepared by.
흑색강판은 흑화처리를 통해 강판 표면에 무기계 흑색피막이 형성된 착색강판으로서, 수요가의 도장공정이 생략되기 때문에 제조비용을 저감시킬 수 있으며, 흑색표면형상이 균일하고 미려하기 때문에 최근 가전제품, 음향기기, OA기기, 자동차용 부품 등 여러 분야에 사용되고 있으며, 최근 그 용도가 확대되고 있다.
Black steel sheet is a colored steel sheet with an inorganic black film formed on the surface of the steel sheet through blackening treatment, which can reduce the manufacturing cost because the coating process of the demand is omitted, and the black surface shape is uniform and beautiful, so it is the latest home appliances and sound equipment. It is used in various fields such as OA equipment, automotive parts, and the like, and its use is expanding recently.
이와 같은 흑색강판은 종래 아연합금도금강판, 주로 Zn-Ni합금도금강판을 이용해 산화법, 음극처리 또는 화성처리를 통해 흑색피막을 형성시키는 방법으로 제조되어 왔다. 대표적으로, 일본 특개소 61-291981호와 일본 특개 1990-282485호에는 Ni, Co, Fe, Al, Mg, Cu, Sn, C, Cr, Mo, Ag 등의 금속이온이 함유된 산성 수용액을 이용하여 산화법을 통해 아연합금도금강판에 흑색피막을 형성시키는 방법이 개시되어 있다.
Such a black steel sheet has been manufactured by a method of forming a black film through an oxidation method, an anodization process, or a chemical conversion process using a conventional zinc alloy plated steel sheet, mainly Zn-Ni alloy plated steel sheet. Typically, Japanese Patent Laid-Open No. 61-291981 and Japanese Patent Laid-Open No. 1990-282485 use acidic aqueous solutions containing metal ions such as Ni, Co, Fe, Al, Mg, Cu, Sn, C, Cr, Mo, and Ag. The method for forming a black film on a zinc alloy plated steel sheet through an oxidation method is disclosed.
또한, 일본 특개소 62-263995호와 일본 특개평6-346288호에서는 일반강판 또는 표면처리강판을 수용액에서 음극처리하여 흑색피막을 형성시키는 방법을 개시하고 있으며, 일본 특개소 63-161176호 및 일본 특개소 62-290880호에서는 아연 또는 아연 합금도금강판을 금속이온이 함유된 용액중에서 화성처리하여 흑색피막을 형성시키는 방법이 개시되어 있다.
In addition, Japanese Patent Laid-Open Nos. 62-263995 and 6-346288 disclose a method of forming a black film by cathodic treatment of an ordinary steel sheet or a surface-treated steel sheet in an aqueous solution, and Japanese Patent Laid-Open Nos. 63-161176 and Japan Japanese Patent Laid-Open No. 62-290880 discloses a method of forming a black film by chemically treating a zinc or zinc alloy plated steel sheet in a solution containing metal ions.
그러나, 이와 같은 종래 기술들은 아연합금도금강판을 사용하여 음극법 또는 산화법으로 흑색피막을 형성시키기 때문에 비용이 상승하는 문제가 있으며, 아연도금강판을 화성처리를 하더라도, 흑화층의 밀착성 저하로 인하여 흑화층이 부서지거나 떨어져 나가는 파우더링(powdering)현상이 심하다는 단점이 있다. 실제로, 일본 특개 1990-093077호에는 Sn과 Ni 또는 Co화합물을 포함하는 용액을 이용하여 아연 또는 아연계합금도금강판에 흑색피막을 형성시키는 방법이 개시되어 있으나, 상기 제조방법에 의한 흑화처리층의 경우, 파우더링이 심하여 흑화처리층의 밀착성이 떨어지는 문제점이 발생하였다.
However, these prior arts have a problem in that the cost increases due to the formation of a black film by an anode method or an oxidation method using a zinc alloy plated steel sheet, and even if the galvanized steel sheet is chemically treated, blackening is caused due to a decrease in adhesion of the blackening layer. There is a drawback in that the powdering phenomenon in which the layer breaks or falls off is severe. In fact, Japanese Patent Application Laid-Open No. 1990-093077 discloses a method of forming a black film on a zinc or zinc-based alloy plated steel sheet using a solution containing Sn and Ni or Co compounds, but in the case of the blackened layer according to the manufacturing method , The powdering is so severe that the adhesion of the blackening layer is inferior.
뿐만 아니라, 종래 흑화처리기술의 용액 조성은 주로 3종이상 성분으로 이루어져 있어서, 조성이 복잡하고 조업중 용액관리에 어려움이 있으며, 크롬이나 중금속 및 강산과 같은 유해성분을 포함하여 폐수처리의 어려움이 있고, 환경오염의 우려가 있다.In addition, the solution composition of the conventional blackening treatment technology mainly consists of three or more components, the composition is complicated, difficult to manage the solution during operation, and difficult to treat wastewater, including harmful components such as chromium, heavy metals and strong acids And environmental pollution.
본 발명의 일측면은 아연계 도금강판의 흑화층 밀착성이 개선되고, 표면외관이 우수한 흑색강판을 제공하고, 이를 용이하고, 친환경적으로 제조하는 방법을 제공하고자 하는 것이다.One aspect of the present invention is to provide a black steel sheet with improved blackening layer adhesion of the zinc-based galvanized steel sheet, excellent surface appearance, and to provide a method for easily and eco-friendly manufacturing.
본 발명은 아연 또는 아연계 합금도금강판;The present invention is a zinc or zinc-based alloy plated steel sheet;
상기 아연 또는 아연계 합금도금강판의 표면에 형성된 Ni층; 및Ni layer formed on the surface of the zinc or zinc-based alloy plated steel sheet; And
상기 Ni층 위에 형성된 흑화층을 포함하는 흑화층 밀착성 및 표면외관이 우수한 흑색강판을 제공한다.
It provides a black steel sheet excellent in blackening layer adhesion and surface appearance including a blackening layer formed on the Ni layer.
또한, 본 발명은 아연 또는 아연계 합금도금강판의 표면에 Ni을 부착하여 Ni층을 형성하는 단계;In addition, the present invention comprises the steps of attaching Ni to the surface of the zinc or zinc-based alloy plated steel sheet to form a Ni layer;
상기 Ni층을 갖는 강판에 흑화처리를 행하여 흑화층을 형성하는 단계를 포함하는 흑화층 밀착성 및 표면외관이 우수한 흑색강판의 제조방법을 제공한다.It provides a method for producing a black steel sheet excellent in blackening layer adhesion and surface appearance comprising the step of forming a blackening layer by performing a blackening treatment on the steel sheet having the Ni layer.
본 발명에 의하면, 흑화처리시 발생하는 파우더링(powdering)현상을 억제하여 흑화층의 밀착성을 향상시키고 표면외관이 우수하여 가격경쟁력이 높은 흑색강판을 제조할 수 있다. 또한, 제조과정에서 파우더링에 의한 롤(roll)오염을 방지할 수 있기 때문에 연속 작업성을 향상하고 후공정인 보호수지 코팅시 수지층 밀착성도 향상시킬 수 있다. 또한, 흑화처리용액을 간단히 조제할 수 있고, 조업 중 용액관리가 용이하며, 친환경적인 제조가 가능하다는 장점이 있다.According to the present invention, by suppressing the powdering (phendering) generated during the blackening process to improve the adhesion of the blackening layer and excellent surface appearance can be produced a black steel sheet with high price competitiveness. In addition, since it is possible to prevent the roll (roll) contamination by powdering in the manufacturing process, it is possible to improve the continuous workability and also to improve the adhesion of the resin layer during the protective resin coating process. In addition, the blackening treatment solution can be easily prepared, the solution management during the operation, there is an advantage that the environment-friendly manufacturing is possible.
도 1은 본 발명의 흑색강판의 일예를 나타낸 단면도임.1 is a cross-sectional view showing an example of the black steel sheet of the present invention.
이하, 본 발명에 대하여 상세히 설명한다. 본 발명자들은 충분한 흑색도를 유지하면서, 흑화층 밀착성을 개선하기 위해서는 흑화층의 화학형태와 표면구조가 중요인자로 작용하는 것을 인자하고, 이를 위해서는 적절한 흑화처리용액 및 처리공정조건의 설정이 중요한 과제임을 인지하고 본 발명에 이르게 되었다.
Hereinafter, the present invention will be described in detail. The inventors of the present invention print that the chemical form and surface structure of the blackening layer act as important factors in order to improve the blackening layer adhesion while maintaining sufficient blackness, and for this purpose, it is important to set appropriate blackening treatment solution and treatment process conditions. It was recognized that the present invention has been achieved.
먼저, 본 발명의 흑색강판에 대하여 상세히 설명한다.First, the black steel sheet of this invention is demonstrated in detail.
본 발명의 흑색강판은 아연 또는 아연계 합금도금강판과 상기 아연 또는 아연계 합금도금강판의 표면에 형성된 Ni층 및 상기 Ni층 위에 형성된 흑화층을 포함한다. The black steel sheet of the present invention includes a zinc or zinc-based alloy plated steel sheet, a Ni layer formed on the surface of the zinc or zinc-based alloy plated steel sheet, and a blackening layer formed on the Ni layer.
상기 아연 또는 아연계 합금도금은 특별한 방법으로 형성된 것이 아니며, 당업계의 통상의 방법으로 형성된 것이면 충분하다.
The zinc or zinc-based alloy plating is not formed by a special method, it is sufficient that it is formed by a conventional method in the art.
상기 Ni층은 후술하는 Ni부착 공정에 의해 형성된다. 상기 Ni층은 50㎎/㎡ 이상의 부착량으로 부착되어 형성되는 것이 바람직하다.
The said Ni layer is formed by the Ni adhesion process mentioned later. It is preferable that the said Ni layer is attached by the adhesion amount of 50 mg / m <2> or more.
상기 흑화층은 금속산화물 또는 금속수산화물과 이들의 혼합물을 포함한다. 상기 금속산화물과 금속수산화물은 주로 Ni산화물, Ni수산화물, Zn산화물 및 Zn수산화물이 될 수 있다. 상기 흑화층은 본 발명에서 제안하는 흑화처리용액으로 화성처리(침지, 분사 등)에 의해 형성되는 것이다.
The blackening layer includes a metal oxide or a metal hydroxide and a mixture thereof. The metal oxide and the metal hydroxide may be mainly Ni oxide, Ni hydroxide, Zn oxide and Zn hydroxide. The blackening layer is formed by chemical conversion treatment (immersion, spraying, etc.) with the blackening treatment solution proposed in the present invention.
본 발명의 흑색강판은 금속이온을 포함하는 흑화처리용액에 의한 기존 화성처리로 얻어지는 흑화층과 달리 금속산화물이 입자상으로 석출되는 것이 아니고, 석출된 금속표면이 산화되어 형성된 흑화층을 가지기 때문에, 기존 화성처리에서 문제시 되었던 흑화층 밀착성 문제(석출입자의 탈리 현상, powdering)가 크게 개선된다. 또한, 본 발명에서 제안하는 흑화처리용액은 종래 3종이상의 성분으로 구성되는 용액과 달리, 최소 2 성분계의 용액조성으로 간단하며 유해성분을 포함하지 않기 때문에, 폐수처리가 용이하고 환경친화적인 흑색강판의 제조방법을 제공할 수 있다.
Unlike the blackening layer obtained by the conventional chemical conversion treatment by the blackening treatment solution containing metal ions, the black steel sheet of the present invention does not precipitate metal oxide in particulate form, and thus has a blackening layer formed by oxidizing the deposited metal surface. The blackening layer adhesion problem (desorption phenomenon of the precipitated particles, powdering), which was a problem in the chemical conversion treatment, is greatly improved. In addition, the blackening treatment solution proposed in the present invention, unlike the solution consisting of three or more components of the prior art, because it is simple in the composition of a minimum of two components and does not contain harmful components, waste water treatment is easy and environmentally friendly black steel sheet It can provide a manufacturing method of.
본 발명의 흑색강판은 상기 흑화층상에 수지층을 더 포함한다. 상기 수지층은 보호수지의 코팅으로 형성되는 것으로서, 보호수지는 보호수지는 폴리우레탄계 수용성 코팅재가 주로 사용되나, 그 종류를 특별히 한정하는 것은 아니며 수용성이나 용제형 모두 사용 가능하다.
The black steel sheet of this invention further contains a resin layer on the said blackening layer. The resin layer is formed of a coating of a protective resin, the protective resin is a protective resin mainly used for polyurethane-based water-soluble coating material, it is not particularly limited in its type can be used both water-soluble or solvent type.
또한, 본 발명의 흑색강판은 상기 수지층과 흑화층 사이에 수지밀착성, 내식성 및 가공성 등의 물성확보를 위해 유기계, 무기계 또는 유/무기혼합계의 하도층을 추가적으로 포함할 수 있다. 상기 하도층은 1개 이상의 층이 될 수 있다.
In addition, the black steel sheet of the present invention may further include an undercoat layer of organic, inorganic, or organic / inorganic mixed system for securing physical properties such as resin adhesion, corrosion resistance and processability between the resin layer and the blackening layer. The undercoat may be one or more layers.
이하, 본 발명 흑색강판의 제조방법에 대하여 상세히 설명한다.Hereinafter, the manufacturing method of the black steel sheet of the present invention will be described in detail.
먼저, 아연 또는 아연계 합금도금강판의 표면에 Ni을 부착하여 Ni층을 형성한다. 상기 Ni을 부착하는 방법은 그 방법을 특별히 한정하지 않으며, 일예로는 전기도금, 진공증착도금, 환원제를 이용한 무전해 도금, 치환도금 등이 가능하다. 바람직하게는 기존 설비를 이용하면서 치밀한 Ni층을 형성할 수 있는 전기도금법에 의한 Ni플래쉬(flash)를 사용한다.
First, Ni is attached to the surface of the zinc or zinc-based alloy plated steel sheet to form a Ni layer. The method of attaching Ni is not particularly limited, and examples thereof include electroplating, vacuum deposition plating, electroless plating using a reducing agent, and substitution plating. Preferably, Ni flash using an electroplating method that can form a dense Ni layer while using existing equipment is used.
상기 Ni의 부착시 그 부착량은 50㎎/㎡ 이상인 것이 바람직하다. 상기 Ni부착량이 50㎎/㎡ 미만에서는 흑화층을 형성하기 위한 Ni량이 충분하지 않아 흑화처리시 충분한 흑색도를 얻을 수 없기 때문이다. 상기 부착량의 상한을 특별히 한정하는 것은 아니나, 생산비용 등의 경제성을 고려할 때, 500㎎/㎡를 초과하지 않는 것이 보다 바람직하다.
It is preferable that the adhesion amount at the time of adhesion of said Ni is 50 mg / m <2> or more. This is because when the amount of Ni deposited is less than 50 mg /
상기 상기 Ni층을 갖는 강판에 흑화처리를 행하여 흑화층을 형성한다. 상기 흑화처리는 유기산 5~50g/l, 무기산이온 5~100g/l을 포함하는 최소 2성분계의 흑화처리용액을 이용하여 행하며, 필요시 금속이온 및 기타 첨가체가 첨가될 수 있다.
The blackening process is performed to the steel plate which has the said Ni layer, and a blackening layer is formed. The blackening treatment is performed using a blackening treatment solution of a minimum two-component system containing 5-50 g / l of an organic acid and 5-100 g / l of an inorganic acid, and metal ions and other additives may be added if necessary.
상기 유기산의 종류는 초산, 구연산, 주석산, 사과산, 옥살산, 프탈산, 말레산 등이 사용 가능하다. 상기 유기산을 첨가하는 이유는 용액 pH를 낮추고, Ni층 또는 아연도금층의 Zn를 산화시켜 Ni산화물, Ni수산화물, Zn산화물 또는 Zn수산화물의 형태로 흑화층을 형성하고, 용액안정성(흑화처리시 용출되어 나오는 금속이온과 착물을 형성하여 금속이온의 가수분해에 의한 침전 방지)과 균일한 표면외관을 형성하기 위함이다. 상기 유기산의 함량이 5g/l 미만이면 산화력이 떨어지기 때문에 충분한 흑색도를 얻을 수 없으며, 동시에 용액중 침전 발생으로 용액안정성이 저하되고, 50g/l을 초과하면 Ni층의 과반응으로 표면외관(흑색도) 및 흑화층 밀착성이 불량해지며, 비용상승으로 경제적이라 할 수 없다.
The organic acid may be acetic acid, citric acid, tartaric acid, malic acid, oxalic acid, phthalic acid, maleic acid, or the like. The reason for adding the organic acid is to lower the solution pH, oxidize the Zn of the Ni layer or the galvanized layer to form a blackening layer in the form of Ni oxide, Ni hydroxide, Zn oxide or Zn hydroxide, and solution stability (elution is performed during blackening treatment. To form a complex with the metal ions coming out to prevent precipitation by hydrolysis of the metal ions) and to form a uniform surface appearance. If the content of the organic acid is less than 5g / l oxidizing power is not enough sufficient blackness can not be obtained, at the same time solution stability is lowered by the occurrence of precipitation in the solution, if the content exceeds 50g / l surface appearance ( Blackness) and blackening layer adhesion becomes poor, and cost is not economical.
상기 무기산 이온의 종류는 NO3 -, SO4 2-, PO4 3-, Cl-, ClO3 -, ClO4 - 등이 사용될 수 있다. 상기 무기산 이온은 흑화층 형성 촉진제로서, 그 함량이 5~100g/l인 것이 바람직한데, 그 함량이 5g/l 미만이면 충분한 흑색도를 얻을 수 없을 뿐만 아니라, 흑화층 형성속도가 느려져 실제 조업 적용이 어렵고, 100g/l을 초과하면 과반응으로 표면외관(흑색도) 및 흑화층 밀착성이 불량해지며, 비용상승으로 경제적이라 할 수 없다.
The type of the inorganic acid ions NO 3 -, SO 4 2-, PO 4 3-, Cl -, ClO 3 -, ClO 4 - and the like can be used. The inorganic acid ion is a blackening layer formation accelerator, it is preferable that the content is 5 ~ 100g / l, if the content is less than 5g / l not only sufficient blackness can be obtained, but also the rate of blackening layer formation is slow, practical application If this is difficult and exceeds 100 g / l, the surface reaction (blackness) and blackening layer adhesion are poor due to overreaction, and the cost is not economical.
상기 흑화처리용액은 Fe2+, Co2+, Ni2+, Sn2+, Sb2+ Ti2+, Al3+, Cu2+, Mo2+, V3+, Mn2+ 등의 금속이온을 더 포함할 수 있으며, 첨가제로서 용액안정제, 착화제, 산화촉진제 등을 더 포함할 수 있다.
The blackening solution is a metal such as Fe 2+ , Co 2+ , Ni 2+ , Sn 2+ , Sb 2+ Ti 2+ , Al 3+ , Cu 2+ , Mo 2+ , V 3+ , Mn 2+ It may further include ions, and may further include a solution stabilizer, a complexing agent, an oxidation promoter, and the like as an additive.
상기 흑화처리용액의 pH는 1.5~4.0으로 하는 것이 바람직하다. 상기 pH가 1.5 미만이면 산화력이 강하여 흑화층 형성보다 Ni층 또는 아연계 도금층 용해가 심하게 발생하고, 4.0을 초과하게 되면 산화력이 떨어질 뿐만 아니라, 용출된 금속이온의 가수분해로 인한 침전 발생으로 용액안정성이 떨어지기 때문에 바람직하지 않다.
The pH of the blackening treatment solution is preferably set to 1.5 ~ 4.0. If the pH is less than 1.5, the oxidizing power is stronger, so that the Ni layer or zinc-based plating layer dissolves more severely than the blackening layer formation, and when the pH is higher than 4.0, the oxidizing power is not only degraded, but solution stability is caused by precipitation due to hydrolysis of the eluted metal ions. It is not desirable because it falls.
본 발명에서는 상기 흑화층 위에 수지층을 형성하는 단계를 더 포함한다. 상기 수지층은 흑화층을 보호하고, 내식성 및 가공성 등의 물성 확보를 위한 것이다. 상기 수지층의 종류는 특별히 한정되는 것은 아니며, 수용성이나 용제형 모두 사용이 가능하고, 바람직하게는 폴리우레탄계의 수용성 코팅재이다.
In the present invention, further comprising the step of forming a resin layer on the blackening layer. The resin layer protects the blackening layer and is for securing physical properties such as corrosion resistance and workability. The kind of the resin layer is not particularly limited, and both water-soluble and solvent-type can be used, and preferably a water-soluble coating material of polyurethane type.
또한, 본 발명은 상기 흑화층과 수지층 사이에 수지밀착성, 내식성 및 가공성 등의 물성을 확보하기 위해서, 유기계, 무기계 또는 유/무기 혼합계의 하도층을 더 형성할 수 있다.
In addition, the present invention may further form an undercoat layer of an organic, inorganic or organic / inorganic mixed system in order to secure physical properties such as resin adhesion, corrosion resistance and processability between the blackening layer and the resin layer.
이하, 본 발명의 실시예에 대하여 상세히 설명한다. 하기 실시예는 본 발명의 이해를 위한 것일 뿐, 이에 본 발명이 한정되는 것은 아니다.
Hereinafter, embodiments of the present invention will be described in detail. The following examples are only for the understanding of the present invention, but the present invention is not limited thereto.
본 발명의 제조공정에 따른 흑색강판의 피막구성의 일예를 도 1에 나타내었다. 도 1에 나타난 바와 같이, 아연 또는 아연합금도금층(1)이 형성된 강판에 Ni층(2)을 형성하고, 이어 흑화처리를 통해 흑화층(3)을 형성한다. 추가적으로 수지층(4)을 형성할 수 있으며, 상기 흑화층(3)과 수지층(4)사이에 유기계, 무기계 또는 유/무기혼합계 하도층(5)을 더 형성할 수 있다.
An example of the film structure of the black steel sheet according to the manufacturing process of the present invention is shown in FIG. As shown in FIG. 1, a
(실시예)(Example)
아연 부착량이 20g/㎡인 전기아연도금강판을 사용하여 하기 표 1의 Ni 부착량을 갖도록 Ni 플래쉬 도금을 행하고, 이후 표 1의 용액조성을 이용하여 흑화처리를 행하여, 흑색강판을 제조하였다. 상기 흑화처리는 40℃에서 4초간 침치처리를 이용하였다.
Ni flash plating was carried out using an electrogalvanized steel sheet having a zinc adhesion amount of 20 g /
이렇게 제조된 흑색강판의 흑화처리 평가는 표면외관과 파우더링을 측정하여 그 결과를 표 1에 나타내었다. 표면외관은 색차계를 이용하여 백색도(L*)를 측정하였으며, 0에 가까울수록 흑색도가 높음을 의미한다. 파우더링 평가는 흑화층에 셀로판테이프의 접착면을 강하게 부착시킨 후 떼어냄으로써, 접착면에 떨어져 나오는 흑화입자(powder)를 관찰하는 것으로 행하여졌다.The blackening treatment evaluation of the black steel sheet thus prepared was measured in the surface appearance and powdering and the results are shown in Table 1. Surface appearance measured the whiteness (L *) using a color difference meter, and the closer to 0, the higher the blackness. Powdering evaluation was performed by observing blackening particles which fall off on the adhesive surface by strongly attaching and detaching the adhesive surface of the cellophane tape to the blackening layer.
파우더링 특성을 정량화하기 위하여, 색차계를 사용하여 파우더링 부분의 백색도(Lp)를 측정하였으며, 테이핑 테스트를 하지 않은 미처리샘플의 Lp값인 88.92에 가까울수록 파우더링 발생이 저하됨을 의미한다.
In order to quantify the powdering properties, the whiteness (Lp) of the powdered portion was measured using a color difference meter, and the closer to the Lp value of the untreated sample, 88.92, the less powdering occurred.
상기 표 1에 나타난 바와 같이, 발명예들은 L*이 30 정도의 흑색도를 보이며, 파우링성(Lp)도 우수한 것을 확인할 수 있다. 그러나, 비교예 1 내지 4와 같이, Ni 부착량이 50㎎/㎡ 미만이거나, 구연산, 질산암모늄이 5g/l에 미치지 않는 경우, 흑화층 밀착성은 양호하나, 충분한 흑색도를 얻을 수 없다. 또한, 비교예 5 내지 8에 나타난 바와 같이, 구연산, 질산암모늄이 각각 50g/l, 100g/l을 초과하게 되면, 흑색도는 양호하나, 흑화층 밀착성이 열약해지는 경향을 보았다.
As shown in Table 1, the inventive examples show that L * shows a degree of blackness of about 30, and also has excellent powdering property (Lp). However, when Ni adhesion amount is less than 50 mg / m <2> or citric acid and ammonium nitrate are less than 5 g / l like Comparative Examples 1-4, blackening layer adhesiveness is favorable but sufficient blackness is not obtained. In addition, as shown in Comparative Examples 5 to 8, when citric acid and ammonium nitrate exceeded 50 g / l and 100 g / l, respectively, the blackness was good, but the blackening layer adhesion was inferior.
한편, 표 1에서의 발명예 3을 이용하여, Ni 플래쉬, 흑화처리, 수지코팅을 행한 후, 백색도(L*)를 평가하여 표 2에 나타내었다. 이때의 보호수지는 폴리우레탄계 수용성 코팅재이다.
On the other hand, using Inventive Example 3 in Table 1, after performing Ni flash, blackening treatment and resin coating, the whiteness (L *) was evaluated and shown in Table 2. The protective resin at this time is a polyurethane-based water-soluble coating material.
상기 표 2에 나타난 바와 같이, 본 발명의 흑화처리강판은 보호수지를 코팅할 경우, 백색도는 더욱 낮아지게 되어 우수한 표면외관을 얻을 수 있음을 확인할 수 있다. As shown in Table 2, when the blackened steel sheet of the present invention is coated with a protective resin, it can be seen that the whiteness is further lowered to obtain an excellent surface appearance.
1.....아연 또는 아연합금도금 2.....Ni층
3.....흑화층 4.....수지층
5.....유기계, 무기계 또는 이들의 혼합계의 피막층1 ..... zinc or zinc alloy plating 2 ..... Ni layer
3 .....
5 ..... coating layers of organic, inorganic or mixed systems
Claims (15)
상기 아연 또는 아연계 합금도금강판의 표면에 형성된 Ni층; 및
상기 Ni층 위에 형성된 흑화층
을 포함하고, 상기 흑화층은 유기산 5~50g/l, 무기산이온 5~100 g/l을 포함하는 흑화처리용액으로 흑화처리되어 형성된 것인 흑화층 밀착성 및 표면외관이 우수한 흑색강판.
Zinc or zinc-based alloy plated steel sheet;
Ni layer formed on the surface of the zinc or zinc-based alloy plated steel sheet; And
Blackening layer formed on the Ni layer
It includes, the blackening layer is a black steel sheet excellent in blackening layer adhesion and surface appearance that is formed by blackening treatment with a blackening treatment solution containing 5 ~ 50g / l, organic acid ions 5 ~ 100 g / l.
상기 Ni층은 50㎎/㎡ 이상의 부착량으로 부착되어 형성된 것인 흑화층 밀착성 및 표면외관이 우수한 흑색강판.
The method according to claim 1,
The Ni layer is a black steel sheet excellent in blackening layer adhesion and surface appearance that is formed by being attached with an adhesion amount of 50 mg / ㎡ or more.
상기 흑화층은 Ni산화물, Ni수산화물, Zn산화물 및 Zn 수산화물로 이루어진 그룹에서 선택된 1종 이상을 포함하는 흑화층 밀착성 및 표면외관이 우수한 흑색강판.
The method according to claim 1,
The blackening layer is a black steel sheet excellent in blackening layer adhesion and surface appearance including at least one selected from the group consisting of Ni oxide, Ni hydroxide, Zn oxide and Zn hydroxide.
상기 흑화층 위에 수지층을 더 포함하는 흑화층 밀착성 및 표면외관이 우수한 흑색강판.
The method according to claim 1,
The black steel sheet excellent in blackening layer adhesiveness and surface appearance which further contain a resin layer on the said blackening layer.
상기 흑화층과 수지층 사이에 유기계, 무기계 또는 유/무기 혼합계의 하도층을 더 포함하는 흑화층 밀착성 및 표면외관이 우수한 흑색강판.
The method of claim 4,
The black steel sheet excellent in blackening layer adhesiveness and surface appearance further including the undercoat layer of organic type, inorganic type, or organic / inorganic type system between the said blackening layer and resin layer.
상기 Ni층을 갖는 강판에 흑화처리를 행하여 흑화층을 형성하는 단계
를 포함하고,
상기 흑화처리는 유기산 5~50g/l, 무기산이온 5~100 g/l을 포함하는 흑화처리용액을 이용하여 행하는 흑화층 밀착성 및 표면외관이 우수한 흑색강판의 제조방법.
Attaching Ni to the surface of the zinc or zinc-based alloy plated steel sheet to form a Ni layer;
Blackening the steel sheet having the Ni layer to form a blackening layer
Lt; / RTI >
The blackening treatment is a method for producing a black steel sheet excellent in blackening layer adhesion and surface appearance is carried out using a blackening treatment solution containing 5 ~ 50g / l, organic acid ions 5 ~ 100 g / l.
상기 Ni의 부착량은 50㎎/㎡ 이상인 흑화층 밀착성 및 표면외관이 우수한 흑색강판의 제조방법.
The method of claim 6,
The Ni adhesion amount is 50mg / ㎡ or more blackening layer adhesion method and manufacturing method of the black steel sheet excellent in surface appearance.
상기 유기산은 초산, 구연산, 주석산, 사과산, 옥살산, 프탈산 및 말레산 중 1종인 흑화층 밀착성 및 표면외관이 우수한 흑색강판의 제조방법.
The method of claim 6,
The organic acid is a method for producing a black steel sheet excellent in blackening layer adhesion and surface appearance of acetic acid, citric acid, tartaric acid, malic acid, oxalic acid, phthalic acid and maleic acid.
상기 무기산이온은 NO3 -, SO4 2-, PO4 3-, Cl-, ClO3 - 및 ClO4 - 중 1종 이상인 흑화층 밀착성 및 표면외관이 우수한 흑색강판의 제조방법.
The method of claim 6,
The inorganic acid ions NO 3 -, SO 4 2-, PO 4 3-, Cl -, ClO 3 - , and ClO 4 - 1 jong or more blackening layer adhesion and surface appearance The method of producing a superior black steel sheet of the.
상기 흑화처리용액은 Fe2+, Co2+, Ni2+, Sn2+, Sb2+ Ti2+, Al3+, Cu2+, Mo2+, V3+ 및 Mn2+중 1종 이상인 금속이온을 더 포함하는 흑화층 밀착성 및 표면외관이 우수한 흑색강판의 제조방법.
The method of claim 6,
The blackening solution is one of Fe 2+ , Co 2+ , Ni 2+ , Sn 2+ , Sb 2+ Ti 2+ , Al 3+ , Cu 2+ , Mo 2+ , V 3+ and Mn 2+ The method for producing a black steel sheet excellent in blackening layer adhesion and surface appearance further comprising the above metal ions.
상기 흑화처리용액은 용액안정제, 착화제 및 산화촉진제 중 1종 이상이 추가적으로 포함할 수 있는 흑화층 밀착성 및 표면외관이 우수한 흑색강판의 제조방법.
The method of claim 6,
The blackening treatment solution is a method for producing a black steel sheet excellent in blackening layer adhesion and surface appearance that may further include one or more of a solution stabilizer, a complexing agent and an oxidation promoter.
상기 흑화처리용액의 pH는 1.5~4.0인 흑화층 밀착성 및 표면외관이 우수한 흑색강판의 제조방법.
The method of claim 6,
PH of the blackening treatment solution is 1.5 ~ 4.0 method for producing a black steel sheet excellent in blackening layer adhesion and surface appearance.
상기 흑화층상에 수지층을 더 형성하는 단계를 포함하는 흑화층 밀착성 및 표면외관이 우수한 흑색강판의 제조방법.
The method of claim 6,
The method of manufacturing a black steel sheet excellent in blackening layer adhesiveness and surface appearance comprising the step of further forming a resin layer on the blackening layer.
상기 수지층 형성전에 유기계, 무기계 또는 유/무기 혼합계의 하도층을 더 형성하는 단계를 포함하는 흑화층 밀착성 및 표면외관이 우수한 흑색강판의 제조방법.The method according to claim 14,
The method of manufacturing a black steel sheet excellent in blackening layer adhesiveness and surface appearance, further comprising the step of further forming an undercoat layer of organic, inorganic or organic / inorganic mixed system before forming the resin layer.
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JPH08257492A (en) * | 1995-03-22 | 1996-10-08 | Nippon Steel Corp | Guard film free type image clarity precoated steel sheet excellent in adhesion of coating film, punching durability and pressure marking resistance |
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