JPS62180081A - Colored galvanized steel sheet - Google Patents
Colored galvanized steel sheetInfo
- Publication number
- JPS62180081A JPS62180081A JP2006286A JP2006286A JPS62180081A JP S62180081 A JPS62180081 A JP S62180081A JP 2006286 A JP2006286 A JP 2006286A JP 2006286 A JP2006286 A JP 2006286A JP S62180081 A JPS62180081 A JP S62180081A
- Authority
- JP
- Japan
- Prior art keywords
- ions
- colored
- steel sheet
- galvanized steel
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 28
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 28
- 150000002500 ions Chemical class 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 150000002978 peroxides Chemical class 0.000 claims abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 27
- 239000011701 zinc Substances 0.000 claims description 20
- 238000007747 plating Methods 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000011253 protective coating Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001439 antimony ion Inorganic materials 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910001432 tin ion Inorganic materials 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims 1
- 229940005991 chloric acid Drugs 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 claims 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 abstract description 21
- 239000010959 steel Substances 0.000 abstract description 21
- 238000004040 coloring Methods 0.000 abstract description 17
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 14
- 230000001681 protective effect Effects 0.000 abstract description 9
- 239000010960 cold rolled steel Substances 0.000 abstract description 4
- 229910002651 NO3 Inorganic materials 0.000 abstract description 3
- 150000001455 metallic ions Chemical class 0.000 abstract 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 abstract 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 abstract 1
- 238000009713 electroplating Methods 0.000 abstract 1
- 229920006254 polymer film Polymers 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 30
- 238000000576 coating method Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- -1 silver ions Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007743 anodising Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 229920000592 inorganic polymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910018605 Ni—Zn Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000019658 bitter taste Nutrition 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
Classifications
-
- 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
- C23C22/10—Orthophosphates containing oxidants
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は一般に亜鉛メッキ鋼板が使用される分野におい
て装飾が必要な部材に用いる着色亜鉛メッキ鋼板および
其の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention generally relates to a colored galvanized steel sheet used for members requiring decoration in fields where galvanized steel sheets are used, and a method for manufacturing the same.
（従来の技術）
表面処理鋼板は汎用的な品質と低コストの両面から広範
囲な分野に利用され、今後もその需要は品質改良により
増加することが確実視されている。(Prior Art) Surface-treated steel sheets are used in a wide range of fields because of their general-purpose quality and low cost, and it is certain that their demand will continue to increase due to quality improvements.
亜鉛メッキ鋼板の品質改良は、母材の高品質と共に、外
貌、防錆、加工性、塗装性の点で多くの新製品全発生さ
せ、自動車用鋼板、家電製品、建材分野の要求に答えて
米た。Improvements in the quality of galvanized steel sheets have led to the creation of many new products in terms of appearance, rust prevention, workability, and paintability, as well as the high quality of the base material, to meet the demands of automotive steel sheets, home appliances, and building materials. It was rice.
近年、需要家の要求は、製品の品質全同上させながらト
ータルコストミニマム化、処理プロセスの単純化を狙っ
た表面処理鋼板の導入をはかつている。即ち、従来、表
面処理鋼板を加工した後、前処理塗装して来た製品に対
してプレコートされた鋼板を導入することによって＊要
家工程で行っていた前処理、塗装を省、Ｉ！６シ、低コ
ストで高品質の製品を得るプレコート鋼板がその１つで
ある。In recent years, demands from customers have led to the introduction of surface-treated steel sheets aimed at minimizing total costs and simplifying treatment processes while maintaining the same quality of products. In other words, by introducing a pre-coated steel plate to a product that has conventionally been pre-treated and painted after processing a surface-treated steel plate, *the pre-treatment and painting that were performed in the main process can be omitted, and I! One of them is pre-painted steel sheet, which provides high quality products at low cost.
これらの要求に答え得るプレコート鋼板とじて当初は２
０〜３０μの高級プレコート鋼板が用いられて来たが、
徹底したコストダウンの追求と、溶接性等の観点から、
着色表面処理鋼板の要求が望まれている。これらの要求
に答える材料の具備すべき品質としては耐食性、加工性
に加え、外観の均一性が重要であり、必要によっては溶
接性、；耐薬品性が要求される。色調としては黒色系統
のものが好まれている。Initially, the pre-painted steel sheet that could meet these demands was 2.
High-grade pre-coated steel sheets of 0 to 30μ have been used,
In pursuit of thorough cost reduction and from the viewpoint of weldability,
There is a demand for colored surface-treated steel sheets. In addition to corrosion resistance and workability, it is important for materials to have uniformity in appearance in order to meet these demands, and weldability and chemical resistance are also required as necessary. Black-ish colors are preferred.
亜鉛メッキ鋼板の着色処理として知られている公知の技
術は銀イオンを含むクロメート溶液中で亜鉛メッキを処
理する特開昭５２−４５５４４公報の方法、リン酸およ
びリン酸塩をベースとしたクロメート溶液中で処理する
特開昭５８−１７７４７７（京都クロメート工業）の方
法がある。これらは酸化銀をクロメート皮膜に共析させ
、黒色外観を得る方法である。又硫化物を形成させ黒化
処理をする方法として、特開昭５２−６５１３９（外国
）の方法が公開されている。又クロメート皮膜を形成後
染料を用いて着色させる方法として、特開昭５４−１４
５３３６（三井金属鉱業）特公昭５２−２８７３０（三
井金属鉱業）の方法が公開されている。その他、陽極酸
化法によって黒色表面を得る方法が公開されている。例
えば、Ｎｉ 、 Ｃｏ 。Known techniques for coloring galvanized steel sheets include the method of JP-A-52-45544 for treating galvanizing in a chromate solution containing silver ions, a chromate solution based on phosphoric acid and phosphates; There is a method disclosed in Japanese Patent Application Laid-Open No. 58-177477 (Kyoto Chromate Kogyo) in which the process is carried out in a medium. These methods eutectoid silver oxide on a chromate film to obtain a black appearance. Furthermore, as a method for blackening treatment by forming sulfides, a method disclosed in Japanese Patent Application Laid-open No. 52-65139 (foreign) has been disclosed. In addition, as a method of coloring a chromate film using a dye after forming it, Japanese Patent Application Laid-Open No. 54-14
5336 (Mitsui Metal Mining Co., Ltd.) The method of Special Publication No. 52-28730 (Mitsui Mining Co., Ltd.) has been published. In addition, a method of obtaining a black surface by an anodizing method has been disclosed. For example, Ni, Co.
ＭＯとＺｎの合金メッキ鋼板を硫酸アンモニウム水溶液
中で陽極処理する特開昭５８−１５１４９１の方法、Ｎ
ｉ 、 Ｃｏ 、 ＭｏとＺｎの合金メッキ浴中で陽極
処理する特開昭５８−１５１４９０の方法等が代表的な
公開技術である。A method of anodizing a steel plate plated with an alloy of MO and Zn in an aqueous ammonium sulfate solution, disclosed in JP-A-58-151491, N
Typical published techniques include the method disclosed in JP-A-58-151490, which involves anodizing in an alloy plating bath of Co, Mo, and Zn.
（発明が解決しようとする問題点）
従来の着色方法は優れた方法であるが、残念なことにス
チールメーカーが保有している製造設備に必ずしもマツ
チングしていない。例えば、高速生産性の点でより短時
間化が必要である。又、従来法では亜鉛メッキの悪化処
理の場合、処理直後の黒色皮膜がゲル状で、密着性に於
て劣り、コイル生産への大きな障害であり、硬化処理等
が必要であるためプロセスを複雑化している。(Problems to be Solved by the Invention) Conventional coloring methods are excellent methods, but unfortunately they do not necessarily match the manufacturing equipment owned by steel manufacturers. For example, shorter processing times are required for high-speed productivity. In addition, in the case of deterioration treatment of galvanizing using conventional methods, the black film immediately after treatment is gel-like and has poor adhesion, which is a major hindrance to coil production, and requires hardening treatment, which complicates the process. It has become
いずれにしても広巾のコイル製品を塗装以外の方法で均
一に着色化する方法は従来経験しなかった事である。本
発明は高品質の低コストの着色鋼板を提供し高速短時間
で現行のプロセス条件で均一な着色亜鉛メッキ鋼板を得
る方法を提供するものである。In any case, we have never experienced a method of uniformly coloring a wide coil product using a method other than painting. The present invention provides a high-quality, low-cost colored steel sheet and provides a method for obtaining uniformly colored galvanized steel sheet at high speed and in a short time under current process conditions.
（問題点を解決するための手段）
上述したように亜鉛メッキ鋼板の着色化上の問題の１つ
は、着色化処理直後のゲル状物質の生成と下地の亜鉛の
腐食による密層不良が挙げられる。(Means for solving the problem) As mentioned above, one of the problems with coloring galvanized steel sheets is the formation of a gel-like substance immediately after the coloring process and the failure of the dense layer due to corrosion of the underlying zinc. It will be done.
この解決策として、いろいろ考えられるが、基本的には
、下地の亜鉛の溶解を抑え、水和していないコンパクト
な皮膜例えばメッキの如き連続膜を形成させることが有
効であることを見出した。Although there are various possible solutions to this problem, we have found that basically it is effective to suppress the dissolution of the underlying zinc and form a continuous film that is not hydrated and compact, such as plating.
本発明は上述した問題点を解決し均一な着色外観を有す
る高品質な着色亜鉛メッキ鋼板を提供するものである。The present invention solves the above-mentioned problems and provides a high quality colored galvanized steel sheet having a uniform colored appearance.
本発明は、亜鉛メッキとの置換で析出する着色金属もし
くは金属化合物およびその着色物を亜鉛メッキ上に固定
化する金属もしくは金属化合物を形成させる少くとも２
成分の金属イオンを含み更にその着色被膜の色と密着性
を向上させるイオンを含む水溶液で着色化した被膜とそ
の上に保護被膜を有する亜鉛メッキ鋼板で構成している
。The present invention provides at least two colored metals or metal compounds that are precipitated by substitution with zinc plating, and a metal or metal compound that fixes the colored product on the zinc plating.
It consists of a coating colored with an aqueous solution containing component metal ions and ions that improve the color and adhesion of the colored coating, and a galvanized steel sheet having a protective coating thereon.
本発明の着色亜鉛メッキ鋼板は次に示す構成のものであ
る。The colored galvanized steel sheet of the present invention has the following configuration.
（１） 亜鉛メッキ上に着色化金属イオンと固着化金
属イオンを含み且つ酸化性イオン、リン酸イオンのいず
れかもしくは両者を含む水溶液で着色化処理した層金有
し、さらにその上層に保護膜を有することを特徴とする
着色亜鉛メッキ鋼板（２）着色化金属イオンとして鋼イ
オンを固着化金属イオンとしてニッケル、コバルト、モ
リブデン、アンチモン、クロム、スズの各イオンの一種
以上、酸化性５イオンとして硝酸、瓜素酸、過酸化、重
クロム酸の各イオンの一種以上を含む水浴液で着色処理
した層を有し、さらにその上に保護被膜を有する特許請
求範囲第１項記載の着色亜鉛メッキ鋼板
（作用）
不発明の着色亜鉛メッキ鋼板を模式化して第１図に示す
。(1) A layer metal containing colored metal ions and fixed metal ions is formed on the zinc plating, and is colored with an aqueous solution containing oxidizing ions, phosphate ions, or both, and a protective film is further formed on top of the metal layer. Colored galvanized steel sheet characterized by having (2) Steel ions as colored metal ions, one or more of each of nickel, cobalt, molybdenum, antimony, chromium, and tin ions as metal ions, and five oxidizing ions as metal ions. The colored zinc plating according to claim 1, which has a layer colored with a water bath solution containing one or more of nitric acid, uric acid, peroxide, and dichromic acid ions, and further has a protective coating thereon. Steel Plate (Function) A colored galvanized steel plate according to the invention is schematically shown in FIG.
冷延鋼板よりなる素地４上に亜鉛又はｗ＠１合金メツキ
層３を有し、その上層に着色層２を有する。A zinc or w@1 alloy plating layer 3 is provided on a base 4 made of a cold-rolled steel plate, and a colored layer 2 is provided on top of the plating layer 3.
着色層は後述するように亜鉛メッキの溶解に伴い置換析
出する着色化および固着化金属およびその化合物で構成
している。化合物は酸化物ちるいは浴中に加えられたイ
オンと置換析出する金属との反「６で画成される。As will be described later, the colored layer is composed of colored and fixed metals and their compounds that are precipitated by displacement as the zinc plating is dissolved. The compound is defined by the reaction between the oxide oxide or the ions added to the bath and the metal which displaces and precipitates.
保護被膜１は、■クロメート処理＋有機、無機の洞分子
被膜あるいは０Ｍ機・無機の高分子被膜、塗油、ワック
ス等を単独に被覆する場合がある。The protective coating 1 may be independently coated with (1) chromate treatment + organic or inorganic molecular coating, 0M organic or inorganic polymer coating, oil coating, wax, or the like.
クロメート処理は公矧の塗布型クロメート、電解クロメ
ートが適用出来る。有機、無機の高分子被膜としては水
溶性、水分散性、有機溶剤溶性の有機ポリマー、あるい
はケイ酸塩、リン酸塩の無機ポリマーおよびこれらの複
合被膜である。For chromate treatment, commercial coating type chromate and electrolytic chromate can be applied. Examples of organic and inorganic polymer coatings include water-soluble, water-dispersible, and organic solvent-soluble organic polymers, inorganic polymers of silicate and phosphate, and composite coatings thereof.
本発明に用いる亜鉛メッキ鋼板には通常電気亜鉛メッキ
鋼版、光沢電気亜鉛メッキ鋼板、各種亜鉛合金メッキ鋼
板および溶融亜鉛メッキ鋼板が含まれる。The galvanized steel sheets used in the present invention include ordinary electrogalvanized steel sheets, bright electrogalvanized steel sheets, various zinc alloy plated steel sheets, and hot-dip galvanized steel sheets.
本発明における着色金属イオンは亜鉛メッキの溶解に伴
って置換して亜鉛メッキ上に析出するが密着性が悪い。The colored metal ions in the present invention are substituted as the zinc plating dissolves and precipitate on the zinc plating, but the adhesion is poor.
この被膜の着色度は析出する量とその物性および下地の
メッキ組成によって異る。The degree of coloring of this film varies depending on the amount deposited, its physical properties, and the underlying plating composition.
又、後述する酸化性イオンを加えるとその酸化物系統の
色調の外観が得られる。固定代金′萬イオンは本発明に
おいて重要な役割を果している。即ち、着色金属イオン
と共に亜鉛メッキの溶解によって亜鉛メッキ表面に析出
する。固定化金属イオンから析出する金属もしくは化合
物は着色度には殆んど薔与しない。しかし、着色金属イ
オン／亜鉛メッキ間の電位差を着色金属イオン／固定化
金属イオン／亜鉛メッキの電位差に軽減し、得られる着
色被膜を連続層とし、被膜の密着性を改善させる。Further, when oxidizing ions, which will be described later, are added, an appearance with an oxide-based color tone can be obtained. The fixed price ion plays an important role in the present invention. That is, they are deposited on the galvanized surface together with colored metal ions due to the dissolution of the zinc plating. Metals or compounds precipitated from immobilized metal ions have little effect on the degree of coloration. However, the potential difference between colored metal ions/zinc plating is reduced to the potential difference between colored metal ions/immobilized metal ions/zinc plating, and the resulting colored film is made into a continuous layer, improving the adhesion of the film.
着色金属イオンとしては、銅、銀等の責な金属で浴中の
イオンとの反応、酸化によって発色する。Coloring metal ions include harmful metals such as copper and silver, which develop color through reaction with ions in the bath and oxidation.
亜鉛メッキ組成がＮｉ、Ｆｅ等の水素過電圧の低い金属
との合金である場合は低電荷の金属化合物や金属が析出
し易くその系統の色彩になる。固定化金属イオンとして
はＺｎ／Ｚｎ２＋と２Ｈ”／Ｈ２の間の電位に相当する
金属でありＮｉ”＋が最も良好である。When the zinc plating composition is an alloy with a metal having a low hydrogen overvoltage such as Ni or Fe, low-charge metal compounds and metals tend to precipitate, resulting in the color of that type. The immobilized metal ion is a metal corresponding to a potential between Zn/Zn2+ and 2H''/H2, and Ni''+ is the best.
又、Ｍｏ” 、 Ｃｒ’＋は２次的に加え亜鉛メッキの
溶解を制御し緻密々着色被膜を得るのに効果的である。Further, Mo'' and Cr'+ are added secondarily and are effective in controlling the dissolution of zinc plating and obtaining a dense colored coating.
酸化性イオンは反応過程で水素ガスの発生を抑え得られ
る被膜の一部もしくは全部を酸化物に変え化成被膜的の
強い構成し密着性を向上させ黒色系統の着色被膜が安定
に得られる。酸化性イオンの種類は前述した通シである
が、硝酸が望ましい。The oxidizing ions suppress the generation of hydrogen gas during the reaction process, and change part or all of the resulting film into oxides, making it strong like a chemical conversion film, improving adhesion, and stably producing a black colored film. The types of oxidizing ions are the same as described above, but nitric acid is preferable.
リン酸イオンは亜鉛メッキの溶解により置換析出する金
属のイオンおよび溶出した亜鉛イオンと結合し、リン酸
塩として被膜を構成し緻密で密着性に優れた被膜を提供
すると共に、保護被膜との付着性を向上させ、更に耐食
性を向上させる多方向の作用を持っている。酸化性イオ
ンとリン酸イオンの共存はリン酸塩と酸化物の被膜の品
質向上に最も効果的であり両者の共存下が望ましい。Phosphate ions combine with the metal ions that replace and precipitate due to dissolution of the zinc plating, and the zinc ions that dissolve, forming a film as phosphate, providing a dense film with excellent adhesion, as well as adhesion to the protective film. It has a multidirectional action that improves corrosion resistance and corrosion resistance. The coexistence of oxidizing ions and phosphate ions is most effective in improving the quality of the phosphate and oxide film, and the coexistence of both is desirable.
以下本発明の水溶液の濃度について述べる。The concentration of the aqueous solution of the present invention will be described below.
着色化金属イオン（Ａとする）の濃度は析出速度に関連
し、目的に応じた濃度に制御する。一般的には０．１〜
１０ ？／Ｌ望ましくは０．５〜５り／ｌが好ましい。The concentration of colored metal ions (referred to as A) is related to the precipitation rate, and is controlled to a concentration depending on the purpose. Generally 0.1~
10? /L is preferably 0.5 to 5L/L.
固着化金属イオン（Ｂとする）は着色化金属イオン濃度
と関連がありＢ／Ａの比は、モル比で０．５〜５．０の
範囲で制御し、好ましくは１以上である。The fixed metal ion (referred to as B) is related to the colored metal ion concentration, and the ratio of B/A is controlled in the range of 0.5 to 5.0 in molar ratio, preferably 1 or more.
０．５以下では密着性が不充分である。又５．０以上で
は着色金属イオンの析出量に比べ固定化金属イオンの析
出量が多くなり色調が悪くなる。酸化性イオンは１０２
μ以上で前述の効果が発揮される。If it is less than 0.5, the adhesion is insufficient. If it is 5.0 or more, the amount of precipitated immobilized metal ions will be greater than the amount of colored metal ions, resulting in poor color tone. Oxidizing ions are 102
The above-mentioned effect is exhibited above μ.
２００ ？ ／ Ｌ超では着色金属の析出が抑制され着
色化が困難になる傾向がある。好ましくは３０〜１００
２μである。リン酸イオンは１０ ｆ／を以上で前述し
た効果が発揮される。好ましくは１５〜１００ ？／Ｌ
である。200? /L, precipitation of colored metals tends to be suppressed and coloring becomes difficult. Preferably 30-100
It is 2μ. Phosphate ion exhibits the above-mentioned effect at 10 f/ or more. Preferably 15-100? /L
It is.
ｐＨは化学処理によって異る。以下化学処理について述
べる。pH varies depending on the chemical treatment. The chemical treatment will be described below.
化学処理は亜鉛メッキ鋼板と本発明の水浴液を浸漬、ス
プレー、流し塗り、等の手段で接触させ化学反応させる
方法および水溶液中で電解する方法がある。水溶液の最
適ｐＨは浸漬、スプレーの場合１〜３が好ましく電解で
は１〜５と広くなる。The chemical treatment includes a method in which a galvanized steel sheet is brought into contact with the water bath solution of the present invention by means such as dipping, spraying, and flow coating to cause a chemical reaction, and a method in which the galvanized steel sheet is electrolyzed in an aqueous solution. The optimum pH of the aqueous solution is preferably 1 to 3 for dipping and spraying, and widens to 1 to 5 for electrolysis.
ｐＨが低い程反応速度が犬きく短時間で着色化が達成で
きる。ｐＨ＝２で浸漬の例では、３秒で黒色化する。着
色化した亜鉛メッキ鋼板はすぐに水洗し、保護被膜を被
覆する。The lower the pH, the faster the reaction rate and the faster coloring can be achieved. In the example of immersion at pH=2, it turns black in 3 seconds. Colored galvanized steel sheets are immediately washed with water and coated with a protective coating.
保護被膜の被覆方法は一般的に行われている方法例エバ
ロールコート、リングロール、エアーナイフ絞り、ナイ
フコーター等でコーティングした後乾燥又は焼付等の手
段によって着色被膜上に被覆する。The protective film is coated using a commonly used method such as Everor coat, ring roll, air knife squeezer, knife coater, etc., and then coated on the colored film by drying or baking.
保護被膜は色調を高級化すると共に耐食性、加工性、耐
傷付性を向上させるが、溶接性に対しては有害であり、
塗布厚みとしては、クロメートがり・ロムとして２００
ｍ９／ｆｆ！！以下ポリマー被膜は０．５〜３μが望
ましい。Protective coatings enhance the color tone and improve corrosion resistance, workability, and scratch resistance, but they are harmful to weldability.
The coating thickness is 200% as chromate and ROM.
m9/ff! ! The thickness of the polymer coating is preferably 0.5 to 3μ.
実施例１
冷延鋼板に硫酸浴で電気亜鉛メッキを３μ行ったのち、
第１表に示す処理浴（ｐＨは水酸化ナトリウムで調節）
で３秒間浸漬して黒色化したのちクロメート処理および
樹脂を被覆した。その結果第１表に示す黒色外装（Ｌ値
く２０）で密着性の良好（板厚の２倍に相当する１８０
°曲げ後テーピング剥離で評価した）な着色鋼板が得ら
れた。Example 1 After electrolytic galvanizing 3μ in a sulfuric acid bath on a cold-rolled steel plate,
Treatment bath shown in Table 1 (pH adjusted with sodium hydroxide)
After being immersed in water for 3 seconds to turn it black, it was treated with chromate and coated with resin. As a result, the black exterior (L value - 20) shown in Table 1 has good adhesion (180, which is twice the board thickness).
A colored steel plate was obtained, which was evaluated by tape peeling after bending.
尚、保護被膜は以下の通りでおる。The protective coating is as follows.
クロメート処理は市販の塗布型クロメートをロールで塗
布（Ｃｒ付着量４ ｏ ｍ９／ｒｒ？ ） Ｌ、たのち
板温６０゛Ｃに達するまで整風乾燥する、又樹脂は市販
の水分散性の有機樹脂とシリカの複合被膜を膜厚ｌμに
なるようにロールコートして被覆し板温１２０ ’Ｃに
到達するように焼付けた。For chromate treatment, apply a commercially available coated chromate using a roll (Cr coating amount: 4 m9/rr?), then dry with regular air until the plate temperature reaches 60°C.The resin is a commercially available water-dispersible organic resin. A composite film of silica and silica was coated by roll coating to a film thickness of lμ, and baked to reach a plate temperature of 120'C.
発明（１）〜（７）は、着色金属イオン（Ａ）として銅
イオン固着金属イオン（Ｂ）としてト１１２＋およびＮ
ｉ” ＋ （Ｃｒ＋６ 、 Ｓｎ２＋’ 、 Ｍ０６＋
、 ｃｏ２＋ ）をＢ／Ａで約０．８７に調合しそし
て酸化性＃ （Ｃ）として硝酸イオンおよびリン酸を含
む本発明例で黒色度、苦湿性に良好な例である。発明（
６） 、 （７）はｐＨ’？、下げた水溶液で黒色度が
強い。発明（８）は硝ｖを除いたもので発明（９）はリ
ン酸を除いたもので黒色度、密着性でや＼発明（１）〜
（７）に比べ劣る結果を示した。Inventions (1) to (7) are based on the colored metal ions (A) and copper ion-fixed metal ions (B).
i” + (Cr+6, Sn2+', M06+
, co2+) to a B/A of approximately 0.87, and contains nitrate ions and phosphoric acid as oxidizing #(C), this is an example of good blackness and bitterness. invention(
6) and (7) are pH'? , the blackness is strong in the lowered aqueous solution. Invention (8) is a product without nitric acid, and invention (9) is a product without phosphoric acid, which improves blackness and adhesion.＼Invention (1)~
(7) showed inferior results.
発明（１０） （１１）は硝酸イオンの濃度を変えた例
、発明（１２）はリン酸の偵度をｌ Ｏｆｆ／ｌにした
例でめる。密着性、着色度で若干最適条件より劣る結果
全示した。発明（１３） （１４）はＢ／Ａを０．２１
および２．１５とした組成の結果である。Inventions (10) and (11) are examples in which the concentration of nitrate ions are changed, and invention (12) is an example in which the rectification rate of phosphoric acid is set to l Off/l. All results showed that the adhesion and degree of coloring were slightly inferior to the optimal conditions. Invention (13) (14) has a B/A of 0.21
and 2.15.
比較例（１） 、 （２）は固層化金属イオンを含まな
い例で密着性が悪い。比較例３は保護被膜を被覆しない
例で黒色度が不充分で密着性が悪く傷が入り易い。Comparative Examples (1) and (2) do not contain solidified metal ions and have poor adhesion. Comparative Example 3 is an example in which no protective film was applied, and the blackness was insufficient, the adhesion was poor, and scratches were likely to occur.
実施例２
溶融亜鉛メッキ鋼板を実施例１の発明（１）の条件で処
理し、同様の保護皮膜を被覆したところＬ値１２光沢２
５で剥離のない黒色亜鉛メッキ鋼板を得か。Example 2 A hot-dip galvanized steel sheet was treated under the conditions of invention (1) of Example 1 and coated with the same protective film, resulting in an L value of 12 and gloss of 2.
In step 5, a black galvanized steel sheet with no peeling was obtained.
実施例３
Ｎ１を８％含むＮｉ −Ｚｎ合金メッキ鋼板を実施例２
と同様の処理を行い、茶褐色の着色メッキ鋼板を得だ。Example 3 Ni-Zn alloy plated steel sheet containing 8% N1 was prepared in Example 2.
A brown-colored plated steel sheet was obtained using the same process as above.
密着性も良好でめった。The adhesion was also very good.
実施例９
Ｎｉ” ｌ Ｏ？／ｌ 、 Ｃｕ” ２ ｆ／ｌ 、
Ｎ、ＮＯ３５０ｆ／ｌとＮＨ４ＳＣＮ ２０ ｆ／
ｌのｐ）ｉ＝５．３ の水浴液に亜鉛メッキ鋼板、溶
融亜鉛メッキ鋼板および１０％Ｎｉ −Ｚｎ 合金メッ
キ鋼板を１５秒間浸漬して着色層を得、次いで１／４稀
釈のサージェント浴中で電解クロメートを行ったのちコ
ロイダルシリカ含有のアクリル系エマルジョンを乾燥塗
膜厚１．０μ狙いで塗装して焼付けた。Example 9 Ni” l O?/l, Cu” 2 f/l,
N, NO350f/l and NH4SCN 20f/l
l p) A colored layer was obtained by immersing a galvanized steel sheet, a hot-dip galvanized steel sheet, and a 10% Ni-Zn alloy plated steel sheet in a water bath solution of i=5.3 for 15 seconds, and then in a 1/4 diluted Sargent bath. After electrolytic chromating, an acrylic emulsion containing colloidal silica was applied and baked to a dry film thickness of 1.0 μm.
得られた品質は、Ｌ値がいずれも１４以下の黒色外観で
密着性が良好であった。The quality obtained was that all had an L value of 14 or less, a black appearance, and good adhesion.
（発明の効果）
本発明は亜鉛メッキ鋼板を化学的に着色する方法を骨子
としておシ、従来の如き塗装と異る色調、強度を持って
いる。(Effects of the Invention) The present invention is based on a method of chemically coloring galvanized steel sheets, and has a color tone and strength different from conventional coatings.
従って、プレコート材として塗装省略型の低価格製品を
供給出来る。又、高速生産ラインに追随できる短時間処
理が可能であり、既存の処理設備での対応が可能である
。Therefore, it is possible to supply a low-cost product that does not require painting as a pre-coat material. Furthermore, it is possible to perform short-time processing that can follow high-speed production lines, and can be handled using existing processing equipment.
第１図は本発明の着色亜鉛メッキ鋼板の断面模式図を示
すものである。冷延鋼板／亜鉛メッキ層／着色層／保護
皮膜層で構成している。
保護皮膜層
素地FIG. 1 shows a schematic cross-sectional view of a colored galvanized steel sheet of the present invention. Consists of cold-rolled steel sheet/galvanized layer/colored layer/protective film layer. Protective film layer base
Claims (2)
オンを含み且つ酸化性イオン、リン酸イオンのいずれか
もしくは両者を含む水溶液で着色化処理した層を有しさ
らにその上層に保護被膜を有することを特徴とする着色
亜鉛メッキ鋼板(1) A layer containing colored metal ions and fixed metal ions and colored with an aqueous solution containing either or both of oxidizing ions and phosphate ions is provided on the zinc plating, and a protective coating is provided on top of the layer. Colored galvanized steel sheet characterized by having
オンとしてニッケル、コバルト、モリブデン、アンチモ
ン、クロム、スズの各イオンの一種以上、酸化性イオン
として硝酸、塩素酸、過酸化、重クロム酸の各イオンの
一種以上を含む水溶液で着色処理した層を有し、さらに
その上に保護被膜を有する特許請求範囲第１項記載の着
色亜鉛メッキ鋼板。(2) Copper ions are fixed as colored metal ions; one or more of nickel, cobalt, molybdenum, antimony, chromium, and tin ions are used as metal ions; nitric acid, chloric acid, peroxide, and dichromic acid are used as oxidizing ions; The colored galvanized steel sheet according to claim 1, which has a layer colored with an aqueous solution containing one or more of each ion, and further has a protective coating thereon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006286A JPS62180081A (en) | 1986-02-03 | 1986-02-03 | Colored galvanized steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006286A JPS62180081A (en) | 1986-02-03 | 1986-02-03 | Colored galvanized steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62180081A true JPS62180081A (en) | 1987-08-07 |
Family
ID=12016597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006286A Pending JPS62180081A (en) | 1986-02-03 | 1986-02-03 | Colored galvanized steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62180081A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0432543A (en) * | 1990-05-29 | 1992-02-04 | Nikko Aen Kk | Jig for colored zinc plating |
| JPH0432542A (en) * | 1990-05-29 | 1992-02-04 | Nikko Aen Kk | Jig for colored zing plating |
| EP0839931A2 (en) * | 1996-10-30 | 1998-05-06 | Nihon Hyomen Kagaku Kabushiki Kaisha | Treating solution and treating method for forming protective coating films on metals |
| WO2002079539A3 (en) * | 2001-03-29 | 2003-06-05 | Macdermid Plc | Treatment of zinc and zinc alloy surfaces |
| US7204871B2 (en) | 2005-05-24 | 2007-04-17 | Wolverine Plating Corp. | Metal plating process |
-
1986
- 1986-02-03 JP JP2006286A patent/JPS62180081A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE38285E1 (en) | 1909-05-09 | 2003-10-28 | Nihon Hyomen Kagaku Kabushiki Kaisha | Treating solution and treating method for forming protective coating films on metals |
| JPH0432543A (en) * | 1990-05-29 | 1992-02-04 | Nikko Aen Kk | Jig for colored zinc plating |
| JPH0432542A (en) * | 1990-05-29 | 1992-02-04 | Nikko Aen Kk | Jig for colored zing plating |
| EP0839931A2 (en) * | 1996-10-30 | 1998-05-06 | Nihon Hyomen Kagaku Kabushiki Kaisha | Treating solution and treating method for forming protective coating films on metals |
| EP0839931A3 (en) * | 1996-10-30 | 1998-08-05 | Nihon Hyomen Kagaku Kabushiki Kaisha | Treating solution and treating method for forming protective coating films on metals |
| US6096140A (en) * | 1996-10-30 | 2000-08-01 | Nihon Hyomen Kagaku Kabushiki Kaisha | Treating solution and treating method for forming protective coating films on metals |
| WO2002079539A3 (en) * | 2001-03-29 | 2003-06-05 | Macdermid Plc | Treatment of zinc and zinc alloy surfaces |
| US7204871B2 (en) | 2005-05-24 | 2007-04-17 | Wolverine Plating Corp. | Metal plating process |
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