JP4086149B2 - Blackened zinc-plated steel sheet with excellent design - Google Patents
Blackened zinc-plated steel sheet with excellent design Download PDFInfo
- Publication number
- JP4086149B2 JP4086149B2 JP2003095153A JP2003095153A JP4086149B2 JP 4086149 B2 JP4086149 B2 JP 4086149B2 JP 2003095153 A JP2003095153 A JP 2003095153A JP 2003095153 A JP2003095153 A JP 2003095153A JP 4086149 B2 JP4086149 B2 JP 4086149B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- zinc phosphate
- nickel
- steel sheet
- plated steel
- 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.)
- Expired - Fee Related
Links
- 229910000831 Steel Inorganic materials 0.000 title claims description 40
- 239000010959 steel Substances 0.000 title claims description 40
- 238000013461 design Methods 0.000 title claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 98
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 96
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 96
- 239000011701 zinc Substances 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 239000000126 substance Substances 0.000 claims description 52
- 239000013078 crystal Substances 0.000 claims description 40
- 229910052759 nickel Inorganic materials 0.000 claims description 35
- 229910052725 zinc Inorganic materials 0.000 claims description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 32
- 238000001556 precipitation Methods 0.000 claims description 30
- 238000007746 phosphate conversion coating Methods 0.000 claims description 19
- 238000007747 plating Methods 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000007739 conversion coating Methods 0.000 claims description 2
- 235000019646 color tone Nutrition 0.000 description 24
- 239000000243 solution Substances 0.000 description 21
- 239000007788 liquid Substances 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 230000003750 conditioning effect Effects 0.000 description 9
- 229910001335 Galvanized steel Inorganic materials 0.000 description 8
- 239000008397 galvanized steel Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910018134 Al-Mg Inorganic materials 0.000 description 2
- 229910018467 Al—Mg Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910007570 Zn-Al Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007744 chromate conversion coating Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LKCUKVWRIAZXDU-UHFFFAOYSA-L zinc;hydron;phosphate Chemical compound [Zn+2].OP([O-])([O-])=O LKCUKVWRIAZXDU-UHFFFAOYSA-L 0.000 description 1
Images
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Chemical Treatment Of Metals (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、亜鉛系めっき鋼板にリン酸亜鉛化成処理を施して黒灰色の色調を付与した意匠性に優れる黒色化亜鉛系めっき鋼板に関する。
【０００２】
【従来の技術】
亜鉛めっき鋼板又は亜鉛合金（例えばZn-Al合金，Zn-Al-Mg合金）めっき鋼板等の亜鉛系めっき鋼板は、耐食性に優れ、家電製品の外装材、建材等として広く使用されている。これらの部材の表面に、黒灰色の色調を付与して意匠性を高める黒色化法として、リン酸亜鉛化成処理を施し黒灰色のリン酸亜鉛化成皮膜を形成することが行なわれている。
【０００３】
黒色化亜鉛系めっき鋼板は、亜鉛系めっき鋼板（母材鋼板）を脱脂・水洗した後、表面調整剤処理液による表面調整処理を行ない、ついで黒色化リン酸亜鉛化成処理を施す工程により製造される。なお、リン酸亜鉛化成皮膜は比較的脆いので、その後に行なわれるプレス等の成形工程における皮膜の破損・剥離を防止する目的で、リン酸亜鉛化成皮膜の表面にクリア塗装を施しクリア樹脂塗膜で被覆保護するのが通常である。
【０００４】
従来、黒色化亜鉛系めっき鋼板の皮膜品質の改良や色調の調整等について種々の提案がなされている。例えば、
(1)リン酸亜鉛化成皮膜のリン酸亜鉛結晶を、Ｎｉ含有量1〜3mass％,結晶粒の大きさ5〜20μmとし、かつ結晶面の配向を調整することにより色差計による明度指数Ｌ値で２５〜４０の色調を得る（特許文献１）。
(2)表面調整処理に使用される表面調整処理剤の粒子濃度の規定およびリン酸亜鉛化成処理における化成処理液の全酸濃度の調整等により、短時間で黒灰色化でき、明度指数Ｌ値４５〜６０の色調が得られる（特許文献２）。
(3)リン酸亜鉛化成皮膜のうえにクロメート化成皮膜とクリア樹脂塗膜をこの順に形成する場合、塗膜の光沢でリン酸亜鉛化成皮膜の色調のムラが強調される。クリア樹脂塗膜に体質顔料を配合して、塗膜の光沢を少なくすることにより色調のムラや見る角度による色調の変化が抑えられる（特許文献３）。
【０００５】
【特許文献１】
特開平7-316834号公報、ｐ.2段落0004-0007,表1
【特許文献２】
特開平8-218181号公報、ｐ.2段落0005-0008,表1,表2
【特許文献３】
特開平8-258215号公報、ｐ.2、[0005]-[0007],表1
【０００６】
【発明が解決しようとする課題】
従来、黒色化亜鉛系めっき鋼板の色調は、色差計で測定される明度指数Ｌ値で評価されている。しかし、黒灰色表面の意匠性は、濃淡やつや・くすみの度合い等で多様かつ微妙に変化し、同じ明度指数Ｌ値でも視覚効果に大きな相違のあることも多い。本発明者等は、リン酸亜鉛化成皮膜の構造及び色調について、詳細な実験に基づき、明度指数Ｌ値と併せて光沢度を考慮することにより、微妙に変化する種々の色調をより的確・定量的に表示することができ、またリン酸亜鉛化成皮膜を構成するニッケル置換析出層とリン酸亜鉛結晶層のそれぞれを制御することにより、明度指数Ｌ値と光沢度とを調整し、例えば重厚感のある黒灰色の色調をはじめ、製品鋼板の具体的な用途・使用態様に応じた色調を得ることができるとの知見を得た。本発明は上記知見に基づいてなされたものである。
【０００７】
【課題を解決するための手段】
本発明の黒色化亜鉛系めっき鋼板は、亜鉛めっき鋼板又は亜鉛合金めっき鋼板に、ニッケル含有リン酸亜鉛化成処理液による化成処理を施し、めっき表面にニッケル置換析出層と該ニッケル置換析出層を被覆するリン酸亜鉛結晶層とからなるリン酸亜鉛化成皮膜を形成してなる黒色化亜鉛系めっき鋼板において、ニッケル置換析出層のニッケル付着量：１０〜８０mg/ｍ２、リン酸亜鉛結晶層のＮｉ/Ｚｎ比（質量比）：０．０２〜０．０５５、リン酸亜鉛化成皮膜の付着量：２．０〜５．０ｇ/ｍ２であり、その表面の明度指数Ｌ値：２５〜５０、および光沢度：１０以下であることを特徴としている。
【０００８】
上記黒色化亜鉛系めっき鋼板は、亜鉛めっき鋼板又は亜鉛系めっき鋼板の表面を脱脂・水洗した後、チタンコロイド系表面調整剤処理液による表面調整処理を施し、ついで化成処理に付し、Ｎｉ/Ｚｎ比及びニッケル濃度を一定の範囲に調整保持されたニッケル含有リン酸亜鉛化成処理液で処理することにより製造される。
【０００９】
黒色化リン酸亜鉛化成処理でめっき表面に形成された、リン酸亜鉛化成皮膜のニッケル置換析出層は、黒灰色の外観を付与し、リン酸亜鉛結晶層はニッケル置換析出層の光沢を抑える働きをなす。上記リン酸亜鉛化成皮膜で被覆された本発明の黒色化亜鉛系めっき鋼板は、色差計による明度指数Ｌ値：約２５〜５０、光沢度：約１０以下の重厚感を備えた色調を呈し、見る方向による色調のムラが少なく、均質性に優れている。
なお、本発明にいう明度指数L値は、JIS-Z8730の規定されたハンターの色差式に基づく数値であり、光沢度はJIS-Z8741「鏡面光沢度測定方法」の規定に準拠して測定される数値である。
【００１０】
【発明の実施の形態】
図６は、亜鉛系めっき鋼板の表面に形成されたリン酸亜鉛化成処理膜の積層構造を示している。Ｍは母材鋼板（亜鉛系めっき鋼板）のめっき層、１はリン酸亜鉛化成皮膜である。リン酸亜鉛化成皮膜（１）は、ニッケル置換析出層（１１）とこれを被覆するリン酸亜鉛結晶層（１２）とからなる層構造を有する。ニッケル置換析出層（１１）は、リン酸亜鉛化成処理液中のＮｉイオンがめっき層（Ｍ）の表面で亜鉛（Ｚｎ）と置換して析出生成した層であり、リン酸亜鉛結晶層（１２）は、リン酸亜鉛化成処理液から析出したリン酸亜鉛[Zn３(PO４)２・4H２O]（無色透明）を主成分とする結晶層である。
【００１１】
リン酸亜鉛化成処理による黒色化亜鉛系めっき鋼板の色調（明度指数Ｌ値及び光沢度）は、ニッケル置換析出層のニッケル付着量（mg/m２）、リン酸亜鉛化成皮膜の付着量（ｇ/m２）及び該結晶層中のＮｉとＺｎの質量比「Ｎｉ/Ｚｎ（mg/mg）」等により制御される。
ニッケル置換析出層は黒灰色の外観を付与する層であり、そのニッケル付着量が不足すると明度指数L値が過度に高くなり、所要の黒灰色の外観が得られなくなる。意匠性の良好な黒灰色の外観を得るには、ニッケル付着量が１０mg/m２以上であることを要する。ニッケル付着量の増加に伴い、明度指数Ｌ値は低くなるが、約８０mg/m２を超えると、その効果はほぼ飽和するので、これを上限とする。好ましくは１５〜８０mg/m２である。
【００１２】
明度指数Ｌ値は、リン酸亜鉛結晶層のＮｉ/Ｚｎ比による影響を受ける。意匠性の良好な黒灰色の色調を確保するには、前記ニッケル置換析出層のニッケル付着量の規定と併せて、リン酸亜鉛結晶層のＮｉ/Ｚｎ比（質量比）が０.０２〜０ . ０５５の範囲にあることを要する。このようにニッケル置換析出層のニッケル付着量およびリン酸亜鉛結晶のＮｉ/Ｚｎ比を規定することにより、明度指数Ｌ値２５〜５０の黒灰色を確保することができる。
【００１３】
黒色化亜鉛系めっき鋼板の光沢度はニッケル置換析出層を被覆するリン酸亜鉛結晶層により調整される。リン酸亜鉛結晶層は、ニッケル置換析出層の金属光沢を抑え、黒灰色の外観に重厚感を付与する働きをなす。従って程よく光沢が抑制された黒灰色の色調を得るには、適正なリン酸亜鉛化成皮膜の付着量が必要である。その好ましい付着量は２．０ｇ/ｍ２以上である。増量により光沢抑制効果を増すが、付着量を過度に増加することは経済的に無駄であるばかりか、皮膜の耐剥離性の低下を招くので、好ましくは５．０ｇ/ｍ２を上限とする。
【００１４】
次に、本発明に係る黒色化亜鉛系めっき鋼板の製造工程について説明する。
母材鋼板（亜鉛系めっき鋼板）は、亜鉛めっき鋼板又は亜鉛合金めっき鋼板（例えばZn-Al系合金,Zn-Al-Mg系合金等）である。母材鋼板は、常法に従って、アルカリ水溶液による脱脂と水洗によるめっき表面の清浄化処理の後、表面調整処理が施され、ついでリン酸亜鉛化成処理工程に送給される。なお、表面調整処理は、リン酸亜鉛化成処理におけるリン酸亜鉛結晶の析出核となる微粒子をめっき表面に付与する処理であり、Ｔｉ水酸化物粒子含有表面調整剤等の一般的な表面調整剤を使用して行なわれる。
【００１５】
リン酸亜鉛化成処理は、黒色化リン酸亜鉛化成処理液を、スプレー、浸漬法等でめっき表面に接触させることにより行われる。
黒色化リン酸亜鉛化成処理液は、基本的にはリン酸溶液に酸化亜鉛及びニッケルを溶解したリン酸酸性溶液であり、亜鉛はリン酸水素亜鉛[Zn(H２PO４)２]の状態で溶解し一定の平衡状態を保っている（3Zn２＋＋2H２PO４ −⇔Zn３(PO４)２＋4H＋）。 このリン酸亜鉛化成処理液を、母材鋼板（亜鉛系めっき鋼板）のめっき表面に接触させると、液中のＮｉイオンはめっき層の亜鉛（遊離リン酸により液中に溶出）と置換し、めっき層表面にニッケル置換析出層（１１）が形成される。また亜鉛の溶解に伴う処理液のｐＨ上昇によりリン酸亜鉛[Zn３(PO４)２]が生成し、水化物（Zn３(PO４)２・4H２O）として析出することによりリン酸亜鉛結晶層（１２）が形成される。
【００１６】
化成処理の浴液のＮｉ/Ｚｎ比及びニッケル濃度の維持調整は重要である。化成処理浴液のＮｉ/Ｚｎ比は０．４〜１．４の範囲に調整維持される。Ｎｉ/Ｚｎ比が０．４に満たないと、ニッケルの置換析出反応（ニッケル置換析出層11の形成）を効率よく行なわせることができず、黒色化が不十分（明度指数Ｌ値上昇）となるからであり、より好ましくは０．７以上である。他方、浴液のＮｉ/Ｚｎ比が１．４を超えると、リン酸亜鉛結晶の析出反応が抑制され、リン酸亜鉛結晶層（１２）にスケ（結晶片相互の隙間）が生じ易く、結果としてリン酸亜鉛結晶層による光沢抑制効果を確保することが困難となる。より好ましくは０．９以下である。
【００１７】
また、上記化成処理浴液のニッケル濃度は、３〜１１ｇ/ｌの範囲に調整維持するのが好ましい。浴液のニッケル濃度が３ｇ/ｌに満たないと、健全なリン酸亜鉛化成皮膜を短時間の効率的な化成処理で形成することが困難となり、他方１１ｇ/ｌより高くしても、黒色化の効果が増すことはない。
【００１８】
上記浴液のＮｉ/Ｚｎ比及びニッケル濃度は、化成処理におけるニッケル置換析出層（１１）及びリン酸亜鉛結晶層（１２）の生成反応に伴って経時的に低下するが、Ｎｉ/Ｚｎ比及びニッケル濃度が調整された補給液を適時浴液に追加供給することにより所望の浴液組成を維持することができる。このようにリン酸亜鉛化成処理の浴液組成の適切な維持管理により、健全なニッケル置換析出層（１１）及びリン酸亜鉛結晶層（１２）からなるリン酸亜鉛化成皮膜（１）が形成され、程よく光沢が抑制された黒灰色の色調を有する意匠性に優れた黒色化亜鉛系めっき鋼板が得られる。
【００１９】
なお、本発明におけるリン酸亜鉛化成処理は、上記浴液組成の調整のほかは特別の制限や条件の付加を必要とせず、例えば化成処理浴液の全酸度、浴液温度等の調整は常法に従って行なえばよい。
【００２０】
上記黒色化リン酸亜鉛化成処理の後、所望によりクリア塗装が施される。リン酸亜鉛化成皮膜は脆い皮膜であり、プレス加工等の成形加工で剥離・損傷を生じ易いため、クリア塗装を施して皮膜表面をクリア樹脂塗膜で被覆保護するのが通常である。クリア塗装は、公知の樹脂塗料、例えばエポキシ系,塩化ビニル系,アクリル系,フッ素系等を使用し常法に従って行なえばよい。塗膜厚さ（乾燥後）は、例えば７〜１０μｍ程度である。
【００２１】
【実施例】
連続ラインにおいて下記の工程及び処理条件により黒色化亜鉛系めっき鋼板を製造する。
(1)母材鋼板
Zn-6%Al-3%Mg合金溶融めっき鋼板
めっき付着量（両面合計）290〜400g/m２
(2)脱脂・水洗
アルカリ系脱脂剤で処理した後、上水でスプレー洗浄する。
(3)表面調整処理
Ｔｉ水酸化物粒子含有表面調整剤[日本パーカライジング（株）製、商品名：PL-Z]を含む処理液（液温:常温）で10秒間処理。
【００２２】
(4)黒色化リン酸亜鉛化成処理
被処理材（母材鋼板）の連続通板下、スプレー方式により鋼板表面に化成処理液を接触させる。化成処理槽の浴液は、化成処理剤「商品名：PB-37」[日本パーカライジング（株）製]で建浴し、化成処理の進行に伴う浴液組成の変化に応じ、別途用意した補給剤を適時追加投与することにより浴液のNi/Zn比及びニッケル濃度等を調整した。
【００２３】
表１に、化成処理浴液の組成、及びリン酸亜鉛化成皮膜の構成及び色調の測定結果を示す。各供試材について、図１に明度指数L値とリン酸亜鉛化成皮膜のニッケル置換析出層（１１）のニッケル付着量との相関、図２に明度指数L値とリン酸亜鉛結晶層（１２）のNi/Zn比との相関、図３に光沢度とリン酸亜鉛化成皮膜(１)の付着量との相関、図４に光沢度とリン酸亜鉛結晶層（１２）のNi/Zn比との相関、及び図５にリン酸亜鉛結晶層のNi/Zn比と化成処理浴液のNi/Zn比との相関をそれぞれ示す。なお、リン酸亜鉛結晶層中のニッケル量の測定は、蛍光Ｘ線による定量分析法を適用し、リン酸亜鉛化成皮膜（1）（ニッケル置換析出層11＋リン酸亜鉛結晶層12）で測定されるニッケル量の定量分析値（これをＡとする）と、リン酸亜鉛結晶層（12）を溶解除去（処理液：重クロム酸のアンモニア水溶液）し露出させた状態で測定されるニッケル置換析出層（11）のニッケル量の定量分析値（これをBとする）との差値（=A-B）として求めた。
【００２４】
【表１】
表１及び図１〜５に示したように、黒色化亜鉛系めっき鋼板の明度指数Ｌ値及び光沢度は、ニッケル置換析出層のニッケル付着量,リン酸亜鉛結晶層のＮｉ/Ｚｎ比及びリン酸亜鉛化成皮膜の付着量等により変化している。化成処理における浴液のＮｉ/Ｚｎ比及びニッケル濃度を調節することにより、製品鋼板に所望の明度指数Ｌ値及び光沢度を有する色調を付与し得ることがわかる。そしてニッケル置換析出層のニッケル付着量10〜80mg/ｍ２,リン酸亜鉛結晶層のＮｉ/Ｚｎ比0.02〜0.055,リン酸亜鉛化成皮膜の付着量2.0〜5.0ｇ/ｍ２の皮膜構成とすることにより、明度指数Ｌ値５０以下及び光沢度１０以下という十分に黒色化しかつ光沢が程よく抑制された重厚感のある色調を得ている。なお、No.7及びNo.8は、ニッケル置換析出層のニッケル付着量に不足はないものの、リン酸亜鉛結晶層のＮｉ/Ｚｎ比が不足しているため、黒色化が不十分（明度指数Ｌ値＞50）となり、他方No.9及びNo.10では、黒色化は十分であるが、リン酸亜鉛化成皮膜の付着量が不十分であるため、光沢抑制効果に不足をきたしている。
【００２６】
【発明の効果】
本発明によれば、リン酸亜鉛化成皮膜を構成するニッケル置換析出層とリン酸亜鉛結晶層の調整効果として黒色化亜鉛系めっき鋼板に明度及び光沢度が制御された色調を付与することができる。光沢が抑制された深い黒灰色をもつ外観を得ることも容易であり、家電製品部材や建材、その他の各種分野における個々の具体的用途・使用態様に応じて要望される種々の色調を有する黒色化亜鉛系めっき鋼板を得ることができ、黒色化亜鉛系めっき鋼板の用途の拡大多様化を可能とするものである。また本発明におけるリン酸亜鉛化成皮膜の制御は、リン酸亜鉛化成処理の浴液のＮｉ/Ｚｎ比及びニッケル濃度の調整により行なわれ、特殊な制限や条件の付加を必要とせず、工業的実用価値に優れている。
【図面の簡単な説明】
【図１】明度指数L値とリン酸亜鉛化成皮膜のニッケル置換析出層のニッケル付着量との相関を示すグラフである。
【図２】明度指数L値とリン酸亜鉛化成皮膜のリン酸亜鉛結晶層のNi/Zn比との相関を示すグラフである。
【図３】光沢度とリン酸亜鉛化成皮膜の付着量との相関を示すグラフである。
【図４】光沢度とリン酸亜鉛化成皮膜のリン酸亜鉛結晶層のNi/Zn比との相関を示すグラフである。
【図５】リン酸亜鉛化成処理液中のNi/Zn比とリン酸亜鉛化成皮膜のリン酸亜鉛結晶層のNi/Zn比との相関を示すグラフである。
【図６】黒色化リン酸亜鉛化成皮膜の層構造を模式的に示す断面説明図である。
【符号の説明】
１：リン酸亜鉛化成皮膜
１１：ニッケル置換析出層
１２：リン酸亜鉛結晶層
Ｍ：亜鉛系めっき層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a blackened zinc-based plated steel sheet having excellent design properties in which a zinc-based plated steel sheet is subjected to zinc phosphate chemical conversion treatment to give a black gray color tone.
[0002]
[Prior art]
Zinc-plated steel sheets such as galvanized steel sheets or zinc alloy (eg, Zn-Al alloy, Zn-Al-Mg alloy) -plated steel sheets are excellent in corrosion resistance and are widely used as exterior materials and building materials for home appliances. As a blackening method for imparting a black-gray color tone to the surface of these members to enhance the design, a zinc phosphate chemical conversion treatment is performed to form a black gray zinc phosphate chemical film.
[0003]
Blackened galvanized steel sheet is manufactured by degreasing and washing zinc-based galvanized steel sheet (base material steel sheet), followed by surface conditioning treatment with a surface conditioning agent treatment liquid, followed by blackening zinc phosphate chemical conversion treatment. The Since the zinc phosphate conversion coating is relatively brittle, the clear coating is applied to the surface of the zinc phosphate conversion coating for the purpose of preventing damage and peeling of the coating in the subsequent molding process such as pressing. It is usual to cover and protect with.
[0004]
Conventionally, various proposals have been made for improving the film quality and adjusting the color tone of the blackened zinc-based plated steel sheet. For example,
(1) The zinc phosphate crystal of the zinc phosphate conversion coating has a Ni content of 1 to 3 mass%, a crystal grain size of 5 to 20 μm, and a crystallinity by adjusting the orientation of the crystal plane, and a lightness index L value by a color difference meter Thus, a color tone of 25 to 40 is obtained (Patent Document 1).
(2) By adjusting the particle concentration of the surface conditioning agent used in the surface conditioning treatment and adjusting the total acid concentration of the chemical conversion solution in the zinc phosphate chemical conversion treatment, it can be turned grayish in a short time, and the lightness index L value A color tone of 45 to 60 is obtained (Patent Document 2).
(3) When the chromate conversion coating and the clear resin coating are formed in this order on the zinc phosphate conversion coating, unevenness in the color tone of the zinc phosphate conversion coating is emphasized by the gloss of the coating. By adding an extender pigment to the clear resin coating and reducing the gloss of the coating, variations in color tone and changes in color tone due to viewing angle can be suppressed (Patent Document 3).
[0005]
[Patent Document 1]
JP 7-316834 A, p. 2 paragraphs 0004-0007, Table 1.
[Patent Document 2]
JP-A-8-218181, p.2 paragraphs 0005-0008, Table 1, Table 2
[Patent Document 3]
JP-A-8-258215, p.2, [0005]-[0007], Table 1
[0006]
[Problems to be solved by the invention]
Conventionally, the color tone of a blackened zinc-based plated steel sheet has been evaluated by the brightness index L value measured with a color difference meter. However, the design of the black-gray surface varies variously and delicately depending on the degree of shading, luster, dullness, etc., and visual effects often vary greatly even with the same lightness index L value. The present inventors, based on detailed experiments on the structure and color tone of the zinc phosphate chemical conversion film, more accurately and quantitatively determine various color tones that change slightly by considering the glossiness in combination with the lightness index L value. By controlling each of the nickel-substituted precipitation layer and the zinc phosphate crystal layer constituting the zinc phosphate chemical conversion film, the lightness index L value and the glossiness are adjusted. In addition to the black and gray color tone, it was found that it is possible to obtain a color tone according to the specific application and usage of the product steel plate. The present invention has been made based on the above findings.
[0007]
[Means for Solving the Problems]
The blackened zinc-based plated steel sheet of the present invention is formed by subjecting a zinc-plated steel sheet or a zinc alloy-plated steel sheet to a chemical conversion treatment with a nickel-containing zinc phosphate chemical conversion treatment solution, and coating the nickel-substituted deposited layer and the nickel-substituted deposited layer on the plated surface. In a blackened zinc-based plated steel sheet formed with a zinc phosphate conversion coating composed of a zinc phosphate crystal layer, the nickel deposition amount of the nickel-substituted precipitation layer: 10 to 80 mg / m 2 , Ni of the zinc phosphate crystal layer / Zn ratio (mass ratio): 0.02 to 0.055, the adhesion amount of the zinc phosphate conversion coating: 2.0~5.0g / m 2 der is, the lightness index L value of the surface: 25 to 50 , and the glossiness: is characterized in 10 or less der Rukoto.
[0008]
The blackened galvanized steel sheet is degreased and washed with galvanized steel sheet or galvanized steel sheet, then surface-adjusted with a titanium colloidal surface conditioner treatment solution, and then subjected to chemical conversion treatment. It is manufactured by processing with a nickel-containing zinc phosphate chemical conversion liquid whose Zn ratio and nickel concentration are adjusted and maintained within a certain range.
[0009]
The nickel-substituted precipitation layer of the zinc phosphate conversion coating formed on the plating surface by blackening zinc phosphate conversion treatment gives a black-gray appearance, and the zinc phosphate crystal layer works to suppress the gloss of the nickel-substituted precipitation layer. Make. The blackened zinc-based plated steel sheet of the present invention coated with the zinc phosphate chemical coating exhibits a color tone with a heavy feeling of lightness index L value by color difference meter: about 25-50, glossiness: about 10 or less, There is little unevenness in color tone depending on the viewing direction, and excellent uniformity.
The lightness index L value referred to in the present invention is a numerical value based on the Hunter's color difference formula specified in JIS-Z8730, and the glossiness is measured according to the specification of JIS-Z8741 “Specular Gloss Measurement Method”. It is a numerical value.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
FIG. 6 shows a laminated structure of the zinc phosphate chemical conversion film formed on the surface of the zinc-based plated steel sheet. M is a plating layer of a base steel plate (zinc-based plated steel plate), and 1 is a zinc phosphate conversion coating. The zinc phosphate chemical coating (1) has a layer structure composed of a nickel-substituted precipitation layer (11) and a zinc phosphate crystal layer (12) covering the nickel-substituted precipitation layer (11). The nickel-substituted precipitation layer (11) is a layer formed by precipitation by substitution of Ni ions in the zinc phosphate chemical conversion solution with zinc (Zn) on the surface of the plating layer (M), and the zinc phosphate crystal layer (12 ) Is a crystal layer mainly composed of zinc phosphate [Zn 3 (PO 4 ) 2 .4H 2 O] (colorless and transparent) precipitated from the zinc phosphate chemical conversion treatment solution.
[0011]
The color tone (lightness index L value and glossiness) of the blackened zinc-based plated steel sheet by the zinc phosphate conversion treatment is the amount of nickel deposited on the nickel-substituted precipitation layer (mg / m 2 ), the amount of zinc phosphate coated coating (g / m 2 ) and the mass ratio “Ni / Zn (mg / mg)” of Ni and Zn in the crystal layer.
The nickel-substituted precipitation layer is a layer that gives a black-gray appearance. If the nickel adhesion amount is insufficient, the lightness index L value becomes excessively high, and the required black-gray appearance cannot be obtained. In order to obtain a black-gray appearance with good design, it is necessary that the nickel adhesion amount is 10 mg / m 2 or more. The lightness index L value decreases as the amount of nickel deposited increases, but if it exceeds about 80 mg / m 2 , the effect is almost saturated, so this is the upper limit. Preferably it is 15-80 mg / m < 2 >.
[0012]
The lightness index L value is affected by the Ni / Zn ratio of the zinc phosphate crystal layer. In order to ensure a black-gray color tone with good design properties, the Ni / Zn ratio (mass ratio) of the zinc phosphate crystal layer is 0.02 to 0 in combination with the definition of the nickel adhesion amount of the nickel-substituted precipitation layer. . required to be in the range of 055. Thus, by defining the nickel adhesion amount of the nickel-substituted precipitation layer and the Ni / Zn ratio of the zinc phosphate crystal, a black gray color having a lightness index L value of 25 to 50 can be secured.
[0013]
The glossiness of the blackened zinc-based plated steel sheet is adjusted by the zinc phosphate crystal layer covering the nickel-substituted precipitation layer. The zinc phosphate crystal layer functions to suppress the metallic luster of the nickel-substituted precipitation layer and to add a profound feeling to the black-gray appearance. Therefore, in order to obtain a black-gray color tone with moderately suppressed gloss, an appropriate amount of zinc phosphate conversion coating is required. The preferable adhesion amount is 2.0 g / m 2 or more. The gloss suppression effect is increased by increasing the amount, but excessively increasing the adhesion amount is not only economically wasteful but also causes a decrease in the peel resistance of the film, so preferably 5.0 g / m 2 is the upper limit. .
[0014]
Next, the manufacturing process of the blackened zinc-based plated steel sheet according to the present invention will be described.
The base steel sheet (zinc-based plated steel sheet) is a galvanized steel sheet or a zinc alloy-plated steel sheet (for example, a Zn-Al alloy, a Zn-Al-Mg alloy, etc.). The base steel sheet is subjected to a surface conditioning treatment after a degreasing treatment with an alkaline aqueous solution and a cleaning treatment of the plating surface by rinsing in accordance with a conventional method, and then fed to a zinc phosphate chemical conversion treatment step. The surface conditioning treatment is a treatment for imparting fine particles, which are precipitation nuclei of zinc phosphate crystals, to the plating surface in the zinc phosphate chemical conversion treatment, and is a general surface conditioning agent such as a surface conditioning agent containing Ti hydroxide particles. Is done using.
[0015]
The zinc phosphate chemical conversion treatment is performed by bringing a blackened zinc phosphate chemical conversion treatment solution into contact with the plating surface by spraying, dipping, or the like.
The blackened zinc phosphate chemical conversion treatment solution is basically a phosphoric acid acidic solution in which zinc oxide and nickel are dissolved in a phosphoric acid solution, and zinc is in a state of zinc hydrogen phosphate [Zn (H 2 PO 4 ) 2 ]. in that dissolved remained constant equilibrium (3Zn 2+ + 2H 2 PO 4 - ⇔Zn 3 (PO 4) 2 + 4H +). When this zinc phosphate chemical conversion treatment solution is brought into contact with the plating surface of a base steel plate (zinc-based plated steel plate), Ni ions in the solution are replaced with zinc in the plating layer (eluted into the solution by free phosphoric acid), A nickel-substituted precipitation layer (11) is formed on the surface of the plating layer. In addition, zinc phosphate [Zn 3 (PO 4 ) 2 ] is generated due to the increase in pH of the treatment liquid accompanying dissolution of zinc, and precipitated as a hydrate (Zn 3 (PO 4 ) 2 · 4H 2 O). A zinc crystal layer (12) is formed.
[0016]
It is important to maintain and adjust the Ni / Zn ratio and nickel concentration of the bath solution for chemical conversion treatment. The Ni / Zn ratio of the chemical conversion bath liquid is adjusted and maintained in the range of 0.4 to 1.4. If the Ni / Zn ratio is less than 0.4, the nickel substitution deposition reaction (formation of the nickel substitution deposition layer 11) cannot be performed efficiently, and blackening is insufficient (brightness index L value rise). It is because it becomes, More preferably, it is 0.7 or more. On the other hand, when the Ni / Zn ratio of the bath liquid exceeds 1.4, the precipitation reaction of zinc phosphate crystals is suppressed, and the zinc phosphate crystal layer (12) is likely to be squeezed (gap between crystal pieces). As a result, it is difficult to ensure the gloss suppressing effect of the zinc phosphate crystal layer. More preferably, it is 0.9 or less.
[0017]
Moreover, it is preferable to adjust and maintain the nickel concentration of the said chemical conversion bath liquid in the range of 3-11 g / l. If the nickel concentration of the bath solution is less than 3 g / l, it will be difficult to form a healthy zinc phosphate chemical conversion film by an efficient chemical conversion treatment in a short time. The effect of will not increase.
[0018]
The Ni / Zn ratio and nickel concentration of the bath solution decrease with time with the formation reaction of the nickel-substituted precipitation layer (11) and the zinc phosphate crystal layer (12) in the chemical conversion treatment, but the Ni / Zn ratio and A desired bath liquid composition can be maintained by additionally supplying a replenisher with a nickel concentration adjusted to the bath liquid in a timely manner. Thus, the zinc phosphate chemical conversion film (1) which consists of a sound nickel substitution precipitation layer (11) and a zinc phosphate crystal layer (12) is formed by appropriate maintenance management of the bath liquid composition of a zinc phosphate chemical conversion treatment. Thus, a blackened zinc-based plated steel sheet having a black-gray color tone with moderate glossiness and excellent design can be obtained.
[0019]
In addition, the zinc phosphate chemical conversion treatment in the present invention does not require any special restriction or addition of conditions other than the adjustment of the above bath liquid composition. For example, adjustment of the total acidity of the chemical conversion bath liquid, the bath liquid temperature, etc. is usually performed. Just follow the law.
[0020]
After the blackening zinc phosphate conversion treatment, a clear coating is applied as desired. Since the zinc phosphate chemical conversion film is a brittle film and is likely to be peeled off or damaged in a molding process such as a press process, it is usual to coat and protect the surface of the film with a clear resin coating. The clear coating may be performed according to a conventional method using a known resin paint such as epoxy, vinyl chloride, acrylic or fluorine. The coating thickness (after drying) is, for example, about 7 to 10 μm.
[0021]
【Example】
A blackened zinc-based plated steel sheet is produced by the following process and processing conditions in a continuous line.
(1) Base steel sheet
Zn-6% Al-3% Mg alloy hot-dip galvanized steel plate coating weight (both sides total) 290-400g / m 2
(2) Degreasing and washing After treating with an alkaline degreasing agent, spray wash with clean water.
(3) Surface Conditioning Treatment Treated for 10 seconds with a treatment liquid (liquid temperature: normal temperature) containing a surface conditioner containing Ti hydroxide particles [manufactured by Nippon Parkerizing Co., Ltd., trade name: PL-Z].
[0022]
(4) The chemical conversion treatment solution is brought into contact with the steel plate surface by a spray method under the continuous passage of the blackened zinc phosphate chemical treatment material (base material steel plate). The bath liquid in the chemical conversion treatment tank is built with the chemical conversion treatment agent “trade name: PB-37” (manufactured by Nihon Parkerizing Co., Ltd.) and replenished separately according to changes in the composition of the bath liquid as the chemical conversion treatment progresses. The Ni / Zn ratio, nickel concentration, etc. of the bath solution were adjusted by adding the agent as needed.
[0023]
Table 1 shows the composition of the chemical conversion bath solution, the composition of the zinc phosphate chemical conversion film, and the measurement results of the color tone. FIG. 1 shows the correlation between the lightness index L value and the amount of nickel deposited on the nickel-substituted precipitation layer (11) of the zinc phosphate conversion coating, and FIG. 2 shows the brightness index L value and the zinc phosphate crystal layer (12). ) With the Ni / Zn ratio, FIG. 3 shows the correlation between the glossiness and the amount of zinc phosphate conversion coating (1), and FIG. 4 shows the Ni / Zn ratio between the glossiness and the zinc phosphate crystal layer (12). FIG. 5 shows the correlation between the Ni / Zn ratio of the zinc phosphate crystal layer and the Ni / Zn ratio of the chemical conversion bath solution. The amount of nickel in the zinc phosphate crystal layer is measured by a quantitative analysis method using fluorescent X-rays and measured with a zinc phosphate conversion coating (1) (nickel-substituted precipitation layer 11 + zinc phosphate crystal layer 12). Value of the amount of nickel to be measured (referred to as A) and the zinc phosphate precipitation measured by dissolving and removing the zinc phosphate crystal layer (12) (treatment solution: aqueous ammonia solution of dichromic acid) It was determined as a difference value (= AB) from the quantitative analysis value of the nickel amount of the layer (11) (this is B).
[0024]
[Table 1]
As shown in Table 1 and FIGS. 1 to 5, the lightness index L value and the glossiness of the blackened zinc-based plated steel sheet are the nickel adhesion amount of the nickel-substituted precipitation layer, the Ni / Zn ratio of the zinc phosphate crystal layer, and phosphorus. It varies depending on the amount of zinc acid conversion coating deposited. It can be seen that by adjusting the Ni / Zn ratio and the nickel concentration of the bath solution in the chemical conversion treatment, a color tone having a desired lightness index L value and glossiness can be imparted to the product steel plate. And the coating composition of
[0026]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the color tone by which the brightness and the glossiness were controlled can be provided to the blackening zinc-based plating steel plate as an adjustment effect of the nickel substitution precipitation layer and zinc phosphate crystal layer which comprise a zinc phosphate chemical conversion film. . It is also easy to obtain a deep black-gray appearance with suppressed luster, and black with various tones required according to individual specific applications and usage in various fields such as household appliances and building materials A zinc-plated steel sheet can be obtained, and the use of the blackened zinc-based steel sheet can be expanded and diversified. In addition, the control of the zinc phosphate conversion coating in the present invention is performed by adjusting the Ni / Zn ratio and nickel concentration of the bath solution of the zinc phosphate conversion treatment, and does not require any special restrictions or addition of conditions, and is industrially practical. Excellent value.
[Brief description of the drawings]
FIG. 1 is a graph showing a correlation between a lightness index L value and a nickel adhesion amount of a nickel-substituted precipitation layer of a zinc phosphate conversion coating.
FIG. 2 is a graph showing a correlation between a lightness index L value and a Ni / Zn ratio of a zinc phosphate crystal layer of a zinc phosphate chemical conversion film.
FIG. 3 is a graph showing the correlation between glossiness and the amount of zinc phosphate conversion coating deposited.
FIG. 4 is a graph showing the correlation between the glossiness and the Ni / Zn ratio of the zinc phosphate crystal layer of the zinc phosphate chemical conversion film.
FIG. 5 is a graph showing the correlation between the Ni / Zn ratio in the zinc phosphate chemical conversion treatment liquid and the Ni / Zn ratio of the zinc phosphate crystal layer of the zinc phosphate chemical conversion film.
FIG. 6 is a cross-sectional explanatory view schematically showing the layer structure of a blackened zinc phosphate chemical conversion film.
[Explanation of symbols]
1: Zinc phosphate conversion coating 11: Nickel-substituted precipitation layer 12: Zinc phosphate crystal layer M: Zinc-based plating layer
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003095153A JP4086149B2 (en) | 2003-03-31 | 2003-03-31 | Blackened zinc-plated steel sheet with excellent design |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003095153A JP4086149B2 (en) | 2003-03-31 | 2003-03-31 | Blackened zinc-plated steel sheet with excellent design |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004300523A JP2004300523A (en) | 2004-10-28 |
| JP4086149B2 true JP4086149B2 (en) | 2008-05-14 |
Family
ID=33407545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003095153A Expired - Fee Related JP4086149B2 (en) | 2003-03-31 | 2003-03-31 | Blackened zinc-plated steel sheet with excellent design |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4086149B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4868748B2 (en) * | 2005-03-01 | 2012-02-01 | 日新製鋼株式会社 | Phosphated steel sheet |
| GB0813273D0 (en) * | 2008-07-19 | 2008-08-27 | Nanoco Technologies Ltd | Method for producing aqueous compatible nanoparticles |
-
2003
- 2003-03-31 JP JP2003095153A patent/JP4086149B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004300523A (en) | 2004-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104561874B (en) | Hot-dip zn-al alloy coated steel sheet and its manufacturing method | |
| JP4546848B2 (en) | High corrosion-resistant Zn-based alloy plated steel with hairline appearance | |
| JP6733839B2 (en) | Zinc-based electroplated steel sheet | |
| JP6447800B1 (en) | Plated steel | |
| JP6540930B1 (en) | Zinc-based electroplated steel sheet | |
| JP6973683B2 (en) | Galvanized steel sheet | |
| TWI287050B (en) | Phosphate treated zinc-coated steel sheet | |
| JP4086149B2 (en) | Blackened zinc-plated steel sheet with excellent design | |
| JP3209686B2 (en) | Colored resin-coated metal sheet and method for producing the same | |
| JP2004360056A (en) | BLACKENED HOT DIP Zn-Al-Mg BASED ALLOY PLATED STEEL SHEET, AND ITS PRODUCTION METHOD | |
| JPH0679842B2 (en) | Black surface treated steel plate | |
| JP2009079263A (en) | Surface-treated galvanized metallic material, and method for producing the same | |
| JP3335261B2 (en) | Method for producing blackened zinc-based plated steel sheet | |
| JP2001040494A (en) | Electrogalvanized steel sheet excellent in surface appearance and its production | |
| JPH0359996B2 (en) | ||
| JPH09195063A (en) | White chromate treated steel sheet excellent in corrosion resistance and appearance | |
| JP2009209419A (en) | Electrogalvanized steel having excellent color tone and method of manufacturing the same | |
| JP3401385B2 (en) | Black galvanized steel sheet with stable color tone | |
| JP2701145B2 (en) | Chromate conversion treatment method for steel plate | |
| JP2002097559A (en) | Black steel sheet and manufacturing method therefor | |
| JPH0340116B2 (en) | ||
| JP3003110B2 (en) | Chromated galvanized steel sheet with excellent color tone stability | |
| JP3230907B2 (en) | Method for producing blackened steel sheet excellent in productivity and blackening | |
| JP3241170B2 (en) | Pretreatment method for cationic electrodeposition coating of aluminum-based metal materials | |
| JPH08983B2 (en) | Chromate treatment method with excellent corrosion resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060327 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20071029 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20071101 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071230 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080213 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080213 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110228 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4086149 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110228 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120229 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130228 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140228 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |