JP5164120B2 - Painted BA stainless steel sheet with excellent coating adhesion - Google Patents
Painted BA stainless steel sheet with excellent coating adhesion Download PDFInfo
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- JP5164120B2 JP5164120B2 JP2009062802A JP2009062802A JP5164120B2 JP 5164120 B2 JP5164120 B2 JP 5164120B2 JP 2009062802 A JP2009062802 A JP 2009062802A JP 2009062802 A JP2009062802 A JP 2009062802A JP 5164120 B2 JP5164120 B2 JP 5164120B2
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- 238000000576 coating method Methods 0.000 title claims description 53
- 239000011248 coating agent Substances 0.000 title claims description 52
- 239000010935 stainless steel Substances 0.000 title claims description 46
- 229910001220 stainless steel Inorganic materials 0.000 title claims description 46
- 239000000126 substance Substances 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229920001225 polyester resin Polymers 0.000 claims description 7
- 239000004645 polyester resin Substances 0.000 claims description 7
- 238000007739 conversion coating Methods 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
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- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 238000005211 surface analysis Methods 0.000 claims description 2
- 238000001420 photoelectron spectroscopy Methods 0.000 claims 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000010936 titanium Substances 0.000 description 23
- 239000010410 layer Substances 0.000 description 20
- 238000005530 etching Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
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- 239000000203 mixture Substances 0.000 description 5
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 4
- 239000001263 FEMA 3042 Substances 0.000 description 4
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
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- 150000007524 organic acids Chemical class 0.000 description 4
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 4
- 229940033123 tannic acid Drugs 0.000 description 4
- 235000015523 tannic acid Nutrition 0.000 description 4
- 229920002258 tannic acid Polymers 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
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- 238000013461 design Methods 0.000 description 2
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- 229910052748 manganese Inorganic materials 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000002436 steel type Substances 0.000 description 2
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- -1 C: 0.12% or less Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- OXAUNDBQHKIUSD-UHFFFAOYSA-N azanium;titanium;fluoride Chemical compound [NH4+].[F-].[Ti] OXAUNDBQHKIUSD-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Application Of Or Painting With Fluid Materials (AREA)
- Chemical Treatment Of Metals (AREA)
Description
本発明は、ＢＡ仕上げステンレス鋼板のＢＡ皮膜を化成処理したのち塗膜を形成した塗装ＢＡステンレス鋼板に関する。 The present invention relates to a coated BA stainless steel sheet in which a coating film is formed after chemical conversion of the BA film of a BA-finished stainless steel sheet.
従来、耐食性の良いステンレス鋼板を塗装原板に用いた塗装ステンレス鋼板が屋根・外装用途を中心に広く使用されている。意匠性の観点から、ステンレス鋼に特有の金属表面肌による外観を活かしたクリア塗装ステンレス鋼板が適用されることもある。 Conventionally, a coated stainless steel plate using a stainless steel plate having good corrosion resistance as a coating original plate has been widely used mainly for roof and exterior applications. From the viewpoint of designability, a clear-coated stainless steel sheet utilizing the appearance due to the metal surface skin unique to stainless steel may be applied.
ステンレス鋼表面には不動態皮膜が存在するため、そのままでは良好な塗膜密着性を得ることは困難である。このため従来、塗装前処理としてクロメート処理等の化成処理が施されていた。最近では六価クロムによる環境汚染に配慮して、クロムフリー化成処理が適用されるようになってきた。特許文献１には、チタンフッ化物のアンモニウム塩などを成分に持つクロムフリーの化成処理液を使用して密着性の良い塗装ステンレス鋼板を得る技術が記載されている。 Since a passive film exists on the surface of stainless steel, it is difficult to obtain good coating film adhesion as it is. For this reason, conventionally, chemical conversion treatment such as chromate treatment has been performed as pretreatment for coating. Recently, chromium-free chemical conversion treatment has been applied in consideration of environmental pollution by hexavalent chromium. Patent Document 1 describes a technique for obtaining a coated stainless steel plate having good adhesion by using a chromium-free chemical conversion treatment liquid having a titanium fluoride ammonium salt as a component.
ステンレス鋼板には、酸洗仕上げ（２Ｄ）、酸洗スキンパス仕上げ（２Ｂ）、研磨仕上げ（Ｎｏ.４、ＨＬ）、ＢＡ（光輝焼鈍）仕上げなど、種々の表面肌のものがある。しかし、特許文献１のクロムフリー化成処理では、ＢＡ仕上げステンレス鋼板に対して密着性の良い塗膜を形成させることが困難であることがわかった。昨今では意匠性に対する要求も多様化し、ＢＡ仕上げステンレス鋼板の表面肌を活かしたクリア塗装ＢＡステンレス鋼板の製品化が待たれている。しかし、塗膜密着性の観点から、塗装ＢＡステンレス鋼板を量産する技術は確立されていない。 Stainless steel sheets include various types of surface skin such as pickling finish (2D), pickling skin pass finish (2B), polishing finish (No. 4, HL), and BA (bright annealing) finish. However, it has been found that the chromium-free chemical conversion treatment of Patent Document 1 makes it difficult to form a coating film having good adhesion to the BA-finished stainless steel plate. In recent years, the demand for design has diversified, and the commercialization of clear-coated BA stainless steel sheets that take advantage of the surface skin of BA-finished stainless steel sheets is awaited. However, from the viewpoint of coating film adhesion, a technique for mass-producing a coated BA stainless steel sheet has not been established.
本発明は、塗装前処理としてクロムフリーの化成処理を適用することによって製造可能な塗装ＢＡステンレス鋼板を提供することを目的とする。 An object of the present invention is to provide a coated BA stainless steel sheet that can be manufactured by applying a chromium-free chemical conversion treatment as a pretreatment for coating.
上記目的は、ＢＡ仕上げステンレス鋼板のＢＡ皮膜を、少なくとも最表層にＢＡ皮膜成分、例えば少なくともＳｉを取り込んだクロムフリー化成処理皮膜が存在するように改質して改質ＢＡ皮膜とし、その改質ＢＡ皮膜の上に塗膜を形成してなる塗膜密着性に優れた塗装ＢＡステンレス鋼板によって達成される。そのクロムフリー化成処理皮膜は、例えば最表層から深さ方向にクロムフリー化成処理液に由来するＴｉの濃度が傾斜的に減少しているものである。 The above purpose is to modify the BA film of the BA-finished stainless steel sheet so that at least the outermost layer has a BA film component, for example, a chromium-free chemical conversion film containing at least Si, to obtain a modified BA film. This is achieved by a coated BA stainless steel sheet having excellent coating film adhesion formed by forming a coating film on the BA film. In the chromium-free chemical conversion coating, for example, the concentration of Ti derived from the chromium-free chemical conversion solution is gradually decreased from the outermost layer in the depth direction.
改質ＢＡ皮膜は、例えばフッ化水素チタン酸（Ｈ2ＴｉＦ6）を配合するｐＨ１.７以下の化成処理液により改質したものである。塗膜は、例えば樹脂成分がポリエステル樹脂、エポキシ樹脂、アクリル樹脂、フッ素樹脂の１種以上で構成されるクリア塗膜が適用される。ポリエステル樹脂系やフッ素樹脂系のクリア塗膜が特に好適な対象となる。ここで、ポリエステル樹脂系およびフッ素樹脂系とは、塗膜を構成する樹脂のうち５０質量％以上がそれぞれポリエステル樹脂およびフッ素樹で占められるものをいう。 The modified BA film is modified with a chemical conversion treatment solution having a pH of 1.7 or less and containing, for example, hydrofluoric titanate (H 2 TiF 6 ). As the coating film, for example, a clear coating film in which the resin component is one or more of a polyester resin, an epoxy resin, an acrylic resin, and a fluororesin is applied. A polyester resin-based or fluororesin-based clear coating film is particularly suitable. Here, the polyester resin system and the fluororesin system are those in which 50% by mass or more of the resin constituting the coating film is occupied by the polyester resin and the fluororesin, respectively.
ＢＡ皮膜はＢＡ（光輝焼鈍）処理によって形成されるステンレス鋼板表面の不動態皮膜である。ＢＡ条件として、例えば、雰囲気：７０〜１００体積％Ｈ2＋３０〜０体積％Ｎ2、露点：−４５〜−７０℃、焼鈍温度：８５０〜１１００℃が挙げられる。改質ＢＡ皮膜は、ＢＡ皮膜を改質することによって得られる皮膜である。「最表層」は、当該皮膜の表面をＸＰＳ（例えばＥＳＣＡ）によりエッチングすることなく測定される領域である。なお、本明細書では、ＸＰＳにより深さ方向における酸素の検出強度のプロファイルを作成し、このプロファイルにおいて酸素の検出強度が、最表層の１／２になる深さまでを皮膜とみなす。すなわちＢＡ皮膜あるいは改質ＢＡ皮膜の厚さは、酸素の検出強度が最表層の１／２になるエッチング深さをいう。エッチング深さは、ＳｉＯ2標準試料によるエッチング速度から換算されるエッチング深さを適用する。 The BA film is a passive film on the surface of a stainless steel plate formed by a BA (bright annealing) treatment. Examples of the BA condition include an atmosphere: 70 to 100% by volume H 2 +30 to 0% by volume N 2 , a dew point: −45 to −70 ° C., and an annealing temperature: 850 to 1100 ° C. The modified BA film is a film obtained by modifying the BA film. The “outermost layer” is an area measured without etching the surface of the film by XPS (for example, ESCA). In the present specification, a profile of oxygen detection intensity in the depth direction is created by XPS, and in this profile, a depth up to half the outermost layer of the oxygen detection intensity is regarded as a film. That is, the thickness of the BA film or the modified BA film is an etching depth at which the detected oxygen intensity is ½ of the outermost layer. As the etching depth, an etching depth converted from the etching rate of the SiO 2 standard sample is applied.
このような改質ＢＡ皮膜は、例えば、ＸＰＳによる表面分析において、当該皮膜の表面からＳｉＯ2換算スパッタ深さが少なくとも２.５ｎｍまでの全領域、より好ましくは５ｎｍまでの全領域に、クロムフリー化成処理液のみに由来する成分（例えばＴｉ）が検出されるものである。 Such modification BA coating, for example, in the surface analysis by XPS, the entire region from the surface of the skin through terms of SiO 2 sputtering depth of at least 2.5 nm, more preferably the entire area of up to 5 nm, chromium-free A component (for example, Ti) derived only from the chemical conversion solution is detected.
本発明によれば、塗膜密着性の良いＢＡ塗装ステンレス鋼板を実現することができた。これにより、ＢＡ仕上げステンレス鋼板に特有の光沢表面を活かしたクリア塗装ステンレス鋼板が提供可能になり、意匠性を重視する用途での塗装ステンレス鋼板のバリエーション拡大に寄与しうる。 According to the present invention, it is possible to realize a BA-coated stainless steel sheet having good coating film adhesion. This makes it possible to provide a clear-coated stainless steel sheet that makes use of the glossy surface unique to the BA-finished stainless steel sheet, and can contribute to the expansion of variations in the coated stainless steel sheet in applications that emphasize design.
〔ＢＡ仕上げステンレス鋼板〕
本発明ではＢＡ仕上げステンレス鋼板を化成処理用原板に使用する。そのステンレス鋼種には特に制限はなく、オーステナイト系、フェライト系、マルテンサイト系、析出硬化系の他、複相組織を有するステンレス鋼種なども適用可能である。ここで、ステンレス鋼とは、ＪＩＳ Ｇ０２０３：２０００の番号４２０１に記載されるように、Ｃｒ含有量が１０.５質量％以上の鋼である。Ｃｒ含有量の上限は概ね３０質量％程度とすることが望ましい。既存の規格鋼種としては、ＪＩＳ Ｇ４３０５：２００５に規定されるオーステナイト系、フェライト系等の鋼種が挙げられる。
[BA finish stainless steel sheet]
In the present invention, a BA-finished stainless steel plate is used as a raw sheet for chemical conversion treatment. The stainless steel type is not particularly limited, and a stainless steel type having a multiphase structure as well as an austenite type, a ferrite type, a martensite type, and a precipitation hardening type can be applied. Here, the stainless steel is a steel having a Cr content of 10.5 mass% or more as described in the number 4201 of JIS G0203: 2000. The upper limit of the Cr content is preferably about 30% by mass. Examples of the existing standard steel types include austenitic and ferritic steel types defined in JIS G4305: 2005.
成分組成の範囲を示すと、例えば、オーステナイト系の場合、質量％で、Ｃ：０.１２％以下、Ｓｉ：４％以下とくに１％以下、Ｍｎ：５％以下とくに２％以下、Ｐ：０.０４５％以下、Ｓ：０.０３％以下、Ｎｉ：６〜２８％とくに８〜１４％、Ｃｒ：１５〜２６％とくに１６〜２６％、Ｎ：０.３％以下、Ｍｏ：０〜７％とくに０〜３％、Ｃｕ：０〜４％とくに０〜２％、Ｔｉ＋Ｎｂ＋Ｚｒの合計：０〜０.８％、Ｂ：０〜０.１％、残部実質的にＦｅの組成を挙げることができる。 For example, in the case of the austenite type, the range of the component composition is C: 0.12% or less, Si: 4% or less, particularly 1% or less, Mn: 5% or less, particularly 2% or less, P: 0%. 0.045% or less, S: 0.03% or less, Ni: 6-28%, especially 8-14%, Cr: 15-26%, especially 16-26%, N: 0.3% or less, Mo: 0-7 %, Especially 0 to 3%, Cu: 0 to 4%, especially 0 to 2%, Ti + Nb + Zr total: 0 to 0.8%, B: 0 to 0.1%, the balance being substantially Fe. it can.
フェライト系の場合、Ｃ：０.１２％以下、Ｓｉ：１％以下、Ｍｎ：１％以下、Ｐ：０.０４％以下、Ｓ：０.０３％以下、Ｃｒ：１０.５〜３０％とくに１１〜２０％、Ｍｏ：０〜３％、Ｃｕ：０〜１％、Ｔｉ＋Ｎｂ＋Ｚｒの合計：０〜０.８％、Ｂ：０〜０.１％、残部実質的にＦｅの組成を挙げることができる。 In the case of ferrite, C: 0.12% or less, Si: 1% or less, Mn: 1% or less, P: 0.04% or less, S: 0.03% or less, Cr: 10.5 to 30% 11 to 20%, Mo: 0 to 3%, Cu: 0 to 1%, Ti + Nb + Zr total: 0 to 0.8%, B: 0 to 0.1%, the balance being substantially Fe. it can.
上記各組成範囲において、含有量の下限を０％と規定したものは、任意選択元素であり、無添加（不可避的不純物レベル）とすることができる。「残部実質的にＦｅ」とは、本発明の効果を阻害しない限り上記以外の元素の混入が許容できることを意味する。例えば、Ｖ：１質量％以下、Ｃａ：０.１質量％以下、Ｍｇ：０.１質量％以下、Ｙ：０.１質量％以下、ＲＥＭ（希土類元素）：０.１質量％以下の混入が許容される。フェライト系の場合はＮｉ：０.６質量％まで許容される。「残部実質的にＦｅ」には「残部Ｆｅおよび不可避的不純物からなる」場合が含まれる。 In each of the above composition ranges, what defines the lower limit of the content as 0% is an optional element and can be made additive-free (inevitable impurity level). “Remainder substantially Fe” means that an element other than the above can be mixed unless the effect of the present invention is impaired. For example, V: 1 mass% or less, Ca: 0.1 mass% or less, Mg: 0.1 mass% or less, Y: 0.1 mass% or less, REM (rare earth element): 0.1 mass% or less Is acceptable. In the case of a ferrite system, Ni: up to 0.6% by mass is allowed. “The balance is substantially Fe” includes a case of “consisting of the balance Fe and inevitable impurities”.
ＢＡ仕上げステンレス鋼板は、ＢＡ処理による不動態皮膜（ＢＡ皮膜）を有する鋼板である。必ずしも鏡面光沢を有するものである必要はない。ＢＡ皮膜は、Ｃｒの他にＳｉが濃化している点に特徴がある。すなわち、ＢＡ皮膜中にはＳｉ酸化物が多量に含まれている。そのために、従来のクロムフリー化成処理液（例えばバルブメタルをアンモニウム塩の形で含有するもの）では、十分にエッチング効果が発揮されず、塗膜密着性の良い化成処理皮膜を形成させることが困難であった。 The BA-finished stainless steel plate is a steel plate having a passive film (BA film) by BA treatment. It does not necessarily have to have a specular gloss. The BA film is characterized in that Si is concentrated in addition to Cr. That is, the BA film contains a large amount of Si oxide. Therefore, conventional chromium-free chemical conversion treatment liquids (for example, those containing valve metal in the form of ammonium salts) do not exhibit sufficient etching effects and it is difficult to form a chemical conversion treatment film with good coating film adhesion. Met.
〔改質ＢＡ皮膜〕
本発明の塗装ステンレス鋼板は、ステンレス鋼素地と塗膜の間に、改質されたＢＡ皮膜（改質ＢＡ皮膜）が介在している点に特徴がある。この改質ＢＡ皮膜は、塗膜との密着性が良好なものである。
[Modified BA film]
The coated stainless steel sheet of the present invention is characterized in that a modified BA film (modified BA film) is interposed between the stainless steel substrate and the coating film. This modified BA film has good adhesion to the film.
具体的には、この改質ＢＡ皮膜は、少なくとも最表層に化成処理液に由来する成分（例えばＴｉ）と、ＢＡ皮膜を構成していた成分（例えばＳｉ）の両方が存在していることに特徴がある。特に、ＳｉＯ2換算スパッタ深さが少なくとも２.５ｎｍまでの領域、より好ましくは５ｎｍまでの領域に、クロムフリー化成処理液のみに由来する成分（例えばＴｉ）が検出されるものが、より好適な対象となる。化成処理液に由来する成分が存在している深さまでが改質された部分であると捉えることができる。この改質された部分（本明細書では「クロムフリー化成処理皮膜」と呼んでいる）は、最表層から内部に進むに従って、化成処理液に由来する成分（例えばＴｉ）の濃度が傾斜的に減少していき、いわゆる傾斜機能材料と見ることができる。本発明の改質ＢＡ皮膜は、その全部がクロムフリー化成処理皮膜で占められていても構わないし、「クロムフリー化成処理皮膜の部分」と「元のＢＡ皮膜が残存している部分」で構成されていてもよい。 Specifically, the modified BA film has at least the component (for example, Ti) derived from the chemical conversion treatment liquid and the component (for example, Si) constituting the BA film at least on the outermost layer. There are features. In particular, it is more preferable that the component (for example, Ti) derived only from the chromium-free chemical conversion treatment liquid is detected in a region where the SiO 2 equivalent sputtering depth is at least 2.5 nm, more preferably in a region up to 5 nm. It becomes a target. It can be considered that the depth to which the components derived from the chemical conversion liquid are present is the modified portion. This modified portion (referred to as “chromium-free chemical conversion coating” in this specification) has a concentration of components (for example, Ti) derived from the chemical conversion solution in a gradient as it progresses from the outermost layer to the inside. It can be seen as a so-called functionally gradient material. The modified BA film of the present invention may be entirely composed of a chromium-free chemical conversion film, and is composed of “a part of the chromium-free chemical conversion film” and “a part where the original BA film remains”. May be.
種々検討の結果、少なくとも最表層に化成処理液に由来する成分（例えばＴｉ）と、ＢＡ皮膜を構成していた成分（例えばＳｉ）の両方が存在しており、最表層から内部に進むに従って、化成処理液に由来する成分（例えばＴｉ）の濃度が傾斜的に減少していく形態の改質ＢＡ皮膜を形成した場合に、ポリエステル樹脂系やフッ素樹脂系をはじめとする塗膜との密着性が実用レベルに改善されることがわかった。そのメカニズムについては現時点で明確ではない。 As a result of various studies, at least the component (for example, Ti) derived from the chemical conversion treatment liquid and the component (for example, Si) constituting the BA film are present at least on the outermost layer, and progressing from the outermost layer to the inside, Adhesiveness with coating films including polyester resin and fluororesin systems when a modified BA film is formed in a form in which the concentration of components derived from the chemical conversion treatment solution (for example, Ti) gradually decreases. Was found to be improved to a practical level. The mechanism is not clear at this time.
発明者らの調査によれば、特許文献１に開示されるようなチタンフッ化物のアンモニウム塩を成分とするクロムフリー化成処理液では、Ｓｉの濃化したＢＡ皮膜をエッチングする作用が弱く、ＢＡ仕上げステンレス鋼板の塗装前処理には適さないことが判明した。 According to the investigation by the inventors, the chromium-free chemical conversion treatment containing an ammonium salt of titanium fluoride as disclosed in Patent Document 1 has a weak effect of etching a BA film concentrated in Si, and has a BA finish. It turned out to be unsuitable for pre-painting of stainless steel sheets.
そこで種々検討したところ、上記のような改質ＢＡ皮膜は、Ｔｉを含有し、かつエッチング性を比較的高めた化成処理液によって形成させることが可能になることがわかった。具体的には、アンモニウム塩を含まず、Ｔｉをフッ化水素チタン酸（Ｈ2ＴｉＦ6）の形で配合したクロムフリー化成処理液を使用することが、ＢＡ皮膜の最表層にＴｉとＮを濃化させる上で極めて有効であることが明らかになった。ｐＨは１.７以下、特に１.５程度に低下させたものが好適である。例えば、フッ化水素チタン酸を５〜１５ｇ／Ｌ、有機酸を５〜１４ｇ／Ｌ含有し、ｐＨが１.７以下好ましくは１.５±０.２に調整された水溶液が好適である。バルブメタルとしてはＴｉが含まれていればよく、Ｚｒその他のバルブメタルは必要ない。有機酸としては例えばタンニン酸が挙げられる。フッ化水素チタン酸、有機酸以外の成分としては、ＳｉＯ2成分をゾルとして含んでいても構わないが、ＢＡ皮膜中には本来Ｓｉ酸化物が濃化しているので、化成処理液中にはＳｉＯ2成分は特に必要ない。すなわち本発明では、フッ化水素チタン酸を５〜１５ｇ／Ｌ、有機酸としては例えばタンニン酸を５〜１４ｇ／Ｌ含有し、ｐＨが１.７以下好ましくは１.５±０.２に調整され、残部は水で構成されるシンプルな組成のクロムフリー化成処理液が使用できる。 As a result of various studies, it has been found that the modified BA film as described above can be formed by a chemical conversion treatment solution containing Ti and having relatively high etching properties. Specifically, it is possible to use a chromium-free chemical conversion treatment liquid containing no ammonium salt and containing Ti in the form of hydrofluoric titanate (H 2 TiF 6 ), so that Ti and N are added to the outermost layer of the BA film. It became clear that it was extremely effective for thickening. The pH is preferably 1.7 or lower, particularly about 1.5. For example, an aqueous solution containing 5 to 15 g / L of hydrofluoric titanate and 5 to 14 g / L of an organic acid and having a pH adjusted to 1.7 or less, preferably 1.5 ± 0.2 is suitable. The valve metal only needs to contain Ti, and Zr and other valve metals are not necessary. An example of the organic acid is tannic acid. As components other than hydrofluoric titanate and organic acid, SiO 2 component may be included as a sol, but since the Si oxide is originally concentrated in the BA film, The SiO 2 component is not particularly necessary. That is, in the present invention, 5 to 15 g / L of hydrofluoric titanate and 5 to 14 g / L of tannic acid as an organic acid are contained, and the pH is adjusted to 1.7 or less, preferably 1.5 ± 0.2. In addition, a chromium-free chemical conversion treatment liquid having a simple composition composed of water can be used as the balance.
改質ＢＡ皮膜は例えば以下のようにして形成することができる。
化成処理用原板となるＢＡ仕上げステンレス鋼板の被処理面を通常の方法で脱脂した後、その表面に上述のクロムフリー化成処理液を一般的な手法にて塗布する。ただし、ＢＡ皮膜の全部をエッチングして改質する必要はなく、少なくとも最表層を改質すればよい。したがって、過剰な塗布量とならないように調整することが望ましい。例えば、ｐＨを１.５に調整した化成処理液の場合、フッ化水素チタン酸中のＴｉ換算塗布量で０.５〜４０ｍｇ／ｍ2とすればよい。塗布後に鋼板を大気中で乾燥させることにより改質ＢＡ皮膜が形成される。乾燥温度は５０〜２００℃とすればよい。
The modified BA film can be formed, for example, as follows.
The surface to be treated of the BA-finished stainless steel plate to be the chemical conversion treatment original plate is degreased by a normal method, and then the above-described chromium-free chemical conversion treatment solution is applied to the surface by a general method. However, it is not necessary to modify the entire BA film by etching, and at least the outermost layer may be modified. Therefore, it is desirable to adjust so that it may not become an excessive coating amount. For example, in the case of a chemical conversion treatment liquid having a pH adjusted to 1.5, the Ti conversion coating amount in hydrofluoric titanic acid may be 0.5 to 40 mg / m 2 . The modified BA film is formed by drying the steel sheet in the air after application. The drying temperature may be 50 to 200 ° C.
〔塗膜〕
上記のように化成処理（塗装前処理）を施して改質ＢＡ皮膜を形成させた鋼板を塗装原板として、通常の塗装工程に供し、改質ＢＡ皮膜の上に塗膜を形成することによって本発明の塗装ＢＡステンレス鋼板が得られる。塗料は、従来からクロムフリー化成処理を施したステンレス鋼板を塗装原板とする塗装ステンレス鋼板に使用されている種々のものが適用可能である。例えばフッ素樹脂系のクリア塗膜を形成すれば、耐久性に優れ、ＢＡ仕上げ表面に特有の光沢外観を活かした従来実現できなかったクリア塗装ＢＡステンレス鋼板が得られる。
[Coating]
The steel sheet, which has been subjected to chemical conversion treatment (pre-painting treatment) to form a modified BA film as described above, is used as a coating base plate, and is subjected to a normal coating process to form a coating film on the modified BA film. The inventive coated BA stainless steel sheet is obtained. As the coating material, various types of paints conventionally used for coated stainless steel sheets using a stainless steel sheet subjected to chromium-free chemical conversion treatment as a coating original sheet can be applied. For example, if a fluororesin-based clear coating film is formed, a clear-coated BA stainless steel sheet that is excellent in durability and takes advantage of the glossy appearance peculiar to the BA finish surface cannot be achieved.
《実施例１》
市販のＳＵＳ４３０ＢＡ仕上げ鋼板（板厚０.５ｍｍ）を入手した。
一方、化成処理液として、フッ化水素チタン酸を１０ｇ／Ｌ、タンニン酸を１０ｇ／Ｌ含有し、ｐＨが１.５に調整され、残部が水で構成されるシンプルな組成のクロムフリー化成処理液を用意した。
Example 1
A commercially available SUS430BA finished steel plate (thickness 0.5 mm) was obtained.
On the other hand, as a chemical conversion treatment solution, a simple composition of chromium-free chemical conversion containing 10 g / L of hydrofluoric titanate and 10 g / L of tannic acid, adjusted to pH 1.5, and the balance of water. A liquid was prepared.
上記ＳＵＳ４３０ＢＡ仕上げ鋼板の片面について、通常の脱脂を行った後、上記化成処理液をフッ化水素チタン酸中のＴｉ換算塗布量１０ｍｇ／ｍ2となるようにロールコーター法にて塗布した。その後、その鋼板を大気中１５０℃の炉中に装入して３０秒間保持することにより化成処理液を乾燥させ、改質ＢＡ皮膜を得た。 About the single side | surface of the said SUS430BA finish steel plate, after performing normal degreasing | defatting, the said chemical conversion liquid was apply | coated by the roll coater method so that it might become the application amount of 10 mg / m < 2 > of Ti conversion in hydrofluoric titanate. Thereafter, the steel sheet was placed in a furnace at 150 ° C. in the atmosphere and held for 30 seconds to dry the chemical conversion solution, thereby obtaining a modified BA film.
図１に、ＳＵＳ４３０ＢＡ仕上げ鋼板のＢＡ皮膜について、ＸＰＳにより深さ方向の元素分析を行った結果を示す。縦軸の原子％は表示されている元素の全カウント数を１００とした場合の相対的な原子％である（後述図２、図３において同じ）。酸素濃度の深さ方向プロファイルから、このＢＡ皮膜の厚さ（酸素濃度が最表層の１／２となる深さ）はＳｉＯ2換算スパッタ深さで約８ｎｍである。皮膜中には最表層までＳｉとＣｒが濃化していることがわかる。 FIG. 1 shows the results of elemental analysis in the depth direction by XPS for the BA film of the SUS430BA finished steel sheet. The atomic% on the vertical axis is the relative atomic% when the total count of the displayed elements is 100 (the same applies to FIGS. 2 and 3 described later). From the profile of the oxygen concentration in the depth direction, the thickness of this BA film (the depth at which the oxygen concentration is ½ of the outermost layer) is about 8 nm in terms of the SiO 2 equivalent sputtering depth. It can be seen that Si and Cr are concentrated in the film up to the outermost layer.
図２に、上記化成処理後の改質ＢＡ皮膜について、ＸＰＳにより深さ方向の元素分析を行った結果を示す。酸素濃度の深さ方向プロファイルから、このＢＡ皮膜の厚さ（酸素濃度が最表層の１／２となる深さ）はＳｉＯ2換算スパッタ深さで約８ｎｍであり、化成処理前（図１のもの）と同等であった。皮膜中には最表層までＳｉとＣｒが濃化していることには変わりないが、最表層を含む皮膜表層部にはＴｉおよびＳｉが検出された。Ｔｉが検出された領域は、化成処理液によってエッチングされ、ＢＡ皮膜中の成分（例えばＳｉ）を取り込みながら新たな化成処理皮膜が形成された領域（すなわちクロムフリー化成処理皮膜）であると考えられる。クロムフリー化成処理皮膜においてＴｉの濃度は深さ方向に進むに従って傾斜的に減少している。改質ＢＡ皮膜のメタル界面付近にはＴｉが存在せず、化成処理前の皮膜組成が概ねそのまま維持されている領域がある（７.５ｎｍ深さのデータ参照）。このことから、得られた改質ＢＡ皮膜は、元のＢＡ皮膜の最表層を含む一部の深さ領域が化成処理液によってエッチングされて改質されたものであると言える。すなわち、この改質ＢＡ皮膜はＢＡ皮膜中の成分（Ｓｉなど）を取り込んだ傾斜形態をとる化成処理皮膜を上層に持ち、下層部に元のＢＡ皮膜部分を持つ複層構造を呈している。 FIG. 2 shows the results of elemental analysis in the depth direction by XPS for the modified BA film after the chemical conversion treatment. From the depth profile of the oxygen concentration, the thickness of this BA film (the depth at which the oxygen concentration is ½ of the outermost layer) is about 8 nm in terms of the SiO 2 equivalent sputtering depth, and before the chemical conversion treatment (in FIG. 1). ). In the film, Si and Cr were concentrated to the outermost layer, but Ti and Si were detected in the film surface layer portion including the outermost layer. The region where Ti is detected is considered to be a region where a new chemical conversion film is formed while the component (for example, Si) is etched by the chemical conversion solution and a component (for example, Si) is taken in (ie, a chromium-free chemical conversion film). . In the chromium-free chemical conversion coating, the Ti concentration decreases in a slope as it progresses in the depth direction. In the vicinity of the metal interface of the modified BA film, there is a region where Ti is not present and the film composition before the chemical conversion treatment is maintained as it is (see data at a depth of 7.5 nm). From this, it can be said that the obtained modified BA film was modified by etching a part of the depth region including the outermost layer of the original BA film with the chemical conversion solution. That is, this modified BA film has a multilayer structure having a chemical conversion treatment film having an inclined form incorporating components (such as Si) in the BA film in the upper layer and the original BA film portion in the lower layer.
次に、この改質ＢＡ皮膜の上に、従来塗装ステンレス鋼板用として一般的に使用されているポリエステル樹脂系クリア塗料をロールコーター法にて塗布し、２３０℃で焼き付けることにより平均塗膜厚さ１０μｍのクリア塗膜を形成した。その後、この塗膜表面にカッターナイフにより１ｍｍ間隔の平行な直線状のカットを一定方向に１１本入れ、さらにそれらに直角の方向に１１本入れることにより、碁盤目状のカットを形成し、その碁盤目の部分についてＪＩＳ Ｚ１５２２に規定されるセロハン粘着テープを使用して塗膜剥離試験を実施し、セロハン粘着テープを貼付した目のうち、塗膜が剥離した目の割合を測定した。この塗膜剥離率が２％以下であれば、従来一般的なクリア塗装ステンレス鋼板と遜色のない実用的な塗膜密着性を有していると判断される。
本例のものは、繰り返し数ｎ＝３で上記の塗膜剥離試験を行った結果、最も成績の悪い場合の塗膜剥離率が１％であり、良好な塗膜密着性を有していることが確認された。
Next, on this modified BA film, a polyester resin-based clear paint which has been generally used for a conventional stainless steel sheet is applied by a roll coater method and baked at 230 ° C. to obtain an average coating thickness. A 10 μm clear coating film was formed. After that, 11 straight straight cuts with a 1 mm interval are put in a fixed direction on the surface of the coating film, and 11 cuts are made in a direction perpendicular to them to form a grid-like cut. A coating film peeling test was carried out using the cellophane adhesive tape defined in JIS Z1522 for the grid area, and the ratio of the eyes where the coating film was peeled out of the eyes to which the cellophane adhesive tape was applied was measured. If this coating film peeling rate is 2% or less, it is judged that it has practical coating film adhesion comparable to conventional clear-coated stainless steel sheets.
As a result of performing the above-mentioned coating film peeling test with the repetition number n = 3, the coating film peeling rate in the worst case is 1%, and this example has good coating film adhesion. It was confirmed.
《比較例１》
化成処理液として、（ＮＨ4）2ＴｉＦ6を１６ｇ／Ｌ、Ｈ3ＰＯ4を４０ｇ／Ｌ、タンニン酸を４ｇ／Ｌ含有し、ｐＨが１.８に調整され、残部が水で構成される従来のクロムフリー化成処理液を使用するとともに、この化成処理液はエッチング力が比較的弱いことを考慮してＴｉ換算塗布量が４０ｍｇ／ｍ2となるように多めに塗布したことを除き、実施例１と同様の方法で実験を行った。
<< Comparative Example 1 >>
The chemical conversion treatment solution contains (NH 4 ) 2 TiF 6 (16 g / L), H 3 PO 4 (40 g / L) and tannic acid (4 g / L), the pH is adjusted to 1.8, and the balance is composed of water. In addition to using a conventional chromium-free chemical conversion treatment solution, and considering that the chemical conversion treatment solution has a relatively weak etching power, it was applied in a large amount so that the Ti conversion coating amount was 40 mg / m 2 , The experiment was performed in the same manner as in Example 1.
図３に、上記化成処理後の皮膜について、ＸＰＳにより深さ方向の元素分析を行った結果を示す。化成処理液のエッチング力が弱いために、皮膜は単に膜厚が増大しているだけであり、化成処理液に由来するＴｉは最表層にしか検出されなかった。すなわち、皮膜深さ方向におけるＴｉ濃度の傾斜傾向は認められず、表面からＳｉＯ2換算スパッタ深さが少なくとも２.５ｎｍまでの領域にＴｉとＳｉの両方が存在するような改質ＢＡ皮膜は形成されていなかった。
得られた塗膜面を目視により観察した結果、テンパーカラーの発生は認められなかった。しかし、塗膜剥離試験の結果、ｎ＝３のうち最も成績の良かった場合の塗膜剥離率が１０％であり、塗膜密着性の良好な塗装ＢＡステンレス鋼板は得られなかった。
In FIG. 3, the result of having conducted the elemental analysis of the depth direction by XPS about the film | membrane after the said chemical conversion treatment is shown. Since the etching power of the chemical conversion solution is weak, the film only has an increased film thickness, and Ti derived from the chemical conversion solution was detected only on the outermost layer. That is, there is no tendency to tilt Ti concentration in the film depth direction, and a modified BA film in which both Ti and Si are present in the region from the surface to a SiO 2 equivalent sputtering depth of at least 2.5 nm is formed. Was not.
As a result of visual observation of the obtained coating film surface, generation of temper color was not recognized. However, as a result of the coating film peeling test, the coating film peeling rate when n = 3 was the best was 10%, and a coated BA stainless steel sheet with good coating film adhesion was not obtained.
なお、上記の各ＸＰＳ分析は以下の条件で行ったものである。
〔ＸＰＳ分析条件〕
・使用装置： ＰＨＩ社製；１６００Ｓ型 Ｘ線光電子分光装置
・測定条件： Ｘ線源；ＡｌＫα（４００Ｗ）
脱出深さ；２.７ｎｍ（ＳｉＯ2換算）
分析領域；最表面のワイドスペクトル０.８×２.０ｍｍ
エッチング面０.８ｍｍφ
・エッチング： Ａｒイオン銃使用
・エッチング領域： ３×３ｍｍ（設定値４×２ｍｍ）
・エッチング速度： １.８７ｎｍ／ｍｉｎ（ＳｉＯ2換算）
・デプス測定は最表面のナロースペクトルを２回測定した後、「１.３４ｍｉｎエッチング→スペクトル測定」のサイクルを１０回繰り返して行った（ＳｉＯ2換算で２５ｎｍまで１０水準測定）。
The above XPS analyzes were performed under the following conditions.
[XPS analysis conditions]
-Equipment used: manufactured by PHI; 1600S type X-ray photoelectron spectrometer-Measurement conditions: X-ray source; AlKα (400 W)
Escape depth: 2.7 nm (in terms of SiO 2 )
Analysis area: outermost wide spectrum 0.8 × 2.0 mm
Etching surface 0.8mmφ
・ Etching: Ar ion gun used ・ Etching area: 3 × 3 mm (set value 4 × 2 mm)
Etching rate: 1.87 nm / min (SiO 2 equivalent)
Depth measurement was performed by measuring the narrow spectrum on the outermost surface twice and then repeating the cycle of “1.34 min etching → spectrum measurement” 10 times (10 level measurement up to 25 nm in terms of SiO 2 ).
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