JPH04120294A - Method for undercoating treatment for stainless steel - Google Patents
Method for undercoating treatment for stainless steelInfo
- Publication number
- JPH04120294A JPH04120294A JP24076790A JP24076790A JPH04120294A JP H04120294 A JPH04120294 A JP H04120294A JP 24076790 A JP24076790 A JP 24076790A JP 24076790 A JP24076790 A JP 24076790A JP H04120294 A JPH04120294 A JP H04120294A
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- zinc phosphate
- electrode
- corrosion resistance
- sus
- 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
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 22
- 239000010935 stainless steel Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 13
- 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 abstract description 19
- 229910000165 zinc phosphate Inorganic materials 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims description 12
- 239000003973 paint Substances 0.000 claims description 11
- 238000010422 painting Methods 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 23
- 239000011248 coating agent Substances 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 9
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 abstract description 6
- 239000011701 zinc Substances 0.000 abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 239000011247 coating layer Substances 0.000 abstract 1
- 229910052745 lead Inorganic materials 0.000 abstract 1
- 239000011133 lead Substances 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 29
- 238000000465 moulding Methods 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 8
- 235000021317 phosphate Nutrition 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- -1 hydrogen ions Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical group 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- 229910017108 Fe—Fe Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はステンレススチールの塗装下地処理方法、更に
詳しくは塗装すべきステンレススチールの表面を、塗装
に先立って処理する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for treating a stainless steel surface for painting, and more particularly to a method for treating a stainless steel surface to be painted prior to painting.
（従来の技術）
自動車には装飾効果、保護効果等を目的として、金属光
沢や黒色、有彩色を有する線状や帯状のモールが車内外
に装着されている。(Prior Art) Linear or band-shaped moldings having metallic luster, black, or chromatic colors are installed inside and outside the vehicle for the purpose of decoration, protection, etc.
各種のモールのうち、例えばウィンドシールドモール、
ジヨイントモール等の自動車外装用モールにおいては、
モール端部からの赤錆発生によって外板が汚染され易い
ことから、外装用モールの基材には錆びにくいステンレ
ススチール（ＳＵＳ）が用いられている。又、モールの
殆どは有色モールであることが要求されており、ＳＵＳ
基材を塗装するか、或いはポリ塩化ビニルの共押出し成
形によってＳＵＳ基材表面を着色したポリ塩化ビニル層
で被覆することにより着色モールが製造されてきた。Among various malls, for example, Windshield Mall,
In automobile exterior moldings such as joint moldings,
Since the outer panel is easily contaminated by red rust generated from the edges of the molding, rust-resistant stainless steel (SUS) is used as the base material of the exterior molding. In addition, most of the moldings are required to be colored moldings, and SUS
Colored moldings have been produced by coating the substrate or by coating the SUS substrate surface with a colored polyvinyl chloride layer by coextrusion of polyvinyl chloride.
着色モールの製造方法としては、上記方法以外にも種々
の方法が提案されている。例えば、特開平１−１８４０
８１号公報には、ＳＵＳ基材に亜鉛メツキ層を形成させ
た後、リン酸亜鉛化成処理を行い、次いで非塗装部位に
マスキングを施してから着色塗装し、塗装焼付後にマス
キングをはずし、非塗装部位の亜鉛メツキ層を溶解除去
して、その部位の金属表面を不動態化する部分着色モー
ルの製造方法が開示されている。In addition to the above methods, various methods have been proposed for producing colored moldings. For example, JP-A-1-1840
Publication No. 81 discloses that after forming a galvanized layer on a SUS base material, a zinc phosphate chemical conversion treatment is performed, then masking is applied to non-painted areas, and then color painting is applied, and after the paint is baked, the masking is removed and the non-painted areas are coated. A method for producing a partially colored molding is disclosed, in which the galvanized layer in the area is dissolved and removed to passivate the metal surface in that area.
ところで、一般に塗膜の素地（鋼板）への密着性を向上
させるためにリン酸亜鉛系の処理液（例えば、日本ペイ
ント製５Ｄ５０００Ａ、日本パー力うイジング製ＰＢ−
Ｌ３０８０）を用いた素地の化成処理が有効であること
が知られている。リン酸亜鉛化成処理によって、鋼板表
面には（Ｚｎ ＊ Ｆｅ）ｈＨｚ（ＰＯ４）４Ｈ２０で
表わされる組成を有する皮膜が生成する。By the way, in order to improve the adhesion of the coating film to the substrate (steel plate), zinc phosphate treatment solutions (for example, 5D5000A manufactured by Nippon Paint, PB- manufactured by Nippon Paint) are generally used.
It is known that chemical conversion treatment of the substrate using L3080) is effective. By the zinc phosphate chemical conversion treatment, a film having a composition represented by (Zn*Fe)hHz(PO4)4H20 is generated on the surface of the steel sheet.
鋼板をリン酸亜鉛系処理液に浸漬すると、以下の反応が
起こる。When a steel plate is immersed in a zinc phosphate treatment solution, the following reaction occurs.
１）初期反応
次式（Ｉ）により、リン酸による鋼板面の溶解腐食が起
こる。1) Initial reaction According to the following formula (I), phosphoric acid causes dissolution corrosion of the steel plate surface.
Ｆｅ−Ｆｅ”＋２ｅ−（Ｉ） −アノード反応ここで
生じた電子ｅ−は、カソード部で水素イオンＨ＋と反応
して次式（ｎ）によりＨ”を還元する。Fe-Fe''+2e-(I) -Anode reaction The electron e- generated here reacts with hydrogen ion H+ at the cathode part to reduce H'' according to the following formula (n).
２Ｈ”＋２ ｅ−Ｈ２（ＩＩ） −−−カソード反応
アノード反応とカソード反応が同時に進行して、処理液
中の遊離酸による鋼板面の腐食が起こる。これにより、
水素イオンが消耗され鋼板面のｐＨが上昇するため次式
（ＩＩＩ）により皮膜生成が起こる。2H”+2 e-H2(II) ---Cathode reaction The anode reaction and cathode reaction proceed simultaneously, causing corrosion of the steel plate surface due to the free acid in the treatment solution.
Since hydrogen ions are consumed and the pH of the steel plate surface increases, film formation occurs according to the following formula (III).
Ｆｅ＋２ＨｓＰＯｉ−Ｆｅ （８２ＰＯ４） ｔ＋Ｈｚ
（Ｉ［［）・遊離酸消費反応
２）成長反応
処理液中の亜鉛イオン及び鉄イオンとリン酸との間に成
立していた次式（ＩＶ）、 （Ｖ）及び（ＶＩ）の平
衡が破れて右側に移行し、水溶性の第一リン酸塩が分解
して非水溶性の第二及び第三リン酸塩と遊離リン酸を生
じるので、鋼板面に皮膜が成長する。Fe+2HsPOi-Fe (82PO4) t+Hz
(I[[)・Free acid consumption reaction 2) Growth reaction The equilibrium of the following formulas (IV), (V) and (VI) that was established between zinc ions and iron ions in the treatment solution and phosphoric acid is It breaks and moves to the right side, and the water-soluble primary phosphate decomposes to produce water-insoluble secondary and tertiary phosphates and free phosphoric acid, and a film grows on the surface of the steel plate.
Ｚｎ （８２ＰＯ４）！−ＺｎＨＰＯａ＋Ｈ２ＰＯ４
（Ｎ）Ｆｅ （Ｈ２ＰＯ４）２ ＦｅＨＰＯ４＋
ＨｚＰＯａ （Ｖ）ＺｎＨＰＯｎ＋ＦｅＨＰＯｓ−ｍ＝
（Ｚ ｎ ” Ｆ ｅ ’） ６Ｈ２（Ｐ ０４） ４
＋Ｈｓｐ ０４ （ＶＩ）上記の各式をまとめると次
式（■）となる。Zn (82PO4)! -ZnHPOa+H2PO4
(N)Fe (H2PO4)2 FeHPO4+
HzPOa (V)ZnHPOn+FeHPOs-m= (Z n ” Fe ') 6H2 (P 04) 4
+Hsp 04 (VI) The above equations are summarized as the following equation (■).
Ｚｎ （ＨｉＰＯ４）ｔ＋Ｆｅ （Ｈ＊ＰＯ４）２
（Ｚｎ ＊ Ｆ ｅ） ｓＨｚ （Ｐ ０４）
４＋４８ＩＰＯ４（■）
なお、初期には溶出した鉄イオン濃度が高くなり鉄イオ
ンの一部が先にカソード部に析出することとなるため、
Ｆｅｓ （ＰＯ４）ｘ・ＦｅＨＰＯａが結晶核となって
成長する。Zn (HiPO4)t+Fe (H*PO4)2
(Zn * Fe) sHz (P 04)
4+48IPO4 (■) In addition, initially, the concentration of eluted iron ions becomes high and some of the iron ions precipitate at the cathode, so
Fes(PO4)x·FeHPOa grows as a crystal nucleus.
（発明が解決しようとする課題）
ＳＵＳ基材においては、塗装によって着色しようとして
も表面が不動態であるため、塗膜のＳＵＳ基材に対する
密着性が不十分であり、短期間で塗膜が剥離するという
欠点があった。この剥離は、モールの意匠的効果を損な
わせる。(Problem to be solved by the invention) Even if an attempt is made to color the SUS base material by painting, the surface is passive, so the adhesion of the paint film to the SUS base material is insufficient, and the paint film will fade in a short period of time. It had the disadvantage of peeling. This peeling impairs the design effect of the molding.
上記不具合を防止する目的で、ＳＵＳ基材上にブライマ
ーを塗布してから着色塗装を行う方法も試みられている
が、ＳＵＳ基材素地に対して強い付着性を示すブライマ
ーは無いのが現状である。又、ＳＵＳ基材に対して上記
リン酸亜鉛系処理液を用いた化成処理を行おうとしても
、ＳＵＳ基材の表面が不動態化しているため、上記式（
Ｉ）で表わされる反応が起こらず、そのためそれ以後の
式（ｎ）ないしく■）で表わされる反応も起こらないの
で、リン酸亜鉛系皮族は得られない。In order to prevent the above-mentioned problems, attempts have been made to apply a brimer on the SUS base material and then apply colored coating, but at present there is no brimer that shows strong adhesion to the SUS base material. be. In addition, even if an attempt is made to perform chemical conversion treatment on the SUS base material using the above zinc phosphate treatment liquid, the surface of the SUS base material is passivated, so the above formula (
Since the reaction represented by I) does not occur, and therefore the subsequent reactions represented by formulas (n) to 2) also do not occur, a zinc phosphate-based skin group cannot be obtained.
他方、着色したポリ塩化ビニルの共押出し成形によりＳ
ＵＳ基材表面を被覆しようとする場合には、ポリ塩化ビ
ニル層のＳＵＳ基材表面に対する密着性は十分であって
もポリ塩化ビニル層の耐候性が不十分であり、早期に表
面の劣化をきたし、艶の低下やひび割れ等が起こるとい
う欠点があった。この現象を防止するために、ポリ塩化
ビニル層上を更に塗装することも考えられるが、作業工
程が多くなり且つコスト高となるため、一般的ではない
。On the other hand, by coextrusion molding of colored polyvinyl chloride, S
When trying to coat the surface of a US base material, even if the adhesion of the polyvinyl chloride layer to the surface of the SUS base material is sufficient, the weather resistance of the polyvinyl chloride layer is insufficient, causing early surface deterioration. However, there were drawbacks such as a decrease in gloss and the occurrence of cracks. In order to prevent this phenomenon, it is conceivable to further coat the polyvinyl chloride layer, but this is not common because it requires many work steps and increases costs.
又、特開平１−１８４０８１号公報に開示された方法は
、多くの工程が必要となり煩雑である。Further, the method disclosed in Japanese Patent Application Laid-Open No. 1-184081 requires many steps and is complicated.
本発明は上記従来技術の問題点を解決するためのもので
ある。本発明の目的は、ＳＵＳ基材表面のリン酸亜鉛系
処理液による処理を可能とする方法を提供することにあ
る。The present invention is intended to solve the problems of the prior art described above. An object of the present invention is to provide a method that enables the surface of an SUS substrate to be treated with a zinc phosphate treatment liquid.
（課題を解決するための手段）
本発明のステンレススチールの塗装下地処理方法は、塗
装下地処理を行うべきステンレススチール基材を一方の
電極となし、導電性物質を他方の電極となし、両電極を
リン酸亜鉛系処理液中に浸漬した後、両電極間にＰＲパ
ルス電流を流して電解するという特徴を有している。(Means for Solving the Problems) The stainless steel paint base treatment method of the present invention uses a stainless steel base material to be subjected to paint base treatment as one electrode, a conductive substance as the other electrode, and both electrodes. It has the characteristic that after the electrode is immersed in a zinc phosphate treatment solution, a PR pulse current is passed between both electrodes to cause electrolysis.
塗装下地処理を行うべきステンレススチール基材の材質
、大きさ、形状等の性状は、目的とする製品の性状に応
じて適宜選択する。材質としては、例えばＪＩＳ規格の
ＳＵＳ材を用いることができる。The material, size, shape, and other properties of the stainless steel base material to be subjected to surface treatment for painting are appropriately selected depending on the properties of the intended product. As the material, for example, a JIS standard SUS material can be used.
導電性物質は、導電性の物質であれば材質、大きさ、形
状等の性状は特に限定されず、例えば所望性状のＳＵＳ
板、パラジウム板、鉛板、鉄板等を用いてよい。The conductive substance is not particularly limited in properties such as material, size, shape, etc. as long as it is conductive. For example, SUS with desired properties can be used.
A plate, palladium plate, lead plate, iron plate, etc. may be used.
リン酸亜鉛系処理液は、市販のもの例えば前述の日本ペ
イント製５Ｄ５０００Ａ、 日本パー力うイジング製
ＰＢ−Ｌ３０８０等を用いることができる。As the zinc phosphate treatment liquid, commercially available ones such as the aforementioned Nippon Paint Co., Ltd. 5D5000A, Nippon Par Ising Co., Ltd. PB-L3080, etc. can be used.
Ｐ Ｒ（Ｐｕｌｓｅ Ｒｅｐｅｔｉｔｉｏｎ、パルス繰
り返し）パルス電流の等通条件は、所望の塗装下地処理
ができるように選択するが、以下の条件が好ましい。即
ち、第２図に示す如＜ ＳＵＳ基材を陽極、対極を陰極
とした場合のパルス時間をｔｏｌ、パルス電流をｉ、４
：陽極と陰極とを交換した場合のパルス時間をｔｏ、−
、パルス電流をｉ、−：休止時間をｊ＠ＴＴ；デユーテ
ィサイクル（θ）をθ＝（ｔ、、”＋ｔ、、−）／ （
ｔ、、’＋ｔ、、−＋ｔ、ｔｒ＞とすると、
０．００１≦θ≦０．１
望ましくは
０．０１≦θ≦０．１
である。P R (Pulse Repetition) The conditions for uniform pulse current are selected so that the desired coating base treatment can be achieved, and the following conditions are preferred. That is, as shown in Fig. 2, the pulse time is tol, the pulse current is i, and 4
: Pulse time to, - when the anode and cathode are replaced
, pulse current i, -: pause time j@TT; duty cycle (θ) θ=(t,,"+t,,-)/(
t,,'+t,,-+t,tr>, then 0.001≦θ≦0.1, preferably 0.01≦θ≦0.1.
又、１．４通電時のパルス電流密度をｄ（ｔｔ”″）／
ｄＳ〔ＳはＳＵＳ基材の処理面積（ｄｎｆ））とすると
、
０．０１Ａ／ｄｒｒｒ≦ｄ（ｉ 、”）／ｄＳ≦３０Ａ
／ｄｍ望ましくは
０．１Ａ／ｄＴｄ≦ｄ（ｉ 、”）／ｄＳ≦３Ａ／ｄｒ
ｄである。In addition, the pulse current density during 1.4 energization is d(tt"")/
dS [S is the treated area (dnf) of the SUS base material], then 0.01A/drrr≦d(i,”)/dS≦30A
/dm preferably 0.1A/dTd≦d(i,”)/dS≦3A/dr
It is d.
又、ｔ 、４とｉ、−との絶対値の比（ｉ比）０．２５
≦ｌ ｉ、−ｌ／ｌ ｉ、”ｌ≦０．７５望ましくは
０．４５≦ｌ ｉ−Ｉ／Ｉ ｉ、”ｌ≦０．５５である
。Also, the ratio of the absolute values of t, 4 and i, - (i ratio) is 0.25
≦l i, -l/l i, ``l≦0.75, preferably 0.45≦l i-I/I i, ``l≦0.55.
更に、ｔｌ、４とｔｏ、−との比（を比）は、１≦ｔ
、、−／ ｔ 、、”≦４
望ましくは
１．８≦ｔ 、、−／ ｔ 、、”≦２．２は、
である。Furthermore, the ratio between tl,4 and to,- is 1≦t
,,-/t,,"≦4, preferably 1.8≦t,,-/t,,"≦2.2.
上記の如くリン酸亜鉛系処理液中で電解処理したＳＵＳ
基材は、次いで適する塗料例えばメラミンアルキッド樹
脂系塗料（例えば関西ペイント製アラミックＴＭ−１３
）を用いて常法により塗装する。SUS electrolytically treated in zinc phosphate treatment solution as above
The substrate is then coated with a suitable paint such as a melamine alkyd resin paint (e.g. Aramic TM-13 manufactured by Kansai Paint Co., Ltd.).
) using a conventional method.
（作用） ＳＵＳ基材表面では以下の反応が起こる。(effect) The following reactions occur on the surface of the SUS base material.
１）パルス電流ｉ、４（パルス時間ｔ ａｍつを流すと
次式（■）及び（ＩＸ）で表わされる反応が起こり、Ｓ
ＵＳ基材表面の鉄成分が一部溶解する。1) When pulse current i, 4 (pulse time t am) is passed, reactions expressed by the following equations (■) and (IX) occur, and S
Part of the iron component on the surface of the US base material is dissolved.
Ｆ ｅ −Ｆ ｅ ”″）＋２ｅ−（■＞ −・主反
応２ ＨｔＯ−０＊＋ ４８”＋ ４ ｅ −（ＩＸ）
・−・副反応、ｐＨ上昇
２）パルス電流ｉ、−（パルス時間ｔ。−）ヲ流すと次
式（Ｘ）及び（ＸＩ）で表わされる反応が起こり、水の
電気分解により水素ガスが発生して界面ｐＨが上昇し、
処理液中の遊離酸（リン酸）と鉄成分とが反応して皮膜
が生成する。F e −F e ”″)+2e-(■> −・Main reaction 2 HtO-0*+ 48”+ 4 e −(IX)
・-・Side reaction, pH increase 2) When pulse current i, - (pulse time t.-) is passed, reactions expressed by the following formulas (X) and (XI) occur, and hydrogen gas is generated by electrolysis of water. and the interfacial pH increases,
The free acid (phosphoric acid) in the treatment solution reacts with the iron component to form a film.
２ＨｔＯ＋２ ｅ−Ｈｚ↑＋２０Ｈ−（Ｘ）Ｆｅ″”＋
２ ＨＩＰ ０４＋ ２ ｅ −Ｆ ｅ （ＨｔＰ
０４）＋Ｈ，↑（ＸＩ）
３）パルス電流体止（休止時間ｔ、ｔｔ’）時に、処理
液中の亜鉛イオン及び鉄イオンとリン酸との間に成立し
ていた前記式（ＩＶ）、 （Ｖ）及び（■）の平衡が
破れて右側に移行し、水溶性の第一リン酸塩が分解して
非水溶性の第二及び第三リン酸塩と遊離リン酸を生じる
ので、ＳＵＳ基材表面に皮膜が成長する。2HtO+2 e-Hz↑+20H-(X)Fe″”+
2 HIP 04+ 2 e -Fe (HtP
04) +H, ↑ (XI) 3) The above formula (IV) that was established between zinc ions and iron ions in the treatment liquid and phosphoric acid when the pulse current stopped (rest time t, tt'), The equilibrium of (V) and (■) is broken and shifts to the right, and the water-soluble primary phosphate decomposes to produce water-insoluble secondary and tertiary phosphates and free phosphoric acid. A film grows on the surface of the base material.
４）上記１）ないし３）の反応を繰り返すことにより、
ＳＵＳ基材表面に緻密で細かい結晶粒のリン酸亜鉛系皮
膜が形成される。この皮膜は、後に施す着色層の塗膜の
十分な密着性を得るための下地となるとともに、それ自
体の良好な耐蝕性とＳＵＳ基材自体の良好な耐蝕性とが
相まって、より一層耐候性及び耐蝕性を向上させる。4) By repeating the reactions 1) to 3) above,
A zinc phosphate film with dense and fine crystal grains is formed on the surface of the SUS substrate. This film serves as a base for obtaining sufficient adhesion for the colored layer that will be applied later, and the combination of its own good corrosion resistance and the good corrosion resistance of the SUS base material makes it even more weather resistant. and improve corrosion resistance.
（実施例） 以下に、本発明の詳細な説明する。(Example) The present invention will be explained in detail below.
第１図に示す如く、ＳＵＳ基材１とＳＵＳ板２（又は鉄
板等でもよい）とを電源３に接続して処理槽４中の所定
のリン酸亜鉛系処理液５に浸漬し、次いでＳＵＳ基材１
とＳＵＳ板２との間にＰＲパルス電流を１０分間流して
電解した。As shown in FIG. 1, a SUS base material 1 and a SUS plate 2 (or a steel plate, etc. may be used) are connected to a power source 3 and immersed in a predetermined zinc phosphate treatment solution 5 in a treatment tank 4. Base material 1
A PR pulse current was passed between the substrate and the SUS plate 2 for 10 minutes to perform electrolysis.
デユーティサイクル（θ）、パルス電流密度：ｄ（１＊
”）／ｄｓ 、 ｉ ｗ’とｉ、−との絶対値の比（
ｉ比）、ｔ＠ＩＩとｔ ａｓ−との比（を比）を種々に
変化させて、試験品を作製した。Duty cycle (θ), pulse current density: d(1*
”)/ds, the ratio of the absolute values of i w' and i, - (
Test products were prepared by variously changing the ratio of t@II and t as-.
上記電解処理後、ＳＵＳ基材１をリン酸亜鉛系処理液５
から引き上げた後乾燥させた。次いでＳＵＳ基材１の表
面にメラミンアルキッド樹脂系塗料を塗装後、４０℃の
脱イオン水槽に試験品を浸漬し、４８時間経過後水槽よ
り取り出し、２１１ｍ角のゴバン目を塗膜に切り（ＩＯ
Ｘ １０＝１００目）ニチバン社製セロテープを用いて
塗膜剥離試験を行った。この結果を第１表に示す。評価
は、ゴバン目１００目当たりの剥離個数を数えることに
より行った。剥離個数が少ないほど塗膜のＳＵＳ基材１
に対する密着性が優れていることを示す。After the above electrolytic treatment, the SUS substrate 1 was treated with zinc phosphate treatment solution 5.
After pulling it out, it was dried. Next, after coating the surface of the SUS substrate 1 with a melamine alkyd resin paint, the test specimen was immersed in a deionized water tank at 40°C, and after 48 hours, it was taken out from the water tank and the coating film was cut into 211 m square squares (IO
X 10 = 100 eyes) A coating film peeling test was conducted using cellophane tape manufactured by Nichiban Co., Ltd. The results are shown in Table 1. The evaluation was performed by counting the number of peeled pieces per 100 stitches. The smaller the number of peeled pieces, the better the SUS base material 1 of the coating film.
Indicates excellent adhesion to.
第１表より、以下のことが分かった。From Table 1, the following was found.
１）θについて
■０．００１より小
不溶性リン酸塩の細かい結晶の析出はあるが、ＳＵＳ基
材１の表面の全面を覆えず皮膜となり難い。1) About θ ■ Although fine crystals of insoluble phosphate smaller than 0.001 were precipitated, they could not cover the entire surface of the SUS base material 1 and were difficult to form a film.
■０．１より大
不溶性リン酸塩の大きな結晶粒がＳＵＳ基材１の表面に
疎に析出し、皮膜となり難い。(2) Crystal grains of insoluble phosphate larger than 0.1 precipitate sparsely on the surface of the SUS base material 1, making it difficult to form a film.
２） ｄ（ｉ 、”）／ｄＳ （ｃｘｄ（ｉ 、つ／ｄ
Ｓ〕ニツイテ■０．０１より小
式（■）で表わされる反応が起こり難い。2) d(i,”)/dS (cxd(i, t/d
S] The reaction represented by the small formula (■) is less likely to occur than 0.01.
■３０より大
式（Ｘ）で表わされる反応と次式（ＸＩ［）で表わされ
る反応とが強（起こり、式（ＸＩ）で表わされる反応が
起こり難い。(2) Greater than 30 The reaction represented by the formula (X) and the reaction represented by the following formula (XI[) occur strongly, and the reaction represented by the formula (XI) is difficult to occur.
Ｆｅ”＋２ｅ−Ｆｅ （ＸＩ）
８）ｌ ｉ、−ｌ／ｌ ｉ、”ｌについて■０．２５よ
り小
式（Ｘ）及び式（Ｘ Ｉ ）で表わされる反応が起こり
難い〔式（ＩＸ）で表わされる反応が強（起こり、ｐＨ
が変化し難い〕。Fe"+2e-Fe (XI) 8) l i, -l/l i, "l ■ From 0.25, the reactions represented by the smaller formula (X) and formula (X I ) are less likely to occur [Formula (IX) The reaction represented by is strong (occurs, and the pH
is difficult to change].
■０．７５より大
式（■）で表わされる反応が弱く、式（ＶＩ）で表わさ
れる反応によりリン酸亜鉛系処理液５から不溶性リン酸
塩が直接析出するのみなので、ＳＵＳ基材１の表面に対
する皮膜の密着力が弱い。■The reaction expressed by the larger formula (■) is weaker than 0.75, and insoluble phosphate is only directly precipitated from the zinc phosphate treatment solution 5 due to the reaction expressed by the formula (VI). The adhesion of the film to the surface is weak.
４ ） ｔ 、、７ ｔ 、、”について■ｌより小
式（Ｘ）及び式（ＸＩ）で表わされる反応が起こり難い
〔式（ＩＸ）で表わされる反応が強く起こり、ｐＨが変
化し難い〕。4) Regarding t,, 7 t,, `` ■ Reactions represented by formula (X) and formula (XI) are less likely to occur [reactions represented by formula (IX) occur strongly and pH is difficult to change] .
■４より大
不溶性リン酸塩が大きな結晶粒となり、ＳＵＳ基材１の
表面に対する皮膜の密着力が劣る。(2) Larger insoluble phosphates form larger crystal grains than in 4, and the adhesion of the film to the surface of the SUS base material 1 is poor.
（発明の効果）
上述の如く、本発明のステンレススチールの塗装下地処
理方法は、塗装下地処理を行うべきステンレススチール
基材を一方の電極となし、導電性物質を他方の電極とな
し、両電極をリン酸亜鉛系処理液中に浸漬した後、両電
極間にＰＲパルス電流を流して電解するため、ステンレ
ススチールの表面に不溶性リン酸塩からなる強固な皮膜
を直接形成することができる。このため、任意の形状の
ＳＵＳ基材の表面に簡便迅速に塗装下地処理を行うこと
が可能となり、この塗装下地処理を行ったＳＵＳ基材を
塗装・着色することにより、端部からの錆の発生が無く
、着色塗膜のＳＵＳ基材に対する密着性が優れたステン
レススチール製着色モールを容品に得ることができる。(Effects of the Invention) As described above, the stainless steel coating base treatment method of the present invention uses the stainless steel base material to be coated as one electrode, uses a conductive substance as the other electrode, and connects both electrodes. After immersing the stainless steel in a zinc phosphate treatment solution, a PR pulse current is passed between both electrodes for electrolysis, making it possible to directly form a strong film made of insoluble phosphate on the surface of the stainless steel. For this reason, it is possible to easily and quickly apply a base coating treatment to the surface of an SUS base material of any shape, and by painting and coloring the SUS base material that has undergone this base coat treatment, rust can be removed from the edges. It is possible to obtain a stainless steel colored molding on a container that does not cause generation and has excellent adhesion of the colored coating film to the SUS substrate.
第１図は、本発明のステンレススチールの塗装下地処理
方法の一実施例の説明図、
第２図は、本発明の方法におけるＰＲパルス電流の通電
状態の説明図である。
図中、
１・−・・ＳＵＳ基材 ２・−・−５ＵＳ板 ８・
・−・電源４−・・・処理槽 ５−・リン酸亜鉛
系処理液第
図FIG. 1 is an explanatory diagram of one embodiment of the method for treating the base for coating stainless steel of the present invention, and FIG. 2 is an explanatory diagram of the energization state of the PR pulse current in the method of the present invention. In the figure, 1.--SUS base material 2.--5US plate 8.
・-・Power supply 4-・Processing tank 5-・Zinc phosphate treatment liquid diagram
Claims (1)
方の電極となし、導電性物質を他方の電極となし、両電
極をリン酸亜鉛系処理液中に浸漬した後、両電極間にＰ
Ｒパルス電流を流して電解することを特徴とするステン
レススチールの塗装下地処理方法。One electrode is the stainless steel substrate to be subjected to surface treatment for painting, and the other electrode is a conductive material. After both electrodes are immersed in a zinc phosphate treatment solution, P is applied between the two electrodes.
A method for treating a stainless steel paint surface, which is characterized by electrolyzing by flowing an R pulse current.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24076790A JPH04120294A (en) | 1990-09-11 | 1990-09-11 | Method for undercoating treatment for stainless steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24076790A JPH04120294A (en) | 1990-09-11 | 1990-09-11 | Method for undercoating treatment for stainless steel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04120294A true JPH04120294A (en) | 1992-04-21 |
Family
ID=17064410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24076790A Pending JPH04120294A (en) | 1990-09-11 | 1990-09-11 | Method for undercoating treatment for stainless steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04120294A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993022481A1 (en) | 1992-04-30 | 1993-11-11 | Nippondenso Co., Ltd. | Phosphating process |
| US5645706A (en) * | 1992-04-30 | 1997-07-08 | Nippondenso Co., Ltd. | Phosphate chemical treatment method |
| CN102877097A (en) * | 2012-08-02 | 2013-01-16 | 湖北三江航天红林探控有限公司 | Electroplating method for improving purity of galvanized coating |
-
1990
- 1990-09-11 JP JP24076790A patent/JPH04120294A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993022481A1 (en) | 1992-04-30 | 1993-11-11 | Nippondenso Co., Ltd. | Phosphating process |
| US5645706A (en) * | 1992-04-30 | 1997-07-08 | Nippondenso Co., Ltd. | Phosphate chemical treatment method |
| CN102877097A (en) * | 2012-08-02 | 2013-01-16 | 湖北三江航天红林探控有限公司 | Electroplating method for improving purity of galvanized coating |
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