JPH03249183A - Galvanized steel sheet having excellent press formability and chemical conversion treatability - Google Patents
Galvanized steel sheet having excellent press formability and chemical conversion treatabilityInfo
- Publication number
- JPH03249183A JPH03249183A JP4821090A JP4821090A JPH03249183A JP H03249183 A JPH03249183 A JP H03249183A JP 4821090 A JP4821090 A JP 4821090A JP 4821090 A JP4821090 A JP 4821090A JP H03249183 A JPH03249183 A JP H03249183A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- chemical conversion
- galvanized steel
- colloidal
- zinc
- 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.)
- Granted
Links
- 239000000126 substance Substances 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 24
- 229910001335 Galvanized steel Inorganic materials 0.000 title abstract description 18
- 239000008397 galvanized steel Substances 0.000 title abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims description 42
- 229910052725 zinc Inorganic materials 0.000 claims description 35
- 229910000831 Steel Inorganic materials 0.000 claims description 31
- 239000010959 steel Substances 0.000 claims description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 22
- 238000007747 plating Methods 0.000 abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- 229910052681 coesite Inorganic materials 0.000 abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 6
- 229910001297 Zn alloy Inorganic materials 0.000 description 5
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000007739 conversion coating Methods 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 101100467574 Mus musculus Mras gene Proteins 0.000 description 1
- 229910001455 Ni+ Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BKCGDVXAGFLTDN-UHFFFAOYSA-N [F].P(O)(O)(O)=O.[Zn] Chemical compound [F].P(O)(O)(O)=O.[Zn] BKCGDVXAGFLTDN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、プレス成形性、化成処理性に優れた亜鉛系め
っき鋼板に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a zinc-based plated steel sheet with excellent press formability and chemical conversion treatment properties.
亜鉛めっき鋼板のプレス性を向上させる方法として、例
えば特開昭６２−１８５８８３号公報記載の如く、めっ
き鋼板表面に電解クロメート処理を施し、Ｃｒ２Ｏ：、
の酸化物皮膜を生成せしめる方法や、特開昭６２−１９
２５９７号公報記載の如く、鉄亜鉛合金めっきを施す方
法等の亜鉛系めっき鋼板上に硬い皮膜を形成し、プレス
時のめっきとダイスのかじりを防止してプレスの潤滑性
の向上をはかることが開示されている。As a method of improving the pressability of a galvanized steel sheet, for example, as described in JP-A-62-185883, the surface of the galvanized steel sheet is subjected to electrolytic chromate treatment, and Cr2O:
A method for producing an oxide film of
As described in Publication No. 2597, it is possible to form a hard film on a zinc-based plated steel sheet, such as by applying iron-zinc alloy plating, to prevent galling of the plating and die during pressing and to improve the lubricity of the press. Disclosed.
又特開平１−１３６９５２号公報記載の如く、めっき鋼
板の表面に有機潤滑皮膜や潤滑油等の有機物を塗布、ま
たは被覆しプレス成形性を向上させることが開示されて
いる。Furthermore, as described in JP-A-1-136952, it is disclosed that the surface of a plated steel sheet is coated or coated with an organic substance such as an organic lubricating film or lubricating oil to improve press formability.
しかしながら、このような製品は自動車ユーザーの使用
において、以下のような不十分な点がある。However, such products have the following disadvantages when used by automobile users.
自動車ユーザーでの処理工程の概略は、鋼板を油で洗浄
する工程、プレス工程、脱脂工程、化成処理工程、塗装
工程からなっているが、電解クロメート処理鋼板の場合
は、化成処理工程で化成処理皮膜が形成せず、また潤滑
油や潤滑皮膜などを塗布した鋼板の場合は、洗浄工程で
油が落ちるので十分な潤滑性能を発揮しない。さらに、
化成処理前の脱脂工程に負荷がかかりコストが高くなる
。一方、亜鉛系めっき鋼板に鉄−亜鉛合金フラッシュめ
っきを施したものは電解クロメート処理に比較して鋼板
のコストが高くなるという問題点がある。The processing process for automobile users generally consists of the process of cleaning the steel plate with oil, pressing process, degreasing process, chemical conversion process, and painting process, but in the case of electrolytic chromate treated steel plate, chemical conversion treatment is performed in the chemical conversion process. If a steel plate does not form a film or is coated with lubricating oil or a lubricating film, the oil will come off during the cleaning process and it will not exhibit sufficient lubrication performance. moreover,
The degreasing process before chemical conversion treatment is burdensome and increases costs. On the other hand, a zinc-plated steel sheet subjected to iron-zinc alloy flash plating has a problem in that the cost of the steel sheet is higher than that of electrolytic chromate treatment.
本発明はかかる現状み鑑みて、低コストで、化成処理が
可能で、脱脂等の工程に負荷をかけずに製造し得るプレ
ス成形性に優れた亜鉛系めっき鋼板を提供することを目
的とする。In view of the current situation, it is an object of the present invention to provide a zinc-based plated steel sheet that is low cost, can be subjected to chemical conversion treatment, and has excellent press formability that can be manufactured without imposing stress on processes such as degreasing. .
本発明の要旨とするところは、亜鉛系めっき鋼板表面に
Ｍｎ酸化物５〜５００ｍｇ／ｍ２（Ｍｎとして）、リン
酸トコロイダルＳｉＯ２、コロイダルＴｉＯ２、コロイ
ダル７Ｖ２０３の１種又は２種以上１０００■／ボ以下
（Ｐ、 ５ｉｎ２． Ｔｉｅ、、 ７Ｖｚｏ、として）
及びその他酸化物からなる皮膜を被覆したプレス成形性
、化成処理性に優れた亜鉛系めっき鋼板にある。The gist of the present invention is to apply 5 to 500 mg/m2 of Mn oxide (as Mn) to the surface of a zinc-based plated steel sheet, 1000 μ/m of one or more of tocolloidal phosphate SiO2, colloidal TiO2, and colloidal 7V203. Below (as P, 5in2. Tie, 7Vzo)
and other zinc-based plated steel sheets coated with a film made of oxides and having excellent press formability and chemical conversion treatment properties.
本発明の対象とする亜鉛系めっきｍｉとは、例えば溶融
めっき法、電気めっき法、蒸着めっき法、溶射法などの
各種の製造方法によるものがあり、めっき組成としては
純Ｚｎの他、ＺｎとＦｅ、 ＺｎとＮｉ。The zinc-based plating mi that is the object of the present invention can be produced by various manufacturing methods such as hot-dip plating, electroplating, vapor deposition plating, and thermal spraying, and the plating composition includes pure Zn as well as Zn and Fe, Zn and Ni.
Ｚｎと／ＩＪ、ＺｎとＭｎ、 ＺｎとＣｒ、 ＺｎとＴ
ｉ、 ＺｎとＭｇなどＺｎを主成分として、耐食性など
諸機能の向上のためＦｅ、Ｎｔ、 Ｃｏ、Ｎ、 Ｐｂ＋
Ｓｎ、 ｓｂ、 Ｃｕ、 Ｔｌｌ Ｓｌｌ ＢＩ Ｐ
Ｎ、 Ｓ、 Ｏ等の１種ないし２種以上の合金元素およ
び不純物元素を含み、また５ｉＯｚ、 ｋ１２０３など
のセラミック微粒子、ＴｉＯ２、 ＢａＣｒ０．などの
酸化物、アクリル樹脂などの有機高分子をめっき層中に
分散させたものがあり、めっき層の厚み方向で単一組成
のもの、連続的あるいは層状に組成が変化するものがあ
り、さらに多層めっき鋼板では、最上層に、めっき組成
としては純Ｚｎの他、ＺｎとＦｅ、 ＺｎとＮｉ＋ Ｚ
ｎとＡ７．ＺｎとＭｎ、 ＺｎとＣｒ、 ＺｎとＴｉ、
ＺｎとＭｇなどＺｎを主成分として、耐食性などの諸
機能の向上のため１種ないし２種以上の合金元素および
不純物元素を含み、また、５ｉＯ１，Ａｊｔ０３などの
セラミックス微粒子、ＴｉＯ２、 ＢａＣｒ０．などの
酸化物、アクリル樹脂などの有機高分子をめっき層中に
分散させたものがある。Zn and /IJ, Zn and Mn, Zn and Cr, Zn and T
i, Zn and Mg, etc., with Zn as the main component, and Fe, Nt, Co, N, Pb+ to improve various functions such as corrosion resistance.
Sn, sb, Cu, Tll Sll BI P
It contains one or more alloying elements such as N, S, O, etc. and impurity elements, and also contains ceramic fine particles such as 5iOz, k1203, TiO2, BaCr0. There are some types in which organic polymers such as oxides such as acrylic resins are dispersed in the plating layer, some have a single composition in the thickness direction of the plating layer, some have a composition that changes continuously or layered, and In multilayer plated steel sheets, the top layer contains pure Zn, Zn and Fe, Zn and Ni+Z.
n and A7. Zn and Mn, Zn and Cr, Zn and Ti,
The main component is Zn such as Zn and Mg, and contains one or more alloying elements and impurity elements to improve various functions such as corrosion resistance, and also contains ceramic fine particles such as 5iO1, Ajt03, TiO2, BaCr0. There are some types in which oxides such as oxides, organic polymers such as acrylic resins are dispersed in the plating layer.
例えば、溶融亜鉛めっき鋼板、蒸着亜鉛めっき鋼板、鉄
−亜鉛合金化溶融亜鉛めっき鋼板、亜鉛を主とするアル
ミニウム、鉄などの合金溶融亜鉛めっき鋼板、めっき層
断面方向で下層が合金化されている合金化溶融亜鉛めっ
き鋼板（一般にハーフアロイと称する）、片面鉄−亜鉛
合金化溶融亜鉛めっき層、他面溶融亜鉛めっき層からな
るめっき鋼板、これらのめっき層上に電気めっき、蒸着
めっき等により亜鉛、または亜鉛を主成分とし、鉄、ニ
ッケルを含む金属をめっきした鋼板、あるいは、電気亜
鉛めっき鋼板、亜鉛、ニッケル、クロム等合金電気めっ
き鋼板等、更に単一合金層又は多層合金電気めっき鋼板
、亜鉛および亜鉛含有金属の蒸着めっき鋼板等がある。For example, hot-dip galvanized steel sheets, vapor-deposited galvanized steel sheets, iron-zinc alloyed hot-dip galvanized steel sheets, hot-dip galvanized steel sheets made of zinc-based alloys such as aluminum and iron, and the lower layer is alloyed in the cross-sectional direction of the plating layer. Alloyed hot-dip galvanized steel sheet (generally referred to as half-alloy), galvanized steel sheet consisting of an iron-zinc alloyed hot-dip galvanized layer on one side and a hot-dip galvanized layer on the other side, zinc coated on these plating layers by electroplating, vapor deposition plating, etc. or steel sheets plated with metals containing zinc as the main component and iron and nickel, electrogalvanized steel sheets, zinc, nickel, chromium alloy electroplated steel sheets, etc., single alloy layer or multilayer alloy electroplated steel sheets, There are steel sheets coated with zinc and zinc-containing metals.
その他、５ｉＯｚ。Others, 5iOz.
Ｎ２Ｏ３などのセラミックス微粒子、ＴｉＯ□酸化物微
粒子及び有機高分子などを亜鉛又は亜鉛合金めっき中に
分散させた分散めっき鋼板がある。There is a dispersion-plated steel sheet in which ceramic fine particles such as N2O3, TiO□ oxide fine particles, organic polymers, etc. are dispersed in zinc or zinc alloy plating.
このような亜鉛系めっき鋼板の表面に前記のごとき、酸
化物を被覆し、プレス成形性等を向上しようとするもの
である。The surface of such a zinc-based plated steel sheet is coated with an oxide as described above to improve press formability and the like.
即ち、プレスの潤滑性をめっき鋼板に付与するには、め
っき鋼板表面に硬質の皮膜を形成することが有効である
。この点で電解クロメート処理、鉄亜鉛合金めっきは有
効であるが、前者は化成処理皮膜が形成できず、後者は
処理量が多くコスト高になる。That is, in order to impart press lubricity to a plated steel plate, it is effective to form a hard film on the surface of the plated steel plate. Electrolytic chromate treatment and iron-zinc alloy plating are effective in this regard, but the former cannot form a chemical conversion film, and the latter requires a large amount of treatment and is expensive.
これらの解決には、めっき鋼板表面の硬質皮膜としては
、酸化物皮膜であって、かつ化成処理液中で溶融し、化
成処理皮膜を形成できるとともに、皮膜成分が化成処理
液に溶は出しても化成処理に悪影響を与えないものであ
ることが必要である。To solve these problems, the hard coating on the surface of the galvanized steel sheet is an oxide coating, which can be melted in the chemical conversion treatment solution to form a chemical conversion treatment coating, and at the same time, the coating components cannot be dissolved into the chemical conversion treatment solution. It is also necessary that the chemical conversion treatment is not adversely affected.
本発明者らは、このような観点から、亜鉛系めっき鋼板
表面にＭｎ系酸化物皮膜を形成すれば良いことを見出し
た。Ｍｎ系酸化物皮膜はクロメート皮膜と同様ガラス状
の皮膜となり、プレス時にめっきのダイスへのかじりを
抑制し、摺動性を良好とする。さらに、化成処理液には
溶解するためクロメート皮膜と異なり、化成処理皮膜を
形成することができ、また、化成処理皮膜の成分でもあ
るため、化成処理液に溶出しても悪影響はない。From this point of view, the present inventors have discovered that it is sufficient to form a Mn-based oxide film on the surface of a zinc-based plated steel sheet. The Mn-based oxide film forms a glass-like film similar to the chromate film, suppresses galling of the plating onto the die during pressing, and improves sliding properties. Furthermore, since it dissolves in the chemical conversion treatment solution, it can form a chemical conversion coating unlike a chromate coating, and since it is also a component of the chemical conversion coating, there is no adverse effect even if it is eluted into the chemical conversion treatment solution.
Ｍｎ系酸化物皮膜の構造は明確ではないが、Ｍｎ −０
結合、Ｐ−０結合、５ｉ−０結合、Ｔｉ−０結合、Ａｆ
−０結合からなるネットワークが主体で、部分的に−Ｏ
Ｈ，Ｃｏ、基等が、さらにはめっきから供給される金属
が置換したアモルファス状の巨大分子構造であろうと推
定している。The structure of the Mn-based oxide film is not clear, but Mn -0
bond, P-0 bond, 5i-0 bond, Ti-0 bond, Af
The network is mainly composed of -0 bonds, and partially -O
It is presumed that it is an amorphous macromolecular structure in which H, Co, groups, etc. are substituted with metals supplied from plating.
また、Ｍｎ系酸化物皮膜は酸化物皮膜のため、油による
洗浄工程や、脱油工程でも溶解しないので、潤滑性能の
低下や、他の工程に負荷を与えない。Furthermore, since the Mn-based oxide film is an oxide film, it does not dissolve even in the cleaning process with oil or the deoiling process, so it does not reduce the lubricating performance or impose a burden on other processes.
Ｍｎ系酸化物皮膜の密着性、成膜性を向上させるために
リン酸とコロイダルＳｉｎ、、コロイダルＴｉｅ、、コ
ロイダル７Ｖ２０．の１種又は２種以上１０００■／ボ
以下（Ｐ、 ＳｉＯ２、 ＴｆＯ２、 ７１１７．Ｏ，
として）を混入する。かくして、Ｍｎ系酸化物の皮膜構
造が均一化し、成膜性も向上し、プレス成形性が良好に
なり、又化成処理性をも向上することができる。To improve the adhesion and film formability of the Mn-based oxide film, phosphoric acid and colloidal Sin, colloidal Tie, colloidal 7V20. 1 type or 2 or more types and 1000 ■/bo or less (P, SiO2, TfO2, 7117.O,
(as). In this way, the film structure of the Mn-based oxide is made uniform, film formability is improved, press formability is improved, and chemical conversion treatment properties can also be improved.
このような酸化物皮膜は、亜鉛系めっき鋼板を水溶液中
へ浸漬するか、水溶液を散布するか、又は水溶液中で陰
極電解処理することにより確実に生成させることができ
る。このときに前記の如きめっき金属の亜鉛、亜鉛合金
めっきの場合は、亜鉛と合金元素（金属）、水溶液中の
不純物等がその他の酸化物として混入する。Such an oxide film can be reliably produced by immersing a zinc-based plated steel sheet in an aqueous solution, spraying the aqueous solution, or subjecting it to cathodic electrolysis treatment in an aqueous solution. At this time, in the case of zinc or zinc alloy plating of the plating metal as described above, zinc, alloying elements (metals), impurities in the aqueous solution, etc. are mixed in as other oxides.
次に、本発明の皮膜の皮膜量範囲について述べる。Next, the coating amount range of the coating of the present invention will be described.
Ｍｎ酸化物の皮膜量はプレス性を良好とするには、Ｍｎ
として５■／ボ以上あればよいが、皮膜量が５００■／
ｍ２を越えると化成処理皮膜の形成が不十分となる。ゆ
えに、Ｍｎ酸化物の適正な皮膜量は、Ｍｎとして５■／
ボ以上５００．／ｒｒｒ以下、好ましくは５〜２００■
／ボである。For good pressability, the amount of Mn oxide film is
It is sufficient if the coating amount is 5 ■/bo or more, but the film amount is 500 ■/bo or more.
If it exceeds m2, the formation of the chemical conversion film will be insufficient. Therefore, the appropriate amount of Mn oxide film is 5 /
More than 500. /rrr or less, preferably 5 to 200■
/ It's Bo.
次にリン酸とコロイダルＳｉＯ２、コロイダルＴｉＯ２
、コロイダルＡ １２０３の１種又は２種以上の合計量
としては１０００Ｍ／ｍ２以下（Ｐ 、 ５ｉＯｚ、
Ｔｉ０２Ａ１２０３として）、好ましくは２００■／イ
以下がよ＜１０００■／ボ超になると、化成処理性が劣
化することがあり好ましくない。下限は存在していれば
よい。Next, phosphoric acid, colloidal SiO2, colloidal TiO2
, the total amount of one or more types of colloidal A 1203 is 1000 M/m2 or less (P, 5 iOz,
(as Ti02A1203), preferably less than 200 .mu./a, but if it exceeds 1000 .mu./o, the chemical conversion properties may deteriorate, which is not preferable. The lower limit only needs to exist.
次に上記のごとき酸化物皮膜の生成方法としては、例え
ば、過マンガン酸カリウム１ ｇ／ｌ−溶解比、リン酸
１〜６０ ｇ／ｌ、コロイダルＳｉＯ２、コロイダルＴ
ｉＯ２、コロイダルＡｌ２Ｏ３はそれぞれ１〜６０ｇ／
ｆで十分であり、この他エツチング補助剤として硫酸等
を用いるものである。Next, as a method for producing the above oxide film, for example, potassium permanganate 1 g/l-dissolution ratio, phosphoric acid 1 to 60 g/l, colloidal SiO2, colloidal T
iO2 and colloidal Al2O3 are each 1 to 60g/
f is sufficient, and sulfuric acid or the like may also be used as an etching aid.
このような水溶液に前記のごとき亜鉛系めっき鋼板を浸
漬するか、水溶液を散布するか、又は水溶液中で電解処
理することにより確実に皮膜を生成することができる。A film can be reliably formed by immersing the aforementioned zinc-based plated steel sheet in such an aqueous solution, by spraying the aqueous solution, or by electrolytically treating it in the aqueous solution.
次に本発明の実施例を比較例とともに挙げる。 Next, examples of the present invention will be listed together with comparative examples.
めっき鋼板：
ＡＳ：合金化溶融亜鉛めっき鋼板（Ｆｅ １０％、 Ａ
７１０．２５％、残Ｚｎ）、ＥＧ：電気亜鉛めっき鋼板
、 ＧＩ：溶融亜鉛めっき鋼板（Ａ７０．３％、 Ｆｅ
Ｏ，８％、 ＰｂＯ，１％、残Ｚｎ）、ｌ（Ａ：半合
金化溶融亜鉛めっき鋼板（Ｆｅ ５％、 Ａ７０．３％
、残Ｚｎ）、ＣＲ：冷延鋼板、鋼板厚はいずれも０．８
＠ｍの普通鋼。Coated steel sheet: AS: Alloyed hot-dip galvanized steel sheet (Fe 10%, A
710.25%, residual Zn), EG: electrogalvanized steel sheet, GI: hot dip galvanized steel sheet (A70.3%, Fe
O, 8%, PbO, 1%, residual Zn), l (A: semi-alloyed hot-dip galvanized steel sheet (Fe 5%, A70.3%)
, residual Zn), CR: cold rolled steel plate, steel plate thickness is 0.8
@m ordinary steel.
プレス成形性（摩擦係数）：
サンプルサイズ： １７ｍｍ Ｘ ３００ｍｍ 、引張
り速度： ５００ｍｍ／ｍｉｎ、角ビート肩Ｒ： １
．０／３．０ｍｍ、 摺動長： ２００ｍｍ、 塗
油：ノンクスラス）５３０Ｆ−４０（パーカー興産株式
会社）塗油量１ ｇ／ｍ”の条件で、面圧を１００〜６
００ｋｇｆの間で数点試験を行い、引き抜き加重を測定
し、面圧と引き抜き加重の傾きから摩擦係数を求めた。Press formability (friction coefficient): Sample size: 17mm x 300mm, Tensile speed: 500mm/min, Square beat shoulder R: 1
．． 0/3.0mm, sliding length: 200mm, oiling: non-xras) 530F-40 (Parker Kosan Co., Ltd.) with an oiling amount of 1 g/m'' and a surface pressure of 100 to 6
Tests were conducted at several points between 00 kgf, the pull-out load was measured, and the friction coefficient was determined from the surface pressure and the slope of the pull-out load.
注３）化成処理性：
化成処理液（亜鉛−リン酸−弗素系処理浴）には５Ｄ５
０００ （日本ペイント社製）を注１）
注２）
用い、処方どおり脱脂、表面調整を行った後化成処理を
行った。化成処理皮膜の判定は、ＳＥＭ （、２次電子
線像）により、均一に皮膜が形成されているものは○、
部分的に皮膜が形成されているものはΔ、皮膜が形成さ
れていないものは×と判定した。Note 3) Chemical conversion treatment properties: 5D5 is used in the chemical conversion treatment solution (zinc-phosphoric acid-fluorine treatment bath).
000 (manufactured by Nippon Paint Co., Ltd.) (Note 1) Note 2) was used, and after degreasing and surface conditioning as prescribed, a chemical conversion treatment was performed. Chemical conversion coatings are judged by SEM (secondary electron beam image), and if the coating is uniformly formed, it is rated as ○.
Those with a partially formed film were evaluated as Δ, and those with no film formed were evaluated as ×.
注４）酸化皮膜量は、Ｍｎ酸化物二Ｍｎ量、リン酸：Ｐ
量、コロイダルＳｉＯ□： Ｓｉ０ｇ量、コロイダルＴ
ｔ０２ ： ＴｉＯ２、コロイダルｌＶ２Ｏ３：Ｎ ｚ
Ｏ３量でそれぞれ表示。Note 4) Oxide film amount is Mn oxide diMn amount, phosphoric acid: P
Amount, colloidal SiO□: Si0g amount, colloidal T
t02: TiO2, colloidal lV2O3:Nz
Each is displayed as O3 amount.
注５）酸化物生成は、過マンガン酸カリウム３０ｇｅｌ
、リン酸１０ｇ／ｌ、コロイダルＳｉＯ２、コロイダル
Ｔｉ０ｚ、コロイダルＡ／２０．は各４０ｇ／ ｆ、エ
ツチング補助剤として硫酸３ｇ／ｌをそれぞれ選択して
合成し、亜鉛系めっき鋼板の浸漬時間を調整して施し
た。Note 5) For oxide generation, use 30 gel of potassium permanganate.
, phosphoric acid 10g/l, colloidal SiO2, colloidal TiOz, colloidal A/20. 40 g/f each and 3 g/l sulfuric acid as an etching aid were selected and synthesized, and the immersion time of the zinc-based plated steel sheet was adjusted.
本発明によれば、プレス成形において摺動性が冷延鋼板
並以上に向上し、かつ化成処理皮膜も形成可能な亜鉛系
めっき鋼板を提供し得るので、ユーザーの工程における
負荷を低減でき、プレス成形に際しての生産性を向上さ
せることができるなど、本発明は産業上極めて有用であ
る。According to the present invention, it is possible to provide a galvanized steel sheet whose slidability in press forming is improved to a level higher than that of a cold rolled steel sheet, and which is also capable of forming a chemical conversion coating. The present invention is extremely useful industrially, as it can improve productivity during molding.
Claims (1)
＾２（Ｍｎとして）、リン酸とコロイダルＳｉＯ＿２、
コロイダルＴｉＯ＿２、コロイダルＡｌ＿２Ｏ＿３の１
種又は２種以上１０００ｍｇ／ｍ＾２以下（Ｐ，ＳｉＯ
＿２，ＴｉＯ＿２，Ａｌ＿２Ｏ＿３として）及びその他
酸化物からなる皮膜を被覆したことを特徴とするプレス
成形性、化成処理性に優れた亜鉛系めっき鋼板。Mn oxide 5 to 500 mg/m on the surface of zinc-based plated steel sheet
^2 (as Mn), phosphoric acid and colloidal SiO_2,
Colloidal TiO_2, Colloidal Al_2O_3 1
species or two or more species or more and 1000 mg/m^2 or less (P, SiO
_2, TiO_2, Al_2O_3) and other oxides. A zinc-based plated steel sheet with excellent press formability and chemical conversion treatment properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2048210A JPH0696781B2 (en) | 1990-02-28 | 1990-02-28 | Galvanized steel sheet with excellent press formability and chemical conversion treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2048210A JPH0696781B2 (en) | 1990-02-28 | 1990-02-28 | Galvanized steel sheet with excellent press formability and chemical conversion treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03249183A true JPH03249183A (en) | 1991-11-07 |
| JPH0696781B2 JPH0696781B2 (en) | 1994-11-30 |
Family
ID=12797040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2048210A Expired - Lifetime JPH0696781B2 (en) | 1990-02-28 | 1990-02-28 | Galvanized steel sheet with excellent press formability and chemical conversion treatment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0696781B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007092134A (en) * | 2005-09-29 | 2007-04-12 | Jfe Steel Kk | Cold-rolled steel sheet excellent in chemical conversion treatment, and manufacturing method therefor |
| JP2009235431A (en) * | 2008-03-26 | 2009-10-15 | Jfe Steel Corp | Galvanized steel sheet and manufacturing method therefor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5028449A (en) * | 1973-07-17 | 1975-03-24 | ||
| JPS5573875A (en) * | 1978-11-22 | 1980-06-03 | Nippon Steel Corp | Excellently workable mn-plated steel material having pretreatment layer for painting |
| JPS6063394A (en) * | 1983-09-17 | 1985-04-11 | Nippon Steel Corp | Galvanized steel sheet with superior weldability |
| JPH01246398A (en) * | 1988-03-28 | 1989-10-02 | Sumitomo Metal Ind Ltd | Production of composite dispersive particles and composite plating method |
-
1990
- 1990-02-28 JP JP2048210A patent/JPH0696781B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5028449A (en) * | 1973-07-17 | 1975-03-24 | ||
| JPS5573875A (en) * | 1978-11-22 | 1980-06-03 | Nippon Steel Corp | Excellently workable mn-plated steel material having pretreatment layer for painting |
| JPS6063394A (en) * | 1983-09-17 | 1985-04-11 | Nippon Steel Corp | Galvanized steel sheet with superior weldability |
| JPH01246398A (en) * | 1988-03-28 | 1989-10-02 | Sumitomo Metal Ind Ltd | Production of composite dispersive particles and composite plating method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007092134A (en) * | 2005-09-29 | 2007-04-12 | Jfe Steel Kk | Cold-rolled steel sheet excellent in chemical conversion treatment, and manufacturing method therefor |
| JP2009235431A (en) * | 2008-03-26 | 2009-10-15 | Jfe Steel Corp | Galvanized steel sheet and manufacturing method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0696781B2 (en) | 1994-11-30 |
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