JPS59208076A - Surface treatment for preventing corrosion of steel plate - Google Patents
Surface treatment for preventing corrosion of steel plateInfo
- Publication number
- JPS59208076A JPS59208076A JP8176283A JP8176283A JPS59208076A JP S59208076 A JPS59208076 A JP S59208076A JP 8176283 A JP8176283 A JP 8176283A JP 8176283 A JP8176283 A JP 8176283A JP S59208076 A JPS59208076 A JP S59208076A
- Authority
- JP
- Japan
- Prior art keywords
- steel plate
- film
- metal
- coating
- surface treatment
- 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
Landscapes
- Laminated Bodies (AREA)
- Chemically Coating (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【発明の詳細な説明】
この発明は鋼板を防食するための表面処理方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a surface treatment method for preventing corrosion of a steel plate.
従 来 技 術
従来から鋼板の表面を防食するため種々の処理方法が知
られており、例えば「金属表面技術便覧」日Tl1工業
新聞社昭和52年12月25日2版発行には、鉄鋼素地
を防食するため亜鉛めっきをする方法、亜鉛めっきに加
えてクロメート処理を行う方法、ほうろうのようなセラ
ミックコーティング方法および有機質被覆全行う方法な
どが記載され、よく知られている。Conventional technology A variety of treatment methods have been known to prevent corrosion on the surface of steel plates. Methods of galvanizing to prevent corrosion, methods of applying chromate treatment in addition to zinc plating, methods of ceramic coating such as enamel, and methods of completely covering with organic materials have been described and are well known.
しかしながらこのような従来の鋼板表面処理法Gこあっ
ては、亜鉛のような金属のめつきおよび亜鉛めっきに加
えてクロメート処理する方法のいずれの方法についても
鉄素地に達する傷がついた場合に十分な鉄素地防食性が
得られない。更に塗装を施した場合には長期に亘って十
分な塗膜密着性を確保することができないか或いは傷か
ら著しい錆またはふくれを生じ易い。また従来のセラミ
ックコーティングにより無機質被覆を行う方法では被膜
の耐衝撃性、耐熱衝撃性に問題がある。また有機質被覆
を行う方法では鋼板の上を一般に市販されているジンク
ロメタルで被膜し、更に有機質皮膜を形成する方法も提
案されているが、このような皮膜は経年劣化すること、
耐熱性が劣る等の問題点があった。However, with such conventional steel sheet surface treatment methods, both methods of plating with metals such as zinc and chromate treatment in addition to zinc plating can cause scratches that reach the steel substrate. Sufficient anti-corrosion properties for iron substrates cannot be obtained. Furthermore, if a coating is applied, sufficient adhesion of the coating film may not be ensured over a long period of time, or significant rust or blistering may occur due to scratches. Furthermore, the conventional method of applying an inorganic coating using a ceramic coating has problems with the impact resistance and thermal shock resistance of the coating. In addition, as an organic coating method, a method has been proposed in which the steel plate is coated with a commercially available zinc chrome metal and an organic film is further formed, but such a film deteriorates over time.
There were problems such as poor heat resistance.
発 明 の 開 示
この発明は、従来の鋼板表面処理方法の前記問題点に着
目してなされたもので、鋼板に鉄より電気化学的に卑な
金属をめっきし、その表面にケイ素、アルミニウム、チ
タン、亜鉛およびタンタルからなる群から選ばれた少な
くとも1種の金属を含む非晶質皮膜を形成することを特
徴とする。DISCLOSURE OF THE INVENTION This invention was made by focusing on the above-mentioned problems of conventional steel plate surface treatment methods, and involves plating a steel plate with a metal that is electrochemically more base than iron, and coating the surface with silicon, aluminum, It is characterized by forming an amorphous film containing at least one metal selected from the group consisting of titanium, zinc, and tantalum.
この発明のlA版防食用表面処理方法においては、先ず
鋼板の表面に鉄よりも電気化学的に卑なる金属をめっき
する。この発明で「鉄より電気化学的に卑なる金属」と
は、電気化学的に卑なる金属単体のみならず、これと他
の金属との合金を包含した広い範囲のものを意味し、例
えば亜鉛、亜鉛−鉄合金、亜鉛−ニッケル合金等が含ま
れる。In the 1A version anticorrosive surface treatment method of the present invention, first, the surface of a steel plate is plated with a metal that is electrochemically less noble than iron. In this invention, "a metal that is electrochemically less base than iron" refers to a wide range of metals, including not only single metals that are electrochemically base but also alloys of this and other metals, such as zinc. , zinc-iron alloy, zinc-nickel alloy, etc.
次に、このように表面に電気化学的に卑なる金属をめっ
きした鋼板の表面に、前記金属を含む非晶質皮膜を形成
するが、かかる皮膜の形成方法としては、ケイ素、アル
ミニウム、チタン、亜鉛およびタンタルの内のいずれか
1種または2種以上の金属のアルコキシドを溶媒、例え
ばエチルアルコールのようなアルコール、酢酸エチル、
酢酸ブチルのようなエステル等に溶解した溶液をめっき
表面に塗布した後加熱することにより非晶質皮膜を形成
する方法がある。この際使用するアルコキシドとしては
炭素原子が6個以上になると加熱処理により炭化物が生
成するようになるので、1〜5個の炭素原子を有するも
のが好ましい。前記金属のアルコキシド溶液の塗布方法
はスプレー、浸漬、ハケ塗り、ロール塗布法等いずれの
方法も用いることができる。加熱雰囲気は空気中、アル
ゴン(Arl中、窒素(N2)甲等のいずれでもよく、
加熱速度の緩急も性能Gこ影響を与えることはない。Next, an amorphous film containing the metal is formed on the surface of the steel plate whose surface has been electrochemically plated with a base metal. An alkoxide of one or more metals selected from zinc and tantalum is mixed with a solvent such as an alcohol such as ethyl alcohol, ethyl acetate,
There is a method of forming an amorphous film by applying a solution dissolved in an ester such as butyl acetate to the plated surface and then heating it. The alkoxide used in this case is preferably one having 1 to 5 carbon atoms, since if the number of carbon atoms is 6 or more, a carbide will be generated by heat treatment. The metal alkoxide solution can be applied by any method such as spraying, dipping, brushing, or roll coating. The heating atmosphere may be air, argon (Arl), nitrogen (N2), etc.
The speed of the heating rate does not affect the performance.
加熱温度は]00°C未満では非晶質膜が形成されず、
600°Cより高くなると非晶質膜が結晶化するので1
00〜600°Cが好ましい。この方法によると所望の
金属のち密な酸化非晶質皮膜が容易ニ得うれる。この皮
膜の厚さは、アルコキシドの濃度および塗布量によって
異なるが、50oo人より厚くなると塗膜密着性が悪く
なることがあり、・一方100A未満では皮膜の耐食性
が得られない(7)テ、1.00〜5000Aの範囲と
するのが好ましい。またこの非晶質の薄膜の厚ざは、コ
ーティング法の調整により自由にコントロールすること
ができ、かつ塗布後の焼付は温度、時間により表面膜の
性状を自由に選択できる。例えば金属材料を所定の金属
のアルコキシド溶液に浸漬した後引き上げによりコーテ
ィングする場合に、予め引き上げ速度と膜厚との関係全
庁すキャルブレーションカープを実験によってつくって
おき、このカーブから所望の膜厚に対応する引上げ速度
を求めて金属材料を引上げることにより所望の膜厚を得
ることができる。If the heating temperature is below 00°C, an amorphous film will not be formed.
If the temperature rises above 600°C, the amorphous film will crystallize, so 1
00-600°C is preferred. According to this method, a dense oxidized amorphous film of the desired metal can be easily obtained. The thickness of this film varies depending on the concentration of the alkoxide and the amount of coating, but if it is thicker than 50 mm, the film adhesion may deteriorate; on the other hand, if it is less than 100 A, the film will not have corrosion resistance (7) It is preferable to set it as the range of 1.00-5000A. Furthermore, the thickness of this amorphous thin film can be freely controlled by adjusting the coating method, and the properties of the surface film can be freely selected by adjusting the temperature and time of baking after coating. For example, when coating a metal material by dipping it in a predetermined metal alkoxide solution and then pulling it up, a calibration curve that determines the relationship between pulling speed and film thickness is created in advance through experiments, and the desired film is determined from this curve. A desired film thickness can be obtained by pulling the metal material at a pulling rate corresponding to the thickness.
上述のように、この発明の方法によりめっきされた表面
に非晶質皮膜の形成された鋼板は、表面が非晶質で不活
性のため表面からの腐食アタックに対して極めて強い。As mentioned above, the steel plate plated by the method of the present invention with an amorphous coating formed on the surface is extremely resistant to corrosion attack from the surface because the surface is amorphous and inert.
また塗膜をその上に塗布した場合さらに防食性が高まり
、鉄素地まで傷がついた場合でも従来必ず問題となって
いる赤錆発生、塗膜のふくれ或いははがれも少なく、良
好な鉄索・地防食性が得られる。In addition, when a coating film is applied on top of the coating, the corrosion resistance is further improved, and even if the iron substrate is damaged, there is less occurrence of red rust, blistering or peeling of the coating film, which has always been a problem in the past, and the iron cables and substrate are in good condition. Provides corrosion protection.
更に非晶質の表面皮膜が極めて薄いため、(1)電着塗
装が可能であす、(2)抵抗溶接性も従来の表面処理鋼
板と同等で、(3)プレス成形等で皮膜の1波壊、脱落
が少ない。Furthermore, since the amorphous surface film is extremely thin, (1) electrodeposition coating is possible, (2) resistance weldability is equivalent to conventional surface-treated steel sheets, and (3) one wave of the film can be removed by press forming, etc. Less breakage and falling off.
発明の実施例
実施例
厚さ0.8朋、幅7Qmm、長さ1.5011m17)
大きざを有する6個の鋼板(SPCIを試料とし、各試
料の表面に第1表に示す表面処理を行った(第1表扁]
〜6)。ざらにこれらの処理材上に自動車外板塗装を想
定した塗装を次に示すように行った。Embodiments of the inventionExample Thickness: 0.8mm, Width: 7Qmm, Length: 1.5011m17)
Six steel plates (SPCI) having different sizes were used as samples, and the surface of each sample was subjected to the surface treatment shown in Table 1.
~6). Roughly, coating intended for automobile exterior panels was applied to these treated materials as shown below.
先ず処理済試料をアルカリ脱脂し、脱イオン水で水洗後
、110°Cで5分間乾燥し、パワートップU30(日
本ペイント(株)製、商品名)をカチオン定着塗装(O
EDlにより膜厚20μm塗布し、次いで中塗塗料とし
て852Eシーラー(日本ペイント(株)製、商品名)
を膜厚20μm塗布し、]40°Cで30分間焼付け、
最後に上塗塗料としてオルガG−26+日本ペイント(
株)製、商品名)を膜厚4.0μm塗布し、140゛C
で30分間焼付けた。このようにして塗装した試料につ
き密着性、耐屈曲性、耐1nG撃性、耐温水性および耐
食性を評価し、得た結果を第1表に併記する。First, the treated sample was degreased with alkali, washed with deionized water, dried at 110°C for 5 minutes, and coated with Power Top U30 (trade name, manufactured by Nippon Paint Co., Ltd.) with cationic fixation coating (O
A film thickness of 20 μm was applied using EDl, and then 852E Sealer (manufactured by Nippon Paint Co., Ltd., trade name) was applied as an intermediate coating.
was applied to a film thickness of 20 μm, and baked at 40°C for 30 minutes.
Finally, as a top coat, Olga G-26 + Nippon Paint (
Co., Ltd., product name) with a film thickness of 4.0 μm and heated at 140°C.
Bake for 30 minutes. The thus coated samples were evaluated for adhesion, bending resistance, 1 nG impact resistance, hot water resistance, and corrosion resistance, and the obtained results are also listed in Table 1.
比較例
実施例と同様に6個の鋼板(SPC)を試料とし、各試
料の表面Oこ第1表に示す表面処理を行った(第1表/
f57〜]2)。さらに実施例と同様に塗装を行った。Comparative Example As in the example, six steel plates (SPC) were used as samples, and the surface of each sample was subjected to the surface treatments shown in Table 1 (Table 1/
f57~]2). Furthermore, painting was performed in the same manner as in the example.
このようにして得られた試料につき実施例と同様に評価
を行ない、その結果を第1表に併記する。The samples thus obtained were evaluated in the same manner as in the Examples, and the results are also listed in Table 1.
表中
1表面処理
(注イ)めっきの種類
Zn・・・電気亜鉛めっき、目付量209/m2Fe−
Zn−1,1%Fe−89%Zn合金メッキ、目付量4
59/mz
Ni−Zn−12%Ni−88%Zn合金めつき、目付
量209/i2
りo ム酸+ zn/有a皮膜+Zn・・・シンクロメ
タル(270°C焼付)
(8E口) SiO□・・・ケイ累のエトキシドの5%
エタノール溶液に常温浸漬し、引上速度57 C/mi
nで定速引上げた後、300°Cで]5分間加熱した。1 Surface treatment in the table (Note A) Type of plating Zn...Electrogalvanizing, area weight 209/m2Fe-
Zn-1,1%Fe-89%Zn alloy plating, basis weight 4
59/mz Ni-Zn-12%Ni-88%Zn alloy plating, basis weight 209/i2 Limic acid + Zn/A film + Zn... Synchro metal (baked at 270°C) (8E opening) SiO □...5% of Kei's ethoxide
Immersed in ethanol solution at room temperature, pulling speed 57 C/mi
After pulling at a constant speed of n, it was heated at 300°C for 5 minutes.
膜厚2,0OOA
TiO□・・チタンのエトキシドの1.5係エタノール
溶液を用い、引上速度を33C□inとした以外は5i
02の場合と同様に処理した。膜厚2.OOOA
TaO2・・・タンタルのエトキシドの6チエタノール
溶液を用いた以外は5102の場合と同様に処理した。Film thickness 2,0OOA TiO□...5i except that a 1.5% ethanol solution of titanium ethoxide was used and the pulling speed was 33C□in.
It was treated in the same manner as in case 02. Film thickness 2. OOOA TaO2...Processed in the same manner as in the case of 5102 except that a 6-thiethanol solution of tantalum ethoxide was used.
膜厚2,000人
Zn3 tpo4)2++・ボンデライト+3004
(日本パー力ライジング(株)製、商品名)、皮膜重量
2.59人2
クロメート・・・ボンデライト1355 (日本パー力
ライジング(株)製、商品名)。Film thickness: 2,000 Zn3 tpo4) 2++/Bonderite +3004
(manufactured by Nippon Parriki Rising Co., Ltd., trade name), film weight: 2.59 people 2 Chromate: Bonderite 1355 (manufactured by Nippon Parriki Rising Co., Ltd., trade name).
2、試験法
密着性・・・ごばん目試験:塗膜の表面Qこ1朋平万の
正号形100個より成るごばん目をつくり、その上にセ
ロハン粘着テープを密着させ、ただちにテープを引きは
がしたとき、塗面にはくりがないかどうか調べる。2.Test method Adhesion...Round test: Make a grid consisting of 100 positive signs of Q1 on the surface of the coating film, stick cellophane adhesive tape on top of it, and immediately apply the tape. When you peel it off, check to see if there are any cracks in the painted surface.
耐屈曲性・・・長方形の試料の中央にT字型のクロスカ
ットを入れておき直径2Qmmのマンドレルに左右均等
にのせ両側をマンドレルに沿い180°折曲げ、塗膜が
屈曲を受けたときの塗膜の可撓性を調べる。0が耐屈曲
性なく、100が耐屈曲性有りとする。Bending resistance: A T-shaped cross cut is made in the center of a rectangular sample, placed on a mandrel with a diameter of 2Qmm evenly on both sides, and both sides are bent 180° along the mandrel. Examine the flexibility of the coating. 0 indicates no bending resistance and 100 indicates bending resistance.
耐衝撃性・・・デュポン式衝撃試験による。直径12.
7問(y2インチ)5009のおもりで、30cmの距
離から衝撃を与え、われ、ひびが入らないか調べる。Impact resistance: Based on DuPont impact test. Diameter 12.
Question 7 (Y2 inches) Apply an impact with a 5009 weight from a distance of 30 cm and check for cracks.
耐温水性・・・+o’cの温水に500時間浸漬し、引
上げ24時間後にごばん目試験を行う。Hot water resistance: Soaked in warm water at +o'c for 500 hours, and 24 hours after lifting, a second eye test was conducted.
耐食性・・・評価基準○・・赤錆なし、△・・・赤錆、
ふくれ少し有り、×・・・赤錆、ふくれの発生大。Corrosion resistance...Evaluation criteria ○...No red rust, △...Red rust,
There is a little blistering, ×...Red rust and a lot of blistering.
SST・・・JIS Z 2371に準する塩水噴霧試
験、X字型クロスカントを入れ1.000時間]載霧。SST...Salt water spray test according to JIS Z 2371, X-shaped cross cant inserted for 1,000 hours] Spraying.
CCT・・・塩水噴霧4時間→60°Cで2時間乾燥−
50°C1湿、1f(RH)95チで2時間処理のサイ
クルを2(〕00回う。X字型クロスカットを入れた。CCT...Salt water spray for 4 hours → Dry at 60°C for 2 hours.
Repeat the cycle of treatment for 2 hours at 50°C, 1 humidity, 1f (RH), 95cm 2 (〕000 times).An X-shaped cross cut was made.
自然曝露・・・沖縄系で1年間自然曝露試験。Natural exposure: One year natural exposure test in Okinawa.
X字型クロスカットを入れる。Make an X-shaped cross cut.
上表より試料1〜6の実施例の方法により処理した鋼板
が比較例7〜]2の銅板より優れていることがわかる。From the above table, it can be seen that the steel plates of Samples 1 to 6 treated by the method of Example are superior to the copper plates of Comparative Examples 7 to 2.
次に第2表に示す試料A 1未処理鋼板(SPC八Aへ
@板に亜鉛めっきをしたもの、A3亜鉛めっきに加えて
クロメート処理を行ったもの、164シンクロメタル処
理を有し有機皮膜を塗布したもの、S、5@板表面にセ
ラミック皮膜を形成したものおよび煮6第1表の試料1
と同様に表面処理したものにつき、夫々化成処理後前記
と同様にしで塗装し、耐食性、プレス成型性、溶接性、
電着特性(FD特性)および塗装仕上り訃を評価し、得
た結果を第2表に併記する。Next, sample A1 shown in Table 2: untreated steel sheet (SPC 8A @ plate with zinc plating, A3 with chromate treatment in addition to galvanization, 164 with synchrometal treatment and organic coating) Coated, S, 5 @ plate with a ceramic film formed on the surface, and boiled 6 Sample 1 in Table 1
After the surface treatment was carried out in the same manner as above, after each chemical conversion treatment, paint was applied in the same manner as above to improve corrosion resistance, press formability, weldability,
The electrodeposition characteristics (FD characteristics) and paint finish were evaluated, and the obtained results are also listed in Table 2.
表中 数値の犬なる程良好。The higher the numbers in the table, the better.
*1 同一型で所定回プレス成形したとき型に付着する
塗料粉末の量で判定する。*1 Determined by the amount of paint powder that adheres to the mold when the same mold is press-molded a specified number of times.
*2所定間隔でスボツNfJ接し、ナゲツト径が所定の
大きざに達しなくなるまでの溶接回数判定。*2 Determine the number of welding times until the slots NfJ touch each other at a predetermined interval and the nugget diameter no longer reaches the predetermined size.
*3 ガスの発生によるクレータの無有。*3 No craters due to gas generation.
上表より実施例の方法で処理したA6の鋼板は従来の処
理鋼板A l〜5より優れていることが明らかである。From the table above, it is clear that the A6 steel plate treated by the method of the example is superior to the conventionally treated steel plates A1-5.
発 明 効 果
よりも電気化学的に卑な金属をめっきし、その表面にケ
イ素、アルミニウム、チタン、亜鉛およびタンタルの内
のいずれか1種または2種以上の金属を含む非晶質皮膜
の薄膜を形成させる方法としたため、この発明の方法に
より処理した鋼板は、(1)防食性が良好、(2)電着
塗装が可能、(3)抵抗溶接が可能、(4)プレス成型
で皮膜の破壊、脱落が少ない上に(5)耐熱性が向上、
(6)塗膜の密tFIEが向上するという効果が得られ
る。A thin film of an amorphous film plated with a metal that is electrochemically more base than the invention effect and containing one or more metals selected from silicon, aluminum, titanium, zinc, and tantalum on the surface thereof. As a result, steel sheets treated by the method of the present invention (1) have good corrosion resistance, (2) can be electrodeposited, (3) can be resistance welded, and (4) can be formed by press forming. In addition to less breakage and falling off, (5) improved heat resistance,
(6) The effect of improving the coating film density tFIE can be obtained.
特許出願人 日産自動車株式会社
同 9f埋士 杉 何 興 袢 X、(、
、、aQ。Patent applicant: Nissan Motor Co., Ltd.
,,aQ.
Claims (1)
し、その表面にケイ素、アルミニウム、チタン、亜鉛お
よびタンタルからなる解方)ら選ばれた少なくとも1種
の金属を含む酸化物の非晶質皮膜を形成することを特徴
とする鋼板防食用表向処理方法。1 A steel plate is electrochemically plated with a metal less noble than iron, and the surface is coated with an oxide containing at least one metal selected from silicon, aluminum, titanium, zinc, and tantalum. A surface treatment method for preventing corrosion of steel sheets, which is characterized by forming an amorphous film.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8176283A JPS59208076A (en) | 1983-05-12 | 1983-05-12 | Surface treatment for preventing corrosion of steel plate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8176283A JPS59208076A (en) | 1983-05-12 | 1983-05-12 | Surface treatment for preventing corrosion of steel plate |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59208076A true JPS59208076A (en) | 1984-11-26 |
JPH0116315B2 JPH0116315B2 (en) | 1989-03-23 |
Family
ID=13755459
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8176283A Granted JPS59208076A (en) | 1983-05-12 | 1983-05-12 | Surface treatment for preventing corrosion of steel plate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59208076A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63242531A (en) * | 1987-03-30 | 1988-10-07 | ぺんてる株式会社 | Decorating |
-
1983
- 1983-05-12 JP JP8176283A patent/JPS59208076A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63242531A (en) * | 1987-03-30 | 1988-10-07 | ぺんてる株式会社 | Decorating |
Also Published As
Publication number | Publication date |
---|---|
JPH0116315B2 (en) | 1989-03-23 |
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