JPS59159987A - Surface-treated steel sheet with superior suitability to chemical conversion treatment - Google Patents
Surface-treated steel sheet with superior suitability to chemical conversion treatmentInfo
- Publication number
- JPS59159987A JPS59159987A JP3505083A JP3505083A JPS59159987A JP S59159987 A JPS59159987 A JP S59159987A JP 3505083 A JP3505083 A JP 3505083A JP 3505083 A JP3505083 A JP 3505083A JP S59159987 A JPS59159987 A JP S59159987A
- Authority
- JP
- Japan
- Prior art keywords
- chemical conversion
- steel sheet
- conversion treatment
- cold
- oxide
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
Abstract
Description
【発明の詳細な説明】
この発明は化成処理性にすぐれた表面処理鋼板に関する
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a surface-treated steel sheet with excellent chemical conversion treatment properties.
自動車用鋼板は一般に、実際使用浣際してはプレス成形
などの加工を行った後、塗料下地処理としての化成処理
（例えばリン酸塩処理〕を施し、しかる後その上に例え
ばカチオン電着塗装を施して最終用途に硬用されるが、
前記電着塗装の塗膜か良好な塗装耐食性を得るためには
、まず下地処理において良好な化成皮膜を得ることが必
要不可欠の条件となる。この良好な化成皮膜を得るため
には、素材の冷延鋼板表面が化成皮膜結晶の核発生や成
長を阻害しないような良好な性′＄（化成処理性にすぐ
れた性状〕を有していることが必要となる０
さて、自動車用銅板として用いられる冷延鋼板は、従来
は連続焼鈍後における冷却を無酸化雰囲気でのガスジェ
ットクール等の方法で行っていたので、化成皮膜の形成
に有利とされる１山等の表面濃化層が存在するとともに
水酸化鉄等の腐食生成物の付着等か無いだめ、化成処理
性にすぐれた鋼板であった。しかし最近、上記連続焼鈍
におけるヒートサイクルの合理化を図るため、無酸化雰
囲気でのガスジェットクールに代えて水冷または気水冷
却の方法を採用する傾向にある。この場合、冷却過程が
酸化性雰囲気とガるため表面に酸化膜か生成し、従って
この酸化膜を除去するだめの例えば酸洗処理が必要とな
る。この酸洗処理を行った鋼板は、上記１Ｖｂ
洗残渣（水酸化鉄）の表面吸着、水錆の発生等があって
表面性状が悪化し化成処理性が劣化してきている。In general, when steel sheets for automobiles are actually used, they are processed by press forming, etc., and then subjected to chemical conversion treatment (for example, phosphate treatment) as a base treatment for paint, and then coated with, for example, cationic electrodeposition coating. It is hardened for final use after being subjected to
In order to obtain good paint corrosion resistance of the electrodeposition coating, it is essential to first obtain a good chemical conversion film in the surface treatment. In order to obtain this good chemical conversion coating, the surface of the cold-rolled steel sheet used as the raw material must have good properties that do not inhibit the nucleation and growth of chemical conversion coating crystals (properties with excellent chemical conversion treatment properties). Conventionally, cold-rolled steel sheets used as copper sheets for automobiles were cooled by a method such as gas jet cooling in a non-oxidizing atmosphere after continuous annealing, which is advantageous for the formation of chemical conversion coatings. It was a steel sheet with excellent chemical conversion treatment properties, as it had a surface concentration layer such as a single peak, which is said to be a single peak, and there was no adhesion of corrosion products such as iron hydroxide.However, recently, the heat cycle in the continuous annealing mentioned above In order to streamline the cooling process, there is a tendency to adopt water cooling or air/water cooling instead of gas jet cooling in a non-oxidizing atmosphere.In this case, the cooling process interacts with the oxidizing atmosphere, resulting in the formation of an oxide film on the surface. Therefore, in order to remove this oxide film, for example, pickling treatment is required.The steel plate subjected to this pickling treatment is susceptible to surface adsorption of the above-mentioned 1Vb washing residue (iron hydroxide) and generation of water rust. As a result, the surface quality has deteriorated and the chemical conversion treatment properties have deteriorated.
まだ冷延鋼板を自動車車体等に用いる場合、車体腐食が
安全上の問題となるが、近時特に自動車外板で腐食を激
しく受ける片面のみを耐食性にすぐれたメッキ被覆面と
し、他面を裸面のままとして車体腐食の軽減を図るよう
にした片面メッキ鋼板が用いられるようになってきた。When cold-rolled steel sheets are still used for automobile bodies, etc., body corrosion is a safety issue, but recently, especially on the exterior of automobiles, only one side, which is subject to severe corrosion, is coated with a highly corrosion-resistant plated surface, and the other side is bare. Single-sided plated steel sheets have come into use, which are designed to reduce car body corrosion by leaving the surface intact.
片面メッキ鋼板としては、電気メツキ法と溶融メッキ法
の２種類の製造方法かあるか、電気メツキ法の場合は前
処理として酸洗が行われ、また多くの場合酸性浴である
電気メッキ浴を通過して酸洗効果を受けるため、非メッ
キ面の冷延鋼板の化成処理性は劣化する。また溶融メッ
キ法の場合は、高温＄、態で溶融メッキ浴中から大気中
に出てくるため非メンキ面の酸化は避は難く、このため
メッキ終了後酸洗匙埋が必要となり、上記と同様に非メ
ッキ面の化成処理性は劣化する。近年特にＦｅ系または
Ｆｅ−Ｚｎ系合金電気メッキが一般的となりつつあるが
、この場合酸院メッキ浴中に多量のＦｅ３＋イオンを含
有しているため、非メッキ面はメッキ槽中の浸漬により
酸焼はピンティング状態を呈しており、化成処理性が極
めて劣悪になっている０また電気Ｚｎメッキ法によるも
のもあるか、この場合も高電流密度操業の傾向が進むに
つれて腐食性の強い塩化浴が使用されるだめ、非メツキ
面側に極めて激しい溶解が起り、このだめ化成処理性か
極めて劣悪になっている。また特にメッキ浴槽内での浸
漬時間の長いたて型メッキ槽を用いた場合は、よこ型メ
ッキ槽を用いた場合に比較して非メッキ面の化成処理性
の劣化は極めて激しくなり深刻な事態を生じるに至って
いる。近年、自動車・家電業界において高張力冷延鋼板
の使用比率か高１っているが、高張力冷延鋼板は、一般
冷延鋼板に比較して、一層、酸性液による浸漬で化成処
理性が劣悪となるので問題である。There are two manufacturing methods for single-sided plated steel sheets: electroplating and hot-dip plating.In the case of electroplating, pickling is performed as a pretreatment, and in many cases, electroplating bath, which is an acidic bath, is used. Since it passes through and receives the pickling effect, the chemical conversion treatment property of the cold rolled steel sheet on the non-plated surface deteriorates. In addition, in the case of the hot-dip plating method, oxidation of the non-coated surface is difficult to avoid because the high-temperature metal comes out from the hot-dip plating bath into the atmosphere, so it is necessary to bury the non-coated surface after plating is completed. Similarly, the chemical conversion treatment property of the non-plated surface deteriorates. In recent years, Fe-based or Fe-Zn-based alloy electroplating has become particularly popular, but in this case, the acidic plating bath contains a large amount of Fe3+ ions, so the non-plated surface is immersed in the plating bath. Zn plating exhibits a pinting state, and the chemical conversion properties are extremely poor.Also, electrolytic Zn plating may be used, or in this case, as the trend toward high current density operation progresses, highly corrosive chloride baths are used. When used, extremely severe dissolution occurs on the non-plated side, resulting in extremely poor chemical conversion treatment properties. In addition, especially when a vertical plating bath is used, which requires a long immersion time, the deterioration of the chemical conversion properties of the non-plated surface will be much more severe than when a horizontal plating bath is used, resulting in a serious situation. This has led to the occurrence of In recent years, the usage rate of high-strength cold-rolled steel sheets has increased by 1 in the automobile and home appliance industries, but high-strength cold-rolled steel sheets are more easily chemically treated by immersion in acidic liquid than ordinary cold-rolled steel sheets. This is a problem because it becomes inferior.
まだ一方、自動車用鋼板に化成処理を施す場合は、前述
の如く自動車メーカー側で素材鋼板を成形加工した後、
化成処理量産ラインで化成処理するのか通例であるが、
この場合例えばリン酸亜鉛処理液中の浴成分（Ｚｎ”ｓ
Ｆｅ２＋、硝酸塩、亜硝酸塩、塩素酸塩等の酸化促進
剤）の経時変化が起り・狭少な浴管理条件範囲から外れ
るトラブルが頻発し易いために、浴成分の変動に対して
も常にすぐれた化成処理性を維持できるような対応性に
すぐれた冷延９岡板が望まれていた。On the other hand, when chemical conversion treatment is applied to automobile steel sheets, as mentioned above, after the automobile manufacturer has formed the raw steel sheets,
Chemical conversion treatmentIt is customary to perform chemical conversion treatment on a mass production line,
In this case, for example, the bath component (Zn”s) in the zinc phosphate treatment solution
Oxidation promoters such as Fe2+, nitrates, nitrites, chlorates, etc.) change over time, and troubles that deviate from the narrow bath management condition range tend to occur frequently. A cold-rolled 9-way board with excellent adaptability that can maintain processability has been desired.
本発明は上記酸洗を受けた冷延鋼板面ならびに片面メッ
キ鋼板の非メッキ面において化成処理性の劣化がなく、
化成処理量産ラインにおいて浴成分の変動沈対する対応
性にすぐれた化成処理性が碍らｎるような表面処理鋼板
を提供しようとするものである。The present invention has no deterioration in chemical conversion treatment properties on the pickled cold-rolled steel sheet surface and the non-plated surface of the single-sided plated steel sheet,
The object of the present invention is to provide a surface-treated steel sheet that has excellent chemical conversion treatment properties and is highly adaptable to fluctuations and settling of bath components in a chemical conversion treatment mass production line.
化成処理性に劣る冷延鋼板表面の改善を図ることを目的
として、冷延鋼板表面に金属Ｎｉを０３〜ｂ報で開示さ
れている。この発明によれば、処理条件の安定したリン
酸塩処理試験においては確かに化成処理性（化成皮膜の
結晶サイズ、付着量等）や塗装耐食性の向上効果は得ら
れる。しかし金属Ｎ１を付着した冷延鋼板表面は、表面
析出した金属Ｎｉの局部電池の構成作用が極めて強く、
化成処理作業に対して極めて敏感な表面状態となってい
る。For the purpose of improving the surface of a cold rolled steel sheet which has poor chemical conversion treatment properties, the 2003-B report discloses the addition of metallic Ni to the surface of a cold rolled steel sheet. According to the present invention, in a phosphate treatment test under stable treatment conditions, the effect of improving chemical conversion treatment properties (crystal size, adhesion amount, etc. of the chemical conversion film) and coating corrosion resistance can certainly be obtained. However, on the surface of the cold-rolled steel sheet to which metal N1 is attached, the local battery formation effect of the metal Ni precipitated on the surface is extremely strong.
The surface condition is extremely sensitive to chemical conversion treatment.
上述したようにリン酸非鉛処理量産ラインにおける化成
処理作業においては、浴成分の経時変化が生じ易いが、
浴成分中の酸化促進剤の添加量や金属Ｎｉの付着量は極
めて微量であるだめそれらの量の変化の割合は特に犬き
くなシ勝ちである。従ってこれらの量の変化は金属Ｎｉ
を付着しだ冷延網板の化成処理作業に敏感に反映され、
これらの量が多くなると化成処理医応速度（化成皮膜形
成の速度）が過大となって、化成皮膜中に塗装耐食性に
悪い影響を与えるホーバイトの粗な針状結晶か多く生じ
易くなる。公知の如く、リン酸唾鉛処理における化成皮
膜は、ホーバイト結とフォスフオフイライト結晶（緻密
な柱状結晶）との複合リン酸亜鉛皮膜で構成されており
、この内ホーバイト結晶が多くなると塗装耐食性が劣化
する性質を有しているので、金属Ｎ１を付着させだ冷延
導板は対応性が敏感すぎて、化成処理量産ライン等実際
面で用いるには必ずしも適しているとはいい雉い。As mentioned above, in the chemical conversion treatment work on the phosphate-free mass production line, the bath components tend to change over time.
Since the amount of oxidation promoter added and the amount of metal Ni deposited in the bath components are extremely small, the rate of change in these amounts is particularly sensitive. Therefore, changes in these amounts are
The adhesion is sensitively reflected in the chemical conversion treatment of cold-rolled mesh sheets,
When these amounts increase, the reaction rate of chemical conversion treatment (speed of formation of chemical conversion film) becomes excessive, and many coarse acicular crystals of hovite, which have a negative effect on paint corrosion resistance, tend to form in the chemical conversion film. As is well known, the chemical conversion film in lead phosphate treatment is composed of a composite zinc phosphate film consisting of hovite crystals and phosphofluorite crystals (dense columnar crystals), and as the number of hovite crystals increases, the corrosion resistance of the coating deteriorates. Since it has the property of deteriorating, cold-rolled conductive plates to which metal N1 is attached are too sensitive and are not necessarily suitable for practical use such as chemical conversion treatment mass production lines.
そこで本発明者らは、良好な化成処理性が得られるとと
もに、化成処理の浴成分等の経時変化に対して金属Ｎｉ
のように化成処理反応が敏感に反映しないような性質を
持つ化成処理性にすぐれた表面処理鋼板の開発を意図し
て、まず対象として金属Ｎ１より反応が敏感でない半型
導性の性質を有するＮ１酸化物・Ｎ１水酸物を表面に付
着させた冷延鋼板を考えて種々実験研究を重ねた。Therefore, the present inventors have discovered that metal Ni can be used to obtain good chemical conversion treatment properties and to resist changes over time in bath components, etc. of chemical conversion treatment.
With the intention of developing a surface-treated steel sheet with excellent chemical conversion treatment properties that does not reflect the chemical conversion reaction as sensitively, we first targeted steel sheets with semi-conducting properties that are less sensitive to reactions than metal N1. We have conducted various experimental studies on cold-rolled steel sheets with N1 oxide and N1 hydroxide attached to their surfaces.
本発明者らは、化成処理性にすぐれた表面処理鋼板の標
準材として、無酸化ガス雰囲気中で焼鈍後の冷却を行っ
だ後０５φ圧下率の調質圧延工程をη径たアルミキルド
冷延網板（板厚Ｑ、 ３ ｍｍ ）を用い、これを酸洗
→水洗→乾燥処理して化成処理性を劣化させた冷延困板
ＫＮｉ酸化物・Ｎｉ水酸物をＮｉ元素重量換算で３０ワ
／ｍ２付着させて供試材■）を得た。また比較のため上
記標準材の冷延鋼板■、標準冷延鋼板（３）を酸洗処理
した冷延鋼板（Ｂ）、前記冷延鋼板Ｂ）に金属Ｎｉ １
５ｍＶｉ付着させた鋼板Ωを供試材とした。上記各供試
材ＩＡ）■（Ｃ）Ｑ）ｌをリン酸唾鉛処理液Ｃボンデラ
イ） ３０３０）による浸漬時間を様々に変えた浸漬処
理でリン酸塩付着量および化成処理反応速度（化成処理
皮膜形成が完了するまでの所要時間）を調査した。結果
を第１図に示す。As a standard material for surface-treated steel sheets with excellent chemical conversion properties, the present inventors developed an aluminum killed cold-rolled net with a diameter of η after cooling after annealing in a non-oxidizing gas atmosphere and then performing a temper rolling process with a reduction of 05φ. A cold-rolled plate (thickness Q, 3 mm) was processed by pickling, water washing, and drying to degrade the chemical conversion properties. /m2 to obtain a test material (■). For comparison, the standard cold-rolled steel sheet ■, the cold-rolled steel sheet (B) obtained by pickling the standard cold-rolled steel sheet (3), and the cold-rolled steel sheet B) with metal Ni 1
A steel plate Ω to which 5 mVi was attached was used as a test material. Each of the above test materials IA) (C) The time required to complete film formation was investigated. The results are shown in Figure 1.
第１図は上記供試材（２）（２）（Ｃ）０の化成反応時
間とリン酸塩付着量との関係を示す図である。FIG. 1 is a diagram showing the relationship between the chemical conversion reaction time and the amount of phosphate deposited on the above-mentioned sample material (2) (2) (C)0.
図に見る如く、供試材（３）０［Ｆ］はいずれも２分程
度で略々化成皮膜の形成が完了し化成処理性にすぐれて
いることが示され、これに対し供試材（２）は化成処理
性に劣っていることが示された。また化成処理反応速度
については、供試材０か最も速く、供試材Ｄ）は供試材
（ト）と略々間等の成績が示され、供試材［Ｆ］）に比
較して顕著な化成処理性の向上が示された。As shown in the figure, the formation of the chemical conversion film was almost completed in about 2 minutes for all sample materials (3) 0[F], indicating that the chemical conversion coatings were excellent in chemical conversion treatment properties. 2) was shown to be inferior in chemical conversion treatment properties. Regarding the chemical conversion reaction rate, test material 0 was the fastest, test material D) was about the same as test material (G), and compared to test material [F]). A remarkable improvement in chemical conversion treatment properties was shown.
また化成処理反応の敏感ｉ生については、供試材（Ｃ）
は金属Ｎｉの付着量が多くなると、化成処理反応速度は
たちまち過大となり、化成結晶にホーバイト分の多い粗
な針状結晶が多く生じるようにガるが、これに対し供試
材０）はＮｉ酸化物・Ｎ１水酸化物の付着量が多くなっ
ても化成処理反応速度は殆んど変化を示さず、フォスフ
オフエライト分の多い緻密な結晶が得られ、供試材０よ
りははるかに対応性が鈍感であった。In addition, for sensitive materials for chemical conversion reactions, test material (C)
When the amount of metallic Ni deposited increases, the chemical conversion reaction rate quickly becomes excessive, and many coarse needle-like crystals with a high hovite content are formed in the chemical crystal. Even if the amount of oxide/N1 hydroxide attached increases, the chemical conversion reaction rate shows almost no change, and dense crystals with a high phosphoopherite content are obtained, which is much more responsive than sample material 0. I was sexually insensitive.
これらの研究結果をふまえてさらに研究を重ねた結果、
Ｎｉ酸化物・Ｎｉ水酸物を鋼板表面に適正密度で分散付
着せしめた場合は、リン酸塩処理においてリン酸塩皮膜
結晶核の形成効果は金属Ｎｉ付着にくらべて同等以上の
作用を示すとともに、冷延鋼板表面とのミクロセル形成
効果か金属Ｎｉにくらべて稍々鈍感となる。従って化成
処理液に組成変動かあっても、これが敏感に化成処理反
応にス映して過度な反応加速を起すような事態如ならず
に断み、実用化成処理量産ラインで安定して緻密な柱状
フォスフオフエライト結晶を有する塗装耐食性にすぐれ
た冷延鋼板表面が得られるという新しい事実を知見した
。As a result of further research based on these research results,
When Ni oxide/Ni hydroxide is dispersed and adhered to the steel plate surface at an appropriate density, the effect of forming phosphate film crystal nuclei during phosphate treatment is equivalent to or higher than that of metal Ni adhesion. , it is slightly less sensitive than metallic Ni, probably due to the microcell formation effect with the surface of the cold-rolled steel sheet. Therefore, even if there is a compositional change in the chemical conversion treatment solution, this will be sensitively reflected in the chemical conversion reaction and will not cause an excessive acceleration of the reaction. A new fact has been discovered that it is possible to obtain a cold-rolled steel sheet surface with excellent paint corrosion resistance that has phosphoopherite crystals.
本発明は上記知見に基いてなされたものであって、その
要旨とするところは、少くとも片面にＮｉ酸化物および
またはＮｉ水酸化物が、Ｎｉ元素重量換算で、１〜１５
ｏｍｙ／、１付着していることを特徴とする化成処理性
にすぐれた表面処理鋼板にある。The present invention has been made based on the above findings, and the gist thereof is that at least one side contains Ni oxide and/or Ni hydroxide in an amount of 1 to 15
omy/, 1 is attached to the surface treated steel sheet with excellent chemical conversion treatment properties.
次にＮ１酸化物・Ｎｉ水酸化物の付着方法について説明
する。Next, a method for depositing N1 oxide/Ni hydroxide will be explained.
付着方法としては、化学メッキ、電気メッキ、蒸着後酸
化処理、気イ・目メッキ等のいずれの方法を用いてもよ
く、特に限定するものではない。The deposition method may be any method such as chemical plating, electroplating, oxidation treatment after vapor deposition, or square/eye plating, and is not particularly limited.
例えば電気メツキ法の一例を示せば次の通りである。For example, an example of the electroplating method is as follows.
下記の浴組成からなるワット浴に、
浴組成： Ｎ１５Ｏ，−６Ｈ２０１５０？＃ＮｉＣＡ２
・６Ｈ２０２０グ／β
）Ｉ３ＢＯ３１５ｆ＃を
酸化剤としてＨ２０□、Ｎｏ−２有機系浴安定剤等を適
量添加して鋼板を電解処理すればよい。In a Watts bath consisting of the following bath composition: Bath composition: N15O, -6H20150? #NiCA2
・6H2020g/β) I3BO315f# may be used as an oxidizing agent and an appropriate amount of H20□, No-2 organic bath stabilizer, etc. may be added to electrolytically treat the steel plate.
次に本発明における各要件の限定理由を説明する。Next, the reasons for limiting each requirement in the present invention will be explained.
Ｎｉ酸酸化物上びまたはＮｉ水酸化物の付着量を、Ｎｉ
元素重量換算で、１−１５０ｍｆｌ／ｒｒ？としたのは
、 １）５ｙ／、１未満ではミクロセル形成密度が不十
分で塗装耐食性の改善効果が不十分となるからである。The amount of Ni acid oxide or Ni hydroxide deposited on Ni
1-150mfl/rr in terms of elemental weight? This is because: 1) If the ratio is less than 5y/.1, the microcell formation density will be insufficient and the effect of improving coating corrosion resistance will be insufficient.
また１ ５０ ’ｎｔ／ｍ２を越えると、Ｎｉ酸化物・
Ｎｉ、／ｌ（酸物にょる被覆率が過大となって化成処理
反応に適した（カソード〕（アノード）面積比率が得ら
れなくなり、むしろリン酸塩結晶生成を抑制し、皮膜に
スケｅ寸着量不足）、を抜き等の化成ムラが発生するの
で好ましくないからである。Moreover, if it exceeds 150'nt/m2, Ni oxide/
Ni,/l (the coverage by the acid becomes excessive, making it impossible to obtain the (cathode) (anode) area ratio suitable for the chemical conversion reaction, and rather suppresses the formation of phosphate crystals and increases the scale of the film. This is because it is undesirable because it may cause formation unevenness (insufficient amount of coating), plucking, etc.
またＮｌ酸化物、Ｎｉ水酸化物としてはそれぞれの各種
単体もしくは双方が結合しているもの、およびそれらに
さらに水分子が結合して水和したもののいずれでも差し
支えない。Further, the Nl oxide and Ni hydroxide may be either a single substance or a combination of both, or a hydrated product in which a water molecule is further bonded to the Nl oxide and Ni hydroxide.
なお、本発明に基〈化成処理性にすぐれた表面処理別板
の構造は、常に鋼板の両面（て対して適用しなければな
ら々いというものでなく、片面についてのみこの構造を
採用し他側の面は例えば異なる構造のメッキ面とする形
で実確するのも何等差し支えない。こうした鋼板も、本
発明の表面処理別板の範萌に属するものである。Note that the structure of the surface-treated separate plate with excellent chemical conversion treatment properties based on the present invention does not always have to be applied to both sides of the steel plate, but can be applied only to one side. For example, the side surfaces may be plated with a different structure.Such steel plates also belong to the scope of the surface-treated plates of the present invention.
次に芙施例を掲げて本発明の詳細な説明する。Next, the present invention will be described in detail with reference to several examples.
アルミキルド連続鋳造鋳片を素）オとして厚さ０８ｍｍ
に冷間圧延した後、連続焼鈍ラインで焼鈍し、気水冷却
（Ｎ２＋水）で室温まで冷却しした後０５φ圧下率で調
質圧延し、さらに酸洗工程を経たアルミキルド冷延鋼板
を用いて、第１表に示す基本浴組成に安定化添加剤を少
量加えて電気メッキによりＮｉ酸化物・Ｎｉ水酸化物を
前記鋼板表面に本発明範囲で付着量を種々に変えて付着
させ、本発明例の供試材０〜■を得た。Thickness: 08mm using aluminum killed continuous casting slab
After cold-rolling, annealing on a continuous annealing line, cooling to room temperature with air-water cooling (N2 + water), skin-pass rolling at a rolling reduction of 05φ, and then a pickling process. , a small amount of stabilizing additive was added to the basic bath composition shown in Table 1, and Ni oxide/Ni hydroxide was deposited on the surface of the steel sheet by electroplating in various amounts within the range of the present invention. Example test materials 0 to ■ were obtained.
第１表
また比較のため、同様に酸洗工程を経蓬７ア７ルミキル
ド冷延鋼板に、同様のメッキ浴を７用４□４で本発明か
ら外れた範囲でＮｉ酸化物・Ｎ１水酸化物を付着せしめ
て比較例の供試材（Ａ）ＣＢ）（ＩＸＪ）を得た。Table 1 Also, for comparison, Ni oxide and N1 hydroxide were added to a cold-rolled steel sheet using the same pickling process, and the same plating bath was applied to a cold-rolled steel sheet using the same pickling process. A sample material (A) CB) (IXJ) of a comparative example was obtained by attaching a substance.
ひきつづいてこれらの供試付代〜０）を第２表に示す条
件でリン酸塩処理およびカチオン電着塗装を施しだ後、
化成処理性および塗装耐食性を調査した０
第 ２ 表
なお化成処理性については次のＣ）〜（ハ）（でより評
価しンｔ０
ピ）化成皮膜のフォスフオフエライトＣ）とホーバイト
（６）との比Ｐ／Ｐ＋ＨをＸ線回折から求めた。Subsequently, these test samples ~0) were subjected to phosphate treatment and cationic electrodeposition coating under the conditions shown in Table 2, and then
The chemical conversion treatment properties and paint corrosion resistance were investigated in Table 2.The chemical conversion treatment properties are further evaluated in the following C) to (C). The ratio P/P+H was determined from X-ray diffraction.
（ロ）走査型電子顕微鏡により結晶の大きさを求めた０ ｅ→ 化成皮膜の付着量を重量法にょυ求めた。(b) The size of the crystal was determined using a scanning electron microscope. e→ The amount of attached chemical conversion film was determined by gravimetric method.
また塗装耐食１生沈ついては、電着塗膜に２簡間隔でゴ
バン目状に切れ目を入れたクロスカント部の塩水噴霧試
験９６０時１間後のセロテープ剥離中で評価した。The corrosion resistance of the coating was evaluated by peeling off the cellophane tape after a salt spray test of 960 hours and 1 hour on a cross-cant area in which cuts were made in the shape of gongs at 2-segment intervals in the electrodeposited coating.
上記結果をまとめて第３表に示す。The above results are summarized in Table 3.
第３表
第３表に見る通り、比較例（Ａ）（Ｂ）はＰ／Ｐ＋Ｈが
１００で良好、皮膜付着量も十分であったが、Ｎ１酸化
物・Ｎ１水酸化物の付着量がＱ、 ０５ ｍＶｍ２と過
少であるためミクロセル形成密度か不十分で結晶が粗大
となり、皮膜Ｑてムラ・スケが多発し化成処理性が不良
で、かつ塗膜剥離中も犬で塗装耐食性も不良であった。Table 3 As shown in Table 3, Comparative Examples (A) and (B) had a good P/P+H of 100 and a sufficient amount of film adhesion, but the amount of N1 oxide/N1 hydroxide adhesion was Q. , 05 mVm2, which is too low, the microcell formation density is insufficient and the crystals become coarse, the film Q has many unevenness and scratches, the chemical conversion processability is poor, and the corrosion resistance of the paint is also poor. Ta.
また比較例（Ｉ）ｔＪ）はＮｉ酸化物・Ｎ１水酸化物の
付着量か過多で、これらの被覆率が過大のため、リン酸
塩結晶の生成が抑制されて化成皮膜付着量か僅少となり
、化成皮膜にスケが発生し化成処理性が不良で、かつ塗
膜剥離中も犬で塗装耐食性も不良であった。これに対し
、本発明例（Ｃ）〜■はいずれもＰ／Ｐ＋Ｈが１００％
で良好、化成皮膜付着量が適正、結晶の太きさも微細緻
密であり、ムラ・スケの発生もなく良好な化成処理性を
示すとともに、塗膜剥離中もＬＯ７１Ｆ以下と極めて良
好な塗装耐食性を示した。In addition, in Comparative Example (I) tJ), the amount of Ni oxide and N1 hydroxide deposited was excessive, and the coverage rate of these was excessive, so the formation of phosphate crystals was suppressed and the amount of chemical conversion coating deposited was very small. The chemical conversion coating had scratches, resulting in poor chemical conversion treatment properties, and the corrosion resistance of the coating was also poor even during coating peeling. On the other hand, in all of the invention examples (C) to ■, P/P+H is 100%.
The chemical conversion film has an appropriate amount of adhesion, the crystal size is fine and dense, and it shows good chemical conversion treatment properties without unevenness or scattering.It also has extremely good paint corrosion resistance with an LO of 71F or less even during paint film peeling. Indicated.
以上述べた如く本発明の表面処理鋼板は、酸洗工程を経
ないで製造された従来の冷延鋼板なみのすぐれた化成処
理性を有するとともに、化成処理後のカチオン電着塗装
において塗装耐食性の良好な塗膜の形成を可能とする詐
ってなく、実用化成処理ラインにおける化成処理液の組
成変動に対して過度な反応加速を示さず安定して良好な
化成結晶を形成し得るという有利性を備えているので、
従って自動車用鋼板として極めて実用価Ｉ直の高い鋼板
といえる。As described above, the surface-treated steel sheet of the present invention has excellent chemical conversion treatment properties comparable to conventional cold-rolled steel sheets manufactured without going through a pickling process, and also has excellent paint corrosion resistance in cationic electrodeposition coating after chemical conversion treatment. It has the advantage of not only being able to form good coating films, but also being able to stably form good chemical crystals without excessively accelerating the reaction in response to changes in the composition of the chemical conversion liquid in practical chemical conversion treatment lines. Since it is equipped with
Therefore, it can be said that this steel sheet has extremely high practical value as a steel sheet for automobiles.
第１図は化成反応時間とリン酸塩付着量の関係を示した
図である。FIG. 1 is a diagram showing the relationship between the chemical conversion reaction time and the amount of phosphate deposited.
Claims (1)
酸化物か、Ｎｉ元素重量換算で１〜１５０ ｍ！／Ｗ付
着していることを特徴とする化成処理性にすぐれた表面
処理鋼板。(1) At least one side has Ni oxide and Ni hydroxide, or 1 to 150 m in terms of Ni element weight! A surface-treated steel sheet with excellent chemical conversion treatment property characterized by adhesion of /W.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3505083A JPS59159987A (en) | 1983-03-02 | 1983-03-02 | Surface-treated steel sheet with superior suitability to chemical conversion treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3505083A JPS59159987A (en) | 1983-03-02 | 1983-03-02 | Surface-treated steel sheet with superior suitability to chemical conversion treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59159987A true JPS59159987A (en) | 1984-09-10 |
| JPS6229510B2 JPS6229510B2 (en) | 1987-06-26 |
Family
ID=12431206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3505083A Granted JPS59159987A (en) | 1983-03-02 | 1983-03-02 | Surface-treated steel sheet with superior suitability to chemical conversion treatment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59159987A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017077514A1 (en) * | 2015-11-05 | 2017-05-11 | Phosfan Ltd. | Composite phosphate coatings |
| US11142828B2 (en) | 2015-05-07 | 2021-10-12 | Phosfan Ltd. | Method for applying ultrafine phosphate conversion crystal coatings |
-
1983
- 1983-03-02 JP JP3505083A patent/JPS59159987A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11142828B2 (en) | 2015-05-07 | 2021-10-12 | Phosfan Ltd. | Method for applying ultrafine phosphate conversion crystal coatings |
| WO2017077514A1 (en) * | 2015-11-05 | 2017-05-11 | Phosfan Ltd. | Composite phosphate coatings |
| US11505868B2 (en) | 2015-11-05 | 2022-11-22 | Phosfan Ltd. | Composite phosphate coatings |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6229510B2 (en) | 1987-06-26 |
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