JPS5831390B2 - Kouzainohiyoumenshiyorihou - Google Patents
KouzainohiyoumenshiyorihouInfo
- Publication number
- JPS5831390B2 JPS5831390B2 JP12734875A JP12734875A JPS5831390B2 JP S5831390 B2 JPS5831390 B2 JP S5831390B2 JP 12734875 A JP12734875 A JP 12734875A JP 12734875 A JP12734875 A JP 12734875A JP S5831390 B2 JPS5831390 B2 JP S5831390B2
- Authority
- JP
- Japan
- Prior art keywords
- corrosion resistance
- solution
- pyrazole
- water glass
- paint adhesion
- 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.)
- Expired
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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
【発明の詳細な説明】
従来、鋼板の表面処理に多くの種類の方法があるが、そ
れらの中で最も代表的なものはクロメート処理及びリン
酸塩処理である。DETAILED DESCRIPTION OF THE INVENTION Conventionally, there are many types of methods for surface treatment of steel sheets, the most typical of which are chromate treatment and phosphate treatment.
これらのうちクロメート処理は主に耐食性の向上を目的
とし、リン酸塩処理は塗料密着性を向上するために行な
われている。Among these, chromate treatment is mainly used to improve corrosion resistance, and phosphate treatment is used to improve paint adhesion.
しかし、最近公害防止が強くさけばれるようになり、極
力クロメート処理をやめようとする傾向にあるが、現在
ではそれにかわる耐食性向上のための新しい表面処理方
法は開発されていない。However, recently there has been a strong emphasis on pollution prevention, and there is a tendency to avoid chromate treatment as much as possible, but no new surface treatment method for improving corrosion resistance has been developed to replace it.
従って、各工場では配水関係をクローズド化し、クロム
イオンが外部に排出するのを極力防止して公害対策を講
じているが、これらは膨大な設備と費用が必要である。Therefore, each factory takes measures against pollution by closing the water distribution system and preventing chromium ions from being discharged to the outside as much as possible, but these measures require a huge amount of equipment and expense.
これに対し、本発明者等は種々検討を行なった結果、無
公害で、かつきわめて優れた耐食性及び塗料密着性を有
する新しい表面処理方法を開発した。In response, the present inventors conducted various studies and developed a new surface treatment method that is non-polluting and has extremely excellent corrosion resistance and paint adhesion.
本発明を冷延薄板に処理する事によって、耐食性及び塗
料密着性の優れた層板を製造する事が出来、また、薄板
（熱延薄板材）、中板、厚板、その他、熱延材に処理す
る事によって赤錆防止を行なう事も出来る。By processing the present invention into a cold-rolled thin plate, it is possible to produce a layered plate with excellent corrosion resistance and paint adhesion. It is also possible to prevent red rust by treating it.
本発明は希薄ケイ酸ソーダあるいは水ガラス溶液に特殊
有機物を微量添加した液からなる。The present invention consists of a solution in which a trace amount of a special organic substance is added to a dilute sodium silicate or water glass solution.
一般にケイ酸ソーダや水ガラスはアノードインヒビター
として使用され、水溶液中に適当量添加して腐食を極力
抑制するのに使用されている。Generally, sodium silicate and water glass are used as anode inhibitors, and are added in appropriate amounts to an aqueous solution to suppress corrosion as much as possible.
しかし、これらを鋼材に塗布した場合には耐食性はほと
んど示さず、例えば水ガラス溶液を塗布して耐食性を得
ようとする場合には、きわめて高濃度の水ガラス溶液を
塗布しなければならない。However, when these are applied to steel materials, they exhibit almost no corrosion resistance. For example, when applying a water glass solution to obtain corrosion resistance, an extremely highly concentrated water glass solution must be applied.
マタ、多くの有機物が同様にインヒビターとして使用さ
れている。Mata, many organic substances have been used as inhibitors as well.
これらインヒビターは界面活性剤の１種で、水溶液中に
適当量添加すると、金属表面のカソード、アノードに吸
着する事によって腐食を抑制する。These inhibitors are a type of surfactant, and when added in an appropriate amount to an aqueous solution, they suppress corrosion by adsorbing to the cathode and anode on the metal surface.
しかし、これら有機インヒビターも水溶液の中でのみ効
果を発揮し、これら液を鋼板上に塗布しても発錆防止効
果は皆無に近い。However, these organic inhibitors are effective only in aqueous solutions, and even when these solutions are applied to steel plates, they have almost no rust prevention effect.
これに対し、本発明者等は種々検討を行なった結果、ケ
イ酸ソーダあるいは水ガラスの希薄溶液に下記の一般式
で示されるピラゾール又はその誘導体（ヒドロキシピラ
ゾール）を特定量添加した液を鋼材上に塗布するときわ
めて優れた耐食性及び塗料密着性を有する被膜が形成さ
れる事をみいだした。In response to this, the present inventors conducted various studies and found that a solution in which a specific amount of pyrazole or its derivative (hydroxypyrazole) represented by the following general formula was added to a dilute solution of sodium silicate or water glass was applied to the steel material. It has been found that a film with extremely excellent corrosion resistance and paint adhesion is formed when applied to the surface.
式中Ｒ１はＨ、−ＣＨ２０ＨもしくはＣＨ３ＣＯ０Ｈを
、Ｒ２およびＲ４は各々Ｈ又はＣ１〜ＣＩＯのアルキル
基、−０Ｈもしくは−ＣＨ２０Ｈを、また、Ｒ３はＨ，
−ＮＨ２の官能基を示す。In the formula, R1 is H, -CH20H or CH3CO0H, R2 and R4 are each H or an alkyl group of C1 to CIO, -0H or -CH20H, and R3 is H,
- Shows the functional group of NH2.
ケイ酸ソーダや水ガラスの希薄溶液に各種インヒビター
、例えばトルイジン、βナフチルアミン、αナフトキノ
リン、チオ尿素、アルキルジサルファイド、トリエタノ
ールアミン、モルホリン、オレイン酸ソーダ、安息香酸
ソーダ、その他多くの有機系インヒビターを添加し、鋼
材に塗布、乾燥して被膜の特性調査を行なった結果、無
添加の場合と比べ耐食性は差がないかむしろ劣る事が判
った。Various inhibitors such as toluidine, β-naphthylamine, α-naphthoquinoline, thiourea, alkyl disulfide, triethanolamine, morpholine, sodium oleate, sodium benzoate, and many other organic inhibitors are added to a dilute solution of sodium silicate or water glass. As a result of investigating the properties of the coating after adding it to steel and drying it, it was found that there was no difference in corrosion resistance compared to the case without the addition, or in fact it was inferior.
一方、ピラゾール又はその誘導体を水、重リン酸アルミ
、ポＩＪ ＩＪン酸、その他無機系バインダーあるいは
各種水溶性樹脂にとかし鋼板に塗布、乾燥した場合、無
処理材と比べ耐食性は多少向上するものの、大きな差は
認められない事が判った。On the other hand, when pyrazole or its derivatives are dissolved in water, aluminum biphosphate, polyphosphoric acid, other inorganic binders, or various water-soluble resins and applied to a steel plate and dried, the corrosion resistance is slightly improved compared to the untreated material. It was found that no significant difference was observed.
これに対し特定濃度のケイ酸ソーダあるいは水ガラスの
液にピラゾール又はその誘導体を特定量添加するといち
じるしい相乗効果が生じ、鋼材に塗布、乾燥するときわ
めて優れた耐食性及び塗料密着性を有する事が判った。On the other hand, when a specific amount of pyrazole or its derivatives was added to a solution of sodium silicate or water glass at a specific concentration, a remarkable synergistic effect was produced, and when applied to steel and dried, it was found to have extremely excellent corrosion resistance and paint adhesion. .
第１表〜第４表は水ガラス溶液に
構造式
で示すピラゾールの誘導体を種々の濃度添加して鋼板に
塗布し耐食性及び塗料密着性を調べた結果である。Tables 1 to 4 show the results of adding various concentrations of pyrazole derivatives represented by the structural formula to water glass solutions and applying them to steel plates to examine corrosion resistance and paint adhesion.
これらの結果から明らかなように、水ガラスの濃度が０
．１％以上、かつピラゾール又はその誘導体の濃度が０
．０５〜５％添加するとよい事が判った。As is clear from these results, when the concentration of water glass is 0
．． 1% or more and the concentration of pyrazole or its derivative is 0
．． It was found that it is good to add 0.05 to 5%.
なお、水ガラス濃度の上限値は、塗布のしやすさなどの
点から３０％に止めるのがよい。Note that the upper limit of the water glass concentration is preferably kept at 30% from the viewpoint of ease of application.
これらの結果はケイ酸ソーダ溶液にピラゾール又はその
誘導体を添加した場合にも同様の結果が得られた。Similar results were obtained when pyrazole or its derivatives were added to the sodium silicate solution.
また、ケイ酸ソーダあるいは水ガラス溶液に前記構造式
で示される以外に下記構造式
但し、
Ｒ，：Ｈ，−ＣＨ２０Ｈ１もしくはＣＨ３ＣＯ０ＨＲ２
，Ｒ４：Ｃ１〜Ｃ１ｏのアルキル基、−ＯＨもしくは−
ＣＨ２０Ｈ
Ｒ３：Ｈ，−ＮＨ２の官能基
で示されるピラゾールまたはその誘導体でも同種の実験
を行ったがいずれも同様の結果が得られた。In addition, in addition to the above structural formula, sodium silicate or water glass solution may have the following structural formula, provided that R, :H, -CH20H1 or CH3CO0HR2
, R4: C1 to C1o alkyl group, -OH or -
Similar experiments were conducted using pyrazole or its derivatives represented by the functional groups CH20H R3:H, -NH2, and similar results were obtained in all cases.
従って本発明においては請求範囲は次の通りとする。Accordingly, the scope of the present invention shall be defined as follows.
水ガラ７ある０゛はケイ酸ソーダ 。Water glass 7 and 0 are sodium silicate.
１、％〜３ｏ％のもしくはその両者濃度 上記液９′″添加する１ラゾー″又 。1.% to 3o% or both concentrations Add 9'' of the above liquid and add 1 razo''.
、。５〜５％はその誘導体の濃度
本発明処理剤は冷延薄板（層板）に処理して耐食性、塗
料密着性を向上する事が出来るが、ブリキ、亜鉛メッキ
、クロムメッキ、銅メッキなど各種メッキ製品に処理し
て特性を向上する事が出来る。,. 5 to 5% is the concentration of its derivative The treatment agent of the present invention can be applied to cold-rolled sheets (laminates) to improve corrosion resistance and paint adhesion, but it can also be applied to various types of tinplate, zinc plating, chrome plating, copper plating, etc. It can be processed into plated products to improve their properties.
さらに、ホット材（熱延鋼板）、中板、厚板、形鋼、パ
イプ、線材、その他各種熱延材に処理して発錆防止及び
塗料密着性を向上する事が出来、しかも、これらは無公
害であるため、その経済的メリットはきわめて大きなも
のである。Furthermore, hot rolled steel sheets, medium plates, thick plates, shaped steel, pipes, wire rods, and various other hot rolled materials can be treated to prevent rust and improve paint adhesion. Since it is non-polluting, its economic benefits are extremely large.
以下実施例について説明する。Examples will be described below.
実施例 １
水ガラス１％、ピラゾール０．１％の混合液に層板を浸
漬後、ロールで絞り乾燥して被膜の特性を調査した。Example 1 A laminate was immersed in a mixed solution of 1% water glass and 0.1% pyrazole, and then squeezed and dried with a roll to investigate the properties of the film.
耐食性はＪＩＳ−Ｚ−２３７１規格に準拠した塩水噴霧
試験（食塩水濃度５％、槽内温度３５℃、噴霧圧力２０
ｐｓｉ ）により２４時間後の発錆状況を肉眼で評価し
たが、発錆はまったく認められなかった。Corrosion resistance was determined by a salt spray test in accordance with the JIS-Z-2371 standard (salt water concentration 5%, tank temperature 35°C, spray pressure 20°C).
The rusting condition was visually evaluated after 24 hours using psi), but no rusting was observed.
また、メラミン系（焼付温度１２０°Ｃ）、アクリル系
（焼付温度１８０℃）の焼付塗料を使用し、塗料密着評
価法はＪＩＳ−５４００により描画、ゴバン目エリクセ
ン、衝撃、２Ｔ折曲げの各試験を行なったが、剥離の形
跡はまったく認められなかった。In addition, melamine-based (baking temperature: 120°C) and acrylic-based (baking temperature: 180°C) baking paints were used, and the paint adhesion evaluation methods were drawing, Erichsen, impact, and 2T bending tests according to JIS-5400. However, no evidence of peeling was observed at all.
実施例 ２
からなるピラソール誘導体０．３％の混合液にブリキ板
を浸漬し、ロールで絞り、乾燥して被膜の特性を調査し
た。A tin plate was immersed in a mixed solution of 0.3% pyrazole derivative consisting of Example 2, squeezed with a roll, and dried to investigate the properties of the film.
耐食性は実施例１と同一条件で行ない、１週間行なった
が発錆はまったく認められなかった。Corrosion resistance was tested under the same conditions as in Example 1 for one week, but no rust was observed.
また、実施例１と同一条件で塗料密着性を評価したが、
剥離の形跡はまったく認められなかった。In addition, paint adhesion was evaluated under the same conditions as in Example 1.
No evidence of peeling was observed.
実施例
なるピラゾール誘導体１％の混合液をスプレーで２次ス
ケール（黒皮）のある厚板に塗布し、乾燥した。A 1% mixed solution of the pyrazole derivative of the example was applied by spray to a thick board with secondary scale (black scale) and dried.
６ケ月問屋外に曝露したが赤錆の発生はまったく認めら
れなかった。Although exposed outdoors for 6 months, no red rust was observed.
実施例 ４
るピラゾール誘導体を０．１％添加した混合液に厚板を
浸漬後、ロールで絞り乾燥して被膜の特性を調査した。Example 4 A thick plate was immersed in a mixed solution containing 0.1% of a pyrazole derivative, and then squeezed and dried with a roll to investigate the properties of the film.
耐食性は実施例１と同一条件で行ない、１週間行ったが
発錆はまったく認められなかった。Corrosion resistance was tested under the same conditions as in Example 1 for one week, but no rust was observed.
また、実施例１と同一条件で塗料密着性を評価したが、
剥離の形跡はまったく認められなかった。In addition, paint adhesion was evaluated under the same conditions as in Example 1.
No evidence of peeling was observed.
Claims (1)
の混合された０、１％〜３０％の濃度の溶液に一般式（
ａ）に示すピラゾール又はその誘導体を０．０５〜５．
０％含有せしめた溶液を鋼材に塗布し、乾燥する事を特
徴とする鋼材の表面処理法一般式（ａ） 式中Ｒ１はＨｌ−ＣＨ２０ＨもしくはＣＨ３ＣＯ０Ｈを
、Ｒ３及びＲ４は各々Ｈ又はＣ１〜ＣＩＯのアルキル基
、ＯＨもしくは−ＣＨ２０Ｈを、また、Ｒ３は、Ｈ２Ｎ
Ｈ２の官能基を示す。[Claims] 1. A solution of the general formula (
The pyrazole or its derivative shown in a) is 0.05 to 5.
General formula (a): A method for surface treatment of steel materials, characterized by applying a solution containing 0% to steel materials and drying. an alkyl group, OH or -CH20H, and R3 is H2N
Indicates the functional group of H2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12734875A JPS5831390B2 (en) | 1975-10-24 | 1975-10-24 | Kouzainohiyoumenshiyorihou |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12734875A JPS5831390B2 (en) | 1975-10-24 | 1975-10-24 | Kouzainohiyoumenshiyorihou |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5252134A JPS5252134A (en) | 1977-04-26 |
| JPS5831390B2 true JPS5831390B2 (en) | 1983-07-05 |
Family
ID=14957692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12734875A Expired JPS5831390B2 (en) | 1975-10-24 | 1975-10-24 | Kouzainohiyoumenshiyorihou |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5831390B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS613822U (en) * | 1984-06-13 | 1986-01-10 | トキハ産業株式会社 | Flat structure plate |
| JPH0170985U (en) * | 1987-10-28 | 1989-05-11 | ||
| WO2007148801A1 (en) | 2006-06-23 | 2007-12-27 | Nippon Steel Corporation | Surface-treated metal material and metal surface treating agent |
-
1975
- 1975-10-24 JP JP12734875A patent/JPS5831390B2/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS613822U (en) * | 1984-06-13 | 1986-01-10 | トキハ産業株式会社 | Flat structure plate |
| JPH0170985U (en) * | 1987-10-28 | 1989-05-11 | ||
| WO2007148801A1 (en) | 2006-06-23 | 2007-12-27 | Nippon Steel Corporation | Surface-treated metal material and metal surface treating agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5252134A (en) | 1977-04-26 |
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