JP2003155437A - Water-base surface treating composition and method for surface treatment of galvanized steel stock - Google Patents
Water-base surface treating composition and method for surface treatment of galvanized steel stockInfo
- Publication number
- JP2003155437A JP2003155437A JP2001356679A JP2001356679A JP2003155437A JP 2003155437 A JP2003155437 A JP 2003155437A JP 2001356679 A JP2001356679 A JP 2001356679A JP 2001356679 A JP2001356679 A JP 2001356679A JP 2003155437 A JP2003155437 A JP 2003155437A
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- Prior art keywords
- surface treatment
- zinc
- parts
- water
- weight
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Classifications
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水性表面処理組成
物、なかでも亜鉛系メッキ鋼材の表面処理に好適な塗布
無水洗型の水性表面処理組成物、及び該組成物を用いた
亜鉛メッキ鋼材の表面処理方法に関する。TECHNICAL FIELD The present invention relates to a water-based surface treatment composition, in particular, a coating-anhydrous wash-type water-based surface treatment composition suitable for surface treatment of zinc-based plated steel material, and a galvanized steel material using the composition. Surface treatment method.
【０００２】[0002]
【従来の技術およびその課題】近年、自動車部品、弱電
製品、汎用機器などの用途に用いられる電気亜鉛メッキ
鋼材として、特に耐食性に優れた表面処理材料が強く求
められており、その必要性は今後ますます強くなる傾向
にある。従来より鋼材の耐食性を向上させるための金属
メッキとして、一般に亜鉛メッキが行われており、さら
に耐食性を向上させるために亜鉛メッキ皮膜中に亜鉛以
外の金属を含有させたＺｎ−Ｎｉ、Ｚｎ−Ｎｉ−Ｃｏ、
Ｚｎ−Ｆｅ、Ｚｎ−Ａｌなどの各種の合金化亜鉛メッキ
も施されている。これらの亜鉛系メッキは、亜鉛の犠牲
防食によって鋼材の腐食を抑止するもので、高耐食性を
得ようとすれば、亜鉛付着量を増加させなければならな
いが、加工性、溶接性、生産性の低下などの問題が生じ
る。さらに、亜鉛系メッキを施した後にクロム酸塩処理
などの化成処理を施し、耐食性、塗装下地性を高めるこ
とも行われている。2. Description of the Related Art In recent years, there has been a strong demand for a surface-treated material having particularly excellent corrosion resistance as an electrogalvanized steel material used in applications such as automobile parts, light electrical appliances and general-purpose equipment. It tends to become stronger and stronger. Conventionally, zinc plating is generally performed as a metal plating for improving the corrosion resistance of steel materials, and Zn-Ni and Zn-Ni in which a metal other than zinc is contained in the zinc plating film to further improve the corrosion resistance. -Co,
Various alloyed zinc platings such as Zn-Fe and Zn-Al are also applied. These zinc-based platings suppress the corrosion of steel materials by sacrificial corrosion of zinc, and in order to obtain high corrosion resistance, it is necessary to increase the zinc adhesion amount, but the workability, weldability, and productivity Problems such as deterioration occur. Further, it is also practiced to perform a chemical conversion treatment such as a chromate treatment after applying a zinc-based plating to enhance the corrosion resistance and the coating base property.
【０００３】合金化亜鉛メッキの場合、不働態化皮膜を
形成し亜鉛の溶解を抑制することができるので、通常の
亜鉛メッキに比べて大幅に耐食性が向上しているが、合
金化亜鉛メッキ鋼材でも屋外で使用すると、水や海浜地
方における塩水、さらには酸性雨、工場煤煙、都市部に
於ける排気ガスなどの影響を受けて、白錆、赤錆が発生
しやすく、需要家の要求を満足させるには十分なものと
はいえない。また、亜鉛系メッキを施した後にクロム酸
塩処理を施すことにより不働態化皮膜を形成でき亜鉛の
溶解を抑制することができるので上記したように耐食性
を向上させることができるが、上記したと同様に屋外で
使用すると、水や海浜地方における塩水、さらには酸性
雨、工場煤煙、都市部に於ける排気ガスなどの影響を受
けて、白錆、赤錆が発生しやすく、需要家の要求を満足
させるには十分なものとはいえない。In the case of alloyed zinc plating, since a passivation film can be formed and the dissolution of zinc can be suppressed, the corrosion resistance is greatly improved as compared with normal zinc plating. However, when used outdoors, white rust and red rust easily occur due to the effects of water, salt water in the coastal area, acid rain, factory soot, exhaust gas in urban areas, etc. It's not enough to let you do it. In addition, it is possible to form a passivation film by performing a chromate treatment after applying a zinc-based plating and suppress dissolution of zinc, so that it is possible to improve corrosion resistance as described above. Similarly, when it is used outdoors, white rust and red rust easily occur under the influence of water, salt water in the coastal area, acid rain, factory soot, exhaust gas in urban areas, etc. Not enough to be satisfied.
【０００４】また、亜鉛系メッキ鋼材の耐食性を向上さ
せる目的でクロム酸塩処理した後、常温乾燥型の水溶性
樹脂やエマルションタイプの樹脂を主成分とする塗料を
塗装して室温ないしは低温で乾燥させたり、焼付塗料
（例えばアクリルメラミン樹脂系、アルキドメラミン樹
脂系、エポキシ樹脂系など）を塗装して１２０℃以上の
高温で焼付硬化させて２０〜４０μｍ程度の皮膜を形成
させる方法が行われている。しかしながら、常温乾燥型
塗料の皮膜を形成したものは、耐食性、耐水性において
劣り、他方、焼付塗料の皮膜を形成したものは、皮膜形
成に際し高温で焼付けるため、クロム酸塩皮膜に割れが
生じ易く、また、6価クロムが不溶化するため、クロム
酸塩処理皮膜固有の自己修復作用が低下し耐食性が著し
く劣化するなどの問題がある。Chromate treatment is carried out for the purpose of improving the corrosion resistance of the zinc-plated steel material, followed by coating with a paint mainly composed of a room temperature dry type water-soluble resin or an emulsion type resin and drying at room temperature or low temperature. Or a baking paint (for example, acrylic melamine resin-based, alkyd melamine resin-based, epoxy resin-based) is applied and baked at a high temperature of 120 ° C. or higher to form a film of about 20 to 40 μm. There is. However, those with a room temperature dry coating film formed are inferior in corrosion resistance and water resistance.On the other hand, those with a baking coating film formed are cracked in the chromate film because they are baked at a high temperature during film formation. In addition, since hexavalent chromium is insolubilized, there is a problem that the self-repairing action peculiar to the chromate treatment film is lowered and the corrosion resistance is significantly deteriorated.
【０００５】また、これら常温乾燥型樹脂または焼付乾
燥型樹脂を主成分とする塗料にクロム系防錆顔料（例え
ば、クロム酸ストロンチウム、クロム酸バリウム、クロ
ム酸鉛、塩基性クロム酸亜鉛など）を含有させた塗料
や、水溶性樹脂と水溶性クロム化合物とを組み合わせた
表面処理剤などを用いて耐食性の向上を図る方法がある
が、重金属による安全衛生および環境保全の面で極めて
問題が多い。In addition, a chromium-based rust preventive pigment (for example, strontium chromate, barium chromate, lead chromate, basic zinc chromate, etc.) is added to the paint containing the room temperature dry type resin or the baking dry type resin as a main component. Although there is a method of improving the corrosion resistance by using a coating material containing a water-soluble resin and a surface treatment agent in which a water-soluble resin and a water-soluble chromium compound are combined, there are many problems in terms of safety and hygiene due to heavy metals and environmental protection.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上述した
問題を解決でき、従来の表面処理組成物に比べ耐食性に
優れた亜鉛系メッキ鋼材を得ることができ、しかも鉛、
クロム、カドミウムなどの有害重金属を含有しない表面
処理組成物を提供することを目的に鋭意研究を重ねた結
果、α−オレフィンとα，β−エチレン性不飽和カルボ
ン酸との共重合体樹脂ディスパージョンとシリカ変性リ
ン酸マグネシウムとを組合せた水性表面処理組成物の処
理皮膜を形成した亜鉛系メッキ鋼材が優れた耐食性を示
すことを見出し本発明を完成するに至った。Means for Solving the Problems The present inventors have been able to solve the above-mentioned problems, obtain a zinc-based plated steel material that is more excellent in corrosion resistance than conventional surface treatment compositions, and lead,
As a result of intensive studies aimed at providing a surface treatment composition which does not contain harmful heavy metals such as chromium and cadmium, a copolymer resin dispersion of α-olefin and α, β-ethylenically unsaturated carboxylic acid The present invention has been completed by finding that a zinc-based plated steel material on which a treated film of an aqueous surface treatment composition in which the above and a silica-modified magnesium phosphate are combined exhibits excellent corrosion resistance.
【０００７】かくして、本発明に従えば、α−オレフィ
ンとα，β−エチレン性不飽和カルボン酸との共重合体
樹脂ディスパージョンの固形分１００重量部に対して、
シリカ変性リン酸マグネシウムを５〜６０重量部含有す
ることを特徴とする水性表面処理組成物が提供される。Thus, according to the present invention, based on 100 parts by weight of the solid content of the copolymer resin dispersion of α-olefin and α, β-ethylenically unsaturated carboxylic acid,
An aqueous surface treatment composition comprising 5 to 60 parts by weight of silica-modified magnesium phosphate is provided.
【０００８】また、本発明に従えば、さらに上記共重合
体樹脂ディスパージョンの固形分１００重量部に対し
て、チオウレア化合物及びジチオカルバミン酸塩から選
ばれる少なくとも１種の化合物を固形分量で１０重量部
以下含有する上記水性表面処理組成物が提供される。Further, according to the present invention, 10 parts by weight of a solid content of at least one compound selected from a thiourea compound and a dithiocarbamate salt is further added to 100 parts by weight of the solid content of the copolymer resin dispersion. There is provided the above-mentioned aqueous surface treatment composition containing:
【０００９】さらに、本発明に従えば、さらに上記共重
合体樹脂ディスパージョンの固形分１００重量部に対し
て、水分散性シリカを固形分量で１００重量部以下含有
する上記水性表面処理組成物が提供される。Furthermore, according to the present invention, the above-mentioned aqueous surface treatment composition further comprises 100 parts by weight or less of water-dispersible silica as a solid content based on 100 parts by weight of the solid content of the copolymer resin dispersion. Provided.
【００１０】また、本発明に従えば、亜鉛系メッキ鋼材
の表面に、上記水性表面処理組成物を塗布することを特
徴とする亜鉛系メッキ鋼材の表面処理方法が提供され
る。以下、本発明について詳細に説明する。Further, according to the present invention, there is provided a surface treatment method for a zinc-based plated steel material, which comprises applying the above-mentioned aqueous surface treatment composition to the surface of a zinc-based plated steel material. Hereinafter, the present invention will be described in detail.
【００１１】[0011]
【発明の実施の形態】まず、本発明の水性表面処理組成
物について詳細に説明する。本発明の水性表面処理組成
物は、下記の共重合体樹脂ディスパージョン、シリカ変
性リン酸マグネシウム、ならびに特定のチオウレア化合
物及びジチオカルバミン酸の塩から選ばれる化合物（以
下、「チオカルボニル基含有化合物」と略称することが
ある）を必須成分とする水性表面処理組成物である。BEST MODE FOR CARRYING OUT THE INVENTION First, the aqueous surface treatment composition of the present invention will be described in detail. The aqueous surface treatment composition of the present invention is a compound selected from the following copolymer resin dispersion, silica-modified magnesium phosphate, and a salt of a specific thiourea compound and dithiocarbamic acid (hereinafter, referred to as "thiocarbonyl group-containing compound"). It is an abbreviated name), which is an aqueous surface treatment composition.
【００１２】共重合体樹脂ディスパージョン
本発明組成物における共重合体樹脂ディスパージョン
は、α−オレフィンとα，β−エチレン性不飽和カルボ
ン酸との共重合体樹脂のディスパージョンである。α−
オレフィンとしては、例えば、エチレン、プロピレン、
ブチレン、イソブチレンなどを挙げることができる。
α，β−エチレン性不飽和カルボン酸としては、例え
ば、アクリル酸、メタクリル酸、マレイン酸などを挙げ
ることができる。該共重合体樹脂中におけるα，β−エ
チレン性不飽和カルボン酸の量は、水分散化のために必
要な量であって且つ耐水性を劣化させない量であればよ
く、通常、該共重合体樹脂を構成する全モノマー量中、
５〜４０重量％、好ましくは５〜２０重量％の範囲であ
ることが好適である。この共重合体の水分散化は樹脂骨
格中に導入されたカルボキシル基をアミン化合物（例え
ば、モノエチルアミンに代表される脂肪族アミン類、ジ
エタノールアミンに代表されるアルカノールアミン類、
モルフォリン、ピリジンなどの環状アミン類）、アンモ
ニア水などの塩基性物質で中和し水性媒体中に分散する
ことによって行うことができる。 Copolymer Resin Dispersion The copolymer resin dispersion in the composition of the present invention is a dispersion of a copolymer resin of α-olefin and α, β-ethylenically unsaturated carboxylic acid. α-
Examples of the olefin include ethylene, propylene,
Examples thereof include butylene and isobutylene.
Examples of the α, β-ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid and the like. The amount of the α, β-ethylenically unsaturated carboxylic acid in the copolymer resin may be an amount necessary for water dispersion and does not deteriorate the water resistance. Of the total amount of monomers that make up the united resin,
A range of 5 to 40% by weight, preferably 5 to 20% by weight is suitable. Water dispersion of this copolymer is carried out by introducing a carboxyl group introduced into the resin skeleton into an amine compound (for example, aliphatic amines represented by monoethylamine, alkanolamines represented by diethanolamine,
It can be carried out by neutralizing with a basic substance such as morpholine and pyridine) and a basic substance such as aqueous ammonia, and dispersing in an aqueous medium.
【００１３】また、共重合体樹脂ディスパージョンは、
低温硬化性を図るなどのために、樹脂中のカルボキシル
基が金属イオン、例えばＮａイオンなどによってイオン
結合されたアイオノマー（イオン性共重合体）であって
もよい。Further, the copolymer resin dispersion is
An ionomer (ionic copolymer) in which a carboxyl group in the resin is ion-bonded with a metal ion, for example, a Na ion may be used for the purpose of achieving low-temperature curability.
【００１４】シリカ変性リン酸マグネシウム
本発明組成物を構成するシリカ変性リン酸マグネシウム
は、リン酸マグネシウム１００重量部に対してケイ酸１
５重量部及びケイ酸カルシューム５重量部を加え、湿式
（水中で）反応させて得られるものであり、リン酸マグ
ネシウムの表面をシリカ処理することで、水溶出分を制
御したものである。表面処理の目的はアニオン性の前記
共重合体樹脂ディスパージョンの安定性を損なうことな
く、かつリン酸マグネシウムの持つキレート化能などに
よる亜鉛メッキに対する優れた防錆力を発揮させるため
である。水溶出分は、下記試験方法によって求めること
ができる。
（水溶出分の試験方法）２０℃の純水１００重量部中に
試験サンプルを１０重量部加え、懸濁させ、２０℃で７
日静置させた後の濾液について高周波誘導結合プラズマ
原子発光分析装置（ＩＣＰ−ＡＥＳ）を用いて、溶出元
素の分析を行う。 Silica-Modified Magnesium Phosphate The silica-modified magnesium phosphate constituting the composition of the present invention contains 1 part of silicic acid based on 100 parts by weight of magnesium phosphate.
It is obtained by adding 5 parts by weight and 5 parts by weight of calcium silicate and carrying out a wet reaction (in water), and the amount of water elution is controlled by treating the surface of magnesium phosphate with silica. The purpose of the surface treatment is not to impair the stability of the anionic copolymer resin dispersion, but to exert excellent rust preventive power against zinc plating due to the chelating ability of magnesium phosphate. The water elution content can be determined by the following test method. (Test method for water-eluted content) 10 parts by weight of a test sample was added to 100 parts by weight of pure water at 20 ° C., and the suspension was suspended at 7 ° C. at 20 ° C.
The filtrate after being left standing for a day is analyzed for eluting elements using a high frequency inductively coupled plasma atomic emission spectrometer (ICP-AES).
【００１５】無処理のリン酸マグネシウムの場合は、上
記試験方法によるマグネシウムの溶出量が水１ｍｌ中に
１２０μｇ以上であり、リンの溶出量が水１ｍｌ中に１
３０μｇ以上であって、マグネシウム及びリンとも溶出
量が多い。溶出量が多くなるとα−オレフィンとα，β
−エチレン性不飽和カルボン酸との共重合体樹脂ディス
パージョンの安定性が損なわれる。即ち、共重合体樹脂
ディスパージョンと溶出金属イオンとのイオン結合の進
行とリン酸イオンが中和剤を捕捉することから生じる共
重合体樹脂の疎水化の進行により、樹脂の凝集が生じて
くる。In the case of untreated magnesium phosphate, the elution amount of magnesium according to the above test method is 120 μg or more in 1 ml of water, and the elution amount of phosphorus is 1 in 1 ml of water.
It is 30 μg or more, and both magnesium and phosphorus have a large elution amount. When the amount of elution increases, α-olefin and α, β
-The stability of the copolymer resin dispersion with the ethylenically unsaturated carboxylic acid is impaired. That is, resin ionization occurs due to the progress of ionic bond between the copolymer resin dispersion and the eluted metal ions and the progress of hydrophobicization of the copolymer resin resulting from the capture of the neutralizing agent by the phosphate ions. .
【００１６】本発明組成物におけるシリカ変性リン酸マ
グネシウムは、水溶出分を抑制したものであるが、抑制
し過ぎると耐食性の向上効果が少なくなるため、通常、
水１ｍｌに対して、マグネシウム元素の溶出量が２０〜
５０μｇ／ｍｌ、特に２５〜４５μｇ／ｍｌの範囲内に
あり、リン元素の溶出量が３０〜８０μｇ／ｍｌ、特に
４０〜７０μｇ／ｍｌの範囲内にあることが、樹脂ディ
スパージョンの安定性及び耐食性の観点から好適であ
る。The silica-modified magnesium phosphate in the composition of the present invention suppresses the elution of water. However, if it is suppressed too much, the effect of improving the corrosion resistance is reduced, and therefore, it is usually
The elution amount of elemental magnesium is 20 to 1 ml of water.
Stability and corrosion resistance of the resin dispersion should be within the range of 50 μg / ml, especially 25 to 45 μg / ml, and the elution amount of elemental phosphorus within the range of 30 to 80 μg / ml, especially 40 to 70 μg / ml. From the viewpoint of
【００１７】本発明組成物において、シリカ変性リン酸
マグネシウムの配合量は、前記共重合体樹脂ディスパー
ジョンの固形分１００重量部に対して、５〜６０重量
部、特に１０〜３０重量部の範囲内にあることが耐食性
及び組成物の安定性の観点から好適である。In the composition of the present invention, the amount of silica-modified magnesium phosphate compounded is in the range of 5 to 60 parts by weight, particularly 10 to 30 parts by weight, based on 100 parts by weight of the solid content of the copolymer resin dispersion. It is preferable that it is within the range from the viewpoint of corrosion resistance and stability of the composition.
【００１８】本発明組成物は、前記共重合体樹脂ディス
パージョン及びシリカ変性リン酸マグネシウムを必須成
分とするものであるが、さらに必要に応じて、チオウレ
ア化合物、ジチオカルバミン酸塩、水分散性シリカ、水
可溶性有機溶剤、水；その他の防錆顔料、体質顔料や着
色顔料などの顔料類などを含有することができる。The composition of the present invention contains the above-mentioned copolymer resin dispersion and silica-modified magnesium phosphate as essential components. If necessary, a thiourea compound, dithiocarbamate, water-dispersible silica, It may contain a water-soluble organic solvent, water; other rust preventive pigments, pigments such as extender pigments and coloring pigments.
【００１９】上記本発明組成物中に必要に応じて配合さ
れるチオウレア化合物やジチオカルバミン酸塩は、金属
への強い吸着性を示し、キレート化能を有するものであ
り、これらの配合によってさらに耐食性の向上を図るＭ
ことができる。The thiourea compound and dithiocarbamate, which are optionally blended in the composition of the present invention, exhibit strong adsorption to metals and have chelating ability, and by blending these compounds, corrosion resistance is further improved. M to improve
be able to.
【００２０】チオウレア化合物の具体例としては、例え
ば、チオ尿素、トリメチルチオ尿素、Ｎ，Ｎ'−ジエチ
ルチオ尿素、トリブチルチオ尿素、Ｎ，Ｎ'−ジフェニ
ルチオ尿素、１，３−ビス（ジメチルアミノプロピル）
−２−チオ尿素、エチレンチオ尿素などを挙げることが
できる。Specific examples of the thiourea compound include thiourea, trimethylthiourea, N, N'-diethylthiourea, tributylthiourea, N, N'-diphenylthiourea and 1,3-bis (dimethylaminopropyl). )
2-thiourea, ethylene thiourea, etc. can be mentioned.
【００２１】ジチオカルバミン酸塩としては、例えば、
Ｎ，Ｎ−ジメチルジチオカルバミン酸、Ｎ，Ｎ−ジエチ
ルジチオカルバミン酸、Ｎ，Ｎ−ジブチルジチオカルバ
ミン酸、Ｎ，Ｎ−ジベンジルジチオカルバミン酸、Ｎ−
メチルＮ−フェニルジチオカルバミン酸、Ｎ−ペンタメ
チレンジチオカルバミン酸などのジチオカルバミン酸
の、金属塩、アミン塩などを挙げることができる。As the dithiocarbamate salt, for example,
N, N-dimethyldithiocarbamic acid, N, N-diethyldithiocarbamic acid, N, N-dibutyldithiocarbamic acid, N, N-dibenzyldithiocarbamic acid, N-
Examples thereof include metal salts and amine salts of dithiocarbamic acid such as methyl N-phenyldithiocarbamic acid and N-pentamethylenedithiocarbamic acid.
【００２２】ジチオカルバミン酸塩の具体例としては、
例えば、Ｎ，Ｎ−ジメチルジチオカルバミン酸亜鉛、
Ｎ，Ｎ−ジエチルジチオカルバミン酸亜鉛、Ｎ，Ｎ−ジ
ブチルジチオカルバミン酸亜鉛、Ｎ，Ｎ−ジベンジルジ
チオカルバミン酸亜鉛、Ｎ−メチルＮ−フェニルジチオ
カルバミン酸亜鉛、Ｎ−ペンタメチレンジチオカルバミ
ン酸亜鉛、Ｎ，Ｎ−ジメチルジチオカルバミン酸銅、
Ｎ，Ｎ−ジメチルジチオカルバミン酸第二鉄、Ｎ，Ｎ−
ジエチルジチオカルバミン酸ナトリウム、Ｎ，Ｎ−ジブ
チルジチオカルバミン酸ナトリウム、Ｎ，Ｎ−ジエチル
ジチオカルバミン酸テルル、Ｎ，Ｎ−ジエチルジチオカ
ルバミン酸ニッケル、Ｎ，Ｎ−ジブチルジチオカルバミ
ン酸ニッケル、Ｎ−ペンタメチレンジチオカルバミン酸
ピペリジン塩などを挙げることができる。Specific examples of the dithiocarbamate salt include:
For example, zinc N, N-dimethyldithiocarbamate,
N, N-diethyldithiocarbamate zinc, N, N-dibutyldithiocarbamate zinc, N, N-dibenzyldithiocarbamate zinc, N-methyl N-phenyldithiocarbamate zinc, N-pentamethylenedithiocarbamate zinc, N, N- Copper dimethyldithiocarbamate,
Ferric N, N-dimethyldithiocarbamate, N, N-
Sodium diethyldithiocarbamate, sodium N, N-dibutyldithiocarbamate, tellurium N, N-diethyldithiocarbamate, nickel N, N-diethyldithiocarbamate, nickel N, N-dibutyldithiocarbamate, N-pentamethylenedithiocarbamate piperidine salt, etc. Can be mentioned.
【００２３】チオウレア化合物及びジチオカルバミン酸
塩の配合量は、いずれも、得られる処理皮膜による耐食
性及び水性表面処理組成物の貯蔵安定性などの面から、
前記共重合体樹脂ディスパージョンの固形分１００重量
部に対して、固形分量で１０重量部以下、好ましくは１
〜５重量部の範囲内にあることが適している。The amounts of the thiourea compound and the dithiocarbamate salt are both selected from the viewpoints of the corrosion resistance of the resulting treatment film and the storage stability of the aqueous surface treatment composition.
With respect to 100 parts by weight of the solid content of the copolymer resin dispersion, the solid content is 10 parts by weight or less, preferably 1
Suitably it is in the range of -5 parts by weight.
【００２４】上記本発明組成物中に必要に応じて配合さ
れる水分散性シリカは、亜鉛系メッキ鋼材の表面に対す
る処理皮膜の密着性の向上などを目的に配合されるもの
であり、いわゆるコロイダルシリカであって、平均粒子
径が７〜１００ｎｍ、特に１０〜８０ｎｍの範囲のもの
が好ましく、通常、水性分散液として供給されるそれ自
体既知のものをそのまま使用することができる。水分散
性シリカの配合量は、前記共重合体樹脂ディスパージョ
ンの固形分１００重量部に対して、一般に、固形分量で
５〜１００重量部の範囲内であると配合の効果を効果的
に発揮できる。なかでも、平均粒子径が１０ｎｍ以上で
３０ｎｍ未満の水分散性シリカは、５〜６０重量部、平
均粒子径が３０〜８０ｎｍの水分散性シリカは、４０〜
８０重量部の配合量であることが特に好ましい。The water-dispersible silica, which is optionally added to the composition of the present invention, is added for the purpose of improving the adhesion of the treated film to the surface of the zinc-plated steel material, so-called colloidal. Silicas having an average particle diameter of 7 to 100 nm, particularly 10 to 80 nm are preferable, and those which are known per se and which are usually supplied as an aqueous dispersion can be used as they are. The amount of the water-dispersible silica is generally in the range of 5 to 100 parts by weight in terms of the solid content based on 100 parts by weight of the solid content of the copolymer resin dispersion. it can. Among them, the water-dispersible silica having an average particle diameter of 10 nm or more and less than 30 nm is 5 to 60 parts by weight, and the water-dispersible silica having an average particle diameter of 30 to 80 nm is 40 to 40 parts by weight.
A blending amount of 80 parts by weight is particularly preferable.
【００２５】本発明組成物中に必要に応じて配合される
水可溶性有機溶剤は、消泡、被塗物への濡れ性向上、凍
結温度の低下、粘度調整などの種々の目的で配合され
る。上記水可溶性有機溶剤としては、エタノール、ｎ−
プロパノール、イソプロパノール、ｎ−ブタノール、エ
チレングリコール、エチレングリコールモノエチルエー
テル、エチレングリコールモノブチルエーテル、ジエチ
レングリコールモノエチルエーテル、プロピレングリコ
ールモノチルエーテルなどのアルコール系有機溶剤；酢
酸エチル、酢酸プロピル、酢酸ブチルなどのエステル系
などの有機溶剤；アセトンなどを挙げることができる。
水可溶性有機溶剤の添加量は、表面処理組成物中、１５
重量％以下の範囲が好ましく、過剰に添加した場合、共
重合体樹脂ディスパージョンや水分散性シリカの安定性
を損ない、粘度上昇や凝集を引き起こす場合もあり、貯
蔵安定性の低下の原因となるため、注意が必要である。The water-soluble organic solvent, which is optionally blended in the composition of the present invention, is blended for various purposes such as defoaming, improvement of wettability to an object to be coated, lowering of freezing temperature and adjustment of viscosity. . Examples of the water-soluble organic solvent include ethanol and n-
Alcohol-based organic solvents such as propanol, isopropanol, n-butanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monotyl ether; esters of ethyl acetate, propyl acetate, butyl acetate, etc. An organic solvent such as a system; acetone and the like can be mentioned.
The amount of the water-soluble organic solvent added is 15 in the surface treatment composition.
The range of less than or equal to wt% is preferable, and when added in excess, it may impair the stability of the copolymer resin dispersion or water-dispersible silica, and may cause viscosity increase or aggregation, which causes a decrease in storage stability. Therefore, caution is required.
【００２６】本発明組成物中に必要に応じてシリカ変性
リン酸マグネシウムと併用して配合される防錆顔料とし
ては、有害重金属を含まないものが好ましく、例えば、
リン酸亜鉛、リン酸カルシウム、リンモリブデン酸カル
シウム、リンモリブデン酸アルミニウムなどのリン酸塩
系防錆顔料；亜リン酸亜鉛、亜リン酸ストロンチウム、
亜リン酸カルシウム、亜リン酸アルミニウムなどの亜リ
ン酸塩系防錆顔料；トリポリリン酸二水素アルミニウ
ム；シリカ系防錆顔料；及びこれらの防錆顔料に亜鉛化
合物、カルシウム化合物、マグネシウム化合物、シリカ
などによる表面処理を施した顔料を挙げることができ
る。これらの防錆顔料の総配合量は、前記共重合体樹脂
ディスパージョンの固形分１００重量部に対して、一般
に、固形分量で６０重量部以下である。The rust preventive pigment which is optionally used in combination with the silica-modified magnesium phosphate in the composition of the present invention is preferably one which does not contain harmful heavy metals.
Phosphate-based rust preventive pigments such as zinc phosphate, calcium phosphate, calcium phosphomolybdate, aluminum phosphomolybdate; zinc phosphite, strontium phosphite,
Phosphite-based rust preventive pigments such as calcium phosphite and aluminum phosphite; Aluminum dihydrogen tripolyphosphate; Silica rust preventive pigments; and surfaces of these rust preventive pigments with zinc compounds, calcium compounds, magnesium compounds, silica, etc. A pigment which has been treated may be mentioned. The total amount of these rust-preventive pigments is generally 60 parts by weight or less in terms of solid content, relative to 100 parts by weight of solid content of the copolymer resin dispersion.
【００２７】次に、本発明の表面処理方法について詳細
に説明する。本発明の表面処理方法は、亜鉛系メッキ鋼
材の表面に、上記本発明の水性表面処理組成物を塗布す
ることを特徴とするものである。Next, the surface treatment method of the present invention will be described in detail. The surface treatment method of the present invention is characterized in that the aqueous surface treatment composition of the present invention is applied to the surface of a zinc-based plated steel material.
【００２８】本発明の表面処理方法が適用される亜鉛系
メッキ鋼材としては、亜鉛メッキ鋼材；ニッケル−亜鉛
（Ｎｉ−Ｚｎ）メッキ、ニッケル−亜鉛−コバルト（Ｎ
ｉ−Ｚｎ−Ｃｏ）メッキ、亜鉛−アルミニウム（Ｚｎ−
Ａｌ）メッキ、鉄−亜鉛（Ｆｅ−Ｚｎ）メッキなどの亜
鉛合金メッキを施した亜鉛合金メッキ鋼材；上記亜鉛メ
ッキ鋼材や亜鉛合金メッキ鋼材の表面にリン酸塩処理ま
たはクロメート処理などの化成処理が施されたものなど
を挙げることができる。なかでも表面がクロメート処理
された亜鉛系メッキ鋼材が好適である。Zinc-based plated steel materials to which the surface treatment method of the present invention is applied include zinc-plated steel materials; nickel-zinc (Ni-Zn) plating, nickel-zinc-cobalt (N).
i-Zn-Co) plating, zinc-aluminum (Zn-
Al) plating, zinc alloy plated steel material plated with zinc alloy such as iron-zinc (Fe-Zn) plating; chemical conversion treatment such as phosphate treatment or chromate treatment on the surface of the zinc plated steel material or the zinc alloy plated steel material Examples of such products are those that have been applied. Among them, zinc-based plated steel material whose surface is chromated is suitable.
【００２９】本発明方法において、上記亜鉛系メッキ鋼
材の表面に前記本発明の水性表面処理組成物を塗布する
方法は特に限定されるものではなく、例えば、浸漬塗
装、スプレー塗装、刷毛塗装、シャワーコートなどの塗
布方法が利用でき、また、ボルトやナットのようなネジ
部品などの小物の亜鉛系メッキ鋼材を多量に処理する場
合は、浸漬塗装後に余滴を遠心分離するディップ・スピ
ン方式の塗装方法が効率的である。塗布された水性表面
処理組成物皮膜の乾燥は、処理皮膜が乾燥される条件で
あればよいが、省エネルギー、化成処理膜を劣化させな
いなどの観点から通常、鋼材温度が約１００℃以下、好
ましくは６０〜１００℃で約１０分間〜２５分間程度乾
燥させることによって達成される。１００℃以下の比較
的低温で乾燥させる場合には、亜鉛系メッキ鋼材の表面
がクロム酸塩処理されたものである場合にもクロム酸塩
処理膜を劣化させることはなく、亜鉛系メッキ鋼材は良
好な耐食性を示すことができる。In the method of the present invention, the method for applying the aqueous surface treatment composition of the present invention to the surface of the zinc-plated steel material is not particularly limited, and examples thereof include dip coating, spray coating, brush coating, and shower. If a coating method such as a coat can be used, or if a large amount of small zinc-based plated steel materials such as screw parts such as bolts and nuts are to be treated, a dip / spin method is used to centrifuge the remaining drops after immersion coating. Is efficient. The applied aqueous surface treatment composition film may be dried under the condition that the treated film is dried, but from the viewpoint of energy saving and not deteriorating the chemical conversion treatment film, the steel material temperature is usually about 100 ° C. or less, preferably It is achieved by drying at 60 to 100 ° C. for about 10 to 25 minutes. When the zinc-based plated steel material is dried at a relatively low temperature of 100 ° C. or lower, it does not deteriorate the chromate-treated film even when the surface of the zinc-based plated steel material is chromate-treated, and the zinc-based plated steel material is It can exhibit good corrosion resistance.
【００３０】本発明方法によって水性表面処理組成物か
らの処理塗膜を形成した表面処理亜鉛系メッキ鋼材が卓
越した耐食性を示すことができる。その理由は、形成さ
れた皮膜が共重合体樹脂ディスパージョンに基づくため
透湿率が小さく、腐食形成要因物質に対する障壁的働き
を有することとシリカ変性リン酸マグネシウムのキレー
ト作用との相乗効果によるものと考えられる。The surface-treated zinc-based plated steel material on which a treated coating film from the aqueous surface-treatment composition is formed by the method of the present invention can exhibit excellent corrosion resistance. The reason is that the formed film has a low moisture permeability because it is based on the copolymer resin dispersion, and has a synergistic effect with the chelating action of silica-modified magnesium phosphate, which has a barrier function against corrosion-forming factor substances. it is conceivable that.
【００３１】水性表面処理組成物が、さらに、チオウレ
ア化合物及び／又はジチオカルバミン酸塩を含有する場
合には、強い吸着能、キレート化作用による耐食性のさ
らなる向上ができる。水性表面処理組成物が、さらに水
分散性シリカを含有する場合には、腐食電流の局部集中
防止、処理塗膜の密着性の向上を図ることができ、これ
に基づいて、さらなる耐食性の向上を図ることができ
る。When the aqueous surface treatment composition further contains a thiourea compound and / or a dithiocarbamate, the strong adsorption ability and the corrosion resistance due to the chelating action can be further improved. When the water-based surface treatment composition further contains water-dispersible silica, it is possible to prevent local concentration of corrosion current and improve the adhesion of the treated coating film, and based on this, further improvement in corrosion resistance can be achieved. Can be planned.
【００３２】[0032]
【実施例】以下に実施例を示し、本発明をさらに具体的
に説明するが、本発明は以下の実施例に限定されるもの
ではない。以下、「部」および「％」はそれぞれ重量基
準によるものである。EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. Hereinafter, “part” and “%” are based on weight.
【００３３】実施例1
エチレン−アクリル酸共重合体樹脂ディスパージョン
（樹脂はエチレン８０％とアクリル酸２０％との共重合
体樹脂であり、アンモニア中和されてなるディスパージ
ョン、樹脂の数平均分子量は約８０００、固形分約２０
％）５００部（樹脂固形分量で１００部）に対して、シ
リカ変性リン酸マグネシウム（前記水溶出分の試験方法
による水溶出分は、濾液１ｍｌ中、マグネシウムが３４
μｇ、リンが５５μｇである）を２０部、予めＮ，Ｎ'
−ジエチルチオ尿素３部をエチレングリコールモノブチ
ルエーテル７部に溶解してなる濃度３０％の溶解液１０
部を混合してなる水性液に対して、エチレングリコール
モノブチルエーテル１７．６部及び脱イオン水を混合し
て固形分約２０％の水性表面処理組成物を得た。組成物
中のエチレングリコールモノブチルエーテル量は約４％
である。Example 1 Dispersion of ethylene-acrylic acid copolymer resin (The resin is a copolymer resin of 80% ethylene and 20% acrylic acid, and is a dispersion obtained by neutralizing with ammonia, and the number average molecular weight of the resin. Is about 8000, solid content is about 20
%) 500 parts (100 parts in terms of resin solid content), silica-modified magnesium phosphate (the water elution content according to the above-mentioned water elution content test method) was 34 mg of magnesium in 1 ml of the filtrate.
μg, phosphorus is 55 μg), 20 parts in advance, N, N ′
A solution of 3% of diethylthiourea dissolved in 7 parts of ethylene glycol monobutyl ether and having a concentration of 30% 10
17.6 parts of ethylene glycol monobutyl ether and deionized water were mixed with an aqueous liquid obtained by mixing the parts to obtain an aqueous surface treatment composition having a solid content of about 20%. The amount of ethylene glycol monobutyl ether in the composition is about 4%
Is.
【００３４】実施例２
実施例１で得た水性表面処理組成物６１５部に対して、
コロイダルシリカ水分散液ａ（＊１）６０部（固形分量
で３０部）及び脱イオン水８４部及びエチレングリコー
ルモノブチルエーテル６部を混合して固形分約２０％の
水性表面処理組成物を得た。組成物中のエチレングリコ
ールモノブチルエーテル量は約４％である。
（＊１）コロイダルシリカ水分散液ａ：平均粒子径約２
０ｎｍのコロイダルシリカ水分散液、固形分５０％。Example 2 With respect to 615 parts of the aqueous surface treatment composition obtained in Example 1,
60 parts of colloidal silica aqueous dispersion a (* 1) (30 parts by solid content), 84 parts of deionized water and 6 parts of ethylene glycol monobutyl ether were mixed to obtain an aqueous surface treatment composition having a solid content of about 20%. . The amount of ethylene glycol monobutyl ether in the composition is about 4%. (* 1) Colloidal silica aqueous dispersion a: average particle size about 2
0 nm colloidal silica aqueous dispersion, solid content 50%.
【００３５】実施例３
実施例１で用いたと同様のエチレン−アクリル酸共重合
体樹脂ディスパージョン５００部（樹脂固形分量で１０
０部）に対して、実施例１で用いたと同様のシリカ変性
リン酸マグネシウム２０部及びジエチルジチオカルバミ
ン酸亜鉛３部を混合してなる水性液に対して、エチレン
グリコールモノブチルエーテル２４．６部及び脱イオン
水を混合して固形分約２０％の水性表面処理組成物を得
た。組成物中のエチレングリコールモノブチルエーテル
量は約４％である。Example 3 500 parts of the same ethylene-acrylic acid copolymer resin dispersion as used in Example 1 (10 parts by resin solid content)
0 parts), 20 parts of the same silica-modified magnesium phosphate as used in Example 1 and 3 parts of zinc diethyldithiocarbamate were mixed, and 24.6 parts of ethylene glycol monobutyl ether and Ionized water was mixed to obtain an aqueous surface treatment composition having a solid content of about 20%. The amount of ethylene glycol monobutyl ether in the composition is about 4%.
【００３６】実施例４〜１１及び比較例１〜３
実施例１において、エチレン−アクリル酸共重合体樹脂
ディスパージョン５００部（樹脂固形分量１００部）に
対して配合する、シリカ変性リン酸マグネシウム、チオ
カルボニル基含有化合物、コロイダルシリカ水分散液、
その他の防錆顔料の種類及び量を後記表１に示すとおり
とする以外は実施例１と同様にして固形分約２０％の各
水性表面処理組成物を得た。各水性表面処理組成物中の
エチレングリコールモノブチルエーテル量は約４％であ
る。Examples 4 to 11 and Comparative Examples 1 to 3 Silica-modified magnesium phosphate blended with 500 parts of ethylene-acrylic acid copolymer resin dispersion (100 parts of resin solid content) in Example 1, Thiocarbonyl group-containing compound, colloidal silica aqueous dispersion,
Each aqueous surface treatment composition having a solid content of about 20% was obtained in the same manner as in Example 1 except that the types and amounts of other rust preventive pigments were changed as shown in Table 1 below. The amount of ethylene glycol monobutyl ether in each aqueous surface treatment composition is about 4%.
【００３７】実施例３〜６及び８〜１０並びに比較例２
及び３の各例において、その他の防錆顔料、チオウレア
化合物及びジチオカルバミン酸塩は、それぞれ同量のエ
チレングリコールモノブチルエーテル中に配合し粒子径
１０μｍ以下になるまで予め分散した固形分５０％の分
散液として使用した。Examples 3 to 6 and 8 to 10 and Comparative Example 2
In each of Examples 3 and 3, the other rust preventive pigment, the thiourea compound and the dithiocarbamate are mixed in the same amount of ethylene glycol monobutyl ether and dispersed in advance until the particle diameter becomes 10 μm or less. Used as.
【００３８】表１中の配合量はいずれも固形分重量部に
よる表示とする。The blending amounts in Table 1 are all expressed in parts by weight of solid content.
【００３９】上記実施例１〜１１及び比較例１〜３で得
た各水性表面処理組成物を密封容器に入れ、貯蔵安定性
の試験を行ない下記基準で評価した。貯蔵条件は４０℃
で１０日間とした。
○：粘度変化がほとんどなく良好、
△：粘度変化がかなり認められる、
×：著しい増粘が認められるか又はゲル化する。Each of the aqueous surface treatment compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 3 was placed in a hermetically sealed container, and a storage stability test was conducted and evaluated according to the following criteria. Storage condition is 40 ℃
For 10 days. ◯: Almost no change in viscosity, good Δ: Significant change in viscosity, ×: Significant increase in viscosity or gelation.
【００４０】下記表１における（註）は下記の意味を有
する。
（＊２）コロイダルシリカ水分散液ｂ：平均粒子径約５
５ｎｍのコロイダルシリカの水分散液、固形分５０％。
（＊３）多孔質シリカ：細孔容積が１．８ｍｌ／ｇ、平
均粒子径（コールターカウンター法）が３．５μｍであ
る非結晶構造（多孔質のスポンジ状構造）を持った高多
孔質シリカ。(Note) in Table 1 below has the following meanings. (* 2) Colloidal silica aqueous dispersion b: Average particle size of about 5
Aqueous dispersion of 5 nm colloidal silica, solid content 50%. (* 3) Porous silica: Highly porous silica having an amorphous structure (porous sponge-like structure) having a pore volume of 1.8 ml / g and an average particle size (Coulter counter method) of 3.5 μm. .
【００４１】[0041]
【表１】 [Table 1]
【００４２】比較例４
水性エポキシ変性アルキド樹脂とメラミン樹脂とを樹脂
成分とする樹脂溶液に、該樹脂溶液の樹脂固形分１００
部に対して２５部の亜鉛処理トリポリリン酸アルミニウ
ムを配合して水性表面処理組成物を得た。Comparative Example 4 A resin solution containing an aqueous epoxy-modified alkyd resin and a melamine resin as resin components was added to a resin solid content of 100%.
An aqueous surface treatment composition was obtained by blending 25 parts of zinc-treated aluminum tripolyphosphate with respect to 1 part.
【００４３】上記実施例１〜１１及び比較例１〜４の水
性表面処理組成物を使用して各表面処理鋼板を作成し
た。Each surface-treated steel sheet was prepared using the aqueous surface-treatment compositions of Examples 1 to 11 and Comparative Examples 1 to 4 above.
【００４４】亜鉛系メッキ鋼材の表面処理方法
実施例１２
亜鉛付着量２０ｇ／ｍ2（片面）の電気亜鉛メッキ鋼板
の表面にクロメート処理を施した鋼板（新日本製鉄
（株）製、商品名「ジンコートＥＧ−Ｃ」、表２におい
て「Ｚｎ」と表示する）の表面に実施例１で得た水性表
面処理組成物を乾燥膜厚が約４μｍとなるように塗布
し、８０℃で２０分間乾燥させて表面処理鋼板を得た。 Surface treatment method for zinc-based plated steel material Example 12 A galvanized steel sheet having a zinc adhesion amount of 20 g / m 2 (one side) and a chromate-treated steel sheet (manufactured by Nippon Steel Corporation, trade name " ZINCOAT EG-C ", indicated as" Zn "in Table 2), was coated with the aqueous surface treatment composition obtained in Example 1 to a dry film thickness of about 4 µm and dried at 80 ° C for 20 minutes. Then, a surface-treated steel sheet was obtained.
【００４５】実施例１３〜２２及び比較例５〜６
実施例１２において、使用する表面処理組成物の種類を
後記表２に示すとおりとする以外は実施例１２と同様に
行い、各表面処理鋼板を得た。Examples 13 to 22 and Comparative Examples 5 to 6 Each of the surface-treated steel sheets was carried out in the same manner as in Example 12 except that the type of the surface treatment composition used was as shown in Table 2 below. Got
【００４６】実施例２３
メッキ付着量４０ｇ／ｍ2（片面）の亜鉛−アルミニウ
ム合金化亜鉛メッキ（亜鉛９５％、アルミニウム５％、
表２において、「Ｚｎ−Ａｌ」と表示する）の表面にク
ロメート処理を施した鋼板の表面に、実施例２で得た水
性表面処理組成物を乾燥膜厚が約４μｍとなるように塗
布し、８０℃で２０分間乾燥させて表面処理鋼板を得
た。Example 23 Zinc-aluminum alloyed zinc plating with a coating weight of 40 g / m 2 (one side) (95% zinc, 5% aluminum,
In Table 2, "Zn-Al" is indicated) and the surface of the steel sheet subjected to chromate treatment was coated with the aqueous surface treatment composition obtained in Example 2 so that the dry film thickness was about 4 μm. Then, it was dried at 80 ° C. for 20 minutes to obtain a surface-treated steel sheet.
【００４７】実施例２４
メッキ付着量４０ｇ／ｍ2（片面）のニッケル−亜鉛合
金化亜鉛メッキ鋼板の表面にクロメート処理を施した鋼
板（表２において、「Ｎｉ−Ｚｎ」と表示する）の表面
に、実施例２で得た水性表面処理組成物を乾燥膜厚が約
４μｍとなるように塗布し、８０℃で２０分間乾燥させ
て表面処理鋼板を得た。Example 24 The surface of a nickel-zinc alloyed zinc-plated steel sheet having a coating weight of 40 g / m 2 (one side) and a chromate-treated surface (indicated as "Ni-Zn" in Table 2). Was coated with the aqueous surface treatment composition obtained in Example 2 so that the dry film thickness was about 4 μm, and dried at 80 ° C. for 20 minutes to obtain a surface-treated steel sheet.
【００４８】比較例７
実施例１２において、実施例１で得た水性表面処理組成
物のかわりに比較例４で得た水性表面処理組成物を使用
し、乾燥膜厚が約３０μｍとなるように塗布し、且つ乾
燥条件を８０℃で２０分間の条件から１４０℃で３０分
間の条件に変更する以外は実施例１２と同様に行い、表
面処理鋼板を得た。Comparative Example 7 In Example 12, the aqueous surface treatment composition obtained in Comparative Example 4 was used in place of the aqueous surface treatment composition obtained in Example 1, and the dry film thickness was about 30 μm. A surface-treated steel sheet was obtained in the same manner as in Example 12, except that the coating and drying conditions were changed from 80 ° C. for 20 minutes to 140 ° C. for 30 minutes.
【００４９】比較例８
亜鉛付着量２０ｇ／ｍ2（片面）の電気亜鉛メッキ鋼板
の表面にクロメート処理を施した鋼板（新日本製鉄
（株）製、商品名「ジンコートＥＧ−Ｃ」）そのものを
比較例８とする。Comparative Example 8 An electrogalvanized steel sheet having a zinc adhesion amount of 20 g / m 2 (one side) and a chromate-treated steel sheet (manufactured by Nippon Steel Co., Ltd., trade name “Zincoat EG-C”) itself was used. This is Comparative Example 8.
【００５０】上記実施例１２〜２４及び比較例５〜７で
得た各表面処理鋼板及び比較例８としての「ジンコート
ＥＧ−Ｃ」そのものを、７０×１５０ｍｍの大きさに切
断し、エッジ部を防錆塗料にてシールした鋼板を試験板
として、下記試験方法に基づいて耐塩水噴霧性及び耐水
性の試験を行った。その試験結果を後記表2に示す。The surface-treated steel sheets obtained in Examples 12 to 24 and Comparative Examples 5 to 7 and "Zincoat EG-C" as Comparative Example 8 themselves were cut into a size of 70 x 150 mm, and the edge portions were cut. Using a steel plate sealed with an anticorrosive paint as a test plate, salt water spray resistance and water resistance tests were conducted based on the following test methods. The test results are shown in Table 2 below.
【００５１】試験方法
塩水噴霧性：ＪＩＳ Ｚ２３７１に規定する塩水噴霧試
験法に準じて試験板に塩水噴霧試験を行い、試験時間２
５０時間及び５００時間のときの試験板表面における白
錆と赤錆の錆発生面積率（％）を求めた。
耐水性：
（塗面状態） ４０℃の脱イオン水中に試験板に２４０
時間浸漬後、試験板を引き上げ、処理塗膜の塗面状態を
目視にて下記基準により評価した。
○：異常なし
△：フクレ又は錆の発生が認められるが、異常発生面積
率が３０％未満
×：フクレ又は錆の発生が認められ、異常発生面積率が
３０％以上。 Test method Salt sprayability: A salt spray test was conducted on the test plate in accordance with the salt spray test method specified in JIS Z2371, and the test time was 2
The rust generation area ratio (%) of white rust and red rust on the surface of the test plate at 50 hours and 500 hours was determined. Water resistance: (Coating state) 240 in a deionized water of 40 ° C on a test plate
After immersion for a period of time, the test plate was pulled up, and the state of the coated surface of the treated coating film was visually evaluated according to the following criteria. ◯: No abnormality Δ: Occurrence of blisters or rust is observed, but abnormal area ratio is less than 30% ×: Occurrence of blisters or rust is observed, abnormal area ratio is 30% or more.
【００５２】（耐水性試験後の密着性） 上記耐水性試
験を行った試験板を室温で１時間放置して乾燥させた
後、素地に達する２ｍｍ間隔の平行な切り傷を縦、横各
１１本ナイフにて入れて２×２ｍｍの大きさの碁盤目を
計１００個作成し、この碁盤目部分にセロハン粘着テー
プを密着させ瞬時に剥離したときの碁盤目の剥離状態を
下記基準にて評価した。
○：剥離が認められない
△：剥離が認められるが、碁盤目部分の剥離面積は５０
％未満である
×：碁盤目部分の剥離面積は５０％以上である(Adhesion after Water Resistance Test) After the test plate subjected to the water resistance test was left to dry at room temperature for 1 hour, parallel cuts reaching the substrate at intervals of 2 mm were formed in 11 rows each. A total of 100 cross-cuts having a size of 2 × 2 mm were made by inserting with a knife, and a cellophane adhesive tape was brought into close contact with the cross-cut portion, and the peeled state of the cross-cut was evaluated according to the following criteria. . ◯: No peeling was observed Δ: Peeling was observed, but the peeled area of the cross-cut was 50
% Is less than x: The peeled area of the cross-cut portion is 50% or more
【００５３】[0053]
【表２】 [Table 2]
【００５４】[0054]
【発明の効果】本発明の水性表面処理組成物は、透湿率
の皮膜を形成することができ、腐食形成要因物質に対す
る障壁的働きと、シリカ変性リン酸マグネシウムとチオ
カルボニル基含有化合物のキレート化能、吸着能による
亜鉛系メッキ層の不溶化作用との相乗効果により亜鉛系
メッキ鋼材に対して卓越した耐食性を示す処理塗膜を形
成することができる。本発明の水性表面処理組成物は、
さらに水分散性シリカを含有する場合には、亜鉛系メッ
キに対する処理膜の密着性が向上するため耐食性の向上
に寄与することができる。INDUSTRIAL APPLICABILITY The aqueous surface treatment composition of the present invention can form a film having a moisture permeability, acts as a barrier against a corrosion-forming factor substance, and chelate a silica-modified magnesium phosphate and a thiocarbonyl group-containing compound. It is possible to form a treated coating film exhibiting excellent corrosion resistance to a zinc-based plated steel material by a synergistic effect with the insolubilizing action of the zinc-based plating layer due to the chemical conversion ability and the adsorption ability. The aqueous surface treatment composition of the present invention,
Further, when the water-dispersible silica is contained, the adhesion of the treated film to the zinc-based plating is improved, which can contribute to the improvement of corrosion resistance.
【００５５】また、本発明の表面処理組成物は、人体お
よび環境に有害な重金属類を含まず、また塗布無水洗型
の組成物であるため、排水、スラッジの発生などの問題
もなく、処理工程の簡略化、省力化などを図ることがで
きる。The surface-treating composition of the present invention does not contain heavy metals harmful to the human body and environment, and is a coating anhydrous washing type composition. Therefore, there are no problems such as drainage and sludge generation. It is possible to simplify the process and save labor.
【００５６】さらに、本発明の表面処理組成物からの塗
装膜は、１００℃以下の低温で乾燥させることが可能で
あり、省エネルギー、及び亜鉛系メッキ鋼材表面がクロ
ム酸塩処理された場合である場合の熱によるクロム酸塩
処理の劣化を起こさないという効果も有する。Furthermore, the coating film from the surface treatment composition of the present invention can be dried at a low temperature of 100 ° C. or lower, which is energy saving and is the case where the surface of the zinc-based plated steel material is treated with chromate. It also has an effect of not causing deterioration of chromate treatment due to heat in some cases.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｄ 5/00 Ｃ０９Ｄ 5/00 Ｚ Ｃ２３Ｃ 22/22 Ｃ２３Ｃ 22/22 28/00 28/00 Ａ Ｆターム(参考） 4D075 CA33 CA47 DA06 DA23 DB02 DB05 DC11 DC15 DC18 EA06 EA07 EA10 EA19 EB13 EB20 EB56 EC03 EC07 EC54 4J038 CB001 CB061 CB101 CB111 GA06 HA416 HA446 JC05 JC06 KA05 NA03 PC02 4K026 AA02 AA12 AA22 BA03 BB08 BB10 CA03 CA23 DA02 DA11 EB11 4K044 AA02 AB02 BA06 BA10 BA21 BB03 BC02 CA16 CA53 CA62─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C09D 5/00 C09D 5/00 Z C23C 22/22 C23C 22/22 28/00 28/00 A F term ( Reference) 4D075 CA33 CA47 DA06 DA23 DB02 DB05 DC11 DC15 DC18 EA06 EA07 EA10 EA19 EB13 EB20 EB56 EC03 EC07 EC54 4J038 CB001 CB061 CB101 CB111 GA06 HA416 HA446 JC05 JC06 KA05 NA03 PC02 4K026 A22 DA02 A02 BA02 A02 A02 A03 A02 A03 A02 A02 A02 A02 A02 A03 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A02 A03 BA06 BA10 BA21 BB03 BC02 CA16 CA53 CA62
Claims (4)
飽和カルボン酸との共重合体樹脂ディスパージョンの固
形分１００重量部に対して、シリカ変性リン酸マグネシ
ウムを５〜６０重量部含有することを特徴とする水性表
面処理組成物。1. A silica-modified magnesium phosphate is contained in an amount of 5 to 60 parts by weight with respect to 100 parts by weight of a solid content of a copolymer resin dispersion of an α-olefin and an α, β-ethylenically unsaturated carboxylic acid. An aqueous surface treatment composition comprising:
ンの固形分１００重量部に対して、チオウレア化合物及
びジチオカルバミン酸塩から選ばれる少なくとも１種の
化合物を固形分量で１０重量部以下含有する請求項１記
載の水性表面処理組成物。2. The solid content of at least one compound selected from a thiourea compound and a dithiocarbamate salt is 10 parts by weight or less based on 100 parts by weight of the solid content of the copolymer resin dispersion. The aqueous surface treatment composition described.
ンの固形分１００重量部に対して、水分散性シリカを固
形分量で１００重量部以下含有する請求項１又は２記載
の水性表面処理組成物。3. The aqueous surface treatment composition according to claim 1, further comprising 100 parts by weight or less of water-dispersible silica as a solid content based on 100 parts by weight of the solid content of the copolymer resin dispersion.
３のいずれか１項に記載の水性表面処理組成物を塗布す
ることを特徴とする亜鉛系メッキ鋼材の表面処理方法。4. The surface of the zinc-based plated steel material according to claim 1.
4. A surface treatment method for a zinc-based plated steel material, which comprises applying the aqueous surface treatment composition according to any one of 3 above.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005194627A (en) * | 2003-12-10 | 2005-07-21 | Sumitomo Metal Ind Ltd | Water based treatment chemical for metal surface |
| JP2016505350A (en) * | 2012-11-07 | 2016-02-25 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Mixtures for coating metal surfaces |
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2001
- 2001-11-21 JP JP2001356679A patent/JP4061054B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005194627A (en) * | 2003-12-10 | 2005-07-21 | Sumitomo Metal Ind Ltd | Water based treatment chemical for metal surface |
| JP2016505350A (en) * | 2012-11-07 | 2016-02-25 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Mixtures for coating metal surfaces |
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