JP2001059184A - Surface treating solution for plated steel sheet and treatment thereby - Google Patents
Surface treating solution for plated steel sheet and treatment therebyInfo
- Publication number
- JP2001059184A JP2001059184A JP23167699A JP23167699A JP2001059184A JP 2001059184 A JP2001059184 A JP 2001059184A JP 23167699 A JP23167699 A JP 23167699A JP 23167699 A JP23167699 A JP 23167699A JP 2001059184 A JP2001059184 A JP 2001059184A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- plated steel
- urethane resin
- nonionic
- resin
- 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.)
- Withdrawn
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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐食性、塗装後密着性
および抵抗溶接性に優れた皮膜を形成できるめっき鋼板
用表面処理液および処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treating solution for a plated steel sheet capable of forming a film excellent in corrosion resistance, adhesion after painting and resistance welding, and a treating method.
【０００２】[0002]
【従来技術】亜鉛、アルミニウム、銅またはこれらの各
金属の合金等のめっき鋼板の後処理や塗装前処理には、
従来よりクロメ−ト処理が広く使用されているが、形成
されるクロメ−ト皮膜が人体に有害な６価クロムイオン
を微量含有しているため、従来よりその安全性が問題に
なっている。例えば、めっき鋼板の塗装材を家電製品や
事務機器のように人体が日常頻繁に接触する用途に使用
した場合、塗装が摩耗して、クロメ−ト皮膜が露出し、
クロメ−ト皮膜に接触することが考えられる。このた
め、めっき鋼板の後処理や塗装前処理には、非クロム酸
系の表面処理を施して、めっき鋼板の安全性を高めるこ
とが試みられ、従来より種々の表面処理液が開発されて
いる。2. Description of the Related Art Zinc, aluminum, copper or alloys of these metals are used for post-treatment and painting pre-treatment of plated steel sheets.
Conventionally, chromate treatment has been widely used. However, since the formed chromate film contains a trace amount of hexavalent chromium ions harmful to the human body, its safety has conventionally been a problem. For example, if the coating material of the plated steel sheet is used in applications where the human body frequently comes into contact, such as home appliances and office equipment, the coating will wear and the chromate film will be exposed,
Contact with the chromate coating is conceivable. For this reason, the post-treatment and the pre-coating treatment of the plated steel sheet have been attempted to enhance the safety of the plated steel sheet by applying a non-chromic acid-based surface treatment, and various surface treatment solutions have been developed conventionally. .
【０００３】本発明者らは、この非クロム酸系処理液の
１種として、水性ウレタン樹脂分散水溶液である水性ク
リヤ−塗料を利用して薄膜を形成することを考えた。こ
の塗料は水性ウレタン樹脂としてポリマ−骨格中にスル
ホン酸基、カルボキシル基、イソシアネ−ト基、水酸基
などの親水成分を直接導入した自己乳化型のものを用い
て、乳化剤を使用せずにウレタン樹脂粒子を水溶液中に
分散させたもので、樹脂皮膜はウレタン樹脂がアクリ
ル、エポキシ、ポリエステルなどの樹脂に比較して延
性、強度、密着性に優れていることから、薄膜にでき
る。しかし、この塗料は通常の１０μｍ以上の塗膜厚を
目的とするものであるため、抵抗溶接を可能にするた
め、樹脂皮膜を乾燥皮膜厚で０.１〜５μｍとなるよう
な薄膜にすると、耐食性、塗装後密着性が低下してしま
うという欠点があった。The present inventors have thought of forming a thin film by using an aqueous clear coating which is an aqueous urethane resin-dispersed aqueous solution as one type of the non-chromic acid-based treatment liquid. This paint is a self-emulsifying type in which a hydrophilic component such as a sulfonic acid group, a carboxyl group, an isocyanate group, or a hydroxyl group is directly introduced into a polymer skeleton as an aqueous urethane resin, and the urethane resin is used without using an emulsifier. Particles are dispersed in an aqueous solution, and the resin film can be formed into a thin film because urethane resin is superior in ductility, strength, and adhesion as compared with resins such as acrylic, epoxy, and polyester. However, since this paint is intended to have a coating thickness of 10 μm or more, in order to enable resistance welding, when the resin film is formed into a thin film having a dry film thickness of 0.1 to 5 μm, There is a disadvantage that the corrosion resistance and the adhesion after coating are reduced.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、有機系の非
クロム酸系処理液において、樹脂皮膜を抵抗溶接可能な
薄膜にしても、耐食性、塗装後密着性が低下しないめっ
き鋼板用表面処理液およびその処理方法を提供するもの
である。SUMMARY OF THE INVENTION The present invention relates to a surface treatment for a plated steel sheet in which the corrosion resistance and the adhesion after coating are not deteriorated even when the resin film is formed into a thin film capable of resistance welding in an organic non-chromic acid treatment solution. The present invention provides a liquid and a method for treating the liquid.
【０００５】[0005]
【課題を解決するための手段】本発明の表面処理液は、
ポリマ−骨格中に親水成分を直接導入した自己乳化型水
性ウレタン樹脂の分散水溶液にシランカップリング剤を
水性ウレタン樹脂の１〜９０重量％添加して、ｐＨを
２.５〜４.５に調節するとともに、水性ウレタン樹脂の
平均粒子径を２００ｎｍ以下にしたことを特徴としてい
る。水性ウレタン樹脂はノニオンイオン性のもの単独に
するか、アニオンイオン性、カチオンイオン性、ノニオ
ンイオン性の３種の親水成分を有するものの混合物の場
合、ノニオンイオン性のもの／（アニオンイオン性のも
の＋カチオンイオン性のもの＋ノニオンイオン性のも
の）の比率を０.９以上にするのが好ましい。また、シ
ランカップリング剤はオルガノアルコキシシランとオル
ガノシラノ−ルとの混合物にして、前者の29Ｓｉ−ＯＲ
と後者の29Ｓｉ−ＯＨの核磁気共鳴分析（ＮＭＲ）ピ−
ク強度比29Ｓｉ−ＯＲ／29Ｓｉ−ＯＨを１.０以下にす
るのが好ましい。処理方法はこの表面処理液をめっき鋼
板表面に乾燥皮膜厚が０.１〜５μｍになるように塗布
した後、水洗せず、板温８０〜２５０℃で乾燥すること
を特徴としている。Means for Solving the Problems The surface treating solution of the present invention comprises:
A silane coupling agent is added to a dispersion aqueous solution of a self-emulsifying aqueous urethane resin in which a hydrophilic component is directly introduced into a polymer skeleton by adding 1 to 90% by weight of the aqueous urethane resin to adjust the pH to 2.5 to 4.5. In addition, the average particle diameter of the aqueous urethane resin is set to 200 nm or less. The aqueous urethane resin may be nonionic alone or in the case of a mixture of those having three kinds of hydrophilic components of anionic, cationic and nonionic, nonionic / (anionic) + Cationic ion + nonionic ion) is preferably 0.9 or more. The silane coupling agent is a mixture of an organoalkoxysilane and an organosilanol, and the mixture of the former 29 Si-OR
And 29 Si-OH nuclear magnetic resonance spectroscopy (NMR)
The strength ratio 29 Si-OR / 29 Si-OH is preferably set to 1.0 or less. The treatment method is characterized in that the surface treatment liquid is applied to the surface of the plated steel sheet so that the dry film thickness becomes 0.1 to 5 μm, and then the sheet is dried at a sheet temperature of 80 to 250 ° C. without washing with water.
【０００６】[0006]
【作用】水性ウレタン樹脂の分散水溶液にシランカップ
リング剤を添加すると、加水分解して、脱水縮合を起こ
し、高分子皮膜下側のめっき鋼板や上側の塗膜と結合す
る。このため、処理液による樹脂皮膜は緻密になり、薄
くても耐食性や塗装後密着性も向上する。シランカップ
リング剤の添加量は水性ウレタン樹脂の１重量％未満で
あると、めっき鋼板との密着性が不充分となるため、耐
食性、塗装後密着性が改善されず、９０重量％より高い
と、造膜性、処理液安定性が低下することから、水性ウ
レタン樹脂の１〜９０重量％にする。処理液はシランカ
ップリング剤の加水分解促進と脱水縮合抑制のため、ｐ
Ｈを２.５〜４.５に調節する。シランカップリング剤の
添加により樹脂皮膜の密着性を改善するには、シランカ
ップリング剤を処理液中で加水分解させる必要がある
が、あまり加水分解させると、ゲル化して、処理液の安
定性が損なわれ、樹脂皮膜の耐食性も低下することがあ
る。加水分解速度、脱水縮合速度ともｐＨの影響を受
け、加水分解速度はｐＨ７前後で最も遅くなり、それよ
りｐＨが大きくなっても、小さくなっても次第に速くな
る。脱水縮合速度はｐＨ４.５前後で最も遅くなり、そ
れよりｐＨが大きくなっても、小さくなっても次第に速
くなる。したがって、ｐＨが４.５より低ければ、加水
分解速度とともに脱水縮合速度も促進されるが、ｐＨが
２.５より低くなると、処理液のゲル化、安定性損失が
大きくなる。一方、ｐＨを４.５より高くすると、脱水
縮合速度が遅くなり、好都合であるものの、加水分解速
度も遅くなるため、添加効果が小さくなる。ｐＨの調節
を無機酸により行う場合はリン酸、硝酸を用いるのが好
ましく、有機酸により行う場合には蟻酸、酢酸、マロン
酸を用いるのが好ましい。とくに、リン酸を用いると、
理由は不明であるが、耐食性が向上する。When a silane coupling agent is added to an aqueous urethane resin dispersion aqueous solution, the silane coupling agent is hydrolyzed to cause dehydration-condensation, and is bonded to a plated steel plate below the polymer film and the upper film. For this reason, the resin film formed by the treatment liquid becomes dense, and even if it is thin, the corrosion resistance and the adhesion after painting are improved. If the addition amount of the silane coupling agent is less than 1% by weight of the aqueous urethane resin, the adhesion to the plated steel sheet becomes insufficient, so that the corrosion resistance and the adhesion after coating are not improved. The content is 1 to 90% by weight of the aqueous urethane resin because the film-forming property and the stability of the processing solution are reduced. The treatment liquid is p-type to promote hydrolysis of the silane coupling agent and suppress dehydration condensation.
Adjust H to 2.5-4.5. In order to improve the adhesion of the resin film by adding a silane coupling agent, it is necessary to hydrolyze the silane coupling agent in the processing solution. And the corrosion resistance of the resin film may be reduced. Both the hydrolysis rate and the dehydration condensation rate are affected by the pH, and the hydrolysis rate is the slowest at around pH 7, and gradually increases as the pH becomes higher or lower. The dehydration / condensation rate is the slowest at around pH 4.5, and gradually increases as the pH increases or decreases. Therefore, when the pH is lower than 4.5, the rate of dehydration and condensation is accelerated as well as the rate of hydrolysis. However, when the pH is lower than 2.5, gelation and stability loss of the treatment liquid increase. On the other hand, when the pH is higher than 4.5, the rate of dehydration / condensation is slowed, which is convenient, but the rate of hydrolysis is also slowed, so that the effect of addition is reduced. When adjusting the pH with an inorganic acid, it is preferable to use phosphoric acid or nitric acid, and when adjusting the pH with an organic acid, it is preferable to use formic acid, acetic acid, or malonic acid. In particular, when phosphoric acid is used,
For unknown reasons, the corrosion resistance is improved.
【０００７】自己乳化型のウレタン樹脂には、導入した
親水成分によりイオン性がアニオン、カチオン、ノニオ
ンのものがあるが、水性クリヤ−塗料の場合、目的に応
じてそれらを適宜使用していた。しかし、処理液にシラ
ンカップリング剤を添加して、処理液ｐＨを２.５〜４.
５にすると、イオン性がアニオンやカチオンのものには
ウレタン樹脂粒子の凝集が起こり、平均粒径の増大、ゲ
ル化を招くことが判明した。一方、イオン性がノニオン
のものにはこのような現象が生じないことが判明した。
そこで、ウレタン樹脂はイオン性がノニオンのものだけ
を使用するか、アニオンのものやカチオンのものが混合
している場合には、ノニオンイオン性のもの／（アニオ
ンイオン性のもの＋カチオンイオン性のもの＋ノニオン
イオン性のもの）の比率を０.９以上にして、処理液が
ゲル化しないようにする。ウレタン樹脂のイオン性をノ
ニオンにするにはポリマ−骨格中にポリエチレングリコ
−ル、イソシアネ−トなどを導入すればよく、アニオン
にするには水酸基を、カチオンにするにはスルホン酸
（塩）基、カルボキシル（塩）基などを導入すればよ
い。[0007] Self-emulsifying urethane resins include those having anionic properties such as anions, cations and nonionics depending on the hydrophilic component introduced. In the case of aqueous clear coatings, these have been appropriately used depending on the purpose. However, a silane coupling agent is added to the processing solution to adjust the pH of the processing solution to 2.5 to 4.5.
When it was set to 5, it was found that when the ionicity is an anion or a cation, the urethane resin particles aggregate, causing an increase in the average particle diameter and gelation. On the other hand, it has been found that such a phenomenon does not occur in nonionic ionic substances.
Therefore, the urethane resin uses only the nonionic urethane resin, or when the anionic resin or the cationic resin is mixed, the nonionic resin / (anionic resin + cationic resin) (The ratio of the nonionic and nonionic components) is set to 0.9 or more to prevent the treatment liquid from gelling. To make the ionicity of the urethane resin nonionic, polyethylene glycol, isocyanate, or the like may be introduced into the polymer skeleton. A hydroxyl group is used as an anion, and a sulfonic acid (salt) group is used as cation. , A carboxyl (salt) group or the like may be introduced.
【０００８】樹脂皮膜を、厚みが５μｍ以下であるにも
拘わらず、耐食性、塗装後密着性の良好なものにするに
は、ウレタン樹脂の平均粒子径を２００ｎｍ以下にす
る。ここで、平均粒子径はｐＨを２.５〜４.５に調整し
た状態でのものであるが、耐食性は、図１に示すよう
に、平均粒子径が２００ｎｍを超えると、急激に低下す
る。付加重合法などで製造したものの中性水溶液での平
均粒子径が２００ｎｍ以下であっても、シランカップリ
ング剤を添加して、ｐＨを２.５〜４.５にすると、相互
に凝集し、平均粒子径が２００ｎｍより大きくなってし
まう。なお、図１はノニオン割合が１.０のウレタン樹
脂に29Ｓｉ−ＯＲと29Ｓｉ−ＯＨとのＮＭＲピ−ク強度
比を29Ｓｉ−ＯＲ／29Ｓｉ−ＯＨ＝０.５に調整したシ
ランカップリング剤（メルカプトプロピルトリメトキシ
シラン）を５重量％添加した後、ｐＨを３.５に調整し
た処理液において、ウレタン樹脂の平均粒子径を種々変
動させたものを調製して、それを電気亜鉛めっき鋼板
（板厚０.８ｍｍ、めっき付着量２０ｇ／ｍ2）に乾燥樹
脂皮膜厚で１.０μｍになるように塗布した後、板温１
６０℃で乾燥して、ＪＩＳ Ｚ ２３７１による塩水噴
霧試験を１２０時間実施することにより未加工部白錆発
生率（％）がウレタン樹脂の平均粒子径によりどのよう
に変化するのかを調査したものである。In order to make the resin film excellent in corrosion resistance and adhesion after coating, despite the thickness being 5 μm or less, the urethane resin has an average particle diameter of 200 nm or less. Here, the average particle diameter is a state in which the pH is adjusted to 2.5 to 4.5, but the corrosion resistance rapidly decreases when the average particle diameter exceeds 200 nm as shown in FIG. . Even if the average particle size in a neutral aqueous solution produced by an addition polymerization method or the like is 200 nm or less, when a silane coupling agent is added and the pH is adjusted to 2.5 to 4.5, they are mutually aggregated, The average particle size is larger than 200 nm. FIG. 1 shows a silane obtained by adjusting the NMR peak intensity ratio of 29 Si-OR and 29 Si-OH to a urethane resin having a nonionic ratio of 1.0 to 29 Si-OR / 29 Si-OH = 0.5. After adding 5% by weight of a coupling agent (mercaptopropyltrimethoxysilane), a treatment liquid in which the average particle size of the urethane resin is varied in a treatment liquid whose pH is adjusted to 3.5 is prepared, and the resultant is treated with an electric power. After coating on a galvanized steel sheet (sheet thickness 0.8 mm, coating weight 20 g / m 2 ) so that the dry resin film thickness becomes 1.0 μm, the sheet temperature is 1
After drying at 60 ° C. and conducting a salt spray test according to JIS Z 2371 for 120 hours, it was investigated how the white rust occurrence rate (%) in the unprocessed portion changes depending on the average particle diameter of the urethane resin. is there.
【０００９】シランカップリング剤にオルガノアルコキ
シシランを使用する場合、その加水分解物であるオルガ
ノシラノ−ルを一部混合しておくと、樹脂皮膜のめっき
鋼板との密着性が向上し、それに伴って、耐食性も向上
する。オルガノシラノ−ルの混合量は前者の29Ｓｉ−Ｏ
Ｒと後者の29Ｓｉ−ＯＨの核磁気共鳴分析（ＮＭＲ）ピ
−ク強度比29Ｓｉ−ＯＲ／29Ｓｉ−ＯＨが１.０以下に
なるようにするのが好ましい。なお、Ｒはアルキル基、
エポキシ基、ビニル基、アミノ基、（メタ）アクリル基
などである。When an organoalkoxysilane is used as the silane coupling agent, if the organosilanol, which is a hydrolyzate thereof, is partially mixed, the adhesion of the resin film to the plated steel sheet is improved, and the Therefore, the corrosion resistance is also improved. The mixing amount of organosilanol is the same as that of the former 29 Si-O
R and the latter 29 Si-OH of the nuclear magnetic resonance analysis (NMR) peak - click intensity ratio 29 Si-OR / 29 Si- OH is preferably used so that a 1.0 or less. Here, R is an alkyl group,
Examples include an epoxy group, a vinyl group, an amino group, and a (meth) acryl group.
【００１０】本発明でのウレタン樹脂は、以下の有機ポ
リイソシアネ−ト化合物とポリオ−ル化合物とを反応さ
せて得られるものでかまわない。まず、有機ポリイソシ
アネ−ト化合物としては、フェニレンジイソシアネ−
ト、トリレンジイソシアネ−ト、ジフェニルメタンジイ
ソシアネ−ト、ナフタレンジイソシアネ−ト等の芳香族
ジイソシアネ−トやヘキサメチレンジイソシアネ−ト、
リジンジイソシアネ−ト等の脂肪族ジイソシアネ−ト、
シクロヘキサンジイソシアネ−ト、ジシクロヘキシルメ
タンジイソシアネ−ト、イソホロンジイソシアネ−ト、
ノルボルナンジイソシアネ−ト、キシリレンジイソシア
ネ−ト、テトラメチルキシリレンジイソシアネ−ト等の
脂環族ジイソシアネ−トが挙げられる。また、ポリオ−
ル化合物としては、ポリエステルポリオ−ル、ポリエ−
テルポリオ−ル、ポリカ−ボネ−トポリオ−ル、ポリア
セタ−ルポリオ−ル、ポリアクリレ−トポリオ−ル、ポ
リエステルアミドポリオ−ル、ポリブタジエン系等のポ
リオレフィンポリオ−ル等が挙げられる。The urethane resin in the present invention may be obtained by reacting the following organic polyisocyanate compound with a polyol compound. First, as the organic polyisocyanate compound, phenylene diisocyanate
Aromatic diisocyanates such as benzene, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate and hexamethylene diisocyanate;
Aliphatic diisocyanates such as lysine diisocyanate,
Cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate,
Alicyclic diisocyanates such as norbornane diisocyanate, xylylene diisocyanate, and tetramethyl xylylene diisocyanate; Polio-
Polyester compounds such as polyester polyols and polyesters.
Examples include terpolyol, polycarbonate polyol, polyacetal polyol, polyacrylate polyol, polyesteramide polyol, and polyolefin polyol such as polybutadiene.
【００１１】シランカップリング剤の種類としては、と
くに制限はなく、例えば、アミノ系、ウレイド系、ビニ
ル系、メタクリル系、エポキシ系、メルカプト系、イソ
シアネ−ト系のアルコキシドシランの１種または２種以
上を使用すればよい。具体的には、アミノ系として、γ
−アミノプロピルトリエトキシシラン、γ−アミノプロ
ピルトリメトキシシラン、Ｎ−（β−アミノエチル）−
γ−アミノプロピルトリメトキシシラン、γ−フェニル
アミノプロピルトリメトキシシランなどが挙げられ、ウ
レイド系としては、ウレイドプロピルトリエトキシシラ
ン、ビニル系としては、ビニルトリエトキシシラン、ビ
ニルトリメトキシシラン、ビニルトリス（β−メトキシ
エトキシ）シランなどが挙げられる。また、メタクリル
系としては、γ−メタクリロキシプロピルトリメトキシ
シラン、γ−メタクリロキシプロピルメチルジメトキシ
シランが、エポキシ系としては、β−（３,４−エポキ
シシクロヘキシル）エチルトリメトキシシラン、γ−グ
リシドキシプロピルトリメトキシシランが挙げられる。
さらに、メルカプト系としては、γ−メルカプトプロピ
ルトリメトキシシランが、イソシアネ−ト系としては、
γ−イソシアネ−トプロピルトリエトキシシランなどが
挙げられる。The type of the silane coupling agent is not particularly limited. For example, one or two of an alkoxide silane of an amino type, a ureide type, a vinyl type, a methacryl type, an epoxy type, a mercapto type, and an isocyanate type. The above may be used. Specifically, as an amino group, γ
-Aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-
Examples of γ-aminopropyltrimethoxysilane and γ-phenylaminopropyltrimethoxysilane include ureido-based ureidopropyltriethoxysilane and vinyl-based vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β -Methoxyethoxy) silane and the like. Also, methacryl-based γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane, and epoxy-based β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and γ-glycid Xypropyltrimethoxysilane.
Further, as a mercapto type, γ-mercaptopropyltrimethoxysilane is used, and as an isocyanate type,
γ-isocyanatopropyltriethoxysilane and the like.
【００１２】処理液には、樹脂皮膜の耐指紋性、耐食
性、耐湿性などを高めるために必要に応じて、シリカゾ
ル、アルミナゾル、ジルコニアゾルなどのような無機ゾ
ルあるいはベンゾトリアゾ−ルのような有機防錆剤を添
加することが可能である。この場合、添加量がウレタン
樹脂の４０重量％より多いと、処理液の造膜性や安定性
が低下するので、４０重量％以下にするのが好ましい。
また、樹脂皮膜の潤滑性、加工性を高めるために必要に
応じて固体潤滑剤、例えば、フッ素樹脂、高圧ポリエチ
レンのようなオレフィン樹脂、ポリエチレンテレフタレ
−トのようなポリエステル樹脂の粉末を添加することも
可能である。この場合、添加量は処理液を安定させるた
めウレタン樹脂の２０重量％以下にするのが好ましい。The treatment liquid may contain an inorganic sol such as silica sol, alumina sol, zirconia sol, or an organic protective material such as benzotriazole, if necessary, in order to enhance the fingerprint resistance, corrosion resistance, moisture resistance, etc. of the resin film. It is possible to add rust agents. In this case, if the added amount is more than 40% by weight of the urethane resin, the film forming property and stability of the treatment liquid will be reduced.
In order to enhance the lubricity and workability of the resin film, a solid lubricant, for example, a powder of a fluorinated resin, an olefin resin such as high-pressure polyethylene, or a polyester resin such as polyethylene terephthalate is added as necessary. It is also possible. In this case, the addition amount is preferably 20% by weight or less of the urethane resin in order to stabilize the processing solution.
【００１３】めっき鋼板への処理液の塗布は、公知方
法、例えば、ロ−ルコ−ト法、エア−カ−テン法、静電
霧化法、スクイズロ−ルコ−ト法などにより行えばよい
が、塗布後は水洗せずに乾燥する。乾燥は板温８０〜２
５０℃で行う。８０℃より低いと、樹脂皮膜が十分乾燥
していないため、めっき鋼板を重ねたり、コイルに巻取
った場合、ブロッキングを起こし易く、２５０℃より高
いと、ウレタン樹脂が部分的に分解して、下地めっき鋼
板との密着性、皮膜の耐食性などが低下する。The treatment liquid may be applied to the plated steel sheet by a known method, for example, a roll coating method, an air-curtain method, an electrostatic atomization method, a squeeze roll coating method, or the like. After application, it is dried without washing with water. Drying at a plate temperature of 80-2
Perform at 50 ° C. If the temperature is lower than 80 ° C., the resin film is not sufficiently dried, so that when a plated steel sheet is piled up or wound on a coil, blocking easily occurs, and when the temperature is higher than 250 ° C., the urethane resin is partially decomposed, Adhesion with the base-plated steel sheet, corrosion resistance of the coating, etc. decrease.
【００１４】樹脂皮膜の厚みは、０.１〜５.０μｍにす
るのが好ましい。０.１μｍ未満では耐食性や塗装後の
塗膜密着性が不十分となり、５μｍより厚くすると、家
電製品の部材に加工後スポット溶接する場合の抵抗溶接
性が低下する。The thickness of the resin film is preferably 0.1 to 5.0 μm. When the thickness is less than 0.1 μm, the corrosion resistance and the adhesion of the coating film after coating are insufficient, and when the thickness is more than 5 μm, the resistance weldability in spot welding after processing to a member of a home appliance is reduced.
【００１５】めっき鋼板としては、Ｚｎ系めっき鋼板、
例えば、Ｚｎ、Ｚｎ−Ａｌ系合金、Ｚｎ−Ｎｉ系合金、
Ｚｎ−Ｍｎ系合金、Ｚｎ−Ｍｇ系合金、Ｚｎ−Ａｌ−Ｍ
ｇ系合金などのめっき鋼板、Ａｌ系めっき鋼板として
は、Ａｌ、Ａｌ−Ｚｎ系合金、Ａｌ−Ｓｉ系合金などの
めっき鋼板が挙げられる。さらに、Ｃｕ系めっき鋼板、
Ｎｉ系めっき鋼板などの処理も可能である。As the plated steel sheet, Zn-based plated steel sheet,
For example, Zn, Zn-Al alloy, Zn-Ni alloy,
Zn-Mn alloy, Zn-Mg alloy, Zn-Al-M
Examples of a plated steel sheet such as a g-based alloy and an Al-based plated steel sheet include plated steel sheets such as Al, an Al-Zn-based alloy, and an Al-Si-based alloy. Furthermore, Cu-based plated steel sheets,
It is also possible to treat Ni-based plated steel sheets.
【００１６】[0016]
【実施例】実施例１ 水性ウレタン樹脂の分散水溶液にシランカップリング剤
を添加して、リン酸によりｐＨを調整した。そして、こ
の処理液を電気亜鉛めっき鋼板（板厚０.６ｍｍ、めっ
き片面付着量２０ｇ／ｍ2）に塗布し、板温１６０℃で
乾燥した。表１に処理液組成、皮膜厚を示す。Example 1 A silane coupling agent was added to an aqueous urethane resin dispersion and the pH was adjusted with phosphoric acid. Then, this treatment liquid was applied to an electrogalvanized steel sheet (sheet thickness: 0.6 mm, adhesion amount on one side of plating: 20 g / m 2 ), and dried at a sheet temperature of 160 ° C. Table 1 shows the composition of the processing solution and the film thickness.
【００１７】[0017]
【表１】 （注１）ノニオン割合＝ノニオンイオン性のもの／（ア
ニオンイオン性のもの＋カチオンイオン性のもの＋ノニ
オンイオン性のもの）。実施例、比較例においてノニオ
ン割合が１.０未満のもの（実施例Ｎｏ.２、６、比較例
Ｎｏ.３〜５、８）はいずれもノニオンのものとアニオ
ンのものとの混合物もしくはアニオンのもの単独であ
る。 （注２）シランカップリング剤の種類 Ａ：メルカプトプロピルトリメトキシシラン Ｂ：γ−グリシドキシプロピルトリメトキシシラン Ｃ：ＡとＢとを１：１のモル比で混合したもの （注３）比較例Ｎｏ.３と５は処理液ゲル化のため被覆
できない。[Table 1] (Note 1) Nonion ratio = nonionic ionic / (anionic ionic + cationic ionic + nonionic ionic). In Examples and Comparative Examples, those having a nonion ratio of less than 1.0 (Examples Nos. 2, 6 and Comparative Examples Nos. 3 to 5 and 8) were all mixtures of nonionic and anionic ones or anionic ones. Things alone. (Note 2) Type of silane coupling agent A: Mercaptopropyltrimethoxysilane B: γ-glycidoxypropyltrimethoxysilane C: A mixture of A and B at a molar ratio of 1: 1 (Note 3) Comparison Examples Nos. 3 and 5 cannot be coated due to gelation of the processing liquid.
【００１８】次に、表１の処理液で、処理液安定性の良
好なもので処理した電気亜鉛めっき鋼板について、次の
ような性能試験を実施した。この結果を表２に示す。 （１）未加工部耐食性試験 塩水噴霧試験（ＪＩＳ Ｚ ２３７１）を１２０時間実
施して、白錆発生率が全面積の３％未満のものを記号◎
で、３％以上、１０％未満のものを記号○で、１０％以
上、３０％未満のものを記号△で、３０％以上のものを
記号×で評価した。 （２）加工部耐食性試験 ドロ−ビ−ド（摺動変形）試験を加圧力２００ｋｇｆ、
引き抜き速度５００ｍｍ／ｍｉｎの条件で実施した後、
上記塩水噴霧試験を７２時間実施して、白錆発生率が全
面積の５％未満のものを記号◎で、５％以上、１０％未
満のものを記号○で、１０％以上、３０％未満のものを
記号△で、３０％以上のものを記号×で評価した。Next, the following performance tests were carried out on electrogalvanized steel sheets treated with the treatment liquids shown in Table 1 having good treatment liquid stability. Table 2 shows the results. (1) Corrosion resistance test of unprocessed portion A salt spray test (JIS Z 2371) was performed for 120 hours.
, Those of 3% or more and less than 10% were evaluated with the symbol で, those of 10% or more and less than 30% were evaluated with the symbol 、, and those of 30% or more were evaluated with the symbol x. (2) Corrosion resistance test of processed part Draw bead (sliding deformation) test was performed with a pressing force of 200 kgf.
After performing under the condition of a drawing speed of 500 mm / min,
The above salt spray test was conducted for 72 hours, and those with a white rust occurrence rate of less than 5% of the total area were marked with ◎, those with 5% or more and less than 10% were marked with ○, and 10% or more and less than 30% Were evaluated with the symbol △, and those with 30% or more were evaluated with the symbol x.
【００１９】（３）塗膜密着性試験 有機溶剤系のアクリル塗料を乾燥塗膜厚３０μｍ塗装し
て、４０℃の温水に２４０時間浸漬した後、ＪＩＳ Ｋ
５４００の碁盤目法に準拠した塗膜密着性試験を行
い、塗膜残存率が１００％のものを記号◎で、８０％以
上、１００％未満のものを記号○で、４０％以上、８０
％未満のものを記号△で、４０％未満のものを記号×で
評価した。 （４）抵抗溶接性試験 ＣＦ型のＣｕ−Ｃｒ電極（先端径５ｍｍ）を用いて連続
スポット溶接を行い、連続打点数が２０００打点以上の
ものを記号◎、５００打点以上、１９９９打点以下のも
のを記号○で、２００打点以上、４９９打点以下のもの
を記号△で、１９９打点以下のものを記号×で評価し
た。 （５）処理液の経時変化試験 調製後３日経過した処理液を塗布して、塩水噴霧試験
（ＪＩＳ Ｚ ２３７１）を１２０時間実施し、白錆発
生率が全面積の３％未満のものを記号◎で、３％以上、
１０％未満のものを記号○で、１０％以上、３０％未満
のものを記号△、３０％以上のものを記号×で評価し
た。(3) Coating film adhesion test An organic solvent-based acrylic coating material was applied on a dry coating film having a thickness of 30 μm and immersed in warm water at 40 ° C. for 240 hours.
A coating film adhesion test based on the cross-cut method of 5400 was performed. A coating film surviving rate of 100% was indicated by a symbol 、, and a coating film remaining rate of 80% or more and less than 100% was indicated by a symbol ○.
% And less than 40% were evaluated with symbol x. (4) Resistance weldability test Continuous spot welding was performed using a CF-type Cu-Cr electrode (tip diameter: 5 mm). Was evaluated with the symbol 、, those with 200 to 499 spots or less were evaluated with the symbol △, and those with 199 or less were evaluated with the symbol ×. (5) Temporal change test of treatment liquid A treatment liquid three days after preparation was applied, and a salt spray test (JIS Z 2371) was performed for 120 hours. 3% or more with symbol ◎
Those with less than 10% were evaluated with the symbol ○, those with 10% or more and less than 30% were evaluated with the symbol △, and those with 30% or more were evaluated with the symbol x.
【００２０】[0020]
【表２】 [Table 2]
【００２１】[0021]
【発明の効果】以上のように、ポリマ−骨格中に親水成
分を直接導入した自己乳化型水性ウレタン樹脂の分散水
溶液において、水溶液中にシランカップリング剤を水性
ウレタン樹脂の１〜９０重量％添加して、ｐＨを２.５
〜４.５に調節するとともに、水性ウレタン樹脂の平均
粒子径を２００ｎｍ以下にすると、めっき鋼板の表面に
乾燥皮膜厚で０.１〜５μｍのような樹脂皮膜を形成し
た場合、樹脂皮膜の耐食性、塗装後密着性および抵抗溶
接性は向上し、処理液の経時変化も少ない。また、水性
ウレタン樹脂をノニオンイオン性のもの単独であるか、
アニオンイオン性、カチオンイオン性、ノニオンイオン
性の３種の親水成分を有するものの混合物の場合、ノニ
オンイオン性のもの／（アニオンイオン性のもの＋カチ
オンイオン性のもの＋ノニオンイオン性のもの）の比率
が０.９以上であると、処理液のゲル化を抑制でき、さ
らに、シランカップリング剤がオルガノアルコキシシラ
ンとオルガノシラノ−ルとの混合物で、前者の29Ｓｉ−
ＯＲと後者の29Ｓｉ−ＯＨの核磁気共鳴分析（ＮＭＲ）
ピ−ク強度比29Ｓｉ−ＯＲ／29Ｓｉ−ＯＨが１.０以下
であると、めっき鋼板との密着性が良好になる。また、
本発明の表面処理液はめっき鋼板表面に乾燥皮膜厚が
０.１〜５μｍになるように塗布した後、水洗せず、板
温８０〜２５０℃で乾燥すれば、耐食性、塗装後密着性
および抵抗溶接性に優れた樹脂皮膜を形成できる。As described above, in a dispersion aqueous solution of a self-emulsifying aqueous urethane resin in which a hydrophilic component is directly introduced into a polymer skeleton, a silane coupling agent is added to the aqueous solution in an amount of 1 to 90% by weight of the aqueous urethane resin. To a pH of 2.5
When the average particle size of the aqueous urethane resin is adjusted to 200 nm or less while adjusting to 4.5 to 4.5, when a resin film having a dry film thickness of 0.1 to 5 μm is formed on the surface of the plated steel sheet, the corrosion resistance of the resin film is In addition, the adhesion and resistance weldability after painting are improved, and there is little change over time of the treatment liquid. Also, whether the aqueous urethane resin is nonionic alone or
In the case of a mixture having three kinds of hydrophilic components of anionic, cationic and nonionic, the mixture of nonionic / (anionic + cationic + nonionic) When the ratio is 0.9 or more, gelation of the processing solution can be suppressed, and the silane coupling agent is a mixture of an organoalkoxysilane and an organosilanol, and the former 29 Si-
Nuclear magnetic resonance analysis (NMR) of OR and the latter 29 Si-OH
Peak - the click intensity ratio 29 Si-OR / 29 Si- OH is 1.0 or less, the better adhesion to the plated steel sheet. Also,
The surface treatment solution of the present invention is applied to the surface of the plated steel sheet so that the dry film thickness becomes 0.1 to 5 μm, and is not washed with water. If dried at a sheet temperature of 80 to 250 ° C., corrosion resistance, adhesion after coating and A resin film with excellent resistance weldability can be formed.
【図１】本発明の表面処理液におけるウレタン樹脂の平
均粒子径と処理液塗布電気亜鉛めっき鋼板の未加工部耐
食性との関係を示すグラフである。FIG. 1 is a graph showing the relationship between the average particle diameter of a urethane resin in a surface treatment liquid of the present invention and the corrosion resistance of an unprocessed portion of a galvanized steel sheet coated with a treatment liquid.
───────────────────────────────────────────────────── 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） Ｂ０５Ｄ 7/24 ３０３ Ｂ０５Ｄ 7/24 ３０３Ｅ Ｃ０９Ｄ 5/02 Ｃ０９Ｄ 5/02 175/04 175/04 183/06 183/06 (72)発明者 武津 博文 大阪府堺市石津西町５番地 日新製鋼株式 会社技術研究所表面処理研究部内 Ｆターム(参考） 4D075 BB24Z CA13 CA33 DB02 EA06 EA13 EB38 EC35 EC37 4J038 DG111 DG121 DG131 DG171 DG191 DG221 DL052 DL092 GA03 HA336 HA416 JA37 JC32 JC33 JC34 JC35 JC36 KA03 MA10 MA14 NA03 NA12 NA14 PA19 PC02 4K026 AA02 AA12 AA22 BB06 BB08 CA13 CA39 DA02 EB11 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B05D 7/24 303 B05D 7/24 303E C09D 5/02 C09D 5/02 175/04 175/04 183/06 183/06 (72) Inventor Hirofumi Takezu 5th Ishizu Nishimachi, Sakai City, Osaka Prefecture F-term (Reference) 4D075 BB24Z CA13 CA33 DB02 EA06 EA13 EB38 EC35 EC37 4J038 DG111 DG121 DG131 DG171 DG191 DG221 DL052 DL092 GA03 HA336 HA416 JA37 JC32 JC33 JC34 JC35 JC36 KA03 MA10 MA14 NA03 NA12 NA14 PA19 PC02 4K026 AA02 AA12 AA22 BB06 BB08 CA13 CA39 DA02 EB11
Claims (4)
した自己乳化型水性ウレタン樹脂の分散水溶液にシラン
カップリング剤を水性ウレタン樹脂の１〜９０重量％添
加して、ｐＨを２.５〜４.５に調節するとともに、水性
ウレタン樹脂の平均粒子径を２００ｎｍ以下にしたこと
を特徴とするめっき鋼板用表面処理液。1. A silane coupling agent is added to an aqueous dispersion of a self-emulsifying aqueous urethane resin in which a hydrophilic component is directly introduced into a polymer skeleton by adding 1 to 90% by weight of the aqueous urethane resin to adjust the pH to 2.5. A surface treating solution for a plated steel sheet, wherein the surface treating solution is adjusted to 4.5 and the average particle size of the aqueous urethane resin is set to 200 nm or less.
のもの単独であるか、アニオンイオン性、カチオンイオ
ン性、ノニオンイオン性の３種の親水成分を有するもの
の混合物の場合、ノニオンイオン性のもの／（アニオン
イオン性のもの＋カチオンイオン性のもの＋ノニオンイ
オン性のもの）の比率が０.９以上であることを特徴と
する請求項１に記載のめっき鋼板用表面処理液。2. When the aqueous urethane resin is a nonionic ionic resin alone or a mixture of three nonionic hydrophilic components having anionic ionic, cationic ionic and nonionic ionic properties, the nonionic ionic resin / ( The surface treatment solution for a plated steel sheet according to claim 1, wherein the ratio of (anionic ion + cationic ion + nonionic ion) is 0.9 or more.
コキシシランとオルガノシラノ−ルとの混合物で、前者
の29Ｓｉ−ＯＲと後者の29Ｓｉ−ＯＨの核磁気共鳴分析
（ＮＭＲ）ピ−ク強度比29Ｓｉ−ＯＲ／29Ｓｉ−ＯＨが
１.０以下であることを特徴とする請求項１に記載のめ
っき鋼板用表面処理液。3. A silane coupling agent comprising a mixture of an organoalkoxysilane and an organosilanol, wherein a peak intensity ratio of nuclear magnetic resonance analysis (NMR) of the former 29 Si-OR and the latter 29 Si-OH is 29. plated steel sheet for surface treatment solution according to claim 1, Si-OR / 29 Si-OH is equal to or less than 1.0.
処理液をめっき鋼板表面に乾燥皮膜厚が０.１〜５μｍ
になるように塗布した後、水洗せず、板温８０〜２５０
℃で乾燥することを特徴とするめっき鋼板の表面処理方
法。4. A dry film thickness of 0.1 to 5 μm on the surface of a plated steel sheet by applying any one of the surface treatment solutions according to claim 1 to 3.
After applying so that it does not wash with water, plate temperature 80-250
A method for treating a surface of a plated steel sheet, characterized by drying at a temperature of ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23167699A JP2001059184A (en) | 1999-08-18 | 1999-08-18 | Surface treating solution for plated steel sheet and treatment thereby |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23167699A JP2001059184A (en) | 1999-08-18 | 1999-08-18 | Surface treating solution for plated steel sheet and treatment thereby |
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| Publication Number | Publication Date |
|---|---|
| JP2001059184A true JP2001059184A (en) | 2001-03-06 |
Family
ID=16927248
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005120469A (en) * | 2003-09-26 | 2005-05-12 | Nippon Parkerizing Co Ltd | Composition for treating surface of metallic material, and surface treatment method |
| WO2007148801A1 (en) | 2006-06-23 | 2007-12-27 | Nippon Steel Corporation | Surface-treated metal material and metal surface treating agent |
| JP2009155688A (en) * | 2007-12-26 | 2009-07-16 | Nisshin Steel Co Ltd | Chemical conversion treatment liquid superior in storage stability for steel sheet |
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