JPH0696774B2 - Highly corrosion-resistant colored surface-treated steel sheet with excellent lubricity - Google Patents
Highly corrosion-resistant colored surface-treated steel sheet with excellent lubricityInfo
- Publication number
- JPH0696774B2 JPH0696774B2 JP6968385A JP6968385A JPH0696774B2 JP H0696774 B2 JPH0696774 B2 JP H0696774B2 JP 6968385 A JP6968385 A JP 6968385A JP 6968385 A JP6968385 A JP 6968385A JP H0696774 B2 JPH0696774 B2 JP H0696774B2
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- weight
- treated steel
- solid lubricant
- colored surface
- 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 - Lifetime
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- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は鋼板表面に着色樹脂皮膜が形成された塗装性に
優れた表面処理鋼板において、着色樹脂皮膜の耐食性、
密着性および潤滑性を向上させた高耐食性着色表面処理
鋼板に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to a surface-treated steel sheet having a colored resin film formed on the surface of the steel sheet and having excellent coatability, and the corrosion resistance of the colored resin film,
The present invention relates to a highly corrosion-resistant colored surface-treated steel sheet having improved adhesion and lubricity.
（従来技術） 冷延鋼板やめっき鋼板を有色顔料を含有した水分散性も
しくは水溶性の樹脂で処理して、その表面に塗装性、耐
食性を付与する着色樹脂皮膜を形成した表面処理鋼板の
うち、従来より比較的塗装性、耐食性に優れたものとし
て、鋼板表面にクロメート皮膜を形成し、さらにそのク
ロメート皮膜の上に着色樹脂単独皮膜もしくは顔料以外
の無機物を含む着色樹脂皮膜を形成したものがある。こ
の表面処理鋼板は第１層のクロメート皮膜により耐食性
を付与し、第２層の着色樹脂皮膜で塗装性を付与したも
のであるが、着色樹脂皮膜の樹脂としては樹脂皮膜を水
溶性で形成する都合上分子内に水酸基を有する親水性の
ものが用いられていた。(Prior Art) Among the surface-treated steel sheets on which a cold-rolled steel sheet or a plated steel sheet is treated with a water-dispersible or water-soluble resin containing a colored pigment, and a colored resin film that imparts coatability and corrosion resistance to the surface is formed , Which has relatively excellent paintability and corrosion resistance compared to the conventional one, has a chromate film formed on the surface of the steel sheet, and a colored resin film formed on the chromate film or a colored resin film containing an inorganic substance other than pigment. is there. This surface-treated steel sheet has corrosion resistance imparted by the first layer of chromate film and coatability by the second layer of colored resin film, and the resin film of the colored resin film is water-soluble. For convenience, hydrophilic ones having a hydroxyl group in the molecule have been used.
（発明が解決しようとする問題点） しかしながら上記のような表面処理鋼板の場合、その耐
食性は第１層のクロメート皮膜に依存しているため、耐
食性を向上させようとしてもその向上には限界があっ
た。このため耐食性をさらに向上させるには第２層の着
色樹脂皮膜の耐食性を向上させる必要があった。(Problems to be Solved by the Invention) However, in the case of the surface-treated steel sheet as described above, its corrosion resistance depends on the chromate film of the first layer, so even if it is attempted to improve the corrosion resistance, there is a limit to the improvement. there were. Therefore, in order to further improve the corrosion resistance, it is necessary to improve the corrosion resistance of the colored resin film of the second layer.
着色樹脂皮膜の耐食性を向上させる方法としては着色樹
脂皮膜中に６価クロムに含有させる方法が考えられる
が、この方法により６価クロムを含有させるには６価ク
ロムを含有する樹脂皮膜処理液で処理する必要がある。
しかし樹脂皮膜処理液に６価クロムを含有させるのに無
水クロム酸やクロム酸塩を添加すると樹脂分子の水酸基
が酸化されて、処理液はゲル化し、鋼板に塗布できなく
なり、６価クロムも３価クロムに還元されて耐食性を発
揮しなくなる。このため従来着色樹脂皮膜中に６価クロ
ムを含有させることは困難であった。As a method for improving the corrosion resistance of the colored resin film, a method of adding hexavalent chromium to the colored resin film is conceivable. To add hexavalent chromium by this method, a resin film treatment liquid containing hexavalent chromium is used. Need to be processed.
However, if chromic anhydride or chromate is added to contain hexavalent chromium in the resin coating solution, the hydroxyl groups of the resin molecules will be oxidized, the treatment solution will gel, and it will not be possible to apply it to the steel sheet. It is reduced to valent chromium and no longer exhibits corrosion resistance. Therefore, it has been difficult to include hexavalent chromium in the conventional colored resin film.
また従来の表面処理鋼板はロールフォーミング加工やプ
レス加工を施すと、しごきにより樹脂皮膜に傷や剥離が
発生して、耐食性、意匠性が損なわれ、耐成形加工性が
まだ不十分であった。Further, when the conventional surface-treated steel sheet is subjected to roll forming or pressing, the resin film is scratched or peeled off due to ironing, impairing the corrosion resistance and the designability, and the formability is still insufficient.
（問題点を解決するための手段） 本発明は従来このように困難であった着色樹脂皮膜中へ
の６価クロムの含有を可能にするとともに、潤滑性をも
向上させた高耐食性着色表面処理鋼板を提供するもので
ある。(Means for Solving Problems) The present invention makes it possible to include hexavalent chromium in a colored resin film, which has been difficult in the past, and also has a highly corrosive resistant colored surface treatment with improved lubricity. It provides a steel plate.
本発明の高耐食性表面処理鋼板は着色樹脂皮膜の樹脂を
水酸基を有しない水分散性共重合体にすることにより処
理液段階で樹脂が６価クロムで酸化されないようにする
とともにその共重合体の酸価調整、シランカップリング
剤または／およびチタネートカップリング剤の配合によ
り皮膜の耐水性、密着性および塗装性を向上させ、さら
に固体潤滑性を含有させることにより潤滑性を向上させ
たものである。すなわち本発明は着色樹脂皮膜の樹脂と
して（Ａ）一般色CH2＝CR1−COOR2（式中R1はＨ、CH3,R
2はＣが１〜８のアルキル基）で示される単量体の１種
または２種以上１〜95重量％と、（Ｂ）α、β不飽和カ
ルボン酸単量体３〜20重量％と、（Ｃ）これらの単量体
と共重合可能な単量体0.1〜50重量％とを［但し
（Ａ）、（Ｂ）および（Ｃ）の合計は100重量％］乳化
重合して得られる固形分当りの酸価10〜200の共重合体
樹脂にシランカップリング剤または／およびチタネート
カップリング剤を配合したものを用いるのである。The highly corrosion-resistant surface-treated steel sheet of the present invention prevents the resin from being oxidized by hexavalent chromium in the treatment liquid stage by making the resin of the colored resin film a water-dispersible copolymer having no hydroxyl group, and The water resistance, adhesion, and coatability of the film are improved by adjusting the acid value and the addition of a silane coupling agent and / or a titanate coupling agent, and the lubricity is improved by the addition of solid lubricity. . That is, in the present invention, as the resin of the colored resin film, (A) general color CH 2 = CR 1 -COOR 2 (wherein R 1 is H, CH 3 , R
2 is 1 to 95% by weight of one or more monomers represented by C is an alkyl group having 1 to 8), and (B) 3 to 20% by weight of α, β unsaturated carboxylic acid monomer. , (C) 0.1-50% by weight of a monomer copolymerizable with these monomers [however, the total of (A), (B) and (C) is 100% by weight] and obtained by emulsion polymerization. A copolymer resin having an acid value per solid content of 10 to 200 and a silane coupling agent and / or a titanate coupling agent is used.
ここで共重合体樹脂を構成する一般式CH2＝CR1−COOR2
単量体の例としては（メタ）アクリル酸メチル、（メ
タ）アクリル酸エチル、（メタ）アクリル酸プロピル、
（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エ
チルヘキシルなどを、またα、β不飽和カルボン酸単量
体の例としてはアクリル酸、メタアクリル酸、イタコン
酸、マレイン酸などを、さらにこれらの単量体と共重合
可能な単量体の例としてはスチレン、α−メチルスチレ
ン、酢酸ビニル、塩化ビニル、塩化ビニリデンなどを挙
げることができる。Here, the general formula CH 2 ═CR 1 —COOR 2 constituting the copolymer resin is used.
Examples of the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like, and examples of α, β unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and the like. Examples of the monomer copolymerizable with the above monomer include styrene, α-methylstyrene, vinyl acetate, vinyl chloride, vinylidene chloride and the like.
本発明で上記のような共重合体樹脂を用いるのは目的と
する物性の皮膜が得られ、共重合体樹脂の工業的製造も
容易であるからである。また共重合体樹脂の酸価を固形
分当り10〜200にするのは、10未満であると耐水性はよ
いが鋼板に対する密着性が劣るからであり、また200を
越えると耐水性が劣って耐食性が低下してくるからであ
る。この酸価についてはとくに15〜100にすると皮膜は
耐水性、密着性が良好になるので、その範囲にするのが
好ましい。The reason why the copolymer resin as described above is used in the present invention is that a film having the desired physical properties can be obtained, and the industrial production of the copolymer resin is easy. The acid value of the copolymer resin is set to 10 to 200 per solid content because when it is less than 10, the water resistance is good but the adhesion to the steel sheet is poor, and when it exceeds 200, the water resistance is poor. This is because the corrosion resistance decreases. With respect to this acid value, if the acid value is in the range of 15 to 100, the water resistance and adhesion of the film will be good, so it is preferable to set it in this range.
シランカップリング剤、チタネートカップリング剤は一
方または両方を配合するにしても共重合体樹脂100重量
部に対して0.05〜10重量部配合するのが好ましい。シラ
ンカップリング剤としては種々のタイプのものがある
が、水分散性もしくは水溶性のものであれば、モノマー
タイプ［例えばビニルトリ（β−メトキシエトキシ）シ
ラン、γ−グリシドキシプロピルトリメトキシシラ
ン］、オリゴマータイプ（例えばグリシド系のもの）、
樹脂変形タイプ（例えばアクリル変形のもの、エポキシ
変形のもの）、カチオン系タイプのものなどいずれでも
使用できる。またチタネートカップリング剤も水分散性
もしくは水溶性のものであれば用いることができ、好ま
しいものを挙げればテトラ（2,2−ジアリルオキシメチ
ル−１−ブチル）ビス（ジ−トリデシル）ホスファイト
チタネート、ビス（ジオクチルパイロホスフェート）オ
キシアセテートチタネート、ビス（ジオクチルパイロホ
スフェート）エチレンチタネートなどがある。Even if one or both of the silane coupling agent and the titanate coupling agent are blended, it is preferable to blend 0.05 to 10 parts by weight with respect to 100 parts by weight of the copolymer resin. There are various types of silane coupling agents, but if they are water-dispersible or water-soluble, monomer types [eg vinyltri (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane] , Oligomer type (eg glycidic type),
Any of resin deformation type (for example, acrylic deformation type, epoxy deformation type), and cationic type can be used. Further, a titanate coupling agent can also be used as long as it is water-dispersible or water-soluble, and preferable examples thereof include tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate. , Bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate and the like.
本発明は着色樹脂皮膜を上述のようにして、その皮膜中
に６価クロム源としてクロム酸塩を、また皮膜の物性や
耐食性を向上させるためにシリカゾルを、さらに潤滑性
を向上させるために固体潤滑剤を含有させる。ここで含
有させるクロム酸塩としては水溶性で、安価なものが好
ましく、例えばクロム酸アンモニウム、クロム酸マグネ
シウム、重クロム酸カリウム、クロム酸カルシウム、ク
ロム酸亜鉛、クロム酸マンガン、クロム酸ニッケル、ク
ロム酸コバルト、クロム酸ストロンチウムなどが適して
いる。The present invention provides a colored resin film as described above, containing chromate as a hexavalent chromium source in the film, silica sol for improving the physical properties and corrosion resistance of the film, and solid for improving the lubricity. Contains a lubricant. The chromate contained herein is preferably water-soluble and inexpensive, and examples thereof include ammonium chromate, magnesium chromate, potassium dichromate, calcium chromate, zinc chromate, manganese chromate, nickel chromate, and chromium. Cobaltate and strontium chromate are suitable.
なお着色樹脂皮膜は皮膜厚を0.2〜10μにするのが好ま
しいので、顔料としては粒径が１μ以下、好ましくは0.
1μ以下の微粒ものを使用し、一次粒子に近い状態で安
定に分散させる。顔料の種類としてはカーボンブラッ
ク、チタン白、フタロシアニンブルー、フタロシアニン
グリーンなど有機系、無機系いずれのものでも使用でき
る。Since the colored resin film preferably has a film thickness of 0.2 to 10 μm, the pigment has a particle size of 1 μm or less, preferably 0.1 μm.
Use fine particles of 1μ or less and stably disperse in a state close to the primary particles. As the type of pigment, any of organic and inorganic pigments such as carbon black, titanium white, phthalocyanine blue, and phthalocyanine green can be used.
固体潤滑剤としては種々のものがあるが、クロム酸塩と
同様に水分散性が良好で、しかも安価で、皮膜中に含有
させても皮膜の耐食性、密着性、耐候性などを低下させ
ないものが好ましい。このようなものとしては有機系固
体潤滑剤より無機系固体潤滑剤のものが好ましく、例え
ば二硫化モリブデン、二硫化タングステン、窒化ほう
素、黒鉛、フッ化黒鉛などが好ましい。これらのうちで
も特に二硫化モリブデンと黒鉛が皮膜中の添加物との反
応性がなく、安価で好ましい。これらの固体潤滑剤は混
合使用してもよい。なお潤滑剤を固体潤滑剤にしたのは
液状のもの（例えば合成潤滑油）、半固体状のもの（例
えばワックス）なども使用できるが、これらは潤滑効
果、長期安定性、処理液中での分散性や安定性において
固体潤滑剤より劣るからである。Although there are various solid lubricants, they have good water dispersibility like chromium salts and are inexpensive, and even if they are contained in the coating, they do not deteriorate the corrosion resistance, adhesion, weather resistance, etc. of the coating. Is preferred. As such a material, an inorganic solid lubricant is preferable to an organic solid lubricant, and for example, molybdenum disulfide, tungsten disulfide, boron nitride, graphite, fluorinated graphite and the like are preferable. Of these, molybdenum disulfide and graphite are particularly preferable because they do not react with the additives in the coating and are inexpensive. These solid lubricants may be mixed and used. Liquid lubricants (such as synthetic lubricants) and semi-solid lubricants (such as wax) can be used as solid lubricants, but these are effective for lubricating effect, long-term stability, and treatment liquid. This is because the dispersibility and stability are inferior to those of the solid lubricant.
固体潤滑剤の粒径は平均粒径で0.3〜1.0μのものが好ま
しい。これは平均粒径が0.3μ未満であると、固体潤滑
剤が樹脂皮膜の表面よりあまり突出しないため、潤滑効
果が少なく、逆に1.0μを超えると、皮膜の平滑性が損
なわれ、処理液中への分散も困難になるからである。The average particle size of the solid lubricant is preferably 0.3 to 1.0 μ. When the average particle size is less than 0.3μ, the solid lubricant does not protrude much from the surface of the resin film, so the lubricating effect is small, and when it exceeds 1.0μ, the smoothness of the film is impaired and the treatment liquid It is also difficult to disperse it inside.
着色樹脂皮膜中に含有させるこれらのクロム酸塩、シリ
カゾルおよび顔料の量としては共重合体樹脂100重量部
当りクロム酸塩の場合0.1〜50重量部、シリカゾルの場
合0.5〜100重量部、顔料の場合0.1〜50重量部および固
体潤滑剤の場合３〜10重量部にするのが好ましい。The amount of these chromate, silica sol and pigment contained in the colored resin film is 0.1 to 50 parts by weight in the case of chromate per 100 parts by weight of the copolymer resin, 0.5 to 100 parts by weight in the case of silica sol, and the pigment It is preferably 0.1 to 50 parts by weight and 3 to 10 parts by weight in the case of a solid lubricant.
固体潤滑剤含有量に関しては、添付図面に示すように、
含有量増加に伴い動摩擦係数が低下し、加工時の潤滑性
は良好になるが、含有量が樹脂100重量部に対して３重
量部未満であると添加効果はあまり認められず、また10
重量部を超えると、鋼板に対する皮膜の密着性が低下
し、かつ処理液中での分散性が悪くなって、固体潤滑剤
が沈降したり、処理液がゲル化したりする。このため固
体潤滑剤の含有量は上記のような範囲にするのが好まし
いのである。Regarding the solid lubricant content, as shown in the attached drawings,
The dynamic friction coefficient decreases as the content increases, and the lubricity at the time of processing becomes good, but if the content is less than 3 parts by weight relative to 100 parts by weight of the resin, the effect of addition is not observed, and 10
When it exceeds the weight part, the adhesion of the coating film to the steel sheet is deteriorated and the dispersibility in the treatment liquid is deteriorated, so that the solid lubricant is precipitated or the treatment liquid is gelled. Therefore, it is preferable that the content of the solid lubricant be within the above range.
上記のような含有量の着色樹脂皮膜は共重合体樹脂200
〜400g/、シランカップリング剤または／およびチタ
ネートカップリング剤0.1〜40g/、クロム酸塩0.2〜20
0g/、シリカゾル１〜400g/、顔料0.2〜200g/およ
び固体潤滑剤0.3〜200g/を含有する処理液により形成
することができる。The colored resin film with the above content is a copolymer resin 200
~ 400g /, silane coupling agent or / and titanate coupling agent 0.1-40g /, chromate 0.2-20
It can be formed by a treatment liquid containing 0 g /, silica sol 1 to 400 g /, pigment 0.2 to 200 g /, and solid lubricant 0.3 to 200 g /.
着色樹脂皮膜はクロム酸塩を含有しているので、鋼板の
上に直接形成しても耐食性を発揮するが、更に耐食性を
発揮させるために鋼板の表面にクロメート皮膜を形成し
て、その上に着色樹脂皮膜を形成する。この場合クロメ
ート皮膜は反応型、塗布型など一般に種類を問わない
が、皮膜量は全クロム量で５〜200mg/m2にするのが好ま
しい。Since the colored resin film contains chromate, it exhibits corrosion resistance even if it is formed directly on the steel plate, but in order to further exhibit corrosion resistance, a chromate film is formed on the surface of the steel plate Form a colored resin film. In this case, the chromate film may be of any type such as a reaction type or a coating type, but it is preferable that the total amount of chromium is 5 to 200 mg / m 2 .
なお鋼板は冷延鋼板、めっき鋼板（例えば溶融めっき鋼
板、電気めっき鋼板、蒸着めっき鋼板、各種合金めっき
鋼板）いずれでもよい。The steel sheet may be either a cold rolled steel sheet or a plated steel sheet (for example, hot dip plated steel sheet, electroplated steel sheet, vapor deposition plated steel sheet, various alloy plated steel sheet).
（実施例） メチルメタアクリレート50重量％と、ブチルアクリレー
ト40重量％と、アクリル酸9.8重量％と、スチレン0.2重
量％とを乳化重合して得られたアクリルエマルション
［樹脂分40重量％、PH2.3、粘度25cps（25℃、Ｂ型粘度
計）、固形分当りの酸価約78、以下このエマルション中
の共重合体樹脂をＸとする］およびメチルアクリレート
55重量％と、ブチルアクリレート40重量％と、アクリル
酸５重量％と、酢酸ビニル0.3重量％とを乳化重合して
得られたアクリルエマルション［樹脂分40重量％、PH2.
6、粘度150cps（同上）、固形分当りの酸価約40、以下
このエマルション中の共重合体樹脂をＹとする］にシラ
ンカップリング剤または／およびチタネートカップリン
グ剤、クロム酸塩、シリカゾル（スノーテックスＯ、日
産化学製品）、微粒子顔料および固体潤滑剤を種々添加
して着色樹脂皮膜処理液を調整した後、この処理液を表
面にクロメート皮膜を形成した板厚0.6mmの溶融亜鉛め
っき鋼板の上に塗布して表面処理鋼板を製造した。この
際の製造工程、クロメート皮膜の形成条件は次のとうり
である。(Example) Acrylic emulsion obtained by emulsion-polymerizing 50% by weight of methyl methacrylate, 40% by weight of butyl acrylate, 9.8% by weight of acrylic acid, and 0.2% by weight of styrene [resin content 40% by weight, PH2. 3, viscosity 25 cps (25 ° C, B-type viscometer), acid value per solid content of about 78, hereinafter the copolymer resin in this emulsion is designated as X] and methyl acrylate
Acrylic emulsion obtained by emulsion polymerization of 55% by weight, 40% by weight of butyl acrylate, 5% by weight of acrylic acid and 0.3% by weight of vinyl acetate [resin content 40% by weight, PH2.
6, viscosity 150 cps (same as above), acid value per solid content of about 40, hereinafter the copolymer resin in this emulsion is referred to as Y]] to silane coupling agent or / and titanate coupling agent, chromate, silica sol ( Snowtex O, NISSAN CHEMICAL PRODUCTS, various fine particle pigments and solid lubricants are added to prepare a colored resin film treatment liquid, and a chromate film is formed on the surface of this treatment liquid. To produce a surface-treated steel sheet. The manufacturing process and the conditions for forming the chromate film at this time are as follows.
（イ）製造工程 鋼板→脱脂→クロメート処理→着色樹脂皮膜処理液塗布
→乾燥（150℃、10秒）、 （ロ）クロメート皮膜の形成条件、 CrO320g/、Na2SiF61g/の処理液中に40℃で５秒間浸
漬した後ロールスクイズした。(A) Manufacturing process Steel sheet → Degreasing → Chromate treatment → Colored resin film treatment liquid application → Drying (150 ° C, 10 seconds), (b) Chromate film forming conditions, CrO 3 20g /, Na 2 SiF 6 1g / treatment After immersing in the liquid at 40 ° C. for 5 seconds, roll squeeze was performed.
第１表にこのようにして製造した表面処理鋼板を示す。Table 1 shows the surface-treated steel sheets manufactured in this way.
次にこの表面処理鋼板より試験片を採取して塩水噴霧試
験、湿潤試験を行うとともに、残りの表面処理鋼板に高
速自動ダクトハゼ成形機で成形し、樹脂皮膜の破損状態
を観察した後塩水噴霧試験および湿潤試験に供した。第
２表にこれらの試験結果を示す。なお上記各試験は次の
要領で行った。Next, a test piece is taken from this surface-treated steel sheet and subjected to a salt spray test and a wet test, and the remaining surface-treated steel sheet is molded by a high-speed automatic duct haze molding machine, and after observing the damage state of the resin film, the salt spray test is performed. And subjected to a wet test. Table 2 shows the results of these tests. The above-mentioned tests were conducted as follows.
（イ）成形加工後の樹脂皮膜破損状態 ◎…樹脂皮膜が全く破損しないもの ○…わずかに樹脂皮膜が破損したもの △…かなり樹脂皮膜が破損したもの ×…著しく樹脂皮膜が破損したもの （ロ）塩水噴霧試験 加工前後のものともナイフにより鋼板表面に達する切込
みを入れて、JIS Z 2371に基づき1000時間試験を行った
後、切込み部にセロテープを張付けて、それを急速には
がし、そのはがした部分の樹脂皮膜剥離状態と白錆発生
状態を次の基準で評価した。(A) Damaged state of the resin film after molding ◎ ... No damage to the resin film ○ ... Slight damage to the resin film △… Severe damage to the resin film ×… Severe damage to the resin film ) Salt spray test Before and after processing, make a notch that reaches the surface of the steel plate with a knife, perform a test for 1000 hours based on JIS Z 2371, then attach cellophane tape to the notch and peel it off rapidly. The peeled state of the resin film and the white rust generation state of the exposed portion were evaluated according to the following criteria.
◎…剥離および白錆の発生なし ○…剥離幅または白錆の発生幅が切込み部より1mm以下 △…剥離幅または白錆の発生幅が切込み部より1mmを超
え3mm以下 ×…剥離幅または白錆の発生幅が切込み部より3mm超 （ハ）湿潤試験 加工前後のものとも上記同様に切込みを入れ、それらを
温度50℃、湿度98％の雰囲気中に1500時間入れて、切込
み部にセロテープを張付けて急速にはがし、そのはがし
た部分の樹脂皮膜剥離状態と白錆発生状態を前記塩水噴
霧試験の場合と同基準で評価した。◎ ... Peeling and white rust are not generated ○ ... Peeling width or white rust occurrence width is 1 mm or less from the cut portion △ ... Peeling width or white rust generation width is more than 1 mm and 3 mm or less from the cut portion × ... Peeling width or white The width of rust exceeds 3mm from the cut (c) Wet test We make cuts in the same way as above before and after processing, put them in an atmosphere with a temperature of 50 ° C and a humidity of 98% for 1500 hours, and put a tape on the cut. It was adhered and rapidly peeled off, and the peeling state of the resin film and the white rusting state of the peeled portion were evaluated according to the same criteria as in the salt spray test.
第２表より明らかなごとく、本発明の高耐食性着色表面
処理鋼板は耐食性、樹脂皮膜の密着性が優れており、ま
た樹脂表面処理中に固体潤滑剤が含有されているので、
成形加工しても樹脂皮膜が破損されることがない。 As is clear from Table 2, the highly corrosion-resistant colored surface-treated steel sheet of the present invention has excellent corrosion resistance and adhesiveness of the resin film, and since the resin surface treatment contains a solid lubricant,
The resin film will not be damaged even by molding.
（効果） 以上説明したごとく、本発明の表面処理鋼板は着色樹脂
皮膜の樹脂が水酸基を有しないので、製造の際処理液中
にクロム酸塩を含有していても、樹脂は酸化されず、ゲ
ル化はしない。また着色樹脂皮膜中にクロム酸塩を含有
しているので、耐食性は向上し、しかもシランカップリ
ング剤または／およびチタネートカップリング剤、シリ
カゾルをも含有しているので、密着性は向上する。(Effect) As described above, in the surface-treated steel sheet of the present invention, since the resin of the colored resin film does not have a hydroxyl group, even if the treatment solution contains chromate, the resin is not oxidized, Does not gel. Further, since the colored resin film contains the chromate, the corrosion resistance is improved, and the silane coupling agent and / or the titanate coupling agent and the silica sol are also contained, so that the adhesion is improved.
さらに樹脂皮膜中に固体潤滑剤を含有しているので、成
形加工しても樹脂皮膜は破損されず、耐食性や意匠性が
低下したりすることがない。Further, since the resin film contains a solid lubricant, the resin film is not damaged even if it is molded, and the corrosion resistance and the designability are not deteriorated.
添付図面は本発明の高耐食性着色表面処理鋼板における
樹脂皮膜の固体潤滑剤含有量と動摩擦係数との関係を示
すグラフである。The accompanying drawings are graphs showing the relationship between the dynamic friction coefficient and the solid lubricant content of the resin film in the highly corrosion-resistant colored surface-treated steel sheet of the present invention.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ３２Ｂ 15/08 Ｑ １０１ 7148−4Ｆ Ｃ０９Ｄ 5/08 ＰＮＦ 6904−4Ｊ Continuation of front page (51) Int.Cl. 5 Identification number Office reference number FI technical display location B32B 15/08 Q 101 7148-4F C09D 5/08 PNF 6904-4J
Claims (6)
そのクロメート皮膜上に（Ａ）一般式 CH2＝CR1−COOR2（式中R1はＨ、CH3,R2はＣが１〜８の
アルキル基）で示される単量体の１種または２種以上１
〜95重量％と、（Ｂ）α、β不飽和カルボン酸単量体３
〜20重量％と、（Ｃ）これらの単量体と共重合可能な単
量体0.1〜50重量％とを［但し（Ａ）、（Ｂ）および
（Ｃ）の合計は100重量％］乳化重合して得られる固形
分当りの酸価10〜200の共重合体樹脂にシランカップリ
ング剤または／およびチタネートカップリング剤を配合
した樹脂皮膜で、その皮膜中にクロム酸塩、シリカゾ
ル、微粒子有色顔料および固体潤滑剤を含有するものが
形成されていることを特徴とする潤滑性に優れた高耐食
性着色表面処理鋼板。1. A chromate film is formed on the surface of a steel plate,
Its on chromate film (A) the general formula CH 2 = CR 1 -COOR 2 (wherein R 1 is H, CH 3, R 2 is C alkyl group of 1 to 8) one monomer represented by Or 2 or more 1
~ 95% by weight, (B) α, β unsaturated carboxylic acid monomer 3
To 20% by weight and (C) 0.1 to 50% by weight of a monomer copolymerizable with these monomers [however, the total of (A), (B) and (C) is 100% by weight] Resin film obtained by mixing a silane coupling agent and / or a titanate coupling agent with a copolymer resin having an acid value per solid content of 10 to 200 obtained by polymerization, and chromate, silica sol, and fine particles in the film. A highly corrosion-resistant colored surface-treated steel sheet excellent in lubricity, characterized in that a material containing a pigment and a solid lubricant is formed.
り３〜10重量部含有することを特徴とする特許請求の範
囲第１項に記載の潤滑性に優れた高耐食性着色表面処理
鋼板。2. A highly corrosion-resistant colored surface-treated steel sheet excellent in lubricity according to claim 1, wherein the resin coating contains 3 to 10 parts by weight of a solid lubricant per 100 parts by weight of the resin. .
特許請求の範囲第１項に記載の潤滑性に優れた高耐食性
着色表面処理鋼板。3. The highly corrosion-resistant colored surface-treated steel sheet having excellent lubricity according to claim 1, wherein the solid lubricant is graphite.
を特徴とする特許請求の範囲第１項に記載の潤滑性に優
れた高耐食性着色表面処理鋼板。4. The highly corrosion-resistant colored surface-treated steel sheet excellent in lubricity according to claim 1, wherein the solid lubricant is molybdenum disulfide.
混合したものであることを特徴とする特許請求の範囲第
１項に記載の潤滑性に優れた高耐食性着色表面処理鋼
板。5. The highly corrosive-resistant colored surface-treated steel sheet having excellent lubricity according to claim 1, wherein the solid lubricant is a mixture of graphite and molybdenum disulfide.
ことを特徴とする特許請求の範囲第１項に記載の潤滑性
に優れた高耐食性着色表面処理鋼板。6. The highly corrosion-resistant colored surface-treated steel sheet excellent in lubricity according to claim 1, wherein the solid lubricant has an average particle size of 0.3 to 1.0 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6968385A JPH0696774B2 (en) | 1985-04-02 | 1985-04-02 | Highly corrosion-resistant colored surface-treated steel sheet with excellent lubricity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6968385A JPH0696774B2 (en) | 1985-04-02 | 1985-04-02 | Highly corrosion-resistant colored surface-treated steel sheet with excellent lubricity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61231177A JPS61231177A (en) | 1986-10-15 |
| JPH0696774B2 true JPH0696774B2 (en) | 1994-11-30 |
Family
ID=13409908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6968385A Expired - Lifetime JPH0696774B2 (en) | 1985-04-02 | 1985-04-02 | Highly corrosion-resistant colored surface-treated steel sheet with excellent lubricity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0696774B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3276470B2 (en) * | 1993-08-09 | 2002-04-22 | 川崎製鉄株式会社 | Surface treated metal plate with excellent conductivity and workability |
| US5897948A (en) * | 1995-06-15 | 1999-04-27 | Nippon Steel Corporation | Surface-treated steel sheet with resin-based chemical treatment coating and process for its production |
| JPH1180624A (en) * | 1997-09-09 | 1999-03-26 | Nisshin Steel Co Ltd | Heat reflecting coating composition and coated product |
| JP6310361B2 (en) * | 2014-08-14 | 2018-04-11 | 株式会社神戸製鋼所 | Black painted metal plate |
-
1985
- 1985-04-02 JP JP6968385A patent/JPH0696774B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61231177A (en) | 1986-10-15 |
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