JPH0788587B2 - Surface-treated steel sheet with excellent corrosion resistance and lubricity - Google Patents
Surface-treated steel sheet with excellent corrosion resistance and lubricityInfo
- Publication number
- JPH0788587B2 JPH0788587B2 JP60068657A JP6865785A JPH0788587B2 JP H0788587 B2 JPH0788587 B2 JP H0788587B2 JP 60068657 A JP60068657 A JP 60068657A JP 6865785 A JP6865785 A JP 6865785A JP H0788587 B2 JPH0788587 B2 JP H0788587B2
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- corrosion resistance
- lubricity
- weight
- treated steel
- 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
Links
Landscapes
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (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クロム酸塩、シリカゾルおよび固体
潤滑剤を含有する特定の樹脂皮膜を形成して、樹脂皮膜
の耐食性および潤滑性を向上させた表面処理鋼板に関す
る。DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention forms a specific resin film containing chromate, silica sol and a solid lubricant on the surface of a steel sheet to improve the corrosion resistance and lubricity of the resin film. The surface-treated steel sheet.
（従来技術） 冷延鋼板やめっき鋼板を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樹脂
単独皮膜もしくは無機物を含む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層の樹脂皮膜で塗装性を付与
したものであるが、樹脂皮膜の樹脂としては樹脂皮膜を
水溶液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) Of the surface-treated steel sheets, which have been treated with a water-dispersible or water-soluble resin to form cold-rolled steel sheets or plated steel sheets and have a resin film that imparts paintability and corrosion resistance to them As a material having excellent resistance and corrosion resistance, there is a material in which a chromate film is formed on the surface of a steel sheet, and a resin single film or a resin film containing an inorganic substance is further formed on the chromate film. This surface-treated steel sheet is provided with corrosion resistance by the first layer of chromate film and coatability by the second layer of resin film. However, as the resin of the resin film, the resin film is formed by an aqueous solution for the sake of convenience. A hydrophilic one having a hydroxyl group was 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 second layer resin film.
樹脂皮膜の耐食性を向上させる方法としては樹脂皮膜中
に６価クロムを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 of improving the corrosion resistance of the resin film, a method of containing hexavalent chromium in the resin film can be considered, but in order to contain hexavalent chromium by this method, it is treated with a resin film treatment liquid containing hexavalent chromium. There is a need. 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 resin film.
また従来の樹脂皮膜は鋼板にロールフォーミング加工プ
レス加工を施すと、傷が付いたり、剥離したりしてしま
い、耐成形加工性はまだ不十分であった。Further, when the conventional resin film is subjected to roll forming press processing on a steel sheet, it is scratched or peeled off, and the molding workability 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、潤滑性も向上さ
せた表面処理鋼板を提供するものである。(Means for Solving Problems) In the present invention, it has been difficult to form a resin film in such a manner as described above.
The present invention provides a surface-treated steel sheet capable of containing valent chromium and having improved lubricity.
本発明の表面処理鋼板は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
脂が酸化されないようにするとともにその共重合体の酸
価を調整することにより樹脂皮膜の耐水性、密着性およ
び物性並びに塗装した場合の塗膜との密着性を向上させ
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）一般式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）水酸基を有しな
い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水酸基を有しない単
量体０〜50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の共重合体樹脂を用い、かつ樹脂
皮膜中には固体潤滑剤を含有させて、耐成形加工性を向
上させたものである。The surface-treated steel sheet of the present invention makes the resin of the resin film a water-dispersible copolymer having no hydroxyl group to prevent the resin from being oxidized in the treatment liquid stage and to adjust the acid value of the copolymer. The resin film has improved water resistance, adhesion and physical properties and adhesion with a coating film when applied. That is, the present invention provides (A) the general formula 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 of the monomers represented by C is an alkyl group having 1 to 8), and (B) an α, β unsaturated carboxylic acid monomer having no hydroxyl group 3 to 20% by weight,
(C) Emulsion polymerization of these monomers and 0 to 50% by weight of a monomer having no copolymerizable hydroxyl group (however, the total of (A), (B) and (C) is 100% by weight) A copolymer resin having an acid value of 10 to 200 per solid content obtained is used, and a solid lubricant is contained in the resin film to improve the molding workability.
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、また水酸基を有しない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水酸基を有しない単量体の例と
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, etc., and examples of α, β unsaturated carboxylic acid monomers having no hydroxyl group are acrylic acid, methacrylic acid, itaconic acid, maleic acid, etc. Further, examples of the monomer having no hydroxyl group which is copolymerizable with these monomers include styrene, α-methylstyrene, vinyl acetate, vinyl chloride and vinylidene chloride.
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.
本発明は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含有さて、さらに皮膜の
物性や耐食性を向上させるためにシリカゾルを、また成
形加工時の潤滑性を向上させるために潤滑性を含有させ
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。In the present invention, the resin film is formed as described above,
Chromate is contained as a source of valent chromium, and silica sol is further contained in order to improve the physical properties and corrosion resistance of the film, and lubricity is contained in order to improve the lubricity during molding. 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.
同様に固体潤滑性剤としても水分散性が良好で、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く、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。なお潤滑性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。Similarly, as a solid lubricant, it has good water dispersibility and is inexpensive, and even if it is contained in the coating, it has corrosion resistance, adhesion, and
Those that do not reduce the weather resistance are preferable. As such a material, an inorganic solid lubricant is preferable to an organic solid lubricant, for example, molybdenum disulfide, tungsten disulfide, boron nitride, graphite, graphite fluoride, etc. are preferable, and molybdenum disulfide and graphite are particularly preferable. It is inexpensive and preferable because it has no reactivity with the additives. 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 the solid lubricant for lubricity, but these have a lubricating effect, long-term stability, and This is because the dispersibility and stability are inferior to those of the solid lubricant.
樹脂皮膜中に含有させるこれらのクロム酸塩、シリカゾ
ルおよび固体潤滑剤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、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 solid lubricant contained in the resin film is 0.1 to 50 parts by weight for chromate per 100 parts by weight of copolymer resin, 0.5 to 100 parts by weight for silica sol, and solid. In the case of lubricant, it is preferable to use 3 to 10 parts by weight.
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.
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.
樹脂皮膜は皮膜厚を0.2〜10μにするのが好ましい。The resin film preferably has a film thickness of 0.2 to 10 μm.
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、さらに耐食性を発揮
させるには鋼板にクロメート皮膜を形成して、その上に
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。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、合金化溶融めっき鋼板、溶
融もしくは電気合金めっき鋼板など）いずれでもよい。
次に実施例により本発明を説明する。Since the resin film contains chromate, it exhibits corrosion resistance even if it is formed directly on the steel plate, but to further demonstrate corrosion resistance, a chromate film is formed on the steel plate and a resin film is formed on it. To do. 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 . 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, alloyed hot dip plated steel sheet, hot dip or electroalloy plated steel sheet, etc.).
Next, the present invention will be described with reference to examples.
（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10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］に種々のクロム酸塩とシリカゾル（スノーテック
スＯ、日産化学製品）とを添加し、この水溶液をＸとし
た。(Example) Acrylic emulsion obtained by emulsion polymerization of 50 wt% methyl methacrylate, 40 wt% butyl acrylate, and 10 wt% acrylic acid [resin content 40 wt%, PH2.
3. Add various chromates and silica sol (Snowtex O, Nissan Chemicals) to a viscosity of 25 cps (25 ° C, B-type viscometer), acid value per solid content of about 78], and add this aqueous solution as X. did.
一方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］に上
記同様に種々のクロム酸とシリカゾル（スノーテックス
Ｏ、日産化学製品）とを添加し、この水溶液をＹとし
た。On the other hand, an acrylic emulsion obtained by emulsion polymerization of 55% by weight of methyl acrylate, 40% by weight of butyl acrylate, and 5% by weight of acrylic acid [resin content 40% by weight, PH2.
6, various chromic acid and silica sol (Snowtex O, Nissan Chemical Co., Ltd.) were added in the same manner as above to a viscosity of 150 cps (same as above) and an acid value per solid content of 40], and this aqueous solution was designated as Y.
以上のように調整した水溶液ＸおよびＹと、それらに異
なる固体潤滑剤を加え、次のように調整した６種の水溶
液とで冷延鋼板、溶融亜鉛めっき鋼板（いずれも板厚は
0.6mm）を処理し、表面処理鋼板を製造した。The cold-rolled steel sheet and the hot-dip galvanized steel sheet (both of which have plate thicknesses of the above-prepared aqueous solutions X and Y and six types of aqueous solutions prepared by adding different solid lubricants to them)
0.6 mm) was processed to produce a surface-treated steel plate.
水溶液Ｘ−１およびＹ−１ 水溶液ＸおよびＹに溶液中の樹脂100重量部当り二硫化
モリブデン［商品名モリコロイドCF626、日本黒鉛工業
（株）製］をともに１〜15重量部添加し、それらをそれ
ぞれ水溶液Ｘ−１およびＹ−１とした。Aqueous Solution X-1 and Y-1 To the aqueous solutions X and Y, 1 to 15 parts by weight of molybdenum disulfide [trade name: Mori Colloid CF626, manufactured by Nippon Graphite Industry Co., Ltd.] was added per 100 parts by weight of the resin in the solution. Were designated as aqueous solutions X-1 and Y-1, respectively.
水溶液Ｘ−２およびＹ−２） 水溶液ＸおよびＹに溶液中の樹脂100重量部当り二硫化
モリブデン（同上）と黒鉛 ［商品名オイルハイトG307、日本黒鉛工業（株）製］と
の混合物をともに１〜15重量部添加し、それらをそれぞ
れＸ−２およびＹ−２とした。Aqueous solutions X-2 and Y-2) Aqueous solutions X and Y were mixed with a mixture of molybdenum disulfide (same as above) and graphite [trade name: Oil Height G307, manufactured by Nippon Graphite Industry Co., Ltd.] per 100 parts by weight of resin in the solution. 1 to 15 parts by weight were added, and they were designated as X-2 and Y-2, respectively.
水溶液Ｘ−３およびＹ−３ 水溶液ＸおよびＹに溶液中の樹脂100重量部当り黒鉛
［商品名アルダイスF33G、日本黒鉛工業（株）製］をと
もに１〜15重量部添加し、それらをそれぞれＸ−３およ
びＹ−３とした。Aqueous Solution X-3 and Y-3 To each of the aqueous solutions X and Y, 1 to 15 parts by weight of graphite [trade name: Aldais F33G, manufactured by Nippon Graphite Industry Co., Ltd.] was added per 100 parts by weight of the resin in the solution. -3 and Y-3.
なお製造工程およびクロメート皮膜の形成は次のように
した。The manufacturing process and formation of the chromate film were as follows.
（イ）製造工程 鋼板→脱脂→クロメート処理→樹脂皮膜処理水溶液塗布
→乾燥（150℃、10秒） （ロ）クロメート皮膜の形成 無水クロム酸 20g/、Na2SiF6 1g/、40℃の処理液中
に５秒間浸漬後ロールスクイズで過剰に付着した水溶液
を除去した。(B) Manufacturing process Steel plate → Degreasing → Chromate treatment → Resin coating treatment Aqueous solution coating → Drying (150 ° C, 10 seconds) (B) Chromate coating formation Chromic anhydride 20g /, Na 2 SiF 6 1g /, 40 ° C treatment After being immersed in the liquid for 5 seconds, the excessively adhered aqueous solution was removed by roll squeeze.
第１表にこのようにして製造した表面処理鋼板の基材鋼
板、使用水溶液および形成された樹脂皮膜の関係を、ま
た第２表にその表面処理鋼板の樹脂皮膜の密着性および
耐食性並びに動摩擦係数および加工時の潤滑性（ロール
フォーミング性、エリクセン試験機によるハット曲げ
性）を示す。Table 1 shows the relationship between the base steel sheet, the aqueous solution used and the formed resin film of the surface-treated steel sheet thus produced, and Table 2 shows the adhesion and corrosion resistance of the resin film of the surface-treated steel sheet and the coefficient of dynamic friction. And the lubricity during processing (roll forming, hat bendability by Erichsen tester).
なお樹脂皮膜の密着性はデュポン衝撃試験で調査し、次
の基準により評価した。The adhesiveness of the resin film was investigated by the DuPont impact test and evaluated according to the following criteria.
◎ 皮膜が全く剥離しないもの ○ わずかに皮膜が剥離したもの △ かなり皮膜が剥離したもの × 著しく皮膜が剥離したもの また耐食性は加工前後の耐食性を塩水雰霧試験（JIS Z
2371による）と湿潤試験（温度50℃、湿度98％）とによ
り調査した。試験は両試験とも平板の状態で鋼板表面に
達する切込みを入れ、加工前のものはそのまま試験に供
し、また加工後のものはロールフォーミング成形後試験
に供し、試験後切込み部にセロテープを一旦貼付け、そ
の後急速に剥離する方法で行い、皮膜の剥離状態を次の
基準で評価した。試験は、塩水噴霧試験の場合、基材鋼
板が冷延鋼板であるものに対して24時間行い、溶融亜鉛
めっき鋼板であるものに対しては500時間行った。一方
湿潤試験の場合は基材鋼板に関係なく500時間行った。◎ No peeling of film ○ Slight peeling of film △ Significant peeling of film × Significant peeling of film Corrosion resistance was measured by salt water atmosphere fog test (JIS Z
2371) and a wetting test (temperature 50 ° C, humidity 98%). In both tests, make a notch that reaches the surface of the steel plate in the flat plate state, the one before processing is subjected to the test as it is, the one after processing is subjected to the test after roll forming, and the cellophane tape is once attached to the notch after the test Then, the peeling state of the film was evaluated by the following criteria. In the case of the salt spray test, the test was carried out for 24 hours for the cold rolled steel sheet as the base steel sheet and 500 hours for the hot rolled galvanized steel sheet. On the other hand, the wet test was performed for 500 hours regardless of the base steel sheet.
◎ 剥離なし ○ 剥離幅または錆の発生幅が切込み部より1mm以下 △ 剥離幅または錆の発生幅が切込み部より1mmを超
え、3mm以下 × 剥離幅または錆の発生幅が切込み部より3mm超 さらにロールフォーミング性、ハット曲げ性の評価は次
の基準により行った。◎ No peeling ○ Peeling width or rust generation width is 1 mm or less from the notch △ Peeling width or rust generation width is more than 1 mm from the notch and 3 mm or less × Peeling width or rust generation width is more than 3 mm from the notch The roll forming property and hat bendability were evaluated according to the following criteria.
◎ 皮膜が全く破損しないもの ○ わずかに皮膜が破損したもの △ かなり皮膜が破損したもの × 著しく皮膜が破損したもの 第２表より明らかなごとく、本発明の表面処理鋼板は耐
食性が優れており、また樹脂皮膜中の固体潤滑剤含有両
が増加する程動摩擦係数が小さくなり、加工時の樹脂皮
膜破損程度が少なくなる。しかし潤滑剤の含有量が樹脂
100重量部に対して10重量部を超えると、樹脂皮膜の密
着性は悪くなる。◎ The coating is not damaged at all ○ The coating is slightly damaged △ The coating is considerably damaged × The coating is significantly damaged As is clear from Table 2, the surface-treated steel sheet of the present invention has excellent corrosion resistance, and the dynamic friction coefficient decreases as the content of the solid lubricant in the resin film increases, and the degree of damage to the resin film during processing decreases. Become. However, if the lubricant content is resin
If it exceeds 10 parts by weight with respect to 100 parts by weight, the adhesion of the resin film will deteriorate.
（効果） 以上のごとく、本発明の表面処理鋼板は樹脂皮膜の樹脂
が水酸基を有しないので、製造の際処理液中にクロム酸
塩を含させても、樹脂は酸化されず、ゲル化しない。ま
た樹脂皮膜はクロム酸塩およびシリカゾルを含有してい
るので、それらを含有しないものより耐食性が優れてい
る。さらに樹脂皮膜は固体潤滑剤を含有しているので、
潤滑性が優れており、ロールフォーミングやプレス加工
を施しても樹脂皮膜に傷が付いたり、樹脂皮膜が剥離し
たりすることがない。(Effect) As described above, since the resin of the resin film of the surface-treated steel sheet of the present invention does not have a hydroxyl group, the resin is not oxidized and does not gel even if chromate is included in the treatment liquid during production. . In addition, since the resin film contains chromate and silica sol, it has better corrosion resistance than those not containing them. Furthermore, since the resin film contains a solid lubricant,
It has excellent lubricity, and does not scratch or peel off the resin film even when roll forming or pressing is applied.
添付図面は本発明の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の関係を示すグラフであ
る。The accompanying drawings are graphs showing the relationship between the content of solid lubricant in the resin coating and the dynamic friction coefficient in the surface-treated steel sheet of the present invention.
Claims (12)
2（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）水酸基を有しない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
水酸基を有しない単量体０〜50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
樹脂皮膜で、その樹脂皮膜中にクロム酸塩、シリカゾル
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
を特徴とする耐食性および潤滑性に優れた表面処理鋼
板。1. A surface of a steel sheet having (A) the general formula CH 2 = CR 1 = COOR
1 (or more than 1) of the monomer represented by 2 (wherein R 1 is H, CH 3 , R 2 is an alkyl group in which C is 1 to 8) and 1 to 95% by weight,
(B) 3 to 20% by weight of an α, β unsaturated carboxylic acid monomer having no hydroxyl group, and (C) 0 to 50% by weight of a monomer having no hydroxyl group copolymerizable with these monomers. [However, the total of (A), (B) and (C) is 100% by weight] A copolymer resin film having an acid value per solid content of 10 to 200 obtained by emulsion polymerization, and chromium in the resin film. A surface-treated steel sheet excellent in corrosion resistance and lubricity, characterized in that a material containing an acid salt, silica sol 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項に記載の耐食性および潤滑性に優れた表面処理
鋼板。2. A surface-treated steel sheet excellent in corrosion resistance and 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項に記載の耐食性および潤滑性に優
れた表面処理鋼板。3. The surface-treated steel sheet having excellent corrosion resistance and 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項に記載の耐食性およ
び潤滑性に優れた表面処置鋼板。4. The surface-treated steel sheet excellent in corrosion resistance and 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項に記載の耐食性および潤滑性に優れた表面処理鋼
板。5. The surface-treated steel sheet excellent in corrosion resistance and 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項に記載の耐食性
および潤滑性に優れた表面処理鋼板。6. A surface-treated steel sheet excellent in corrosion resistance and lubricity according to claim 1, characterized in that the solid lubricant has an average particle diameter of 0.3 to 1.0 μm.
そのクロメート皮膜の上に（Ａ）一般式CH2＝CR1＝COOR
2（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）水酸基を有しない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
水酸基を有しない単量体０〜50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
樹脂皮膜で、その樹脂皮膜中にクロム酸塩、シリカゾル
および固体潤滑性を含有するものが形成されていること
を特徴とする耐食性および潤滑性に優れた表面処理鋼
板。7. A chromate film is formed on the surface of a steel plate,
On the chromate film, (A) General formula CH 2 = CR 1 = COOR
1 (or more than 1) of the monomer represented by 2 (wherein R 1 is H, CH 3 , R 2 is an alkyl group in which C is 1 to 8) and 1 to 95% by weight,
(B) 3 to 20% by weight of an α, β unsaturated carboxylic acid monomer having no hydroxyl group, and (C) 0 to 50% by weight of a monomer having no hydroxyl group copolymerizable with these monomers. [However, the total of (A), (B) and (C) is 100% by weight] A copolymer resin film having an acid value per solid content of 10 to 200 obtained by emulsion polymerization, and chromium in the resin film. A surface-treated steel sheet excellent in corrosion resistance and lubricity, characterized in that a salt containing an acid salt, silica sol and solid lubricity 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７項に記載の耐食性および潤滑性に優れた表面処理
鋼板。8. A surface-treated steel sheet excellent in corrosion resistance and lubricity according to claim 7, 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７項に記載の耐食性および潤滑性に優
れた表面処理鋼板。9. The surface-treated steel sheet excellent in corrosion resistance and lubricity according to claim 7, wherein the solid lubricity is graphite.
とを特徴とする特許請求の範囲第７項に記載の耐食性お
よび潤滑性に優れた表面処理鋼板。10. The surface-treated steel sheet excellent in corrosion resistance and lubricity according to claim 7, wherein the solid lubricity is molybdenum disulfide.
を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７項に記載の耐食性および潤滑性に優れた表面処理鋼
板。11. A surface-treated steel sheet excellent in corrosion resistance and lubricity according to claim 7, wherein the solid lubricant is a mixture of graphite and molybdenum disulfide.
ることを特徴とする特許請求の範囲第７項に記載の耐食
性および潤滑性に優れた表面処理鋼板。12. A surface-treated steel sheet excellent in corrosion resistance and lubricity according to claim 7, characterized in that the average particle diameter of solid lubricity is 0.3 to 1.0 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60068657A JPH0788587B2 (en) | 1985-04-01 | 1985-04-01 | Surface-treated steel sheet with excellent corrosion resistance and lubricity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60068657A JPH0788587B2 (en) | 1985-04-01 | 1985-04-01 | Surface-treated steel sheet with excellent corrosion resistance and lubricity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61227179A JPS61227179A (en) | 1986-10-09 |
| JPH0788587B2 true JPH0788587B2 (en) | 1995-09-27 |
Family
ID=13379988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60068657A Expired - Lifetime JPH0788587B2 (en) | 1985-04-01 | 1985-04-01 | Surface-treated steel sheet with excellent corrosion resistance and lubricity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0788587B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5106675A (en) * | 1989-12-29 | 1992-04-21 | Nihon Parkerizing Co., Ltd. | Nonaqueous coating composition and coated metal |
| JPH0659717B2 (en) * | 1991-02-27 | 1994-08-10 | 株式会社淀川製鋼所 | Coated surface treated metal plate |
| CA2113968C (en) * | 1993-07-29 | 2000-05-30 | Junichi Mano | Chromated metal sheet having high corrosion resistance with improved lubricity and electric conductivity |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54148139A (en) * | 1978-04-24 | 1979-11-20 | Nippon Steel Corp | Bolt set excellent in ease to paint, corrosion resistance, lubricativity, and co-turning inhibition |
| JPH0647741B2 (en) * | 1983-04-26 | 1994-06-22 | 日本ペイント株式会社 | Corrosion-resistant metal surface treatment composition with excellent coating adhesion |
-
1985
- 1985-04-01 JP JP60068657A patent/JPH0788587B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61227179A (en) | 1986-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0696775B2 (en) | Surface-treated steel sheet with excellent corrosion resistance, adhesion and lubricity | |
| JPH0788587B2 (en) | Surface-treated steel sheet with excellent corrosion resistance and lubricity | |
| JP4122531B2 (en) | Film-removal type lubricating coating composition with excellent deep drawability, anti-scoring and temporary anti-rust properties | |
| JPH0696774B2 (en) | Highly corrosion-resistant colored surface-treated steel sheet with excellent lubricity | |
| JP3817944B2 (en) | Resin composition and resin-coated galvanized steel sheet | |
| JPH0316726A (en) | Lubricating resin-treated steel plate with excellent moldability | |
| JPH01301332A (en) | Lubricating resin treated steel plate excellent in moldability | |
| JPH0696776B2 (en) | Colored surface-treated steel sheet with excellent scratch resistance, adhesion and lubricity | |
| JP3536489B2 (en) | Stripped lubricated steel sheet with excellent deep drawability and galling resistance | |
| JP2577676B2 (en) | Painted aluminum plated steel sheet for building materials with excellent workability | |
| JP2868332B2 (en) | Surface-treated steel sheet with excellent paintability | |
| JPH01110140A (en) | Composite coated steel sheet excellent in corrosion resistance and lubrication property | |
| JPH0559194B2 (en) | ||
| JPH0723541B2 (en) | Highly corrosion resistant surface treated steel sheet | |
| JPH0557838A (en) | Surface treated steel plate excellent in resistance to blackening of worked part and adhesion of coating | |
| JP3536490B2 (en) | Stripped lubricated steel sheet with excellent press workability and primary rust resistance | |
| JPH0494771A (en) | Lubricant thin film resin steel sheet excellent in corrosion resistance and weldability | |
| JPH0592173A (en) | Surface-treated steel plate excellent in processed part blackening resistance, film adhesion and corrosion resistance | |
| JPS6199679A (en) | Organic coating hot-dipped aluminum coated steel sheet | |
| JP2004169121A (en) | Surface treated steel sheet having excellent film adhesiveness under wet environment | |
| JPH01301333A (en) | Lubricating resin treated steel plate excellent in moldability and corrosion resistance | |
| JP3006455B2 (en) | Lubricated metal material with excellent galling resistance and film removal | |
| JPH09176890A (en) | Organic composite clad steel sheet having excellent corrosion resistance and flawing resistance | |
| JPH06155655A (en) | Lubricating steel panel excellent in corrosion resistance | |
| JPH0825559A (en) | Lubricating organic coated composite metallic sheet |