JP3135815B2 - Method for producing surface-treated steel sheet with excellent press workability - Google Patents
Method for producing surface-treated steel sheet with excellent press workabilityInfo
- Publication number
- JP3135815B2 JP3135815B2 JP07061181A JP6118195A JP3135815B2 JP 3135815 B2 JP3135815 B2 JP 3135815B2 JP 07061181 A JP07061181 A JP 07061181A JP 6118195 A JP6118195 A JP 6118195A JP 3135815 B2 JP3135815 B2 JP 3135815B2
- Authority
- JP
- Japan
- Prior art keywords
- lubricating
- coating
- resin
- weight
- steel sheet
- 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 - Fee Related
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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、プレス加工性の優れた
家電、建材、自動車等の部品に利用する表面処理鋼板の
製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a surface-treated steel sheet having excellent press workability and used for parts of household appliances, building materials, automobiles and the like.
【０００２】[0002]
【従来の技術】従来、加工性の優れた潤滑樹脂処理鋼板
として被膜中に潤滑剤を分散させることで加工潤滑特性
を持たせているものであるが、プレスによる金型温度の
上昇により加工性が一般に劣化することが知られてい
る。これは特にベース樹脂が軟化することで粘着性を帯
び金型との潤滑性が損なわれるためであると言われてい
る。これらの解決法として、高ガラス転移温度を含有す
る樹脂を用いた特開平１−３０１３３３号公報のよう
に、めっき鋼板の片面に水酸基および／またはカルボキ
シル基を有する樹脂とシリカと固形潤滑剤とを含む樹脂
混合物または複合物のガラス転移温度が７０℃以上であ
る樹脂被膜を有し、他面には、水酸基および／またはカ
ルボキシル基を有する樹脂とシリカとを含む樹脂被膜を
有する成形性、耐食性に優れた潤滑樹脂処理鋼板とか、
被膜厚よりも大きな粒子径を持つ潤滑剤を用いる方法な
いしは高溶融点潤滑剤の採用等が図られいる。しかし、
これらの技術については選択可能な樹脂の種類が限定さ
れ、かつ、延び特性が十分でないこと、塗料が分離し易
いという作業性に問題があり、また、膜厚に応じて最適
潤滑径が変化する等の問題がある。2. Description of the Related Art Conventionally, as a lubricated resin-treated steel sheet having excellent workability, a lubricating property is provided by dispersing a lubricant in a coating film. Is generally known to deteriorate. It is said that this is because the base resin is particularly softened and becomes tacky, and the lubricity with the mold is impaired. As a solution to these problems, a resin having a hydroxyl group and / or a carboxyl group on one side of a plated steel sheet, silica and a solid lubricant, as disclosed in JP-A-1-301333 using a resin having a high glass transition temperature. Having a resin coating having a glass transition temperature of 70 ° C. or higher of the resin mixture or the composite containing the resin, and having, on the other surface, a resin coating containing a resin having a hydroxyl group and / or a carboxyl group and silica to improve moldability and corrosion resistance. Excellent lubricated resin treated steel sheet,
A method using a lubricant having a particle diameter larger than the coating thickness, a high melting point lubricant, and the like have been attempted. But,
These techniques are limited in the types of resins that can be selected, and have problems in workability such as insufficient elongation properties and easy separation of paint, and the optimal lubricating diameter varies depending on the film thickness. There are problems such as.
【０００３】そこで、本出願人らは特開平６−１５５１
８４号公報に記載するように、めっき鋼板の表面に第１
層としてＣｒ付着量５〜１００ｍｇ／ｍ2 のクロメート
被膜もしくは付着量０．２〜２．０ｇ／ｍ2 のりん酸塩
被膜の化成被膜、第２層としてビスフェノール型骨格、
エステル骨格およびカルボキシル基を有するエーテル・
エステル型ウレタン樹脂（ａ）とエポキシ樹脂（ｂ）の
総和（ａ＋ｂ）が全固形分に対して５０〜８５重量％、
ポリオレフィンワックス（ｃ）を３〜３０重量％、粒径
３〜３０ｎｍのシリカ（ｄ）を１０〜４０重量％含有す
る水性潤滑塗料を塗布・焼き付けて得られる膜厚０．２
〜５μｍの被膜を設けたプレス油省略可能非脱膜型潤滑
めっき鋼板を既に提案している。Accordingly, the present applicants have disclosed Japanese Patent Application Laid-Open No. Hei 6-1551.
No. 84, the first surface of the plated steel sheet
A chromate coating having a Cr adhesion of 5 to 100 mg / m 2 or a chemical conversion coating of a phosphate coating having an adhesion of 0.2 to 2.0 g / m 2 as a layer, a bisphenol type skeleton as a second layer,
Ether having an ester skeleton and a carboxyl group
The sum (a + b) of the ester type urethane resin (a) and the epoxy resin (b) is 50 to 85% by weight based on the total solid content;
A film thickness of 0.2 obtained by applying and baking an aqueous lubricating paint containing 3 to 30% by weight of polyolefin wax (c) and 10 to 40% by weight of silica (d) having a particle size of 3 to 30 nm.
There has already been proposed a non-delamination type lubricated plated steel sheet which can be omitted from press oil and has a coating of ~ 5 µm.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上述し
た特開平６−１５５１８４号公報では、図９に示すよう
に、薄鋼板１の上にめっき被膜２、クロメートもしくは
りん酸塩被膜の化成被膜３、潤滑被膜４からなる被膜構
造において、潤滑被膜４中に潤滑剤５を分散させること
で加工潤滑特性を持たせているが、プレスによる金型温
度の上昇によって加工性が劣化し十分な潤滑性が得られ
ないという問題が生ずる。一方、これらの塗装鋼板を得
るためには、塗装専用設備としてのオフラインでの処
理、またはメッキライン内の設備では大規模な設備での
処理が必要となるため、その通板速度も塗装焼付け工程
に大きく律速されるのが実状である。そこで潤滑被膜４
の表面に特に潤滑性能の高い層を形成する方法が提案さ
れている。However, in the above-mentioned Japanese Patent Laid-Open Publication No. Hei 6-155184, as shown in FIG. 9, a plating film 2, a chromate or phosphate conversion film 3, In the coating structure composed of the lubricating coating 4, the lubricant 5 is dispersed in the lubricating coating 4 to provide processing lubricating properties. There is a problem that it cannot be obtained. On the other hand, in order to obtain these coated steel sheets, off-line processing as dedicated equipment for painting or processing on large-scale equipment in the plating line is required. The reality is that the rate is greatly controlled by. So lubricating coating 4
There has been proposed a method of forming a layer having particularly high lubricating performance on the surface.
【０００５】図１０は潤滑被膜の表面状態を示す概念図
である。図１０に示すように、原板７上の潤滑被膜４が
水系エマルジョン塗料の場合に焼付けを高温急速加熱に
より高速で行なおうとすると、最表面の水の急激な蒸発
により表面に皮張り８が発生する。この表面の皮張り８
は内部からの蒸発水分によりガス抜け孔９を形成し、特
に潤滑鋼板においては、この表面の皮張り現象によって
表面潤滑被覆層の形成を阻害するという問題があり、高
速加熱においては潤滑性能の高い層を形成することが出
来ない。従って、これらの問題を解消するため、発明者
らは鋭意開発を進めた結果、表面の潤滑剤層が樹脂と金
型の直接接触を防ぎ、また被膜中に分散する粒子が深絞
り加工などにおいて被膜が激しく変形しても絶えず被膜
中から潤滑が補給され、良好な潤滑加工性が保持される
構造を持つ被膜を高温短時間焼付けによる高速通板を可
能によって、メッキライン内の簡便な塗装、焼付け設備
で製造可能とした加工性の優れた表面処理鋼板の製造方
法を提供するものである。FIG. 10 is a conceptual diagram showing a surface state of a lubricating film. As shown in FIG. 10, when the lubricating coating 4 on the original plate 7 is a water-based emulsion paint, if baking is performed at high speed by high-temperature rapid heating, skinning 8 occurs on the surface due to rapid evaporation of water on the outermost surface. I do. Skinning of this surface 8
Has a problem that a gas vent hole 9 is formed by moisture evaporated from the inside. Particularly, in a lubricated steel plate, there is a problem that the formation of a surface lubricating coating layer is hindered by the skinning phenomenon of the surface, and the lubricating performance is high in high-speed heating. Layer cannot be formed. Therefore, in order to solve these problems, the inventors have made intensive developments, and as a result, the lubricant layer on the surface prevents direct contact between the resin and the mold, and the particles dispersed in the coating film are used in deep drawing etc. Even if the coating is severely deformed, lubrication is constantly supplied from the coating, and high-speed short-time baking of the coating, which has a structure that maintains good lubrication workability, at high temperature and short time, enables simple painting in the plating line. An object of the present invention is to provide a method for producing a surface-treated steel sheet having excellent workability, which can be produced by a baking facility.
【０００６】[0006]
【課題を解決するための手段】本発明は、上述のような
従来技術の課題を有利に解決するものであって、その発
明の要旨とするところは、 （１）高速塗装ラインにおいて、めっき鋼板にクロメー
ト被膜もしくはりん酸塩被膜の化成被膜を形成した鋼板
に、ライン速度５０〜１５０ｍｐｍにて、ビスフェノー
ル型骨格、エステル骨格およびカルボキシル基を有する
エーテル・エステル型ウレタン樹脂（ａ）とエポキシ樹
脂（ｂ）の総和（ａ＋ｂ）が全固形分に対して５０〜８
５重量％、ポリオレフィンワックス（ｃ）を３〜３０重
量％、粒径３〜３０ｎｍのシリカ（ｄ）を１０〜４０重
量％及び高沸点溶媒（ｅ）を２〜１０重量％含有させた
水性潤滑塗料を塗布した後、焼付け時間２〜５秒で該水
性潤滑塗料よりなる潤滑層上に表面潤滑被覆層厚み０．
０４〜１μｍ形成せしめたことを特徴とするプレス加工
性の優れた表面処理鋼板の製造方法。 （２）（１）記載の方法において、水性潤滑塗料中の高
沸点溶媒がプロピレングリコールであり、その添加量が
２〜５重量％であることを特徴とするプレス加工性の優
れた表面処理鋼板の製造方法にある。SUMMARY OF THE INVENTION The present invention advantageously solves the above-mentioned problems of the prior art. The gist of the invention is as follows: (1) In a high-speed coating line, a plated steel sheet is used. An ether-ester type urethane resin (a) having a bisphenol type skeleton, an ester skeleton, and a carboxyl group and an epoxy resin (b) were applied to a steel sheet having a chromate film or a phosphate conversion film formed thereon at a line speed of 50 to 150 mpm. ) Is 50 to 8 with respect to the total solid content.
Aqueous lubrication containing 5% by weight, 3 to 30% by weight of polyolefin wax (c), 10 to 40% by weight of silica (d) having a particle size of 3 to 30 nm, and 2 to 10% by weight of high boiling solvent (e). After applying the paint, the baking time is 2 to 5 seconds.
A method for producing a surface-treated steel sheet having excellent press workability, wherein the surface-treated steel sheet is formed to have a thickness of from 0.4 to 1 μm. (2) The method according to (1), wherein the high-boiling solvent in the water-based lubricating coating material is propylene glycol, and the amount of addition is 2 to 5% by weight. Manufacturing method.
【０００７】[0007]
【作用】以下、本発明について図面に従って詳細に説明
する。図１は本発明に係るプレス加工性の優れた表面処
理鋼板の被膜構造を示す断面図である。すなわち、薄鋼
板１の上にめっき被膜２、クロメートもしくはりん酸塩
被膜の化成被膜３、潤滑被膜４および表面潤滑被覆層６
からなる被膜構造から成り、潤滑被膜４中に潤滑剤５が
分散した状態で存在する。この各被膜は用途に応じて両
面もしくは片面もしくは表裏の膜厚、被膜組成の異なる
構成をとることが可能である。また、例えば潤滑被膜は
樹脂＋シリカ＋ポリオレフィンワックス０．３〜５．０
μｍ、化成被膜はＣｒ５〜１００ｍｇ／ｍ2 もしくはり
ん酸塩０．２〜２．０ｇ／ｍ2 、めっきはＺｎ，Ｚｎ合
金、Ａｌ，Ａｌ合金のめっき、めっき量５〜２００ｇ／
ｍ2 から成る。本発明は基本的にはすべての薄鋼板即ち
アルミキルド鋼板、極低炭素鋼板、高張力鋼板に適用で
きる。Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a sectional view showing a coating structure of a surface-treated steel sheet having excellent press workability according to the present invention. That is, a plating film 2, a conversion film 3 of a chromate or phosphate film, a lubricating film 4, and a surface lubricating coating layer 6
The lubricant 5 is present in a dispersed state in the lubricating coating 4. Each of the coatings can have a different configuration with different thicknesses on both sides, one side, or both sides, and the coating composition, depending on the application. Further, for example, the lubricating film is made of resin + silica + polyolefin wax 0.3 to 5.0.
μm, conversion coating: Cr 5 to 100 mg / m 2 or phosphate 0.2 to 2.0 g / m 2 , plating: Zn, Zn alloy, Al, Al alloy plating, plating amount: 5 to 200 g /
consisting of m 2. The present invention is basically applicable to all thin steel sheets, ie, aluminum-killed steel sheets, ultra-low carbon steel sheets, and high-strength steel sheets.
【０００８】めっきは電気めっき、溶融めっき、気相め
っきで得られる亜鉛、亜鉛合金めっき、および複層めっ
き鋼板、アルミニウム、アルミニウム合金めっきおよび
複層めっき鋼板である。化成被膜としてはクロメート被
膜もしくはりん酸塩被膜を用いる。化成被膜はめっき面
と潤滑被膜の間に位置し加工時の密着性、耐食性等を与
える。クロメートは３価クロム水和酸化物を主成分とす
る後水洗型の電解還元クロメート、３価クロムと６価ク
ロム水和酸化物を主成分とする後水洗型のエッチングク
ロメート液を塗布し乾燥する無水洗型の塗布クロメート
被膜を採用できる。付着量はＣｒ換算で５〜１００ｍｇ
／ｍ2 である。５ｍｇ／ｍ2 未満では耐食性が得られな
いので好ましくない。１００ｍｇ／ｍ2 超ではクロメー
ト自身の凝集破壊が生じ易く密着性が得られない。クロ
メート被膜は３価クロム／６価クロム比率の高い水系潤
滑塗料に溶解しにくいものが望ましい。[0008] The plating is zinc, zinc alloy plating, multi-layer plated steel sheet, aluminum, aluminum alloy plated and multi-layer plated steel sheet obtained by electroplating, hot-dip plating, vapor phase plating. As the conversion coating, a chromate coating or a phosphate coating is used. The chemical conversion coating is located between the plating surface and the lubricating coating and provides adhesion during processing, corrosion resistance, and the like. The chromate is a post-wash type electrolytic reduction chromate containing a trivalent chromium hydrated oxide as a main component, and a post-wash type etching chromate liquid containing a trivalent chromium and a hexavalent chromium hydrated oxide as a main component is applied and dried. An anhydrous washing type chromate coating can be used. The amount of adhesion is 5 to 100 mg in terms of Cr.
/ M 2 . If it is less than 5 mg / m 2 , corrosion resistance cannot be obtained, which is not preferable. If it exceeds 100 mg / m 2 , the cohesive failure of the chromate itself is likely to occur, and the adhesion cannot be obtained. It is desirable that the chromate film hardly dissolves in an aqueous lubricating paint having a high trivalent chromium / hexavalent chromium ratio.
【０００９】りん酸塩被膜は亜鉛、鉄、ニッケル、マン
ガン、カルシウム等のリン酸塩で構成されるものであ
る。付着量は、０．３〜２．０ｇ／ｍ2 の範囲が耐食性
および密着性の理由で望ましい。０．３ｇ／ｍ2 未満で
は耐食性が得られない。２．０ｇ／ｍ2 超ではりん酸塩
被膜の凝集破壊により、厳しい加工で密着性が得られな
い。The phosphate coating is formed of a phosphate such as zinc, iron, nickel, manganese, calcium and the like. The amount of adhesion is preferably in the range of 0.3 to 2.0 g / m 2 for reasons of corrosion resistance and adhesion. If it is less than 0.3 g / m 2 , corrosion resistance cannot be obtained. If it exceeds 2.0 g / m 2 , adhesion cannot be obtained by severe processing due to cohesive failure of the phosphate film.
【００１０】本発明の潤滑被膜について以下説明する。
本発明に係る樹脂としては、ベース樹脂として適切な種
類の樹脂を一定重量比で配合させることにある。この樹
脂は、密着性、伸び、せん断強度、耐食性、耐摩耗性、
耐薬品性のバランスの取れた成分にする必要がある。こ
れらの性能を満足するためには、本発明の樹脂の組合せ
使用が好ましいのである。本発明者らは、既にウレタン
樹脂とエポキシ樹脂を配合しかつ特定のポリオレフィン
ワックスを配合することにより強度の加工性と耐食性を
得ることを達成していたが、さらに鋭意研究の結果、ウ
レタン樹脂の構造を特定することにより、特に優れた性
能を発揮することを見いだした。The lubricating coating of the present invention will be described below.
The resin according to the present invention is to mix a resin of an appropriate type as a base resin at a constant weight ratio. This resin has adhesion, elongation, shear strength, corrosion resistance, abrasion resistance,
It is necessary that the components have a well-balanced chemical resistance. In order to satisfy these performances, it is preferable to use a combination of the resins of the present invention. The present inventors have already obtained a strong workability and corrosion resistance by blending a urethane resin and an epoxy resin and blending a specific polyolefin wax, but as a result of further intensive research, the urethane resin By specifying the structure, it was found that particularly excellent performance was exhibited.
【００１１】高加工性と高耐食性を達成するためには、
塗膜が均一でありかつ密着性が優れていることが前提で
あり、かつ強度と伸びのバランスが取れていることが重
要である。分子量の大きいウレタン樹脂と、エポキシ樹
脂とを併用することで、低分子量同士の樹脂の架橋によ
ってできた膜より基本的な物性を制御しやすく、かつ塗
膜量で０．３〜５μｍの薄膜でも、均一物性が得られ易
いことを見いだした。尚、低分子量のウレタン樹脂と
は、各種イソシアネート系の架橋剤を含む種類の物であ
る。樹脂として、分子量３０００以上の耐摩耗性に優れ
たウレタン樹脂と密着性または膜強度の向上に優れたエ
ポキシ樹脂を配合した樹脂系の組合せが特に高加工性と
耐食性等の諸特性を発揮するのに適したベース樹脂であ
る。In order to achieve high workability and high corrosion resistance,
It is premised that the coating film is uniform and has excellent adhesion, and it is important that the strength and the elongation are balanced. By using a urethane resin with a high molecular weight and an epoxy resin in combination, it is easier to control the basic physical properties than a film formed by cross-linking low molecular weight resins, and even a thin film with a coating amount of 0.3 to 5 μm. It was found that uniform physical properties could be easily obtained. The low-molecular-weight urethane resin is of a type containing various isocyanate-based crosslinking agents. As a resin, a combination of a urethane resin with a molecular weight of 3000 or more and excellent abrasion resistance and an epoxy resin with an excellent adhesion or film strength improvement exhibits various properties such as high workability and corrosion resistance. Base resin suitable for
【００１２】本発明のウレタン樹脂は、分子量が３００
０以上でビスフェノール型骨格とエステル骨格を有しか
つカルボキシル基を有する水分散性のエーテル・エステ
ル型ウレタン樹脂（ａ）で、エポキシ樹脂（ｂ）は、グ
リコール骨格またはビスフェノール骨格を有するタイプ
であって、（ａ）のカルボキシル基の２０〜１００％を
反応させる比率で配合されたものである。本発明の高分
子ウレタン樹脂を使用することで薄膜での均一な成膜性
が得られ本発明の目的は達成されるが、より好ましくは
塗膜の伸びが１００％以上でかつ抗張力が１００ｋｇ／
ｃｍ2 以上になる樹脂を適用すれば、最高の高加工性が
得られる。The urethane resin of the present invention has a molecular weight of 300
A water-dispersible ether / ester type urethane resin (a) having a bisphenol type skeleton and an ester skeleton and having a carboxyl group of 0 or more, and the epoxy resin (b) having a glycol skeleton or a bisphenol skeleton; , (A) in a ratio that causes 20 to 100% of the carboxyl groups to react. By using the polymer urethane resin of the present invention, uniform film formability in a thin film can be obtained and the object of the present invention can be achieved, but more preferably, the elongation of the coating film is 100% or more and the tensile strength is 100 kg /
The highest workability can be obtained by applying a resin having a size of 2 cm 2 or more.
【００１３】本発明に使用するウレタン樹脂骨格のポリ
エーテルポリオールとしては、エチレングリコール、プ
ロピレングリコール、ビスフェノールＡなどの低分子グ
リコール類にエチレンオキサイドやプロピレンオキサイ
ドなどを付加したポリオール、ポリオキシテトラメチレ
ングリコールなどが挙げられるが、特にビスフェノール
Ａ骨格を有するポリエーテルポリオールが好適である。
ポリエステルポリオールとしては、低分子グリコール類
と２塩基酸との脱水縮合反応によって得られるポリエス
テル類およびε−カプロラクタムなどのラクタム類を低
分子グリコールの存在下で開環重合したラクタムポリオ
ール類が挙げられる。Examples of the polyether polyol having a urethane resin skeleton used in the present invention include polyols obtained by adding ethylene oxide and propylene oxide to low molecular weight glycols such as ethylene glycol, propylene glycol and bisphenol A, and polyoxytetramethylene glycol. Among them, a polyether polyol having a bisphenol A skeleton is particularly preferable.
Examples of the polyester polyol include a polyester obtained by a dehydration condensation reaction of a low molecular glycol and a dibasic acid, and a lactam polyol obtained by ring-opening polymerization of a lactam such as ε-caprolactam in the presence of a low molecular glycol.
【００１４】ウレタン樹脂のエステル骨格とエーテル骨
格を結合させるイソシアネート基としては、トリレジイ
ソシアネート、ジフェニルメタジイソシアネート、キシ
リレンジイソシアネートなどの芳香族ジイソシアネート
の単量体、２量体、３量体、および、それらとポリエー
テルポリオールやポリエステルポリオールなどとの反応
物、およびそれらの水素添加誘導体である脂環族イソシ
アネート、イソホロンジイソシアネート、ヘキサメチレ
ンジイソシアネートなどの脂環族、および脂肪族イソシ
アネートの単量体、２量体、３量体とポリエーテルポリ
オールやポリエステルポリオールなどとの反応物、およ
びそれらの混合物も使用できる。配合量は、使用するポ
リエステルポリオール、ポリエーテルポリオールおよび
後述するカルボキシル基導入成分の分子量と比率による
が、ＮＣＯ換算でウレタン樹脂の５〜２０重量％が、樹
脂物性として最適の加工特性を得られる。Examples of the isocyanate group for bonding the ester skeleton and the ether skeleton of the urethane resin include aromatic diisocyanate monomers such as tolylene diisocyanate, diphenyl metadiisocyanate and xylylene diisocyanate, and dimers and trimers. And dimer of aliphatic and isocyanate such as alicyclic isocyanate, isophorone diisocyanate, and hexamethylene diisocyanate, which are hydrogenated derivatives thereof with polyether polyol, polyester polyol and the like. A reaction product of a trimer with a polyether polyol or a polyester polyol, or a mixture thereof can also be used. The blending amount depends on the molecular weights and ratios of the polyester polyol, polyether polyol and the carboxyl group-introducing component to be used, but 5 to 20% by weight of the urethane resin in terms of NCO can obtain optimum processing characteristics as resin properties.
【００１５】カルボキシル基は、自己乳化するための官
能基であると共に金属表面との密着性に大きな寄与を発
揮する。カルボキシル基の導入成分としては、２個以上
のヒドロキシル基、またはアミノ基と１個以上のカルボ
キシル基を含む化合物であり、２，２−ジメチロールプ
ロピオン酢酸、２，２−ジメチロールプロピオン酸、
２，２−ジメチロール酪酸、２，２−ジメチロールペン
タン酸などのジヒドロキシカルボン酸やリジン、アルギ
ニンなどのジアミノカルボン酸類が挙げられる。これら
から選ばれるカルボキシル基化合物は、前記ポリエステ
ルポリオールおよびポリエーテルポリオールとの組合せ
でイソシアネート化合物で高分子化される。この方法に
より、本発明で使用する分子量が３０００以上のカルボ
キシル基を有するエーテル・エステル型ウレタン樹脂が
できる。The carboxyl group is a functional group for self-emulsification and exerts a great contribution to the adhesion to the metal surface. The carboxyl group-introducing component is a compound containing two or more hydroxyl groups or an amino group and one or more carboxyl groups, 2,2-dimethylolpropionacetic acid, 2,2-dimethylolpropionic acid,
Examples thereof include dihydroxycarboxylic acids such as 2,2-dimethylolbutyric acid and 2,2-dimethylolpentanoic acid, and diaminocarboxylic acids such as lysine and arginine. A carboxyl group compound selected from these is polymerized with an isocyanate compound in combination with the polyester polyol and polyether polyol. According to this method, an ether / ester type urethane resin having a carboxyl group having a molecular weight of 3000 or more used in the present invention can be obtained.
【００１６】前記のウレタン樹脂を水に分散する方法と
しては、カルボキシル基をアンモニア、トリメチルアミ
ン等のアルカリで中和して自己乳化する方法、または乳
化剤を用いてエマルジョン分散する方法が挙げられる。
作業環境対策としては、水系化以前のウレタン製造工程
中に含有する溶剤を回収して、最終的に無溶剤タイプの
水分散体を得ることが最も好ましい。カルボキシル基の
量は、ウレタン固形分当りの酸価で１０〜５０であるこ
とが適切である。１０未満の場合、密着性が不十分で加
工性及び耐食性が劣る。５０を超える場合、耐水性、耐
アルカリ性が劣るため耐食性が低下する。Examples of the method of dispersing the urethane resin in water include a method of neutralizing a carboxyl group with an alkali such as ammonia or trimethylamine to self-emulsify, or a method of emulsifying and dispersing using an emulsifier.
As a work environment countermeasure, it is most preferable to recover the solvent contained in the urethane production step before the aqueous system is used and finally obtain a solvent-free type aqueous dispersion. The amount of the carboxyl group is suitably from 10 to 50 in terms of acid value per urethane solid content. If it is less than 10, the adhesion is insufficient and the workability and the corrosion resistance are poor. If it exceeds 50, the water resistance and the alkali resistance are inferior, so that the corrosion resistance is reduced.
【００１７】反応性の官能基（水酸基，エポキシ基な
ど）を有するエポキシ樹脂の配合量としては、好ましく
はウレタン樹脂のカルボキシル基の２０〜１００％が反
応する比率で配合するのが適切である。２０％未満では
配合効果が乏しく、１００％を超える量ではエポキシ樹
脂が可塑剤的役割となるため高度の加工性が低下する。
尚、エポキシ樹脂は、耐薬品性、耐食性向上効果が大き
い。エポキシ樹脂にビスフェノールＡ型骨格を有する構
造物を用いると、密着性及び耐食性向上効果が特に大き
い。環境対策として無溶剤タイプ及び塗膜性能低下を防
ぐため無乳化剤タイプが必要であるときは、グリコール
骨格で親水性を付与することにより水溶性エポキシ樹脂
を得ることができる。The amount of the epoxy resin having a reactive functional group (hydroxyl group, epoxy group, etc.) is preferably compounded in such a ratio that 20 to 100% of the carboxyl groups of the urethane resin react. If the amount is less than 20%, the compounding effect is poor. If the amount exceeds 100%, the epoxy resin plays a role of a plasticizer, so that a high degree of processability is reduced.
In addition, the epoxy resin has a large effect of improving chemical resistance and corrosion resistance. When a structure having a bisphenol A-type skeleton is used for the epoxy resin, the effect of improving adhesion and corrosion resistance is particularly large. When a solvent-free type or an emulsifier-free type is required as an environmental measure to prevent a decrease in coating film performance, a water-soluble epoxy resin can be obtained by imparting hydrophilicity with a glycol skeleton.
【００１８】ウレタン樹脂の酸価に応じてエポキシ樹脂
の配合量を決定する必要があり、その計算方法は、次の
通りである。ウレタン樹脂のカルボキシル基とエポキシ
樹脂のエポキシ基が当量で反応するとして、所定の酸価
（ＡＶ）を有するウレタン樹脂に対し、１００％の反応
をするためのエポキシ樹脂の必要量を求めた式が式１で
ある。 （式１） エポキシ固形分重量（ｇ）＝ウレタン樹脂のＡＶ値×
（１／５６）／１０００×エポキシ当量×ウレタン樹脂
配合重量（ｇ）It is necessary to determine the compounding amount of the epoxy resin according to the acid value of the urethane resin, and the calculation method is as follows. Assuming that the carboxyl group of the urethane resin reacts with the epoxy group of the epoxy resin in an equivalent amount, the equation for calculating the required amount of the epoxy resin to react 100% with the urethane resin having a predetermined acid value (AV) is as follows. Equation 1 (Equation 1) Epoxy solid weight (g) = AV value of urethane resin ×
(1/56) / 1000 x epoxy equivalent x urethane resin compounding weight (g)
【００１９】本発明で配合されるエポキシ基はカルボキ
シル基と架橋するため、密着性に寄与するカルボキシル
基は反応相当分なくなるが、エポキシ基の開環によりＯ
Ｈ基が生ずるため密着性は確保される。また、エポキシ
樹脂の配合により、耐食性も大きく向上する。分子量が
３０００未満のウレタン樹脂と上記エポキシ樹脂の組合
せでは、安定して高加工性が達成されない。また、分子
量３０００以上のウレタン樹脂単独の成膜では、高度の
加工性及び耐食性が得られない。Since the epoxy group compounded in the present invention crosslinks with the carboxyl group, the carboxyl group contributing to the adhesion is substantially eliminated by the reaction.
Since H groups are generated, adhesion is secured. In addition, the corrosion resistance is greatly improved by blending the epoxy resin. A combination of a urethane resin having a molecular weight of less than 3000 and the above-described epoxy resin does not stably achieve high workability. In addition, high film formability and high corrosion resistance cannot be obtained by film formation using only a urethane resin having a molecular weight of 3000 or more.
【００２０】本発明の水系潤滑塗料組成物のウレタン樹
脂（ａ）とエポキシ樹脂（ｂ）の合計重量は、全固形分
に対する固形分比で５０〜８５％が適切である。５０％
未満の場合および８５％を超える場合、耐食性と加工性
が不十分である。しかし、これらの樹脂系被膜のみでは
目的の加工性を達成することはできないため、潤滑添加
物の併用が必要となる。The total weight of the urethane resin (a) and the epoxy resin (b) in the water-based lubricating coating composition of the present invention is suitably from 50 to 85% in terms of a solid content ratio based on the total solid content. 50%
If it is less than or more than 85%, the corrosion resistance and workability are insufficient. However, the desired workability cannot be achieved only by using these resin-based coatings, and therefore, a combined use of a lubricating additive is required.
【００２１】潤滑添加物としては、公知のフッ素系，炭
化水素系，脂肪酸アミド系，エステル系，アルコール
系，金属石鹸系および無機系等の滑剤が挙げられる。加
工性向上のための潤滑添加物の選択基準としては、添加
した滑剤が成膜した樹脂膜に分散して存在するよりも樹
脂膜表面に存在するような物質を選択するのが、成型加
工物の表面と金型の摩擦を低減させ潤滑効果を最大限発
揮させる点から必要である。即ち、滑剤が成膜した樹脂
膜に分散して存在する場合、表面摩擦係数が高く樹脂膜
が破壊されやすく粉状物質が剥離堆積してパウダリング
現象と言われる外観不良および加工性低下を生じる。樹
脂膜表面に存在するような物質としては、樹脂に相溶せ
ずかつ表面エネルギーの小さいものが選ばれる。Examples of the lubricating additive include known lubricants such as fluorine-based, hydrocarbon-based, fatty acid amide-based, ester-based, alcohol-based, metal soap-based and inorganic lubricants. As a criterion for selecting a lubricating additive for improving processability, it is necessary to select a substance in which the added lubricant is present on the surface of the resin film rather than being dispersed in the formed resin film. It is necessary in order to reduce the friction between the surface of the mold and the mold and maximize the lubrication effect. That is, when the lubricant is dispersed in the formed resin film, the surface friction coefficient is high and the resin film is easily broken, and the powdery substance is separated and deposited, resulting in poor appearance and reduced workability called a powdering phenomenon. . As the substance existing on the surface of the resin film, a substance which is not compatible with the resin and has a small surface energy is selected.
【００２２】本発明者らが検討した結果、ポリオレフィ
ンワックスを使用すると、加工性が大きく向上し加工後
の耐食性及び耐薬品性等の性能も良好にすることが判っ
た。このワックスとしては、パラフィン、マイクロクリ
スタリンまたはポリエチレン等の炭化水素系のワックス
が上げられる。加工時には、素材の変形熱と摩擦熱によ
って被膜温度が上昇するため、ワックスの融点は７０〜
１６０℃が適切であり、７０℃未満では加工時に軟化溶
融して固体潤滑添加物としての優れた特性が発揮されな
い。また、１６０℃を超える融点のものは、硬い粒子が
表面に存在することとなり摩擦特性を低下させるので高
度の成形加工性は得られない。As a result of investigations by the present inventors, it has been found that the use of polyolefin wax greatly improves workability and also improves the performance such as corrosion resistance and chemical resistance after processing. Examples of the wax include hydrocarbon waxes such as paraffin, microcrystalline or polyethylene. At the time of processing, the melting point of the wax is 70 to
160 ° C. is appropriate, and if it is lower than 70 ° C., it softens and melts during processing and does not exhibit excellent properties as a solid lubricating additive. On the other hand, if the melting point exceeds 160 ° C., hard particles are present on the surface and the frictional characteristics are reduced, so that high moldability cannot be obtained.
【００２３】好ましくは、ポリオレフィンワックスのケ
ン化価としては、３０以下または０であり、かつ分岐構
造を有するものを使用することが好ましい。ケン化価が
３０を超えるものは、極性が大きく樹脂に相溶しやすい
ため、成膜時に樹脂表面に存在しにくくなるため、高度
な加工性能レベルが必要な場合には適切とは言えない。
特に好ましいのは、樹脂との相溶性のより小さいエステ
ル結合を持たないケン化価が０のワックスである。Preferably, the polyolefin wax has a saponification value of 30 or less or 0 and has a branched structure. Those having a saponification value of more than 30 have a high polarity and are easily compatible with the resin, so that they are unlikely to be present on the resin surface at the time of film formation. Therefore, they cannot be said to be appropriate when a high processing performance level is required.
Particularly preferred is a wax having a saponification value of 0 and having no ester bond having a lower compatibility with the resin.
【００２４】これらのワックスの粒径は、０．１〜７．
０μｍが適切である。７．０μｍを超えるものは、固体
化したワックスの分布が不均一となるため好ましくな
い。又、０．１μｍ未満の場合は、加工性が不十分であ
る。潤滑添加物の量は、潤滑性塗料の全固形分重量に対
して固形分比で３〜３０％を添加する。３％未満の場
合、加工性向上効果が小さく、３０％を超える量では、
加工性および耐食性が低下する。The particle size of these waxes is 0.1-7.
0 μm is appropriate. If it exceeds 7.0 μm, the distribution of the solidified wax is not uniform, which is not preferable. If the thickness is less than 0.1 μm, workability is insufficient. The amount of the lubricating additive is 3 to 30% in terms of a solid content based on the total solid weight of the lubricating paint. If it is less than 3%, the processability improvement effect is small, and if it exceeds 30%,
Workability and corrosion resistance decrease.
【００２５】その他の添加物として、耐食性の向上のた
めＳｉＯ2 を全固形分に対して１０〜４０％を添加す
る。ＳｉＯ2 の添加により、耐食性の大幅な向上及び加
工性の向上効果がある。１０％未満の場合耐食性及び加
工性の向上効果が小さく、４０％を超える量では樹脂の
バインダー効果が小さくなり耐食性が低下すると共に樹
脂の伸びと強度が低下するため加工性が低下する。Ｓｉ
Ｏ2 の粒径については、３〜３０μｍが適切である。３
０μｍを超える場合及び３μｍ未満の場合、より高度の
加工性及び耐食性が得られない。シリカの種類として
は、液相コロイダルシリカおよび気相シリカがあるが、
本発明では特に限定するものではない。また、溶接性の
向上のために導電性物または意匠性向上のため着色顔料
物を添加することもある。また、沈降防止剤、レベリン
グ剤、増粘剤など各種添加剤を添加し得る。As other additives, SiO 2 is added in an amount of 10 to 40% based on the total solid content to improve corrosion resistance. The addition of SiO 2 has the effect of significantly improving corrosion resistance and processability. If it is less than 10%, the effect of improving the corrosion resistance and workability is small, and if it exceeds 40%, the binder effect of the resin becomes small, the corrosion resistance is reduced, and the elongation and strength of the resin are reduced, so that the workability is reduced. Si
As for the particle diameter of O 2 , 3 to 30 μm is appropriate. 3
If it exceeds 0 μm or less than 3 μm, higher workability and corrosion resistance cannot be obtained. Types of silica include liquid-phase colloidal silica and gas-phase silica,
The present invention is not particularly limited. In addition, a conductive material for improving weldability or a coloring pigment for improving design may be added. Further, various additives such as an anti-settling agent, a leveling agent, and a thickener may be added.
【００２６】本発明の潤滑被膜の膜厚範囲は０．３〜
５．０μｍである。最適な膜厚はプレスの形態によって
異なり、限定するのが難しいが、深絞りには厚膜が、Ｌ
曲げには薄膜が有利である。０．３μｍ未満では潤滑性
能が不安定である。５．０μｍ長ではコイルのブロッキ
ングやプレスかすが多量に発生し好ましくない。The thickness range of the lubricating coating of the present invention is from 0.3 to
It is 5.0 μm. The optimum film thickness depends on the type of press and it is difficult to limit it.
Thin films are advantageous for bending. If it is less than 0.3 μm, the lubrication performance is unstable. If the length is 5.0 μm, a large amount of blocking and press debris of the coil is generated, which is not preferable.
【００２７】図２は本発明に係る潤滑鋼板の被膜形成過
程を示す図である。先ず塗装直後の焼付け工程における
第１工程において塗膜液中に対流現象が発生し、それに
伴い第２工程において分散している潤滑剤粒子が表面に
露出する。このとき表面に露出した潤滑剤粒子表面が第
３工程では炉内雰囲気により乾燥、表面活性が低下す
る。このため一度表面に露出した潤滑剤粒子は塗膜中に
沈み込まずに表面に固定され、そのまま融点以上の温度
で焼付けられることで、第４工程のように被膜表面で融
解し潤滑剤の層を形成する。これが表面潤滑被覆層であ
る。FIG. 2 is a view showing a process of forming a film on a lubricated steel sheet according to the present invention. First, a convection phenomenon occurs in the coating liquid in the first step of the baking step immediately after coating, and accordingly, the dispersed lubricant particles are exposed on the surface in the second step. At this time, in the third step, the surface of the lubricant particles exposed on the surface is dried by the atmosphere in the furnace, and the surface activity is reduced. For this reason, the lubricant particles once exposed on the surface are fixed on the surface without sinking into the coating film, and are baked as they are at a temperature equal to or higher than the melting point. To form This is the surface lubrication coating layer.
【００２８】図３は本発明に係る潤滑剤中へのプロピレ
ングリコール添加による高温急速加熱時での潤滑被膜の
表面状態を示す概念図である。この図に示すように、原
板７上での潤滑被膜４を高温急速加熱する場合に、本発
明の特徴である潤滑塗料中に高沸点溶媒であるプロピレ
ングリコールを添加することで、前述した高温急速加熱
により潤滑被膜上に皮張り現象の発生を防止することが
出来る。すなわち、潤滑塗料中に水よりも蒸発しにくい
高沸点溶媒を混入させることで、この高沸点溶媒の存在
により最表面において水が急速に蒸発しても、高沸点溶
媒１０が残存し、濃度の上昇は起こるとしても皮張りま
でには至らない。従って、この濃度上昇部を内部からの
蒸発水分が通り抜けて蒸発するため、最後まで皮張りは
発生しないで表面潤滑被覆層を形成する。FIG. 3 is a conceptual diagram showing a surface state of a lubricating film during rapid heating at a high temperature by adding propylene glycol to the lubricant according to the present invention. As shown in this figure, when the lubricating film 4 on the original plate 7 is rapidly heated at a high temperature, by adding propylene glycol which is a high boiling point solvent to the lubricating paint which is a feature of the present invention, the aforementioned high temperature rapid heating is performed. Heating can prevent skinning on the lubricating coating. That is, by mixing a high-boiling solvent that is less likely to evaporate than water into the lubricating coating, even if water evaporates rapidly on the outermost surface due to the presence of the high-boiling solvent, the high-boiling solvent 10 remains, The rise, if any, does not reach skinning. Accordingly, since the moisture from the inside passes through the concentration increasing portion and evaporates, the surface lubrication coating layer is formed without skinning until the end.
【００２９】図４は本発明に係る潤滑被膜での焼付け時
間と表面潤滑被覆層厚みとの関係を示す図である。この
図によれば焼付け時間２秒行うことで本発明の潤滑効果
を達成するための表面潤滑被覆層厚さ０．０４μｍを
得、５秒で１．０μｍを得ることが出来る。また、５秒
を超える焼付け時間では飽和状態となり、それ以上を得
ることが出来ない。従って、本発明の潤滑効果を達成す
るための表面潤滑被覆層の厚さ０．０４〜１．０μｍを
得るためには焼付け時間２〜５秒が好ましい。図５は本
発明塗料及び従来塗料での焼付け時間と潤滑特性との関
係を示す図である。この図に示すように、本発明塗料に
よると焼付け時間が２秒以上で極めて良好な潤滑性能を
示していることが判る。同様に、図６は本発明塗料及び
従来塗料での焼付け時間と加工特性との関係を示す図で
あり、この図に示すように、本発明に係る塗料を用いて
焼付け時間が２秒以上において加工評点５という極めて
良好な加工性を示している。FIG. 4 is a diagram showing the relationship between the baking time of the lubricating coating according to the present invention and the thickness of the surface lubricating coating. According to this figure, when the baking time is 2 seconds, the surface lubricating coating layer thickness for achieving the lubricating effect of the present invention is 0.04 μm, and in 5 seconds, 1.0 μm can be obtained. In addition, if the baking time exceeds 5 seconds, the baking time will be saturated, and no longer can be obtained. Therefore, in order to obtain the thickness of the surface lubricating coating layer of 0.04 to 1.0 μm for achieving the lubricating effect of the present invention, the baking time is preferably 2 to 5 seconds. FIG. 5 is a diagram showing the relationship between the baking time and the lubrication characteristics of the paint of the present invention and the conventional paint. As shown in this figure, the paint of the present invention shows extremely good lubrication performance when the baking time is 2 seconds or longer. Similarly, FIG. 6 is a diagram showing the relationship between the baking time and the processing characteristics of the paint of the present invention and the conventional paint, and as shown in this figure, the baking time using the paint of the present invention is 2 seconds or more. It shows a very good workability of a processing score of 5.
【００３０】図７は焼付け時間２〜５秒での高沸点溶媒
添加濃度と潤滑特性との関係を示す図であり、この図に
示すように、高沸点溶媒の添加量２〜１０重量％の場合
に焼付け時間２秒〜５秒で潤滑性が良好であることを示
している。また、図８は焼付け時間２〜５秒での高沸点
溶媒添加濃度と加工特性との関係を示す図である。この
図より、高沸点溶媒２〜１０重量％を添加した場合の焼
付け時間２秒〜５秒において良好な加工性を示してい
た。これら図７及び図８より高沸点溶媒の添加量は２〜
１０重量％、好ましいは塗料として危険物の規制を受け
ない５％以下の２〜５重量％が最適である。また、高沸
点溶媒としてはプロピレングリコールが望ましい。FIG. 7 is a graph showing the relationship between the high-boiling-point solvent addition concentration and the lubricating properties at a baking time of 2 to 5 seconds. As shown in FIG. In this case, a baking time of 2 to 5 seconds indicates good lubricity. FIG. 8 is a graph showing the relationship between the high-boiling-point solvent addition concentration and the processing characteristics at a baking time of 2 to 5 seconds. From this figure, good workability was exhibited in the baking time of 2 to 5 seconds when the high boiling point solvent of 2 to 10% by weight was added. 7 and 8, the amount of the high boiling point solvent added is 2 to 2.
The optimum content is 10% by weight, preferably 2 to 5% by weight of 5% or less, which is not restricted by dangerous substances as a paint. Propylene glycol is desirable as the high boiling point solvent.
【００３１】[0031]
【実施例】以下、本発明について溶融亜鉛めっき鋼板に
適用した実施例によって具体的に説明する。Ｃｒ付着量
１５ｍｇ／ｍ2 の塗布クロメート処理した溶融亜鉛めっ
き鋼板に高速塗装ラインでのライン速度１００ｍｐｍに
おいて、分子量５０００のエーテルエステルウレタン樹
脂（ビスフェノールＡエーテル：酸価１８、エーテル／
エステル比３０／７０、イソシアネート含有率８）とプ
ロピレングリコールエポキシ樹脂（エポキシ当量２２
０）に平均粒径８ｎｍのシリカゾルを２１％，粒径０．
６μｍのポリエチレンワックス（比重０．９３、軟化点
１２０℃）１３％及びプロピレングリコール４重量％を
配合した潤滑塗料を塗布し、板温１４０℃、焼付け時間
５秒及び板温１７０℃、焼付け時間３秒にて焼き付けて
表面潤滑被覆層厚み０．０４μｍ及び０．１０μｍの潤
滑鋼板を作成した。得られた表面潤滑被覆層厚み０．０
４μｍ及び０．１０μｍの潤滑鋼板の潤滑特性である摩
擦係数はそれぞれ０．０７及び０．０６という良好な潤
滑性能を得た。また、加工特性である加工評価はそれぞ
れ４及び５と極めて良好な加工性能が得られた。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to embodiments applied to a galvanized steel sheet. An ether ester urethane resin having a molecular weight of 5,000 (bisphenol A ether: acid number 18, ether / 18) was applied to a hot-dip galvanized steel sheet coated with chroma at 15 mg / m 2 at a line speed of 100 mpm in a high-speed coating line.
Ester ratio 30/70, isocyanate content 8) and propylene glycol epoxy resin (epoxy equivalent 22
In 0), 21% of a silica sol having an average particle size of 8 nm was used,
A lubricating paint containing 13% of 6 μm polyethylene wax (specific gravity 0.93, softening point 120 ° C.) and 4% by weight of propylene glycol was applied, and the plate temperature was 140 ° C., the baking time was 5 seconds, and the plate temperature was 170 ° C., and the baking time was 3 By baking in seconds, a lubricated steel sheet having a surface lubricating coating layer thickness of 0.04 μm and 0.10 μm was prepared. Obtained surface lubricating coating layer thickness 0.0
The lubricating steel plates of 4 μm and 0.10 μm obtained good lubricating performances of 0.07 and 0.06, respectively. In addition, the processing evaluation as processing characteristics was 4 and 5, respectively, and extremely good processing performance was obtained.
【００３２】[0032]
【発明の効果】以上述べたように、本発明による高温短
時間焼付けによる高速通板での塗装にもかかわらず、表
面の潤滑層が樹脂と金型の直接接触を防ぎ、また被膜中
に分散する粒子が深絞り加工などにおいて被膜が激しく
変形しても絶えず被膜中から潤滑剤が補給され、良好な
潤滑加工性を保持することが出来る潤滑層上への表面潤
滑被覆層が形成され、優れたプレス加工性の優れた表面
処理鋼板を製造することが出来る。これによって、高温
短時間処理が可能なり、しかもメッキライン内の簡便な
塗装焼付け設備による高生産性並びに炉長短縮設備が可
能となったことは工業上極めて有効である。As described above, despite the high-speed and short-time baking according to the present invention, the surface lubricating layer prevents direct contact between the resin and the mold and disperses in the coating, despite the high-speed passing plate coating. Even if the film is severely deformed in deep drawing etc., the lubricant is constantly replenished from the film, and a surface lubricating coating layer is formed on the lubricating layer that can maintain good lubricating workability, excellent A surface-treated steel sheet having excellent press workability can be manufactured. This makes it possible to perform high-temperature and short-time processing, and also to achieve high productivity and simple furnace length shortening equipment by simple paint baking equipment in the plating line, which is extremely industrially effective.
【図１】本発明に係るプレス加工性の優れた表面処理鋼
板の被膜構造を示す断面図、FIG. 1 is a cross-sectional view showing a coating structure of a surface-treated steel sheet having excellent press workability according to the present invention;
【図２】本発明に係る潤滑鋼板の被膜形成過程を示す
図、FIG. 2 is a view showing a process of forming a film on a lubricated steel sheet according to the present invention;
【図３】本発明に係る潤滑剤中へのプロピレングリコー
ル添加による高温急速加熱時での潤滑被膜の表面状態を
示す概念図、FIG. 3 is a conceptual diagram showing a surface state of a lubricating film at the time of high-temperature rapid heating by adding propylene glycol to a lubricant according to the present invention;
【図４】本発明に係る潤滑被膜での焼付け時間と表面潤
滑被覆層厚みとの関係を示す図FIG. 4 is a diagram showing the relationship between the baking time and the thickness of the surface lubricating coating layer in the lubricating coating according to the present invention.
【図５】本発明塗料及び従来塗料での焼付け時間と潤滑
特性との関係を示す図、FIG. 5 is a diagram showing the relationship between the baking time and lubrication characteristics of the paint of the present invention and the conventional paint;
【図６】本発明塗料及び従来塗料での焼付け時間と加工
特性との関係を示す図、FIG. 6 is a diagram showing a relationship between baking time and processing characteristics of the paint of the present invention and the conventional paint;
【図７】焼付け時間２〜５秒での高沸点溶媒添加濃度と
潤滑特性との関係を示す図、FIG. 7 is a graph showing the relationship between the high-boiling-point solvent addition concentration and the lubricating properties at a baking time of 2 to 5 seconds;
【図８】焼付け時間２〜５秒での高沸点溶媒添加濃度と
加工特性との関係を示す図、FIG. 8 is a diagram showing the relationship between the high-boiling-point solvent addition concentration and the processing characteristics at a baking time of 2 to 5 seconds;
【図９】従来のプレス加工用表面処理鋼板の被膜構造を
示す断面図、FIG. 9 is a cross-sectional view showing a coating structure of a conventional surface-treated steel sheet for press working;
【図１０】従来の潤滑被膜の表面状態を示す概念図であ
る。FIG. 10 is a conceptual diagram showing a surface state of a conventional lubricating film.
１ 薄鋼板 ２ めっき被膜 ３ 化成被膜 ４ 潤滑被膜 ５ 潤滑剤 ６ 表面潤滑被覆層 ７ 原板 ８ 皮張り ９ ガス抜け孔 １０ 高沸点溶媒 DESCRIPTION OF SYMBOLS 1 Thin steel plate 2 Plating coating 3 Chemical conversion coating 4 Lubrication coating 5 Lubricant 6 Surface lubrication coating layer 7 Original plate 8 Skinning 9 Gas vent hole 10 High boiling point solvent
───────────────────────────────────────────────────── フロントページの続き (72)発明者 圓山 勝俊 千葉県君津市君津１番地 新日本製鐵株 式会社 君津製鐵所内 (56)参考文献 特開 平６−299367（ＪＰ，Ａ) 特開 平６−145559（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 15/08 B05D 7/14 C23C 22/24 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Katsutoshi Enyama 1 Kimitsu, Kimitsu City, Chiba Prefecture Nippon Steel Corporation Kimitsu Works (56) References JP-A-6-299367 (JP, A) Kaihei 6-145559 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) B32B 15/08 B05D 7/14 C23C 22/24
Claims (2)
クロメート被膜もしくはりん酸塩被膜の化成被膜を形成
した鋼板に、ライン速度５０〜１５０ｍｐｍにて、ビス
フェノール型骨格、エステル骨格およびカルボキシル基
を有するエーテル・エステル型ウレタン樹脂（ａ）とエ
ポキシ樹脂（ｂ）の総和（ａ＋ｂ）が全固形分に対して
５０〜８５重量％、ポリオレフィンワックス（ｃ）を３
〜３０重量％、粒径３〜３０ｎｍのシリカ（ｄ）を１０
〜４０重量％及び高沸点溶媒（ｅ）を２〜１０重量％含
有させた水性潤滑塗料を塗布した後、焼付け時間２〜５
秒で該水性潤滑塗料よりなる潤滑層上に表面潤滑被覆層
厚み０．０４〜１μｍ形成せしめたことを特徴とするプ
レス加工性の優れた表面処理鋼板の製造方法。In a high-speed coating line, a steel plate having a chromate film or a phosphate conversion film formed on a plated steel plate is coated at a line speed of 50 to 150 mpm at an ether speed having a bisphenol type skeleton, an ester skeleton and a carboxyl group. The total (a + b) of the ester type urethane resin (a) and the epoxy resin (b) is 50 to 85% by weight based on the total solid content, and the polyolefin wax (c) is 3%.
To 30% by weight, silica (d) having a particle size of 3 to 30 nm
After applying an aqueous lubricating paint containing さ せ 40% by weight and 2 to 10% by weight of a high boiling point solvent (e), the baking time is 2 to 5%.
A method for producing a surface-treated steel sheet having excellent press workability, wherein a surface lubricating coating layer having a thickness of 0.04 to 1 μm is formed on a lubricating layer made of the aqueous lubricating paint in seconds.
塗料中の高沸点溶媒がプロピレングリコールであり、そ
の添加量が２〜５重量％であることを特徴とするプレス
加工性の優れた表面処理鋼板の製造方法。2. The method according to claim 1, wherein the high-boiling solvent in the aqueous lubricating paint is propylene glycol, and the amount of the solvent is 2 to 5% by weight. Manufacturing method of treated steel sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07061181A JP3135815B2 (en) | 1995-03-20 | 1995-03-20 | Method for producing surface-treated steel sheet with excellent press workability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07061181A JP3135815B2 (en) | 1995-03-20 | 1995-03-20 | Method for producing surface-treated steel sheet with excellent press workability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08258214A JPH08258214A (en) | 1996-10-08 |
| JP3135815B2 true JP3135815B2 (en) | 2001-02-19 |
Family
ID=13163744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07061181A Expired - Fee Related JP3135815B2 (en) | 1995-03-20 | 1995-03-20 | Method for producing surface-treated steel sheet with excellent press workability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3135815B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169885C (en) * | 1998-12-25 | 2004-10-06 | 日本巴卡莱近估股份有限公司 | Water-based metal surface treatment composition forming lubricating film with excellent maring resistance |
| JP2001140080A (en) * | 1999-11-12 | 2001-05-22 | Nippon Steel Corp | Lubricated stainless steel sheet, lubricated stainless steel tube and method for producing lubricated stainless steel tube |
| US20040121162A1 (en) * | 2001-03-30 | 2004-06-24 | Ikuro Yamaoka | Metal product surface-treated with alkali-soluble lubricating film exhibiting excellent formability and excellent film removal property being stable for a long time and independent of temperature for drying film |
| JP4938054B2 (en) * | 2009-07-02 | 2012-05-23 | 新日本製鐵株式会社 | Organic coated molten Sn-Zn plated steel sheet |
-
1995
- 1995-03-20 JP JP07061181A patent/JP3135815B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08258214A (en) | 1996-10-08 |
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