JP4665821B2 - Painted steel plate with excellent corrosion resistance - Google Patents
Painted steel plate with excellent corrosion resistance Download PDFInfo
- Publication number
- JP4665821B2 JP4665821B2 JP2006122204A JP2006122204A JP4665821B2 JP 4665821 B2 JP4665821 B2 JP 4665821B2 JP 2006122204 A JP2006122204 A JP 2006122204A JP 2006122204 A JP2006122204 A JP 2006122204A JP 4665821 B2 JP4665821 B2 JP 4665821B2
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- rust preventive
- coated steel
- undercoat
- silica
- 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.)
- Active
Links
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
本発明は、家電製品.建材、自動車部品などの製造に有用な塗装鋼板に関する。本発明の塗装鋼板は、硬度と加工性のバランスがよく、同時に改善された耐食性を有する。 The present invention relates to a coated steel sheet useful for manufacturing home appliances, building materials, automobile parts, and the like. The coated steel sheet of the present invention has a good balance between hardness and workability, and at the same time has improved corrosion resistance.
塗装鋼板（プレコート鋼板、ＰＣＭ）は、素地鋼板に塗装と焼付けにより塗膜を形成した後、コイル状に巻き取られ、その状態でユーザーに納入される。その後、ユーザーはコイルを巻き戻して、打ち抜き、折り曲げ、絞り加工、またはこれらを組み合わせた加工を行う。作業環境を悪化させ、廃液処理が面倒な塗装作業をユーザーが行う必要がないことから、塗装鋼板の適用は多くの分野に普及している。 A coated steel plate (pre-coated steel plate, PCM) forms a coating film on a base steel plate by painting and baking, and is then wound into a coil shape and delivered to the user in that state. Thereafter, the user unwinds the coil and performs punching, bending, drawing, or a combination thereof. The application of coated steel sheets is widespread in many fields because the user does not need to perform painting work that makes the working environment worse and waste liquid treatment is troublesome.
塗装鋼板の製造は、素地鋼板（典型的には亜鉛系めっき鋼）に前処理として化成処理を施した後、下塗り塗料の塗布と焼付け、次に上塗り塗料の塗布と焼付けを順に行う２コート２ベーク方式が一般的である。ただし、外面となる「おもて面」の反対側の面、すなわち、裏面側については、前処理後に裏面用に開発された塗料を用いて１コート１ベーク方式で塗装が行われることもある。この工程からわかるように、使用する塗料は焼付け型であり、ベース樹脂と架橋剤とを含有する。 The coated steel sheet is manufactured by subjecting a base steel sheet (typically galvanized steel) to a chemical conversion treatment as a pretreatment, followed by the application and baking of an undercoat, followed by the application and baking of a topcoat in sequence. A bake method is common. However, the surface opposite to the “front surface” that is the outer surface, that is, the back surface side, may be coated by a 1-coat 1-bake method using a paint developed for the back surface after the pretreatment. . As can be seen from this step, the paint used is a baking type and contains a base resin and a crosslinking agent.
塗装鋼板の塗装面、特におもて面は、ユーザーによる上記のような加工が行われた後、そのまま製品の外面、品質保証面として使用されるため、加工性と硬度の高度のバランスが要求される。硬度は耐傷付き性の確保に必要な特性である。また、厳しい成形加工を受けても塗膜剥離を起こさないような優れた塗膜密着性と、良好な潤滑性も必要である。潤滑性を高めるために、上塗り塗膜層は潤滑剤成分を含有するのが普通である。 The painted surface of the coated steel sheet, especially the front surface, is used as it is as the outer surface of the product and the quality assurance surface after being processed by the user as described above, so a high balance between workability and hardness is required. Is done. Hardness is a characteristic necessary for ensuring scratch resistance. Moreover, the coating film adhesion which does not raise | generate peeling of a coating film even if it receives severe shaping | molding processing, and favorable lubricity are also required. In order to enhance the lubricity, the top coat layer usually contains a lubricant component.
エアコン室外機、建材等といった屋外で使用される製品用の塗装鋼板には、上記性能に加えて、耐候性と優れた耐食性がさらに要求される。耐食性は、主に下塗り塗膜に含有させた防錆顔料により改善される。耐候性は、主に上塗り塗膜の樹脂種および硬化剤種により左右されるが、紫外線吸収剤および光安定剤を含有させることにより、向上させることは可能である。 Painted steel sheets for products used outdoors such as air conditioner outdoor units and building materials are required to have weather resistance and excellent corrosion resistance in addition to the above performance. Corrosion resistance is improved mainly by the rust preventive pigment contained in the undercoat film. The weather resistance mainly depends on the resin type and the curing agent type of the top coat film, but can be improved by containing an ultraviolet absorber and a light stabilizer.
しかし、塗装鋼板の製造に従来から使用されてきた塗料では、加工性、硬度、耐食性のいずれにも優れた塗装鋼板を得るのは困難であった。この点を次に説明する。
一般に、加工性に優れた塗装鋼板では、下塗り塗膜層として用いる樹脂のガラス転移温度が低く、素地鋼板との密着性が良くない上に、防錆顔料の濃度を高くできず、耐食性と塗膜硬度が劣る傾向がある。逆に、耐食性に優れた塗装鋼板では、下塗り塗膜層中の防錆顔料濃度が高いため、加工性が劣る傾向がある。
However, it has been difficult to obtain a coated steel sheet that is excellent in workability, hardness, and corrosion resistance with the paints that have been conventionally used in the production of coated steel sheets. This point will be described next.
In general, a coated steel sheet with excellent workability has a low glass transition temperature of the resin used as an undercoat coating layer, has poor adhesion to the base steel sheet, and cannot increase the concentration of anticorrosive pigments. The film hardness tends to be inferior. On the contrary, in the coated steel sheet having excellent corrosion resistance, the workability tends to be inferior because the rust preventive pigment concentration in the undercoat coating layer is high.
硬度は、耐食性との両立のため下塗り塗膜に大量の防錆顔料を加え、上塗り塗膜には硬度を発現させるための顔料を添加し、さらにガラス転移温度の高い樹脂を用いることにより高めることができる。しかし、そうすると加工性が極度に劣る傾向がある。 Hardness is increased by adding a large amount of anti-corrosion pigment to the undercoat film for compatibility with corrosion resistance, adding a pigment for developing hardness to the top coat film, and using a resin with a high glass transition temperature. Can do. However, when it does so, workability tends to be extremely inferior.
このように、高度な加工性と硬度のバランスに加え、優れた耐食性をすべて充分に満たす塗装鋼板を実現することは困難であった。
また、最近では、６価クロムの有害性が問題となり、６価クロムを使用する化成処理であるクロメート処理、あるいは６価クロム化合物であるクロム酸塩系防錆顔料の使用が忌避され、さらには３価クロムも含めてクロム化合物を全く含まないノンクロム型の塗装鋼板が求められるようになってきた。しかし、前処理としてのクロメート処理、ならびに特に下塗り塗膜層用の防錆顔料として重宝されてきたクロム酸塩系防錆顔料は、いずれも耐食性改善効果が非常に高い。従って、クロメート処理やクロム酸塩系防錆顔料を使用せずに、塗装鋼板の耐食性を確保することが望まれている。
Thus, it has been difficult to realize a coated steel sheet that sufficiently satisfies all the excellent corrosion resistance in addition to the balance between high workability and hardness.
Recently, the toxicity of hexavalent chromium has become a problem, and the use of chromate treatment, which is a chemical conversion treatment using hexavalent chromium, or the use of chromate-based rust preventive pigments, which are hexavalent chromium compounds, has been avoided. There has been a demand for a non-chromium-type coated steel sheet containing no chromium compound, including trivalent chromium. However, chromate treatment as a pretreatment, and chromate rust preventive pigments that have been particularly useful as rust preventive pigments for undercoat coating layers are all very effective in improving corrosion resistance. Therefore, it is desired to ensure the corrosion resistance of the coated steel sheet without using chromate treatment or chromate rust preventive pigment.
特開平０８−２１８００１号公報（特許文献１）には、耐食性と加工性を両立させるため、下塗り塗料中に平均粒径０.０１〜２μｍの防錆顔料を１１〜７０質量％含有させた塗装金属材料が記載されている。防錆顔料はクロム酸塩またはリン酸塩である。硬度とのバランスについては何ら言及されていない。 In JP 08-218011 (Patent Document 1), in order to achieve both corrosion resistance and workability, a coating in which an anticorrosive pigment having an average particle size of 0.01 to 2 μm is contained in an undercoat paint in an amount of 11 to 70% by mass. Metal materials are described. The rust preventive pigment is chromate or phosphate. No mention is made of the balance with hardness.
特開平０８−２５２５２８号公報（特許文献２）には、亜鉛系めっき鋼板をクロメート処理した後、防錆顔料を含有するアクリル−ポリイソシアネート系の水系塗料の塗布と焼付けにより樹脂皮膜を形成した有機複合被覆鋼板が記載されている。防錆顔料としては、粒径が２〜１２ｍμ（＝ｎｍ）というコロイド粒径の金属酸化物ゾル、シリカ、難溶性クロム酸塩が例示されており、シリカについては、シリカゾル（湿式シリカ）またはフュームドシリカ（気相シリカ）が使用できるとされている。これらのシリカはいずれも、コロイド粒径のものである。 Japanese Patent Application Laid-Open No. 08-252528 (Patent Document 2) describes an organic material in which a zinc-plated steel sheet is chromated and then a resin film is formed by applying and baking an acrylic-polyisocyanate-based water-based paint containing an antirust pigment. A composite coated steel sheet is described. Examples of the antirust pigment include metal oxide sol, silica, and sparingly soluble chromate having a colloidal particle diameter of 2 to 12 mμ (= nm). For silica, silica sol (wet silica) or fume is used. Dosilica (gas phase silica) can be used. All of these silicas have a colloidal particle size.
特開平０８−２６７６５５号公報（特許文献３）には、冷延鋼板に下地のリン酸塩またはクロメート皮膜を形成した後、耐食性確保のために亜鉛粉末を含有する下塗り塗膜と、シリカ／樹脂質の上塗り塗膜とを形成した塗装鋼板が開示されている。上塗り塗膜にシリカを入れるのは、表面硬度を高めて耐傷付き性を改善するためである。使用するシリカは、気相シリカ、湿式シリカ、コロイダルシリカのいずれでもよい。これらのシリカも、上記と同様に、コロイド粒径のシリカ微粉末である。 Japanese Patent Application Laid-Open No. 08-267655 (Patent Document 3) discloses an undercoating film containing zinc powder and a silica / resin for ensuring corrosion resistance after forming a base phosphate or chromate film on a cold-rolled steel sheet. A coated steel sheet having a quality top coat film is disclosed. The reason why silica is added to the top coat is to increase the surface hardness and improve the scratch resistance. The silica used may be any of vapor phase silica, wet silica, and colloidal silica. These silicas are also fine silica powders having a colloidal particle size as described above.
特許文献２、３で使用されているコロイド粒径のシリカ、特に湿式シリカ（コロイダルシリカに同じ）は、塗料中に含有させた場合に、シロキサン結合に基づく架橋構造を塗膜に導入して、塗膜硬度を高める。そのため、この種のシリカはそれ単独でバインダーとして使用することができ、本質的にシリカからなる皮膜を形成することができる。しかし、このようなコロイド粒径のシリカを多量に含有する塗膜は有機樹脂が共存しても硬くなって加工性が低下する傾向があるので、硬度と加工性をバランスさせることはできない。
本発明は、６価クロム化合物を使用せずに、加工性と硬度のバランスがよく、耐食性にも優れ、かつ低コストで製造できる塗装鋼板を提供することを目的とする。 An object of the present invention is to provide a coated steel sheet that does not use a hexavalent chromium compound, has a good balance between workability and hardness, is excellent in corrosion resistance, and can be manufactured at low cost.
本発明者らは、これまでは塗料に艶消し剤として使用されてきた、コロイド粒径より大径のある種のシリカを塗膜に含有させると耐食性が改善され、同時に適度な硬度を塗膜に付与できることに気づいた。そして、このシリカを上塗り塗膜に防錆顔料として含有させると、下塗り塗膜中の防錆顔料の含有量を低減させても、塗装鋼板に必要な耐食性を確保することができ、それにより加工性が改善され、加工性と硬度のバランス及び耐食性のすべての面で満足できる塗装鋼板が得られることを見出した。 The inventors of the present invention have improved the corrosion resistance when a certain type of silica having a diameter larger than the colloidal particle size, which has been used as a matting agent in paints, has been improved. Noticed that can be granted. And when this silica is contained in the top coat as an anticorrosive pigment, the corrosion resistance necessary for the coated steel sheet can be secured even if the content of the anticorrosive pigment in the undercoat is reduced. It has been found that a coated steel sheet that is satisfactory in all aspects of workability and hardness balance and corrosion resistance is obtained.
本発明は、鋼板の少なくとも片面に、下塗りと上塗り少なくとも２層の塗膜層を有する塗装鋼板であって、下塗り塗膜層が５〜３０質量％の防錆顔料を含有し、上塗り塗膜層が、吸油量：１００〜１０００ｍｌ／１００ｇ、比表面積：２００〜１０００ｍ2／ｇ、平均粒径：２〜３０μｍの多孔質シリカ粒子を防錆顔料として含有することを特徴とする塗装鋼板である。 The present invention is a coated steel sheet having an undercoat and at least two coat layers on at least one surface of the steel sheet, the undercoat coat layer containing 5 to 30% by mass of a rust preventive pigment, Is a coated steel sheet characterized by containing porous silica particles having an oil absorption of 100 to 1000 ml / 100 g, a specific surface area of 200 to 1000 m 2 / g, and an average particle size of 2 to 30 μm as a rust preventive pigment.
本発明の好適態様としては下記が挙げられる。
・全ての塗膜層がクロムを含有しない。
・下塗り塗膜層に含有される防錆顔料がリン酸塩系防錆顔料およびシリカから選ばれ、より具体的にはトリポリりん酸アルミニウム、りん酸及び亜りん酸のＺｎ、Ｍｇ及びＡｌ塩、Ｃａ交換シリカ、及び前記多孔質シリカ粒子から選ばれる。
The following is mentioned as a suitable aspect of this invention.
・ All coating layers do not contain chromium.
The rust preventive pigment contained in the undercoat coating layer is selected from phosphate-based rust preventive pigments and silica, and more specifically, aluminum tripolyphosphate, phosphoric acid and phosphorous acid Zn, Mg and Al salts, It is selected from Ca-exchanged silica and the porous silica particles.
・上塗り塗膜層の前記シリカ粒子の含有量が５〜３０質量％である。
・前記鋼板が、塗装下地処理として非クロム系下地処理が施されている。
-Content of the said silica particle of top coat film layer is 5-30 mass%.
-The steel plate is subjected to a non-chromium base treatment as a paint base treatment.
本発明に係る塗装鋼板は、上塗り塗膜中に塗膜を過度に硬くすることのないコロイド粒径より大径のシリカ粒子を含有させることにより、下塗り塗膜中の防錆顔料の含有量を低減させて必要な耐食性を確保することができる。それにより、加工性と硬度の両方をバランスよく確保すると同時に、優れた耐食性も満たすことができる。また、上塗り塗膜に含有させるシリカ粒子はもともと艶消し剤として使用されてきたものであるため、塗装鋼板の外観はつや消し性の美麗な外観となる。 The coated steel sheet according to the present invention contains the silica particles having a diameter larger than the colloidal particle diameter that does not excessively harden the coating film in the overcoating film, thereby reducing the content of the rust preventive pigment in the undercoating film. The required corrosion resistance can be ensured by reducing it. Thereby, both workability and hardness can be secured in a balanced manner, and at the same time, excellent corrosion resistance can be satisfied. Further, since the silica particles contained in the top coat film have been originally used as a matting agent, the appearance of the coated steel sheet has a beautiful appearance with a matte property.
(１)素地鋼板
本発明の塗装鋼板の素地鋼板は、裸の冷延鋼板であってもよいが、耐食性の観点からは、めっき鋼板であることが好ましい。めっき鋼板としては、亜鉛系めっき鋼板及びアルミニウム系めっき鋼板が例示される。
(1) Base steel plate The base steel plate of the coated steel plate of the present invention may be a bare cold-rolled steel plate, but is preferably a plated steel plate from the viewpoint of corrosion resistance. Examples of the plated steel sheet include a zinc-based plated steel sheet and an aluminum-based plated steel sheet.
好ましいのは亜鉛系めっき鋼板である。亜鉛系めっき鋼板は、電気めっき、溶融めっき、気相めっきのいずれで作製したものでもよい。亜鉛系めっき鋼板の例としては、溶融亜鉛めっき鋼板、電気亜鉛めっき鋼板、溶融５％Ａｌ−Ｚｎ合金めっき鋼板、溶融５５％Ａｌ−Ｚｎ合金めっき鋼板、合金化溶融亜鉛めっき鋼板、電気Ｚｎ−Ｎｉ合金めっき鋼板などが挙げられる。めっき付着量も特に限定されず、一般的な範囲内でよい。めっき付着量が少なすぎると耐食性が低下し、多すぎると加工性が劣化する。 A galvanized steel sheet is preferred. The zinc-based plated steel sheet may be produced by any of electroplating, hot dipping, and vapor phase plating. Examples of galvanized steel sheets include hot dip galvanized steel sheets, electrogalvanized steel sheets, molten 5% Al—Zn alloy plated steel sheets, molten 55% Al—Zn alloy plated steel sheets, alloyed hot dip galvanized steel sheets, and electrical Zn—Ni. Examples include alloy-plated steel sheets. The plating adhesion amount is not particularly limited, and may be within a general range. If the coating amount is too small, the corrosion resistance is lowered, and if too much, the workability is deteriorated.
(２)塗装前処理
塗装鋼板の製造では、塗膜密着性と耐食性を確保するため、塗装前に素地鋼板を前処理（下地処理）するのが普通である。この前処理は、一般には化成処理により行われ、その前に、Ｎｉ等の鉄族金属イオンを含む酸性もしくはアルカリ水溶液による表面調整処理を施すことが多い。また、それ以前に、素地鋼板を清浄化するため、酸洗（特に裸の鋼板）および／またはアルカリ脱脂（亜鉛系めっき鋼板）が行われる。
(2) Pre-painting treatment In the production of coated steel plates, it is common to pre-treat (base treatment) the base steel plate before painting in order to ensure coating film adhesion and corrosion resistance. This pretreatment is generally performed by a chemical conversion treatment, and before that, a surface conditioning treatment with an acidic or alkaline aqueous solution containing an iron group metal ion such as Ni is often performed. Prior to that, pickling (particularly bare steel plate) and / or alkali degreasing (zinc-based plated steel plate) is performed to clean the base steel plate.
化成処理は、以前は耐食性改善効果の高いクロメート処理が一般的であったが、上述した事情で、最近では、６価クロムを含有しないか、あるいはクロムを全く含有しない、シリカ系の化成処理腋が使用されるようになってきた。本発明でも、少なくとも６価クロムを含有しない化成処理液を使用することが好ましい。 As the chemical conversion treatment, a chromate treatment having a high effect of improving corrosion resistance has been generally used. However, due to the above-described circumstances, recently, a silica-based chemical conversion treatment containing no hexavalent chromium or no chromium is recently used. Has come to be used. Also in the present invention, it is preferable to use a chemical conversion treatment solution that does not contain at least hexavalent chromium.
シリカ系化成処理液は、コロイダルシリカおよび／またはケイ酸塩などのケイ素化合物を主皮膜成分とする処理液であり、場合により樹脂を共存させる。前述したように、コロイダルシリカから形成された皮膜は硬質であるが、化成処理により形成される皮膜は、下塗り及び上塗り塗膜に比べてごく薄膜であるので、加工性への実質的な影響はない。 The silica-based chemical conversion treatment liquid is a treatment liquid containing a silicon compound such as colloidal silica and / or silicate as a main film component, and in some cases, a resin coexists. As described above, the film formed from colloidal silica is hard, but the film formed by chemical conversion treatment is a very thin film compared to the undercoat and the topcoat film, so there is no substantial influence on the workability. Absent.
化成処理は、シリカ系化成処理に限られるものではない。シリカ系以外にも、塗装下地処理に使用するための各種の化成処理液が提案されており、また今後も提案されることが予想される。そのような化成処理液を使用することもできる。また、化成処理により形成される化成処理皮膜の付着量は、使用する化成処理に応じて、適当な付着量を選択すればよい。 The chemical conversion treatment is not limited to silica-based chemical conversion treatment. In addition to the silica type, various chemical conversion treatment liquids for use in coating base treatment have been proposed and are expected to be proposed in the future. Such a chemical conversion treatment liquid can also be used. Moreover, what is necessary is just to select the adhesion amount of the chemical conversion treatment film formed by chemical conversion treatment according to the chemical conversion treatment to be used.
(３)下塗り塗膜層
下塗り塗膜層は５〜３０質量％の防錆顔料を含有する。すなわち、これは樹脂中に少なくとも防錆顔料を含有する塗膜であるが、防錆顔料の含有量は従来の典型的な塗装鋼板に比べると少なくなっている。例えば、前述した特許文献１では、下塗り塗膜中の防錆顔料の含有量は１１〜７０重量％と規定されているが、実施例での含有量はほとんどが４０〜５０重量％であって、本発明に比べて多い。
(3) Undercoat coating layer The undercoat coating layer contains 5 to 30% by mass of a rust preventive pigment. That is, this is a coating film containing at least a rust preventive pigment in the resin, but the content of the rust preventive pigment is smaller than that of a conventional typical coated steel sheet. For example, in Patent Document 1 described above, the content of the anticorrosive pigment in the undercoat coating is defined as 11 to 70% by weight, but most of the content in the examples is 40 to 50% by weight. More than the present invention.
下塗り塗膜を構成するベース樹脂は特に限定されず、エポキシ樹脂、ポリウレタン樹脂、ポリエステル樹脂など、これまでも塗装鋼板の下塗りに用いられてきた各種の樹脂から選択できる。ベース樹脂に組み合わせる架橋剤としては、例えば、メラミン樹脂、ポリイソシアネート化合物などが挙げられる。必要であれば、架橋触媒を配合する。 The base resin constituting the undercoat coating film is not particularly limited, and can be selected from various resins that have been used for undercoating of coated steel sheets, such as epoxy resins, polyurethane resins, and polyester resins. Examples of the crosslinking agent combined with the base resin include melamine resin and polyisocyanate compound. If necessary, a crosslinking catalyst is blended.
下塗り塗膜層に含有させる防錆顔料は特に制限されず、クロム酸ストロンチウムで代表されるクロム酸塩系防錆顔料も使用可能である。しかし、６価クロム化合物を使用しないという観点から、クロム酸塩系以外の防錆顔料を使用することが好ましい。 The rust preventive pigment to be contained in the undercoat coating layer is not particularly limited, and a chromate-based rust preventive pigment represented by strontium chromate can also be used. However, from the viewpoint of not using a hexavalent chromium compound, it is preferable to use a rust preventive pigment other than chromate.
本発明で使用するのが好ましい防錆顔料としては、トリポリりん酸アルミニウム、りん酸及び亜りん酸のＺｎ、Ｍｇ及びＡｌ塩、Ｃａ交換シリカ、及び後述する上塗り塗膜に使用する多孔質シリカ粒子を挙げることができる。多孔質シリカ粒子の形状は、好ましくは球形、長球形(ラグビーボール形)、扁平球形などの丸みを帯びた形状が好ましい。 Antirust pigments preferably used in the present invention include aluminum tripolyphosphate, Zn, Mg and Al salts of phosphoric acid and phosphorous acid, Ca-exchanged silica, and porous silica particles used in the top coat film described below. Can be mentioned. The shape of the porous silica particles is preferably a round shape such as a spherical shape, a long spherical shape (rugby ball shape), or a flat spherical shape.
下塗り塗膜中の防錆顔料の含有量は５〜３０質量％とする。従って、下塗り塗料中の防錆顔料の含有量は、塗料中の固形分（不揮発分）に対して５〜３０質量％の範囲内であればよい。この防錆顔料の含有量は、下塗り塗膜としては少なめであるが、本発明では上塗り塗膜に含有させる特定のシリカ粒子が防錆顔料として機能するため、下塗り塗膜中の防錆顔料の含有量を低減させても十分な耐食性を確保できる。それにより、多量の防錆顔料の含有による下塗り塗膜の塗膜密着性低下及び加工性低下を防止することができる。 The content of the rust preventive pigment in the undercoat film is 5 to 30% by mass. Therefore, the content of the rust preventive pigment in the undercoat paint may be in the range of 5 to 30% by mass with respect to the solid content (nonvolatile content) in the paint. Although the content of the rust preventive pigment is less as the undercoat coating film, in the present invention, the specific silica particles to be contained in the top coat film function as a rust preventive pigment. Even if the content is reduced, sufficient corrosion resistance can be secured. Thereby, the coating-film adhesive fall and workability fall of an undercoat coating film by containing a lot of antirust pigments can be prevented.
防錆顔料の量が５％より少ないと耐食性の改善効果のみならず、硬度の改善効果も十分に発揮されない。一方、防錆顔料の量が３０％を超えると、シリカを含有する上塗り塗膜層と組み合わせた時に加工性が低下する。この防錆顔料の好ましい含有量は１０〜３０質量％である。 When the amount of the rust preventive pigment is less than 5%, not only the effect of improving the corrosion resistance but also the effect of improving the hardness is not sufficiently exhibited. On the other hand, when the amount of the rust preventive pigment exceeds 30%, the workability deteriorates when combined with the top coat layer containing silica. The preferable content of the rust preventive pigment is 10 to 30% by mass.
下塗り塗膜層は、樹脂（及び架橋剤）と防錆顔料以外に、着色顔料、レベリング剤、ビーズなどの１種または２種以上をさらに含有しうる。但し、顔料類の含有量が増えると、加工性が低下することがあるので、防錆顔料以外の顔料をさらに含有する場合でも、顔料の合計量は３５質量％以下、特に３０質量％以下とすることが好ましい。 In addition to the resin (and the crosslinking agent) and the rust preventive pigment, the undercoat coating film layer may further contain one or more of color pigments, leveling agents, beads, and the like. However, as the pigment content increases, the processability may decrease. Therefore, even when a pigment other than the rust preventive pigment is further contained, the total amount of the pigment is 35% by mass or less, particularly 30% by mass or less. It is preferable to do.
下塗り塗膜層の厚さ（乾燥塗膜厚）は２〜２０μｍであることが望ましい。さらに望ましくは、５〜１５μｍである。塗膜厚が薄すぎると耐食性が低下し、厚すぎるとコスト高に加え．塗膜の内部応力増大に伴って加工性、密着性が低下することがある。 The thickness of the undercoat coating layer (dry coating thickness) is desirably 2 to 20 μm. More desirably, the thickness is 5 to 15 μm. If the coating thickness is too thin, the corrosion resistance decreases, and if it is too thick, the cost is high. As the internal stress of the coating film increases, workability and adhesion may decrease.
(４)上塗り塗膜層
上塗り塗膜層は、樹脂中に防錆顔料として、吸油量：１００〜１０００ｍｌ／１００ｇ、比表面積：２００〜１０００ｍ2／ｇ、平均粒径：２〜３０μｍの多孔質シリカ粒子を含有する。
(4) Top coat film layer The top coat film layer is a porous material having an oil absorption of 100 to 1000 ml / 100 g, a specific surface area of 200 to 1000 m 2 / g, and an average particle size of 2 to 30 μm as a rust preventive pigment in the resin. Contains silica particles.
この特性をもつ多孔質シリカ粒子の市販品の例は、洞海化学工業製のサンスフェア(Ｒ)Ｈ及びＬシリーズの製品（旭硝子から販売）である。この種のシリカ粒子は塗料の艶消し剤として使用されてきたが、防錆性を付与できることは知られていなかった。多孔質シリカ粒子の形状は、好ましくは球形、長球形、扁平球形などの丸みを帯びた形状が好ましい。この比較的大径のシリカ粒子が丸みを帯びていると、塗膜外観が向上する。 Examples of commercially available porous silica particles having this characteristic are products of Sunsphere (R) H and L series (available from Asahi Glass) manufactured by Dokai Chemical Industries. This type of silica particles has been used as a matting agent for paints, but it has not been known that it can impart rust prevention properties. The shape of the porous silica particles is preferably a rounded shape such as a spherical shape, a long spherical shape, and a flat spherical shape. When the relatively large silica particles are rounded, the appearance of the coating film is improved.
上塗り塗膜のベース樹脂も特に限定されず、例えば、ポリエステル樹脂、アクリル樹脂、エポキシ樹脂、ポリウレタン樹脂、シリコーンポリエステル樹脂、ポリ塩化ビニル樹脂、フッ素樹脂などから選んだ１種または２種以上を使用することができる。架橋剤は、下塗り塗膜に関して述べたものと同様でよく、必要に応じて架橋触媒を配合する。 The base resin of the top coat film is not particularly limited, and for example, one or more selected from polyester resin, acrylic resin, epoxy resin, polyurethane resin, silicone polyester resin, polyvinyl chloride resin, fluororesin and the like are used. be able to. The crosslinking agent may be the same as that described for the undercoat film, and a crosslinking catalyst is blended as necessary.
上塗り塗膜は、上記多孔質シリカ粒子からなる防錆顔料に加えて、さらに着色顔料を含有していてもよい。着色顔料の例としては、酸化亜鉛、酸化チタン、炭酸カルシウム、カオリンなどの無機顔料、銅フタロシアニン、トルイジンレッドなどの有機顔料、さらにはカーボンブラックなどが挙げられる。上塗り塗膜中のこれらの顔料の含有量は、シリカが５〜４０質量％、着色顔料は３０質量％以下、顔料の合計量は４５質量％の範囲内とすることが好ましい。 The top coat film may further contain a color pigment in addition to the rust preventive pigment made of the porous silica particles. Examples of the color pigment include inorganic pigments such as zinc oxide, titanium oxide, calcium carbonate, and kaolin, organic pigments such as copper phthalocyanine and toluidine red, and carbon black. The content of these pigments in the top coat film is preferably in the range of 5 to 40% by mass of silica, 30% by mass or less of the colored pigment, and the total amount of pigment in the range of 45% by mass.
上塗り塗膜は、上記の防錆顔料および着色顔料以外の添加剤を含有しうる。そのような添加剤の例は、紫外線吸収剤、光安定剤、潤滑剤、レベリング剤などである。潤滑剤としては、ワックス類、ＰＴＦＥなどが使用できる。 The top coat film may contain additives other than the rust preventive pigment and the color pigment. Examples of such additives are ultraviolet absorbers, light stabilizers, lubricants, leveling agents and the like. As the lubricant, waxes, PTFE and the like can be used.
上塗り塗膜層の膜厚は２〜３０μｍであることが望ましく、さらに望ましくは５〜２０μｍである。塗膜厚が薄すぎると耐食性および隠蔽性が不十分であり、厚すぎるとコスト高おとび塗膜内部応力増大に伴う加工性、密着性低下の点から好ましくない。 The film thickness of the top coat film layer is desirably 2 to 30 μm, and more desirably 5 to 20 μm. If the coating film thickness is too thin, the corrosion resistance and concealing properties are insufficient, and if it is too thick, it is not preferred from the viewpoint of cost increase and workability and adhesion deterioration due to the increase in coating film internal stress.
上述した下塗り塗膜層と上塗り塗膜層は、いずれも必要成分を溶媒中に溶解又は分散させた塗料（すなわち、下塗り塗料及び上塗り塗料）の塗布及び焼付け（加熱乾燥）により形成される。各塗料は溶媒が有機溶剤である溶剤系塗料でも、溶媒が水又は水と少量の水混和性有機溶剤との混合溶媒である水系塗料のいずれでもよい。２コート２ベーク方式ではなく、焼付けを上塗り塗料の塗布後だけに行う２コート１ベーク方式とすることも可能である。 Each of the above-described undercoat film layer and topcoat film layer is formed by applying and baking (heat-drying) a paint in which necessary components are dissolved or dispersed in a solvent (that is, undercoat paint and topcoat paint). Each paint may be either a solvent-based paint whose solvent is an organic solvent or a water-based paint whose solvent is water or a mixed solvent of water and a small amount of a water-miscible organic solvent. Instead of the two-coat two-bake method, a two-coat one-bake method in which baking is performed only after the application of the top coating material is possible.
下塗り塗料および上塗り塗料の塗布方法は特に限定されるものではなく、ロールコーター、カーテンフローコーター、スプレーガン、バーコーター等によって行えばよい。塗布後の焼付けは、塗膜を構成する樹脂及び架橋剤に応じて設定したＰＭＴ（鋼板最高到達温度）となるように行う。この温度は一般に１００〜２８０℃の範囲内である。加熱方法は、熱風乾燥でも、炉内乾燥でもよい。 The method for applying the undercoat and topcoat is not particularly limited, and may be performed by a roll coater, a curtain flow coater, a spray gun, a bar coater, or the like. Baking after application is performed so that the PMT (steel plate maximum temperature) set according to the resin and the cross-linking agent constituting the coating film is obtained. This temperature is generally in the range of 100-280 ° C. The heating method may be hot air drying or oven drying.
本発明によれば、上塗り塗膜が防錆顔料として比較的大径のシリカ粒子を含有する。それにより、下塗り塗膜中の防錆顔料の含有量を低減できるため塗膜密着性が改善される。また、上塗り塗膜中のシリカ粒子は、塗膜に耐傷付き性の付与に必要な適度の硬さを付与しながら、加工性を劣化させることがないので、形成された塗装鋼板は十分な耐食性及び耐久性を示すと同時に、硬度と加工性のバランスに優れ、耐傷付き性も良好である。従って、本発明の塗装鋼板は、厳しい加工を受ける用途にも適用することができる。 According to the present invention, the top coat film contains silica particles having a relatively large diameter as a rust preventive pigment. Thereby, since content of the rust preventive pigment in an undercoat coating film can be reduced, coating-film adhesiveness is improved. In addition, the silica particles in the top coating film do not deteriorate the workability while imparting the appropriate hardness necessary for imparting scratch resistance to the coating film, so the formed coated steel sheet has sufficient corrosion resistance. In addition to exhibiting durability, it has an excellent balance between hardness and workability and good scratch resistance. Therefore, the coated steel sheet of the present invention can be applied to applications that undergo severe processing.
塗装鋼板が３層以上の塗膜層を有する場合、いずれか２つの塗膜層が本発明において規定する条件を満たせばよい。例えば、上中下の３層の塗膜層を有する場合には、下層と中層、中層と上層、又は下層と上層が、本発明で規定する下塗り塗膜層と上塗り塗膜層の条件をそれぞれ満たせばよい。換言すると、下塗り塗膜層の下、上塗り塗膜層の上、あるいは下塗り塗膜層と上塗り塗膜層の間に１または２以上の塗膜層が存在していてもよい。例えば、上塗り塗膜層の上に薄いクリヤー塗膜層を形成したり、下塗り塗膜層の下に、密着性改善のための極薄の塗膜層を形成することも可能である。 When the coated steel sheet has three or more coating layers, any two coating layers may satisfy the conditions specified in the present invention. For example, in the case of having three upper and lower coating layers, the lower layer and the middle layer, the middle layer and the upper layer, or the lower layer and the upper layer are respectively the conditions of the undercoat coating layer and the top coating layer defined in the present invention. Just fill it. In other words, one or two or more coating layers may exist under the undercoat coating layer, on the top coating layer, or between the undercoating coating layer and the top coating layer. For example, it is possible to form a thin clear coating layer on the top coating layer or to form an extremely thin coating layer for improving adhesion under the under coating layer.
板厚０.６ｍｍの溶融亜鉛めっき鋼板（亜鉛付着量は片面６０ｇ／ｍ2）に、常法に従ってアルカリ脱脂及び水洗を行った後、市販のシリカ系クロムフリー化成処理液を用いて下地処理を両面に施した。 A 0.6 mm thick hot-dip galvanized steel sheet (the amount of zinc adhered is 60 g / m 2 on one side) is subjected to alkaline degreasing and water washing according to conventional methods, and then subjected to a ground treatment using a commercially available silica-based chromium-free chemical conversion treatment solution. Made on both sides.
下塗り塗料は、主（ベース）樹脂としての高分子量ポリエステル樹脂（ＧＫ−１４０、東洋紡製）、架橋剤としてメチル化メラミン樹脂（サイメル３２７、日本サイナミッド製）、防錆顔料としてトリポリりん酸アルミニウム（Ｋ−ＷＨＩＴＥ ＃８２、テイカ製）を用い、塗料全固形分に対して表１に記載の量で防錆顔料を含有する下塗り塗料を調製した。主樹脂と架橋剤との比率は、主樹脂８０質量部に対して架橋剤２０質量部とした。この下塗り塗料を、下地処理を施しためっき鋼板の片面にバーコーターで塗布した後、ＰＭＴ（鋼板最高到達温度）が２２０℃±１０℃、焼付け時間５０秒で焼付けを行った。 The undercoat is composed of a high molecular weight polyester resin (GK-140, manufactured by Toyobo) as a main (base) resin, a methylated melamine resin (Cymel 327, manufactured by Nippon Sinamid) as a cross-linking agent, and an aluminum tripolyphosphate (K) as a rust preventive pigment. -WHITE # 82, manufactured by Teika) was used to prepare an undercoat paint containing a rust preventive pigment in an amount shown in Table 1 with respect to the total solid content of the paint. The ratio of the main resin to the crosslinking agent was 20 parts by mass of the crosslinking agent with respect to 80 parts by mass of the main resin. This undercoat paint was applied to one side of a plated steel sheet that had been subjected to a base treatment, and then baked at a PMT (maximum steel sheet temperature) of 220 ° C. ± 10 ° C. and a baking time of 50 seconds.
上塗り塗料は、主樹脂としての高分子量ポリエステル樹脂（２９ＣＳ、東洋紡製）、架橋剤としてメチル化メラミン樹脂（サイメル３０３、日本サイナミッド製）、防錆顔料として非晶質の球形シリカ粒子（サンスフェア Ｈ−３１、Ｌ−３１、ＮＰ−３０、洞海化学工業製）、着色顔料として酸化チタン（ＣＲ−５０、石原産業製）を用い、塗料全固形分に耐指定表２に記載の量で各顔料を含有する上塗り塗料を得た。主樹脂と架橋剤との比率は、主樹脂８０質量部に対して架橋剤２０質量部とした。この上塗り塗料を下塗り塗膜の上に塗布した後、ＰＭＴ（鋼板最高到達温度）が２３０℃±１０℃、焼付け時間６０秒で焼付けを行い、表３に記載の塗装鋼板を得た。 The top coat is composed of a high molecular weight polyester resin (29CS, manufactured by Toyobo Co., Ltd.) as the main resin, a methylated melamine resin (Cymel 303, manufactured by Nippon Sinamid) as the cross-linking agent, and amorphous spherical silica particles (Sunsphere H as the rust preventive pigment). -31, L-31, NP-30, manufactured by Dokai Chemical Industries), titanium oxide (CR-50, manufactured by Ishihara Sangyo Co., Ltd.) as the color pigment, A top coating containing a pigment was obtained. The ratio of the main resin to the crosslinking agent was 20 parts by mass of the crosslinking agent with respect to 80 parts by mass of the main resin. After this top coat was applied onto the undercoat film, baking was carried out at a PMT (steel plate maximum temperature) of 230 ° C. ± 10 ° C. and a baking time of 60 seconds to obtain the coated steel plates shown in Table 3.
なお、サンスフェア Ｈ−３１、Ｌ−３１、ＮＰ−３０はそれぞれ、表２のＮｏ.１〜２、Ｎｏ.３〜４、Ｎｏ.５〜６で使用したものに対応する。このうちＮｏ.５〜６で使用したＮＰ−３０は非多孔質タイプで、比表面積及び吸油量とも本発明で規定する条件の下限より低い比較用のシリカ粒子であり、残りは本発明で規定する特性を有する多孔質タイプのシリカ粒子である。 Sunspheres H-31, L-31, and NP-30 correspond to those used in Nos. 1-2, Nos. 3-4, and Nos. 5-6 in Table 2, respectively. Among these, NP-30 used in Nos. 5 to 6 is a non-porous type, and is a comparative silica particle whose specific surface area and oil absorption are lower than the lower limit of the conditions defined in the present invention, and the rest are defined in the present invention. It is a porous type silica particle having the following characteristics.
こうして得られた塗装鋼板について、加工性、硬度、耐食性を下記の試験により評価した。
(１)加工性試験
試験片に対して０Ｔ折り曲げ試験（２３℃）を行い、１８０°密着曲げ塗膜についてクラック発生有無を１０倍ルーペを用いて調査した。評価基準は下記の通りで、◎印および○印の場合を良好とした。
The coated steel sheet thus obtained was evaluated for workability, hardness and corrosion resistance by the following tests.
(1) Workability test A 0T bending test (23 ° C.) was performed on the test piece, and the presence or absence of cracks in the 180 ° adhesive bending coating film was examined using a 10 × loupe. The evaluation criteria are as follows, and the case of ◎ and ○ is good.
◎：まったくクラックなし、
○：ごくわずかなクラックあり（ルーペでは確認できるが、目視では確認できないレベル）、
△：若干クラックあり（目視で５個以内）、
×：かなり多くのクラックあり（目視で５個より多い）。
A: No crack at all,
○: There are very few cracks (a level that can be confirmed with a magnifying glass but cannot be visually confirmed)
Δ: Slightly cracked (within 5 visually)
X: There are quite many cracks (more than 5 visually).
(２)硬度試験
ＪＩＳ Ｋ５６００−５−４（引っかき硬度（鉛筆法））の方法に従って測定した。評価基準は下記の通りで、○印の場合を良好とした。
(2) Hardness test Measured according to the method of JIS K5600-5-4 (scratch hardness (pencil method)). The evaluation criteria are as follows.
○：Ｆ以上、
△：ＨＢ、
×：Ｂ以下。
○: F or more,
Δ: HB,
X: B or less.
(３)耐食性試験
素地鋼板に達する深さのクロスカットを入れた試験片に１２０時間の塩水噴霧試験を行った後、試験片のカット部からの塗膜フクレ幅（最大値）を測定した。評価基準は下記の通りで、◎印および○印の場合を良好とした。
(3) Corrosion resistance test After performing a 120-hour salt spray test on a test piece with a cross cut having a depth reaching the base steel plate, the coating film width (maximum value) from the cut portion of the test piece was measured. The evaluation criteria are as follows, and the case of ◎ and ○ is good.
◎：１ｍｍ未満
○：１ｍｍ以上、１.５ｍｍ未満
△：１.５ｍｍ以上、３ｍｍ未満
×：３ｍｍ以上。
◎: Less than 1 mm ○: 1 mm or more, less than 1.5 mm Δ: 1.5 mm or more, less than 3 mm ×: 3 mm or more.
同じ上塗り塗料を使用しても、下塗り塗膜中の防錆顔料の量が５０質量％と増大すると、表３のＢ１〜Ｂ４に示すように、耐食性は向上する場合があるものの、加工性が著しく劣化する。一方、下塗り塗膜が防錆顔料を含有しないと、表３のＣ１〜Ｃ４に示すように、加工性は良好であるが、硬度及び耐食性が著しく低下する。 Even if the same top coat is used, when the amount of the rust preventive pigment in the undercoat increases to 50% by mass, as shown in B1 to B4 of Table 3, the corrosion resistance may be improved, but the workability is improved. Deteriorates significantly. On the other hand, when the undercoat does not contain a rust preventive pigment, as shown in C1 to C4 of Table 3, the workability is good, but the hardness and corrosion resistance are remarkably lowered.
一方、下塗り塗膜が本発明に従った量で防錆顔料を含有する下塗り塗料Ａから形成されていても、上塗り塗膜に含有させたシリカが比表面積及び吸油量の小さいものであると、表３のＡ５〜６に示すように、耐食性が不十分となる。すなわち、上塗り塗料にシリカ粒子を含有させることによる耐食性向上効果は、吸油量と比表面積が大きい、すなわち、多孔質のシリカ粒子である場合に限って得られる。一方、上塗り塗膜がシリカ粒子を含有していないと硬度が不十分となる。 On the other hand, even if the undercoating film is formed from the undercoating paint A containing the rust preventive pigment in an amount according to the present invention, the silica contained in the overcoating film has a small specific surface area and oil absorption, As shown to A5-6 of Table 3, corrosion resistance becomes inadequate. That is, the effect of improving the corrosion resistance by adding silica particles to the top coat can be obtained only when the oil absorption amount and the specific surface area are large, that is, porous silica particles. On the other hand, when the top coat film does not contain silica particles, the hardness is insufficient.
なお、表３に示した塗装鋼板は、上塗り塗膜がシリカを含有する表２のＮｏ.１〜６のいずれかである場合は、このシリカによる艶消し効果によって、塗装外観は美麗な艶消し表面となった。この艶消し外観は、観察角度を変化させても大きくは変化せず、均一性に優れていた。塗膜外観の色は、上塗り塗膜が酸化チタンを含有する場合は白、含有しない場合は白みがかった色になり、下塗りの色に左右される。 In addition, the coated steel plate shown in Table 3 has a beautiful matte appearance due to the matting effect of silica when the top coat film is any of Nos. 1 to 6 in Table 2 containing silica. It became the surface. This matte appearance did not change greatly even when the observation angle was changed, and was excellent in uniformity. The color of the appearance of the coating film is white when the top coat film contains titanium oxide, and becomes white when it does not contain titanium oxide, and depends on the color of the undercoat.
Claims (5)
The coated steel sheet according to any one of claims 1 to 4, wherein the content of the silica particles in the top coat layer is 5 to 40% by mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006122204A JP4665821B2 (en) | 2006-04-26 | 2006-04-26 | Painted steel plate with excellent corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006122204A JP4665821B2 (en) | 2006-04-26 | 2006-04-26 | Painted steel plate with excellent corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007289889A JP2007289889A (en) | 2007-11-08 |
| JP4665821B2 true JP4665821B2 (en) | 2011-04-06 |
Family
ID=38761025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006122204A Active JP4665821B2 (en) | 2006-04-26 | 2006-04-26 | Painted steel plate with excellent corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4665821B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5176890B2 (en) * | 2008-11-14 | 2013-04-03 | 新日鐵住金株式会社 | Coated steel sheet and casing for electronic equipment using the same |
| JP5582109B2 (en) * | 2011-07-21 | 2014-09-03 | 新日鐵住金株式会社 | Clear coat steel plate with excellent red rust resistance |
| JP6838195B1 (en) * | 2020-12-10 | 2021-03-03 | 日本ペイント・インダストリアルコ−ティングス株式会社 | Method for manufacturing rust preventive paint composition and rust preventive coating film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002069668A (en) * | 2000-09-04 | 2002-03-08 | Nisshin Steel Co Ltd | Coated steel sheet superior in chalking resistance |
| JP2002225176A (en) * | 2001-01-31 | 2002-08-14 | Nisshin Steel Co Ltd | Coated cold-rolled steel panel excellent in corrosion resistance |
| JP2005288732A (en) * | 2004-03-31 | 2005-10-20 | Jfe Steel Kk | Non-weldable organic coated steel sheet for automobile excellent in corrosion resistance |
-
2006
- 2006-04-26 JP JP2006122204A patent/JP4665821B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002069668A (en) * | 2000-09-04 | 2002-03-08 | Nisshin Steel Co Ltd | Coated steel sheet superior in chalking resistance |
| JP2002225176A (en) * | 2001-01-31 | 2002-08-14 | Nisshin Steel Co Ltd | Coated cold-rolled steel panel excellent in corrosion resistance |
| JP2005288732A (en) * | 2004-03-31 | 2005-10-20 | Jfe Steel Kk | Non-weldable organic coated steel sheet for automobile excellent in corrosion resistance |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007289889A (en) | 2007-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101690470B1 (en) | Black coated metal plate | |
| JP2001089868A (en) | Substrate treating agent for precoated metallic sheet, coated substrate treated metallic sheet coated with the same and precoated metallic sheet excellent in working adhesion of coating film using the same | |
| JP3950370B2 (en) | Precoated metal sheet having excellent press formability and method for producing the same | |
| JP5103111B2 (en) | Painted steel plate | |
| JP2007119858A (en) | Chromium-free precoated steel plate | |
| JP5677337B2 (en) | Pre-treatment metal plate surface treatment agent, coated ground metal plate coated with the same, and pre-coat metal plate using the same | |
| JP4665821B2 (en) | Painted steel plate with excellent corrosion resistance | |
| JP5126548B2 (en) | Coated steel sheet and electronic equipment casing using the same | |
| JP2013193273A (en) | Coated steel sheet, and housing using the same | |
| JP2006321957A (en) | Aqueous surface-treating agent for environmental response type pre-coated metal material and surface-treating method | |
| JP5380033B2 (en) | Painted metal material with excellent corrosion resistance and paint adhesion | |
| JP4873974B2 (en) | Pre-coated metal plate and manufacturing method thereof | |
| JP4598703B2 (en) | Chrome-free pre-coated steel sheet | |
| JP5582109B2 (en) | Clear coat steel plate with excellent red rust resistance | |
| JP4066910B2 (en) | Painted steel sheet not containing chromium | |
| JP2010247347A (en) | Precoated cold-rolled steel sheet and method for manufacturing the same | |
| JP4246689B2 (en) | Pre-coated metal plate with excellent corrosion resistance | |
| JP4947025B2 (en) | Chrome-free painted steel plate with excellent red rust resistance | |
| JP5187221B2 (en) | Chrome-free coated steel sheet and casing made using the same | |
| WO2009093541A1 (en) | Coated metal material | |
| JP2017066446A (en) | Surface-treatment galvanized steel plate excellent in corrosion resistance | |
| JP3090207B1 (en) | Painted steel sheet with excellent corrosion resistance and low environmental load | |
| JP4992500B2 (en) | Chrome-free painted steel plate with excellent red rust resistance | |
| JP5949707B2 (en) | Steel plate for paper passing member | |
| JP2004292943A (en) | Highly corrosion resistant painted steel sheet superior in coating film adhesiveness and image clarity while giving little load to environment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080423 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100907 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101104 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20101214 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101227 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140121 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4665821 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140121 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140121 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |