JP4521764B2 - Painted metal plate with excellent releasability and manufacturing method thereof - Google Patents
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Description
本発明は、アルミニウム鋳物等に対する離型性に優れ、鋳型内部に配置される仕切り板として好適な塗装金属板及びその製造方法に関する。 The present invention relates to a coated metal plate that is excellent in releasability from an aluminum casting or the like and is suitable as a partition plate disposed inside a mold, and a method for manufacturing the same.
複数のアルミニウム鋳物等を製造する際、鋳型内にセットした複数枚の仕切り板でキャビティを複数の区画に分割している。鋳造後、アルミニウム鋳物が仕切り板と共に鋳型から取り出され、仕切り板を分離することにより個々の鋳物製品として扱われる。アルミニウム鋳物と仕切り板との分離を容易にするため、離型剤を仕切り板に塗布している。代表的な離型剤として黒鉛粉末の水性分散液が知られており、雲母，タルク等を主成分とする離型剤も使用されている（特許文献１、段落〔0026〕）。
しかし、離型剤の付着性が劣る仕切り板が多く、仕切り板からアルミニウム鋳物に離型剤粉末が移行しやすい。離型剤の移行は、鋳物表面を汚染し外観を劣化する原因である。離型剤が十分に付着していないと、仕切り板の取扱い時に離型剤の脱落を防ぐ作業を強いられて生産性低下をきたし、仕切り板製造時にも製造ラインの汚染を助長する。 However, there are many partition plates with poor release agent adhesion, and the release agent powder tends to migrate from the partition plate to the aluminum casting. The migration of the release agent is a cause of contaminating the casting surface and deteriorating the appearance. If the release agent is not sufficiently adhered, the work for preventing the release agent from falling off is forced when handling the partition plate, resulting in a decrease in productivity, and also promoting the contamination of the production line during the manufacture of the partition plate.
離型剤に代え、アクリルシリコーン塗膜で離型性を付与する方法も検討されている（特許文献２，３）。しかし、アクリルシリコーン単独では耐熱性に劣り、アルミニウム（融点：６６０℃）又はアルミニウム合金の鋳造時に高温雰囲気に曝されると有機物が消失しやすい。分解した有機物が気泡となって塗膜に巣穴や剥離・脱落が生じると、鋳巣，肌荒れ等の鋳造欠陥になり、或いは塗膜消失個所では鋳物と仕切り板との間に焼付きが生じやすい。
本発明者等は、良好な離型性を維持するアクリルシリコーンベースの塗膜に種々の添加剤を配合し、添加剤が耐熱性に及ぼす影響を調査・検討した。その結果、コロイダルシリカを含むシリカ系バインダとアクリルシリコーンを特定割合で混合して塗膜を形成するとき、６５０℃を超える高温雰囲気下でも健全で耐熱性，離型性共に優れた塗膜となることを解明した。
本発明は、シリカ系バインダが耐熱性の向上に及ぼす知見を基礎とし、アルミニウム鋳造時の仕切り板を初め、高温の部材と接触しても焼付きが生じがたい離型性に優れた塗装金属板を提供することを目的とする。
The present inventors investigated and examined the influence of additives on heat resistance by blending various additives into an acrylic silicone-based coating film that maintains good releasability. As a result, when a silica-based binder containing colloidal silica and acrylic silicone are mixed at a specific ratio to form a coating film, the coating film is sound and excellent in both heat resistance and releasability even in a high temperature atmosphere exceeding 650 ° C. I clarified that.
The present invention is based on the knowledge that a silica-based binder has an effect on improving heat resistance, and is a coated metal excellent in releasability that does not cause seizure even when it comes into contact with a high-temperature member such as a partition plate during aluminum casting. The purpose is to provide a board.
本発明の塗装金属板は、シリカ系バインダ，アクリルシリコーンの混合塗料から成膜された有機・無機複合塗膜が金属板表面に形成されており、塗膜の赤外吸収スペクトル回折において式(１)，(２)で定義される吸光度ピークの高さ比率Ａ，ＢがそれぞれＡ：０.６〜０.８５，Ｂ：０.２〜０.６の範囲に制御されていることを特徴とする。塗膜は、更にＳｉＯ2，Ａｌ2Ｏ3又はＺｒＯ2処理したルチル型ＴｉＯ2，(Ｃｏ1/2,Ｎｉ,Ｚｎ1/2)ＴｉＯ4，ＣｏＡｌ2Ｏ4，Ｃｕ(Ｃｒ,Ｍｎ)3Ｏ4，ＴｉＯ2-ＮｉＯ-Ｓｂ2Ｏ5から選ばれた一種又は二種以上の無機顔料を１０〜７０質量％含むことができる。 In the coated metal plate of the present invention, an organic / inorganic composite coating film formed from a mixed paint of a silica-based binder and acrylic silicone is formed on the surface of the metal plate. ) And (2), the height ratios A and B of the absorbance peaks are controlled within the ranges of A: 0.6 to 0.85 and B: 0.2 to 0.6, respectively. To do. The coating film was further treated with SiO 2 , Al 2 O 3 or ZrO 2 , rutile TiO 2 , (Co 1/2 , Ni, Zn 1/2 ) TiO 4 , CoAl 2 O 4 , Cu (Cr, Mn) 3. One to two or more inorganic pigments selected from O 4 , TiO 2 —NiO—Sb 2 O 5 can be contained in an amount of 10 to 70% by mass.
有機・無機複合塗膜は、金属板表面に直接、或いはＡｌ2Ｏ3，ＳｉＯ2，ＺｒＯ2，Ｃｒ2Ｏ3，ＴｉＯ2の一種又は二種以上を含む酸化物層(下地層)を介して設けられている。
高さ比率Ａ＝(1030cm-1ピーク高さ／1100cm-1ピーク高さ)・・・・(１)
高さ比率Ｂ＝(1730cm-1ピーク高さ／1100cm-1ピーク高さ)・・・・(２)
The organic / inorganic composite coating is directly on the surface of the metal plate or through an oxide layer (underlayer) containing one or more of Al 2 O 3 , SiO 2 , ZrO 2 , Cr 2 O 3 , TiO 2. Is provided.
Height ratio A = (1030 cm -1 peak height / 1100 cm -1 peak height) ... (1)
Height ratio B = (1730 cm -1 peak height / 1100 cm -1 peak height) ... (2)
有機・無機複合塗膜の形成には、アルコキシシランを含むオルガノアルコキシシランの部分加水分解縮合物：２０〜７０質量％，不飽和エチレン性単量体の重合体又は共重合体：２０〜７０質量％，コロイダルシリカ：１０〜６０質量％の固形分を水／エチレングリコールモノブチルエーテルの混合溶媒に分散させた塗料が使用される。塗料には、必要に応じてＳｉＯ2，Ａｌ2Ｏ3又はＺｒＯ2処理したルチル型ＴｉＯ2，(Ｃｏ1/2,Ｎｉ,Ｚｎ1/2)ＴｉＯ4，ＣｏＡｌ2Ｏ4，Ｃｕ(Ｃｒ,Ｍｎ)3Ｏ4，ＴｉＯ2-ＮｉＯ-Ｓｂ2Ｏ5から選ばれた一種又は二種以上の無機顔料を１０〜７０質量％配合できる。 For the formation of the organic / inorganic composite coating film, a partially hydrolyzed condensate of organoalkoxysilane containing alkoxysilane: 20 to 70% by mass, polymer or copolymer of unsaturated ethylenic monomer: 20 to 70% by mass %, Colloidal silica: A coating material in which a solid content of 10 to 60% by mass is dispersed in a mixed solvent of water / ethylene glycol monobutyl ether is used. The coating materials include rutile TiO 2 , (Co 1/2 , Ni, Zn 1/2 ) TiO 4 , CoAl 2 O 4 , Cu (Cr, treated with SiO 2 , Al 2 O 3 or ZrO 2 as necessary. One or two or more inorganic pigments selected from Mn) 3 O 4 and TiO 2 —NiO—Sb 2 O 5 can be blended in an amount of 10 to 70% by mass.
脱脂及び／又は酸洗で表面を清浄化した金属板に塗料を塗布・焼成することにより、アクリルシリコーンを巻き込んだ三次元網目構造をもつ有機・無機複合塗膜が金属板表面に形成される。有機・無機複合塗膜の形成に先立って、Ａｌ2Ｏ3，ＳｉＯ2，ＺｒＯ2，Ｃｒ2Ｏ3，ＴｉＯ2等の酸化物前駆体を含む水性分散液を金属板に塗布・焼成し、酸化物層(下地層)を形成しても良い。 By coating and baking a paint on a metal plate whose surface has been cleaned by degreasing and / or pickling, an organic / inorganic composite coating film having a three-dimensional network structure including acrylic silicone is formed on the surface of the metal plate. Prior to the formation of the organic / inorganic composite coating film, an aqueous dispersion containing an oxide precursor such as Al 2 O 3 , SiO 2 , ZrO 2 , Cr 2 O 3 , TiO 2 is applied and fired on a metal plate, An oxide layer (underlayer) may be formed.
アクリルシリコーンの有機成分は、３００℃付近から分解し始め、６５０℃で１時間加熱するとほとんどの有機成分が消失する。そのため、アクリルシリコーン単独の塗膜を設けた仕切り板が高温のアルミニウム鋳物と接触すると、塗膜に巣穴ができ或いは粉化して脱落しやすくなる。この状態でアルミニウム溶湯を鋳型に注入すると、アクリルシリコーン塗膜の離型作用が活用されず、巣穴や粉体の隙間を通してアルミニウム溶湯が仕切り板の金属表面に接触して焼付きが生じる。 The organic component of acrylic silicone begins to decompose from around 300 ° C., and most of the organic component disappears when heated at 650 ° C. for 1 hour. Therefore, when a partition plate provided with a coating film made of acryl silicone alone comes into contact with a high-temperature aluminum casting, a burrow is formed in the coating film, or it is easily pulverized and dropped off. When the molten aluminum is poured into the mold in this state, the release action of the acrylic silicone coating film is not utilized, and the molten aluminum comes into contact with the metal surface of the partition plate through the nest hole or the gap between the powders and seizure occurs.
そこで、本発明者等は、耐熱性の良好なシリカ系バインダをアクリルシリコーンに複合させることを検討した。シリカ系バインダ，アクリルシリコーンを複合した塗膜が耐熱性，離型性に有効なことは、次のように説明できる。なお、シリカ系バインダとしては、クラックの発生を抑制する上でコロイダルシリカを含むシリカ系バインダが好適である。 Therefore, the present inventors examined combining a silica-based binder with good heat resistance with acrylic silicone. The fact that a coating film composed of a silica binder and acrylic silicone is effective for heat resistance and releasability can be explained as follows. In addition, as a silica type binder, the silica type binder containing colloidal silica is suitable when suppressing generation | occurrence | production of a crack.
シリカ系バインダ単体からなる塗膜では、コロイダルシリカを含ませても膜厚：３μｍ以上になるとクラックが発生しやすくなるので、薄膜塗装せざるを得ない。薄い塗膜を形成した場合でも、離型性の発現に必要なシリコーンが存在しないため塗膜表層にあるシリカの酸素がアルミニウムと結合し、離型性が得られない。逆にアクリルシリコーン単体からなる塗膜では高温雰囲気で有機分が消失するため、塗膜のない部分で仕切り板とアルミニウム鋳物との間に焼付きが生じる。 In the case of a coating film composed of a silica-based binder alone, even if colloidal silica is included, cracks are likely to occur when the film thickness is 3 μm or more. Even when a thin coating film is formed, since there is no silicone necessary for expression of releasability, the oxygen of silica on the surface layer of the coating film binds to aluminum, and releasability cannot be obtained. On the contrary, in the coating film made of a single acrylic silicone, the organic component disappears in a high temperature atmosphere, and therefore seizure occurs between the partition plate and the aluminum casting in a portion without the coating film.
これに対し、シリカ系バインダ，アクリルシリコーンを複合した塗膜では、シリカ系バインダがアクリルシリコーンを巻き込む形で塗膜が形成され、６５０℃前後の高温雰囲気下でも塗膜自体が結合力の高い三次元の網目構造を維持する。シリコーン由来のＳｉ-Ｏ-Ｓｉ構造がアルミニウムに対する仕切り板の濡れを抑えることも、離型性が向上する一因と考えられる。 On the other hand, in the coating film in which the silica-based binder and acrylic silicone are combined, the coating film is formed in such a manner that the silica-based binder entrains the acrylic silicone, and the coating film itself has a high binding force even in a high temperature atmosphere around 650 ° C. Maintain the original mesh structure. It can be considered that the Si-O-Si structure derived from silicone suppresses the wetting of the partition plate with respect to aluminum, which is one of the reasons for improving the release property.
耐熱性，離型性を両立させる上で、シリカ系バインダ，アクリルシリコーンの複合割合が特定される。コロイダルシリカ由来のＳｉ-Ｏ-Ｓｉ，Ｓｉ-ＯＨが少なすぎると、アクリルシリコーンがシリカ系バインダに十分巻き込まれず塗膜の結合力が不十分になる。逆に、コロイダルシリカ由来のＳｉ-Ｏ-Ｓｉ，Ｓｉ-ＯＨが多すぎると、アルミニウムに濡れ易いＳｉ-Ｏ-Ｓｉ構造が塗膜表層に占める割合が多くなり、アルミニウム鋳物と結合して離型性が劣る。また、塗膜の形成を容易にする上で、シリカ系バインダに適量のアクリル分を結合させる必要がある。 In order to achieve both heat resistance and releasability, the composite ratio of silica-based binder and acrylic silicone is specified. If the amount of Si-O-Si, Si-OH derived from colloidal silica is too small, the acrylic silicone will not be sufficiently involved in the silica-based binder and the coating strength will be insufficient. Conversely, if there is too much Si-O-Si, Si-OH derived from colloidal silica, the proportion of the Si-O-Si structure that easily wets aluminum will occupy the surface layer of the coating, and it will be combined with the aluminum casting to release. Inferior. In order to facilitate the formation of the coating film, it is necessary to bind an appropriate amount of acrylic component to the silica-based binder.
シリカ系バインダ，アクリルシリコーンが耐熱性，離型性，成膜性に及ぼす影響を考慮し、塗膜組成を調査・検討した結果、塗膜の赤外吸収スペクトル回折で得られる式(１)の吸光度ピークの高さ比率Ａ，式(２)の吸光度ピークの高さ比率ＢをそれぞれＡ：０.６〜０.８５，Ｂ：０.２〜０.６の範囲に制御した塗膜が有効であることを解明した。
高さ比率Ａ＝(1030cm-1ピーク高さ／1100cm-1ピーク高さ)・・・・(１)
高さ比率Ｂ＝(1730cm-1ピーク高さ／1100cm-1ピーク高さ)・・・・(２)
As a result of investigating and examining the coating composition in consideration of the effects of silica-based binder and acrylic silicone on heat resistance, releasability, and film-forming properties, the formula (1) obtained by infrared absorption spectrum diffraction of the coating film A coating film in which the height ratio A of the absorbance peak and the height ratio B of the absorbance peak of the formula (2) are controlled in the ranges of A: 0.6 to 0.85 and B: 0.2 to 0.6, respectively, is effective. It was clarified that.
Height ratio A = (1030 cm -1 peak height / 1100 cm -1 peak height) ... (1)
Height ratio B = (1730 cm -1 peak height / 1100 cm -1 peak height) ... (2)
赤外吸収スペクトルの1030cm-1に現れるピークはＳｉ-Ｏ-Ｓｉ，Ｓｉ-ＯＨに、1100cm-1に現れるピークは有機分が結合したＳｉ-Ｏ-Ｓｉに、1730cm-1に現れるピークはアクリルのＣ＝Ｏに当る。高さ比率Ａが０.６〜０.８５の範囲にあることはアクリルシリコーンを巻き込むコロイダルシリカ由来のＳｉ-Ｏ-Ｓｉ，Ｓｉ-ＯＨが適正量確保されていることを意味し、高さ比率Ｂが０.２〜０.６の範囲にあることは成膜に好適な量のアクリルがシリコーンに結合していることを意味する。 Peak appearing at 1030 cm -1 in the infrared absorption spectrum Si-O-Si, the Si-OH peak appearing at 1100 cm -1 in the Si-O-Si which organic matter is bound, peak appearing at 1730 cm -1 Acrylic This is equivalent to C = O. When the height ratio A is in the range of 0.6 to 0.85, it means that an appropriate amount of Si—O—Si, Si—OH derived from colloidal silica enclosing acrylic silicone is secured. B in the range of 0.2 to 0.6 means that an amount of acrylic suitable for film formation is bonded to the silicone.
塗装原板には、普通鋼板，めっき鋼板，ステンレス鋼板，銅板，銅合金板，アルミニウム板，アルミニウム合金板等がある。塗装原板には、必要に応じてアルカリ脱脂，クロメート処理又はクロムフリー処理，リン酸塩処理等の塗装前処理が施される。 Examples of the coating original plate include a normal steel plate, a plated steel plate, a stainless steel plate, a copper plate, a copper alloy plate, an aluminum plate, and an aluminum alloy plate. The coating original plate is subjected to pre-coating treatments such as alkali degreasing, chromate treatment or chromium-free treatment, and phosphate treatment as necessary.
塗装前処理後、必要に応じて塗装原板を下塗り塗装し、Ａｌ2Ｏ3，ＳｉＯ2，Ｃｒ2Ｏ3，ＴｉＯ2の一種又は二種以上の酸化物を含む下地層を設けても良い。下地層の形成には、Ａｌ，Ｓｉ，Ｚｒ，Ｃｒ，Ｔｉ等の水酸化物やアルコキシドの加水分解物、水和酸化物等の酸化物前駆体を主成分とする水性分散液が使用される。水性分散液を塗装原板に塗布し、８０〜３００℃で焼成することにより乾燥膜厚：０.０１〜１.０μｍの酸化物層(下地層)が形成される。酸化物層は、均一な膜となって塗装原板を覆い耐熱性を向上させ、カーボンの酸化分解を抑制する作用もあり有機・無機複合塗膜の有機物分解に対する遅延効果を期待できる。 After the pre-coating treatment, the coating original plate may be undercoated as necessary, and an underlayer containing one or more oxides of Al 2 O 3 , SiO 2 , Cr 2 O 3 , and TiO 2 may be provided. For the formation of the underlayer, an aqueous dispersion mainly composed of hydroxides such as Al, Si, Zr, Cr and Ti, hydrolysates of alkoxides, and oxide precursors such as hydrated oxides is used. . An aqueous dispersion is applied to a coating original plate and baked at 80 to 300 ° C. to form an oxide layer (underlayer) having a dry film thickness of 0.01 to 1.0 μm. The oxide layer forms a uniform film, covers the coating original plate, improves heat resistance, suppresses oxidative decomposition of carbon, and can be expected to delay the organic matter decomposition of the organic / inorganic composite coating film.
有機・無機複合塗膜の形成に使用される塗料は、シリカ系バインダ，アクリルシリコーンを混合した組成物であり、たとえばコロイダルシリカ：１０〜６０質量％，オルガノアルコキシシランの部分加水分解縮合物：２０〜７０質量％で構成される固形分，不飽和エチレン性単量体の重合体又は共重合体：２０〜７０質量％で構成される固形分，グリコール誘導体を含む溶媒からなる。 The coating material used for forming the organic / inorganic composite coating film is a composition in which a silica-based binder and acrylic silicone are mixed. For example, colloidal silica: 10 to 60% by mass, organohydroalkoxysilane partially hydrolyzed condensate: 20 Solid content composed of ˜70% by mass, polymer or copolymer of unsaturated ethylenic monomer: Solid content composed of 20 to 70% by mass, and solvent containing glycol derivative.
コロイダルシリカが１０質量％未満では耐熱性が不十分であり、逆に６０質量％を超えると溶融アルミニウムに結合しやすくなって良好な離型性が得られない。オルガノアルコキシシランの部分加水分解縮合物が２０質量％未満では耐熱性のある塗膜を形成できず、逆に７０質量％を超えると高温加熱時にクラックや巣穴が発生しやすくなって十分な離型性が得られない。不飽和エチレン性単量体の重合体又は共重合体が２０質量％未満では塗膜形成が難しくなり、逆に７０質量％を超えると高温加熱時に巣穴が発生しやすくなる。 If the colloidal silica is less than 10% by mass, the heat resistance is insufficient. Conversely, if it exceeds 60% by mass, it is easy to bond to molten aluminum, and good mold release properties cannot be obtained. If the hydrolyzed condensate of organoalkoxysilane is less than 20% by mass, a heat-resistant coating film cannot be formed. Conversely, if it exceeds 70% by mass, cracks and burrows are likely to occur during high-temperature heating, and sufficient separation is achieved. The type is not obtained. When the polymer or copolymer of the unsaturated ethylenic monomer is less than 20% by mass, it is difficult to form a coating film. Conversely, when it exceeds 70% by mass, burrows are likely to occur during high temperature heating.
有機・無機複合塗料は、シリカ，オルガノアルコキシシラン，オルガノアルコキシシランの部分加水分解縮合物からなる固形分，不飽和エチレン性単量体の重合体又は共重合体及び水，グリコール誘導体からなる溶媒で構成されている。
シリカとしては、コロイダルシリカが使用される。コロイダルシリカ分散液は高分子量の無水ケイ酸を水に分散させた水系コロイダルシリカ分散液及びアルコール系溶媒に分散させた非水系コロイダルシリカ分散液に大別されるが、本発明では主として水系コロイダルシリカ分散液を使用する。水系コロイダルシリカ分散液の一部は、非水系コロイダルシリカ分散液で置換できる。分散液に分散しているシリカは、好ましくは平均粒径が１５０μｍ以下で、シリカ系バインダの保存安定性を確保するため酸性に調整されている。
Organic / inorganic composite coatings are solids consisting of silica, organoalkoxysilane, partially hydrolyzed condensate of organoalkoxysilane, polymers or copolymers of unsaturated ethylenic monomers, and solvents consisting of water and glycol derivatives. It is configured.
Colloidal silica is used as the silica. Colloidal silica dispersions are broadly classified into aqueous colloidal silica dispersions in which high molecular weight silicic acid is dispersed in water and non-aqueous colloidal silica dispersions in an alcohol solvent. In the present invention, however, aqueous colloidal silica is mainly used. Use dispersion. A part of the aqueous colloidal silica dispersion can be replaced with a non-aqueous colloidal silica dispersion. The silica dispersed in the dispersion liquid preferably has an average particle diameter of 150 μm or less and is adjusted to be acidic in order to ensure the storage stability of the silica-based binder.
塗料成分に使用されるシリカ系バインダは、オルガノアルコキシシラン及びオルガノアルコキシシランの部分加水分解縮合物である。一般式：Ｒ1Ｓｉ(ＯＲ2)3〔Ｒ1は炭素数１〜３のアルキル基，ビニル基，3,4-エポキシシクロヘキシルエチル基，γ-グリシドキシプロピル基，γ-メルカプトプロピル基，γ-クロロプロピル基の一種又は二種以上、Ｒ2は炭素数１〜４のアルキル基，炭素数１〜４のアルコキシエチル基及びアリール基の一種又は二種以上〕で表す化合物が挙げられ、オルガノヒドロキシシラン又はその部分縮合物である。 The silica-based binder used for the coating component is an organoalkoxysilane and a partially hydrolyzed condensate of organoalkoxysilane. General formula: R 1 Si (OR 2 ) 3 [R 1 is an alkyl group having 1 to 3 carbon atoms, vinyl group, 3,4-epoxycyclohexylethyl group, γ-glycidoxypropyl group, γ-mercaptopropyl group, 1 type or 2 types or more of γ-chloropropyl groups, and R 2 is a compound represented by 1 type or 2 types or more of an alkyl group having 1 to 4 carbon atoms, an alkoxyethyl group having 1 to 4 carbon atoms, and an aryl group, Organohydroxysilane or a partial condensate thereof.
アクリルシリコーン樹脂は、不飽和エチレン性単量体の重合体又は共重合体とオルガノアルコキシシランの部分加水分解縮合物とを反応させることにより調製される。不飽和エチレン性単量体としては、たとえばメチルアクリレート，エチルアクリレート，2-エチルヘキシルアクリレート，t-ブチルアクリレート，2-ヒドロキシメチルアクリレート，2-ヒドロキシエチルアクリレート，n-ブチルメタクリレート，イソブチルメタクリレート，t-ブチルメタクリレート，グリシジルメタクリレート，2-ヒドロキシエチルメタクリレート，2-ヒドロキシプロピルメタクリレート，ジメチルアミノエチルメタクリレート，ジエチルアミノエチルメタクリレート，2-エチルヘキシルメタクリレート，メトキシジエチレングリコールメタクリレート，メトキシテトラエチレングリコールメタクリレート，アリルメタクリレート等の(メタ)アクリル酸エステルが挙げられる。スチレン等の単量体の少量を不飽和エチレン性単量体に添加することもできる。 The acrylic silicone resin is prepared by reacting a polymer or copolymer of an unsaturated ethylenic monomer with a partially hydrolyzed condensate of organoalkoxysilane. Examples of unsaturated ethylenic monomers include methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, t-butyl acrylate, 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl. (Meth) acrylic acid such as methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-ethylhexyl methacrylate, methoxydiethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, allyl methacrylate Examples include esters. A small amount of a monomer such as styrene can be added to the unsaturated ethylenic monomer.
溶媒にグリコール誘導体を使用すると、有機・無機複合塗膜の保存安定性が飛躍的に向上し、塗装作業性，成膜性も改善される。グリコール誘導体としては、エチレングリコール，プロピレングリコール，ブチレングリコール，エチレングリコールモノエチルエーテル，エチレングリコールモノブチルエーテル，酢酸エチレングリコールモノエチルエーテル等があり、なかでもエチレングリコールモノブチルエーテルが好適な溶媒である。 When a glycol derivative is used as the solvent, the storage stability of the organic / inorganic composite coating film is remarkably improved, and the coating workability and film forming property are also improved. Examples of glycol derivatives include ethylene glycol, propylene glycol, butylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene glycol monobutyl ether. Among these, ethylene glycol monobutyl ether is a suitable solvent.
シリカ系バインダは、(１)コロイダルシリカ分散液にオルガノアルコキシシランを添加して加水分解させることによりオルガノヒドロキシシラン及びその部分縮合物を生成し、反応生成物を溶剤で希釈する方法，(２)コロイダルシリカ分散液を溶剤で希釈した後、オルガノアルコキシシランを添加して加水分解させる方法等で用意される。
コロイダルシリカ分散液にオルガノアルコキシシランを添加し加水分解させる場合、液温を１０〜８０℃に保ち、常圧下で約１〜１２時間攪拌させながら反応させることが好ましい。非水性コロイド状シリカの一部は、反応終了後に添加しても良い。
Silica-based binders are: (1) A method in which organoalkoxysilane is added to a colloidal silica dispersion and hydrolyzed to produce organohydroxysilane and its partial condensate, and the reaction product is diluted with a solvent, (2) After the colloidal silica dispersion is diluted with a solvent, it is prepared by a method of adding an organoalkoxysilane and hydrolyzing it.
When the organoalkoxysilane is added to the colloidal silica dispersion for hydrolysis, the reaction is preferably carried out while maintaining the liquid temperature at 10 to 80 ° C. and stirring for about 1 to 12 hours under normal pressure. A part of the non-aqueous colloidal silica may be added after completion of the reaction.
調整されたコロイダルシリカ-オルガノアルコキシシランの部分加水分解縮合物の分散液に不飽和エチレン性単量体の重合体又は共重合体を変性したアクリルシリコーン樹脂及びグリコール誘導体を含む溶剤を添加して十分分散させることにより、有機・無機複合塗料を得る。混合後、液温を１０〜８０℃に保ち、常圧下で約１〜１２時間攪拌させながら反応させることが更に好ましい。 It is sufficient to add a solvent containing an acrylic silicone resin modified with a polymer or copolymer of an unsaturated ethylenic monomer and a glycol derivative to the dispersion of the prepared colloidal silica-organoalkoxysilane partially hydrolyzed condensate By dispersing, an organic-inorganic composite coating is obtained. More preferably, after mixing, the liquid temperature is kept at 10 to 80 ° C. and the reaction is allowed to stir at normal pressure for about 1 to 12 hours.
有機・無機複合塗膜に占める無機顔料の割合が１０〜７０質量％となるように無機顔料を有機・無機複合塗料に配合すると、離型性が更に向上する。無機顔料には、ＳｉＯ2，Ａｌ2Ｏ3又はＺｒＯ2処理したルチル型ＴｉＯ2，(Ｃｏ1/2,Ｎｉ,Ｚｎ1/2)ＴｉＯ4，ＣｏＡｌ2Ｏ4，Ｃｕ(Ｃｒ,Ｍｎ)3Ｏ4，ＴｉＯ2-ＮｉＯ-Ｓｂ2Ｏ5等がある。また、有機・無機複合塗膜の形成に先立って、Ａｌ2Ｏ3，ＳｉＯ2，ＺｒＯ2，Ｃｒ2Ｏ3，ＴｉＯ2から選ばれた一種又は二種以上の酸化物の前駆体を分散させた水性分散液を塗装原板に塗布・焼成して酸化物層を形成すると、一層優れた離型性が付与される。 When the inorganic pigment is blended with the organic / inorganic composite coating so that the proportion of the inorganic pigment in the organic / inorganic composite coating film is 10 to 70% by mass, the releasability is further improved. Inorganic pigments include rutile TiO 2 , (Co 1/2 , Ni, Zn 1/2 ) TiO 4 , CoAl 2 O 4 , Cu (Cr, Mn) 3 treated with SiO 2 , Al 2 O 3 or ZrO 2. O 4 , TiO 2 —NiO—Sb 2 O 5, and the like. Prior to the formation of the organic / inorganic composite coating film, a precursor of one or more oxides selected from Al 2 O 3 , SiO 2 , ZrO 2 , Cr 2 O 3 and TiO 2 is dispersed. When an aqueous layer is applied and fired on a coating original plate to form an oxide layer, further excellent release properties are imparted.
有機・無機複合塗料は、スプレー塗装，浸漬法，フローコート，ロールコート，スクリーン印刷，静電塗装等、従来から採用されている方法で塗装原板に塗布される。塗布後、１５０〜２５０℃で１分程度加熱することにより、基材に対する密着性に優れた有機・無機複合塗膜が得られる。塗膜は、基材全面を覆うように０.２〜２０μｍの膜厚が好ましい。０.２μｍに達しない薄膜ではピンホールが生じやすく離型性に劣り、逆に２０μｍを超える厚膜では塗膜の形成自体が困難になる。 The organic / inorganic composite coating is applied to the coating original plate by a conventionally employed method such as spray coating, dipping method, flow coating, roll coating, screen printing, electrostatic coating or the like. After coating, an organic / inorganic composite coating film having excellent adhesion to the substrate can be obtained by heating at 150 to 250 ° C. for about 1 minute. The coating film preferably has a thickness of 0.2 to 20 μm so as to cover the entire surface of the substrate. A thin film that does not reach 0.2 μm tends to cause pinholes and is inferior in releasability. On the contrary, a thick film exceeding 20 μm makes it difficult to form a coating film.
それぞれ固形分が特定されたシリカ系バインダ及びアクリルシリコーン樹脂を混合比率７０：３０〜２０：８０で混合することにより、有機・無機複合塗料が調製される。シリカ系バインダ：アクリルシリコーン樹脂の混合比率を調整することにより、赤外吸収スペクトル回折において式(１)，(２)で算出される吸光度ピークの高さ比率Ａ，ＢがそれぞれＡ：０.６〜０.８５，Ｂ：０.２〜０.６の範囲になる。 An organic / inorganic composite coating is prepared by mixing a silica-based binder and an acrylic silicone resin each having a specified solid content at a mixing ratio of 70:30 to 20:80. By adjusting the mixing ratio of silica-based binder: acryl silicone resin, the absorbance peak height ratios A and B calculated by the formulas (1) and (2) in the infrared absorption spectrum diffraction are respectively A: 0.6. ˜0.85, B: The range is 0.2 to 0.6.
図１に示す吸光度ピークの高さ比率Ａ，Ｂは、有機・無機複合塗料の各種物性との関係をみると、吸光度ピークの高さ比率Ａの増加に従って耐熱性が向上、高さ比率Ｂの増加に従って加工密着性が向上している。耐熱性，加工密着性の双方を満足させ、良好な離型性を確保する上では、吸光度ピークの高さ比率Ａ，Ｂの制御が必要であることが判る。このようなことから、本発明ではＡ：０.６〜０.８５，Ｂ：０.２〜０.６の範囲に式(１)，(２)で算出される吸光度ピークの高さ比率Ａ，Ｂを調整している。 The absorbance peak height ratios A and B shown in FIG. 1 are related to various physical properties of the organic / inorganic composite paint. As the absorbance peak height ratio A increases, the heat resistance improves. As the number increases, the work adhesion improves. It can be seen that the control of the height ratios A and B of the absorbance peaks is necessary to satisfy both the heat resistance and the work adhesion and to ensure good releasability. Therefore, in the present invention, the height ratio A of the absorbance peak calculated by the formulas (1) and (2) in the range of A: 0.6 to 0.85 and B: 0.2 to 0.6. , B are adjusted.
本発明の塗装金属板は、アルミニウム鋳物の仕切り板として開発されたものであるが、優れた離型性，耐熱性を活用しオーブンの内壁，食品用型，プラスチック成形用金型等、
仕切り板以外の用途にも使用可能である。また、有機・無機複合塗料のロールコートで塗膜が形成されるので連続塗装ラインに適用でき、塗膜がある程度の加工密着性をもっているのでプレコート化も可能である。
The coated metal plate of the present invention was developed as a partition plate for cast aluminum, but by utilizing its excellent releasability and heat resistance, the inner wall of an oven, a food mold, a plastic mold, etc.
It can be used for applications other than the partition plate. In addition, since the coating film is formed by roll coating of the organic / inorganic composite paint, it can be applied to a continuous coating line, and since the coating film has a certain degree of processing adhesion, it can be precoated.
〔シリカ系バインダの調製〕
酸性の水性コロイド状シリカ分散液をメタノール性コロイド状シリカ分散液と混合した後、メチルトリエトキシシラン及び塩基性アルコキシシランを添加し、室温で５時間攪拌することにより加水分解を完了させた。加水分解生成物にエチレングリコールモノブチルエーテルを添加し、固形分約３０％の溶液を調製した。
(Preparation of silica-based binder)
After the acidic aqueous colloidal silica dispersion was mixed with the methanolic colloidal silica dispersion, methyltriethoxysilane and basic alkoxysilane were added and the hydrolysis was completed by stirring at room temperature for 5 hours. Ethylene glycol monobutyl ether was added to the hydrolysis product to prepare a solution having a solid content of about 30%.
〔アクリルシリコーンの調製〕
アクリル酸エステル（メチルメタクリレート：n-ブチルメタクリレート＝２：１の混合物）及びγ-メタクリロキシプロピルトリメトキシシランをエチレングリコールモノブチルエーテルで希釈し、窒素雰囲気中でアゾビスイソブチルニトリルを添加し、８０℃で約６時間重合させることにより固形分約３０％の樹脂溶液を調製した。
調製されたシリカ系バインダ，アクリルシリコーンを混合し、混合比率を種々変えた塗料を調合した。
[Preparation of acrylic silicone]
Acrylic acid ester (mixture of methyl methacrylate: n-butyl methacrylate = 2: 1) and γ-methacryloxypropyltrimethoxysilane are diluted with ethylene glycol monobutyl ether, azobisisobutylnitrile is added in a nitrogen atmosphere, and 80 ° C. For about 6 hours to prepare a resin solution having a solid content of about 30%.
The prepared silica binder and acrylic silicone were mixed to prepare paints with various mixing ratios.
〔塗装〕
板厚：０.８ｍｍのSUS430ステンレス鋼板をアルカリ脱脂した後、ロールコータで塗料を塗布し、２１５℃×１分の焼成によって乾燥膜厚：２.５μｍの塗膜を形成した。
塗膜構造を解析するため、塗膜の赤外吸収スペクトルを調査した。赤外吸収スペクトルの測定には、検出器，ビームスプリッタをＫＢｒとしＧｅを窓材に用いた全反射測定法(ATR法)の一回反射を採用した。
また、塗装鋼板の塗膜密着性，耐熱性，離型性を次のように調査した。
〔Painting〕
Plate thickness: After a 0.8 mm SUS430 stainless steel plate was alkali degreased, a paint was applied by a roll coater, and a coating film having a dry film thickness of 2.5 μm was formed by baking at 215 ° C. for 1 minute.
In order to analyze the coating film structure, the infrared absorption spectrum of the coating film was investigated. For the measurement of the infrared absorption spectrum, a single reflection of the total reflection measurement method (ATR method) using KBr as the detector and beam splitter and Ge as the window material was adopted.
In addition, the coating film adhesion, heat resistance, and releasability of the coated steel sheet were investigated as follows.
〔塗膜密着性試験〕
温度：２０℃の恒温槽から取り出した試験片の塗膜と反対側に等厚の板材を５枚挟んで１８０度折曲げ試験し、曲げ部外側に粘着テープを貼り付け引き剥がした後、塗膜の残存状態を目視観察した。塗膜が剥離していない試験片を○，剥離した試験片を×として加工部の塗膜密着性を評価した。
[Coating adhesion test]
Temperature: A 180 ° bend test with 5 sheets of equal thickness sandwiched on the opposite side to the coating film of the test piece taken out from the thermostat at 20 ° C. The remaining state of the film was visually observed. The test piece from which the coating film was not peeled was evaluated as “◯”, and the peeled test piece was evaluated as “x”.
〔耐熱，離型性評価試験〕
塗装鋼板から切り出した試験片を６５０℃に１時間加熱した後、７５０℃の溶融アルミニウム合金を塗膜表面に流し込み、６５０℃×３０分保持後に冷却凝固した。室温に降温したアルミニウム合金の凝固体を試験片から引き剥がし、塗膜面を観察し、粉化や欠損のない塗膜を○，点状に欠損した塗膜を△，全面に粉化や欠損が生じた塗膜を×として耐熱性を評価した。離型性に関しては、手でアルミニウム合金凝固体を剥がすことができた試験片を○，手で剥がすことができなかった試験片を×と評価した。
[Heat resistance and releasability evaluation test]
After the test piece cut out from the coated steel plate was heated to 650 ° C. for 1 hour, a molten aluminum alloy at 750 ° C. was poured onto the surface of the coating film, and cooled and solidified after holding at 650 ° C. for 30 minutes. The aluminum alloy solidified body cooled to room temperature is peeled off from the test piece, the coating surface is observed, the coating film without pulverization or defect is ◯, the coating film is punctured, and the entire surface is pulverized or defective. The heat resistance was evaluated by setting the coating film on which x was generated as x. Regarding the releasability, the test piece that could be peeled off by hand with the aluminum alloy solidified body was evaluated as ◯, and the test piece that could not be peeled off by hand was evaluated as x.
表１の調査結果にみられるように、シリカ系バインダ，アクリルシリコーンの配合比によって赤外吸収スペクトル回折で得られる吸光度ピークの高さ比率Ａ，ＢをそれぞれＡ：０.６〜０.８５．Ｂ：０.２〜０.６の範囲に調整した塗膜では、アルミニウム合金凝固体から試験片を手で剥がすことができ、耐熱性，離型性の良好な仕切り板として有用なことが確認された。 As seen in the investigation results in Table 1, the height ratios A and B of the absorbance peaks obtained by infrared absorption spectrum diffraction depending on the mixing ratio of the silica-based binder and the acrylic silicone are respectively A: 0.6 to 0.85. B: With the coating film adjusted in the range of 0.2 to 0.6, the test piece can be peeled off from the aluminum alloy solidified body by hand, and it is confirmed that it is useful as a partition plate with good heat resistance and releasability. It was done.
これに対し、高さ比率Ａが０.６未満の塗膜では耐熱性，離型性が劣り、高さ比率Ａが０.８５を超える塗膜では加工密着性。離型性が劣っていた。高さ比率Ｂが０.２未満の塗膜では加工密着性，離型性が劣り、高さ比率Ｂが０.６を超える塗膜では耐熱性，離型性に劣っていた。 On the other hand, heat resistance and releasability are inferior in a coating film having a height ratio A of less than 0.6, and work adhesion is achieved in a coating film having a height ratio A exceeding 0.85. The releasability was inferior. A coating film having a height ratio B of less than 0.2 was inferior in work adhesion and releasability, and a coating film having a height ratio B in excess of 0.6 was inferior in heat resistance and releasability.
密着性，耐熱性，離型性について満足できる結果が得られた試験No.５の塗料をベースに、無機顔料として平均粒径：０.２μｍのＺｒＯ2処理した酸化チタンを添加し、得られた塗料を同様な条件下でステンレス鋼板に塗布・焼成し、乾燥膜厚：２.５μｍの塗膜を形成した。そして、塗膜に配合した酸化チタンが塗膜物性に及ぼす影響を調査した。
表２にみられるように、１０質量％以上の酸化チタン添加で離型性が向上しており、酸化チタンの増量に伴い塗装鋼板からアルミニウム合金凝固体の離型が容易になった。なかでも、酸化チタンの配合量が１０質量％以上の塗膜では、塗装鋼板を傾けるだけでアルミニウム合金凝固体が離型するようになった。しかし、過剰な酸化チタンを配合した塗膜では、表面が粉化する傾向にあった。
Obtained by adding ZrO 2 -treated titanium oxide with an average particle size of 0.2 μm as an inorganic pigment, based on the paint of Test No. 5 that gave satisfactory results for adhesion, heat resistance and releasability The paint was applied and fired on a stainless steel plate under the same conditions to form a coating film having a dry film thickness of 2.5 μm. And the influence which the titanium oxide mix | blended with the coating film has on the physical property of a coating film was investigated.
As can be seen in Table 2, the release property was improved by adding 10% by mass or more of titanium oxide, and the release of the solidified aluminum alloy from the coated steel sheet became easier as the amount of titanium oxide increased. Especially, in the coating film with the compounding amount of titanium oxide of 10% by mass or more, the aluminum alloy solidified body is released only by tilting the coated steel sheet. However, in the coating film which mix | blended the excess titanium oxide, there existed a tendency for the surface to pulverize.
板厚：０.８ｍｍのSUS409ステンレス鋼板を塗装原板とし、アルカリ脱脂，表面調整を経て下塗り塗装した。下塗りでは、コロイダルシリカ，コロイダルジルコニアのゾルを塗装前処理したステンレス鋼板にロールコートし、１００℃×１分の焼成によって乾燥膜厚：０.２μｍのＳｉＯ2-ＺｒＯ2皮膜を形成した。次いで、実施例１の試験No.５の塗料をロールコータで塗布し、２１５℃×１分の焼成によって乾燥膜厚：３μｍの有機・無機複合塗膜を設けた。
有機・無機複合塗膜で被覆された塗装鋼板について、実施例１と同じ条件下で離型性を調査した。その結果、アルミニウム合金凝固体を載せた塗装鋼板を６０度傾けたとき、アルミニウム合金凝固体が塗装金属板から滑り落ち、ＳｉＯ2-ＺｒＯ2皮膜のない場合に比較して離型性が格段に向上していることが判った。
Plate thickness: A SUS409 stainless steel plate having a thickness of 0.8 mm was used as a coating base plate, and was subjected to primer coating after alkali degreasing and surface adjustment. In the undercoating, a sol of colloidal silica and colloidal zirconia was roll-coated on a stainless steel plate pre-coated, and a SiO 2 —ZrO 2 film having a dry film thickness of 0.2 μm was formed by baking at 100 ° C. for 1 minute. Subsequently, the coating material of Test No. 5 of Example 1 was applied with a roll coater, and an organic / inorganic composite coating film having a dry film thickness of 3 μm was provided by baking at 215 ° C. for 1 minute.
About the coated steel plate coat | covered with the organic and inorganic composite coating film, the mold release property was investigated on the same conditions as Example 1. FIG. As a result, when the coated steel sheet carrying the aluminum alloy solidified body is tilted by 60 degrees, the aluminum alloy solidified body slides down from the coated metal plate, and the releasability is markedly greater than when there is no SiO 2 —ZrO 2 film. It turns out that it is improving.
Claims (6)
高さ比率Ａ＝(1030cm-1ピーク高さ／1100cm-1ピーク高さ)・・・・(１)
高さ比率Ｂ＝(1730cm-1ピーク高さ／1100cm-1ピーク高さ)・・・・(２) Films are formed from a mixed paint of silica-based binder and acrylic silicone, and in the infrared absorption spectrum diffraction of the coating film, the absorbance peak height ratios A and B defined by the formulas (1) and (2) are respectively A: 0. A coated metal sheet excellent in releasability, characterized in that an organic / inorganic composite coating film controlled in the range of 6 to 0.85, B: 0.2 to 0.6 is on the surface of the metal sheet.
Height ratio A = (1030 cm -1 peak height / 1100 cm -1 peak height) ... (1)
Height ratio B = (1730 cm -1 peak height / 1100 cm -1 peak height) ... (2)
アルコキシシランを含むオルガノアルコキシシランの部分加水分解縮合物：２０〜７０質量％，不飽和エチレン性単量体の重合体又は共重合体：２０〜７０質量％，コロイダルシリカ：１０〜６０質量％の固形分を水／エチレングリコールモノブチルエーテルの混合溶媒に分散させた塗料を金属板に塗布・焼成し、
アクリルシリコーンを巻き込んだ三次元網目構造をもつ有機・無機複合塗膜を金属板表面に形成することを特徴とする離型性に優れた塗装金属板の製造方法。 Prepare a metal plate whose surface has been cleaned by degreasing and / or pickling,
Partially hydrolyzed condensate of organoalkoxysilane containing alkoxysilane: 20 to 70% by mass, polymer or copolymer of unsaturated ethylenic monomer: 20 to 70% by mass, colloidal silica: 10 to 60% by mass Applying and baking a paint with a solid content dispersed in a mixed solvent of water / ethylene glycol monobutyl ether to a metal plate,
A method for producing a coated metal plate excellent in releasability, characterized in that an organic / inorganic composite coating film having a three-dimensional network structure including acrylic silicone is formed on a metal plate surface.
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| JP4891211B2 (en) * | 2007-12-12 | 2012-03-07 | 日新製鋼株式会社 | Method for producing coated steel sheet having inorganic coating film |
| JP6101295B2 (en) * | 2015-01-22 | 2017-03-22 | 京セラドキュメントソリューションズ株式会社 | Fixing apparatus and image forming apparatus |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0484643A (en) * | 1990-07-27 | 1992-03-17 | Toray Dow Corning Silicone Co Ltd | Emulsion composition for parting of aluminum die casting |
| JPH1177233A (en) * | 1997-08-29 | 1999-03-23 | Toyota Motor Corp | Release agent for die casting |
| JP2001192692A (en) * | 2000-01-14 | 2001-07-17 | Keetekku:Kk | Lubricating and mold-releasing agent composition for mold |
| JP2003266598A (en) * | 2002-03-19 | 2003-09-24 | Toyo Aluminium Kk | Release aluminum foil for manufacturing printed board |
| JP2004018797A (en) * | 2002-06-20 | 2004-01-22 | Shin Etsu Chem Co Ltd | Release agent composition for mold |
| JP2004330550A (en) * | 2003-05-06 | 2004-11-25 | Nisshin Steel Co Ltd | Photocatalyst-coated metal plate excellent in contamination resistance and paint film adhesion property and its production method |
| JP2004338114A (en) * | 2003-05-13 | 2004-12-02 | Nisshin Steel Co Ltd | Photocatalyst coated metal sheet excellent in abrasion resistance, anti-staining properties and coating film adhesion and its manufacturing method |
-
2005
- 2005-03-15 JP JP2005072232A patent/JP4521764B2/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0484643A (en) * | 1990-07-27 | 1992-03-17 | Toray Dow Corning Silicone Co Ltd | Emulsion composition for parting of aluminum die casting |
| JPH1177233A (en) * | 1997-08-29 | 1999-03-23 | Toyota Motor Corp | Release agent for die casting |
| JP2001192692A (en) * | 2000-01-14 | 2001-07-17 | Keetekku:Kk | Lubricating and mold-releasing agent composition for mold |
| JP2003266598A (en) * | 2002-03-19 | 2003-09-24 | Toyo Aluminium Kk | Release aluminum foil for manufacturing printed board |
| JP2004018797A (en) * | 2002-06-20 | 2004-01-22 | Shin Etsu Chem Co Ltd | Release agent composition for mold |
| JP2004330550A (en) * | 2003-05-06 | 2004-11-25 | Nisshin Steel Co Ltd | Photocatalyst-coated metal plate excellent in contamination resistance and paint film adhesion property and its production method |
| JP2004338114A (en) * | 2003-05-13 | 2004-12-02 | Nisshin Steel Co Ltd | Photocatalyst coated metal sheet excellent in abrasion resistance, anti-staining properties and coating film adhesion and its manufacturing method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108690384A (en) * | 2017-03-30 | 2018-10-23 | Dic株式会社 | Actinic-radiation curable composition, cured coating film and laminated body |
| CN108690384B (en) * | 2017-03-30 | 2021-09-17 | Dic株式会社 | Active energy ray-curable composition, cured coating film, and laminate |
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