JP4046322B2 - Heat-resistant clear pre-coated metal sheet with excellent design - Google Patents
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Description
【０００１】
【産業上の利用分野】
本発明は、基材の金属光沢を活かした色調を呈し、耐熱性が要求される加熱調理器具，暖房機器，空調機器，自動車排気系部材等に使用される耐熱クリアプレコート金属板に関する。
【０００２】
【従来の技術】
家電機器，ＯＡ機器，加熱調理器具，暖房機器等の表装材に、金属表面のメタリック感を生かしたクリア塗装金属板が使用され始めている。クリア塗装金属板は、従来の着色塗装金属板では得られない雰囲気がメタリック感で醸し出されるので識別性の高い商品として期待されている。クリア塗装金属板の製造には、ウレタン系，ポリオレフィン系，フッ素系等の種々の有機樹脂塗料が使用されている。比較的透明度の高いものとしてアクリル系，エポキシ系等の有機樹脂塗料を使用する場合もある。
着色顔料を分散させたクリア塗料を基材・金属板に塗布するとき、金属表面のメタリック感を活かしながら任意の色調を付与できる。着色顔料の配合に際しては、メタリック感がなくなるまで金属表面を完全に隠蔽しないように、着色顔料の材質選択，配合量の選定等に工夫を要する。
【０００３】
クリア塗装金属板の用途展開に伴い、加熱調理器具，暖房機器，空調機器，自動車排気系部材等、高温雰囲気に曝される耐熱部位にも使用可能なクリア塗装金属板に対するニーズが強くなっている。しかし、従来の有機樹脂塗料を用いたクリア塗装金属板では、耐熱温度の限界が２００℃程度であり、それ以上の高温で使用すると樹脂の熱分解に起因して塗膜に黄変，クラック，剥離等が生じる。着色剤として有機系顔料や染料を使用した場合には，熱による着色剤の変色や褪色が生じやすい。
耐熱用途に使用されるクリア塗装金属板には、耐熱性に優れたシリコーン樹脂を用いてクリア塗膜を形成することが検討されている。本発明者等も、アルキルシリコーン樹脂を使用した耐熱プレコート鋼板を提案してきた。
【０００４】
【発明が解決しようとする課題】
メチルシリコーン樹脂，フェニルシリコーン樹脂，メチルフェニルシリコーン樹脂等のアルキルシリコーン樹脂に含まれるアルキル基：Ｓｉ−Ｒ（Ｒ：メチル又はフェニル基）は、３００〜３５０℃の加熱で分解反応を開始する。他方、シリコーン樹脂中でシラノール基：Ｓｉ−ＯＨ間の脱水縮合反応によりシロキサン結合：Ｓｉ−Ｏが進行して十分なネットワーク構造を形成する上では、４００℃以上の長時間加熱が必要とされる。
【０００５】
アルキル基：Ｓｉ−Ｒの加熱分解とシロキサン結合：Ｓｉ−Ｏの形成との間に温度差があるため、３００〜４００℃の中間温度域ではアルキル基：Ｓｉ−Ｒが加熱分解するものの、十分なネットワーク構造の形成に必要なシロキサン結合：Ｓｉ−Ｏが進展しない。その結果、アルキルシリコーン樹脂塗料から成膜された塗膜は、中間温度域で一時的に不安定な皮膜状態になる。
加熱調理器具，暖房機器，空調機器，自動車排気系部材等の使用温度や使用環境を考慮すると、耐食性，耐汚染性は勿論、常温から６００℃程度の高温までの広範な温度域にわたって昇温・降温する熱履歴を受けてもクラックや剥離のない優れた塗膜性能が要求される。
【０００６】
【課題を解決するための手段】
本発明は、このような要求に応えるべく案出されたものであり、透明度の高いアルキルシリコーン樹脂をベースとするクリア塗膜に透明感のある鱗片状粉末を分散させることにより、メタリック感を強調して透明感が高く、独特の意匠を発現する金属光沢をもち、耐熱性，加工性に優れた耐熱クリアプレコート金属板を提供することを目的とする。
【０００７】
本発明の耐熱クリアプレコート金属板は、その目的を達成するため、金属光沢を呈する基材・金属板の表面に、半透明の鱗片状無機粉末を分散させたアルキルシリコーン樹脂のクリア塗膜が形成されていることを特徴とする。アルキルシリコーン樹脂には、メチルシリコーン樹脂，フェニルシリコーン樹脂，メチルフェニルシリコーン樹脂から選ばれた１種又は２種以上の混合物又は重合物がある。
【０００８】
鱗片状無機粉末としては、アルミナフレーク，マイカ粉，タルク粉，板状カオリンから選ばれた１種又は２種以上が好ましく、ＴｉＯ２，ＳｉＯ２，ＺｒＯ２，Ｆｅ２Ｏ３，Ｆｅ３Ｏ４，ＳｎＯ２，Ｃｒ２Ｏ３，ＺｎＯ，Ａｌ２Ｏ３の１種又は２種以上から選ばれた透明酸化物で必要に応じて被覆する。
【０００９】
【作用】
クリア塗膜は、メチルシリコーン樹脂，フェニルシリコーン樹脂，メチルフェニルシリコーン樹脂等のアルキルシリコーン樹脂塗料から成膜される。アルキルシリコーン樹脂は、有機樹脂の中で屈折率が最も低いアクリル樹脂やエポキシ樹脂よりも低い屈折率をもち、透明度の高い樹脂である。屈折率の測定値は測定条件によって若干異なるが、アクリル樹脂やエポキシ樹脂の約１.５に対しアルキルシリコーン樹脂の屈折率は約１.４である。両者の差は０.１程度であるが、金属光沢のある基材・金属板に設けた塗膜を目視観察するとき金属光沢の受け取り方に大きな差を生じる。すなわち、アルキルシリコーン樹脂塗膜では金属光沢が全く損なわれておらず鮮明な外観が維持されるが、アクリル樹脂やエポキシ樹脂塗膜では透明性が劣りくすんだ外観になる。
【００１０】
透明度の高いアルキルシリコーン樹脂に半透明の鱗片状無機粉末を配合した塗料組成物でクリア塗膜を成膜すると、これまでにない全く新しい意匠がクリア塗装金属板に付与される。発現した意匠は、屈折率の低いアルキルシリコーン樹脂に半透明の鱗片状無機粉末を分散させることによって始めて得られるものであり、イメージ的には「透明度の高い海に泳ぐクラゲ」と表現される。因みに、同じ鱗片状無機粉末を有機樹脂クリア塗膜に分散させても、アクリル又はエポキシ樹脂と鱗片状無機粉末との屈折率が近いため、塗膜のマトリックスから鱗片状無機粉末を分別できず、同様なイメージの意匠が発現しない。
【００１１】
クリア塗膜に分散させた鱗片状無機粉末は、基材・金属板の面内方向に沿って層状に配向する。そのため、面内方向に直交する視野角でクリア塗装金属板を観察する場合、鱗片状無機粉末の薄い辺を透過する光路となり、高い透明性が維持される。更に、各種の酸化物で被覆した鱗片状無機粉末を分散させると、面内方向に斜交する視野角でクリア塗装金属板を観察する場合、パール調干渉色を呈する意匠が得られる。
【００１２】
アルキルシリコーン樹脂に配合した鱗片状無機粉末は、３００〜４００℃の中間温度域における塗膜性状を改善する上でも有効である。
通常のアルキルシリコーン樹脂塗料から成膜されたクリア塗膜では、アルキル基：Ｓｉ−Ｒの熱分解が３００〜３５０℃の温度域で進行するが、この状態で加熱・冷却が繰り返されると基材・金属板とクリア塗膜との熱膨張差に起因した熱歪がクリア塗膜に蓄積される。熱歪は、クリア塗膜の脆化を加速させ、クラックや剥離の原因になる。しかも、塗膜のバリア効果による耐水性，耐食性，耐食品汚染性も低下しているので、水やイオンが容易に透過して基材／塗膜の界面に達し、基材・金属板に対するクリア塗膜の密着性を低下させる。
【００１３】
これに対し、鱗片状無機粉末を分散させたアルキルシリコーン樹脂塗膜では、基材・金属板の面内方向に配向している鱗片状無機粉末でネットワーク構造が補強され、クリア塗膜の脆化が防止される。基材・金属板とクリア塗膜の熱膨張差に起因する熱応力も鱗片状無機粉末でクリア塗膜の全体に分散されるので、塗膜剥離，脆化等の原因となる局部的な応力集中が抑制される。基材・金属板の面内方向に配向した鱗片状無機粉末が透過水分や腐食促進因子に対するバリアとしても働き、基材／塗膜の界面への水分やイオンの到達が抑制されることによっても塗膜物性が改善される。
【００１４】
タルク粉，カオリン等の鱗片状酸化物やＴｉＯ2，ＳｉＯ2，ＺｒＯ2等の酸化物で被覆したフレークは、−ＯＨ基がある程度存在する表面をもっている。そのため、この種の鱗片状無機粉末を配合したアルキルシリコーン樹脂塗料を基材・金属板に塗布し焼成する過程で鱗片状無機粉末表面の−ＯＨ基がアルキルシリコーン樹脂の−ＯＨ基と脱水縮合反応し、アルキルシリコーン樹脂と鱗片状無機粉末との間に強固な結合が形成される。これによっても、クリア塗膜の脆化防止が図られる。
【００１５】
【実施の形態】
塗装原板には、金属光沢のある表面が観察される製品形態で使用されることから、平坦度の高いステンレス鋼板，アルミニウム板，アルミニウム合金板，銅板，銅合金板，溶融Ａｌめっき鋼板の圧延材，マグネシウム板，マグネシウム合金板等が使用される。
金属光沢は、ブラシ等を用いた物理的な表面研磨，光輝焼鈍，圧延，電解研磨，化学エッチング等によって表面を平滑化することにより基材・金属板に付与される。基材・金属板の光沢度は特に制約されるものではないが、発現する意匠が金属光沢に応じて変化するので用途や好みに応じて金属光沢を調整する。金属光沢は、一般に光沢計で測定した光沢度として表され、金属の種類によって光沢度の絶対値が若干異なるが、目安として２０度鏡面光沢計で測定した光沢度が約５００以上の基材・金属板であれば目標とする意匠が発現する。過度に低い光沢度では、基材表面での乱反射が多くなり、目標とする意匠が得られない。
塗装原板は、クリア塗膜の形成に先立って脱脂，酸洗，クロメート処理，リン酸塩処理，クロムフリー処理等の塗装前処理が適宜施される。
【００１６】
クリア塗膜形成用の塗料組成物は、メチルシリコーン樹脂，フェニルシリコーン樹脂，メチルフェニルシリコーン樹脂等のアルキルシリコーン樹脂に鱗片状無機粉末を配合することにより調製される。鱗片状無機粉末には、アルミナフレーク，マイカ粉，タルク粉，板状カオリン、又は２種以上のこれらのフレークを組み合わせて使用することも可能である。
【００１７】
鱗片状無機粉末は、クリア塗膜に独特の意匠性を付与し、耐熱性，加工性を改善する上で平均粒径を０．５〜５０μｍとし、樹脂固形分に対する配合量を５〜１００質量部の範囲で選定することが好ましい。鱗片状無機粉末の分散による塗膜性状の改善効果は、０．５質量部以上の配合量で顕著になる。しかし、１００質量部を超える過剰量の鱗片状無機粉末を配合すると、クリア塗膜の加工密着性が低下する傾向がみられる。焼成顔料，体質顔料，防錆顔料，金属粉等の各種添加材と鱗片状無機粉末を併用添加できるが、併用添加の場合には合計配合量の上限を２００質量部に設定することが好ましい。
【００１８】
クリア塗膜に分散した鱗片状無機粉末が意匠性，塗膜性状に及ぼす影響は鱗片状無機粉末の形状によっても異なるが、平均粒径０.５μｍ以上で鱗片状無機粉末の分散効果が顕著になる。しかし、５０μｍを超える平均粒径ではクリア塗膜の加工密着性が低下する傾向にある。より好ましくは、平均粒径が１〜３０μｍの範囲にある鱗片状無機粉末を使用する。
平均粒径に対する厚みの比（アスペクト比）１／５以下のフレーク形状をもつ鱗片状無機粉末は、基材・金属板の面内方向に沿った配向性が高く、シロキサン結合：Ｓｉ−Ｏのネットワーク構造を効果的に補強する。アスペクト比が大きくなると、面内方向に交差する方向に鱗片状無機粉末の配向することが避けられず、鱗片状無機粉末の単位重量当り鱗片状無機粉末／シリコーン樹脂の接触面積が小さくなり、鱗片状無機粉末の添加効果が弱くなる。
【００１９】
アスペクト比は、鱗片状無機粉末の必要な透明度を付与する上でも有効である。アスペクト比が大きくなるほど透明度が低下する。逆にアスペクト比が小さくなると透明度が増す。アスペクト比を極端に小さくするとアルキルシリコーン樹脂と同じ透明度になり、目標とする意匠が発現しなくなる。しかし、アルキルシリコーン樹脂の透明度と同程度になるまでアスペクト比を小さくすることは工業的に困難であり、工業的に入手容易なアスペクト比１／５以下の鱗片状無機粉末であれば目標とする意匠の発現に有効な透明度が確保される。
【００２０】
鱗片状無機粉末は、ＴｉＯ2，ＳｉＯ2，ＺｒＯ2，Ｆｅ2Ｏ3，Ｆｅ3Ｏ4，ＳｎＯ2，Ｃｒ2Ｏ3，ＺｎＯ，Ａｌ2Ｏ3等の透明な金属酸化物で被覆しても良い。被覆には湿式法，ＣＶＤ法，粉末スパッタリング法，蒸着法等が採用される。金属酸化物皮膜を設けた鱗片状無機粉末は、光の干渉作用によってパール色の色調をクリア塗膜に付与する。
光の干渉作用で発現する色調は、金属酸化物皮膜の厚みに応じて異なるが、厚すぎる金属酸化物皮膜では干渉色が消え透明性が損なわれる。金属酸化物皮膜の屈折率や透明度は、金属酸化物の種類によって異なり、鱗片状無機粉末の種類や表面形状にも影響されるため、膜厚の上限を一義的に定めることはできないが、０.５μｍ以下を目安として目視観察で判定した発現意匠の視認性から金属酸化物皮膜の厚みを定めることができる。
【００２１】
アルキルシリコーン樹脂塗料には、鱗片状無機粉末の他に着色顔料も配合できる。着色顔料を配合する場合、透明な外観や塗膜の光沢度等の意匠性を損なわず、また耐熱性，塗膜密着性等の諸性能を低下させない着色顔料の種類，粒形状，性状，添加量が決定される。
【００２２】
鱗片状無機粉末が配合される樹脂塗料は、メチルシリコーン樹脂，フェニルシリコーン樹脂，メチルフェニルシリコーン樹脂から選ばれた１種又は２種以上の混合物又は重合物をベース樹脂にしている。
メチルシリコーン樹脂は一般式(ＣＨ3)aＳｉＯ(4-a-b)/2(ＯＨ)bで表される化合物であり、ブロッキングを起こすことなく塗膜に必要硬度を付与し、長時間焼付けを必要とせずコイルでの連続塗装を可能にするため指数ａ，ｂをそれぞれａ=０.５〜１.５，ｂ＝０.５〜１.０５の範囲に設定することが好ましい。ａ＜０.５では塗膜の加工密着性が低下し、ａ＞１.５では耐熱性が劣る。ｂ＜０.５では塗装原板に配向した水酸基との脱水縮合によって結合する起点が少なくなるため、塗膜の加工密着性，硬化性が劣化する。逆にｂ＞１.０５では、焼成時に三次元架橋が過度に進行して塗膜の加工密着性が低下する。
【００２３】
フェニルシリコーン樹脂をベースとする塗料組成物では、一般式(Ｃ6Ｈ5)aＳｉＯ(4-a-b)/2(ＯＨ)bで表されるフェニルシリコーン樹脂が使用される。この場合も、指数ａ，ｂは、メチルシリコーン樹脂と同じ理由でそれぞれａ=０.５〜１.５，ｂ＝０.５〜１.０５の範囲に設定することが好ましい。
メチルフェニルシリコーン樹脂は一般式(ＣＨ3)a(Ｃ6Ｈ5)bＳｉＯ(4-a-b-c)/2(ＯＨ)cで表される化合物であり、指数ａ，ｂ，ｃは同様な理由からそれぞれａ＋ｂ=０.５〜１.５，ｃ＝０.５〜１.０５の範囲に設定することが好ましい。
【００２４】
アルキルシリコーン樹脂は、目的や用途に応じて樹脂種が選択される。たとえば、アルキルシリコーン樹脂のフェニル基はメチル基よりも熱分解温度が高く、TG-DTA分析ではフェニル基が約４５０℃，メチル基が約４１０℃に熱分解のピークが検出される。したがって、フェニル基やメチル基が残存する温度域で使用される用途では、メチル基よりも耐酸性，耐薬品性，耐水性に優れているフェニル基をもつフェニルシリコーン樹脂又はフェニル基を多く含む重合物が使用される。また、アルキル基：Ｓｉ−Ｒの熱分解温度以上でフェニル基から発生するベンゼンが問題となる用途では、メチルシリコーン樹脂単独，或いはフェニル基を許容範囲に抑えたフェニルシリコーン樹脂，メチルフェニルシリコーン樹脂との混合物又は重合物が塗料組成物のベース樹脂に使用される。
【００２５】
鱗片状無機粉末が配合された塗料組成物は、塗装前処理が施された塗装原板に塗布され，加熱・乾燥によってクリア塗膜となる。塗料組成物の塗布には、スプレー法，ロールコート法，バーコート法等を採用できる。塗布された塗料組成物は、クリア塗膜の硬度を保証し、加工密着性を確保するため好ましくは１５０〜２５０℃の範囲で加熱・乾燥される。塗料組成物の塗布量は、クリア塗膜の乾燥膜厚が２〜１５μｍ（好ましくは、１０μｍ以下）となるように選定される。２μｍ以上の膜厚で耐食性改善効果が顕著になるが、１５μｍを超える厚膜ではクリア塗膜の加工密着性が低下する。
【００２６】
【実施例】
塗装原板に板厚０.４ｍｍのSUS304ステンレス鋼板，板厚２ｍｍのアルミニウム板，板厚０.４ｍｍの溶融Ａｌめっき鋼板の圧延材を使用した。ステンレス鋼板は、２％塩酸で酸洗した後、塗布型クロメート処理でＣｒ換算付着量２０ｍｇ／ｍ2のクロメート皮膜を形成した。アルミニム板，溶融Ａｌめっき鋼板圧延材は、脱脂，水洗，乾燥後、Ｔｉ換算付着量４０ｍｇ／ｍ2のＴｉ系クロムフリー処理を施した。
塗料組成物は、アルキルシリコーン樹脂１００質量部に対し各種鱗片状無機粉末を２０質量部配合することにより調製した。用意した塗料組成物の組成，鱗片状無機粉末等を表１に示す。
【００２７】
各塗料組成物を塗装原板にバーコート法で塗布し、最高到達板温２３０℃で加熱焼成することにより乾燥膜厚６μｍのクリア塗膜を形成した。得られたクリア塗装金属板から試験片を切り出し、意匠性試験，耐熱試験，腐食試験，食品汚染試験に供した。
意匠性試験では、試験片表面を目視観察し、クリア塗膜の透明性，基材・金属板の金属光沢，添加粉末に起因する意匠発現の全てを満足するものを○，何れかの性質が損なわれているものを×として官能評価した。
【００２９】
耐熱試験では、試験片を５００℃に１００時間加熱した後、クリア塗膜の密着性をテープ剥離試験で調査した。剥離が生じなかった塗膜を◎，点状の剥離が一部に生じた塗膜を○，著しい点状剥離が生じた塗膜を△，全面剥離した塗膜を×としてクリア塗膜の耐熱性を評価した。
腐食試験では、未加熱の試験片の他に、３００℃×１０時間の加熱を施した試験片を用意した。未加熱試験片，加熱試験片共に１００時間の塩水噴霧試験にかけ、塩水噴霧後の塗膜密着性をテープ剥離試験で判定した。剥離が生じなかった塗膜を◎，点状の剥離が一部に生じた塗膜を○，著しい点状剥離が生じた塗膜を△，全面剥離した塗膜を×としてクリア塗膜の耐食性を評価した。
【００３０】
食品汚染試験では、未加熱の試験片の他に、３５０℃×１０時間の加熱を施した試験片を用意した。未加熱試験片及び加熱試験片に醤油，マヨネーズ，ケチャップを各１ｇ混合した試験液を塗布し、試験片を水平に保った状態で６０℃，９０％ＲＨの恒温恒湿槽に８時間保管した後、室温に１６時間放置した。高温湿潤→室温放置を１サイクルとし、３サイクル繰り返した後で試験片表面を目視観察し、ガーゼを用いて試験液を拭き取った後の汚染状態を調査した。試験液で汚染されていない塗膜を◎，汚染が生じたが拭取り可能な塗膜を○，著しい汚染が生じたが拭取り可能な塗膜を△，汚染が拭き取れずに全面に残留した塗膜を×としてクリア塗膜の耐食品汚染性を評価した。
【００３１】
表２の試験結果にみられるように、アルキルシリコーン樹脂塗膜に鱗片状無機粉末を分散させた本発明例Ｎo.１〜９は、意匠性，耐熱性，耐食性，耐食品汚染性の何れにおいても優れた特性を示した。
他方、アクリル樹脂をベースとするクリア塗膜を設けた比較例Ｎo.１０や鱗片状粉末無添加の比較例Ｎo.１１では、「透明度の高い海に泳ぐクラゲ」のイメージを呈する外観が得られず、耐熱性，耐食性，耐食品汚染性にも劣っていた。なかでも、アクリル樹脂をベースとするクリア塗膜は、３００℃×１０時間や３５０℃×１０時間の加熱によって消失した。球状シリカをクリア塗膜に分散させた比較例Ｎo.１２でも、本発明例Ｎo.１〜９のようなイメージをもつ外観が得られず、耐熱性，耐食性，耐食品汚染性にも劣っていた。
この対比から明らかなように、ベース樹脂として透明度の高いアルキルシリコーン樹脂を使用し、半透明の鱗片状無機粉末を分散させたクリア塗膜を形成することにより、これまでにない意匠を呈し、耐熱性，耐食性，耐食品汚染性にも優れたクリア塗装金属板が得られることが確認された。
【００３２】
【発明の効果】
以上に説明したように、透明度の高いアルキルシリコーン樹脂をベースにし、半透明の鱗片状無機粉末を配合した塗料組成物からクリア塗膜を成膜すると、基材・金属板の面内方向に鱗片状無機粉末が配向し、イメージ的にはこれまでにない外観を呈するクリア塗装金属板が得られる。しかも、クリア塗膜に分散させた鱗片状無機粉末が中間温度域におけるネットワーク構造を補強するため、耐熱性，耐食性，耐食品汚染性も改善される。このようにして得られた耐熱クリアプレコート金属板は、独特の意匠性がある外観と相俟って優れた耐熱性，耐食性，耐食品汚染性を活かし、加熱調理器具，暖房機器，空調機器，自動車排気系部材等の広範な分野で使用される。[0001]
[Industrial application fields]
The present invention relates to a heat-resistant clear pre-coated metal sheet that exhibits a color tone utilizing the metallic luster of a base material and is used in cooking utensils, heating equipment, air-conditioning equipment, automobile exhaust system members, and the like that require heat resistance.
[0002]
[Prior art]
Clear painted metal plates that make use of the metallic surface of metal surfaces have begun to be used for cover materials such as home appliances, OA devices, cooking devices, and heating devices. The clear painted metal plate is expected as a highly discriminating product because an atmosphere that cannot be obtained with a conventional colored painted metal plate is created with a metallic feeling. Various organic resin paints such as urethane, polyolefin, and fluorine are used for the production of clear painted metal plates. In some cases, organic resin paints such as acrylic and epoxy are used as relatively high transparency.
When a clear paint in which a color pigment is dispersed is applied to a substrate or a metal plate, an arbitrary color tone can be imparted while taking advantage of the metallic feel of the metal surface. When blending the color pigment, some ideas are required for selecting the material of the color pigment, selecting the blend amount, etc. so that the metal surface is not completely hidden until the metallic feeling disappears.
[0003]
With the development of applications for clear-painted metal plates, there is an increasing need for clear-painted metal plates that can be used in heat-resistant parts exposed to high-temperature environments, such as cooking utensils, heating equipment, air conditioning equipment, and automobile exhaust systems. . However, the clear coated metal plate using the conventional organic resin paint has a limit of the heat resistance temperature of about 200 ° C, and when used at a higher temperature than that, yellowing, cracks, Peeling occurs. When an organic pigment or dye is used as the colorant, discoloration or discoloration of the colorant due to heat tends to occur.
For clear coated metal plates used for heat resistance applications, it has been studied to form a clear coating film using a silicone resin having excellent heat resistance. The present inventors have also proposed a heat-resistant precoated steel plate using an alkyl silicone resin.
[0004]
[Problems to be solved by the invention]
Alkyl group: Si—R (R: methyl or phenyl group) contained in alkyl silicone resin such as methyl silicone resin, phenyl silicone resin, methyl phenyl silicone resin, etc. starts a decomposition reaction by heating at 300 to 350 ° C. On the other hand, when a siloxane bond: Si-O proceeds by a dehydration condensation reaction between silanol groups: Si-OH in a silicone resin to form a sufficient network structure, heating at 400 ° C or higher is required for a long time. .
[0005]
Since there is a temperature difference between the thermal decomposition of the alkyl group: Si-R and the formation of the siloxane bond: Si-O, the alkyl group: Si-R is thermally decomposed in the intermediate temperature range of 300 to 400 ° C, but sufficient Siloxane bond necessary for forming a simple network structure: Si—O does not progress. As a result, the coating film formed from the alkyl silicone resin paint temporarily becomes an unstable film state in the intermediate temperature range.
Considering the operating temperature and usage environment of cooking utensils, heating equipment, air conditioning equipment, automobile exhaust system members, etc., the temperature rises over a wide temperature range from room temperature to high temperature of about 600 ° C, as well as corrosion resistance and contamination resistance. Excellent coating film performance without cracks or peeling is required even when receiving a heat history of decreasing temperature.
[0006]
[Means for Solving the Problems]
The present invention has been devised to meet such demands, and the metallic feeling is emphasized by dispersing transparent scaly powder in a clear coating film based on a highly transparent alkyl silicone resin. An object of the present invention is to provide a heat-resistant clear pre-coated metal plate that has a high transparency and has a metallic luster that expresses a unique design and is excellent in heat resistance and workability.
[0007]
In order to achieve the object, the heat-resistant clear precoated metal plate of the present invention forms a clear coating film of an alkyl silicone resin in which a translucent scaly inorganic powder is dispersed on the surface of a substrate / metal plate exhibiting a metallic luster. It is characterized by being. The alkyl silicone resin includes one or a mixture of two or more selected from methyl silicone resin, phenyl silicone resin, and methyl phenyl silicone resin.
[0008]
The scale-like inorganic powders, the alumina flakes, mica powder, talc powder, preferably plate-like kaolin or we selected the one or more kinds, TiO 2, SiO 2, ZrO 2, Fe 2 O 3, Fe 3 O 4, SnO 2, Cr 2 O 3, ZnO, coated if necessary with a transparent oxide selected from one or more of Al 2 O 3.
[0009]
[Action]
The clear coating film is formed from an alkyl silicone resin paint such as methyl silicone resin, phenyl silicone resin, or methyl phenyl silicone resin. The alkyl silicone resin is a highly transparent resin having a refractive index lower than that of the acrylic resin or epoxy resin having the lowest refractive index among organic resins. Although the measured value of the refractive index varies slightly depending on the measurement conditions, the refractive index of the alkyl silicone resin is about 1.4 compared to about 1.5 of the acrylic resin or epoxy resin. The difference between the two is about 0.1. However, when visually observing the coating film provided on the metallic glossy substrate / metal plate, a great difference is caused in the way of receiving the metallic gloss. That is, in the alkyl silicone resin coating film, the metallic luster is not impaired at all and a clear appearance is maintained, but in the acrylic resin or epoxy resin coating film, the transparency is inferior and the appearance is dull.
[0010]
When a clear coating film is formed with a coating composition in which a translucent scaly inorganic powder is blended with a highly transparent alkyl silicone resin, an unprecedented new design is imparted to the clear painted metal plate. The developed design is obtained for the first time by dispersing a translucent scaly inorganic powder in an alkyl silicone resin having a low refractive index, and is imagely expressed as “jellyfish swimming in a highly transparent sea”. By the way, even if the same scaly inorganic powder is dispersed in the organic resin clear coating film, since the refractive index of the acrylic or epoxy resin and the scaly inorganic powder is close, the scaly inorganic powder cannot be separated from the coating matrix, The design of the same image does not appear.
[0011]
The scaly inorganic powder dispersed in the clear coating film is oriented in layers along the in-plane direction of the substrate / metal plate. For this reason, when a clear-coated metal plate is observed at a viewing angle orthogonal to the in-plane direction, an optical path is transmitted through the thin side of the scaly inorganic powder, and high transparency is maintained. Furthermore, when the scaly inorganic powder coated with various oxides is dispersed, when a clear painted metal plate is observed at a viewing angle oblique to the in-plane direction, a design exhibiting a pearl-like interference color is obtained.
[0012]
The scaly inorganic powder blended in the alkyl silicone resin is also effective in improving the coating properties in the intermediate temperature range of 300 to 400 ° C.
In a clear coating film formed from an ordinary alkyl silicone resin paint, the thermal decomposition of the alkyl group: Si—R proceeds in the temperature range of 300 to 350 ° C. If the heating and cooling are repeated in this state, the substrate -Thermal strain due to the difference in thermal expansion between the metal plate and the clear coating film is accumulated in the clear coating film. Thermal strain accelerates embrittlement of the clear coating film and causes cracks and peeling. In addition, the water resistance, corrosion resistance, and food contamination resistance due to the barrier effect of the coating film are also reduced, so water and ions can easily pass through and reach the substrate / coating interface, clearing the substrate / metal plate. Reduce the adhesion of the coating.
[0013]
On the other hand, in the alkyl silicone resin coating film in which the flaky inorganic powder is dispersed, the network structure is reinforced by the flaky inorganic powder oriented in the in-plane direction of the substrate / metal plate, and the clear coating film becomes brittle. Is prevented. Thermal stress caused by the difference in thermal expansion between the base material / metal plate and the clear coating is also dispersed throughout the clear coating with scaly inorganic powder, so local stress that causes peeling and embrittlement of the coating Concentration is suppressed. The scale-like inorganic powder oriented in the in-plane direction of the substrate / metal plate also acts as a barrier against permeated moisture and corrosion-promoting factors, and also prevents moisture and ions from reaching the substrate / coating interface. The film properties are improved.
[0014]
Flakes coated with scaly oxides such as talc powder and kaolin and oxides such as TiO 2 , SiO 2 , and ZrO 2 have a surface on which some —OH groups exist. Therefore, dehydration condensation reaction between the —OH group on the surface of the scaly inorganic powder and the —OH group of the alkyl silicone resin in the process of applying and baking an alkyl silicone resin coating containing this kind of scaly inorganic powder on the substrate / metal plate In addition, a strong bond is formed between the alkyl silicone resin and the scaly inorganic powder. This also prevents embrittlement of the clear coating film.
[0015]
Embodiment
Since the coating original plate is used in a product form in which a metallic glossy surface is observed, a rolled material of stainless steel plate, aluminum plate, aluminum alloy plate, copper plate, copper alloy plate, hot-dip Al-plated steel plate with high flatness , Magnesium plate, magnesium alloy plate, etc. are used.
The metallic luster is imparted to the substrate / metal plate by smoothing the surface by physical surface polishing using a brush or the like, bright annealing, rolling, electrolytic polishing, chemical etching, or the like. The glossiness of the base material / metal plate is not particularly limited, but the design to be developed changes according to the metallic luster, so the metallic luster is adjusted according to the use and preference. Metal gloss is generally expressed as gloss measured with a gloss meter, and the absolute value of gloss varies slightly depending on the type of metal. As a guide, substrates with a gloss measured by a 20-degree specular gloss meter of about 500 or more If it is a metal plate, the target design will be manifested. If the glossiness is excessively low, irregular reflection on the surface of the substrate increases, and the target design cannot be obtained.
Prior to the formation of the clear coating film, the coating original plate is appropriately subjected to pre-coating treatments such as degreasing, pickling, chromate treatment, phosphate treatment, and chromium-free treatment.
[0016]
The coating composition for forming a clear coating film is prepared by blending a scaly inorganic powder with an alkyl silicone resin such as a methyl silicone resin, a phenyl silicone resin, or a methyl phenyl silicone resin. The scale-like inorganic powders, the alumina flakes, mica powder, talc powder, it is also possible to use a combination of plate-like kaolin, or two or more of these flakes.
[0017]
The scale-like inorganic powder imparts a unique design to the clear coating, improves the heat resistance and processability, has an average particle size of 0.5 to 50 μm, and a blending amount with respect to the resin solid content of 5 to 100 mass. It is preferable to select within the range of parts. The effect of improving the properties of the coating film due to the dispersion of the scaly inorganic powder becomes significant when the amount is 0.5 parts by mass or more. However, when an excessive amount of scaly inorganic powder exceeding 100 parts by mass is blended, the processing adhesion of the clear coating film tends to be lowered. Various additives such as calcined pigments, extender pigments, rust preventive pigments, metal powders, and scale-like inorganic powders can be added in combination, but in the case of combined addition, the upper limit of the total blending amount is preferably set to 200 parts by mass.
[0018]
The influence of the flaky inorganic powder dispersed in the clear coating on the design and coating properties varies depending on the shape of the flaky inorganic powder, but the dispersion effect of the flaky inorganic powder is significant when the average particle size is 0.5 μm or more. Become. However, when the average particle size exceeds 50 μm, the processing adhesion of the clear coating film tends to decrease. More preferably, a scaly inorganic powder having an average particle diameter in the range of 1 to 30 μm is used.
The scale-like inorganic powder having a flake shape with a thickness ratio (aspect ratio) of 1/5 or less with respect to the average particle diameter has high orientation along the in-plane direction of the base material / metal plate, and has a siloxane bond: Si-O. Effectively reinforce the network structure. When the aspect ratio is increased, it is inevitable that the scale-like inorganic powder is oriented in the direction intersecting the in-plane direction, and the contact area of the scale-like inorganic powder / silicone resin per unit weight of the scale-like inorganic powder is reduced. The effect of adding the inorganic powder becomes weak.
[0019]
The aspect ratio is also effective in providing the necessary transparency of the scaly inorganic powder. As the aspect ratio increases, the transparency decreases. Conversely, the transparency increases as the aspect ratio decreases. If the aspect ratio is extremely small, the transparency becomes the same as that of the alkyl silicone resin, and the target design is not expressed. However, it is industrially difficult to reduce the aspect ratio until the transparency of the alkyl silicone resin is the same as that of the alkyl silicone resin, and a scale-like inorganic powder having an aspect ratio of 1/5 or less that is easily available industrially is the target. Transparency effective for the development of the design is ensured.
[0020]
Scale-like inorganic powder is coated with TiO 2, SiO 2, ZrO 2 , Fe 2 O 3, Fe 3 O 4, SnO 2, Cr 2 O 3, ZnO, transparent metal oxides such as Al 2 O 3 Also good. For coating, a wet method, a CVD method, a powder sputtering method, a vapor deposition method, or the like is employed. The scaly inorganic powder provided with the metal oxide film imparts a pearl color tone to the clear coating film by the interference of light.
The color tone developed by the interference action of light varies depending on the thickness of the metal oxide film, but if the metal oxide film is too thick, the interference color disappears and the transparency is impaired. The refractive index and transparency of the metal oxide film vary depending on the type of metal oxide and are also affected by the type and surface shape of the scaly inorganic powder, so the upper limit of the film thickness cannot be uniquely determined. The thickness of the metal oxide film can be determined from the visibility of the developed design determined by visual observation with a reference of .5 μm or less.
[0021]
In addition to the scaly inorganic powder, a coloring pigment can be blended in the alkyl silicone resin paint. When coloring pigments are blended, the type, grain shape, properties and additions of the colored pigments that do not impair the appearance such as the transparent appearance and the glossiness of the coating film, and do not degrade the performance such as heat resistance and coating adhesion The amount is determined.
[0022]
The resin paint in which the scaly inorganic powder is blended is based on one or a mixture or polymer of two or more selected from methyl silicone resin, phenyl silicone resin, and methyl phenyl silicone resin.
Methyl silicone resin is a compound represented by the general formula (CH 3 ) a SiO (4-ab) / 2 (OH) b , which gives the coating film the required hardness without blocking and requires long-time baking. In order to enable continuous coating with a coil, the indices a and b are preferably set in the range of a = 0.5 to 1.5 and b = 0.5 to 1.05, respectively. When a <0.5, the work adhesion of the coating film decreases, and when a> 1.5, the heat resistance is inferior. When b <0.5, the starting point of bonding due to dehydration condensation with the hydroxyl group oriented on the coating original sheet is reduced, so that the work adhesion and curability of the coating film deteriorate. On the other hand, when b> 1.05, three-dimensional crosslinking proceeds excessively at the time of firing, and the work adhesion of the coating film decreases.
[0023]
In a coating composition based on a phenyl silicone resin, a phenyl silicone resin represented by the general formula (C 6 H 5 ) a SiO (4-ab) / 2 (OH) b is used. Also in this case, the indices a and b are preferably set in the range of a = 0.5 to 1.5 and b = 0.5 to 1.05 for the same reason as that of the methyl silicone resin.
Methylphenyl silicone resin is a compound represented by the general formula (CH 3 ) a (C 6 H 5 ) b SiO (4-abc) / 2 (OH) c , and the indices a, b and c are the same for the same reason. It is preferable to set a + b = 0.5 to 1.5 and c = 0.5 to 1.05, respectively.
[0024]
As the alkyl silicone resin, a resin type is selected according to the purpose and application. For example, the phenyl group of the alkyl silicone resin has a higher thermal decomposition temperature than the methyl group, and the TG-DTA analysis detects a thermal decomposition peak at about 450 ° C. for the phenyl group and about 410 ° C. for the methyl group. Therefore, in applications that are used in the temperature range where phenyl groups or methyl groups remain, phenyl silicone resins having phenyl groups that are superior in acid resistance, chemical resistance, and water resistance to methyl groups, or polymerizations that contain many phenyl groups Things are used. In addition, in applications where alkyl groups: benzene generated from phenyl groups at a temperature higher than the thermal decomposition temperature of Si-R is a problem, methylsilicone resin alone or phenylsilicone resin having a phenyl group within an allowable range, methylphenylsilicone resin and Or a polymer thereof is used as the base resin of the coating composition.
[0025]
The coating composition in which the scaly inorganic powder is blended is applied to a coated original plate that has been subjected to a pre-coating treatment, and becomes a clear coating film by heating and drying. For applying the coating composition, a spray method, a roll coating method, a bar coating method, or the like can be employed. The applied coating composition is preferably heated and dried in the range of 150 to 250 ° C. in order to guarantee the hardness of the clear coating film and to ensure processing adhesion. The coating amount of the coating composition is selected so that the dry film thickness of the clear coating film is 2 to 15 μm (preferably 10 μm or less). When the film thickness is 2 μm or more, the effect of improving the corrosion resistance becomes remarkable. However, when the film thickness exceeds 15 μm, the processing adhesion of the clear coating film decreases.
[0026]
【Example】
A rolled material of a 0.4 mm thick SUS304 stainless steel plate, a 2 mm thick aluminum plate, and a 0.4 mm thick molten Al-plated steel plate was used as the coating original plate. The stainless steel plate was pickled with 2% hydrochloric acid, and then a chromate film having a Cr conversion deposit of 20 mg / m 2 was formed by coating-type chromate treatment. The aluminum sheet and the rolled aluminum-plated steel sheet were degreased, washed with water and dried, and then subjected to a Ti-based chromium-free treatment with a Ti equivalent adhesion amount of 40 mg / m 2 .
The coating composition was prepared by blending 20 parts by mass of various scaly inorganic powders with respect to 100 parts by mass of the alkyl silicone resin. Table 1 shows the composition of the prepared coating composition, the scale-like inorganic powder, and the like.
[0027]
Each coating composition was applied to a coating original plate by a bar coating method, and heated and fired at a maximum reached plate temperature of 230 ° C. to form a clear coating film having a dry film thickness of 6 μm. A test piece was cut out from the obtained clear painted metal plate and subjected to a design test, a heat test, a corrosion test, and a food contamination test.
In the design property test, the surface of the test piece is visually observed, and any of the properties satisfying all of the transparency of the clear coating film, the metallic luster of the base material / metal plate, and the design expression caused by the added powder. Sensory evaluation was carried out by making x what was damaged.
[0029]
In the heat resistance test, the test piece was heated to 500 ° C. for 100 hours, and then the adhesion of the clear coating film was examined by a tape peeling test. Heat resistance of clear coating film: ◎ for coatings that did not peel, ◯ for coatings with some spot-like peeling, △ for coatings with significant spot-like peeling, and × for coatings with full peeling Sex was evaluated.
In the corrosion test, in addition to the unheated test piece, a test piece subjected to heating at 300 ° C. for 10 hours was prepared. Both the unheated test piece and the heated test piece were subjected to a salt spray test for 100 hours, and the adhesion of the coating film after the salt spray was determined by a tape peeling test. Corrosion resistance of clear coatings: ◎ for coatings with no peeling, ○ for coatings with some spot-like peeling, △ for coatings with significant point peeling, and × for coatings with full peeling Evaluated.
[0030]
In the food contamination test, in addition to the unheated test piece, a test piece subjected to heating at 350 ° C. for 10 hours was prepared. A test solution in which 1 g each of soy sauce, mayonnaise, and ketchup was mixed was applied to an unheated test piece and a heated test piece, and the test piece was kept in a horizontal state at 60 ° C. and 90% RH for 8 hours. Then, it was left at room temperature for 16 hours. High temperature wet → left at room temperature as one cycle, and after repeating 3 cycles, the surface of the test piece was visually observed, and the contamination state after wiping off the test solution using gauze was investigated. A coating film that is not contaminated with the test solution ◎, a coating film that has been contaminated but can be wiped off, a coating film that has been markedly contaminated but can be wiped off, and the contamination remained on the entire surface without being wiped off. The food coating resistance of the clear coating film was evaluated with x as the coating film.
[0031]
As seen in the test results of Table 2, Examples No. 1 to 9 of the present invention in which scaly inorganic powder is dispersed in an alkyl silicone resin coating film are in any of the design properties, heat resistance, corrosion resistance, and food contamination resistance. Also showed excellent properties.
On the other hand, Comparative Example No. 10 provided with a clear coating film based on acrylic resin and Comparative Example No. 11 with no scaly powder added have the appearance of a “jellyfish swimming in a highly transparent sea”. In addition, it was inferior in heat resistance, corrosion resistance and food contamination resistance. Especially, the clear coating film based on an acrylic resin disappeared by heating at 300 ° C. × 10 hours or 350 ° C. × 10 hours. Even in Comparative Example No. 12 in which spherical silica is dispersed in a clear coating film, an appearance having the image as in Invention Examples No. 1 to 9 cannot be obtained, and heat resistance, corrosion resistance, and food contamination resistance are inferior. It was.
As is clear from this comparison, a highly transparent alkyl silicone resin is used as the base resin, and by forming a clear coating film in which semi-transparent scale-like inorganic powder is dispersed, an unprecedented design is exhibited, It was confirmed that a clear coated metal plate with excellent resistance, corrosion resistance, and food contamination resistance can be obtained.
[0032]
【The invention's effect】
As explained above, when a clear coating film is formed from a coating composition based on a highly transparent alkyl silicone resin and blended with semitransparent scaly inorganic powder, scaly scales are formed in the in-plane direction of the substrate / metal plate. A clear-coated metal plate is obtained in which the shaped inorganic powder is oriented and has an image unprecedented appearance. In addition, since the scaly inorganic powder dispersed in the clear coating film reinforces the network structure in the intermediate temperature range, heat resistance, corrosion resistance, and food contamination resistance are also improved. The heat-resistant clear pre-coated metal plate obtained in this way, combined with its unique design appearance, makes use of its excellent heat resistance, corrosion resistance, and food contamination resistance, Used in a wide range of fields such as automobile exhaust system members.
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| JP2002214962A JP4046322B2 (en) | 2002-07-24 | 2002-07-24 | Heat-resistant clear pre-coated metal sheet with excellent design |
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| JP2002214962A JP4046322B2 (en) | 2002-07-24 | 2002-07-24 | Heat-resistant clear pre-coated metal sheet with excellent design |
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| JP4046322B2 true JP4046322B2 (en) | 2008-02-13 |
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| JP2006350118A (en) * | 2005-06-17 | 2006-12-28 | Kinyosha Co Ltd | Fixing unit roller |
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| US9011976B2 (en) | 2005-10-05 | 2015-04-21 | Nippon Steel & Sumitomo Metal Corporation | Titanium sheet covered with protective film superior in high temperature oxidation resistance and high temperature salt damage resistance, automobile exhaust system using same, and methods of production of same |
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| CN111816855B (en) * | 2020-07-20 | 2023-02-10 | 湖南金硅科技有限公司 | Preparation method of magnesium-containing silicon monoxide/silicon @ resin carbon/CVD carbon material |
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2002
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