JP3840688B2 - Printed metal plate with excellent design - Google Patents

Description

式中、Ｒｆ及びＲｆ’は、それぞれアルキル基の水素原子の一部又は全部をフッ素原子で置換したフルオロアルキル基，Ｄは−ＣＯ−，−ＳＯ₂ −又は−（ＣＨ₂)_z −（ただし、ｚは１〜１０の整数）、ＹはＣ₁ 〜Ｃ₆ のアルキレン基，Ｍは水素原子，ＮＨ₄ ，アルカリ金属又はアルカリ土類金属，Ｒ¹ は水素原子又は低級アルキル基を示す。
【００１０】
陽イオン性フッ素系界面活性剤

式中、Ｒｆ，Ｄ，Ｒ¹ 及びＹは前述と同じ、Ｒ² はＲ¹ と同じ、Ｒ³ はＣ₂ 〜Ｃ₃ のアルキレン基，ＨＸは酸，Ｘはハロゲン又は酸根である。
両性フッ素系界面活性剤
−Ｎ⁺(Ｒ¹)₂-ＣＯＯ^- ＲｆＤＮＨＹＮ⁺(Ｒ¹)₂ Ｙ’ＣＯＯ^-
式中、Ｒｆ，Ｄ，Ｒ¹ 及びＹは前述と同じ、Ｙ’はＣ₂ 〜Ｃ₆ のアルキレン基を示す。
【００１１】
非イオン性フッ素系界面活性剤

式中、Ｒｆ，Ｄ，Ｒ¹ ，Ｒ³ 及びＹは前述と同じ、Ｒ⁴ はＣ₁ 〜Ｃ₂₂のアルキル基，ｎは１〜３０の整数，ａ，ｂ，ｃはそれぞれ１〜１００の整数を示す。
【００１２】

フッ素系オイル
パーフルオロポリエーテル，クロロトリフルオロエチレン等の重合体や次式で示されるフッ素化炭化水素化合物が使用される。
【００１３】
［Ｌ＝ (Ａ)_q-(Ｂ)_r-(Ｃ)_s］ （ｑ，ｒ，ｓは０又は１）

【００１４】

【００１５】
パーフルオロアルキル基をもつ重合体
たとえば、次式で示されるパーフルオロアルキル基含有エチレン性不飽和単量体の重合体又は、この単量体と共重合しうる単量体からなる共重合体を主成分とするものが使用される。共重合しえる単量体としては、（メタ）アクリル酸のアルキルエステル，（メタ）アクリル酸シクロヘキシル基又はベンジルエステル，ジ（メタ）アクリル酸ポリエチレングリコール，Ｎ−メチロールアクリルアミド，エチレン，塩化ビニル，フッ化ビニル，（メタ）アクリル酸アミド，スチレン，α−メチルスチレン，ｐ−メチルスチレン，ビニルアルキルエーテル，ハロゲン化アルキルビニルエーテル，ビニルアルキルケトン，無水マレイン酸，ブダジエン，イソプレン，クロロプレン等が挙げられる。
【００１６】

【００１７】
式中、Ｒｆ”は炭素数４〜２０のパーフルオロアルキル基，Ｒ⁷ は水素原子又は炭素数１〜１０のアルキル基，Ｒ⁸ は水素原子又はメチル基，Ｒ¹⁰は炭素数１〜１７のアルキル基，ｅは１〜１０の整数，ｆは０〜１０の整数を示す。
塗膜改質剤の他の成分であるシリコーンオイルとしては、撥水・撥油性を発現するために２５℃における粘度が５０ｃＰ以上、或いは側鎖又は末端に反応性基をもつシリコーンオイルが好ましい。たとえば、ジメチルシリコーンオイル，メチル塩化シリコーンオイル，メチルフェニルシリコーンオイル，有機変性シリコーンオイル等があり、なかでも有機変性シリコーンオイルが好ましい。この種のシリコーンオイルとしては、具体的には以下に示す構造をもつものが知られており、ＰＲＸ４１３，ＳＦ８４１７，ＳＹ１６−８５５Ｂ，ＳＦ８４２７，ＳＦ８４２８（東レ・ダウコーニング社製），Ｘ−２２−１６１Ｃ，Ｘ−２２−１６３Ｃ，Ｘ−２２１６２Ａ，ＫＦ−６００１，ＫＦ−８５７（信越化学工業株式会社製）等が市販されている。
【００１８】

【００１９】
ポリフルオロカーボン鎖含有化合物及びシリコーンオイルは、塗膜形成成分１００重量部当りそれぞれ共に０.１０〜１.０重量部の割合で配合される。ポリフルオロカーボン鎖含有化合物及びシリコーン化合物の配合量が０．０１重量部よりも少ないと、撥水・撥油性及び耐汚染性が不十分となる。逆に３．０重量部を超える配合量では、ハジキや流れが生じ易く、平滑な塗膜が得られ難くなる。表面調整剤の添加によりハジキを防止することも可能であるが、ポリフルオロカーボン鎖含有化合物及びシリコーンオイルの量が多いと塗膜の硬度が低下し、耐汚染性が劣化する。耐汚染性及び平滑性を確保するためには、ポリフルオロカーボン鎖含有化合物及びシリコーンオイルの配合量を０.１０〜１.０重量部の範囲に調整する。なお、ポリフルオロカーボン鎖含有化合物及びシリコーンオイルの双方を添加することにより、塗膜の撥水・撥油性及び耐汚染性は相乗的に改善される。
【００２０】
透明又は半透明樹脂４には、レベリング性及びハジキ防止のために表面調整剤を添加することが好ましい。表面調整剤としては、アクリルオリゴマー系，ポリシロキサン系等が挙げられるが、好ましくはポリシロキサン系が使用される。ポリシロキサン系表面調整剤としては、粘度が５０ｃＰ未満であるか、反応性基を持たないポリシロキサンが挙げられ、たとえばポリシロキサンポリエーテルコポリマー，アルキル変性ポリシロキサン，ジメチルポリシロキサン，メチルフェニルポリシロキサン等が使用される。
一般に塗膜形成樹脂との相溶性が良好で、２０℃における粘度が５〜５０ｃＰのものが好ましい。この種のポリシロキサン系表面調整剤としては、ＤＣ１１ＰＡ，ＳＴ８０ＰＡ（東レ・ダウコーニング社製），ＫＰ−３２１，ＫＰ−３２４（信越化学工業株式会社製）等が市販されている。ポリシロキサン系表面調整剤は、好ましくは０．００１〜５．０重量部の範囲で配合される。配合量が０．００１重量部に満たないと、レベリング性やハジキ防止に与える表面調整剤の作用が小さく、平滑な塗膜が得られ難い。しかし、５．０重量部を超える配合量では、却ってハジキが発生し易くなる。平滑な塗膜を得るために表面調整剤は、好ましくは０．００５〜１．０重量部，より好ましくは０．０５〜０．５０重量部の範囲に調整される。
【００２１】
昇華性染料で予め模様を付けた転写シートを下地金属板１に接触させて加熱すると、昇華した染料が透明又は半透明樹脂４の中に浸透し、厚み方向に染着した模様が形成される。転写シートは、グラビア印刷，オフセット印刷，スクリーン印刷等によって作製される。また、小ロット印刷用には、製版工程を必要としないコンピュータグラフィックを用いた電子写真法，静電記録法，インクジェット法，感熱転写法等を採用することもできる。
昇華性染料は、加熱された際に昇華，揮発等の現象によって透明又は半透明樹脂層４に転移しうる染料であり、たとえばキノフタロン誘導体，アントラキノン誘導体，アゾ系色素等の分散染料が好適に用いられる。また、従来から昇華熱転写，昇華転写捺染等に使用されている染料は、特に制約なく使用することができる。
【００２２】
この種のイエロー系昇華染料としては、Ｋａｙａｃｅｔ Ｙｅｌｌｏｗ ＡＧ，Ｋａｙａｃｅｔ Ｙｅｌｌｏｗ ＴＤＮ（日本化薬株式会社製），ＲＴＹ ５２，Ｄｉａｎｉｘ Ｙｅｌｌｏｗ ５Ｒ−Ｅ， Ｄｉａｎｉｘ Ｙｅｌｌｏｗ Ｆ３Ｇ−Ｅ， Ｄｉａｎｉｘ Ｂｒｉｌｌｉａｎｔ Ｙｅｌｌｏｗ ５Ｇ−Ｅ（三菱化学株式会社製），ブラストＹｅｌｌｏｗ ８０４０，ＤＹ１０８（有本化学株式会社製），Ｓｕｍｉｋａｒｏｎ Ｙｅｌｌｏｗ ＥＦＧ，Ｓｕｍｉｋａｒｏｎ Ｙｅｌｌｏｗ Ｅ−４ＧＬ（住友化学株式会社製），ＦＯＲＯＮ Ｂｒｉｌｌｉａｎｔ Ｙｅｌｌｏｗ ＳＧＧＬＰＩ（Ｓａｎｄ社製），ＰＳイエローＧＧ（三井東圧染料株式会社製）等がある。
【００２３】
マゼンタ系の昇華性染料としては、Ｋａｙａｃｅｔ Ｒｅｄ ０２６，Ｋａｙａｃｅｔ Ｒｅｄ １３０，Ｋａｙａｃｅｔ Ｒｅｄ Ｂ（日本化薬株式会社製），Ｏｉｌ Ｒｅｄ ＤＲ−９９，Ｏｉｌ Ｒｅｄ ＤＫ−９９（有本化学株式会社製），Ｄｉａｃｅｌｌｉｔｏｎ Ｐｉｎｋ Ｂ（三菱化学株式会社製），Ｓｕｍｉｋａｒｏｎ Ｒｅｄ Ｅ−ＦＢＬ（住友化学株式会社製），Ｌａｔｙｌ Ｒｅｄ Ｂ（Ｄｕ Ｐｏｎｔ社製），Ｓｕｄａｎ Ｒｅｄ ７Ｂ（ＢＡＳＦ社製），Ｒｅｓｏｌｉｎ Ｒｅｄ ＦＢ，Ｃｅｒｅｓ Ｒｅｄ ７Ｂ（Ｂａｙｅｒ社製）等がある。
【００２４】
シアン系の昇華染料には、Ｋａｙａｌｏｎ Ｆａｓｔ Ｂｌｕｅ ＦＧ，Ｋａｙａｌｏｎ Ｂｌｕｅ ＦＲ，Ｋａｙａｃｅｔ Ｂｌｕｅ １３６，Ｋａｙａｃｅｔ Ｂｌｕｅ ９０６（日本化薬株式会社製），Ｏｉｌ Ｂｌｕｅ ６３（有本化学株式会社製），ＨＳＢ９，ＲＴＢ３１（三菱化学株式会社製），Ｄｉｓｐｅｒｓｅ Ｂｌｕｅ ＃１（住友化学株式会社製），ＭＳ Ｂｌｕｅ ５０（三井東圧染料株式会社製），Ｃｅｒｅｓ Ｂｌｕｅ ＧＮ（Ｂａｙｅｒ社製），Ｄｕａｎｏｌ Ｂｒｉｌｌｉａｎｔ Ｂｌｕｅ ２Ｇ（ＩＣＩ社製）等がある。
各色用の昇華性染料は、単独で使用しても２種以上を併用して使用しても良い。黒色は、イエロー，マゼンタ，シアン系の昇華性染料を適宜配合することにより得られる。イエロー，マゼンタ，シアン以外の色調をもつ昇華性染料としては、昇華温度（液状状態から揮発する場合も含む）が６０℃以上の染料が好ましい。昇華性染料を選択する際には、昇華温度の高い染料の方が比較的分子量が大きく、優れた耐光性及び耐熱性を示すことから好ましい。
【００２５】
下地金属板１と接触した状態で転写シートが加熱されると、転写シートに含まれている昇華性染料が昇華し、図１に示すように透明又は半透明樹脂層４を厚み方向に浸透する。そのため、厚み方向にほぼ均一に染着された透明又は半透明樹脂層４で立体的な印刷模様が発現される。得られた印刷模様は、透明又は半透明樹脂層４の表層のみに昇華性染料が濃化したものでないため、擦れ等によって印刷薄れが生じることなく、また熱転写で意匠を付与した後の転写印刷層を透明樹脂によって保護する後工程も省略される。しかも、厚み方向にほぼ均一に染着された透明又は半透明樹脂層４で印刷模様が発現されるため、深み感，立体感，光沢度及び鮮映度に優れた印刷模様が得られる。
得られた意匠鋼板は、トップ塗膜が非粘着性であることから、昇華性染料の付着残留がない。そのため、印刷後に塗膜表面を拭き取る作業が基本的に不要とされ、しかも鮮明な印刷模様が発現する。また、非粘着性の表面を呈することから、使用時においても油分や油性ペイント等による汚染が少なく、長期間にわたり模様の鮮映性が持続する。
【００２６】
このようにして、必要な模様を必要な時に簡便に付与できるため、各種模様付けが要求される意匠鋼板の小ロット生産が容易になる。しかも、所定の模様を付けた意匠鋼板として在庫する必要がなくなり、ニーズに応じた模様付けが可能になる。また、透明又は半透明樹脂層４と下地金属板１との間に染料層が単独で存在していないので、従来のラミネート鋼板にみられた層間剥離が生じない。
透明又は半透明樹脂層４には、転写時の１５０〜２００℃の加熱で著しく軟化することのない熱硬化型の樹脂を使用することが好ましい。このような樹脂の使用により、熱転写で模様を付けた後に塗装金属板の表面光沢が低下することがほとんどなくなる。
【００２７】
透明又は半透明樹脂層４の塗膜中には、太陽光線や紫外線の透過による昇華性染料の褪色や透明又は半透明樹脂層４の光沢低下を防止するため、透明又は半透明樹脂塗膜中に紫外線吸収剤を添加している。紫外線吸収剤としては、ベンゾトリアゾール系又はトリアジン系が使用される。好ましくは、トリアジン系単独或いはトリアジン系とベンゾトリアゾール系とを複合して添加する。紫外線吸収剤の配合量は、塗料不揮発分に対して３〜２２重量部の範囲に定められる。また、ヒンダートアミン系光安定剤を０〜３．０重量部の割合で配合することが好ましい。紫外線吸収剤としては、空気雰囲気中、昇温速度５℃／分の加熱条件下、３００℃で重量減少が１０重量％以下のものが好ましい。
【００２８】
ベンゾトリアゾール系の紫外線吸収剤には、オクチル−３−［３−ｔ−ブチル−５−（２Ｈ−ベンゾトリアゾ−ル−２−イル）］−４−ヒドロキシフェニル］プロピネート（チバガイギー社製 ＴＩＮＵＶＩＮ ３８４），２−［２−ヒドロキシ−３，５−ビス（α，α’ジメチルベンジル）フェニル］−２Ｈ−ベンゾトリアゾール（チバガイギー社製 ＴＩＮＵＶＩＮ ９００），メチル−３−［３−ｔ−ブチル−５−（２Ｈ−ベンゾトリアゾール−２−イル）］−４−ヒドロキシフェニル］プロピネート−ポリエチレングリコール（分子量約３００）との縮合物（チバガイギー社製 ＴＩＮＵＶＩＮ １１３０），２−［２’−ヒドロキシ−３’−（３”，４”，５”，６”−テトラヒドロフタルイミドメチル）−５’−メチルフェニル］−ベンゾトリアゾール（共同薬品株式会社製 Ｖｉｏｓｏｒｂ ５９０）等が挙げられる。
【００２９】
トリアジン系紫外線吸収剤には、たとえば２−［４−［（２−ヒドロキシ−３−ジデシルオキシプロピル）−オキシ］−２−ヒドロキシフェニル］−４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジンと２−［４−［（２−ヒドロキシ−３−トリデシルオキシプロピル）−オキシ］−２−ヒドロキシフェニル］−４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジンの混合物（チバガイギー社製 ＴＩＮＵＶＩＮ４００）がある。
これら紫外線吸収剤は、単独でも、２種以上を混合しても使用することができる。紫外線吸収剤の配合量は、塗料の不揮発分１００重量部に対して３〜２２重量部に調整することが好ましい。３重量部に満たない配合量では、透明又は半透明樹脂層４に浸透した昇華性染料の耐光性が不十分となる。逆に、２２重量部を超える配合量では、塗膜の耐汚染性，加工性，塗膜外観等が劣化する。また、紫外線吸収剤によるトップ塗膜の着色も観察される。
透明又は半透明樹脂層４の耐光性を更に向上させるため、必要に応じてヒンダートアミン系の光安定剤を塗料不揮発分に対して０〜３重量部の割合で配合させることが好ましい。ヒンダートアミン系の光安定剤には、次のものが挙げられる。
【００３０】
ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート（三共株式会社製 ＳＡＮＯＬ ＬＳ７７０），ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート（三共株式会社製 ＳＡＮＯＬ ＬＳ７６５），１−｛２−［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシ］エチル｝−４−［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシ］−２，２，６，６−テトラメチルピペリジン（三共株式会社製 ＳＡＮＯＬ ＬＳ２６２６），４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン（三共株式会社製 ＳＡＮＯＬ ＬＳ７４４），８−アセチル−３−ドデシル−７，７，９，９−テトラメチル−１，３，８−トリアザスピロ［４，５］デカン−２，４−ジオン（三共株式会社製 ＳＡＮＯＬ ＬＳ４４０），２−（３，５−ジ−ｔ−ヒドロキシベンジル）−２−ｎ−ブチルマロン酸ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）（チバガイギー社製 ＴＩＮＵＶＩＮ １４４），コハク酸ビス（２，２，６，６−テトラメチル−４−ピペリジル）エステル（チバガイギー社製 ＴＩＮＵＶＩＮ ７８０ＦＦ），コハク酸ジメチルと１−（２−ヒドロキシエチル）−４−ヒドロキシ−２，２，６，６−テトラメチルピペリジンの重縮合物（チバガイギー社製 ＴＩＮＵＶＩＮ ６２２ＬＤ），ポリ｛［６−（１，１，３，３−テトラメチルブチル）アミノ−１，３，５−トリアジン−２，４−ジイル］［（２，２，６，６−テトラメチル−４−ピペリジル）イミノ］ヘキサメチレン［（２，２，６，６−テトラメチル−４−ピペリジル）イミノ］｝（チバガイギー社製ＣＨＩＭＡＳＳＯＲＢ ９４４ＬＤ），Ｎ，Ｎ’−ビス（３−アミノプロピル）エチレンジアミンと２，４−ビス［Ｎ−ブチル−Ｎ−（１，２，２，６，６−ペンタメチル−４−ピペリジル）アミノ］−６−クロロ−１，３，５−トリアジンの重縮合物（チバガイギー社製 ＣＨＩＭＡＳＳＯＲＢ １１９ＦＬ），ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート（チバガイギー社製 ＴＩＮＵＶＩＮ ２９２），ビス（１−オクタオキシ−２，２，６，６−テトラメチル−４−ピペリジル）セバケート（チバガイギー社製 ＴＩＮＵＶＩＮ １２３），ＨＡ−７０Ｇ（三共株式会社製），アデカスタブ ＬＡ−５２，アデカスタブ ＬＡ−５７，アデカスタブ ＬＡ−６２，アデカスタブ ＬＡ−６３，アデカスタブ ＬＡ−６７，アデカスタブ ＬＡ−６８，アデカスタブ ＬＡ−８２，アデカスタブ ＬＡ−８７（旭電化工業株式会社製）
【００３１】
これらの光安定剤は、単独でも或いは２種以上を混合しても使用できる。安定剤の配合量を３．０重量部より多量にしても、塗膜中に浸透した昇華性染料の耐光性を向上させる効果が飽和し、増量に見合った改善がみられず、逆に塗装外観が劣化する傾向を示す。光安定剤は、好ましくは０．５〜１．５重量部の範囲で配合される。
透明又は半透明樹脂層４としての透明樹脂塗膜は、ベースコート層２を介して（図１ａ）、ベースコート層２及びプライマー層３を介して（図１ｂ）、或いは下地金属板１に直接（図１ｃ）形成することができる。何れの場合も、下地金属板１やベースコート層２の色調が地模様となり、染着樹脂層５を通して現れる。そのため、下地素材の風合いを活かした独特の深み感をもった意匠性金属板が製造される。
【００３２】
【実施例】
印刷条件１（本発明例１〜４，比較例１，３〜５）
下地金属板として使用する塗装鋼板の製造
板厚０．５ｍｍのＺｎめっき鋼板に塗装前処理を施し、白色ポリエステル系樹脂塗料（関西ペイント株式会社製 ＡＴ−１００１プライマー）を乾燥塗膜厚みで１９μｍになるように塗装した後、板温２２０℃で１分間焼き付けることにより白色ベースコート樹脂塗膜を形成した。次いで、ポリエステル樹脂（三井東圧化学株式会社製 アルマテックスＰ−６４６）７５重量部，完全アルキルヘキサンメチル化メラミン（三井サイアナミッド株式会社製 メラミン硬化剤）２５重量部，ポリフルオロカーボン鎖含有化合物（東レ・ダウコーニング・シリコーン株式会社製 ＦＳ１２６５）０〜５．０重量部，有機変性シリコーンオイル（信越化学株式会社製 ＫＦ６００１）０〜５．０重量部，トリアジン系紫外線吸収剤（チバガイギー社製 ＴＩＮＵＶＩＮ ４００）１２重量部及びヒンダートアミン系光安定剤（チバガイギー社製 ＴＩＮＵＶＩＮ １２３）１．５重量部を含むポリエステル系クリヤー樹脂塗料を乾燥膜厚で１０μｍとなるように塗装した後、板温２４０℃で１分間焼き付けることにより、透明樹脂塗膜を形成した。
【００３３】
昇華性染料を使用した模様の転写
昇華性染料トナー（新日鐵化学株式会社製 昇華捺染用トナー）を使用し、静電プロッタ方式の画像プリントシステム（株式会社Ｅｘｉｓ製 Ｊｕａｎａ）で静電記録紙にシアン色，マゼンタ色，イエロー色のベタ模様を出力した。得られた静電記録紙を塗装鋼板１の塗装面に重ね合わせ、温度１６５℃及び圧力０．５ｋｇ／ｃｍ² で１５０秒間加熱圧着した。圧着完了後、塗装鋼板から静電記録紙を剥離した。
【００３４】
印刷条件２（比較例２）
下地金属板として使用する塗装鋼板の製造
トリアジン系紫外線吸収剤（チバガイギー社製 ＴＩＮＵＶＩＮ ４００）１２重量部，ヒンダートアミン系光安定剤（チバガイギー社製 ＴＩＮＵＶＩＮ １２３）１．５重量部を含むポリエステル系クリヤー樹脂塗料（関西ペイント株式会社製 ＡＴ−１００５プライマー）を乾燥膜厚１５μｍになるように塗装した後、板温２１０℃で１分間焼き付けた外は、実施例１と同じ塗装鋼板を使用した。
昇華性染料を使用した模様の転写
実施例１と同じ昇華性染料トナーを使用し、同様な方法で塗装鋼板に模様を転写した。
【００３５】
以上のように製造した各印刷塗装金属板に対し、転写後の光沢保持率，トナー及び塗工樹脂の拭取り性，塗装外観を調査した。調査結果を表１（本発明例）及び表２（比較例）に示す。表１及び表２における各性質は、次のように試験し評価した。
転写後の光沢保持率
転写前と転写後の６０度鏡面反射率を測定し、転写後の６０度鏡面反射率／転写前の６０度鏡面反射率から転写後の光沢保持率を算出した。
乾拭取り性
転写後の印刷塗装鋼板の表面を綿タオルで乾拭きし、トナー及び塗工紙の塗工樹脂が完全に拭き取れたものを○，多少の曇り又は汚染が残るものを△，明確に曇り又は汚染が残るものを×として評価した。
塗装外観
平滑で一様な外観が得られることを指標とし、ムラのない良好な外観を呈するものを○，ハジキがあり塗膜に多少の凹凸が観察されるものを△，明確にハジキが発生し平滑な塗膜が得られなかったものを×として評価した。
【００３６】

【００３７】

【００３８】
表１と表２との対比から明らかなように、本発明に従った表１では、転写後の光沢保持率，トナー及び塗工樹脂の拭取り性，印刷塗装外観について何れも十分満足する特性を呈した。また、印刷塗装面は、油性インク等の付着がなく、耐汚染性に優れているため長期間にわたって良好な外観を呈した。
これに対し、表２の比較例では、転写後の表面に付着残留する昇華性染料や塗工樹脂に起因するものと推察される光沢保持率の低下がみられた。また、乾拭取り性が悪く、転写後の表面から昇華性染料や塗工樹脂を除去することが困難であった。しかも、油性インク等で印刷表面に落書きすると、油性インクが印刷面と融和し、転写直後の美麗な印刷面に復元できなかった。
【００３９】
【発明の効果】
以上に説明したように、本発明の印刷塗装金属板は、フッ素系界面活性剤，フッ素系オイル，パーフルオロアルキル基を含む重合体，フルオロシリコーンオイルから選ばれたポリフルオロカーボン鎖含有化合物を０.１０〜１.０重量部、シリコーンオイルを０.１０〜１.０重量部の割合で塗膜改質剤としてトップ塗膜に配合することにより、転写時に昇華性染料の浸透性を損なうことなくトップ塗膜を非粘着性としている。そのため、未昇華のままで転写後の印刷面に付着残留する昇華性染料や塗工紙の塗工樹脂が印刷面から乾拭きによって容易に除去され、美麗な印刷面を呈する印刷塗装金属板が得られる。また、印刷面の耐汚染性が優れており、油性ペイント等を使用した落書き等も容易に拭きとることができ、長期間にわたって意匠性の高い印刷模様が維持される。
【図面の簡単な説明】
【図１】 本発明に従った印刷塗装金属板の表層部断面を示し、ベースコート層上に昇華性染料染着層を設けた例（ａ），プライマー層及びベースコート層上に昇華性染料染着層を設けた例（ｂ），下地金属板上に昇華性染料染着層を直接設けた例（ｃ）[0001]
[Industrial application fields]
The present invention relates to a printed metal sheet which is used as a full-color advertising signboard, a decorative interior material, an outer plate of an electric appliance or a fixture, and is suitable for small lots and various types of products with various printed patterns.
[0002]
[Prior art]
When a printed metal sheet is manufactured using a sublimation dye, the sublimation dye is printed on the top clear layer of the painted metal sheet by a printing method such as offset, silk, gravure, or transfer, followed by heat treatment. A sublimation dye is infiltrated into the clear coating film.
For example, in Japanese Patent Application Laid-Open No. 51-24313, a transfer sheet is heated in contact with a coating layer of a curable synthetic resin. In JP-A-54-104907, a printing layer is formed on a coated metal plate by transfer printing using a sublimation dye, and then a top coating film is further formed on the surface, followed by heat treatment, A pattern is formed by infiltrating a sublimable dye from the inside. In JP-A-7-31931, heat sublimation ink is infiltrated into a coating film of a prepainted steel sheet in which a primer coating and a colored top coating are formed on the surface of the steel sheet. Further, in JP-A-7-102733, a transparent resin layer is formed on an opaque resin layer provided on a metal plate substrate, and a sublimation colorant is infiltrated into the transparent resin layer.
[0003]
[Problems to be solved by the invention]
In any conventional printing method using a sublimation dye, a pattern is formed by infiltrating the sublimation dye into the top coating film. In Japanese Patent Application Laid-Open No. 51-139411, after a sublimable dye is infiltrated into a coating film, an excessive sublimation dye remaining on the surface of the coating film is wiped off, whereby a colored surface similar to alumite dyeing with a metallic feeling is obtained. It is supposed to be obtained.
However, it is difficult to remove the sublimation dye that has not completely penetrated into the top coating film and adhered to the coating surface by dry wiping. If the sublimation dye adheres and remains on the surface of the coating film, the sharpness of the printed pattern and the glossiness of the top coating film decrease, which causes a reduction in the commercial value. Therefore, the present situation is that the cloth is wiped off with a cloth containing a solvent such as methanol, hexane, heptane or the like which does not damage the coating film. The operation of wiping off the residual dye with a cloth containing such a solvent decreases the production efficiency as the area of the metal plate increases, and is not preferable as a work environment.
[0004]
By the way, the transfer sheet is manufactured by gravure printing, offset printing, screen printing, or the like. For small lot printing, a computer graphic electrostatic recording method, an electrophotographic method, an ink jet method, a thermal transfer method and the like which do not require a plate making process are employed. In this type of method, coated paper is used in order to prevent ink bleeding and improve adhesion. However, the resin coated on the paper adheres to the coating film together with the non-sublimated sublimable dye after transfer, and causes a decrease in the gloss of the printed metal sheet. In this case, it becomes more difficult to completely remove the resin and sublimation dye remaining on the surface of the coating film even if wiped with a cloth containing a solvent. Depending on the type of coated paper, it may be completely fused on the top coating and cannot be removed, and the appearance of the printed surface is significantly deteriorated.
The present invention has been devised to solve such problems, and by including a polyfluorocarbon chain-containing compound and silicone oil as a coating film modifier, it is sublimable on the surface of the top coating film after transfer. It is an object of the present invention to provide a printed metal sheet which can prevent a dye or a coating resin of a coated paper from adhering and remain and can maintain a beautiful printed pattern with no gloss reduction.
[0005]
[Means for Solving the Problems]
In order to achieve the object, the printed metal sheet of the present invention has a polyfluorocarbon chain-containing compound of 0.1 to 1.0 part by weight as a coating film modifier and 0.1 part by weight per 100 parts by weight of the coating film-forming solid content. A top coating layer of a transparent or translucent resin containing 10 to 1.0 parts by weight of silicone oil is formed, and a sublimable dye is infiltrated into the top coating layer.
As the polyfluorocarbon chain-containing compound, one or more selected from fluorine-based surfactants, fluorine-based oils, polymers containing perfluoroalkyl groups, and fluorosilicone oils are used. The top coating film may further contain a triazine-based UV absorber and a benzotriazole-based UV absorber having good thermal stability and solubility, either alone or in combination, in a proportion of 3 to 22 parts by weight based on the non-volatile content of the paint. it can.
[0006]
Embodiment
As shown in FIG. 1, the printed metal sheet according to the present invention has a transparent or translucent resin layer 4 formed on the surface of a base metal plate 1 such as a plated steel plate, a stainless steel plate, or an aluminum plate. As the base metal plate 1, as long as there is a transparent or translucent resin layer 4 in the outermost layer, a coated metal plate (a) provided with a white base coat layer 2, a painted metal plate (b) further provided with a primer layer 3, and a base coat A coated metal plate (c) or the like having only the transparent or translucent resin layer 4 without the layer 2 or the primer layer 3 is used.
When the base coat layer 2 that hides the color tone of the base metal plate 1 and the primer layer 3 is provided, a base coat layer having another color tone can be formed without being limited to white. The base coat layer 2 preferably has a coating thickness of 10 to 20 μm. In the base coat layer 2 having a film thickness of less than 10 μm, the color tone of the base metal plate 1 and the primer layer 3 is not sufficiently concealed. On the contrary, in the base coat layer 2 having a thickness of more than 20 μm, the solvent remaining in the coating film at the time of baking may be rapidly vaporized to cause a pinhole-shaped coating defect called “baki”.
[0007]
The material of the transparent or translucent resin layer 4 is not limited as long as it is a dyeable resin that receives the sublimation dye transferred from the transfer sheet and dyes it well. For example, vinyl resins such as polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyvinyl acetate, polyvinyl chloride, polyvinyl pyrrolidone, polystyrene, acrylates such as polymethyl (meth) acrylate, polybutyl (meth) acrylate, polyacrylamide, polyacrylonitrile, etc. Resin, polyester resin, polycarbonate resin, polyurethane resin, polyamide resin, urea resin, polycaprolactone resin, polyarylate resin, polysulfone resin, silicone polyester resin, epoxy resin, and their copolymers or mixtures as dyeable resins Can be used. Among them, the polyester resin is preferably dyed as a at least one component of the dyeing resin because it is well dyed by the sublimation dye and the storage stability of the obtained image is also good.
[0008]
The polyfluorocarbon chain-containing compound, which is one component of the coating film modifier, may be either a polymer or a non-polymer, and specifically includes a fluorosurfactant, a fluoro oil, and a perfluoroalkyl group listed below. For example, a polymer or fluorosilicone oil. Such polyfluorocarbon chain-containing compounds are Unidyne DS-101, DS-202, DS-301, DS-406 (manufactured by Daikin Industries, Ltd.), demnum S-20, Daifull # 20 (manufactured by Daikin Industries, Ltd.), It is marketed as Texguard TG-652, TG-664 (Daikin Kogyo Co., Ltd.), FS-1265 (Toray Dow Corning Co., Ltd.), X-22-819, FL-100 (Shin-Etsu Chemical Co., Ltd.), etc. ing.
[0009]
Anionic fluorosurfactant

In the formula, Rf and Rf ′ are each a fluoroalkyl group in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, D is —CO—, —SO₂ -Or- (CH₂)_z -(Where z is an integer from 1 to 10), Y is C₁ ~ C₆ An alkylene group, M is a hydrogen atom, NH_Four , Alkali metal or alkaline earth metal, R¹ Represents a hydrogen atom or a lower alkyl group.
[0010]
Cationic fluorosurfactant

Where Rf, D, R¹ And Y are the same as above, R² Is R¹ Same as R^Three Is C₂ ~ C_Three An alkylene group, HX is an acid, and X is a halogen or an acid radical.
Amphoteric fluorosurfactant
-N⁺(R¹)₂-COO^-           RfDNHYN⁺(R¹)₂ Y’COO^-
Where Rf, D, R¹ And Y are the same as above, Y 'is C₂ ~ C₆ Represents an alkylene group.
[0011]
Nonionic fluorosurfactant

Where Rf, D, R¹ , R^Three And Y are the same as above, R^Four Is C₁ ~ C_{twenty two}N represents an integer of 1 to 30, and a, b and c each represents an integer of 1 to 100.
[0012]

Fluorine oil
Polymers such as perfluoropolyether and chlorotrifluoroethylene and fluorinated hydrocarbon compounds represented by the following formula are used.
[0013]
[L = (A)_q-(B)_r-(C)_s] (Q, r, s is 0 or 1)

[0014]

[0015]
Polymer with perfluoroalkyl group
For example, a polymer containing a perfluoroalkyl group-containing ethylenically unsaturated monomer represented by the following formula or a copolymer composed of a monomer copolymerizable with this monomer is used as a main component. The Monomers that can be copolymerized include alkyl esters of (meth) acrylic acid, cyclohexyl groups or benzyl esters of (meth) acrylic acid, polyethylene glycol di (meth) acrylate, N-methylolacrylamide, ethylene, vinyl chloride, fluorine. Vinyl halide, (meth) acrylic acid amide, styrene, α-methylstyrene, p-methylstyrene, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, maleic anhydride, budadien, isoprene, chloroprene and the like.
[0016]

[0017]
In the formula, Rf ″ is a C 4-20 perfluoroalkyl group, R⁷ Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R⁸ Is a hydrogen atom or a methyl group, R^TenIs an alkyl group having 1 to 17 carbon atoms, e is an integer of 1 to 10, and f is an integer of 0 to 10.
As the silicone oil which is another component of the coating film modifier, a silicone oil having a viscosity at 25 ° C. of 50 cP or more, or having a reactive group at the side chain or terminal is preferable in order to exhibit water repellency and oil repellency. For example, there are dimethyl silicone oil, methyl chloride silicone oil, methylphenyl silicone oil, organic modified silicone oil, etc., among which organic modified silicone oil is preferred. As this type of silicone oil, those having the following structure are specifically known: PRX413, SF8417, SY16-855B, SF8427, SF8428 (manufactured by Toray Dow Corning), X-22-161C X-22-163C, X-22162A, KF-6001, KF-857 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are commercially available.
[0018]

[0019]
Both the polyfluorocarbon chain-containing compound and the silicone oil are blended at a ratio of 0.10 to 1.0 parts by weight per 100 parts by weight of the coating film forming component. When the compounding amount of the polyfluorocarbon chain-containing compound and the silicone compound is less than 0.01 parts by weight, the water / oil repellency and stain resistance are insufficient. On the other hand, if the amount exceeds 3.0 parts by weight, repellency and flow are likely to occur, and it becomes difficult to obtain a smooth coating film. Although it is possible to prevent repellency by adding a surface conditioner, if the amount of the polyfluorocarbon chain-containing compound and the silicone oil is large, the hardness of the coating film decreases and the stain resistance deteriorates. In order to ensure the stain resistance and smoothness, the blending amount of the polyfluorocarbon chain-containing compound and the silicone oil is adjusted to the range of 0.10 to 1.0 parts by weight. By adding both the polyfluorocarbon chain-containing compound and silicone oil, the water / oil repellency and stain resistance of the coating film are synergistically improved.
[0020]
It is preferable to add a surface conditioner to the transparent or translucent resin 4 for leveling properties and prevention of repellency. Examples of the surface conditioner include acrylic oligomers and polysiloxanes, but polysiloxanes are preferably used. Examples of the polysiloxane surface conditioner include polysiloxanes having a viscosity of less than 50 cP or having no reactive group, such as polysiloxane polyether copolymer, alkyl-modified polysiloxane, dimethyl polysiloxane, methylphenyl polysiloxane, and the like. Is used.
In general, those having good compatibility with the film-forming resin and having a viscosity at 20 ° C. of 5 to 50 cP are preferred. As this type of polysiloxane surface conditioner, DC11PA, ST80PA (manufactured by Dow Corning Toray), KP-321, KP-324 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are commercially available. The polysiloxane surface conditioner is preferably blended in the range of 0.001 to 5.0 parts by weight. If the blending amount is less than 0.001 part by weight, the effect of the surface conditioner on leveling properties and repellency prevention is small, and it is difficult to obtain a smooth coating film. However, if the amount exceeds 5.0 parts by weight, repellency is likely to occur. In order to obtain a smooth coating film, the surface conditioner is preferably adjusted in the range of 0.005 to 1.0 part by weight, more preferably 0.05 to 0.50 part by weight.
[0021]
When a transfer sheet preliminarily patterned with a sublimation dye is brought into contact with the base metal plate 1 and heated, the sublimated dye penetrates into the transparent or translucent resin 4 and forms a pattern dyed in the thickness direction. . The transfer sheet is produced by gravure printing, offset printing, screen printing, or the like. For small lot printing, an electrophotographic method using a computer graphic that does not require a plate making process, an electrostatic recording method, an ink jet method, a thermal transfer method, or the like may be employed.
The sublimable dye is a dye that can be transferred to the transparent or translucent resin layer 4 by a phenomenon such as sublimation or volatilization when heated. For example, disperse dyes such as quinophthalone derivatives, anthraquinone derivatives, and azo dyes are preferably used. It is done. In addition, dyes conventionally used for sublimation thermal transfer, sublimation transfer printing, and the like can be used without particular limitation.
[0022]
Examples of this type of yellow-based sublimation dye include Kayacet Yellow AG, Kayacet Yellow TDN (manufactured by Nippon Kayaku Co., Ltd.), RTY 52, Dianix Yellow 5R-E, Dianix Yellow F3G-E, Dianix Brilliant Yell-Ell Blast Yellow 8040, DY108 (Arimoto Chemical Co., Ltd.), Sumikaron Yellow EFG, Sumikaron Yellow E-4GL (Sumitomo Chemical Co., Ltd.), FORON Brilliant Yellow SGGLPI (Sand), PS Yellow GG Mitsui Toatsu Dye Co., Ltd.).
[0023]
Examples of magenta-based sublimable dyes include Kayace Red 026, Kayace Red 130, Kayace Red B (manufactured by Nippon Kayaku Co., Ltd.), Oil Red DR-99, Oil Red DK-99 (manufactured by Arimoto Chemical Co., Ltd.), Diacelton Pink B (manufactured by Mitsubishi Chemical Corporation), Sumikaron Red E-FBL (manufactured by Sumitomo Chemical Co., Ltd.), Lateyl Red B (manufactured by Du Pont), Sudan Red 7B (manufactured by BASF), Resolin Red FB, Ceres Red 7B ( Bayer).
[0024]
Examples of cyan-based sublimation dyes include Kayalon Fast Blue FG, Kayalon Blue FR, Kayacet Blue 136, Kayacet Blue 906 (Nippon Kayaku Co., Ltd.), Oil Blue 63 (Arimoto Chemical Co., Ltd.), HSB9, RTB31 (Mitsubishi) Chemical Co., Ltd., Disperse Blue # 1 (manufactured by Sumitomo Chemical Co., Ltd.), MS Blue 50 (manufactured by Mitsui Toatsu Dye Co., Ltd.), Ceres Blue GN (manufactured by Bayer), Duanol Brilliant Blue 2G (manufactured by ICI), etc. There is.
The sublimable dyes for each color may be used alone or in combination of two or more. Black color can be obtained by appropriately blending yellow, magenta and cyan sublimation dyes. As the sublimation dye having a color tone other than yellow, magenta, and cyan, a dye having a sublimation temperature (including a case where it volatilizes from a liquid state) of 60 ° C. or higher is preferable. When selecting a sublimable dye, a dye having a higher sublimation temperature is preferable because it has a relatively large molecular weight and exhibits excellent light resistance and heat resistance.
[0025]
When the transfer sheet is heated in contact with the base metal plate 1, the sublimable dye contained in the transfer sheet is sublimated, and penetrates the transparent or translucent resin layer 4 in the thickness direction as shown in FIG. . Therefore, a three-dimensional printing pattern is expressed by the transparent or translucent resin layer 4 dyed substantially uniformly in the thickness direction. Since the obtained printed pattern is not the one in which the sublimation dye is concentrated only on the surface layer of the transparent or translucent resin layer 4, there is no printing fading due to rubbing or the like, and the transfer printing after applying the design by thermal transfer Subsequent steps of protecting the layer with a transparent resin are also omitted. In addition, since the printed pattern is expressed by the transparent or translucent resin layer 4 dyed almost uniformly in the thickness direction, a printed pattern having excellent depth, stereoscopic effect, glossiness, and sharpness can be obtained.
The obtained design steel sheet has no adhesion residue of the sublimation dye because the top coating film is non-tacky. Therefore, the operation of wiping the surface of the coating film after printing is basically unnecessary, and a clear printed pattern appears. In addition, since it exhibits a non-adhesive surface, it is less contaminated with oil and oil paint even during use, and the vividness of the pattern is maintained over a long period of time.
[0026]
In this way, since a necessary pattern can be easily provided when necessary, small-lot production of a design steel sheet that requires various patterning becomes easy. Moreover, it is not necessary to stock as a design steel plate with a predetermined pattern, and patterning according to needs is possible. Moreover, since the dye layer does not exist independently between the transparent or translucent resin layer 4 and the base metal plate 1, the delamination seen in the conventional laminated steel sheet does not occur.
For the transparent or translucent resin layer 4, it is preferable to use a thermosetting resin that is not significantly softened by heating at 150 to 200 ° C. during transfer. By using such a resin, the surface gloss of the coated metal plate is hardly lowered after the pattern is formed by thermal transfer.
[0027]
In the coating film of the transparent or translucent resin layer 4, in order to prevent the sublimation dye from fading or the gloss of the transparent or translucent resin layer 4 from being lowered due to the transmission of sunlight or ultraviolet rays, UV absorber is added to As the ultraviolet absorber, benzotriazole or triazine is used. Preferably, the triazine type alone or a combination of triazine type and benzotriazole type is added. The compounding quantity of a ultraviolet absorber is defined in the range of 3-22 weight part with respect to a coating material non volatile matter. Moreover, it is preferable to mix | blend a hindered amine light stabilizer in the ratio of 0-3.0 weight part. As the ultraviolet absorber, those having a weight loss of 10% by weight or less at 300 ° C. under a heating condition of 5 ° C./min in an air atmosphere are preferable.
[0028]
Benzotriazole-based UV absorbers include octyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl)]-4-hydroxyphenyl] propionate (TINUVIN 384 manufactured by Ciba Geigy), 2- [2-hydroxy-3,5-bis (α, α′dimethylbenzyl) phenyl] -2H-benzotriazole (TINUVIN 900, manufactured by Ciba Geigy), methyl-3- [3-t-butyl-5- (2H -Benzotriazol-2-yl)]-4-hydroxyphenyl] propinate-polyethylene glycol (molecular weight about 300) condensate (TINUVIN 1130 manufactured by Ciba Geigy), 2- [2'-hydroxy-3 '-(3 " , 4 ", 5", 6 "-tetrahydrophthalimidomethyl) -5'-methylphenyl] -benzene And Nzotriazole (Viosorb 590, manufactured by Kyodo Yakuhin Co., Ltd.).
[0029]
Examples of triazine ultraviolet absorbers include 2- [4-[(2-hydroxy-3-didecyloxypropyl) -oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). -1,3,5-triazine and 2- [4-[(2-hydroxy-3-tridecyloxypropyl) -oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) There is a mixture of -1,3,5-triazine (TINUVIN 400 from Ciba Geigy).
These ultraviolet absorbers can be used alone or in combination of two or more. The blending amount of the ultraviolet absorber is preferably adjusted to 3 to 22 parts by weight with respect to 100 parts by weight of the nonvolatile content of the paint. If the blending amount is less than 3 parts by weight, the light resistance of the sublimation dye penetrating into the transparent or translucent resin layer 4 becomes insufficient. On the other hand, when the amount exceeds 22 parts by weight, the stain resistance, processability, coating film appearance, etc. of the coating film deteriorate. Moreover, coloring of the top coating film by an ultraviolet absorber is also observed.
In order to further improve the light resistance of the transparent or translucent resin layer 4, it is preferable to add a hindered amine light stabilizer in a proportion of 0 to 3 parts by weight with respect to the non-volatile content of the paint as necessary. Examples of the hindered amine light stabilizer include the following.
[0030]
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (SANOL LS770 manufactured by Sankyo Corporation), Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (Sankyo Corporation) SANOL LS765), 1- {2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl} -4- [3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine (SANOL LS2626 manufactured by Sankyo Corporation), 4-benzoyloxy-2,2,6,6-tetramethylpiperidine (Sankyo Corporation) Manufactured by SANOL LS744), 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4, 5] Decane-2,4-dione (Sanol LS440 manufactured by Sankyo Corporation), 2- (3,5-di-t-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6, 6-pentamethyl-4-piperidyl) (TINUVIN 144 from Ciba Geigy), bis (2,2,6,6-tetramethyl-4-piperidyl) succinate (TINUVIN 780FF from Ciba Geigy), dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (TINUVIN 622LD manufactured by Ciba Geigy), poly {[6- (1,1,3,3-tetramethyl Butyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino ] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]} (CHIMASSORB 944LD manufactured by Ciba Geigy), N, N′-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine polycondensate (CHIMASSORB 119FL, manufactured by Ciba Geigy), Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (TINUVIN 292 manufactured by Ciba Geigy), bis (1-octaoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate ( Ciba Geigy TINUVIN 123), HA-70G (Sankyo Co., Ltd.), ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-63, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-82, ADK STAB LA-87 (manufactured by Asahi Denka Kogyo Co., Ltd.)
[0031]
These light stabilizers can be used alone or in admixture of two or more. Even if the stabilizer is added in an amount larger than 3.0 parts by weight, the effect of improving the light resistance of the sublimation dye that has penetrated into the coating film is saturated, and the improvement corresponding to the increase is not seen. Appearance tends to deteriorate. The light stabilizer is preferably blended in the range of 0.5 to 1.5 parts by weight.
The transparent resin coating as the transparent or translucent resin layer 4 is passed through the base coat layer 2 (FIG. 1a), the base coat layer 2 and the primer layer 3 (FIG. 1b), or directly on the underlying metal plate 1 (FIG. 1c) can be formed. In any case, the color tone of the base metal plate 1 and the base coat layer 2 becomes a ground pattern and appears through the dyed resin layer 5. Therefore, a design metal plate having a unique depth feeling utilizing the texture of the base material is manufactured.
[0032]
【Example】
Printing condition 1 (Invention Examples 1-4, Comparative Examples 1, 3-5)
Manufacture of coated steel sheet to be used as the base metal sheet
A pre-painting treatment was applied to a Zn-plated steel sheet having a thickness of 0.5 mm, and a white polyester resin paint (AT-1001 primer manufactured by Kansai Paint Co., Ltd.) was applied to a dry coating thickness of 19 μm. A white base coat resin coating film was formed by baking at 1 ° C. for 1 minute. Next, 75 parts by weight of a polyester resin (Almatex P-646 manufactured by Mitsui Toatsu Chemical Co., Ltd.), 25 parts by weight of a fully alkyl hexane methylated melamine (melamine curing agent manufactured by Mitsui Cyanamid Co., Ltd.), a compound containing a polyfluorocarbon chain (Toray FS1265 from Dow Corning Silicone Co., Ltd., 0 to 5.0 parts by weight, organic modified silicone oil (KF6001 from Shin-Etsu Chemical Co., Ltd.) 0 to 5.0 parts by weight, triazine-based UV absorber (TINUVIN 400 from Ciba Geigy) 12 A polyester-based clear resin paint containing 1.5 parts by weight of a hindered amine light stabilizer (Ciba Geigy Corporation TINUVIN 123) was applied to a dry film thickness of 10 μm, and then a plate temperature of 240 ° C. for 1 minute. By baking, transparent resin coating film Form was.
[0033]
Pattern transfer using sublimation dyes
Using sublimation dye toner (sublimation printing toner manufactured by Nippon Steel Chemical Co., Ltd.), electrostatic printing paper (Cyan, Magenta, Yellow) The solid pattern was output. The obtained electrostatic recording paper is superposed on the coated surface of the coated steel sheet 1 and the temperature is 165 ° C. and the pressure is 0.5 kg / cm.² For 150 seconds. After completion of the crimping, the electrostatic recording paper was peeled from the coated steel plate.
[0034]
Printing condition 2 (Comparative Example 2)
Manufacture of coated steel sheet to be used as the base metal sheet
Polyester clear resin paint (AT-, manufactured by Kansai Paint Co., Ltd.) containing 12 parts by weight of a triazine UV absorber (TINUVIN 400 manufactured by Ciba Geigy) and 1.5 parts by weight of a hindered amine light stabilizer (TINUVIN 123 manufactured by Ciba Geigy) 1005 primer) was coated to a dry film thickness of 15 μm, and then the same coated steel plate as in Example 1 was used except that it was baked at a plate temperature of 210 ° C. for 1 minute.
Pattern transfer using sublimation dyes
The same sublimable dye toner as in Example 1 was used, and the pattern was transferred to the coated steel sheet in the same manner.
[0035]
Each printed metal sheet produced as described above was examined for gloss retention after transfer, wiping property of toner and coating resin, and coating appearance. The survey results are shown in Table 1 (Examples of the present invention) and Table 2 (Comparative examples). Each property in Table 1 and Table 2 was tested and evaluated as follows.
Gloss retention after transfer
The 60-degree specular reflectance before and after transfer was measured, and the gloss retention after transfer was calculated from the 60-degree specular reflectance after transfer / the 60-degree specular reflectance before transfer.
Dryability
The surface of the printed coated steel plate after transfer is wiped dry with a cotton towel. The toner and coated paper coating resin are completely wiped off. The remaining ones were evaluated as x.
Paint appearance
Using a smooth and uniform appearance as an index, ○ indicates a good appearance with no unevenness, △ indicates that there is repellency and some unevenness is observed on the paint film, and clear repellency occurs. What was not obtained was obtained as x.
[0036]

[0037]

[0038]
As is clear from the comparison between Table 1 and Table 2, in Table 1 according to the present invention, the gloss retention after transfer, the wiping property of the toner and the coating resin, and the appearance of print coating are all satisfactory. Was presented. Further, the printed coated surface had a good appearance over a long period of time because it did not adhere oil-based ink or the like and was excellent in stain resistance.
On the other hand, in the comparative example of Table 2, there was a decrease in gloss retention presumed to be caused by the sublimable dye or coating resin remaining on the surface after transfer. Further, the dry wiping property is poor, and it is difficult to remove the sublimable dye and the coating resin from the surface after transfer. In addition, when the printing surface is graffitied with oil-based ink or the like, the oil-based ink is integrated with the printing surface, and the beautiful printing surface immediately after transfer cannot be restored.
[0039]
【The invention's effect】
As described above, the printed metal sheet of the present invention contains a polyfluorocarbon chain-containing compound selected from a fluorosurfactant, a fluoro oil, a polymer containing a perfluoroalkyl group, and a fluorosilicone oil. By blending 10 to 1.0 parts by weight and silicone oil in the ratio of 0.10 to 1.0 parts by weight as a coating film modifier to the top coating without impairing the permeability of the sublimable dye during transfer. The top coating is non-tacky. Therefore, the sublimation dye remaining on the printed surface after transfer and the coated resin of the coated paper can be easily removed from the printed surface by dry wiping without being sublimated, and a printed metal sheet with a beautiful printed surface can be obtained. It is done. In addition, the printing surface has excellent stain resistance, and graffiti using oil paint can be easily wiped off, and a printed pattern with high design can be maintained over a long period of time.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 shows a cross section of a surface layer part of a printed metal sheet according to the present invention, in which a sublimation dye dye layer is provided on a base coat layer, and a sublimation dye dye on a primer layer and a base coat layer. Example (b) in which a layer is provided, Example (c) in which a sublimation dye-dyed layer is directly provided on a base metal plate

Claims (2)

One or two or more kinds of polyfluorocarbon chain-containing compounds selected from fluorine-based surfactants, fluorine-based oils, polymers containing perfluoroalkyl groups, and fluorosilicone oils per 100 parts by weight of the coating film-forming solid content are 0 . 10 to 1.0 parts by weight, the silicone oil from 0.10 to 1.0 and the top coating layer of a transparent or translucent resin including the weight portion is formed, penetrating the sublimable dye in said top coating layer Printed metal sheet. A triazine-based UV absorber and a benzotriazole-based UV absorber having good thermal stability and solubility are singly or in combination and are contained in the top coating at a ratio of 3 to 22 parts by weight based on the non-volatile content of the paint. 1. The printed metal sheet according to 1.

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