JP4036486B2 - Printed thermoplastic resin product and method for printing thermoplastic resin product - Google Patents

Description

【００２６】
（式中、ｎは１〜４であり、ＲはＨ又はＣＨ₃を示す。）
のビスフェノ−ル型であり、ビスフェノ−ル骨格をビスフェノ−ルＡ、ビスフェノ−ルＦ、ビスフェノ−ルＳ等にかえたものがある。
【００２７】
また、式（２）
【化２】

【００２８】
（式中、ｎは０ないし３であり、ＲはＨ又はＣＨ₃を示す。）
に示すようなフェノ−ルノボラック型のエポキシ（メタ）アクリレ−トも使用される。
【００２９】
また、エピクロルヒドリン変性（ポリ）アルキレングリコ−ルジ（メタ）アクリレ−ト、エポキシ化大豆油（メタ）アクリレ−トなどの脂肪族エポキシ（メタ）アクリレ−ト及び式（３）
【化３】

【００３０】
（ＲはＨ又はＣＨ₃であり、Ｒ₁はジカルボン酸の−ＣＯＯＨ基を除いた残基を示す。）
に示したような脂環族エポキシ（メタ）アクリレ−トも、要求性能に応じて使用される。
【００３１】
ウレタン（メタ）アクリレ−トとしては、式（４）
【化４】

【００３２】
（式中、ｎは１〜４であり、ＲはＨ又はＣＨ₃であり、Ｒ₁はジイソシアネートのＮＣＯを除いた残基であり、ＸはポリオールのＯＨを除いた残基を示す。）
で示される構造の化合物が使用される。
【００３３】
式（４）において、イソシアネ−トはトリレンジイソシアネ−ト、４，４−ジフェニルメタンジイソシアネ−ト、キシリレンジイソシアネ−ト等の芳香族ジイソシアネ−ト、ヘキサメチレンジイソシアネ−ト、トリメチルヘキサメチレンジイソシアネ−ト等の脂肪族ジイソシアネ−ト、イソホロンジイソシアネ−ト、メチレンビス（４−シクロヘキシルイソシアネ−ト）等の脂環族ジイソシアネ−ト、ポリオ−ルとしてはエチレングリコ−ル、プロピレングリコ−ル、１，４−ブタンジオ−ル、１，６−ヘキサンジオ−ル等のグリコ−ル類、ポリグリコ−ルエ−テル類、エトキシ化ビスフェノ−ルＡ等のビスフェノ−ルエ−テル類、スピログリコ−ル、カプロラクトン変性ジオ−ル、カ−ボネ−トジオ−ル等であり、これらジイソシアネ−トとポリオ−ルの組合せで合成されるウレタンの末端を（メタ）アクリル化した市販のものの中から要求性能に合致したものを選択使用する。
【００３４】
またポリエステル（メタ）アクリレ−トは、式（５）
【化５】

【００３５】
（式中、ｎは１〜５であり、ＲはＨ又はＣＨ₃であり、Ｒ₁はＨ又はＣＨ₂＝Ｃ（Ｒ）ＣＯＯ−であり、ＸはポリオールのＯＨ基を除いた残基であり、Ｙはジカルボン酸のＣＯＯＨ基を除いた残基を示す。）
に示す一般的な構造のものであり、これも多くのものが市販に供されており、その中から要求性能に応じて選択使用する。
【００３６】
ポリブタジエン（メタ）アクリレ−トは、ヒドロキシル基末端を１分子中に２個以上有する液状ポリブタジエンを直接（メタ）アクリル酸エステル化したものの他に、ヒドロキシル基をジイソシアネ−トを介してヒドロキシル基を有する（メタ）アクリル酸エステルと結合させた化合物が用いられる。これらは市販のもの、例えばＱｕｉｎｂｅａｍ−１０１（日本ゼオン）、ＴＥ樹脂（日本曹達）、ミケロンＮＵ−Ａ（早川ゴム）等がある。
多官能モノマ−及び／又はオリゴマ−使用の目的は、放射線重合に際し３次元架橋を生ぜしめ、膜の硬度、光沢、耐水性、耐薬品性、耐摩擦性を付与するためである。
【００３７】
上記の多官能モノマ−及び／又はオリゴマ−は、使用に際して１種のみを使用しても差し支えないが、多くの場合は２種以上の混合物がビヒクルの成分として加えられる。その使用量はビヒクルの他の成分を含めて、溶解性、粘度などの物性のほか、硬化時の架橋密度が要求を満たすものかどうかによって決定される。また、この出願発明の主題となるアルカリ脱離性を実現するための、ビヒクルの酸価を目的と合致させることも、使用量を決定する際の制約条件となる。通常の場合はビヒクル１００部中５〜２０部であるが、余り多く用いると硬化時の架橋収縮による応力剥離を生じ、基材への密着性が低下するおそれがある。
【００３８】
単官能モノマ−は、主として組成物粘度を調整する希釈剤として使用される場合が多い化合物で、その中から代表的なものを挙げると、２−エチルヘキシル（メタ）アクリレ−ト、シクロヘキシル（メタ）アクリレ−ト、ジシクロペンタニル（メタ）アクリレ−ト、ベンジル（メタ）アクリレ−ト、フェノキシエチル（メタ）アクリレ−ト、トルイルオキシエチル（メタ）アクリレ−ト、エトキシエチル（メタ）アクリレ−ト、エチルカルビト−ル（メタ）アクリレ−ト、イソボルニル（メタ）アクリレ−ト、メトキシプロピレングリコ−ル（メタ）アクリレ−ト、アクリロイルモルホリン、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレ−ト、ｔ−ブチルアミノエチル（メタ）アクリレ−ト等がある。また、単官能モノマ−は、分子内にヒドロキシル基、エポキシ基、リン酸エステル基などの極性基を含む場合、密着性が著しく向上するが、これらは、この出願発明においても耐水性を低下させない程度に使用することができる。たとえば、２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−ト、３−ブトキシ−２−ヒドロキシプロピル（メタ）アクリレ−ト、カプロラクトン変性２−ヒドロキシエチル（メタ）アクリレ−ト、３−フェノキシ−２−ヒドロキシプロピル（メタ）アクリレ−ト、グリシジル（メタ）アクリレ−ト、エチレンオキサイド変性ブトキシ化リン酸（メタ）アクリレ−ト等がある。これら単官能モノマ−は単独もしくは２種以上を混合して使用されるが、インキビヒクル１００部中、５〜４０部が用いられ、粘度調整は通常１０〜３０部の範囲で行われる。
【００３９】
上記のビヒクル成分は、実験によって求められた望ましい比率により混合されてインキビヒクルが製造されるが、この出願発明の目的である印刷における基材との密着性及び多層印刷における層間密着性を維持するには、請求項１（Ａ）のオリゴマー及び／又はポリマーは配合量が多いほど基材及び層間密着性に優れるが、実用的なインキ物性を得るには２０〜５０部が用いられる。このオリゴマー及び／又はポリマーを使用した基材密着配合は、多層印刷において、例えば５層重ねても層間剥離が生じない。また、アルカリ水溶液によるインキ硬化物の脱離を実現するためには、その酸価が５以上１５０以下となるように組成を決定する。
こうして得られたビヒクルを用いて紫外線硬化型インキとするには、光重合開始剤、光増感剤、有機及び／又は無機顔料、その他の添加剤等を加えて目的が達成されるが、ＥＢ（電子線）硬化を行う場合は、光重合開始剤及び光増感剤は必要ではない。
【００４０】
紫外線重合の場合に用いられる光重合開始剤としては多くのものが知られるが、公知のものの中から代表的なものを挙げると、ベンゾフェノン、ジエトキシアセトフェノン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−（４−メチルチオフェニル）−２−モルホリノ−プロパン−１−オン、ベンゾインアルキルエ−テル、ベンジル、ベンジルジメチルケタ−ル、カンファ−キノン、２−エチルアンスラキノン、ベンゾイル安息香酸メチル、４−フェニルベンゾフェノン、３，３´−ジメチル−４−メトキシベンゾフェノン、チオキサンソン、２，４−ジエチルチオキサンソン、メチルフェニルグリオキシレ−ト、ベンゾイルホスフィンオキサイド、１−トリメチルベンゾイルジフェニルホスフィンオキサイド等がある。
同じく、公知の光増感剤の中から代表的なものを挙げると、トリエタノ−ルアミン、メチルジエタノ−ルアミン、トリイソプロパノ−ルアミン、４，４´−ジエチルアミノベンゾフェノン、４−ジメチルアミノ安息香酸エチル、４−ジメチルアミノ安息香酸−ｎ−ブトキシエチル、４−ジメチルアミノ安息香酸イソアミル等がある。
【００４１】
上記の光重合開始剤は単独でも使用できるが、多くの場合は光増感剤と併用して光重合性を向上させる。光重合開始剤及び光増感剤の種類は、使用するインキヒビクル成分によって、もっとも適したものが選択される。その基準は、硬化速度、硬化時に発生する着色の有無、顔料配合の有無、硬化後の臭いの強弱等、目的に応じて加味検討される。使用量はインキビヒクルに対し、光重合開始剤及び光増感剤それぞれ１〜２０部が可能であるが、多量使用の場合は硬化は速いが分子量が大きくならず、硬化膜の強度は低下し、また臭いも強く好ましくない。もっとも望ましい使用範囲は、両者併用量として２〜１０部である。その場合、光重合開始剤と光増感剤の使用比率は、ビヒクル成分の種類と成分比によって異なり、また後述の着色用顔料を添加したインキでは、顔料に特異的な紫外線吸収能により両者の使用比を変化させる必要があり一律とはならない。
顔料は化学組成的に有機顔料と無機顔料に大別されるが、用途面からは着色顔料と無着色顔料（体質顔料）にも分けられる。紫外線硬化に関していえば、用途面の分類の方が重用される。
【００４２】
この出願発明では、顔料を用いないクリヤーインキとして用いることができるが、多くの場合顔料を添加した加飾インキとして用いられる。
着色顔料のうち、無機顔料には鉛白、亜鉛華、硫化亜鉛、二酸化チタン等の白色顔料、群青、紺青、コバルトブル−等の青色顔料、酸化クロム、ピリジアン、クロムグリ−ン等の緑色顔料、黄鉛、チタンイエロ−、黄色酸化鉄、モリブデ−トオレンジ、カドミウム系顔料、弁柄等の黄〜赤色顔料、鉄黒、チタンブラック、カ−ボンブラック等の黒色顔料、アルミニウム粉、ブロンズ等の金属顔料、マイカ等のパ−ル顔料がある。しかし、無機顔料には安全衛生面から使用を避けなければならないものが多々あり、上記の中から無害のものが選択使用される。有機顔料では、モノアゾ系、ジスアゾ系、縮合アゾ系、インダントロン系、インジゴ系、チオインジゴ系、キナクリドン系、フタロシアニン系、ジオキサジン系、イソインドリノン系、ピロロピロ−ル系等がいずれも使用でき、放射線照射という硬化方法に即して、とくに退色の少ない耐光堅牢度の高い顔料を選んで使用するのが望ましい。
【００４３】
上記着色顔料の使用量は、目的とする色濃度によって変わり、大体インキ全量中０．５〜５０％の範囲である。顔料特性としての着色力によって制約されるが、代表的な白色顔料である酸化チタンの場合は１５ないし４０％、黒色顔料のカ−ボンブラックでは３〜６％が通常量である。有機着色顔料では、鮮明な色を得るには３〜２０％で、紫外線による硬化の場合は４〜１５％が望ましい。この出願発明の特許請求の範囲に記載のビヒクルは、カルボキシル基のような極性基を多く含むことから、一般に着色顔料の分散性は良い。しかしさらに良好な発色を得るには、ビヒクルに少量の顔料分散剤を添加したものに多量の顔料を配合して、その吸油量に起因する粘度向上を利用して物理的に粉砕圧力のかかりやすい状態を作り出し、色材工業における一般的な媒体分散機たとえばボ−ルミルやロ−ルミル等で十分な混練を行う。こうして得た高濃度の顔料分散体（トナ−）を、インキ配合の際、所定の顔料濃度となるように不足分のビヒクルで補充調整する方法がとられる。
【００４４】
この出願発明で使用される放射線硬化型インキ組成物には、粘度、流動性、チクソ性等の印刷インキの特性維持、インキ肉盛保持と増量、硬化時の収縮緩衝、表面つや消し、スリップ性付与、膜の強度向上等の目的で、種々の無着色顔料（体質顔料）を使用することができる。よく使用される体質顔料としては、タルク、カオリン、シリカ、沈降性硫酸バリウム、沈降性炭酸カルシウム、アルミナホワイト、ホワイトカ−ボン等無機体質顔料、ポリエチレンワックス、ポリプロピレンワックス、多フッ化ポリエチレンワックス等のワックス類、ポリアミド樹脂、ポリイミド樹脂、メラミン樹脂、ベンゾグアナミン樹脂、セルロ−ス、コラ−ゲン等の人工及び／又は天然高分子の微粉末である。これらは目的に応じて自由に使用量を決定することができる。この出願発明の放射線硬化型インキ組成物には、硬化膜の仕上がり状態を調整するために、レベリング剤及び／又は消泡剤を加えることができる。これらは、市場で一般に販売されている諸種のレベリング剤、消泡剤の中から、ビヒクル成分によく相溶し、表面平滑性の得られるものを試験によって確認して使用する。種類や使用量は、この出願発明のインキ組成物の内容を制約するものではなく、適宜定めればよいが、通常レベリング剤及び／又は消泡剤の合計量として全インキ量の０．５〜５重量％が使用される。
【００４５】
その他必要に応じて紫外線吸収剤、濡れ性改良剤、酸化防止剤等も使用することができる。
このようにして製造されたこの出願発明で使用される放射線硬化型インキ組成物を用いたインキは、主にスクリ−ン印刷に用いられるが、有機溶剤を用いてより低粘度に調整した場合は、フレキソ印刷及びグラビア印刷等、他の印刷方法におけるインキとしても十分に使用できる。
【００４６】
この出願発明で使用される放射線硬化型インキのポリエチレンテレフタレートまたはポリアクリロニトリル樹脂上の硬化後の印刷物は、これを水酸化ナトリウム、水酸化カリウムなどの強アルカリ水溶液に短時間浸漬することで容易に剥離除去することができ、このときポリエチレンテレフタレートまたはポリアクリロニトリル樹脂を加水分解するなどの激しい条件を必要としない。脱離は溶解脱離から膜状脱離までの諸段階があるが、これらは、（Ｂ）の量比を調整することにより、目的とする性能を得ることが可能である。いずれにしても脱離性状の選択は除去後の廃水の処理方法によって定められるが、脱離後のポリエチレンテレフタレートまたはポリアクリロニトリル樹脂は水洗、乾燥などの簡単な方法で、容易に再生使用、または、再利用、再充填できるだけの清浄な状態で回収できる。
【００４７】
前記印刷インキによりプラスチック製品に文字、模様、図形等の印刷を施す手段としては、一般にシルクスクリ−ン印刷が利用され、通常２５４〜３３０メッシュ程度のシルクスクリ−ン版が使用される。
また、前記放射線硬化性樹脂をビヒクルとする印刷インキによる印刷面に行われる紫外線の照射は、普通２００〜４５０ｎｍ程度の波長を有する高圧水銀ランプやメタルハライドランプ等によって施されるもので、紫外線積算光量としては１００〜５００ｍｊ／ｃｍ²が好適である。又、通常、電子線照射の場合は１０〜１００ＫＧｙの照射量で行われ、３０〜６０ＫＧｙが好適である。
【００４８】
合成例１
実施例に用いられる側鎖に不飽和二重結合を有する線状ポリエステルオリゴマ−及び／又はポリマ−は、下記の表１における（１）の共重合ポリエステルポリオ−ルを（２）の組成でウレタンアクリレ−ト化して得た（単位は重量部）。
【００４９】
【表１】

【００５０】
合成例２
カルボキシル基を１〜１０個有し、不飽和二重結合を２個以上有する酸性オリゴマーの合成について以下に３例を記す。
（ａ）ビスフェノ−ルＡジクリシジルエ−テル１９０．０ｇ（エポキシ当量１９０．０）、アクリル酸７５．０ｇ（１．０５ｍｏｌ）、ジメチルベンジルアミン２ｇ、ｐ−メトキシフェノ−ル０．２ｇを温度計、攪拌器、還流冷却器を付したフラスコに加え、均一に溶解後８０℃に加熱し、２４時間保持し、酸価１０．３のエポキシアクリレ−トを得た。次いで無水フタル酸１４０．６ｇ（０．９５ｍｏｌ）を加え、８０℃で５時間保持し、酸価１３０．７の淡黄色粘稠なビスフェノ−ルＡエポキシアクリレ−トのフタル酸エステルを合成した。
（ｂ）エポキシノボラック樹脂１９０．０ｇ（エポキシ当量１９０．０）、アクリル酸７５．０ｇ（１．０５ｍｏｌ）、テトラメチルアンモニウムクロライド２．０ｇ、ｐ-メトキシフェノ−ル０．２ｇを、上記（ａ）と同様の装置に仕込み、均一に溶解した後８０℃に加熱し、２４時間保持して酸価１０．５のエポキシアクリレ−トを得た。次いで無水コハク酸９５ｇ（０．９５ｍｏｌ）を加え、８０℃で５時間保持し、酸価１４５．２を有する淡黄色粘稠なエポキシノボラックアクリレ−トのコハク酸エステルを得た。
（ｃ）グリセリントリグリシジルエ−テル１５０ｇ（エポキシ当量１５０．０）、アクリル酸７５．０ｇ（１．０５ｍｏｌ）、テトラブチルフォスフォニウムブロマイド２g、ｐ−メトキシフェノ−ル０．２ｇを（ａ）と同様の装置に仕込み、均一に溶解した後８０℃に加熱し、酸価９．８のエポキシアクリレ−トを得た。次いで無水ヘキサヒドロフタル酸１４５ｇ（０．９５ｍｏｌ）を加え、８０℃で５時間保持し、酸価１４１．３を有する淡黄色粘稠なグリセリンエポキシアクリレ−トのヘキサヒドロフタル酸エステルを得た。
【００５１】
製造例１
合成例１ Ｂ−１の不飽和二重結合を有するオリゴマ−２５，０ｇ、脂肪族ウレタンヘキサアクリレ−ト５．０ｇ、脂肪族ウレタンジアクリレート２５．９ｇ、モノアクリロイルオキシエチルフタレ−ト６．５ｇ、合成例２（ａ）のビスフェノ−ルＡエポキシアクリレ−トのフタル酸エステル５．０ｇ、トリメチロ−ルプロパントリアクリレ−ト２．０ｇ、フェノキシエチルアクリレ−ト１４．６ｇ、アクリロイルモルホリン１６．０ｇを混合した酸価１９．３のビヒクル１００部に対し、ミストロンベ−パ−タルク１５部、ベンジルジメチルケタ−ル１０部、ジメチルアミノ安息香酸エチルエステル５部、ポリエチレンワックス粉末３部、レベリング剤（ビックケミ−社 ＢＹＫ−３０６）１部、熱重合禁止剤フェノチアジン０．１部を混合し、これをロ−ルミルで分散粒子径5ミクロン以下の無着色インキを製造した。
【００５２】
【実施例】
実施例１
製造例１によって得た無着色インキを３００メッシュのテトロン製スクリーン版を用いて無処理ポリエチレンテレフタレート製シート上にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより紫外線光量１５０ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。
さらに、この硬化膜の上に印刷、硬化を５回、計６回繰り返した。このときの印刷は上記と同一条件であるが、硬化は同一の露光機を用い、紫外線光量が２回目、３回目、４回目は１８０ｍｊ／ｃｍ²、５回目は２５０ｍｊ／ｃｍ²、６回目は３００ｍｊ／ｃｍ²となるように行ったところ、１回目の印刷面、６回目の印刷面を始め、全ての重ね刷り部分においてセロテープによる剥離試験および爪によるスクラッチ試験で全く剥離を生じなかった。
上記の条件にて作成した重ね印刷片を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は大部分膨潤、一部溶解して脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
【００５３】
製造例２
合成例１ Ｂ−１の不飽和二重結合を有するオリゴマ−１７７ｇをフェノキシエチルアクリレ−ト１１８ｇに溶解し、これに顔料分散剤（ＩＣＩ社製ソルスパ−ス ２４０００／ソルスパ−ス ５０００＝４／１）１．５ｇを混合しておき、これにヘリオゲンブルーＬ-７０８０（ＢＡＳＦ社製）５２．３ｇを加えて、顔料分散粒子径が５ミクロン以下となるまで、ロ−ルミルで十分に混練した。こうして得られたトナ−のうちの４１．６ｇにＢ−１の不飽和二重結合を有するオリゴマー７．６ｇと、多官能ウレタンアクリレート紫光１７００Ｂ（日本合成化学工業）１０．０ｇ、ネオペンチルグリコールエチレンオキサイド２モル付加体ジアクリレート４．６ｇ、モノアクリロイルオキシエチルフタレ−ト１０．０ｇ、合成例２-（ｃ）のグリセリンエポキシアクリレ−トのヘキサヒドロフタル酸エステル６．２ｇ、アクリロイルモルホリン２０．０ｇをよく混合し、着色インキビヒクルとした。このビヒクルの酸価は３０．０であった。
上の着色インキビヒクル１００ｇに対し光重合開始剤ジエチルチオキサンソン３．０ｇ、光増感剤ジメチルアミノ安息香酸イソアミルエステル３．０ｇ、沈降性硫酸バリウム３５ｇ、ホリプロピレンワックス粉末３ｇ、レベリング剤（シャムロック社製バ−サフロ−ベ−ス）２ｇ、熱重合禁止剤ｐ−メトキシフェノ−ル０．０４ｇを加えてよく攪拌した後、ロ−ルミルでよく混練して均質な青色インキを得た。
【００５４】
実施例２
製造例２の青色インキを実施例１と同様に無処理ポリエチレンテレフタレート製シート上にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより紫外線光量２００ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。
さらに、この硬化膜の上に印刷、硬化を５回、計６回繰り返した。このときの印刷は上記と同一条件であるが、硬化は同一の露光機を用い、紫外線光量が２回目、３回目は２３０ｍｊ／ｃｍ²、４回目は２５０ｍｊ／ｃｍ²、５回目は３００ｍｊ／ｃｍ²となるように行ったところ、１回目の印刷面、６回目の印刷面を始め、全ての重ね刷り部分においてセロテープによる剥離試験でおよび爪によるスクラッチ試験で全く剥離を生じなかった。
上記の条件にて作成した重ね印刷片を２％水酸化ナトリウム水溶液中に７０℃で２０分間放置したところ、硬化膜は大部分膨潤、一部溶解して脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
【００５５】
製造例３
合成例１ Ｂ-１の側鎖に不飽和二重結合を有する線状ポリエステルオリゴマ−１６．０ｇ、脂肪族ウレタンヘキサアクリレ−ト４．９ｇ、モノアクリロイルオキシエチルサクシネ−ト５．５ｇ、合成例２-（ｂ）のエポキシノボラックアクリレ−トコハク酸エステル４．５ｇ、トリメチロ−ルプロパントリエポキシアクリレ−ト３．９ｇ、トルイルオキシエチルアルクリレート３．９ｇ、フェノキシエチルアクリレ−ト１１．０ｇ、アクリロイルモルホリン９．８ｇを混合して、酸価５０．８のインキビヒクルを得た。さらに顔料分散剤Ｄｉｓｐｅｒｂｙｋ−１１０（ビックケミ−社製）０．５ｇを添加して均一に混和し、これに酸化チタン タイペ−クＣＲ−９０（石原産業製）を３０．０ｇ、光重合開始剤アシルホスフィンオキサイド６．０ｇ、フッ化ポリエチレンワックス粉末２．０ｇ、レベリング剤 バ−サフロ−ベ−ス（シャムロック社製）１．５ｇ、消泡剤 アクアレンＮ（共栄社油脂化学工業製)１．０ｇ、熱重合禁止剤ｐ-メトキシフェノ−ル０．０４ｇを加え、しばらく攪拌の後、ロ−ルミルを用いて顔料分散粒子径が５ミクロン以下になるまで混練した。
【００５６】
実施例３
製造例３によって得られた白インキを実施例１と同様に無処理ポリエチレンテレフタレート製シート上にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより紫外線光量２５０ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。
さらに、この硬化膜の上に印刷、硬化を４回、計５回繰り返した。このときの印刷は上記と同一条件であるが、硬化は同一の露光機を用い、紫外線光量が２回目、３回目は２８０ｍｊ／ｃｍ²、４回目は３００ｍｊ／ｃｍ²となるように行ったところ、１回目の印刷面、５回目の印刷面を始め、全ての重ね刷り部分においてセロテープによる剥離試験および爪によるスクラッチ試験で全く剥離を生じなかった。
上記の条件にて作成した重ね印刷片を２％水酸化ナトリウム水溶液中に７０℃で２５分間放置したところ、硬化膜は白濁液状に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
【００５７】
実施例４
製造例２によって得られた青色インキを使用し、アルカリ溶液内浸漬による脱離試験を行った。なお、生産使用現行青色インキとのアルカリ溶液内浸漬における脱離性の対比もあわせて行った。
試験試料として次のものを使用した。
容器 ２．７リットル無処理ポリエチレンテレフタレート製容器
重量 １１０ｇ、印刷面積 １５０ｃｍ²、表面積 ９００ｃｍ²
使用インキ ▲１▼ 生産使用現行青色インキ
▲２▼ 製造例２と同様にして得られた青色インキ
最初に▲２▼の出願発明の青インキを３５０メッシュのナイロン製スクリーン版を用いて無処理のポリエチレンテレフタレート製容器胴部の表面にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより、紫外線積算光量２００ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。同一の条件、方法でこの硬化膜の上に重なるように印刷、硬化を３回、計４回繰り返し行った。この様にして得られた硬化膜の全てはセロテープによる剥離試験及び爪によるスクラッチ試験において全く剥離はみられず完全に密着していた。
次に▲１▼の生産使用現行青色インキを３５０メッシュのナイロン製スクリーン版を用いて無処理のポリエチレンテレフタレート製容器胴部の表面にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより、紫外線積算光量２００ｍｊ／ｃｍ²を照射し、硬化膜を得た。同一の条件、方法でこの硬化膜の上に重なるように印刷、硬化を３回、計４回繰り返し行った。この様にして得られた硬化膜はセロテープによる剥離試験では全ての重ね刷り部分において全く剥離はみられなかったが爪によるスクラッチ試験において４回目の印刷塗膜１回目の印刷塗膜との界面から層間剥離を生じた。
同条件にて作成した各々の重ね印刷した試料を下記の方法にてアルカリ溶液内浸漬による脱離試験を行った。
条件
浸漬液 水酸化ナトリウム水溶液
濃度（Ｗｔ％） ０．１％ １％ ５％
浸漬温度 ２０℃ ５０℃ ８０℃
浸漬時間 １分 ５分 ２０分 ５０分
確認項目は自然脱離状態及びガーゼ摩擦による脱離状態である。
試験の結果についての脱離状態の評価はアルカリ溶液内浸漬による印刷部の自然脱離と浸漬後のガーゼ摩擦による脱離の両方を加味し、次のようにした。
評価
◎ ：溶液内で完全に自然脱離し、印刷部が残らない
○ ：自然脱離・ガーゼ摩擦により印刷部が残らない
△ ：自然脱離・ガーゼ摩擦により印刷部が半分以上脱離する
△× ：部分的に自然脱離するがガーゼ摩擦を行っても印刷部の脱離が半分以下である
× ：自然脱離せず、ガーゼ摩を行っても、印刷部の脱離が半分以下である
×× ：ガーゼ摩擦を行うと色移りはあるが印刷部の脱離はない
×××：ガーゼ摩擦を行っても色移りもなく印刷部の脱離もない
【００５８】
【表２】

【００５９】
インキ▲２▼によって作成された重ね印刷の試料は８０℃水酸化ナトリウム１％水溶液内浸漬において５分から２０分の間に全ての硬化膜が完全自然脱離し、８０℃水酸化ナトリウム５％水溶液内浸漬においては１分から５分の間に完全自然脱離する。溶液の温度が同じであれば溶液のアルカリ濃度が高い程、溶液のアルカリ濃度が同じであれば溶液の温度が高い程、印刷が完全自然脱離するまでの時間は短い。
【００６０】
実施例５
実施例４と同一の試験試料を用いて同一の方法で作成した、各々の印刷容器を約１ｃｍ各に粉砕し、フレーク状の材料２００Ｋｇを用意した。
ついで、実際の回収ポリエチレンテレフタレートフレーク精製プロセスで印刷の脱離状態を確認した。主な精製プロセスは次の通りである。
▲１▼ 風選 ：サイクロンによる紙、微粉などの除去
▲２▼ 浮沈分離 ：水槽中で比重分離
▲３▼ アルカリ洗浄：８０℃ ２％水酸化ナトリウム水溶液槽（６０００リットル）で１０分、２０分浸漬
▲４▼ 水洗 ：水槽で２０分洗う。
▲５▼ 乾燥後風選
▲６▼ 完成品
確認結果の評価は、精製後のフレークを観察することにより行い、次のようにした。
評価
◎ ：印刷が付着したフレークがみられない
× ：印刷が付着したフレークが多数混入している
【００６１】
【表３】

【００６２】
製造例４
合成例１ Ｂー１の側鎖に不飽和二重結合を有する線状ポリエステルオリゴマー２５．０ｇ、フェノキシエチルアクリレート１９．７ｇ、トルイロキシエチルアクリレート６．５ｇ、アクリロイルモルホリン１９．３ｇ、ネオペンチルグリコールエチレンオキサイド２モル付加体のジアクリレート３．０ｇ、トリメチロールプロパントリエポキシアクリレート６．６ｇ、６官能ウレタンアクリレート エベクリル１２９０Ｋ（ダイセルユーシービー製）８．０ｇ、モノアクリロイルオキシエチルサクシネート１０．０ｇ、合成例２（ａ）のビスフェノールＡエポキシアクリレートのフタル酸エステル２．０ｇ追加混合攪拌し、酸価２８．６の均一なビヒクルを得た。次いでこのビヒクル９２．０ｇに顔料分散剤アンチテラ−Ｕ（ビックケミー社製）０．２ｇとｐーメトキシフェノール０．０５ｇを予め攪拌溶解しておき、これにラーベン４５０（コロンビアカーボン製）１．５ｇ、ラーベン１３５０（コロンビアカーボン製）１．５ｇ、及びチタンブラック１０Ｓ（三菱マテリアル製）５．０ｇを分散し、ロールミルで分散粒子径が５ミクロン以下となるまで十分に混練を行い着色ビヒクルを得た。
この着色ビヒクル９６．５ｇに対しフッ化ポリエチレンワックス粉末２．０ｇ、レベリング剤ＢＹＫー３０６（ビックケミー社製）０．５ｇ、消泡剤アクアレンＮ（共栄社油脂化学工業製）１．０ｇを加えてディゾルバーを用いて十分なる攪拌を行い、ＥＢ硬化用の黒色インキを製造した。
【００６３】
実施例６
製造例４によって得られた黒色インキを使用し、３３０メッシュのナイロン製スクリーン版を用いて無処理ポリエチレンテレフタレート製シート上にスクリーン印刷を施し、ＥＢ照射装置ＣＢ２５０／１５／１８０Ｌ（岩崎電気社製）を用いて６０ＫＧｙ（１６５ＫＶ、３．２ｍＡ、１０ｍ／ｍｉｎ）の電子線量で硬化し、タックフリーの硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。
また、この硬化膜の上に重なるように同一の条件、方法で印刷、硬化を５回、計６回繰り返した。この様にして得られた硬化膜の全てはセロテープによる剥離試験及び爪によるスクラッチ試験では全く剥離はみられず完全に密着していた。同じ条件にて作成した硬化膜を５％水酸化ナトリウム水溶液中に８０℃で５分間放置したところ、硬化膜は基材から完全に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られず、アルカリ水溶液による浸食の形跡も観察されなかった。
【００６４】
実施例７
製造例１によって得た無着色インキを３００メッシュのテトロン製スクリーン版を用いて表面を金型により粗面化したポリエチレンテレフタレート製容器の表面にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより紫外線光量１５０ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。さらに、この硬化膜の上に印刷、硬化を４回、計５回繰り返した。このときの印刷は上記と同一条件であるが、硬化は同一の露光機を用い、紫外線光量が２回目、３回目は１８０ｍｊ／ｃｍ²、４回目は２００ｍｊ／ｃｍ²、５回目は３００ｍｊ／ｃｍ²となるように行ったところ、１回目の印刷面、５回目の印刷面を始め、全ての重ね刷り部分においてセロテープによる剥離試験、爪によるスクラッチ試験および容器表面を押圧による屈折を繰り返す過酷な剥離試験においてもまったく剥離を生じなかった。
上記の条件にて作成した重ね印刷片を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は完全に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
【００６５】
実施例８
製造例２によって得た青色インキを３００メッシュのテトロン製スクリーン版を用いて表面を吹き付けにより粗面化したポリエチレンテレフタレート製容器の表面にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより紫外線光量２００ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。さらに、この硬化膜の上に印刷、硬化を３回、計４回繰り返した。このときの印刷は上記と同一条件であるが、硬化は同一の露光機を用い、紫外線光量が２回目、３回目は２３０ｍｊ／ｃｍ²、４回目は３００ｍｊ／ｃｍ²となるように行ったところ、１回目の印刷面、４回目の印刷面を始め、全ての重ね刷り部分においてセロテープによる剥離試験、爪によるスクラッチ試験および容器表面を押圧による屈折を繰り返す過酷な剥離試験で全く剥離を生じなかった。
上記の条件にて作成した重ね印刷片を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は完全に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
【００６６】
実施例９
製造例３によって得た白色インキを３００メッシュのテトロン製スクリーン版を用いて表面を水酸化ナトリウム水溶液により粗面化したポリエチレンテレフタレート製容器の表面にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより紫外線光量２００ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。さらに、この硬化膜の上に印刷、硬化を３回、計４回繰り返した。このときの印刷は上記と同一条件であるが、硬化は同一の露光機を用い、紫外線光量が２回目、３回目は２３０ｍｊ／ｃｍ²、４回目は３００ｍｊ／ｃｍ²となるように行ったところ、１回目の印刷面、４回目の印刷面を始め、全ての重ね刷り部分においてセロテープによる剥離試験、爪によるスクラッチ試験および容器表面を押圧による屈折を繰り返す過酷な剥離試験で全く剥離を生じなかった。
上記の条件にて作成した重ね印刷片を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は重ね部分を分離せずに一層の膜となって剥離して液中に浮遊し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
また、水酸化ナトリウム水溶液槽は若干白濁していた。
【００６７】
実施例１０
製造例１によって得た無着色インキを３００メッシュのテトロン製スクリーン版を用いてフレームにより処理したポリエチレンテレフタレート製容器の表面にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより紫外線光量１５０ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。さらに、この硬化膜の上に印刷、硬化を４回、計５回繰り返した。このときの印刷は上記と同一条件であるが、硬化は同一の露光機を用い、紫外線光量が２回目、３回目は１８０ｍｊ／ｃｍ²、４回目は２００ｍｊ／ｃｍ²、５回目は３００ｍｊ／ｃｍ²となるように行ったところ、１回目の印刷面、５回目の印刷面を始め、全ての重ね刷り部分においてセロテープによる剥離試験、爪によるスクラッチ試験および容器表面を押圧による屈折を繰り返す過酷な剥離試験で全く剥離を生じなかった。
上記の条件にて作成した重ね印刷片を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は完全に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
【００６８】
実施例１１
製造例１によって得た無着色インキを３００メッシュのテトロン製スクリーン版を用いてコロナ放電により処理したポリエチレンテレフタレート製容器の表面にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより紫外線光量１５０ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。さらに、この硬化膜の上に印刷、硬化を４回、計５回繰り返した。このときの印刷は上記と同一条件であるが、硬化は同一の露光機を用い、紫外線光量が２回目、３回目は１８０ｍｊ／ｃｍ²、４回目は２００ｍｊ／ｃｍ²、５回目は３００ｍｊ／ｃｍ²となるように行ったところ、１回目の印刷面、５回目の印刷面を始め、全ての重ね刷り部分においてセロテープによる剥離試験、爪によるスクラッチ試験および容器表面を押圧による屈折を繰り返す過酷な剥離試験で全く剥離を生じなかった。
上記の条件にて作成した重ね印刷片を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は完全に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
【００６９】
実施例１２
製造例１によって得た無着色インキを３００メッシュのテトロン製スクリーン版を用いて紫外線照射により処理したポリエチレンテレフタレート製容器の表面にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより紫外線光量１５０ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。さらに、この硬化膜の上に印刷、硬化を４回、計５回繰り返した。このときの印刷は上記と同一条件であるが、硬化は同一の露光機を用い、紫外線光量が２回目、３回目は１８０ｍｊ／ｃｍ²、４回目は２００ｍｊ／ｃｍ²、５回目は３００ｍｊ／ｃｍ²となるように行ったところ、１回目の印刷面、５回目の印刷面を始め、全ての重ね刷り部分においてセロテープによる剥離試験、爪によるスクラッチ試験および容器表面を押圧による屈折を繰り返す過酷な剥離試験で全く剥離を生じなかった。
上記の条件にて作成した重ね印刷片を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は完全に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
【００７０】
製造例５
表４に示した配分組成により、４色の着色インキを製造した。具体的な操作手順を示すと、まず、ビヒクル成分にあらかじめ熱重合禁止剤と顔料分散剤を加えて攪拌溶解しておき、これに顔料を加えてディゾルバーで予備混合を行った後、残りの原料を加えて、さらに混合し、ついでロールミルで十分に混練した。混練は顔料の分散粒子径が５ミクロンに達した時を終点とし、これを目的の着色インキとして捕集した。
【００７１】
【表４】

【００７２】
実施例１３
製造例５によって得られた４色のインキを３００メッシュのナイロン製スクリーン版を用いてポリエチレンテレフタレート製シート上に印刷した。重ね印刷は各色ごとに印刷、硬化を行い、従って２色目は１色目の硬化膜の上に重なるが、故意に基材にも印刷する部分をつくり硬化させた。同様にして３色目及び４色目を印刷、硬化し、図１に示すようなパターン概念の試験片を作成した。
各色の硬化条件は全て１５０ｍｊ／ｃｍ²の同一紫外線光量とし、試験片を作成した。ここの試験片の図１のパターンの全ての印刷部分（１色から４色重ね部分まで）を爪によるスクラッチ試験を行ったが全く剥離はみられず完全に密着していた。
同条件にて作成した印刷片を２％水酸化ナトリウム水溶液中に７０℃で１０分間放置したところ、硬化膜は完全に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
次に製造例５によって得られた４色のインキを３００メッシュのナイロン製スクリーン版を用いてポリエチレンテレフタレート製シート上に印刷した。重ね印刷は各色ごとに印刷、硬化を行い、従って２色目は１色目の硬化膜の上に重なるが、故意に基材にも印刷する部分をつくり硬化させた。同様にして３色目及び４色目を印刷、硬化し、図１に示すようなパターン概念の試験片を作成した。
各色の硬化条件は全て２００ｍｊ／ｃｍ²の同一紫外線光量とし、試験片を作成した。ここの試験片の図１のパターンの全ての印刷部分（１色から４色重ね部分まで）を爪によるスクラッチ試験を行ったが全く剥離はみられず完全に密着していた。
同条件にて作成した印刷片を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は完全に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
さらに製造例４によって得られた４色のインキを３００メッシュのナイロン製スクリーン版を用いてポリエチレンテレフタレート製シート上に印刷した。重ね印刷は各色ごとに印刷、硬化を行い、従って２色目は１色目の硬化膜の上に重なるが、故意に基材にも印刷する部分をつくり硬化させた。同様にして３色目及び４色目を印刷、硬化し、図１に示すようなパターン概念の試験片を作成した。
各色の硬化条件は全て３００ｍｊ／ｃｍ²の同一紫外線光量とし、試験片を作成した。ここの試験片の図１のパターンの全ての印刷部分（１色から４色重ね部分まで）を爪によるスクラッチ試験を行ったが全く剥離はみられず完全に密着していた。
同条件にて作成した印刷片を２％水酸化ナトリウム水溶液中に７０℃で２０分間放置したところ、硬化膜は完全に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
【００７３】
実施例１４
製造例５によって得られた４色のインキを使用し、最初に白色インキを無処理ポリエチレンテレフタレート製容器の表面上にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより、紫外線積算光量１８０ｍｊ／ｃｍ²を照射し、硬化膜を得た。その白色の硬化膜の上に重なるように青色インキを同様の方法で印刷、硬化させ、さらに赤色インキ次いで黄色インキを白色の硬化膜の上に重なるように同様の方法で印刷、硬化させた。この様にして得られた硬化膜の全てはセロテープによる剥離試験および爪によるスクラッチ試験でまったく剥離はみられず、完全に密着していた。
同じ条件にて作成した硬化膜を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は完全に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
また、生産使用現行インキの白色インキ、青色インキ、赤色インキ、黄色インキを使用し、上記と同様の条件、方法でポリエチレンテレフタレート製容器胴部の表面にスクリーン印刷を施し、硬化膜を得た。この硬化膜のすべてはセロテープによる剥離試験で全く剥離はみられなかったが、爪によるスクラッチ試験を行ったところ黄色の硬化膜が白色の硬化膜との界面から層間剥離を生じた。
同じ条件にて作成した硬化膜を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したが、硬化膜はポリエチレンテレフタレート基材から脱離しなかった。
【００７４】
実施例１５
製造例５によって得られた４色のインキを使用し、実施例４と同様にアルカリ溶液内浸漬による脱離試験を行った。なお、生産使用現行インキとのアルカリ溶液内浸漬における脱離性の対比もあわせて行った。
試験試料として次のものを使用した。
容器 ２．７リットル無処理ポリエチレンテレフタレート製容器
重量 １１０ｇ、印刷面積 １５０ｃｍ²、表面積 ９００ｃｍ²
使用インキ ▲１▼ 生産使用現行インキ ４色（白色インキ、青色インキ、赤色インキ、黄色インキ）
▲２▼ 製造例５によって得られた（白色インキ、青色インキ、赤色インキ、 黄色インキ）
最初に▲２▼の白色インキを３５０メッシュのナイロン製スクリーン版を用いて無処理のポリエチレンテレフタレート製容器胴部の表面にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより、紫外線積算光量１５０ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。その白色の硬化膜の上に重なるように青色インキを同様の方法で印刷、硬化させ、さらに赤色インキ次いで黄色インキを白色の硬化膜の上に重なるように同様の方法で印刷、硬化させた。この様にして得られた硬化膜の全てはセロテープによる剥離試験及び爪によるスクラッチ試験では全く剥離はみられず完全に密着していた。
次に▲１▼の白色インキを同様にして３５０メッシュのナイロン製スクリーン版を用いて無処理のポリエチレンテレフタレート製容器胴部の表面にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより、紫外線積算光量１５０ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。その白色の硬化膜の上に重なるように青色インキを同様の方法で印刷、硬化させ、さらに赤色インキ次いで黄色インキを白色の硬化膜の上に重なるように同様の方法で印刷、硬化させた。この様にして得られた硬化膜は全ての重ね刷り部分においてセロテープによる剥離試験では全く剥離はみられなかったが、爪によるスクラッチ試験を行ったところ黄色の硬化膜が白色の硬化膜との界面から層間剥離を生じた。
同条件にて作成した各々の重ね印刷した試料を下記の方法にてアルカリ溶液内浸漬による脱離試験を行った。
条件
浸漬液 水酸化ナトリウム水溶液
濃度（Ｗｔ％） ０．１％ １％ ５％
浸漬温度 ２０℃ ５０℃ ８０℃
浸漬時間 １分 ５分 ２０分 ５０分
確認項目は自然脱離状態及びガーゼ摩擦による脱離状態である。
試験の結果についての脱離状態の評価はアルカリ溶液内浸漬による印刷部の自然脱離と浸漬後のガーゼ摩擦による脱離の両方を加味し、次のようにした。
評価
◎ ：溶液内で完全に自然脱離し、印刷部が残らない
○ ：自然脱離・ガーゼ摩擦により印刷部が残らない
△ ：自然脱離・ガーゼ摩擦により印刷部が半分以上脱離する
△× ：部分的に自然脱離するがガーゼ摩擦を行っても印刷部の脱離が半分以下である
× ：自然脱離せず、ガーゼ摩を行っても、印刷部の脱離が半分以下である
×× ：ガーゼ摩擦を行うと色移りはあるが印刷部の脱離はない
×××：ガーゼ摩擦を行っても色移りもなく印刷部の脱離もない
【００７５】
【表５】

【００７６】
実施例１６
製造例５によって得られた４色のインキを使用し、最初に白色インキをフレームにより処理したポリエチレンテレフタレート製容器の表面上にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより、紫外線積算光量２００ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。その白色の硬化膜の上に重なるように青色インキを同様の方法で印刷、硬化させ、さらに赤色インキ次いで黄色インキを白色の硬化膜の上に重なるように同様の方法で印刷、硬化させた。この様にして得られた硬化膜の全てはセロテープによる剥離試験、爪によるスクラッチ試験及び容器表面を押圧による屈折を繰り返す過酷な剥離試験においてもまったく剥離はみられず、完全に密着していた。
同条件にて作成した硬化膜を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は完全に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
【００７７】
実施例１７
製造例５によって得られた４色のインキを使用し、最初に白色インキをコロナ放電により処理したポリエチレンテレフタレート製容器の表面上にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより、紫外線積算光量２００ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。その白色の硬化膜の上に重なるように青色インキを同様の方法で印刷、硬化させ、さらに赤色インキ次いで黄色インキを白色の硬化膜の上に重なるように同様の方法で印刷、硬化させた。この様にして得られた硬化膜の全てはセロテープによる剥離試験、爪によるスクラッチ試験及び容器表面を押圧による屈折を繰り返す過酷な剥離試験においてもまったく剥離はみられず、完全に密着していた。
同条件にて作成した硬化膜を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は完全に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
【００７８】
実施例１８
製造例５によって得られた４色のインキを使用し、最初に白色インキを紫外線照射により処理したポリエチレンテレフタレート製容器の表面上にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより、紫外線積算光量２００ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。その白色の硬化膜の上に重なるように青色インキを同様の方法で印刷、硬化させ、さらに赤色インキ次いで黄色インキを白色の硬化膜の上に重なるように同様の方法で印刷、硬化させた。この様にして得られた硬化膜の全てはセロテープによる剥離試験、爪によるスクラッチ試験及び容器表面を押圧による屈折を繰り返す過酷な剥離試験においてもまったく剥離はみられず、完全に密着していた。
同条件にて作成した硬化膜を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は完全に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
【００７９】
製造例６
表６に示した配合組成により、４色の着色インキを製造した。具体的な操作手順を示すと、まずビヒクル成分にあらかじめ熱重合禁止剤と顔料分散剤を加えて攪拌溶解しておき、これに顔料を加えてディゾルバーで予備混合を行った後、残りの原料を加えてさらに混合し、次いでロールミルで十分に混練した。混練は顔料の分散粒子径が５ミクロンに達したときを終点とし、これを目的の着色インキとして捕集した。
【００８０】
【表６】

【００８１】
実施例１９
製造例６によって得られた４色のインキを使用し、最初に白色インキを実施例１と同様の方法で無処理ポリエチレンテレフタレート製シート上にスクリーン印刷を施し、ＥＢ照射装置ＣＢ２５０／１５／１８０Ｌ（岩崎電気社製）を用いて４０ＫＧｙ（１６５ＫＶ、３．２ｍＡ、１５ｍ／ｍｉｎ）の電子線量で硬化し、タックフリーの硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず、完全に密着していた。その白色の硬化膜の上に重なるように青色インキを同一の条件、方法で印刷、硬化させ、さらに赤色インキ次いで黄色インキを白色の硬化膜の上に重なるように同一の条件、方法で印刷、硬化させた。この様にして得られた硬化膜の全てはセロテープによる剥離試験及び爪によるスクラッチ試験では全く剥離はみられず完全に密着していた。
同条件にて作成した硬化膜を５％水酸化ナトリウム水溶液中に８００℃で５分間放置したところ、硬化膜は完全に脱離し、ポリエチレンテレフタレート基材には印刷の痕跡が全く見られなかった。
【００８２】
製造例７
表４に示した配合組成により、４色の着色インキを製造した。具体的な操作手順を示すと、まずビヒクル成分にあらかじめ熱重合禁止剤と顔料分散剤を加えて攪拌溶解しておき、これに顔料を加えてディゾルバーで予備混合を行った後、残りの原料を加えてさらに混合し、次いでロールミルで十分に混練した。混練は顔料の分散粒子径が５ミクロンに達したときを終点とし、これを目的の着色インキとして捕集した。
【００８３】
実施例２０
製造例７によって得られた４色のインキを３００メッシュのナイロン製スクリーン版を用いてポリアクリロニトリル製シート上に印刷した。重ね印刷は各色ごとに印刷、硬化を行い、従って２色目は１色目の硬化膜の上に重なるが、故意に基材にも印刷する部分をつくり硬化させた。同様にして３色目及び４色目を印刷、硬化し、図１に示すようなパターン概念の試験片を作成した。
各色の硬化条件は全て１５０ｍｊ／ｃｍ²の同一紫外線光量とし、試験片を作成した。ここの試験片の図１のパターンの全ての印刷部分（１色から４色重ね部分まで）を爪によるスクラッチ試験を行ったが全く剥離はみられず完全に密着していた。
同条件にて作成した印刷片を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は重ね部分を分離せずに一層の膜となって剥離して液中に浮遊し、ポリアクリロニトリル基材には印刷の痕跡が全く見られなかった。つぎに、製造例７によって得られた４色のインキを３００メッシュのナイロン製スクリーン版を用いてポリアクリロニトリル製シート上に印刷した。重ね印刷は各色ごとに印刷、硬化を行い、従って２色目は１色目の硬化膜の上に重なるが、故意に基材にも印刷する部分をつくり硬化させた。同様にして３色目及び４色目を印刷、硬化し、図１に示すようなパターン概念の試験片を作成した。
各色の硬化条件は全て２００ｍｊ／ｃｍ²の同一紫外線光量とし、試験片を作成した。ここの試験片の図１のパターンの全ての印刷部分（１色から４色重ね部分まで）を爪によるスクラッチ試験を行ったが全く剥離はみられず完全に密着していた。
同条件にて作成した印刷片を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は完全に脱離し、ポリアクリロニトリル基材には印刷の痕跡が全く見られなかった。
また、製造例７によって得られた４色のインキを３００メッシュのナイロン製スクリーン版を用いてポリアクリロニトリル製シート上に印刷した。重ね印刷は各色ごとに印刷、硬化を行い、従って２色目は１色目の硬化膜の上に重なるが、故意に基材にも印刷する部分をつくり硬化させた。同様にして３色目及び４色目を印刷、硬化し、図１に示すようなパターン概念の試験片を作成した。
各色の硬化条件は全て３００ｍｊ／ｃｍ²の同一紫外線光量とし、試験片を作成した。ここの試験片の図１のパターンの全ての印刷部分（１色から４色重ね部分まで）を爪によるスクラッチ試験を行ったが全く剥離はみられず完全に密着していた。
同条件にて作成した印刷片を２％水酸化ナトリウム水溶液中に７０℃で２５分間放置したところ、硬化膜は完全に脱離し、ポリアクリロニトリル基材には印刷の痕跡が全く見られなかった。
【００８４】
実施例２１
製造例７によって得られた４色インキを使用し、最初に白色インキを実施例１と同様の方法で無処理ポリアクリロニトリル製シート上にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより、紫外線積算光量１８０ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず完全に密着していた。その白色の硬化膜の上に重なるように青色インキを同様の方法で印刷、硬化させ、さらに赤色インキ次いで黄色インキを白色の硬化膜の上に重なるように同様の方法で印刷、硬化させた。この様にして得られた硬化膜の全てはセロテープによる剥離試験及び爪によるスクラッチ試験では全く剥離はみられず完全に密着していた。
同条件にて作成した硬化膜を２％水酸化ナトリウム水溶液中に７０℃で２５分間（３０分間）放置したところ、硬化膜は完全に脱離し、ポリアクリロニトリル基材には印刷の痕跡が全く見られなかった。
【００８５】
実施例２２
製造例７によって得られた４色のインキを使用し、最初に白色インキをフレームにより処理したポリアクリロニトリル製容器の表面上にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより、紫外線積算光量２００ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず完全に密着していた。その白色の硬化膜の上に重なるように青色インキを同様の方法で印刷、硬化させ、さらに赤色インキ次いで黄色インキを白色の硬化膜の上に重なるように同様の方法で印刷、硬化させた。この様にして得られた硬化膜の全てはセロテープによる剥離試験、爪によるスクラッチ試験及び容器表面を押圧による屈折を繰り返す過酷な剥離試験においてもまったく剥離はみられず、完全に密着していた。
同条件にて作成した硬化膜を２％水酸化ナトリウム水溶液中に７０℃で２０分間放置したところ、硬化膜は完全に脱離し、ポリアクリロニトリル基材には印刷の痕跡が全く見られなかった。
【００８６】
実施例２３
製造例７よって得られた４色のインキを使用し、最初に白色インキをコロナ放電により処理したポリアクリロニトリル製容器の表面上にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより、紫外線積算光量２００ｍｊ／ｃｍ²を照射し、硬化膜を得た。この硬化膜はセロテープによる剥離試験で全く剥離はみられず完全に密着していた。その白色の硬化膜の上に重なるように青色インキを同様の方法で印刷、硬化させ、さらに赤色インキ次いで黄色インキを白色の硬化膜の上に重なるように同様の方法で印刷、硬化させた。この様にして得られた硬化膜の全てはセロテープによる剥離試験、爪によるスクラッチ試験及び容器表面を押圧による屈折を繰り返す過酷な剥離試験においてもまったく剥離はみられず、完全に密着していた。
同条件にて作成した硬化膜を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は重ね部分を分離せずに一層の膜となって剥離して液中に浮遊し、ポリアクリロニトリル基材には印刷の痕跡が全く見られなかった。
【００８７】
実施例２４
製造例７によって得られた４色のインキを使用し、最初に白色インキを紫外線照射により処理したポリアクリロニトリル製容器の表面上にスクリーン印刷を施し、１２０Ｗ／ｃｍメタルハライドランプにより、紫外線積算光量２００ｍｊ／ｃｍ²を照射し、硬化膜を得た。その白色の硬化膜の上に重なるように青色インキを同様の方法で印刷、硬化させ、さらに赤色インキ次いで黄色インキを白色の硬化膜の上に重なるように同様の方法で印刷、硬化させた。この様にして得られた硬化膜の全てはセロテープによる剥離試験、爪によるスクラッチ試験及び容器表面を押圧による屈折を繰り返す過酷な剥離試験においてもまったく剥離はみられず、完全に密着していた。
同条件にて作成した硬化膜を２％水酸化ナトリウム水溶液中に７０℃で１５分間放置したところ、硬化膜は重ね部分を分離せずに一層の膜となって剥離して液中に浮遊し、ポリアクリロニトリル基材には印刷の痕跡が全く見られなかった。
【００８８】
【発明の効果】
この出願発明により、製品にデザインやマ−クを入れ加飾印刷された表示部分が、その流通過程を経て回収後にはアルカリ水溶液で処理し膜状に脱離することにより、回収基材を印刷されていない清浄な状態にすることが可能である。
したがって、回収基材を純粋な状態で再使用することができるので、これまでのように特定された用途のみではなく、本来の材料の用途に使用することができる。また、ポリアクリロニトリル製のビール容器の場合には、ビール会社各社の製品を再使用できるという優れた効果がある。
【図面の簡単な説明】
【図１】印刷パターンを示す図[0001]
[Industrial application fields]
The invention of this application is a colorful display of product names, designs, instructions, barcodes, etc. in multiple colors using a specific radiation curable ink for thermoplastic resin products, particularly polyethylene terephthalate or polyacrylonitrile products. When decorating, not only can be printed directly, but it can also be printed in layers, quickly dried by radiation under a high-speed line, and the dried film is easily distributed with an alkaline aqueous solution after collection through the distribution stage. The present invention relates to a method for printing a plastic product with a radiation curable printing ink and a method for detaching the radiation curable ink, which enables the substrate to be recovered in a clean state by being detached and washed with water.
[0002]
[Prior art]
Thermoplastic resin products, especially polyethylene terephthalate or polyacrylonitrile products, are especially for cosmetics because they are non-toxic, have better gas barrier properties than other synthetic resin molded products, and have a glassy appearance. It is used as containers, liquid seasoning containers, containers for beverages such as beer and roll, containers for pharmaceuticals, etc. The product description, product name, etc. are UV curable on the surface of the container body. In many cases, it is formed of a printing ink using a resin as a vehicle.
[0003]
[Problems to be solved by the invention]
Recently, the problem of incineration of garbage and the problem of pollution of plastic products has been greatly raised, and there is an increasing interest in the recovery, recycling and reuse of plastic products. However, the collected plastic products are difficult to recycle and reuse in various ways, and most of the collected plastic products are simply melted and recycled and used only for limited purposes. Is the current situation. The main reason is that some of the collected products are printed for decoration or other purposes, and the printing ink is recovered from plastic products that are recycled from the collected plastics, or collected and reused. This is to adversely affect the properties of plastic products that are collected or recovered and reused.
[0004]
[Means for Solving the Problems]
In order to make it easy to recycle or reuse the collected plastic product, the invention of the present application is printed on the plastic product with a special ink, and after the collection, the ink is easily detached to incinerate the garbage. Or it is related with the thermoplastic resin product printed with the ink for solving a pollution problem and utilizing collect | recovered plastics in a wide use.
By this invention, the display part that is decorated and printed by putting the design and mark on the product is recovered and then treated with an alkaline aqueous solution to remove the printed part, thereby making the recovered base material in a clean and unprinted state. Is possible.
In particular, when it is used as a returnable like a polyacrylonitrile beer container, it can be used as a container common to each beer company by detaching the printing in the washing step with the alkaline aqueous solution.
[0005]
[Action]
In the printing method of the present invention, printing may be performed without treating the surface of the thermoplastic resin product prior to printing, but printing may be performed after treating the surface of the thermoplastic resin product. Surface treatments include flame, corona discharge, UV irradiation, electron beam irradiation, plasma treatment, annealing treatment, spraying, mold roughening, chemical surface treatment, etc. Processing or anchor coating processing may be performed. The radiation curable ink composition used in the invention of this application is a stress peeling prevention function due to adhesion and low shrinkage based on the basic structure of a polyester oligomer and / or polymer having an unsaturated double bond as a main component. Makes very good adhesion to the substrate. Adhering the cured product of the composition of the present invention to the plastic substrate without treatment has a great merit such as shortening the process in printing work. Further, by treating the surface of the thermoplastic resin product, for example, the printing surface does not peel even under severe conditions such as repeated pressing of the printing surface.
[0006]
[Constitution]
As the thermoplastic resin product, many resin products such as a polyester resin product, a polyacrylonitrile product, and a polyolefin resin product can be used. Among them, a polyethylene terephthalate or a polyacrylonitrile product is particularly suitable.
Polyethylene terephthalate as referred to in the present invention is a polyester having ethylene terephthalate as a repeating unit, the acid component is terephthalic acid, and the glycol component is ethylene glycol, but as the copolymer component, the acid component includes isophthalic acid, Diphenyl ether 4,4'-dicarboxylic acid, naphthalene 1,4- or 2,6-dicarboxylic acid, adipic acid, sebacic acid, decane 1,10-dicarboxylic acid, hexahydroterephthalic acid, glycol components include propylene glycol, 1 , 4-butanediol, neopentyl glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2 Bis (4-hydroxyphenyl) propane, etc. p- hydroxybenzoic acid may be incorporated within a range not exceeding 50%, respectively.
In addition, the polyacrylonitrile referred to in the invention of this application is that the polymer component of the acrylonitrile resin composition is composed of an acrylonitrile polymer, but natural rubber, butadiene polymer, isoprene polymer, neoprene polymer, nitrile rubber, acrylate. Using a mixture in which synthetic rubber such as rubber, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer, chlorinated rubber or the like is mixed at a ratio of 25% by weight or less in the polymer component, an obtained stretch blow hollow molded body is obtained. You may strengthen it.
A composition containing an acrylonitrile polymer component and a rubber component as a polymer component includes, for example, a copolymer obtained by directly polymerizing a monomer and a monomer, and a copolymer obtained by grafting a nitrile monomer to a rubber component skeleton. And those obtained by a polymer blend of a rubber graft polymer and a matrix polymer.
The acrylonitrile polymer which is the main polymer component of the acrylonitrile resin composition is a nitrile monomer unit component in which 55 to 85% by weight of the total weight of the polymer is calculated as acrylonitrile. As the body component, for example, one or more of acrylonitrile, methacrylonitrile, ethacrylonitrile, propacrylonitrile, glutaronitrile, methylene glutaronitrile, furanonitrile and the like are used.
Suitable monomers to be copolymerized with these monomer unit components include aromatic monomers such as styrene and α-methylstyrene, and 2 to 6 carbon atoms such as ethylene, propylene, butylene, and isobutylene. Lower α-olefin, acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and other acrylic acids and derivatives thereof, vinyl acetate and other vinyl esters At least one kind of alkyl vinyl ether having an alkyl group having 1 to 4 carbon atoms, such as ethyl vinyl ether, is used, particularly preferably acrylonitrile-methacrylonitrile-styrene copolymer, acrylonitrile-styrene-methyl vinyl ether copolymer. , Acrylonite An acrylonitrile-based polymer comprising a ril-styrene-ethyl vinyl ether copolymer or the like is used.
The polyethylene terephthalate or polyacrylonitrile in the present invention can contain additives such as a colorant, an ultraviolet absorber, and an antistatic agent in an appropriate ratio, if necessary.
[0007]
  According to the method for printing on a plastic product of the present invention, printing is performed with a printing ink based on a radiation curable ink composition comprising the following vehicles (A) to (B), and then the printed surface is irradiated with radiation. Then, the process of curing the radiation curable component in the printing ink is repeated by repeating as necessary.
(A) An oligomer and / or polymer having a linear polyester as a skeleton and having 1 to 10 unsaturated double bonds in the molecule
(B) at least one in the moleculeCarboxyl groupAnd 1-10 unsaturated double bondsOne or more carboxylic acid esters
  A printing ink based on a radiation curable ink composition containing a vehicle containing the above (A) to (B) and, if necessary, a photopolymerization initiator, a photosensitizer, and an organic and / or inorganic pigment is used. Preferably,
The component (A) is a linear polyester whose skeleton does not contain a polymerizable unsaturated double bond, has substantially no acidic group as a side chain, and contains 1 to 1 polymerizable unsaturated double bonds. 10 oligomers and / or polymers
(B) component is
(C) at least one in the moleculeCarboxyl groupAnd has one unsaturated double bondCarboxylic acid ester
as well as
(D) 1-10 in the moleculeCarboxyl groupHaving two or more unsaturated double bondsCarboxylic acid ester
As a vehicle component,
(E) Carboxylic acid ester having two or more unsaturated double bonds, no acidic group, and different from component (A)
(F) Carboxylic acid ester having one unsaturated double bond and no acidic group
  In the mixture containing the above (A) to (F), preferably 100 to 20 parts of the vehicle having an acid value of 5 to 100, preferably 0 to 20 parts of photopolymerization initiator, 0 to 20 parts of photosensitizer, A printing ink based on a radiation curable ink composition containing 0 to 100 parts of an organic and / or inorganic pigment is used.
[0008]
Polyethylene terephthalate product of the present invention, for example, a container molded from a saturated polyester represented by polyethylene terephthalate as a main raw material, or a polyacrylonitrile product, for example, a container molded from polyacrylonitrile as a main raw material The container used in the printing method on the body surface is a polyester or polyacrylonitrile container obtained by hollow molding, biaxial stretch blow molding, injection molding or the like.
[0009]
The conditions under which the ink composition is desorbed by alkali vary depending on the amount ratio of (B). For example, the alkali concentration is preferably 2% or more, the temperature is 70 ° C. or more, and the time is preferably 5 minutes or more. However, the alkali concentration is reduced to 0.1% by extending the alkali soaking time, soaking the printing surface while brushing, adjusting the amount ratio of (B), and further adding printing and curing conditions. The temperature can be changed to 50 ° C.
In addition, the amount of carboxylic acid and / or carboxylic acid ester and / or carboxylic acid amide having at least one acidic group in the molecule and one unsaturated double bond is 1 to 10 in the molecule. By increasing the amount of carboxylic acid and / or carboxylic acid ester and / or carboxylic acid amide having an acidic group and two or more unsaturated double bonds, the entire ink-cured film is dissolved in an alkaline aqueous solution. Since it can be detached from the surface of the plastic, its application range is further expanded.
When carrying out the alkali desorption treatment on an actual commercial basis, it can be carried out by appropriately selecting those conditions.
[0010]
The radiation curable ink composition of the present invention has at least one acidic group in the molecule and one or more carboxylic acids and / or carboxylic acid esters having 1 to 10 unsaturated double bonds. And / or one or more of carboxylic acid amides, in particular carboxylic acids and / or carboxylic acid esters having at least one acidic group in the molecule and one unsaturated double bond and / or Carboxylic acid amides and carboxylic acids and / or carboxylic acid esters and / or carboxylic acid amides having 1 to 10 acidic groups in the molecule and having two or more unsaturated double bonds are blended. Therefore, the cured film of the ink is easily detached from the printed matter collected after use by treatment with an alkaline aqueous solution, and a plastic product substrate that can be recycled in a clean state can be recovered.
[0011]
An oligomer and / or polymer having a linear polyester as a skeleton and having 1 to 10 unsaturated double bonds in the molecule, in particular, a linear polyester in which the skeleton does not contain a polymerizable unsaturated double bond. An oligomer and / or polymer having substantially no acidic group as a side chain and having 1 to 10 polymerizable unsaturated double bonds is 1 to 10 radiation-polymerizable unsaturated atoms in the molecule. It is an oligomer and / or polymer having a double bond and not only exhibiting radiation polymerizability alone but also copolymerizable with other radiation-polymerizable double bond-containing compounds.
[0012]
Examples of the unsaturated double bond of the oligomer and / or polymer include a vinyl group, an allyl group, a (meth) acryloyl group, a crotonyl group, and the like, and a (meth) acryloyl group that is highly polymerizable by radiation is preferable.
In addition, as the oligomer and / or polymer having a (meth) acryloyl group in the oligomer and / or polymer, a polyurethane (meth) acrylate having a structure capable of following adhesion to the base material or expansion and contraction of the base material. Are particularly used. More preferably, a polyurethane (meth) acrylate using a polyester polyol and a polyol having a high molecular weight chain-extended by a urethane bond as a raw material is used.
[0013]
As shown in Synthesis Example 1, the copolyester polyol is synthesized mainly from a dicarboxylic acid component and a glycol component.
The dicarboxylic acid component is mainly composed of aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid and orthophthalic acid, and at least 60 mol% of the total dicarboxylic acid is used, and succinic acid, adipic acid, 40 mol% or less of aliphatic dicarboxylic acids such as sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as hexahydrophthalic acid and tetrahydrophthalic acid are also used.
Examples of the glycol component include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and diethylene glycol. , Dipropylene glycol, 1,4-cyclohexanedimethanol, spiroglycol, 1,4-phenylene glycol, bisphenol A ethylene oxide adduct or propylene oxide adduct, polyethylene glycol And polypropylene glycol. If necessary, a small amount of triol or tetraol such as trimethylolpropane, glycerin or pentaerythritol may be contained.
In order to obtain a copolyester polyol from such a dicarboxylic acid component and a glycol component, the glycol component is synthesized in excess relative to the dicarboxylic acid raw material. At this time, the carboxyl group terminal is 50 eq / 10 in the copolyester.⁶It is preferable to synthesize so as to be substantially free of acidic groups less than g. 50 eq / 10⁶When it is more than g, when synthesizing a urethane acrylate by further chain extension, the number of inactive ends increases at the time of reaction with the diisocyanate compound, and the intended polyurethane acrylate cannot be obtained.
[0014]
In order to obtain urethane acrylate from the copolymer polyester polyol thus obtained, the above-mentioned copolymer polyester polyol, polyisocyanate compound, and a compound having a (meth) acryloyl group and an active hydrogen group in the molecule are reacted. You can do it.
Examples of polyisocyanate compounds include 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, 1,3-diisocyanate methylcyclohexane, 1,4-diisocyanate methylcyclohexane, 4, 4 ′. -Diisocyanatodicyclohexane, 4,4'-diisocyanatodicyclohexylmethane, isophorone diisocyanate, and many other commercially available diisocyanates can be used. When a polyfunctional acrylate is required, a polyisocyanate higher than triisocyanate may be used alone or mixed with the diisocyanate.
[0015]
The compound having a (meth) acryloyl group and an active hydrogen group in the molecule is a compound having at least one unsaturated double bond and one hydroxyl group in one molecule. The unsaturated double bond applicable in the invention of this application includes a vinyl group, an allyl group, a (meth) acryloyl group, a crotonyl group, etc., but a (meth) acryloyl group having high sensitivity to radiation is preferable. . For example, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, butanediol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono ( Mono (meth) acrylates such as (meth) acrylates, tri (methyl) acrylates, trimethylolethane mono (meth) acrylates, trimethylolethanedi (meth) acrylates, trimethylolpropane mono (meth) acrylates Trivalent alcohol mono- and di (meth) acrylates, pentaerythrates such as trimethylolpropane di (meth) acrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, etc. Lithol mono (meth) acrylate, pentaerythritol di (meth) acrylate Acrylates of tetravalent or higher polyhydric alcohols such as pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, etc., which contain hydroxyl groups, Caprolactone adducts of alcohols (meth) acrylates containing hydroxyl groups, monoglycidyl ethers, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether Diglycidyl ethers of divalent alcohols such as propylene glycol diglycidyl ether and neopentyl glycol diglycidyl ethers, and polyvalent alcohol glycidyl ethers such as trimethylolpropane triglycidyl ether And phenolic hydrol such as diglycidyl ether of bisphenol A Glycidyl compounds having an sill groups - to epoxy compounds such as ether (meth) epoxy obtained by ring-opening addition of acrylic acid (meth) acrylate - is collected by such.
[0016]
These may use only 1 type and may use 2 or more types together.
The polyester oligomer and / or polymer having an unsaturated double bond obtained by reacting the above raw materials may have at least one unsaturated double bond in the molecule, and may be from 1 to 10 Applies. In order to eliminate the tackiness of the cured film surface at a practical curing rate and maintain adhesion and flexibility to the substrate, 3 to 7 unsaturated double bonds are preferable in one molecule.
[0017]
1 or more types of carboxylic acids having at least one acidic group in the molecule and 1 to 10 unsaturated double bonds and / or one or more types of carboxylic acid esters and / or 1 of carboxylic acid amides Species or more, in particular carboxylic acids and / or carboxylic esters and / or carboxylic amides having at least one acidic group in the molecule and one unsaturated double bond, and 1 to 10 in the molecule A carboxylic acid and / or a carboxylic acid ester and / or a carboxylic acid amide having an acidic group and having two or more unsaturated double bonds are generally treated as “acidic monomers” and “acidic oligomers”. . Among these, an acidic monomer is a homopolymer and a copolymer containing the same at a high concentration, which forms a hydrophilic salt with alkali and becomes easily water-soluble.
As the unsaturated double bond, there are a vinyl group, an allyl group, a (meth) acryloyl group, a crotonyl group, and the like. Here, a (meth) acryloyl group having a high radiation polymerization property is desirable. As the acidic group, those capable of forming a water-soluble alkali metal salt such as a carboxyl group, a sulfonyl group, and a phosphoryl group are preferable, but the purpose can usually be achieved by introducing a carboxyl group into the molecule. The number of carboxyl groups must be 1 to 2 per molecule.
The simplest structure of a carboxyl group-containing acidic monomer is (meth) acrylic acid itself, but it has a strong odor and is not preferable as an ink raw material from the viewpoint of safety. Accordingly, the acidic monomer is synthesized by reacting a compound having both an unsaturated double bond and a hydroxyl group in the molecule with a cyclic acid anhydride corresponding to the hydroxyl equivalent. For example, a carboxylate of an alkylene oxide adduct of (meth) acrylic acid and an acid anhydride, a carboxylate of a caprolactone adduct of (meth) acrylic acid and an acid anhydride, a monoglycidyl ether of (meth) acrylic acid Examples thereof include a carboxylate product of an adduct and an acid anhydride, and a carboxylate product of methylol (meth) acrylamide and an acid anhydride. Examples of the acid anhydride include succinic anhydride, maleic anhydride, itaconic anhydride, dodecynyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and trimellitic anhydride. In addition, maleic anhydride itself and after ring-opening esterification have low polymerizability and are difficult to copolymerize with (meth) acrylate, and therefore can be used as the component (B) of the present invention.
[0018]
The carboxyl group can be obtained by adding a cyclic acid anhydride corresponding to the hydroxyl equivalent to the compound having both an unsaturated double bond and a hydroxyl group in the molecule and heating the compound for a certain time. Acid anhydrides include aliphatic saturated dicarboxylic acid anhydrides such as succinic anhydride, aliphatic unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, and alicyclic rings such as tetrahydrophthalic acid and hexahydrophthalic acid. Dicarboxylic acid anhydrides, aromatic dicarboxylic acid anhydrides such as phthalic acid, naphthenic acid, and the like, and tricarboxylic acid anhydrides such as trimellitic acid are used to introduce the carboxyl group.
In addition, acrylic acid dimers, acrylic acid trimers and the like that are by-produced during the synthesis of acrylic acid monomers can be used as they are as carboxyl group-containing monomers.
Mono (meth) acryloxyethyl phosphate and (meth) acryloxyethyl phosphorylphenyl as carboxylic acid esters having an acidic group capable of forming a water-soluble alkali metal salt other than a carboxyl group and having an unsaturated double bond. And phosphoric acid mono- or diesters such as di (meth) acryloxyethyl phosphate, and sulfonic acid esters such as (meth) acryloxyethyl sulfonate and di (meth) acryloxyethyl succinyl sulfonate.
The unsaturated double bond-containing carboxylic acid and / or carboxylic acid ester and / or carboxylic acid amide having an acidic group may be used alone or in combination of two or more. It is determined along with the amount used depending on physical properties.
[0019]
The acidic oligomer is a homopolymer and / or a copolymer containing it in a high concentration has a high crosslinking density, and the alkali metal salt has a property of swelling in water.
In this case as well, as in the case of the acidic monomer, the unsaturated double bond is preferably a (meth) acryloyl group having high radiation polymerizability. The acidic group capable of forming an alkali metal salt is the same, and includes a carboxyl group, a sulfonyl group, a phosphoryl group, etc., and a carboxyl group is common. The number of acidic groups is from 1 to 10 per molecule, but the number must be determined by the molecular weight of the acidic oligomer, and the acidic oligomer synthesized economically from the raw material side. 2 to 6 are practical. The number of unsaturated double bonds (number of functional groups) in one molecule is a so-called polyfunctional two or more, and 2 to 6 functional ones are often used.
[0020]
The acidic oligomer is synthesized by using epoxy acrylate obtained by ring-opening esterification of a polyepoxy compound and (meth) acrylic acid as a raw material, and reacting this with a cyclic acid anhydride to introduce a carboxyl group. .
Epoxy (meth) acrylates include a reaction product of neopentyl glycol diglycidyl ether and (meth) acrylic acid, a reaction of 1,6-hexanediol diglycidyl ether and (meth) acrylic acid. , Aliphatic epoxy acrylates such as a reaction product of trimethylolpropane triglycidyl ether and (meth) acrylic acid, a reaction product of bisphenol A diglycidyl ether and (meth) acrylic acid, epoxy Aromatic epoxy acrylates such as a reaction product of phenol novolak and (meth) acrylic acid, a reaction product of glycidyl phthalate and (meth) acrylic acid, and the like can be mentioned.
[0021]
Cyclic anhydrides for introducing carboxyl groups into the epoxy acrylate include succinic anhydride, maleic anhydride, dodecynyl succinic anhydride, phthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride, tetra Halide phthalic acid, hexahydrophthalic anhydride and the like are available, and these reaction products are those in which the hydroxyl group of epoxy acrylate is half esterified with an acid anhydride and is pendant.
[0022]
The acidic oligomer can be used alone or in combination of two or more. The amount used is determined based on the required performance of the final cured film properties, but in order to facilitate detachment with an alkaline aqueous solution, an appropriate amount is studied while taking into account the blending ratio with the acidic monomer. I have to. If this is expressed as an acid value, the compounding ratio and the compounding amount are determined so that the acid value of the entire vehicle is 3 or more and 150 or less, preferably 20 to 80, particularly preferably 20 to 60.
[0023]
In addition, when the desorption state is to be dissolved and desorbed, it is better to increase the acid value by using a large amount of acidic monomer. When membrane-like desorption is desired, the ratio of acidic oligomers is increased to keep the acid value low. Good.
In particular, in the case of film-like peeling, the ink component can be removed from the alkaline liquid by filtration, so that the chemical oxygen demand in the wastewater is reduced and the treatment becomes easy, which is preferable.
However, these conditions vary depending on the concentration of alkali used for desorption, the processing temperature, the processing time, etc., and therefore it is desirable to obtain an appropriate formulation by experiment in consideration of these desorption conditions.
[0024]
As mentioned above, although the essential component in this application invention was illustrated concretely, it copolymerizes with the said (A) (B) component other than these, and is generally called a polyfunctional monomer, a polyfunctional oligomer, and a monofunctional monomer. Commercially available compounds can be used. Typical examples among them include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate. 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neopentylglycoldi (meth) acrylate, hydroxypentylate neopentylglycol Di (meth) acrylic acid esters of divalent alcohols such as rudi (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, dicyclopentanyl di (meth) acrylate, and trimethylo -Luethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, Tri (meth) acrylic acid esters of trihydric alcohols such as lith [(meth) acryloxyethyl] isocyanurate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, There are (meth) acrylic esters of tetravalent or higher alcohols such as dipentaerythritol hexa (meth) acrylate. In addition, (meth) acrylic esterification of tri- or higher valent alcohols may leave some hydroxyl groups remaining unesterified, and epoxy groups can be opened with (meth) acrylic acid. There may be a hydroxyl group formed upon ring esterification. The polyfunctional oligomer is an oligomer having an unsaturated double bond having a linear polyester as a skeleton of the claimed invention (A) in the present invention and / or an oligomer not corresponding to the polymer, and having a molecular structure. And epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene (meth) acrylate, and the like.
[0025]
The most common epoxy acrylate is represented by the formula (1)
[Chemical 1]

[0026]
(In the formula, n is 1 to 4, and R is H or CH._ThreeIndicates. )
The bisphenol skeleton is replaced with bisphenol A, bisphenol F, bisphenol S, or the like.
[0027]
Moreover, Formula (2)
[Chemical formula 2]

[0028]
Wherein n is 0 to 3 and R is H or CH_ThreeIndicates. )
A phenol novolac type epoxy (meth) acrylate as shown in FIG.
[0029]
In addition, aliphatic epoxy (meth) acrylates such as epichlorohydrin-modified (poly) alkylene glycol di (meth) acrylate, epoxidized soybean oil (meth) acrylate, and the formula (3)
[Chemical Formula 3]

[0030]
(R is H or CH_ThreeAnd R₁Represents a residue excluding the -COOH group of the dicarboxylic acid. )
The alicyclic epoxy (meth) acrylate as shown in Fig. 5 is also used depending on the required performance.
[0031]
As urethane (meth) acrylate, formula (4)
[Formula 4]

[0032]
(In the formula, n is 1 to 4, and R is H or CH._ThreeAnd R₁Is a residue obtained by removing NCO of diisocyanate, and X is a residue obtained by removing OH of polyol. )
The compound of the structure shown by is used.
[0033]
In the formula (4), the isocyanate is an aromatic diisocyanate such as tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, Aliphatic diisocyanates such as trimethylhexamethylene diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate and methylenebis (4-cyclohexyl isocyanate), ethylene glycol as the polyol Bisphenol ethers such as glycols, propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc., polyglycol ethers, ethoxylated bisphenol A, etc. Spiroglycol, caprolactone-modified diol, carbonate diol, etc., and these diisocyanates Polyol - Le of the end of the urethane synthesized in combination (meth) selects use those that match the required performance from among commercially available ones were acrylated.
[0034]
The polyester (meth) acrylate has the formula (5)
[Chemical formula 5]

[0035]
(In the formula, n is 1 to 5, and R is H or CH._ThreeAnd R₁Is H or CH₂= C (R) COO-, X is a residue excluding the OH group of the polyol, and Y is a residue excluding the COOH group of the dicarboxylic acid. )
Many of these are commercially available, and are selected and used according to the required performance.
[0036]
The polybutadiene (meth) acrylate has a hydroxyl group via a diisocyanate in addition to a liquid polybutadiene having two or more hydroxyl group ends in one molecule, which is directly (meth) acrylated. A compound combined with (meth) acrylic acid ester is used. These include commercially available products such as Quinbam-101 (Nippon Zeon), TE resin (Nippon Soda), Michelon NU-A (Hayakawa Rubber) and the like.
The purpose of using the polyfunctional monomer and / or oligomer is to cause three-dimensional crosslinking during radiation polymerization, and to impart film hardness, gloss, water resistance, chemical resistance, and friction resistance.
[0037]
The above polyfunctional monomer and / or oligomer may be used alone in use, but in many cases, a mixture of two or more kinds is added as a component of the vehicle. The amount of use, including other components of the vehicle, is determined by the physical properties such as solubility and viscosity, as well as whether the crosslinking density upon curing satisfies the requirements. In addition, matching the acid value of the vehicle with the purpose to achieve alkali detachment, which is the subject of the present invention, is also a constraint when determining the amount used. Usually, it is 5 to 20 parts in 100 parts of the vehicle, but if it is used too much, stress peeling due to crosslinking shrinkage at the time of curing may occur, and the adhesion to the substrate may be lowered.
[0038]
A monofunctional monomer is a compound that is often used mainly as a diluent for adjusting the viscosity of a composition, and typical examples include 2-ethylhexyl (meth) acrylate and cyclohexyl (meth). Acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, toluyloxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate , Ethyl carbitol (meth) acrylate, isobornyl (meth) acrylate, methoxypropylene glycol (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N, N-diethylaminoethyl (Meth) acrylate, t-butylaminoethyl (meth) acrylate - there is a door or the like. In addition, when the monofunctional monomer contains a polar group such as a hydroxyl group, an epoxy group, or a phosphate group in the molecule, the adhesion is remarkably improved. However, these do not lower the water resistance even in the invention of this application. Can be used to the extent. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-butoxy-2-hydroxypropyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate And 3-phenoxy-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, ethylene oxide modified butoxylated phosphoric acid (meth) acrylate, and the like. These monofunctional monomers are used alone or in admixture of two or more, and 5 to 40 parts are used in 100 parts of the ink vehicle, and the viscosity is adjusted usually in the range of 10 to 30 parts.
[0039]
The above-mentioned vehicle components are mixed at a desirable ratio determined by experiment to produce an ink vehicle, and maintain the adhesion to the substrate in printing and the interlayer adhesion in multilayer printing, which is the object of this invention. The oligomer and / or polymer of claim 1 (A) is more excellent in substrate and interlayer adhesion as the blending amount is larger, but 20 to 50 parts is used to obtain practical ink physical properties. In the base material adhesion blend using this oligomer and / or polymer, delamination does not occur even when, for example, five layers are stacked in multilayer printing. Moreover, in order to implement | achieve detachment | desorption of the ink hardened | cured material by aqueous alkali solution, a composition is determined so that the acid value may be 5 or more and 150 or less.
In order to make an ultraviolet curable ink using the vehicle thus obtained, the purpose is achieved by adding a photopolymerization initiator, a photosensitizer, an organic and / or inorganic pigment, other additives, and the like. When (electron beam) curing is performed, a photopolymerization initiator and a photosensitizer are not necessary.
[0040]
Many photopolymerization initiators used in the case of ultraviolet polymerization are known. Typical examples of known photopolymerization initiators include benzophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl. -(4-Methylthiophenyl) -2-morpholino-propan-1-one, benzoin alkyl ether, benzyl, benzyldimethylketal, camphor-quinone, 2-ethylanthraquinone, methyl benzoylbenzoate, 4-phenyl Examples include benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone, 2,4-diethylthioxanthone, methylphenylglyoxylate, benzoylphosphine oxide, 1-trimethylbenzoyldiphenylphosphine oxide, and the like.
Similarly, representative examples of known photosensitizers include triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4′-diethylaminobenzophenone, ethyl 4-dimethylaminobenzoate, 4 -Dimethylaminobenzoic acid-n-butoxyethyl, 4-dimethylaminobenzoic acid isoamyl and the like.
[0041]
The photopolymerization initiator can be used alone, but in many cases, it is used in combination with a photosensitizer to improve photopolymerization. The most suitable type of photopolymerization initiator and photosensitizer is selected depending on the ink vehicle component used. The criteria are examined according to the purpose, such as the curing speed, the presence or absence of coloring that occurs during curing, the presence or absence of pigments, and the strength of the odor after curing. The amount used can be 1 to 20 parts each of the photopolymerization initiator and photosensitizer relative to the ink vehicle, but when used in large amounts, the curing is fast but the molecular weight does not increase, and the strength of the cured film decreases. Also, the smell is strong and undesirable. The most desirable use range is 2 to 10 parts as the combined amount of both. In that case, the usage ratio of the photopolymerization initiator and the photosensitizer varies depending on the type and component ratio of the vehicle component, and in the ink to which the coloring pigment described later is added, both of the two due to the ultraviolet absorption ability specific to the pigment. It is necessary to change the usage ratio and it is not uniform.
Pigments are broadly classified into organic pigments and inorganic pigments in terms of chemical composition, but they are also classified into colored pigments and non-colored pigments (extreme pigments) from the viewpoint of use. When it comes to UV curing, the classification of usage is more important.
[0042]
In this invention, it can be used as a clear ink without using a pigment, but in many cases, it is used as a decorative ink to which a pigment is added.
Among the colored pigments, inorganic pigments include white pigments such as lead white, zinc white, zinc sulfide, and titanium dioxide, blue pigments such as ultramarine, bitumen, and cobalt blue, green pigments such as chromium oxide, pyridian, and chrome green, Yellow lead, titanium yellow, yellow iron oxide, molybdate orange, cadmium pigments, yellow to red pigments such as petals, black pigments such as iron black, titanium black, carbon black, aluminum powder, bronze, etc. There are par pigments such as metal pigments and mica. However, there are many inorganic pigments that must be avoided from the viewpoint of safety and health, and harmless ones are selected from the above. For organic pigments, monoazo, disazo, condensed azo, indanthrone, indigo, thioindigo, quinacridone, phthalocyanine, dioxazine, isoindolinone, pyrrolopyrrole, etc. can be used. In accordance with the curing method of irradiation, it is desirable to select and use a pigment with high light fastness with little fading.
[0043]
The amount of the color pigment used varies depending on the target color density, and is generally in the range of 0.5 to 50% of the total amount of ink. Although it is limited by coloring power as a pigment characteristic, 15 to 40% is typical amount in the case of titanium oxide which is a typical white pigment, and 3 to 6% in the case of carbon black which is a black pigment. In the case of organic coloring pigments, 3 to 20% is desirable for obtaining a clear color, and 4 to 15% is desirable for curing with ultraviolet rays. Since the vehicle described in the claims of the present invention contains many polar groups such as carboxyl groups, the dispersibility of the color pigment is generally good. However, in order to obtain even better color development, a large amount of pigment is added to the vehicle with a small amount of pigment dispersant added, and it is easy to apply physical crushing pressure by utilizing the viscosity improvement caused by the oil absorption. The state is created, and sufficient kneading is performed with a medium disperser common in the color material industry, such as a ball mill and a roll mill. The high-concentration pigment dispersion (toner) thus obtained is replenished and adjusted with a deficient vehicle so that a predetermined pigment concentration is obtained when the ink is blended.
[0044]
The radiation curable ink composition used in the invention of this application maintains the characteristics of printing inks such as viscosity, fluidity, thixotropy, retains and increases ink build-up, shrinks buffer during curing, surface matte, and imparts slip properties. Various non-colored pigments (extreme pigments) can be used for the purpose of improving the strength of the film. Commonly used extender pigments include talc, kaolin, silica, precipitated barium sulfate, precipitated calcium carbonate, alumina white, white carbon, and other inorganic extender pigments such as polyethylene wax, polypropylene wax, and polyfluorinated polyethylene wax. These are fine powders of artificial and / or natural polymers such as waxes, polyamide resins, polyimide resins, melamine resins, benzoguanamine resins, cellulose and collagen. These can be used freely according to the purpose. In order to adjust the finished state of the cured film, a leveling agent and / or an antifoaming agent can be added to the radiation curable ink composition of this invention. Of these various leveling agents and antifoaming agents that are generally sold on the market, those that are well compatible with the vehicle component and have surface smoothness are confirmed by testing and used. The type and amount used do not limit the content of the ink composition of the present invention, and may be determined as appropriate. Usually, the total amount of the leveling agent and / or antifoaming agent is 0.5 to 5% by weight is used.
[0045]
In addition, an ultraviolet absorber, a wettability improver, an antioxidant and the like can be used as necessary.
The ink using the radiation curable ink composition used in the present invention thus manufactured is mainly used for screen printing, but when adjusted to a lower viscosity using an organic solvent. Further, it can be sufficiently used as an ink in other printing methods such as flexographic printing and gravure printing.
[0046]
The printed matter after curing on the polyethylene terephthalate or polyacrylonitrile resin of the radiation curable ink used in the invention of this application can be easily peeled off by immersing it in a strong alkaline aqueous solution such as sodium hydroxide or potassium hydroxide for a short time. At this time, severe conditions such as hydrolysis of polyethylene terephthalate or polyacrylonitrile resin are not required. Desorption has various stages from dissolution desorption to membrane-like desorption, and these can obtain the target performance by adjusting the quantitative ratio of (B). In any case, the selection of the desorption property is determined by the treatment method of the waste water after the removal, but the polyethylene terephthalate or polyacrylonitrile resin after the desorption is easily recycled and reused by a simple method such as water washing and drying, or It can be recovered in a clean state that can be reused and refilled.
[0047]
As a means for printing characters, patterns, figures, etc. on a plastic product with the printing ink, silk screen printing is generally used, and a silk screen version of about 254 to 330 mesh is usually used.
Further, the ultraviolet irradiation performed on the printing surface with the printing ink using the radiation curable resin as a vehicle is usually performed by a high pressure mercury lamp or a metal halide lamp having a wavelength of about 200 to 450 nm. As 100-500mj / cm²Is preferred. Usually, in the case of electron beam irradiation, the irradiation is performed at a dose of 10 to 100 KGy, and 30 to 60 KGy is preferable.
[0048]
Synthesis example 1
The linear polyester oligomer and / or polymer having an unsaturated double bond in the side chain used in the examples is a copolymer polyester polyol of (1) in the following Table 1 with a composition of (2) urethane. Obtained by acrylate formation (unit: parts by weight).
[0049]
[Table 1]

[0050]
Synthesis example 2
Three examples are given below for the synthesis of acidic oligomers having 1 to 10 carboxyl groups and two or more unsaturated double bonds.
(A) 190.0 g of bisphenol A diglycidyl ether (epoxy equivalent 190.0), 75.0 g (1.05 mol) of acrylic acid, 2 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, In addition to a flask equipped with a stirrer and a reflux condenser, the mixture was uniformly dissolved and heated to 80 ° C. and maintained for 24 hours to obtain an epoxy acrylate having an acid value of 10.3. Next, 140.6 g (0.95 mol) of phthalic anhydride was added and held at 80 ° C. for 5 hours to synthesize a pale yellow viscous bisphenol A epoxy acrylate phthalate having an acid value of 130.7. .
(B) 190.0 g of epoxy novolac resin (epoxy equivalent 190.0), 75.0 g (1.05 mol) of acrylic acid, 2.0 g of tetramethylammonium chloride, and 0.2 g of p-methoxyphenol were added to the above (a ), And uniformly dissolved, heated to 80 ° C., and kept for 24 hours to obtain an epoxy acrylate having an acid value of 10.5. Next, 95 g (0.95 mol) of succinic anhydride was added, and the mixture was kept at 80 ° C. for 5 hours to obtain a pale yellow viscous epoxy novolak acrylate succinate having an acid value of 145.2.
(C) 150 g of glycerin triglycidyl ether (epoxy equivalent 150.0), 75.0 g (1.05 mol) of acrylic acid, 2 g of tetrabutylphosphonium bromide, 0.2 g of p-methoxyphenol (a) Was dissolved in the same apparatus and heated to 80 ° C. to obtain an epoxy acrylate having an acid value of 9.8. Next, 145 g (0.95 mol) of hexahydrophthalic anhydride was added and held at 80 ° C. for 5 hours to obtain a pale yellow viscous glycerol epoxy acrylate hexahydrophthalic acid ester having an acid value of 141.3. .
[0051]
Production Example 1
Synthesis Example 1 B-1 oligomer having an unsaturated double bond-25,0 g, aliphatic urethane hexaacrylate 5.0 g, aliphatic urethane diacrylate 25.9 g, monoacryloyloxyethyl phthalate 6 0.5 g, phthalate ester of bisphenol A epoxy acrylate of Synthesis Example 2 (a) 5.0 g, 2.0 g of trimethylolpropane triacrylate, 14.6 g of phenoxyethyl acrylate, For 100 parts of a vehicle having an acid value of 19.3 mixed with 16.0 g of acryloylmorpholine, 15 parts of mistron vapor talc, 10 parts of benzyldimethylketal, 5 parts of dimethylaminobenzoic acid ethyl ester, 3 parts of polyethylene wax powder , 1 part of a leveling agent (BYC-BYK-306) and 0.1 part of a thermal polymerization inhibitor phenothiazine were mixed. Then, an uncolored ink having a dispersed particle diameter of 5 microns or less was produced using a roll mill.
[0052]
【Example】
Example 1
The uncolored ink obtained in Production Example 1 was subjected to screen printing on an untreated polyethylene terephthalate sheet using a 300-mesh Tetron screen plate, and an ultraviolet light amount of 150 mj / cm was applied using a 120 W / cm metal halide lamp.²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered.
Further, printing and curing were repeated 5 times on this cured film, a total of 6 times. Printing at this time is under the same conditions as above, but curing is performed using the same exposure machine, and the amount of ultraviolet light is 180 mj / cm for the second time, the third time, and the fourth time.²5th time is 250mj / cm²The sixth time is 300mj / cm²As a result, no peeling occurred at all overprinted portions including the first printing surface and the sixth printing surface in the peeling test with the cello tape and the scratch test with the nail.
When the overprinted piece prepared under the above conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, the cured film was mostly swollen, partially dissolved and detached, and printed on a polyethylene terephthalate substrate. No trace of was seen.
[0053]
Production Example 2
Synthesis Example 1 177 g of an oligomer having an unsaturated double bond of B-1 was dissolved in 118 g of phenoxyethyl acrylate, and a pigment dispersant (Solsperse 24000 / Solsperth 5000 = 4 / 1) Mix 1.5 g, add 52.3 g of Heliogen Blue L-7080 (BASF), and knead thoroughly with a roll mill until the pigment dispersed particle size is 5 microns or less. did. 41.6 g of the toner thus obtained was 7.6 g of an oligomer having an unsaturated double bond of B-1, 10.0 g of polyfunctional urethane acrylate purple light 1700B (Nippon Gosei Chemical), neopentyl glycol ethylene Oxide 2-mol adduct diacrylate 4.6 g, monoacryloyloxyethyl phthalate 10.0 g, synthesis example 2- (c) glycerol epoxy acrylate hexahydrophthalate ester 6.2 g, acryloyl morpholine 20 0.0 g was mixed well to obtain a colored ink vehicle. The acid value of this vehicle was 30.0.
Photopolymerization initiator diethylthioxanthone 3.0 g, photosensitizer dimethylaminobenzoic acid isoamyl ester 3.0 g, precipitated barium sulfate 35 g, polypropylene wax powder 3 g, leveling agent (sham) 2 g of Bar Saffron Base manufactured by Rock Inc.) and 0.04 g of thermal polymerization inhibitor p-methoxyphenol were added and stirred well, and then kneaded well in a roll mill to obtain a homogeneous blue ink.
[0054]
Example 2
The blue ink of Production Example 2 was screen-printed on an untreated polyethylene terephthalate sheet in the same manner as in Example 1, and the amount of ultraviolet light was 200 mj / cm using a 120 W / cm metal halide lamp.²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered.
Further, printing and curing were repeated 5 times on this cured film, a total of 6 times. Printing at this time is under the same conditions as above, but curing is performed using the same exposure machine, and the amount of ultraviolet light is 230 mj / cm for the second time and the third time.²The fourth time is 250mj / cm²The fifth time is 300mj / cm²As a result, no peeling occurred at all in the overprinting portion in the peeling test with the cello tape and the scratch test with the nail, including the first printing surface and the sixth printing surface.
When the overprinted piece prepared under the above conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 20 minutes, the cured film was mostly swollen, partially dissolved and detached, and printed on a polyethylene terephthalate substrate. No trace of was seen.
[0055]
Production Example 3
Synthesis Example 1 Linear polyester oligomer 16.0 g having an unsaturated double bond in the side chain of B-1, 4.9 g of aliphatic urethane hexaacrylate, 5.5 g of monoacryloyloxyethyl succinate, Synthesis example 2- (b) epoxy novolac acrylate succinate 4.5 g, trimethylolpropane triepoxy acrylate 3.9 g, toluyloxyethyl acrylate 3.9 g, phenoxyethyl acrylate 11 0.0 g and 9.8 g of acryloylmorpholine were mixed to obtain an ink vehicle having an acid value of 50.8. Furthermore, 0.5 g of a pigment dispersant Disperbyk-110 (manufactured by BYK-Chemical Co., Ltd.) was added and mixed uniformly. 30.0 g of titanium oxide type CR-90 (manufactured by Ishihara Sangyo) was added to the photopolymerization initiator acyl. Phosphine oxide 6.0 g, fluorinated polyethylene wax powder 2.0 g, leveling agent Bar Saffron base (manufactured by Shamrock) 1.5 g, antifoaming agent Aqualene N (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) 1.0 g, After adding 0.04 g of thermal polymerization inhibitor p-methoxyphenol and stirring for a while, the mixture was kneaded using a roll mill until the pigment dispersed particle size became 5 microns or less.
[0056]
Example 3
The white ink obtained in Production Example 3 was subjected to screen printing on an untreated polyethylene terephthalate sheet in the same manner as in Example 1, and the amount of ultraviolet light was 250 mj / cm by a 120 W / cm metal halide lamp.²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered.
Further, printing and curing were repeated 4 times on this cured film, a total of 5 times. Printing at this time is under the same conditions as above, but curing is performed using the same exposure machine, and the amount of ultraviolet light is 280 mj / cm for the second time and the third time.²The fourth time is 300mj / cm²As a result, no peeling occurred at all in the overprinted portion including the first printing surface and the fifth printing surface in the peeling test with the cello tape and the scratch test with the nail.
When the overprinted piece prepared under the above conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 25 minutes, the cured film was detached into a cloudy liquid, and there was no trace of printing on the polyethylene terephthalate substrate. There wasn't.
[0057]
Example 4
Using the blue ink obtained in Production Example 2, a desorption test by immersion in an alkaline solution was performed. In addition, the comparison of the detachability in immersion in an alkaline solution with the current blue ink used for production was also performed.
The following were used as test samples.
Container 2.7 liter untreated polyethylene terephthalate container
Weight 110g, printing area 150cm², Surface area 900cm²
Ink used (1) Current blue ink used in production
(2) Blue ink obtained in the same manner as in Production Example 2.
First, the blue ink of the invention of the application (2) is screen-printed on the surface of a non-treated polyethylene terephthalate container body using a 350-mesh nylon screen plate, and an ultraviolet integrated light quantity of 200 mj is applied by a 120 W / cm metal halide lamp. / Cm²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered. Printing and curing were repeated 3 times, 4 times in total, so as to overlap the cured film under the same conditions and method. All of the cured films thus obtained were completely in contact with each other in the peeling test using the cello tape and the scratching test using the nail.
Next, production and use of (1) Screen printing is performed on the surface of an untreated polyethylene terephthalate container body using a 350 mesh nylon screen plate with the current blue ink, and a UV integrated light quantity of 200 mj is applied by a 120 W / cm metal halide lamp. / Cm²Was irradiated to obtain a cured film. Printing and curing were repeated 3 times, 4 times in total, so as to overlap the cured film under the same conditions and method. The cured film thus obtained showed no peeling at all overprinted portions in the peel test with the cello tape, but in the scratch test with the nail, the fourth printed coating film from the interface with the first printed coating film. Delamination occurred.
Each overprinted sample prepared under the same conditions was subjected to a desorption test by immersion in an alkaline solution by the following method.
conditions
Immersion solution Sodium hydroxide aqueous solution
Concentration (Wt%) 0.1% 1% 5%
Immersion temperature 20 ℃ 50 ℃ 80 ℃
Immersion time 1 minute 5 minutes 20 minutes 50 minutes
Confirmation items are a spontaneous detachment state and a detachment state due to gauze friction.
The evaluation of the detachment state as a result of the test was carried out as follows, taking into account both the natural detachment of the printed part by immersion in an alkaline solution and the detachment by gauze friction after immersion.
Evaluation
◎: Completely detaches spontaneously in the solution, leaving no printed part.
○: No printing part left due to natural detachment / gauze friction
△: More than half of the printed part is detached due to natural detachment and gauze friction
Δ ×: Partially detaches spontaneously, but detachment of printed part is less than half even when gauze friction is performed
×: The separation of the printing part is less than half even when gauze polishing is performed without spontaneous separation.
XX: When gauze rubbing is performed, there is color transfer, but there is no detachment of the printed part
XXX: Even if gauze rubbing is performed, there is no color transfer and no detachment of the printed part
[0058]
[Table 2]

[0059]
In the overprinting sample prepared with ink (2), all cured films were completely detached in 5 to 20 minutes by immersion in 80% sodium hydroxide 1% aqueous solution, and in 80 ° C sodium hydroxide 5% aqueous solution. In the immersion, complete spontaneous detachment takes place between 1 minute and 5 minutes. If the solution temperature is the same, the higher the alkali concentration of the solution, and if the solution alkali concentration is the same, the higher the solution temperature, the shorter the time until printing is completely spontaneously detached.
[0060]
Example 5
Each printing container prepared by the same method using the same test sample as in Example 4 was pulverized to about 1 cm to prepare 200 kg of flaky material.
Next, the detachment state of the printing was confirmed by an actual recovered polyethylene terephthalate flake purification process. The main purification process is as follows.
(1) Wind selection: Removal of paper, fine powder, etc. by cyclone
(2) Flotation / separation: Specific gravity separation in the water tank
(3) Alkaline washing: immersed in a 2% sodium hydroxide aqueous solution bath (6000 liters) at 80 ° C. for 10 minutes and 20 minutes
(4) Washing with water: Wash in a water tank for 20 minutes.
▲ 5 ▼ Wind selection after drying
▲ 6 ▼ Finished product
Evaluation of the confirmation results was performed by observing the flakes after purification, and was performed as follows.
Evaluation
◎: Flakes with printing attached are not seen
X: Many flakes with printing adhered
[0061]
[Table 3]

[0062]
Production Example 4
Synthesis Example 1 25.0 g of a linear polyester oligomer having an unsaturated double bond in the side chain of B-1, 19.7 g of phenoxyethyl acrylate, 6.5 g of toluoxyethyl acrylate, 19.3 g of acryloylmorpholine, neopentyl glycol ethylene Diacrylate 3.0 g of oxide 2-mole adduct, 6.6 g of trimethylolpropane triepoxy acrylate, hexafunctional urethane acrylate Eveacryl 1290K (manufactured by Daicel UC), 10.0 g, 10.0 g of monoacryloyloxyethyl succinate, synthesis example An additional 2.0 g of bisphenol A epoxy acrylate phthalate ester 2 (a) was mixed and stirred to obtain a uniform vehicle having an acid value of 28.6. Next, 0.2 g of the pigment dispersant Antiterra-U (manufactured by Big Chemie) and 0.05 g of p-methoxyphenol were previously stirred and dissolved in 92.0 g of this vehicle, and 1.5 g of Raven 450 (manufactured by Colombia Carbon) was dissolved therein. Raven 1350 (Columbia Carbon) 1.5 g and Titanium Black 10S (Mitsubishi Materials) 5.0 g were dispersed and kneaded sufficiently with a roll mill until the dispersed particle size became 5 microns or less to obtain a colored vehicle.
To 96.5 g of this colored vehicle, 2.0 g of fluorinated polyethylene wax powder, 0.5 g of leveling agent BYK-306 (manufactured by Big Chemie), 1.0 g of antifoaming agent Aqualene N (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) are added and dissolved. Sufficient agitation was performed using, to produce a black ink for EB curing.
[0063]
Example 6
Using the black ink obtained in Production Example 4, screen printing was performed on an untreated polyethylene terephthalate sheet using a 330 mesh nylon screen plate, and an EB irradiation device CB250 / 15 / 180L (manufactured by Iwasaki Electric Co., Ltd.) Was cured with an electron dose of 60 KGy (165 KV, 3.2 mA, 10 m / min) to obtain a tack-free cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered.
Further, printing and curing were repeated 5 times in total under the same conditions and method so as to overlap the cured film, a total of 6 times. All of the cured films thus obtained were completely in contact with each other in the peeling test with a cello tape and the scratch test with a nail, without any peeling. When a cured film prepared under the same conditions was left in a 5% aqueous sodium hydroxide solution at 80 ° C. for 5 minutes, the cured film was completely detached from the base material, and no trace of printing was seen on the polyethylene terephthalate base material. In addition, no evidence of erosion by the alkaline aqueous solution was observed.
[0064]
Example 7
Screen printing was performed on the surface of a polyethylene terephthalate container whose surface was roughened with a mold using a 300-mesh Tetron screen plate and the uncolored ink obtained in Production Example 1 was used, and a 120 W / cm metal halide lamp was used to emit 150 mj of ultraviolet light. / Cm²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered. Further, printing and curing were repeated 4 times on this cured film, a total of 5 times. Printing at this time is under the same conditions as above, but curing is performed using the same exposure machine, and the amount of ultraviolet light is 180 mj / cm for the second time and the third time.²The fourth time is 200mj / cm²The fifth time is 300mj / cm²As a result, the first printing surface, the fifth printing surface, and all overprinted parts were peeled off with cello tape, scratched with a nail, and severely peeled off with repeated refraction by pressing the container surface. No peeling occurred at all.
When the overprinted piece prepared under the above conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, the cured film was completely detached and no trace of printing was seen on the polyethylene terephthalate substrate. It was.
[0065]
Example 8
Screen printing was performed on the surface of a polyethylene terephthalate container having a surface roughened by spraying the surface of the blue ink obtained in Production Example 2 using a 300-mesh Tetron screen plate, and the amount of ultraviolet light was 200 mj / cm using a 120 W / cm metal halide lamp.²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered. Further, printing and curing were repeated 3 times on this cured film, a total of 4 times. Printing at this time is under the same conditions as above, but curing is performed using the same exposure machine, and the amount of ultraviolet light is 230 mj / cm for the second time and the third time.²The fourth time is 300mj / cm²As a result, the first printing surface, the fourth printing surface, and all overprinted parts were peeled with a cellophane tape, scratched with a nail, and severely peeled with repeated refraction by pressing the container surface. No peeling occurred at all.
When the overprinted piece prepared under the above conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, the cured film was completely detached and no trace of printing was seen on the polyethylene terephthalate substrate. It was.
[0066]
Example 9
Screen printing was performed on the surface of a polyethylene terephthalate container whose surface was roughened with an aqueous solution of sodium hydroxide using a 300-mesh Tetron screen plate from the white ink obtained in Production Example 3, and the amount of ultraviolet light emitted from a 120 W / cm metal halide lamp. 200 mj / cm²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered. Further, printing and curing were repeated 3 times on this cured film, a total of 4 times. Printing at this time is under the same conditions as above, but curing is performed using the same exposure machine, and the amount of ultraviolet light is 230 mj / cm for the second time and the third time.²The fourth time is 300mj / cm²As a result, the first printing surface, the fourth printing surface, and all overprinted parts were peeled with a cellophane tape, scratched with a nail, and severely peeled with repeated refraction by pressing the container surface. No peeling occurred at all.
When the overprinted piece prepared under the above conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, the cured film peeled off as a single layer without separating the overlapped portion, It floated and no traces of printing were seen on the polyethylene terephthalate substrate.
Further, the sodium hydroxide aqueous solution tank was slightly cloudy.
[0067]
Example 10
Screen printing was performed on the surface of a polyethylene terephthalate container obtained by treating the non-colored ink obtained in Production Example 1 with a frame using a 300-mesh Tetron screen plate, and the UV light intensity was 150 mj / cm using a 120 W / cm metal halide lamp.²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered. Further, printing and curing were repeated 4 times on this cured film, a total of 5 times. Printing at this time is under the same conditions as above, but curing is performed using the same exposure machine, and the amount of ultraviolet light is 180 mj / cm for the second time and the third time.²The fourth time is 200mj / cm²The fifth time is 300mj / cm²As a result, the first printing surface, the fifth printing surface, and all overprinted parts were peeled off with cello tape, scratched with a nail, and severely peeled off with repeated refraction by pressing the container surface. No peeling occurred at all.
When the overprinted piece prepared under the above conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, the cured film was completely detached and no trace of printing was seen on the polyethylene terephthalate substrate. It was.
[0068]
Example 11
Screen printing was performed on the surface of a polyethylene terephthalate container obtained by treating the uncolored ink obtained in Production Example 1 by corona discharge using a 300-mesh Tetron screen plate, and the UV light intensity was 150 mj / cm using a 120 W / cm metal halide lamp.²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered. Further, printing and curing were repeated 4 times on this cured film, a total of 5 times. Printing at this time is under the same conditions as above, but curing is performed using the same exposure machine, and the amount of ultraviolet light is 180 mj / cm for the second time and the third time.²The fourth time is 200mj / cm²The fifth time is 300mj / cm²As a result, the first printing surface, the fifth printing surface, and all overprinted parts were peeled off with cello tape, scratched with a nail, and severely peeled off with repeated refraction by pressing the container surface. No peeling occurred at all.
When the overprinted piece prepared under the above conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, the cured film was completely detached and no trace of printing was seen on the polyethylene terephthalate substrate. It was.
[0069]
Example 12
Screen printing was performed on the surface of a polyethylene terephthalate container obtained by treating the uncolored ink obtained in Production Example 1 with ultraviolet irradiation using a 300-mesh Tetron screen plate, and the UV light intensity was 150 mj / cm using a 120 W / cm metal halide lamp.²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered. Further, printing and curing were repeated 4 times on this cured film, a total of 5 times. Printing at this time is under the same conditions as above, but curing is performed using the same exposure machine, and the amount of ultraviolet light is 180 mj / cm for the second time and the third time.²The fourth time is 200mj / cm²The fifth time is 300mj / cm²As a result, the first printing surface, the fifth printing surface, and all overprinted parts were peeled off with cello tape, scratched with a nail, and severely peeled off with repeated refraction by pressing the container surface. No peeling occurred at all.
When the overprinted piece prepared under the above conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, the cured film was completely detached and no trace of printing was seen on the polyethylene terephthalate substrate. It was.
[0070]
Production Example 5
According to the distribution composition shown in Table 4, four colored inks were produced. The specific operation procedure is as follows. First, a thermal polymerization inhibitor and a pigment dispersant are added to the vehicle component in advance and stirred and dissolved, and then the pigment is added thereto and premixed with a dissolver, and then the remaining raw materials are mixed. Were further mixed, and then kneaded thoroughly with a roll mill. In the kneading, when the dispersed particle diameter of the pigment reached 5 microns, the end point was collected, and this was collected as the target colored ink.
[0071]
[Table 4]

[0072]
Example 13
The four color inks obtained in Production Example 5 were printed on a polyethylene terephthalate sheet using a 300 mesh nylon screen plate. In the overprinting, printing and curing were performed for each color. Therefore, the second color was superimposed on the cured film of the first color, but a part to be printed on the substrate was intentionally formed and cured. Similarly, the third color and the fourth color were printed and cured to produce test pieces having the pattern concept as shown in FIG.
The curing conditions for each color are all 150 mj / cm²The test pieces were prepared with the same UV light intensity. A scratch test using a nail was performed on all the printed portions (from one color to four color overlapping portions) of the pattern of FIG.
When the printed piece prepared under the same condition was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 10 minutes, the cured film was completely detached and no trace of printing was seen on the polyethylene terephthalate substrate.
Next, the four color inks obtained in Production Example 5 were printed on a polyethylene terephthalate sheet using a 300 mesh nylon screen plate. In the overprinting, printing and curing were performed for each color. Therefore, the second color was superimposed on the cured film of the first color, but a part to be printed on the substrate was intentionally formed and cured. Similarly, the third color and the fourth color were printed and cured to produce test pieces having the pattern concept as shown in FIG.
The curing conditions for each color are all 200 mj / cm.²The test pieces were prepared with the same UV light intensity. A scratch test using a nail was performed on all the printed portions (from one color to four color overlapping portions) of the pattern of FIG.
When the printed piece prepared under the same conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, the cured film was completely detached, and no trace of printing was seen on the polyethylene terephthalate substrate.
Further, the four color inks obtained in Production Example 4 were printed on a polyethylene terephthalate sheet using a 300 mesh nylon screen plate. In the overprinting, printing and curing were performed for each color. Therefore, the second color was superimposed on the cured film of the first color, but a part to be printed on the substrate was intentionally formed and cured. Similarly, the third color and the fourth color were printed and cured to produce test pieces having the pattern concept as shown in FIG.
The curing conditions for each color are all 300 mj / cm²The test pieces were prepared with the same UV light intensity. A scratch test using a nail was performed on all the printed portions (from one color to four color overlapping portions) of the pattern of FIG.
When a printed piece prepared under the same conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 20 minutes, the cured film was completely detached and no trace of printing was seen on the polyethylene terephthalate substrate.
[0073]
Example 14
Using the four color inks obtained in Production Example 5, first, a white ink was screen-printed on the surface of an untreated polyethylene terephthalate container, and an ultraviolet light accumulated light amount of 180 mj / cm was applied by a 120 W / cm metal halide lamp.²Was irradiated to obtain a cured film. The blue ink was printed and cured by the same method so as to be overlaid on the white cured film, and further the red ink and then the yellow ink were printed and cured by the same method so as to be superimposed on the white cured film. All of the cured films thus obtained did not show any peeling in the peeling test with a cellophane and the scratch test with a nail, and were completely adhered.
When the cured film prepared under the same conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, the cured film was completely detached and no trace of printing was seen on the polyethylene terephthalate substrate.
Further, white ink, blue ink, red ink, and yellow ink, which are current production and use inks, were used, and screen printing was performed on the surface of the container body made of polyethylene terephthalate under the same conditions and methods as described above to obtain a cured film. All of the cured films did not peel at all in the peel test using the cello tape. However, when the scratch test was performed using the nail, the yellow cured film caused delamination from the interface with the white cured film.
The cured film prepared under the same conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, but the cured film was not detached from the polyethylene terephthalate substrate.
[0074]
Example 15
Using the four color inks obtained in Production Example 5, a desorption test by immersion in an alkaline solution was conducted in the same manner as in Example 4. A comparison of the detachability in immersion in an alkaline solution with the current ink used for production was also performed.
The following were used as test samples.
Container 2.7 liter untreated polyethylene terephthalate container
Weight 110g, printing area 150cm², Surface area 900cm²
Ink used (1) Current ink used in production 4 colors (white ink, blue ink, red ink, yellow ink)
(2) Obtained by Production Example 5 (white ink, blue ink, red ink, yellow ink)
First, the white ink of (2) was screen-printed on the surface of an untreated polyethylene terephthalate container body using a 350-mesh nylon screen plate, and the UV integrated light quantity was 150 mj / cm using a 120 W / cm metal halide lamp.²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered. The blue ink was printed and cured by the same method so as to be overlaid on the white cured film, and further the red ink and then the yellow ink were printed and cured by the same method so as to be superimposed on the white cured film. All of the cured films thus obtained were completely in contact with each other in the peeling test with a cello tape and the scratch test with a nail, without any peeling.
Next, the white ink of (1) was similarly screen-printed on the surface of an untreated polyethylene terephthalate container body using a 350-mesh nylon screen plate, and a UV integrated light quantity of 150 mj was applied using a 120 W / cm metal halide lamp. / Cm²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered. The blue ink was printed and cured by the same method so as to be overlaid on the white cured film, and further the red ink and then the yellow ink were printed and cured by the same method so as to be superimposed on the white cured film. The cured film thus obtained was not peeled off at all in the overprinted part by the cello tape peeling test. Delamination occurred.
Each overprinted sample prepared under the same conditions was subjected to a desorption test by immersion in an alkaline solution by the following method.
conditions
Immersion solution Sodium hydroxide aqueous solution
Concentration (Wt%) 0.1% 1% 5%
Immersion temperature 20 ℃ 50 ℃ 80 ℃
Immersion time 1 minute 5 minutes 20 minutes 50 minutes
Confirmation items are a spontaneous detachment state and a detachment state due to gauze friction.
The evaluation of the detachment state as a result of the test was carried out as follows, taking into account both the natural detachment of the printed part by immersion in an alkaline solution and the detachment by gauze friction after immersion.
Evaluation
◎: Completely detaches spontaneously in the solution, leaving no printed part.
○: No printing part left due to natural detachment / gauze friction
△: More than half of the printed part is detached due to natural detachment and gauze friction
Δ ×: Partially detaches spontaneously, but detachment of printed part is less than half even when gauze friction is performed
×: The separation of the printing part is less than half even when gauze polishing is performed without spontaneous separation.
XX: When gauze rubbing is performed, there is color transfer, but there is no detachment of the printed part
XXX: Even if gauze rubbing is performed, there is no color transfer and no detachment of the printed part
[0075]
[Table 5]

[0076]
Example 16
Using the four color inks obtained in Production Example 5, screen printing was performed on the surface of a polyethylene terephthalate container in which white ink was first treated with a frame, and an ultraviolet light accumulated light amount of 200 mj / cm was applied by a 120 W / cm metal halide lamp.²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered. The blue ink was printed and cured by the same method so as to be overlaid on the white cured film, and further the red ink and then the yellow ink were printed and cured by the same method so as to be superimposed on the white cured film. All of the cured films thus obtained were completely adhered to each other in a peeling test using a cellophane, a scratch test using a nail, and a severe peeling test in which refraction by pressing the container surface was repeated.
When the cured film prepared under the same conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, the cured film was completely detached and no trace of printing was seen on the polyethylene terephthalate substrate.
[0077]
Example 17
Using the four-color inks obtained in Production Example 5, screen printing was performed on the surface of a polyethylene terephthalate container in which white ink was first treated by corona discharge, and an ultraviolet light integrated light amount of 200 mj / m was obtained with a 120 W / cm metal halide lamp. cm²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered. The blue ink was printed and cured by the same method so as to be overlaid on the white cured film, and further the red ink and then the yellow ink were printed and cured by the same method so as to be superimposed on the white cured film. All of the cured films thus obtained were completely adhered to each other in a peeling test using a cellophane, a scratch test using a nail, and a severe peeling test in which refraction by pressing the container surface was repeated.
When the cured film prepared under the same conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, the cured film was completely detached and no trace of printing was seen on the polyethylene terephthalate substrate.
[0078]
Example 18
Using the four-color inks obtained in Production Example 5, screen printing was performed on the surface of a polyethylene terephthalate container that was first treated with ultraviolet irradiation with a white ink, and an ultraviolet light accumulated light amount of 200 mj / m by a 120 W / cm metal halide lamp. cm²Was irradiated to obtain a cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered. The blue ink was printed and cured by the same method so as to be overlaid on the white cured film, and further the red ink and then the yellow ink were printed and cured by the same method so as to be superimposed on the white cured film. All of the cured films thus obtained were completely adhered to each other in a peeling test using a cellophane, a scratch test using a nail, and a severe peeling test in which refraction by pressing the container surface was repeated.
When the cured film prepared under the same conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, the cured film was completely detached and no trace of printing was seen on the polyethylene terephthalate substrate.
[0079]
Production Example 6
Four colored inks were produced according to the formulation shown in Table 6. The specific operation procedure is as follows. First, a thermal polymerization inhibitor and a pigment dispersant are added to the vehicle component in advance and dissolved by stirring. After adding the pigment and premixing with a dissolver, the remaining raw materials are mixed. In addition, they were further mixed and then thoroughly kneaded with a roll mill. In the kneading, when the dispersed particle diameter of the pigment reached 5 microns, the end point was collected and collected as a target colored ink.
[0080]
[Table 6]

[0081]
Example 19
Using the four color inks obtained in Production Example 6, first, white ink was screen-printed on an untreated polyethylene terephthalate sheet in the same manner as in Example 1, and an EB irradiation apparatus CB250 / 15 / 180L ( Was cured with an electron dose of 40 KGy (165 KV, 3.2 mA, 15 m / min) using Iwasaki Electric Co., Ltd. to obtain a tack-free cured film. This cured film was completely peeled off by a cellophane peeling test and was completely adhered. Blue ink is printed and cured under the same conditions and method so as to overlap the white cured film, and further, red ink and then yellow ink are printed under the same conditions and method so as to overlap the white cured film. Cured. All of the cured films thus obtained were completely in contact with each other in the peeling test with a cello tape and the scratch test with a nail, without any peeling.
When the cured film prepared under the same conditions was left in a 5% aqueous sodium hydroxide solution at 800 ° C. for 5 minutes, the cured film was completely detached, and no trace of printing was seen on the polyethylene terephthalate substrate.
[0082]
Production Example 7
According to the formulation shown in Table 4, four colored inks were produced. The specific operation procedure is as follows. First, a thermal polymerization inhibitor and a pigment dispersant are added to the vehicle component in advance and dissolved by stirring. After adding the pigment and premixing with a dissolver, the remaining raw materials are mixed. In addition, they were further mixed and then thoroughly kneaded with a roll mill. In the kneading, when the dispersed particle diameter of the pigment reached 5 microns, the end point was collected and collected as a target colored ink.
[0083]
Example 20
The four color inks obtained in Production Example 7 were printed on a polyacrylonitrile sheet using a 300 mesh nylon screen plate. In the overprinting, printing and curing were performed for each color. Therefore, the second color was superimposed on the cured film of the first color, but a part to be printed on the substrate was intentionally formed and cured. Similarly, the third color and the fourth color were printed and cured to produce test pieces having the pattern concept as shown in FIG.
The curing conditions for each color are all 150 mj / cm²The test pieces were prepared with the same UV light intensity. A scratch test using a nail was performed on all the printed portions (from one color to four color overlapping portions) of the pattern of FIG.
When a printed piece prepared under the same conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, the cured film peeled off as a single layer without separating the overlapped part and floated in the liquid. No traces of printing were seen on the polyacrylonitrile substrate. Next, the four color inks obtained in Production Example 7 were printed on a polyacrylonitrile sheet using a 300 mesh nylon screen plate. In the overprinting, printing and curing were performed for each color. Therefore, the second color was superimposed on the cured film of the first color, but a part to be printed on the substrate was intentionally formed and cured. Similarly, the third color and the fourth color were printed and cured to produce test pieces having the pattern concept as shown in FIG.
The curing conditions for each color are all 200 mj / cm.²The test pieces were prepared with the same UV light intensity. A scratch test using a nail was performed on all the printed portions (from one color to four color overlapping portions) of the pattern of FIG.
When the printed piece prepared under the same conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 15 minutes, the cured film was completely detached and no trace of printing was seen on the polyacrylonitrile substrate.
Further, the four color inks obtained in Production Example 7 were printed on a polyacrylonitrile sheet using a 300 mesh nylon screen plate. In the overprinting, printing and curing were performed for each color. Therefore, the second color was superimposed on the cured film of the first color, but a part to be printed on the substrate was intentionally formed and cured. Similarly, the third color and the fourth color were printed and cured to produce test pieces having the pattern concept as shown in FIG.
The curing conditions for each color are all 300 mj / cm²The test pieces were prepared with the same UV light intensity. A scratch test using a nail was performed on all the printed portions (from one color to four color overlapping portions) of the pattern of FIG.
When the printed piece prepared under the same conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 25 minutes, the cured film was completely detached and no trace of printing was seen on the polyacrylonitrile substrate.
[0084]
Example 21
Using the four-color ink obtained in Production Example 7, first, a white ink was screen-printed on an untreated polyacrylonitrile sheet in the same manner as in Example 1, and an ultraviolet ray accumulated light quantity was obtained with a 120 W / cm metal halide lamp. 180mj / cm²Was irradiated to obtain a cured film. This cured film was completely adhered with no peeling at all in a peel test using a cello tape. The blue ink was printed and cured by the same method so as to be overlaid on the white cured film, and further the red ink and then the yellow ink were printed and cured by the same method so as to be superimposed on the white cured film. All of the cured films thus obtained were completely in contact with each other in the peeling test with a cello tape and the scratch test with a nail, without any peeling.
When the cured film prepared under the same conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 25 minutes (30 minutes), the cured film was completely detached, and no trace of printing was seen on the polyacrylonitrile substrate. I couldn't.
[0085]
Example 22
Using the four-color inks obtained in Production Example 7, screen printing was performed on the surface of a polyacrylonitrile container in which white ink was first treated with a frame, and an ultraviolet light integrated light amount of 200 mj / cm was applied by a 120 W / cm metal halide lamp.²Was irradiated to obtain a cured film. This cured film was completely adhered with no peeling at all in a peel test using a cello tape. The blue ink was printed and cured by the same method so as to be overlaid on the white cured film, and further the red ink and then the yellow ink were printed and cured by the same method so as to be superimposed on the white cured film. All of the cured films thus obtained were completely adhered to each other in a peeling test using a cellophane, a scratch test using a nail, and a severe peeling test in which refraction by pressing the container surface was repeated.
When the cured film prepared under the same conditions was left in a 2% aqueous sodium hydroxide solution at 70 ° C. for 20 minutes, the cured film was completely detached and no trace of printing was seen on the polyacrylonitrile substrate.
[0086]
Example 23
Using the four-color inks obtained in Production Example 7, screen printing was performed on the surface of a polyacrylonitrile container in which white ink was first treated by corona discharge, and an ultraviolet light integrated light quantity of 200 mj / cm²Was irradiated to obtain a cured film. This cured film was completely adhered with no peeling at all in a peel test using a cello tape. The blue ink was printed and cured by the same method so as to be overlaid on the white cured film, and further the red ink and then the yellow ink were printed and cured by the same method so as to be superimposed on the white cured film. All of the cured films thus obtained were completely adhered to each other in a peeling test using a cellophane, a scratch test using a nail, and a severe peeling test in which refraction by pressing the container surface was repeated.
When the cured film prepared under the same conditions was left in a 2% aqueous solution of sodium hydroxide at 70 ° C. for 15 minutes, the cured film separated into a single layer without separating the overlapped part and floated in the liquid. No traces of printing were seen on the polyacrylonitrile substrate.
[0087]
Example 24
Using the four color inks obtained in Production Example 7, screen printing was performed on the surface of a polyacrylonitrile container which was first treated with white ink by ultraviolet irradiation, and an ultraviolet light accumulated light amount of 200 mj / cm²Was irradiated to obtain a cured film. The blue ink was printed and cured by the same method so as to be overlaid on the white cured film, and further the red ink and then the yellow ink were printed and cured by the same method so as to be superimposed on the white cured film. All of the cured films thus obtained were completely adhered to each other in a peeling test using a cellophane, a scratch test using a nail, and a severe peeling test in which refraction by pressing the container surface was repeated.
When the cured film prepared under the same conditions was left in a 2% aqueous solution of sodium hydroxide at 70 ° C. for 15 minutes, the cured film separated into a single layer without separating the overlapped part and floated in the liquid. No traces of printing were seen on the polyacrylonitrile substrate.
[0088]
【The invention's effect】
According to the invention of this application, the display part printed with a design or mark on the product and decorated and printed is treated with an alkaline aqueous solution after collection through its distribution process, and then released into a film, thereby printing the recovered substrate. It is possible to achieve a clean state that is not done.
Therefore, since the recovered substrate can be reused in a pure state, it can be used not only for the applications specified as described above but also for the original materials. Further, in the case of a beer container made of polyacrylonitrile, there is an excellent effect that the products of beer companies can be reused.
[Brief description of the drawings]
FIG. 1 is a diagram showing a print pattern

Claims (26)

For thermoplastic resin products,
(A) An oligomer and / or polymer having a linear polyester as a skeleton and having 1 to 10 unsaturated double bonds in the molecule. (B) In addition to the carboxylic acid ester, the molecule has at least one carboxyl group in the molecule. And one or more carboxylic acid esters having 1 to 10 unsaturated double bonds, including (A) to (B) above, containing fluorine, and the (co) polymer has a fluorine component on the surface. Radiation curable ink composition comprising a vehicle not containing an unsaturated double bond-containing carboxylic acid ester having water repellency that is oriented and, if necessary, a photopolymerization initiator, a photosensitizer, and an organic and / or inorganic pigment A radiation-curing type characterized in that printing is performed with an ink based on the base, and then the printed surface is irradiated with radiation to be cured, and in some cases, the same operation is repeated several times on the printed surface. Thermoplastic products printed with ink.   The component (A) is a linear polyester whose skeleton does not contain a polymerizable unsaturated double bond, has substantially no acidic group as a side chain, and contains 1 to 1 polymerizable unsaturated double bonds. The thermoplastic resin product printed with the radiation curable ink composition according to claim 1, wherein the thermoplastic resin product is an oligomer and / or a polymer having ten.   (A) Oligomer and / or polymer in which component (A) is synthesized from a linear polyester polyol that does not contain a polymerizable unsaturated double bond, a polyisocyanate compound, and a compound containing a (meth) acryloyl group and an active hydrogen group A thermoplastic resin product printed with the radiation-curable ink composition according to claim 1 or 2.   4. Radiation curing according to claim 3, characterized in that the linear polyester polyol is synthesized from an aromatic dicarboxylic acid, an aliphatic and / or alicyclic dicarboxylic acid and a glycol and / or triol and / or tetraol. Thermoplastic resin product printed with mold ink composition. (B) component is
(C) a carboxylic acid ester having at least one carboxyl group in the molecule and one unsaturated double bond; and (D) in addition to the carboxylic acid ester , 1 to 10 carboxylic acid esters in the molecule The thermoplasticity printed by the radiation curable ink composition according to any one of claims 1 to 4, which is a carboxylic acid ester having a carboxyl group and having two or more unsaturated double bonds. Resin products.   The thermoplastic resin product printed with the radiation curable ink composition according to claim 5, wherein the component (C) is less than the component (D). As a vehicle component,
(E) Carboxylic acid ester having two or more unsaturated double bonds and no acidic group and different from component (A) (F) Carboxy having one unsaturated double bond and no acidic group The thermoplastic resin product printed with the radiation curable ink composition according to claim 1, comprising an acid ester.   It includes 0 to 20 parts of photopolymerization initiator, 0 to 20 parts of photosensitizer, and 0 to 100 parts of organic and / or inorganic pigments with respect to 100 parts of vehicle having an acid value of 3 or more and 150 or less. A thermoplastic resin product printed with the radiation curable ink composition according to claim 1.   The thermoplastic resin product printed with the radiation curable decorative ink composition according to claim 1, wherein the radiation curable ink composition is decorative.   The thermoplastic resin product printed with the radiation curable ink composition according to claim 1, wherein the thermoplastic resin product is repeatedly applied and cured.   The thermoplastic resin product according to claim 1, wherein the thermoplastic resin product is a polyethylene terephthalate or polyacrylonitrile product. For thermoplastic resin products,
(A) An oligomer and / or polymer having a linear polyester as a skeleton and having 1 to 10 unsaturated double bonds in the molecule. (B) In addition to the carboxylic acid ester, the molecule has at least one carboxyl group in the molecule. And one or more carboxylic acid esters having 1 to 10 unsaturated double bonds, including (A) to (B) above, containing fluorine, and the (co) polymer has a fluorine component on the surface. Radiation curable ink composition comprising a vehicle that does not contain an unsaturated double bond-containing carboxylic acid ester having water repellency that is oriented and, if necessary, a photopolymerization initiator, a photosensitizer, and an organic and / or inorganic pigment The thermoplastic resin is characterized in that printing is performed with an ink based on the resin, and then the printed surface is irradiated with radiation to be cured, and in some cases, the same operation is repeated a plurality of times on the printed surface to perform overprinting. How to print the product.   The component (A) is a linear polyester whose skeleton does not contain a polymerizable unsaturated double bond, has substantially no acidic group as a side chain, and contains 1 to 1 polymerizable unsaturated double bonds. 13. The method for printing a thermoplastic resin product according to claim 12, wherein overprinting is optionally performed with an ink based on a radiation curable ink composition which is an oligomer and / or polymer having ten.   (A) Oligomer and / or polymer in which component (A) is synthesized from a linear polyester polyol containing no polymerizable unsaturated double bond, a polyisocyanate compound, and a compound containing a (meth) acryloyl group and an active hydrogen group 14. The method for printing a thermoplastic resin product according to claim 12 or 13, characterized in that overprinting is optionally performed with an ink based on a radiation curable ink composition.   With an ink based on a radiation curable ink composition in which the linear polyester polyol is synthesized from an aromatic dicarboxylic acid, an aliphatic and / or alicyclic dicarboxylic acid, and a glycol and / or triol and / or tetraol, The method for printing a thermoplastic resin product according to claim 14, wherein overprinting is optionally performed. (B) component is
(C) having at least one carboxyl group in addition to the molecule of carboxylic acid esters, organic 1-10 carboxyl groups of unsaturated double bonds in one carboxylic acid ester and a (D) in the molecule And optionally overprinting with an ink based on a radiation curable ink composition which is a carboxylic acid ester having two or more unsaturated double bonds. The printing method of the thermoplastic resin product as described in 2.   The method for printing a thermoplastic resin product according to claim 16, wherein overprinting is optionally performed with an ink based on a radiation curable ink composition in which the component (C) is less than the component (D). As a vehicle component,
(E) Carboxylic acid ester having two or more unsaturated double bonds and no acidic group and different from component (A) (F) Carboxy having one unsaturated double bond and no acidic group 18. The method for printing a thermoplastic resin product according to claim 12, wherein overprinting is optionally performed with an ink based on a radiation curable ink composition containing an acid ester.   Radiation curable type containing 0 to 20 parts of photopolymerization initiator, 0 to 20 parts of photosensitizer, and 0 to 100 parts of organic and / or inorganic pigments for 100 parts of vehicle having an acid value of 3 or more and 150 or less. The method for printing a thermoplastic resin product according to any one of claims 12 to 18, wherein overprinting is optionally performed with an ink based on the ink composition.   The printing of a thermoplastic resin product according to any one of claims 12 to 19, characterized in that overprinting is optionally performed with an ink based on a radiation curable ink composition, wherein the radiation curable ink composition is decorative. Method.   The printing method according to claim 12, wherein the printing is performed after the surface of the thermoplastic resin product is treated.   The surface treatment is spraying, mold roughening, chemical treatment, flame treatment, corona discharge treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, plasma treatment, annealing treatment, or anchor coating. The printing method as described in.   21. The printing method according to claim 12, wherein the thermoplastic resin product is a polyethylene terephthalate or polyacrylonitrile product.   A method for detaching a radiation curable ink printed on a thermoplastic resin product, wherein the film of the printed radiation curable ink composition according to claim 1 is dissolved or swollen with an alkaline aqueous solution. .   A radiation curable ink printed on a thermoplastic resin product, wherein the film of the radiation curable ink composition is dissolved or swollen with an alkaline aqueous solution after printing by the printing method according to claim 12. Desorption method.   The method according to claim 24 or 25, wherein the thermoplastic resin product is a polyethylene terephthalate or polyacrylonitrile product.

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