JP3672691B2 - Water-based printing ink composition for laminating and method for laminating printed matter using the same - Google Patents
Water-based printing ink composition for laminating and method for laminating printed matter using the same Download PDFInfo
- Publication number
- JP3672691B2 JP3672691B2 JP666497A JP666497A JP3672691B2 JP 3672691 B2 JP3672691 B2 JP 3672691B2 JP 666497 A JP666497 A JP 666497A JP 666497 A JP666497 A JP 666497A JP 3672691 B2 JP3672691 B2 JP 3672691B2
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- Prior art keywords
- water
- aqueous
- laminating
- component
- ink composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims description 45
- 238000007639 printing Methods 0.000 title claims description 43
- 238000010030 laminating Methods 0.000 title claims description 42
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- 239000002253 acid Substances 0.000 claims description 16
- 150000007514 bases Chemical class 0.000 claims description 16
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Description
【０００１】
【産業上の利用分野】
本発明は、ラミネート用水性印刷インキ組成物およびそれを用いた印刷物のラミネート方法に関する。さらに詳しくは、特にポリオレフィン系フィルムに対する接着性、溶融ポリプロピレンのダイレクトラミネート適性に優れたラミネート用水性印刷インキ組成物およびそれを用いた印刷物のラミネート方法に関する。
【０００２】
【従来の技術】
環境問題、省資源、労働安全性及び火災等の見地から、近年、有機溶剤の使用を極力抑えた水性タイプの印刷インキの要望が強くなっている。
【０００３】
特にラミネート加工された包装袋では、インキ皮膜が被印刷体フィルムと積層フィルムとの間で埋封されて、有害な有機溶剤が残留し易く、内容物に有害な影響を及ぼすことから、この水性化の要望は強い。
【０００４】
そこで、有機溶剤系ラミネート用インキで用いられていた各種バインダー樹脂を、乳化剤の存在下に水中に分散させる方法、あるいは分子内にイオン性基を導入し、中和により水中に溶解または分散させる方法（以下、これら両処理を併せて水性化という）により、水系での利用が図られている。
【０００５】
しかし、このようにして水性化された樹脂では、プラスチックフィルム表面との接着性が乏しく、十分なラミネート適性が得られないという問題があった。
【０００６】
そこで本出願人は、水性樹脂バインダーの分子内にヒドラジン残基を導入した系（特開平６−２０６９７２号公報）、水性樹脂バインダーの分子内にカルボニル基を導入し、ヒドラジン系架橋剤で架橋する系（特開平６−２５０４６５号公報）により、各種プラスチックフィルムに対する良好な接着性、押出しラミネート適性を有する印刷インキを提案している。
【０００７】
しかし、上記のバインダー樹脂のみでは、ダイレクトラミネート適性の良好な印刷インキを得ることは困難であった。
【０００８】
一般に、ポリウレタン等の極性基を有する樹脂は、ダイレクトラミネート適性に乏しく、有機溶剤系印刷インキにおいても塩素化ポリプロピレンがバインダー樹脂として利用されている。
【０００９】
そこで、水系でのダイレクトラミネート加工適性を向上させるためにも、この塩素化ポリプロピレンの利用が不可欠と考えられることから、塩素化ポリプロピレンを各種変性方法で変性して水性化した系（例えば、特開平１−２２３１７４号公報、特開平２−５８５０４号公報、特開平４−３４２７０３号公報、特開平７−１８４３８５号等）のラミネート用水性印刷インキが提案されている。
【００１０】
しかし、これらの方法により得られる印刷インキ組成物は、印刷適性、フィルムに対する濡れ性、経時粘度安定性等を同時に満たすことは極めて困難である。
【００１１】
この様な理由から、水性でポリオレフィンフィルムに代表されるプラスチックフィルムに対する接着性、ダイレクトラミネート適性の良好な印刷インキ組成物は未だ得られていないというのが現状である。
【００１２】
【発明が解決しようとする課題】
本発明の目的は、上記従来技術の問題を解決し、水性でありながら良好な接着性、ラミネート強度を示し、さらにダイレクトラミネート加工適性の優れた水性印刷インキを提供することである。
【００１３】
【課題を解決するための手段】
本発明はインキ性能の向上のために、塩素化ポリプロピレン自体を変性するという従来の考え方から脱却して、塩素化ポリプロピレンを分散させる乳化剤の見直しを図ったものである。
【００１４】
すなわち本発明は、（１）顔料、水性バインダー樹脂ワニスを主たる成分とするラミネート用水性印刷インキ組成物において、前記水性バインダー樹脂ワニスが、下記のａ成分、ｂ成分および必要に応じてｃ成分からなり、かつその含有量が水性バインダー樹脂ワニスの全固形分に対して、ａ成分の固形分５〜５０重量％、ｂ成分の固形分５０〜９５重量％、ｃ成分の固形分０〜３０重量％（３成分の固形分を合わせて１００重量％とする）であることを特徴とするラミネート用水性印刷インキ組成物に関する。
【００１５】
ａ成分：塩素化度２０〜６０、分子量５，０００〜２００，０００の塩素化ポリプロピレン、および／または塩素化度２０〜６０、分子量５，０００〜５００，０００の塩素化ポリプロピレンを（無水）マレイン酸で変性して得られる（無水）マレイン酸変性塩素化ポリプロピレンを、つぎの一般式（１）で表される化合物の存在下、水中に分散させて得られる水性バインダー樹脂ワニス。
【００１６】
【化３】
ここで、Ｒ1およびＲ2は独立にアルキル基であり、Ｒ1とＲ2の炭素数の合計が１０〜１４であり、Ｘはつぎの一般式（２）：
【００１８】
【化４】
（式中、ｐは１〜１０の整数である）で表される基である。
【００２０】
ｂ成分：ポリウレタン樹脂、アクリル系樹脂、エチレン−アクリル酸系樹脂よりなる群から選ばれる少なくとも１種を、塩基性化合物および／または乳化剤の存在下、水中に溶解または分散させて得られる水性バインダー樹脂ワニス。
【００２１】
ｃ成分：その他の水性樹脂を塩基性化合物および／または乳化剤の存在下、水中に溶解または分散させて得られる水性バインダー樹脂ワニス。
【００２２】
また本発明は、（２）前記一般式（１）におけるＸが−Ｏ−（ＣＨ2ＣＨ2 Ｏ）3Ｈである化合物の存在下で、前記塩素化ポリプロピレンおよび／または（無水）マレイン酸変性塩素化ポリプロピレンを水中に分散させて得られる水性バインダー樹脂ワニスを、ａ成分として使用する前記（１）項記載のラミネート用水性印刷インキ組成物に関する。
【００２３】
また本発明は、（３）分子内にヒドラジン残基を少なくとも１つ有するポリウレタン樹脂を、塩基性化合物および／または乳化剤の存在下、水中に溶解または分散させて得られる水性バインダー樹脂ワニスを、ｂ成分として使用する前記（１）項または（２）項記載のラミネート用水性印刷インキ組成物に関する。
【００２４】
また本発明は、（４）プラスチックフィルムに前記（１）〜（３）項のいずれかに記載のラミネート用水性印刷インキ組成物を印刷した後、プラスチックフィルムを積層することを特徴とする印刷物のラミネート方法に関する。
【００２５】
また本発明は、（５）ポリプロピレンフィルムに前記（１）〜（３）項のいずれかに記載のラミネート用水性印刷インキ組成物を印刷した後、溶融ポリプロピレン樹脂を積層することを特徴とする印刷物のラミネート方法に関する。
【００２６】
【発明の実施の形態】
本発明においては、ラミネート用水性印刷インキ組成物に使用する塩素化ポリプロピレンおよび／または（無水）マレイン酸変性塩素化ポリプロピレンからなる水性バインダー樹脂ワニスとして、塩素化ポリプロピレンおよび／または（無水）マレイン酸変性塩素化ポリプロピレンを一般式（１）で表される特定の化合物の存在下に水中に分散させてえられるものを用いることによって、一般の乳化剤を用いて前記バインダー樹脂を水中に分散させたものにくらべて、プラスチックフィルムに対する接着性が良好で、押出しラミネートおよびダイレクトラミネート加工適性が優れている。
【００２７】
以下に本発明についてさらに詳しく説明する。
【００２８】
本発明の水性印刷インキ組成物は、顔料、水性バインダー樹脂ワニスを主成分とするものである。
【００２９】
本発明で使用する顔料としては、一般に水性インキで使用できる無機、有機顔料あるいは体質顔料が使用できる。
【００３０】
ここで使用可能な無機顔料としては、酸化チタン、ベンガラ、アンチモンレッド、カドミウムレッド、カドミウムイエロー、コバルトブルー、紺青、群青、カーボンブラック、黒鉛など、有機顔料としては、溶性アゾ顔料、不溶性アゾ顔料、アゾレーキ顔料、縮合アゾ顔料、銅フタロシアニン顔料、縮合多環顔料等を挙げることができる。
【００３１】
さらに使用可能な体質顔料としては、炭酸カルシウム、カオリン、クレー、硫酸バリウム、水酸化アルミニウム、タルクなどを挙げることができる。
【００３２】
これらの顏料の通常の使用量は、水性インキ組成物中、１〜５０重量％である。
【００３３】
次に本発明で使用する水性バインダー樹脂ワニスとしては、塩素化ポリプロピレンおよび／または（無水）マレイン酸変性塩素化ポリプロピレンを、特定の乳化剤を用いて水性化して得られる水性バインダー樹脂ワニス（ａ成分）、ポリウレタン樹脂、アクリル系樹脂、エチレン−アクリル酸系樹脂よりなる群から選ばれる少なくとも１種を水性化して得られる水性バインダー樹脂ワニス（ｂ成分）、および必要に応して、その他の水性樹脂を水性化して得られる水性バインダー樹脂ワニス（ｃ成分）の３種である。
【００３４】
＜ａ成分＞
本発明でバインダー樹脂として使用する塩素化ポリプロピレンとは、アイソタクチックな結晶構造を有するポリプロピレンを塩素化して得られるものであり、また（無水）マレイン酸変性塩素化ポリプロピレンとは前記塩素化ポリプロピレンにさらにマレイン酸および／または無水マレイン酸を付加して得られたものである。
【００３５】
ポリプロピレンの塩素化は、公知の方法により行うことができ、例えば、ポリプロピレンを四塩化炭素などの有機溶剤に溶解した後、塩素ガスを反応させて塩素化ポリプロピレンを得る方法が利用できる。
【００３６】
ここで、本発明で使用する塩素化ポリプロピレンの塩素化度（塩素化ポリプロピレン中の塩素の含有率を重量％で表わした値をいう、以下同様）は、２０〜６０、より好ましくは３０〜５０の範囲である。塩素化度がこの範囲より小さくなると、水中での十分な分散性が得られず、一方、この範囲より大きくなるとポリオレフインフィルムに対する接着性、ダイレクトラミネート適性が低下して好ましくない。
【００３７】
塩素化ポリプロピレンに（無水）マレイン酸を付加するには、公知の方法が利用でき、例えばラジカル重合開始剤の存在下で塩素化ポリプロピレンと（無水）マレイン酸とを溶融混合する方法が利用できる。
【００３８】
ここで利用可能なラジカル重合開始剤としては、ジ−tert−ブチルパーオキサイド、tert−ブチルハイドロパーオキサイド、ジクミルパーオキサイド等の過酸化物やアゾビスイソブチロニトリル、アゾビスイソプロピオニトリル等のアゾビス系化合物などが挙げられる。
【００３９】
本発明において、（無水）マレイン酸の付加率は、当該（無水）マレイン酸変性塩素化ポリプロピレンの酸価を５〜１００とする値が適当である。酸価が前記の範囲より小さくなると、（無水）マレイン酸変性の効果が顕著に現れず、一方、酸価が前記の範囲より大きくなるとポリプロピレンフィルムに対する接着性、ダイレクトラミネート適性などが低下して好ましくない。なお、（無水）マレイン酸変性塩素化ポリプロピレンの分子量が高くなるに従って、前記の範囲内で酸価を高くすることが好ましい。
【００４０】
本発明において使用可能な塩素化ポリプロピレンの分子量（数平均分子量、以下同様）は、５，０００〜２００，０００、なかんづく１０，０００〜５０，０００、（無水）マレイン酸変性塩素化ポリプロピレンの分子量は、５，０００〜５００，０００、なかんづく１０，０００〜１００，０００の範囲である。ここで、塩素化ポリプロピレンおよび（無水）マレイン酸変性塩素化ポリプロピレンの分子量が前記の範囲より低くなると、得られるインキ皮膜の凝集力が低下してフィルムとの接着性が不良となる。一方、分子量が高くなるほど、フィルムに対する接着性、ダイレクトラミネート適性の面で有利となるが、水中での分散安定性が低下する。この点からは、より高分子量で分散安定性に優れる（無水）マレイン酸変性塩素化ポリプロピレンの使用が望ましい。
【００４１】
これらの方法より得られた塩素化ポリプロピレンおよび／または（無水）マレイン酸変性塩素化ポリプロピレンを水性化するために、本発明では、つぎの一般式（１）で示される化合物を乳化剤として使用する。
【００４２】
【化５】
ここで、Ｒ1およびＲ2は独立にアルキル基であり、Ｒ1とＲ2の炭素数の合計が１０〜１４であり、Ｘはつぎの一般式（２）：
【００４４】
【化６】
（式中、ｐは１〜１０の整数である）で表される基である。
【００４６】
一般式（１）においてＲ1で表されるアルキル基としては、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシルなど炭素数１〜１３のアルキル基があげられ、分散効果の点からとくに炭素数３〜７のアルキル基が好ましい。Ｒ2で表されるアルキル基としては、前記Ｒ1で表されるアルキル基との炭素数の合計を１０〜１４とするアルキル基があげられる。一般式（２）で表されるＸとしては、ｐ＝１〜１０のものが分散効果の点から好ましい。
【００４７】
このタイプの乳化剤の代表例として、ユニオンカーバイド社製のタージトールＳ（Ｒ1とＲ2の合計炭素数１０〜１４、エチレンオキサイド３モル付加物）や、ユニオンカーバイド社製のソフタノール（Ｒ1とＲ2の合計炭素数１１〜１３、エチレンオキサイド３モル付加物）等が市販されている。
【００４８】
前記乳化剤は塩素化ポリプロピレンおよび／または（無水）マレイン酸変性塩素化ポリプロピレンに対して２〜２０重量％、なかんづく５〜１０重量％の範囲で使用するのが好ましい。乳化剤の使用量が前記範囲より少ないと、塩素化ポリプロピレンおよび／または（無水）マレイン酸変性塩素化ポリプロピレンの分散安定性が低下し、一方、前記範囲より多いと、プラスチックフィルムに対する接着性、ダイレクトラミネート適性が低下する。
【００４９】
なお、（無水）マレイン酸変性塩素化ポリプロピレンの場合、水中での分散安定性をより高くするという観点から、前記乳化剤と、中和の当量以上の塩基性化合物とを併用することが好ましい。塩基性化合物としては、たとえばアンモニア、有機アミン、アルカリ金属水酸化物などがあげられる。
【００５０】
以上の方法により得られたａ成分の使用比率は、本発明の水性インキ組成物中の水性バインダー樹脂ワニスの全固形分に対して、ａ成分の固形分が５〜５０重量％、なかんづく１０〜４０重量％となる量である。ここで、ａ成分の使用比率が前記の範囲より低くなると、ポリオレフィン系フィルムに対する接着性やダイレクトラミネート適性が低下し、一方、高くなるとポリエステルやナイロンフィルムに対する接着性、ラミネート強度が低下して好ましくない。
【００５１】
＜ｂ成分＞
本発明のｂ成分として用いる、水性ポリウレタン樹脂ワニス、水性アクリル系樹脂ワニスおよび水性エチレン−アクリル酸系樹脂ワニスは、一般に水性インキ組成物で使用される公知のものが利用できる。
【００５２】
・水性ポリウレタン樹脂ワニス
水性ポリウレタン樹脂ワニスに使用するポリウレタン樹脂は、有機ジイソシアネー卜化合物と高分子ジオール化合物を反応させて、ウレタンプレポリマーを合成した後、鎖伸長剤、反応停止剤を反応させて得られるもので、必要に応じて、分子内に遊離のカルボキシル基を導入して水性化することができる。ここで利用可能な有機ジイソシアネート化合物としては、ヘキサメチレンジイソシアネートに代表される脂肪族ジイソシアネー卜化合物、イソホロンジイソシアネー卜に代表される脂環族ジイソシアネー卜化合物、α，α，α´，α´−テトラメチルキシリレンジイソシアネー卜に代表される芳香脂環族ジイソシアネー卜化合物、トリレンジイソシアネー卜に代表される芳香族ジイソシアネー卜化合物等が挙げられ、その中でも脂環族および芳香脂環族ジイソシアネー卜化合物が好ましい。
【００５３】
次に、利用可能な高分子ジオール化合物としては、炭素数が２〜８程度のグリコール類等の低分子ジオール化合物を用いて、二塩基酸を重縮合させた重縮合物、あるいはラクトン類などの環状エステル化合物を開環反応させて得られるポリエステルジオール類、また、酸化エチレン、酸化プロピレン等を重合もしくは共重合させて得られるポリエーテルジオール類、更に、前記低分子ジオール化合物をカーボネート成分あるいはホスゲンと反応させて得られるポリカーボネートジオール類、ポリブタジエングリコール類等が挙げられる。
【００５４】
なお、ポリウレタン樹脂の分子内にカルボキシル基を導入するためには、遊離のカルボキシル基を有する高分子ジオール化合物が利用でき、例えば、前記高分子ジオール成分と無水ピロメリット酸などの四塩基酸無水物を反応させるか、あるいは、ジメチロールプロピオン酸等を開始剤として、ラクトン類を開環重合させて得られる高分子ジオール化合物を使用することができる。
【００５５】
これらの高分子ジオール化合物としては、分子量が５００〜４０００のものが好適に使用でき、また、プラスチックフィルムとの接着性やラミネート適性等の面から、ポリエステルジオール類、ポリカーボネートジオール類が好適に使用できる。
【００５６】
次に、利用可能な鎖伸長剤としては、前記低分子ジオール化合物およびジアミン化合物を挙げることができ、さらにこれらと併用できるものとして、水酸基が３つ以上の脂肪族ポリオール類、脂環族ポリオール類、アミノ基が３つ以上の脂肪族ポリアミン類を挙げることができる。
【００５７】
また、ポリウレタン樹脂の分子内に遊離のカルボキシル基を導入するために、遊離のカルボキシル基を有する鎖伸長剤、さらに、プラスチックフィルムに対するより高い接着性を付与させることを目的として、分子内にヒドラジン残基を有する鎖伸剤、例えばポリアミノヒドラジドを使用することができる。
【００５８】
次に、利用可能な反応停止剤としては、アルキルモノアミン類、アルカノールアミン類、モノアルコールなどを挙げることができる。
【００５９】
さらに、ポリウレタン分子内にヒドラジン残基を導入するためには、前記ポリアミノヒドラジドが好適に使用できる他、ヒドラジン、アルキレンジヒドラジン、あるいは、飽和二塩基酸のジヒドラジド化合物等も使用できる。
【００６０】
分子内にヒドラジン残基を有するポリウレタン樹脂は、とくに表面処理されたプラスチックフィルムに対する接着性が良好となる。
【００６１】
以上の各反応成分を用いて、既知の製造方法でポリウレタン樹脂が製造でき、また一般的な乳化剤および／または塩基性化合物を用いる既知の方法により水性化することができる。
【００６２】
なお、塩基性化合物を用いて前記ポリウレタン樹脂を水性化する場合、当該ポリウレタン樹脂として酸価が５〜１００のものを使用するのが好ましい。酸価が前記の範囲より小さくなると、水性化が困難となり、一方、酸価が前記の範囲より大きくなると、耐水性、乾燥性などが低下して好ましくない。
【００６３】
さらに、本発明で好適とするポリウレタン樹脂の分子量は、５，０００〜２００，０００であり、より好適には１０，０００〜１００，０００である。ポリウレタン樹脂の分子量が前記範囲未満では、樹脂皮膜が弾性に乏しく、脆弱なものとなり、一方、分子量が前記範囲を超えると、水中での分散性あるいは溶解安定性が低下する傾向がある。
【００６４】
・水性アクリル系樹脂ワニス
水性アクリル系樹脂ワニスに使用するアクリル系樹脂は、アクリル系モノマーを必須成分として、スチレン系モノマー、マレイン酸系モノマーなどを共重合して得られる共重合体樹脂であり、必要に応じて、分子内に遊離のカルボキシル基を導入して水性化することができる。
【００６５】
まず、アクリル系モノマーとしては、（メタ）アクリル酸および、その炭素数が１〜１８のアルキルエステル、炭素数が１〜１８のアルキルアミド、炭素数が２〜４のヒドロキシアルキルエステル等を挙げることができる。
【００６６】
ここで、（メタ）アクリル酸とは、アクリル酸またはメタクリル酸を表す。
【００６７】
また、スチレン系モノマーとしては、スチレンおよびα−メチルスチレンなどのスチレン誘導体、マレイン酸系モノマーとしては、（無水）マレイン酸と、その炭素数が１〜１８のアルキルエステル、炭素数が１〜１８のアルキルアミド、炭素数が２〜４のヒドロキシアルキルエステル等を挙げることができる。
【００６８】
さらに、前記アクリル系樹脂が、反応成分として前記以外の一般に水性アクリル樹脂の反応成分として使用されるモノマーを含むことは何等差し支えない。
【００６９】
以上の各反応成分を用いて、既知の製造方法でアクリル系樹脂が製造でき、また、一般的な乳化剤および／または塩基性化合物を用いる既知の方法により水性化することができる。
【００７０】
なお、塩基性化合物を用いて前記アクリル系樹脂を水性化する場合、当該アクリル系樹脂として酸価が１０〜２００のものが好ましい。酸価が前記の範囲より小さくなると、水性化が困難となり、一方、酸価が前記の範囲より大きくなると耐水性、乾燥性などが低下して好ましくない。
【００７１】
・水性エチレン−アクリル酸系樹脂ワニス
水性エチレン−アクリル酸系樹脂ワニスに使用するエチレンーアクリル酸系共重合体は、エチレン６０〜９０重量％、アクリル酸またはメタクリル酸１０〜３０重量％、その他の共重合可能なビニル基含有化合物０〜３０重量％の組成で共重合させてなる共重合体が好適であり、塩基性化合物および／または乳化剤の存在下で水中に溶解または分散させて水性ワニス化することができる。
【００７２】
ここで、その他の共重合可能なビニル基含有化合物としては、前記のアクリル酸またはメタクリル酸のアルキルエステル、アルキルアミド、スチレン系モノマー、およびビニルクロライド、ビニルアセテート等が使用できる。
【００７３】
前記エチレン−アクリル酸系共重合体における（メタ）アクリル酸の含有量は１０〜３０重量％が好適であり、（メタ）アクリル酸の含有量が１０重量％より少なくなると、共重合体の水に対する乳化能が低下し、使用が限定され、一方、３０重量％を超えると、乾燥性が低下する。
【００７４】
また、前記エチレンーアクリル酸系共重合体のメルトインデックスは好適には１００〜２０００ｇ／１０分、より好適には３００〜１０００ｇ／１０分の範囲である。共重合体のメルトインデックスが前記範囲より小さくなると、樹脂の水中での分散安定性が低くなり、また前記範囲を超えると、樹脂が柔軟になり過ぎて、得られる水性インキ印刷面とフィルムとの間でブロッキングを起こしやすくなる。
【００７５】
以上の各反応成分を用いて、既知の製造方法でエチレン−アクリル酸樹脂が製造でき、また、一般的な乳化剤および／または塩基性化合物を用いる既知の方法により水性化することができる。
【００７６】
なお、エチレン−アクリル酸系樹脂は固形樹脂および水性樹脂ワニスとして市販されており、例えば、ペレット状の固体樹脂として、エチレン―アクリル酸共重合体Ａ−２００Ｗ（三菱油化（株）製）、塩基性化合物の存在下で水中に分散した樹脂ワニスとして、ザイクセンＡＣ（住友精化（株）製）が入手可能である。
【００７７】
これらｂ成分の使用比率は、本発明の水性インキ組成物中の水性バインダー樹脂ワニスの全固形分に対して、ｂ成分の固形分が５０〜９５重量％、なかんづく６０〜９０重量％となる量である。ｂ成分が前記の範囲より少なくなると、ポリエステルやナイロンフィルムに対する接着性、ラミネート強度が低下し、一方、多くなるとポリオレフイン系フィルムに対する接着徃やダイレクトラミネート適性が低下して好ましくない。
【００７８】
＜ｃ成分＞
本発明では、前記の必須バインダー樹脂の他に、必要に応じてセルロース樹脂、ポリエステル樹脂、ポリアミド樹脂、ハードレジン等の他の各種樹脂を水性化して得られる水性バインダー樹脂ワニスを、固形分として、全水性バインダー樹脂ワニスの固形分の３０重量％程度まで添加することができる。
【００７９】
さらに本発明の水性インキ組成物には、メタノール、エタノール、プロパノール、メトキシプロパノール、Ｎ−メチルピロリドン等の水混和性溶剤、顔料分散剤、ブロッキング防止剤、消泡剤、架橋剤等の各種添加剤を添加することも任意である。
【００８０】
＜インキの製造、印刷およびラミネート方法＞
前記の各種材料を使用して、ラミネート用水性印刷インキ組成物を製造する方法としては、顔料、水性バインダー樹脂ワニスおよび必要に応じて顔料分散用樹脂または顔料分散剤を混合して混練し、さらに所定の材料の残りを添加、混合する方法が一般的である。特に顔料分散性を良好とするためには、水性バインダー樹脂ワニスの中でも、塩基性化合物の存在下、水中に溶解させたものを使用して顔料分散を行うことが好ましい。
【００８１】
以上の方法により得られる印刷インキ組成物は、フレキソあるいはグラビア印刷方式によって、プラスチックフィルムに印刷することができる。
【００８２】
本発明の水性ラミネート用印刷インキ組成物が印刷されるプラスチックフィルムとしては、ポリオレフィン、ポリエステル、ナイロンなどの各種プラスチックフィルムがあげられ、特にコロナ放電処理などの表面処理されたものがより好適である。
【００８３】
さらに本発明のラミネート用水性印刷インキ組成物の印刷物をラミネート加工する方法としては、上記の各種フィルムに本発明の水性印刷インキ組成物を印刷した後、印刷面にイミン系、イソシアネート系、ポリブタジエン系、チタン系などの各種アンカーコート剤を塗工し、溶融ポリエチレン樹脂を積層する通常の押出しラミネート法、印刷面にウレタン系などの接着剤を塗工し、プラスチックフィルムを積層するドライラミネート法、およびポリプロピレンフィルムに本発明の水性印刷インキ組成物を印刷した後、印刷面に直接溶融ポリプロピレン樹脂を積層するダイレクトラミネート法のいずれもが利用できる。
【００８４】
なお、通常の押出しラミネー卜およびドライラミネート法を使用してラミネート加工する場合は、アンカーコート剤あるいは接着剤として水性系のものを使用することにより、完全水系のラミネート加工物が得られ、食品衛生などの点でより有利となる。
【００８５】
本発明の印刷インキ組成物は、水性でありながら、いずれのラミネート加工法でも良好なラミネート適性を有し、特に従来の印刷インキと比較して良好なダイレクトラミネート加工適性を有する。
【００８６】
【実施例】
以下、実施例でもって本発明をより具体的に説明するが、本発明はこれに限定されるものではない。なお、特にことわりのない限り、「部」および「％」は 「重量部」及び「重量％」を表す。
【００８７】
＜水性塩素化ポリプロピレンワニスの製造＞
乳化機を備えたフラスコに、それぞれ表１に示す分子量、塩素化度の塩素化ポリプロピレンのトルエン溶液（固形分３０重量％）１００部、タージトールＳ（ユニオンカーバイド社製）３部を仕込み、注水しながら内容物を均一に乳化し、蒸留・注水を繰り返してトルエンを留去し、水性塩素化ポリプロピレンワニス（水性塩素化ＰＰワニス）Ｎｏ．１〜１０を得た。
【００８８】
また、乳化機を備えたフラスコに、分子量１０，０００、塩素化度４０の塩素化ポリプロピレンのトルエン溶液（固形分３０重量％）１００部、ポリオキシエチレンノニルフェニルエーテル３部を仕込み、注水しながら内容物を均一に乳化し、蒸留・注水を繰り返してトルエンを留去し、水性塩素化ポリプロピレンワニス（水性塩素化ＰＰワニス）Ｎｏ．１１を得た。
【００８９】
＜水性無水マレイン酸変性塩素化ポリプロピレンワニスの製造＞
還流管、温度計、攪拌装置を備えた容器に、表２に示す分子量、塩素化度の塩素化ポリプロピレン及び無水マレイン酸のキシレン溶液を仕込み、窒素置換下１４０℃に昇温後、ジクミルパーオキサイドを添加して４時間反応させた。
【００９０】
減圧下キシレン及び未反応の無水マレイン酸を留去し、固形の無水マレイン酸変性塩素化ポリプロピレンを得た。
【００９１】
乳化機を備えたフラスコに、前記の方法で得た無水マレイン酸変性塩素化ポリプロピレンのトルエン溶液（固形分３０重量％）１００部、タージトールＳ ３部を仕込み、注水しながら内容物を均一に乳化し、蒸留・注水を繰り返してトルエンを留去した後、中和量のアンモニア水を加えて水性塩素化ポリプロピレンワニス（水性無水マレイン酸変性塩素化ＰＰワニス）Ｎｏ．１〜１０を得た。
【００９２】
また、分子量１０，０００、塩素化度４０の塩素化ポリプロピレンを、前記の方法で無水マレイン酸変性して得た酸価１００の無水マレイン酸変性塩素化ポリプロピレンのトルエン溶液（固形分３０重量％）１００部、ポリオキシエチレンノニルフェニルエーテル３部を仕込み、注水しながら内容物を均一に乳化し、蒸留・注水を繰り返してトルエンを留去した後、中和量のアンモニア水を加えて無水マレイン酸変性塩素化ポリプロピレンワニス（水性無水マレイン酸変性塩素化ＰＰワニス）Ｎｏ．１１を得た。
【００９３】
＜水性塩素化ポリプロピレンワニスおよび水性無水マレイン酸変性塩素化ポリプロピレンワニスの分散安定性の評価＞
試験方法
Ｂ型粘度計を使用して、増粘率（４０℃で７日保存後の粘度／初期粘度の比率、ただし、６０ｒｐｍの回転速度で測定したときの粘度値を使用）を求め、その大小から塩素化ポリプロピレンワニスおよび水性無水マレイン酸変性塩素化ポリプロピレンワニスの分散安定性の評価を行った。
【００９４】
評価基準
Ａ：増粘率が１．５以下のもの
Ｂ：増粘率が１．５を超え、３．０以下のもの
Ｃ：増粘率が３．０を超え、５．０以下のもの
Ｄ：増粘率が５．０を超えるもの
―：分離沈降の認められるもの
なお、分離沈降が認められる水性塩素化ポリプロピレンワニスＮｏ．１０および水性無水マレイン酸変性塩素化ポリプロピレンワニスＮｏ．１０は、分散安定性が劣悪と判断し、水性印刷インキ組成物の製造を行わなかった。
【００９５】
＜水性ポリウレタン樹脂ワニスの製造＞
製造例１
温度計、撹拌機、冷却管、および窒素導入管を備えた四つロフラスコに、分子量１，０００のポリネオペンチルグリコールアジペートジオール３００部、イソホロンジイソシアネート１３３．２部を仕込み、窒素ガスを導入しながら、撹拌下１００〜１０５℃で４時問反応させ、次いで、ジメチロールプロピオン酸２４．１部を仕込み、１００〜１１０℃で２時問反応させた。
【００９６】
その後、１００℃まで冷却し、水１０７６部およびトリエチルアミン２０．２部を仕込んで水性化し、更にモノエタノールアミン１２．１部で反応停止させ、固形分３０％、樹脂酸価２４の水性ポリウレタン樹脂ワニス（水性ＰＵ樹脂ワニス）Ｎｏ．１を得た。
【００９７】
製造例２
製造例１と同様の装置に、分子量１２，０００のポリカーボネートジオール３００部、およびα，α，α´，α´−テトラメチルキシレンジイソシアネー卜８０．７部を仕込み、窒素ガスを導入しながら、撹拌下１００〜１０５℃で４時問反応させ、次いで、無水トリメリット酸とトリメチロールプロパンの１：１モル比の反応生成物３９．１部を込み、１００〜１１０℃で２時間反応させた。
【００９８】
その後、１００℃まで冷却し、水９９７部およびトリエチルアミン１４部を仕込んで水性化し、更にアジピン酸ジヒドラジン１３．３部で反応停止させ、固形分３０％、樹脂酸価３１の水性ポリウレタン樹脂ワニス（水性ＰＵ樹脂ワニス）Ｎｏ．２を得た。
【００９９】
製造例３
製造例１と同様の装置に、分子量１，０００のプロピレングリコール５００部、およびイソホロンジイソシアネート２２２部を仕込み、窒素ガスを導入しながら、撹拌下８０〜９０℃で４時間反応させた。
【０１００】
次いで、アセトン２００部を加えて溶解した後、イソプロパノール１００部とエチレンジアミン１８部の混合液を加え、３０℃で１０分間撹拌し、更にヒドラジン２０部を加え、３０℃で１時間撹拌した。
【０１０１】
水６９０部とポリオキシエチレンノニルフェニルエーテル（エチレンオキサイド付加数２５モル）１５０部の撹拌混合物を加えて水性化した後、アセトンとイソプロバノールを留去して、固形分４０％の水性ポリウレタン樹脂ワニス（水性ＰＵ樹脂ワニス）Ｎｏ．３を得た。
【０１０２】
＜水性アクリル系樹脂ワニスの製造＞
製造例１
温度計、撹拌機、冷却管、および滴下ロートを備えた四つロフラスコに、酢酸エチル６００部を仕込み、７５〜７８℃に加熱した後、窒素ガスを導入しながらアクリル酸３８．４部、ブチルアクリレート１８０部、メチルメタアクリレート１８１．６部、重合開始剤としてジターシャリーブチルパーオキサイド４部の混合物を３時間かけて滴下した。さらに滴下終了後、還流温度で３時間重合させて反応を完結し、酢酸エチルを留去して酸価７５のアクリル系共重合体１を得た。撹拌機を備えた容器に、アクリル系共重合体１の破砕物３００部、その中和量に対して１．２倍量のアンモニアを含むアンモニア水７００部を仕込み、撹拌しながら８０℃で加熱溶解し、固形分３０％の水性アクリル系樹脂ワニス（水性Ａｃ樹脂ワニス）Ｎｏ．１を得た。
【０１０３】
製造例２
製造例１と同様の操作で、アクリル酸２５．６部、ブチルアクリレート１８０部、メチルメタクリレート８０部、スチレン１１４．４部、重合開始剤としてジターシャリーブチルパーオキサイド４部の混合物を反応させ、酸価５０のアクリル系共重合体２を得た後、さらに製造例１と同様の操作でアンモニア水中に加熱溶解して、固形分３０％の水性アクリル系樹脂ワニス（水性Ａｃ樹脂ワニス）Ｎｏ．２を得た。
【０１０４】
＜実施例１〜１９及び比較例１〜１５＞
表３、４の配合に従い、まず顔料、顔料分散用水溶性樹脂ワニス混合物をレッドデビル型ペイントコンデイショナーで３０分問混練し、さらに所定の材料を混合・撹拌し、実施例１〜１９及び比較例１〜１５の水性印刷インキ組成物を得た。
【０１０５】
なお、顔料としてリオノールブルーＦＧ−７３３０（東洋インキ製造（株）製）、顔料分散用水性樹脂ワニスとしてジョンクリルＪ−６１（スチレンアクリル系樹脂、固形分３０％、ジョンソンポリマー（株）製）、水性エチレン−アクリル酸系樹脂ワニス（水性ＥＡＡ樹脂ワニス）として、ザイクセンＡＣ（住友精化（株）、アクリル酸の含有量２０％、メルトインデックス３００ｇ／１０分、固形分３０％）を使用した。
【０１０６】
＜水性印刷インキの評価＞
実施例１〜１９及び比較例１〜１５で得られた水性印刷インキの接着性、押出しラミネー卜強度、ダイレクトラミネート強度、および印刷適性として再溶解性、泳ぎを評価し、その結果を表３、４に示した。
【０１０７】
接着性
押出ラミネート強度
ダイレクトラミネート強度
再溶解性
泳ぎ（印刷ムラ）
なお、０ＰＰフィルムとは延伸ポリプロピレンフィルム（東洋紡績（株）製、Ｐ−２１６１、３０μｍ）、ＰＥＴフィルムとはポリエチレンテレフタレートフィルム（東洋紡績（株）製、Ｅ−５１０２、１２μｍ）、Ｎｙフィルムとはナイロンフィルム（ユニチカ（株）製、エンブレム、１５μｍ）を表す。
【０１１３】
【表１】
【表２】
【表３】
【表４】
【発明の効果】
以上、実施例を挙げて具体的に示したように、本発明の水性印刷インキ組成物は、水性タイプでありながら各種プラスチックフィルムに対する良好な接着性を示し、押出しラミネートおよびダイレクトラミネート加工適性に優れ、しかも印刷適性が良好な水性印刷インキ組成物である。[0001]
[Industrial application fields]
The present invention relates to a water-based printing ink composition for laminating and a method for laminating printed matter using the same. More particularly, the present invention relates to a water-based printing ink composition for laminating that is particularly excellent in adhesion to polyolefin-based films and suitability for direct lamination of molten polypropylene, and a method for laminating printed matter using the same.
[0002]
[Prior art]
From the viewpoint of environmental problems, resource saving, occupational safety, fire, etc., in recent years, there has been a strong demand for water-based printing inks that minimize the use of organic solvents.
[0003]
Especially in the case of laminated packaging bags, the ink film is embedded between the film to be printed and the laminated film, and harmful organic solvents are likely to remain. There is a strong demand for conversion.
[0004]
Therefore, a method of dispersing various binder resins used in organic solvent-based laminating inks in water in the presence of an emulsifier, or a method of introducing ionic groups into the molecule and dissolving or dispersing them in water by neutralization. (Hereinafter, these two treatments are collectively referred to as aqueous treatment), and use in aqueous systems is attempted.
[0005]
However, the water-based resin as described above has a problem that adhesiveness to the surface of the plastic film is poor and sufficient laminating properties cannot be obtained.
[0006]
Therefore, the present applicant has introduced a system in which a hydrazine residue is introduced into the molecule of the aqueous resin binder (Japanese Patent Laid-Open No. 6-206972), introduces a carbonyl group into the molecule of the aqueous resin binder, and crosslinks with a hydrazine-based crosslinking agent. JP-A-6-250465 proposes a printing ink having good adhesion to various plastic films and extrusion lamination suitability.
[0007]
However, it has been difficult to obtain a printing ink having good suitability for direct lamination only with the above binder resin.
[0008]
In general, a resin having a polar group such as polyurethane is poor in suitability for direct lamination, and chlorinated polypropylene is also used as a binder resin in organic solvent printing inks.
[0009]
Therefore, it is considered essential to use this chlorinated polypropylene in order to improve the suitability for direct laminating in an aqueous system. Therefore, a system in which chlorinated polypropylene is modified by various modification methods to become aqueous (for example, Japanese Patent Laid-Open JP-A-2-223174, JP-A-2-58504, JP-A-4-342703, JP-A-7-184385, etc.) have been proposed.
[0010]
However, it is extremely difficult for the printing ink composition obtained by these methods to satisfy simultaneously printability, wettability to a film, viscosity stability with time, and the like.
[0011]
For these reasons, a printing ink composition that is water-based and has good adhesion to a plastic film typified by a polyolefin film and good suitability for direct lamination has not yet been obtained.
[0012]
[Problems to be solved by the invention]
An object of the present invention is to provide an aqueous printing ink that solves the above-described problems of the prior art, exhibits good adhesiveness and laminate strength while being aqueous, and is excellent in suitability for direct lamination.
[0013]
[Means for Solving the Problems]
In the present invention, in order to improve the ink performance, the emulsifier for dispersing the chlorinated polypropylene is reexamined from the conventional idea of modifying the chlorinated polypropylene itself.
[0014]
That is, the present invention relates to (1) a water-based printing ink composition for laminating mainly comprising a pigment and an aqueous binder resin varnish, wherein the aqueous binder resin varnish comprises the following a component, b component and optionally c component: And the content thereof is 5 to 50% by weight of the solid content of the component a, 50 to 95% by weight of the solid content of the b component, and 0 to 30% by weight of the solid content of the c component with respect to the total solid content of the aqueous binder resin varnish. It is related with the aqueous | water-based printing ink composition for laminates characterized by the above-mentioned.
[0015]
Component a: Chlorinated polypropylene having a chlorination degree of 20 to 60 and a molecular weight of 5,000 to 200,000 and / or a chlorinated polypropylene having a chlorination degree of 20 to 60 and a molecular weight of 5,000 to 500,000 (anhydrous) male An aqueous binder resin varnish obtained by dispersing (anhydrous) maleic acid-modified chlorinated polypropylene obtained by acid modification in water in the presence of a compound represented by the following general formula (1).
[0016]
[Chemical 3]
Where R1And R2Are independently alkyl groups, R1And R2The total number of carbon atoms is 10 to 14, and X is the following general formula (2):
[0018]
[Formula 4]
(Where p is110 to 10In numberA group represented by:
[0020]
Component b: aqueous binder resin obtained by dissolving or dispersing at least one selected from the group consisting of polyurethane resin, acrylic resin, and ethylene-acrylic acid resin in water in the presence of a basic compound and / or emulsifier varnish.
[0021]
Component c: An aqueous binder resin varnish obtained by dissolving or dispersing other aqueous resin in water in the presence of a basic compound and / or emulsifier.
[0022]
In the present invention, (2) X in the general formula (1) is —O— (CH2CH2 O)ThreeItem (1) above, wherein an aqueous binder resin varnish obtained by dispersing the chlorinated polypropylene and / or (anhydrous) maleic acid-modified chlorinated polypropylene in water in the presence of a compound that is H is used as the component a. The present invention relates to a water-based printing ink composition for laminating.
[0023]
The present invention also provides (3) an aqueous binder resin varnish obtained by dissolving or dispersing a polyurethane resin having at least one hydrazine residue in the molecule in water in the presence of a basic compound and / or an emulsifier. It is related with the water-based printing ink composition for laminates of the said (1) term or (2) term used as a component.
[0024]
Moreover, the present invention provides (4) a printed matter, wherein the plastic film is laminated after the aqueous printing ink composition for laminating according to any one of (1) to (3) is printed on a plastic film. The present invention relates to a laminating method.
[0025]
Further, the present invention is (5) a printed matter characterized in that after the water-based printing ink composition for laminating according to any one of (1) to (3) is printed on a polypropylene film, a molten polypropylene resin is laminated. Relates to the laminating method.
[0026]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, chlorinated polypropylene and / or (anhydrous) maleic acid modification is used as an aqueous binder resin varnish comprising chlorinated polypropylene and / or (anhydrous) maleic acid modification chlorinated polypropylene used in the aqueous printing ink composition for laminating. By using a material obtained by dispersing chlorinated polypropylene in water in the presence of the specific compound represented by the general formula (1), the binder resin is dispersed in water using a general emulsifier. Compared with plastic film, it has better adhesion to plastic film and excellent extrusion and direct laminating suitability.
[0027]
The present invention will be described in more detail below.
[0028]
The aqueous printing ink composition of the present invention is mainly composed of a pigment and an aqueous binder resin varnish.
[0029]
As the pigment used in the present invention, inorganic, organic pigments or extender pigments that can be generally used in water-based inks can be used.
[0030]
Examples of inorganic pigments that can be used here include titanium oxide, bengara, antimony red, cadmium red, cadmium yellow, cobalt blue, bitumen, ultramarine blue, carbon black, and graphite. Organic pigments include soluble azo pigments, insoluble azo pigments, Examples include azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments.
[0031]
Further usable extender pigments include calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide and talc.
[0032]
The usual use amount of these materials is 1 to 50% by weight in the water-based ink composition.
[0033]
Next, as the aqueous binder resin varnish used in the present invention, an aqueous binder resin varnish (component a) obtained by hydrating chlorinated polypropylene and / or (anhydrous) maleic acid-modified chlorinated polypropylene using a specific emulsifier. An aqueous binder resin varnish (component b) obtained by making at least one selected from the group consisting of a polyurethane resin, an acrylic resin, and an ethylene-acrylic acid resin into water, and, if necessary, other aqueous resin There are three types of aqueous binder resin varnish (component c) obtained by making it aqueous.
[0034]
<a component>
The chlorinated polypropylene used as the binder resin in the present invention is obtained by chlorinating polypropylene having an isotactic crystal structure, and (anhydrous) maleic acid-modified chlorinated polypropylene is the same as the chlorinated polypropylene. Further, it was obtained by adding maleic acid and / or maleic anhydride.
[0035]
The chlorination of polypropylene can be performed by a known method. For example, a method of obtaining chlorinated polypropylene by dissolving polypropylene in an organic solvent such as carbon tetrachloride and then reacting with chlorine gas can be used.
[0036]
Here, the degree of chlorination of the chlorinated polypropylene used in the present invention (referring to the value of the chlorine content in the chlorinated polypropylene in terms of% by weight, the same applies hereinafter) is 20 to 60, more preferably 30 to 50. Range. If the degree of chlorination is smaller than this range, sufficient dispersibility in water cannot be obtained. On the other hand, if the degree of chlorination is larger than this range, the adhesiveness to the polyolefin film and the suitability for direct lamination are deteriorated.
[0037]
In order to add (anhydrous) maleic acid to chlorinated polypropylene, a known method can be used. For example, a method of melt-mixing chlorinated polypropylene and (anhydrous) maleic acid in the presence of a radical polymerization initiator can be used.
[0038]
Examples of radical polymerization initiators that can be used here include peroxides such as di-tert-butyl peroxide, tert-butyl hydroperoxide, and dicumyl peroxide, azobisisobutyronitrile, azobisisopropionitrile, and the like. And azobis compounds.
[0039]
In the present invention, the addition rate of (anhydrous) maleic acid is suitably a value in which the acid value of the (anhydrous) maleic acid-modified chlorinated polypropylene is 5 to 100. When the acid value is smaller than the above range, the effect of (anhydrous) maleic acid modification is not remarkably exhibited. On the other hand, when the acid value is larger than the above range, the adhesiveness to the polypropylene film, suitability for direct lamination, etc. are preferably decreased. Absent. In addition, it is preferable to raise an acid value within the said range as the molecular weight of (anhydrous) maleic acid modification chlorinated polypropylene becomes high.
[0040]
The molecular weight of chlorinated polypropylene that can be used in the present invention (number average molecular weight, hereinafter the same) is 5,000 to 200,000, especially 10,000 to 50,000, and the molecular weight of (anhydrous) maleic acid modified chlorinated polypropylene is , 5,000 to 500,000, especially 10,000 to 100,000. Here, when the molecular weight of the chlorinated polypropylene and (anhydrous) maleic acid-modified chlorinated polypropylene is lower than the above range, the cohesive force of the resulting ink film is lowered, resulting in poor adhesion to the film. On the other hand, the higher the molecular weight, the more advantageous in terms of adhesion to the film and suitability for direct lamination, but the dispersion stability in water decreases. From this point, it is desirable to use (anhydrous) maleic acid-modified chlorinated polypropylene having higher molecular weight and excellent dispersion stability.
[0041]
In order to make the chlorinated polypropylene and / or (anhydrous) maleic acid-modified chlorinated polypropylene obtained by these methods aqueous, in the present invention, the compound represented by the following general formula (1) is used as an emulsifier.
[0042]
[Chemical formula 5]
Where R1And R2Are independently alkyl groups, R1And R2The total number of carbon atoms is 10 to 14, and X is the following general formula (2):
[0044]
[Chemical 6]
(Where p is110 to 10In numberA group represented by:
[0046]
In the general formula (1), R1Examples of the alkyl group represented by the formula include alkyl groups having 1 to 13 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and the like. In particular, an alkyl group having 3 to 7 carbon atoms is preferable. R2As the alkyl group represented by the above R1An alkyl group having a total carbon number of 10 to 14 with the alkyl group represented by As X represented by the general formula (2), p = 1 to 1ZeroThose are preferred from the viewpoint of dispersion effect.
[0047]
As a representative example of this type of emulsifier, Taditol S (R1And R2Total carbon number of 10 to 14, ethylene oxide 3 mol adduct) and Union Carbide Softanol (R1And R2(Combined with 11 to 13 carbon atoms, 3 moles of ethylene oxide).
[0048]
The emulsifier is preferably used in an amount of 2 to 20% by weight, particularly 5 to 10% by weight, based on chlorinated polypropylene and / or (anhydrous) maleic acid modified chlorinated polypropylene. When the amount of the emulsifier used is less than the above range, the dispersion stability of the chlorinated polypropylene and / or (anhydrous) maleic acid modified chlorinated polypropylene is reduced. The aptitude decreases.
[0049]
In the case of (anhydrous) maleic acid-modified chlorinated polypropylene, it is preferable to use the emulsifier in combination with a basic compound having a neutralization equivalent or more from the viewpoint of increasing the dispersion stability in water. Examples of basic compounds include ammonia, organic amines, alkali metal hydroxides, and the like.
[0050]
The use ratio of the component a obtained by the above method is such that the solid content of the component a is 5 to 50% by weight with respect to the total solid content of the aqueous binder resin varnish in the aqueous ink composition of the present invention. The amount is 40% by weight. Here, when the use ratio of the component a is lower than the above range, the adhesiveness to the polyolefin film and the suitability for direct lamination are deteriorated. On the other hand, when it is higher, the adhesiveness to the polyester or nylon film and the laminate strength are deteriorated. .
[0051]
<Component b>
The water-based polyurethane resin varnish, the water-based acrylic resin varnish, and the water-based ethylene-acrylic acid resin varnish used as the component b of the present invention can be known ones generally used in water-based ink compositions.
[0052]
・ Water-based polyurethane resin varnish
The polyurethane resin used for the aqueous polyurethane resin varnish is obtained by reacting an organic diisocyanate compound with a polymer diol compound to synthesize a urethane prepolymer, and then reacting with a chain extender and a reaction terminator. Depending on the case, a free carboxyl group can be introduced into the molecule to make it aqueous. Examples of organic diisocyanate compounds that can be used here include aliphatic diisocyanate compounds represented by hexamethylene diisocyanate, alicyclic diisocyanate compounds represented by isophorone diisocyanate, α, α, α ′, α′- Examples include aromatic alicyclic diisocyanate compounds represented by tetramethylxylylene diisocyanate, aromatic diisocyanate compounds represented by tolylene diisocyanate, among which alicyclic and alicyclic diisocyanate compounds. Compounds are preferred.
[0053]
Next, as a usable high molecular diol compound, a polycondensate obtained by polycondensation of a dibasic acid using a low molecular diol compound such as a glycol having about 2 to 8 carbon atoms, or a lactone, etc. Polyester diols obtained by ring-opening reaction of cyclic ester compounds, polyether diols obtained by polymerizing or copolymerizing ethylene oxide, propylene oxide, etc., and further, the low molecular diol compound is converted into a carbonate component or phosgene. Examples thereof include polycarbonate diols and polybutadiene glycols obtained by reaction.
[0054]
In order to introduce a carboxyl group into the polyurethane resin molecule, a polymer diol compound having a free carboxyl group can be used. For example, the polymer diol component and a tetrabasic acid anhydride such as pyromellitic anhydride. Or a polymer diol compound obtained by ring-opening polymerization of a lactone using dimethylolpropionic acid or the like as an initiator.
[0055]
As these polymer diol compounds, those having a molecular weight of 500 to 4000 can be preferably used, and polyester diols and polycarbonate diols can be preferably used from the viewpoints of adhesion to a plastic film and suitability for lamination. .
[0056]
Next, examples of the chain extender that can be used include the low molecular diol compound and the diamine compound, and those that can be used in combination with them include aliphatic polyols having three or more hydroxyl groups, and alicyclic polyols. And aliphatic polyamines having 3 or more amino groups.
[0057]
In addition, in order to introduce a free carboxyl group into the molecule of the polyurethane resin, a hydrazine residue is left in the molecule for the purpose of imparting a chain extender having a free carboxyl group and higher adhesion to a plastic film. Chain extenders having groups, such as polyaminohydrazides, can be used.
[0058]
Next, examples of usable reaction terminators include alkyl monoamines, alkanolamines, monoalcohols, and the like.
[0059]
Furthermore, in order to introduce a hydrazine residue into the polyurethane molecule, the polyaminohydrazide can be preferably used, and hydrazine, alkylene dihydrazine, a dihydrazide compound of a saturated dibasic acid, or the like can also be used.
[0060]
A polyurethane resin having a hydrazine residue in the molecule has good adhesion to a surface-treated plastic film.
[0061]
A polyurethane resin can be produced by a known production method using each of the above reaction components, and can be made aqueous by a known method using a general emulsifier and / or a basic compound.
[0062]
In addition, when making the said polyurethane resin water-based using a basic compound, it is preferable to use a thing with an acid value of 5-100 as the said polyurethane resin. If the acid value is smaller than the above range, it is difficult to make it water-based. On the other hand, if the acid value is larger than the above range, water resistance, drying property and the like are lowered, which is not preferable.
[0063]
Furthermore, the molecular weight of the polyurethane resin suitable for the present invention is 5,000 to 200,000, and more preferably 10,000 to 100,000. When the molecular weight of the polyurethane resin is less than the above range, the resin film has poor elasticity and becomes brittle. On the other hand, when the molecular weight exceeds the above range, the dispersibility or dissolution stability in water tends to decrease.
[0064]
・ Water-based acrylic resin varnish
The acrylic resin used in the aqueous acrylic resin varnish is a copolymer resin obtained by copolymerizing a styrene monomer, a maleic acid monomer, etc., with an acrylic monomer as an essential component. A free carboxyl group can be introduced into the aqueous solution.
[0065]
First, examples of acrylic monomers include (meth) acrylic acid and alkyl esters having 1 to 18 carbon atoms, alkyl amides having 1 to 18 carbon atoms, and hydroxyalkyl esters having 2 to 4 carbon atoms. Can do.
[0066]
Here, (meth) acrylic acid represents acrylic acid or methacrylic acid.
[0067]
Moreover, as a styrene-type monomer, styrene derivatives, such as styrene and (alpha) -methylstyrene, and as a maleic acid-type monomer, (anhydrous) maleic acid and its C1-C18 alkyl ester, C1-C18 And alkyl amides having 2 to 4 carbon atoms.
[0068]
Furthermore, the acrylic resin may contain any monomer that is generally used as a reaction component of an aqueous acrylic resin other than the above as a reaction component.
[0069]
An acrylic resin can be produced by a known production method using each of the above reaction components, and can be made aqueous by a known method using a general emulsifier and / or a basic compound.
[0070]
In addition, when making the said acrylic resin water-based using a basic compound, a thing with an acid value of 10-200 is preferable as the said acrylic resin. When the acid value is smaller than the above range, it is difficult to make it aqueous. On the other hand, when the acid value is larger than the above range, water resistance, drying property and the like are lowered, which is not preferable.
[0071]
・ Aqueous ethylene-acrylic acid resin varnish
The ethylene-acrylic acid copolymer used in the aqueous ethylene-acrylic acid resin varnish is composed of 60 to 90% by weight of ethylene, 10 to 30% by weight of acrylic acid or methacrylic acid, and other copolymerizable vinyl group-containing compounds 0. A copolymer obtained by copolymerization at a composition of ˜30% by weight is suitable, and it can be dissolved or dispersed in water in the presence of a basic compound and / or an emulsifier to form an aqueous varnish.
[0072]
Here, as other copolymerizable vinyl group-containing compounds, the aforementioned alkyl esters of acrylic acid or methacrylic acid, alkylamides, styrenic monomers, vinyl chloride, vinyl acetate and the like can be used.
[0073]
The content of (meth) acrylic acid in the ethylene-acrylic acid copolymer is preferably 10 to 30% by weight, and when the content of (meth) acrylic acid is less than 10% by weight, water of the copolymer The emulsifying ability with respect to is reduced, and its use is limited.
[0074]
The melt index of the ethylene-acrylic acid copolymer is preferably in the range of 100 to 2000 g / 10 minutes, more preferably 300 to 1000 g / 10 minutes. If the melt index of the copolymer is smaller than the above range, the dispersion stability of the resin in water will be low, and if it exceeds the above range, the resin will be too flexible, and the resulting water-based ink printed surface and film It becomes easy to cause blocking between.
[0075]
Using each of the above reaction components, an ethylene-acrylic acid resin can be produced by a known production method, and can be made aqueous by a known method using a general emulsifier and / or a basic compound.
[0076]
The ethylene-acrylic acid-based resin is commercially available as a solid resin and an aqueous resin varnish. For example, as a pellet-shaped solid resin, an ethylene-acrylic acid copolymer A-200W (manufactured by Mitsubishi Yuka Co., Ltd.), Saixen AC (manufactured by Sumitomo Seika Co., Ltd.) is available as a resin varnish dispersed in water in the presence of a basic compound.
[0077]
The use ratio of these component b is such that the solid content of component b is 50 to 95% by weight, especially 60 to 90% by weight, based on the total solid content of the aqueous binder resin varnish in the aqueous ink composition of the present invention. It is. If the component b is less than the above range, the adhesion to the polyester or nylon film and the laminate strength are lowered, while if it is increased, the adhesive flaw to the polyolefin film and the suitability for direct lamination are lowered, which is not preferable.
[0078]
<Component c>
In the present invention, in addition to the essential binder resin, an aqueous binder resin varnish obtained by making other various resins such as a cellulose resin, a polyester resin, a polyamide resin, a hard resin, etc., if necessary, as a solid content, The total aqueous binder resin varnish can be added up to about 30% by weight.
[0079]
Further, the water-based ink composition of the present invention includes various additives such as a water-miscible solvent such as methanol, ethanol, propanol, methoxypropanol, and N-methylpyrrolidone, a pigment dispersant, an antiblocking agent, an antifoaming agent, and a crosslinking agent. It is also optional to add.
[0080]
<Ink production, printing and laminating method>
As a method for producing a water-based printing ink composition for laminating using the above-mentioned various materials, a pigment, an aqueous binder resin varnish and, if necessary, a pigment-dispersing resin or a pigment dispersant are mixed and kneaded, and The method of adding and mixing the remainder of a predetermined material is common. In particular, in order to improve the pigment dispersibility, among the aqueous binder resin varnishes, it is preferable to disperse the pigments by using those dissolved in water in the presence of a basic compound.
[0081]
The printing ink composition obtained by the above method can be printed on a plastic film by a flexographic or gravure printing method.
[0082]
Examples of the plastic film on which the printing ink composition for an aqueous laminate of the present invention is printed include various plastic films such as polyolefin, polyester, and nylon, and those subjected to surface treatment such as corona discharge treatment are more preferable.
[0083]
Furthermore, as a method of laminating the printed matter of the aqueous printing ink composition for laminating of the present invention, the aqueous printing ink composition of the present invention is printed on the above-mentioned various films, and then imine-based, isocyanate-based, polybutadiene-based on the printed surface. A normal extrusion laminating method in which various anchor coating agents such as titanium are applied and laminating a molten polyethylene resin, a dry laminating method in which an adhesive such as urethane is applied to the printed surface, and a plastic film is laminated, and Any of the direct laminating methods in which the water-based printing ink composition of the present invention is printed on a polypropylene film and then a molten polypropylene resin is laminated directly on the printing surface can be used.
[0084]
In addition, when laminating using a normal extrusion laminating bowl and dry laminating method, a completely water-based laminated product can be obtained by using an aqueous coating as an anchor coating agent or an adhesive. It becomes more advantageous in the point.
[0085]
Although the printing ink composition of the present invention is water-based, it has good laminating ability in any lamination method, and particularly has good direct laminating suitability as compared with conventional printing inks.
[0086]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to this. Unless otherwise specified, “parts” and “%” represent “parts by weight” and “% by weight”.
[0087]
<Manufacture of aqueous chlorinated polypropylene varnish>
A flask equipped with an emulsifier was charged with 100 parts of a toluene solution (solid content 30% by weight) of chlorinated polypropylene having a molecular weight and a chlorination degree shown in Table 1, and 3 parts of Taditol S (manufactured by Union Carbide Co.). While the contents were uniformly emulsified, distillation and water injection were repeated to distill off toluene, and aqueous chlorinated polypropylene varnish (aqueous chlorinated PP varnish) No. 1-10 were obtained.
[0088]
A flask equipped with an emulsifier was charged with 100 parts of a toluene solution (solid content 30% by weight) of chlorinated polypropylene having a molecular weight of 10,000 and a chlorination degree of 40, and 3 parts of polyoxyethylene nonylphenyl ether while pouring water. The contents were uniformly emulsified, distilled and poured into water repeatedly to distill off toluene, and aqueous chlorinated polypropylene varnish (aqueous chlorinated PP varnish) No. 11 was obtained.
[0089]
<Production of aqueous maleic anhydride-modified chlorinated polypropylene varnish>
A container equipped with a reflux tube, a thermometer, and a stirrer was charged with a chlorinated polypropylene having the molecular weight and chlorination degree shown in Table 2 and a xylene solution of maleic anhydride, and the temperature was raised to 140 ° C. under nitrogen substitution. Oxide was added and allowed to react for 4 hours.
[0090]
Xylene and unreacted maleic anhydride were distilled off under reduced pressure to obtain solid maleic anhydride-modified chlorinated polypropylene.
[0091]
A flask equipped with an emulsifier was charged with 100 parts of a maleic anhydride-modified chlorinated polypropylene toluene solution (solid content 30 wt%) obtained by the above method and 3 parts of Taditol S, and the contents were uniformly emulsified while pouring water. After repeating distillation and water injection to distill off toluene, a neutralized amount of aqueous ammonia was added to add aqueous chlorinated polypropylene varnish (aqueous maleic anhydride-modified chlorinated PP varnish) No. 1-10 were obtained.
[0092]
Further, a toluene solution of maleic anhydride-modified chlorinated polypropylene having an acid value of 100 obtained by modifying maleic anhydride with a chlorinated polypropylene having a molecular weight of 10,000 and a chlorination degree of 40 by the above method (solid content: 30% by weight) 100 parts, 3 parts of polyoxyethylene nonylphenyl ether are added, and the contents are uniformly emulsified while pouring water. After distillation and water pouring, toluene is distilled off, and then neutralized amount of aqueous ammonia is added to maleic anhydride. Modified chlorinated polypropylene varnish (aqueous maleic anhydride modified chlorinated PP varnish) No. 11 was obtained.
[0093]
<Evaluation of dispersion stability of aqueous chlorinated polypropylene varnish and aqueous maleic anhydride-modified chlorinated polypropylene varnish>
Test method
Using a B-type viscometer, obtain the viscosity increase ratio (ratio of viscosity after storage for 7 days at 40 ° C./initial viscosity ratio, but use the viscosity value when measured at a rotational speed of 60 rpm). The dispersion stability of chlorinated polypropylene varnish and aqueous maleic anhydride modified chlorinated polypropylene varnish was evaluated.
[0094]
Evaluation criteria
A: Thickening rate is 1.5 or less
B: Thickening rate exceeds 1.5 and is 3.0 or less
C: Thickening rate exceeding 3.0 and 5.0 or less
D: Thickening rate exceeds 5.0
―: Separation and sedimentation observed
In addition, aqueous chlorinated polypropylene varnish no. No. 10 and aqueous maleic anhydride modified chlorinated polypropylene varnish no. No. 10 was judged to have poor dispersion stability, and no aqueous printing ink composition was produced.
[0095]
<Manufacture of aqueous polyurethane resin varnish>
Production Example 1
Into a four-neck flask equipped with a thermometer, a stirrer, a condenser tube, and a nitrogen introduction tube were charged 300 parts of polyneopentyl glycol adipate diol having a molecular weight of 1,000 and 133.2 parts of isophorone diisocyanate while introducing nitrogen gas. The mixture was allowed to react for 4 hours at 100 to 105 ° C. with stirring, and then 24.1 parts of dimethylolpropionic acid was charged and reacted at 100 to 110 ° C. for 2 hours.
[0096]
Thereafter, the mixture was cooled to 100 ° C., charged with 1076 parts of water and 20.2 parts of triethylamine, made aqueous, further stopped with 12.1 parts of monoethanolamine, and an aqueous polyurethane resin varnish having a solid content of 30% and a resin acid value of 24 (Water-based PU resin varnish) No. 1 was obtained.
[0097]
Production Example 2
While charging 300 parts of polycarbonate diol having a molecular weight of 12,000 and 80.7 parts of α, α, α ′, α′-tetramethylxylene diisocyanate in an apparatus similar to Production Example 1, while introducing nitrogen gas, The mixture is allowed to react for 4 hours at 100 to 105 ° C. with stirring, and then 39.1 parts of a 1: 1 molar reaction product of trimellitic anhydride and trimethylolpropane is added and reacted at 100 to 110 ° C. for 2 hours. It was.
[0098]
Thereafter, the mixture was cooled to 100 ° C., charged with 997 parts of water and 14 parts of triethylamine, made aqueous, and further quenched with 13.3 parts of dihydrazine adipate, and an aqueous polyurethane resin varnish having a solid content of 30% and a resin acid value of 31 ( Aqueous PU resin varnish) No. 2 was obtained.
[0099]
Production Example 3
In the same apparatus as in Production Example 1, 500 parts of propylene glycol having a molecular weight of 1,000 and 222 parts of isophorone diisocyanate were charged and reacted at 80 to 90 ° C. for 4 hours with stirring while introducing nitrogen gas.
[0100]
Next, 200 parts of acetone was added and dissolved, and then a mixed solution of 100 parts of isopropanol and 18 parts of ethylenediamine was added, stirred at 30 ° C. for 10 minutes, further added with 20 parts of hydrazine, and stirred at 30 ° C. for 1 hour.
[0101]
A mixture of 690 parts of water and 150 parts of polyoxyethylene nonylphenyl ether (ethylene oxide addition number 25 mol) was added to make it aqueous, and then acetone and isopropanol were distilled off to obtain an aqueous polyurethane resin varnish having a solid content of 40%. (Water-based PU resin varnish) No. 3 was obtained.
[0102]
<Production of water-based acrylic resin varnish>
Production Example 1
A four-necked flask equipped with a thermometer, a stirrer, a condenser, and a dropping funnel was charged with 600 parts of ethyl acetate and heated to 75 to 78 ° C., and then 38.4 parts of acrylic acid and butyl were introduced while introducing nitrogen gas. A mixture of 180 parts of acrylate, 181.6 parts of methyl methacrylate and 4 parts of ditertiary butyl peroxide as a polymerization initiator was added dropwise over 3 hours. Furthermore, after completion | finish of dripping, it superposed | polymerized at reflux temperature for 3 hours, reaction was completed, ethyl acetate was distilled off, and the acrylic copolymer 1 of the acid value 75 was obtained. A container equipped with a stirrer is charged with 300 parts of a crushed acrylic copolymer 1 and 700 parts of ammonia water containing 1.2 times the amount of ammonia with respect to the neutralized amount, and heated at 80 ° C. with stirring. Aqueous acrylic resin varnish (aqueous Ac resin varnish) No. 1 was obtained.
[0103]
Production Example 2
In the same manner as in Production Example 1, a mixture of 25.6 parts of acrylic acid, 180 parts of butyl acrylate, 80 parts of methyl methacrylate, 114.4 parts of styrene, and 4 parts of ditertiary butyl peroxide as a polymerization initiator was reacted. After the acrylic copolymer 2 having a valence of 50 was obtained, it was further dissolved by heating in ammonia water in the same manner as in Production Example 1, and an aqueous acrylic resin varnish (aqueous Ac resin varnish) No. 30 having a solid content of 30% was obtained. 2 was obtained.
[0104]
<Examples 1-19 and Comparative Examples 1-15>
According to the composition of Tables 3 and 4, first, the pigment and the water-soluble resin varnish mixture for pigment dispersion were kneaded for 30 minutes with a red devil type paint conditioner, and further, the predetermined materials were mixed and stirred. The aqueous printing ink compositions of Examples 1-15 were obtained.
[0105]
As a pigment, Lionol Blue FG-7330 (manufactured by Toyo Ink Mfg. Co., Ltd.) and as an aqueous resin varnish for dispersing pigment, Jonkrill J-61 (styrene acrylic resin, solid content 30%, manufactured by Johnson Polymer Co., Ltd.) As an aqueous ethylene-acrylic acid resin varnish (aqueous EAA resin varnish), ZAIXEN AC (Sumitomo Seika Co., Ltd., acrylic acid content 20%, melt index 300 g / 10 min, solid content 30%) was used. .
[0106]
<Evaluation of water-based printing ink>
Resolubility and swimming were evaluated as adhesiveness, extrusion laminating strength, direct laminating strength, and printability of the aqueous printing inks obtained in Examples 1 to 19 and Comparative Examples 1 to 15, and the results are shown in Table 3. This is shown in FIG.
[0107]
Adhesiveness
Extrusion laminate strength
Direct laminate strength
Re-solubility
Swimming (uneven printing)
The 0PP film is a stretched polypropylene film (Toyobo Co., Ltd., P-2161, 30 μm), the PET film is a polyethylene terephthalate film (Toyobo Co., Ltd., E-5102, 12 μm), and the Ny film Nylon film (Unitika Ltd., emblem, 15 μm) is represented.
[0113]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
【The invention's effect】
As described above with specific examples, the water-based printing ink composition of the present invention exhibits good adhesion to various plastic films while being water-based, and is excellent in extrusion laminating and direct laminating suitability. Moreover, it is an aqueous printing ink composition having good printability.
Claims (5)
ａ成分：塩素化度２０〜６０、分子量５，０００〜２００，０００の塩素化ポリプロピレン、および／または塩素化度２０〜６０、分子量５，０００〜５００，０００の塩素化ポリプロピレンを（無水）マレイン酸で変性して得られる（無水）マレイン酸変性塩素化ポリプロピレンを、つぎの一般式（１）で表される化合物の存在下、水中に分散させて得られる水性バインダー樹脂ワニス。
ｂ成分：ポリウレタン樹脂、アクリル系樹脂、エチレン−アクリル酸系樹脂よりなる群から選ばれる少なくとも１種を、塩基性化合物および／または乳化剤の存在下、水中に溶解または分散させて得られる水性バインダー樹脂ワニス。
ｃ成分：その他の水性樹脂を塩基性化合物および／または乳化剤の存在下、水中に溶解または分散させて得られる水性バインダー樹脂ワニス。In the water-based printing ink composition for laminating mainly composed of a pigment and an aqueous binder resin varnish, the aqueous binder resin varnish is composed of the following a component, b component and optionally c component, and the content thereof is aqueous. Based on the total solid content of the binder resin varnish, the solid content of component a is 5 to 50% by weight, the solid content of component b is 50 to 95% by weight, the solid content of component c is 0 to 30% by weight (the solid content of the three components is A water-based printing ink composition for laminating characterized in that the total amount is 100% by weight.
Component a: Chlorinated polypropylene having a chlorination degree of 20 to 60 and a molecular weight of 5,000 to 200,000 and / or a chlorinated polypropylene having a chlorination degree of 20 to 60 and a molecular weight of 5,000 to 500,000 (anhydrous) male An aqueous binder resin varnish obtained by dispersing (anhydrous) maleic acid-modified chlorinated polypropylene obtained by acid modification in water in the presence of a compound represented by the following general formula (1).
Component b: aqueous binder resin obtained by dissolving or dispersing at least one selected from the group consisting of polyurethane resin, acrylic resin, and ethylene-acrylic acid resin in water in the presence of a basic compound and / or emulsifier varnish.
Component c: An aqueous binder resin varnish obtained by dissolving or dispersing other aqueous resin in water in the presence of a basic compound and / or emulsifier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP666497A JP3672691B2 (en) | 1997-01-17 | 1997-01-17 | Water-based printing ink composition for laminating and method for laminating printed matter using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP666497A JP3672691B2 (en) | 1997-01-17 | 1997-01-17 | Water-based printing ink composition for laminating and method for laminating printed matter using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10204367A JPH10204367A (en) | 1998-08-04 |
| JP3672691B2 true JP3672691B2 (en) | 2005-07-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP666497A Expired - Lifetime JP3672691B2 (en) | 1997-01-17 | 1997-01-17 | Water-based printing ink composition for laminating and method for laminating printed matter using the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220195215A1 (en) * | 2020-03-03 | 2022-06-23 | Hubergroup Deutschland Gmbh | Hard resin solution and water-based overprint varnish including an amine compound comprising hydroxyl groups |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6716495B1 (en) | 2000-11-17 | 2004-04-06 | Canon Kabushiki Kaisha | Ink-jet recording apparatus and recording medium |
| JP4569121B2 (en) * | 2004-02-17 | 2010-10-27 | Ｄｉｃ株式会社 | Water-based gravure ink for polypropylene tray and polypropylene tray |
| JP4608903B2 (en) * | 2004-02-17 | 2011-01-12 | Ｄｉｃ株式会社 | Water-based gravure ink for polypropylene film and laminate |
| EP1849840B1 (en) | 2005-02-18 | 2016-11-16 | Seiko Epson Corporation | Aqueous ink composition and urethane resin composition for aqueous ink composition |
| JP2013052657A (en) * | 2011-09-06 | 2013-03-21 | Sakata Corp | Polyethylene laminated paper |
| CN103287018B (en) * | 2012-03-01 | 2016-04-06 | 株式会社神户制钢所 | Pigmentary resin coated metal plate |
| JP5798510B2 (en) * | 2012-03-01 | 2015-10-21 | 株式会社神戸製鋼所 | Colored resin coated metal plate |
| JP6688649B2 (en) * | 2015-03-26 | 2020-04-28 | サカタインクス株式会社 | Laminated ink composition for flexible packaging |
| WO2017204073A1 (en) * | 2016-05-27 | 2017-11-30 | Ｄｉｃグラフィックス株式会社 | Binder for water-based liquid inks, water-based liquid ink, and printed matter |
| EP3786240A4 (en) * | 2018-04-27 | 2021-05-26 | Mitsubishi Chemical Corporation | WATER BASED INK |
-
1997
- 1997-01-17 JP JP666497A patent/JP3672691B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220195215A1 (en) * | 2020-03-03 | 2022-06-23 | Hubergroup Deutschland Gmbh | Hard resin solution and water-based overprint varnish including an amine compound comprising hydroxyl groups |
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| Publication number | Publication date |
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| JPH10204367A (en) | 1998-08-04 |
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