JP3872356B2 - Manufacturing method of printing ink - Google Patents
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- JP3872356B2 JP3872356B2 JP2002032699A JP2002032699A JP3872356B2 JP 3872356 B2 JP3872356 B2 JP 3872356B2 JP 2002032699 A JP2002032699 A JP 2002032699A JP 2002032699 A JP2002032699 A JP 2002032699A JP 3872356 B2 JP3872356 B2 JP 3872356B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、従来法の欠点が克服され、改善された品質の印刷インキの製造が可能な、顔料の形態を経ることなく、プレ顔料を使用して直接印刷インキを製造する合理化された印刷インキの製造方法に関する。
【０００２】
【従来の技術】
一般に銅フタロシアニン顔料は、例えば、フタル酸またはその誘導体、尿素またはその誘導体を銅化合物および触媒の存在下に有機溶剤中で加熱反応させる尿素法（ワイラー法）や、フタロジニトリルを銅化合物の存在下に有機溶剤中で加熱反応させるニトリル法などの方法で合成される。合成後の銅フタロシアニンは粗製銅フタロシアニンとよばれ、一次粒子が非常に粗大（１０〜１００μｍ）であることからそのまま顔料として使用することはできない。
【０００３】
このため、従来、印刷インキを製造する際には、粗製銅フタロシアニンを乾式磨砕法や湿式磨砕法に代表される顔料化の方法によって、一次粒子を微細（１μｍ以下）に調整し、顔料としての適性を付与したものが使用されており、印刷インキ組成物は、顔料化された銅フタロシアニン（銅フタロシアニン顔料）を三本ロールなどのロールミル、ニーダーなどの混練分散機やボールミルやビーズミルなどの分散機を使用して印刷インキ用樹脂または樹脂溶液中に均一に分散させることによって製造されている。
【０００４】
この顔料化の工程には多大な労力を要することから、合理化された印刷インキの製造方法として、顔料を使用することなく、粗製銅フタロシアニンとして、例えば、乾式アトライターなどで粉砕（乾式粉砕）して微細に調製したプレ（Ｐｒｅ）顔料（顔料前駆体）を使用し、印刷インキの製造工程で顔料化と同時に印刷インキを製造する方法が提案されている（特公昭５５−６６７０号公報、特開平２−２９４３６５号公報、特開平９−２７２８３３号公報など）。
【０００５】
特に、乾式粉砕を印刷インキ用樹脂の存在下に行う特開平２−２９４３６５号公報や特開平９−２７２８３３号公報などに記載の方法は、プレ顔料の凝集を緩和し、プレ顔料の顔料への転換およびインキ化を効率化する点で、非常に優れた印刷インキの製造方法である。
例えば、特開平９−２７２８３３号公報に記載の方法は、粗製銅フタロシアニンをそれに対して２０〜８０重量％の印刷インキ用樹脂とともに乾式粉砕したものをプレ顔料とし、これを印刷インキ用溶剤または印刷インキ用ワニス中で８０〜１７０℃に加熱することで、プレ顔料の顔料化と同時に印刷インキを製造する方法である。
【０００６】
しかしながら、上記のような印刷インキ用樹脂を使用する方法では、十分な効果を得るためには比較的多量の樹脂を必要とする。しかし、多量の樹脂の使用は、乾式粉砕時の発熱による粉砕機内部への磨砕物の固着や、蓄熱による磨砕物発火の危険性などの安全運転に対する課題を抱えている。また、樹脂は、乾式粉砕時の衝撃や発熱によって酸化や壊（開）裂などの構造破壊を起こす恐れもあり、劣化した樹脂は、インキの色相面だけでなく、粘弾性や乳化特性などの印刷適性にも重大な影響を及ぼすことが考えられる。
【０００７】
【発明が解決しようとする課題】
本発明の課題は、顔料の形態を経ることなく銅フタロシアニンのプレ顔料を使用して直接印刷インキを製造する合理化された方法において、プレ顔料の凝集を緩和し、なお且つ従来法における樹脂を多量に使用することにより生じるような製造工程上および印刷インキに対する種々の悪影響もなく、低コストで、優れた品質の印刷インキを製造する方法を提供することにある。
【０００８】
【課題を解決するための手段】
本発明者らは、乾式粉砕してプレ顔料を調製する際、予めロジン系化合物で表面処理された粗製銅フタロシアニンを使用することで、乾式粉砕時の印刷インキ用樹脂の使用量を大幅に削減でき、しかも樹脂を多量に使用したのと同様の効果が得られることを見出し、この知見に基づいて本発明を完成した。
【０００９】
すなわち、本発明は、少なくとも銅フタロシアニンおよび印刷インキ用樹脂を含む印刷インキを、顔料の形態を経ることなく銅フタロシアニンのプレ顔料を使用して直接製造する方法において、銅フタロシアニンのプレ顔料として、予め、ロジン系化合物で表面処理された粗製銅フタロシアニンを乾式粉砕して調製されたプレ顔料組成物であって、該プレ顔料組成物が、上記の表面処理された粗製銅フタロシアニンを体質顔料および／または印刷インキ用樹脂とともに乾式粉砕してなるものを使用することを特徴とする印刷インキの製造方法である。
【００１０】
【発明の実施の形態】
次に発明の実施の形態を挙げて、本発明をさらに詳細に説明する。
本発明は、顔料化工程を経ていない銅フタロシアニンのプレ（Ｐｒｅ）顔料（顔料前駆体）を用いて直接印刷インキを製造する方法において、予めロジン系化合物で表面処理された粗製銅フタロシアニンを使用することで、乾式粉砕時に印刷インキ用樹脂を全く使用しないか、非常に少ない使用量で調製したプレ顔料組成物を使用することが特徴である。
【００１１】
一般に、合成反応終了後の銅フタロシアニンは、反応スラリーから減圧下に溶媒を留去した後、酸処理、アルカリ処理、さらに温水洗、水洗などの方法で反応不純物を除去し、濾過および乾燥し、粗製銅フタロシアニンとして調製される。
本発明で使用する予めロジン系化合物で表面処理された粗製銅フタロシアニンは、銅フタロシアニンの合成段階や反応終了後の反応スラリー中に、あるいは上記の粗製銅フタロシアニンの調製段階のいずれかの工程でロジン系化合物を混合し、処理する方法で製造される。
【００１２】
ロジン系化合物の処理方法は、ロジン系化合物をアルカリ水溶液として、あるいは有機溶剤に溶解した溶液として、反応系や反応終了後の反応スラリーなどに加えるなどの従来公知の処理方法が使用可能であるが、前記工程中、反応終了後の反応スラリー中での処理や溶媒を留去する工程での処理が、処理量や処理方法の制約が少ないため望ましい。
【００１３】
本発明で使用するロジン系化合物としては、例えば、ウッドロジン、ガムロジン、トール油ロジン、水添ロジン、不均化ロジン、重合ロジンおよびこれらの金属塩、あるいはロジン変性アクリル樹脂、ロジン変性アルキッド樹脂、ロジン変性マレイン酸樹脂、ロジン変性フェノール樹脂、ロジン変性フマル酸樹脂、ロジン変性ポリアミド樹脂、ロジン変性ポリエステル樹脂などの各種ロジン変性樹脂などが挙げられる。これらは１種または２種以上を混合して使用することができる。これらのロジン系化合物の処理量は、粗製銅フタロシアニンに対して１〜５０重量％の範囲が好ましい。
【００１４】
上記のロジン系化合物は、なかでも融点の低いタイプのものは、本来、少量であっても、粗製銅フタロシアニンと混合されて乾式粉砕してプレ顔料組成物を調製する際には、磨砕物の固着や発火の原因となりやすい。しかしながら、ロジン系化合物は、それで粗製銅フタロシアニンの表面を処理する形態で使用された際には、上記のような危険性が著しく改善されると同時に、粗製銅フタロシアニンの表面に均一に処理することで、比較的少量の使用でも、粗製銅フタロシアニン組成物調製段階での粒子の凝集を緩和し、プレ顔料組成物調製時の粒子の凝集を効果的に緩和する。このため、乾式粉砕時に改めて印刷インキ用樹脂を使用しなくともあるいは少量の使用で、樹脂を多量に使用したのと同様の効果が得られ、改善された印刷インキの提供が可能となる。
【００１５】
本発明では、乾式粉砕を体質顔料の存在下に行うことができる。体質顔料としては、屈折率が小さく顔料の色相や透明性に影響の少ないものであればいずれでもよく、例えば、炭酸カルシウムや酸化亜鉛（亜鉛華）、硫酸バリウムおよびバライト粉、クレー、タルク、アルミナホワイト、ホワイトカーボン（微粉シリカ）、およびそれらの混合物などが挙げられる。好ましい体質顔料は、炭酸カルシウムである。
【００１６】
また、本発明では、乾式粉砕を、安全運転に支障の無い程度の印刷インキ用樹脂とともに行うこともできる。使用する印刷インキ用樹脂としては、一般に印刷インキに使用されるものであればいずれの樹脂でもよい。例えば、フェノール樹脂およびその変性物、マレイン酸樹脂およびその変性物、アルキッド樹脂およびその変性物、石油樹脂、変性ロジンなどおよびそれらの混合物が挙げられるが、好ましくはロジン変性フェノール樹脂であり、これは本発明で使用するロジン系化合物にも含まれる。体質顔料および／または印刷インキ用樹脂は、粗製銅フタロシアニンに対して１〜５０重量％の範囲で使用することが好ましい。
【００１７】
本発明の乾式粉砕には、乾式アトライターの他、ボールミルや振動ミルなどのビーズなどの粉砕メディアを使用するタイプのもの、二軸押出機やニーダーなどの混練機、ジェットミルなどの粉砕機、ヘンシェルミキサーなどの強力撹拌機など、あるいは粉砕メディアを使用しないタイプのものがいずれも使用できるが、粉砕効率から粉砕メディアを使用するタイプのものが好ましい。
【００１８】
一般に樹脂共存下での乾式粉砕では、粉砕時の発熱による粉砕機内部への磨砕物の固着や発火に対する注意が必要であり、通常、冷却下８０〜１５０℃の温度範囲で粉砕を行うが、本発明の方法は固着や発火の問題に対しても有利であり、粉砕をより高温で行うこともできる。また逆に、より低温で行うことも差支えなく、粉砕時の温度は特に限定されない。
【００１９】
一般に、粗製銅フタロシアニン中には数重量％程度の反応不純物が含有されるが、反応不純物はプレ顔料の顔料への転換を阻害し、印刷インキの黄ぐすみの原因になったり、印刷インキ適性にも重大な影響を与える。本発明には、硫酸法で測定した純度が９７％以上の高純度の粗製銅フタロシアニンを使用するのが好ましい。
【００２０】
反応不純物としては、通常の洗浄では除去できない銅フタロシアニンの結晶内部に含まれた不純物が特に問題となるが、硫酸法によれば結晶内部に含まれる全ての反応不純物を測定することができる。硫酸法による純度測定は以下の手順に従う。
（硫酸法による純度測定法）
粗製銅フタロシアニン５．０ｇを９８重量％の硫酸５０ｍｌに加熱溶解（９０〜１００℃・４０分）させ、この溶液に１５重量％の硫酸を１５０ｍｌ加えて再結晶させる。放置冷却後、２５ｍｌの水に解膠し、２８重量％のアンモニア水１０ｍｌを加えて加熱（９０〜１００℃・３０分）する。濾過し、充分に水洗した後、１０５〜１１０℃で２時間乾燥する。
純度（％）＝［処理後の質量（ｇ）／処理前の質量（ｇ）］×１００
【００２１】
本発明で使用される粗製銅フタロシアニンは、尿素法（ワイラー法）を加圧下（好ましくは０．１〜０．７ＭＰａ）で行って合成した銅フタロシアニンを用いるのが好ましい。加圧下で合成した銅フタロシアニンは、常圧下で合成した銅フタロシアニンに比べて、銅フタロシアニン結晶内部への反応不純物の取り込み量が少なく、高純度に調製できる利点がある。
【００２２】
なお、乾式粉砕によりプレ顔料組成物を調製する際、必要により従来公知の顔料誘導体や高分子分散剤などの顔料処理剤や分散剤、あるいは界面活性剤、ロジンなどを添加して乾式粉砕することができる。また、一般に印刷インキに使用される石油系などの溶剤や有機溶剤を必要に応じて配合できる点や、樹脂の劣化防止を目的に粉砕を窒素ガス雰囲気下で行うことができる点も従来公知の方法と同様である。
【００２３】
【実施例】
次に顔料製造例、実施例および比較例を挙げて本発明をさらに具体的に説明する。文中、部または％とあるのは重量基準である。
【００２４】
顔料製造例１
５Ｌ容器に、無水フタル酸１０００部、尿素２０００部、モリブデン酸アンモニウム１０部、塩化第一銅１８０部、ハイゾールＰ（日本石油化学社製）２０００部を加え、２００℃で４時間加熱反応させた。
反応終了後、溶剤を減圧留去し、反応生成物を２％希硫酸水溶液２００００部に投入して、８０℃で２時間攪拌し、濾過、湯洗、水洗（濾液が中性となるまで）して粗製銅フタロシアニンの水性ペーストを得た。次に、この水性ペーストを９０℃で乾燥して、硫酸法で測定した純度が９６．０％の粗製銅フタロシアニン９００部を得た。
【００２５】
顔料製造例２
加熱反応を０．３ＭＰａの加圧下に２００℃で４時間行った他は、顔料製造例１と同様にして、硫酸法で測定した純度が９８．０％の粗製銅フタロシアニン８９０部を得た。
【００２６】
顔料製造例３
乾式アトライターに、顔料製造例１で得た粗製銅フタロシアニン１００部を加えて３０分間粉砕した。この粗製銅フタロシアニン磨砕物のβ型結晶形の含有率は４３％であった。次いで、得られた磨砕物１００部に、イソブチルアルコール４００部、水６００部を加え、８０℃に加熱して５時間撹拌混合した。この混合物を１．０％希硫酸水溶液１０００部に投入して、８０℃で１時間加熱処理を行った後、濾過、水洗、乾燥および粉砕して粉末の銅フタロシアニン顔料(C.I.Pigment Blue 15:3)を得た。
【００２７】
比較例１
顔料製造例３で得たβ型銅フタロシアニン顔料１８部を印刷インキ用ワニス（ロジン変性フェノール樹脂系ワニス、不揮発分７０％）６７部に混合し、３本ロールにて３回練肉してベースインキを得た。このベースインキに、さらに印刷インキ用ワニス１９部、７号ソルベント（日本石油社製石油系溶剤）６部、コンパウンド（インキ調整助剤）１０部を加えて青色の印刷インキを得た。
この青色インキを、銅フタロシアニン顔料／酸化チタンの重量比率が１／１０となるように白インキと混合し、淡色インキ（着色力判定）を得た。
この青色インキおよび淡色インキを、従来法による比較用のインキとした。
【００２８】
実施例１
顔料製造例２において、硫酸処理後の粗製銅フタロシアニンの水性ペーストを水２００００部に解膠し、これに水添ロジン４５部をアルカリ水溶液として加え、５０℃で３０分攪拌した。次に、塩酸を加えてｐＨを４．０とし、５０℃で１時間攪拌した後、スラリーを濾過、水洗、乾燥（９０℃）し、水添ロジン５％を表面処理した粗製銅フタロシアニンを調製した。
【００２９】
乾式アトライターに、上記の表面処理粗製銅フタロシアニン５０部、炭酸カルシウム９．５部を加えて１時間粉砕した。次に、印刷インキ用樹脂（ロジン変性フェノール樹脂）８．５部を加えてさらに１０分間粉砕した。得られたプレ顔料組成物のβ型結晶の含有率は４８％であった。
次いで、得られたプレ顔料組成物５０部、印刷インキ用ワニス（ロジン変性フェノール樹脂：不揮発分７０％）１１９部、７号ソルベント３部を、ジャケット付きディゾルバー中で１１０〜１２０℃で２時間撹拌し、混合物を３本ロールにて２回練肉してベースインキを得た。
【００３０】
このベースインキに、さらに印刷インキ用ワニス２９部、７号ソルベント１４部、コンパウンド１９部を加えて青色の印刷インキを調製した。
この青色インキを、銅フタロシアニン顔料／酸化チタンの重量比率が１／１０となるように白インキと混合し、淡色インキを得た。得られた青色インキおよび淡色インキは、比較例１の従来法によって作製したそれぞれのインキと比較して、同等の色相、着色力であり、粘弾性や乳化特性などのインキ適性についても良好な性能を示した。
【００３１】
実施例２
加熱反応後のスラリー中に水添ロジンに代えてロジン変性フェノール樹脂（重量平均分子量：１２．３万、酸価：２０）１７８部を投入し、６０℃で１時間攪拌した後反応溶剤を減圧留去する以外は実施例１と同様にして、ロジン変性フェノール樹脂２０％を表面処理した粗製銅フタロシアニンを調製した。
【００３２】
乾式アトライターに、上記の表面処理粗製銅フタロシアニン６０部、炭酸カルシウム１０部を加えて１時間粉砕した。得られたプレ顔料組成物のβ型結晶の含有率は４９％であった。
次いで、得られたプレ顔料組成物５０部、印刷インキ用ワニス（ロジン変性フェノール樹脂：不揮発分７０％）１２３部、７号ソルベント３部を、ジャケット付きディゾルバー中で１１０〜１２０℃で２時間撹拌し、混合物を３本ロールにて２回練肉してベースインキを得た。
【００３３】
このベースインキに、さらに印刷インキ用ワニス２９部、７号ソルベント１４部、コンパウンド２０部を加えて青色の印刷インキを調製した。
以下は実施例１と同様にして、本発明の青色インキおよび淡色インキを得、比較例１の従来法によって作製したそれぞれのインキと比較したが、同等の色相、着色力であり、粘弾性や乳化特性などのインキ適性についても良好な性能を示した。
【００３４】
実施例３
乾式アトライターに、実施例２で調製したロジン変性フェノール樹脂（重量平均分子量：１２．３万、酸価：２０）を２０％表面処理した粗製銅フタロシアニン６０部、炭酸カルシウム５部を加えて１時間粉砕した。次にこの磨砕物をヘンシェルミキサーに移し、印刷インキ用樹脂（ロジン変性フェノール樹脂）５部を加えて３０分間混合した。
次いで、得られたプレ顔料組成物５０部、印刷インキ用ワニスロジン変性フェノール樹脂：不揮発分７０％）１１８部、７号ソルベント４．５部を、ジャケット付きディゾルバー中で１１０〜１２０℃で２時間撹拌し、混合物を３本ロールにて２回練肉してベースインキを得た。
【００３５】
このベースインキに、さらに印刷インキ用ワニス３３部、７号ソルベント１３部、コンパウンド２０部を加えて青色の印刷インキを調製した。
以下は実施例１と同様にして、本発明の青色インキおよび淡色インキを得、これらと従来法によるそれぞれのインキと比較した結果、同等の色相、着色力であり、粘弾性や乳化特性などのインキ適性についても実用に十分耐え得るものであった。
【００３６】
実施例４
加熱反応後のスラリー中に水添ロジンに代えてロジン変性フェノール樹脂（重量平均分子量：１２．３万、酸価：２０）２６７部を投入し、６０℃で１時間攪拌した後反応溶剤を減圧留去する以外は実施例１と同様にして、ロジン変性フェノール樹脂３０重量％を表面処理した粗製銅フタロシアニンを調製した。
【００３７】
乾式アトライターに、該粗製銅フタロシアニン６５部を加えて１時間粉砕した。次いで、得られたプレ顔料組成物５０部、印刷インキ用ワニス（ロジン変性フェノール樹脂：不揮発分７０％）１２７部、７号ソルベント５部を、ジャケット付きディゾルバー中で１１０〜１２０℃で２時間撹拌し、混合物を３本ロールにて２回練肉してベースインキを得た。
このベースインキに、さらに印刷インキ用ワニス４０部、７号ソルベント１３部、コンパウンド２２部を加えて青色の印刷インキを調製した。
以下は実施例１と同様にして、本発明の青色インキおよび淡色インキを得た。得られた青色インキおよび淡色インキは、従来法によって作製したそれぞれのインキと比較して、同等の色相、着色力であり、良好なインキ適性を示した。
【００３８】
【発明の効果】
本発明は、粗製銅フタロシアニンを例えば乾式アトライターなどで粉砕して微細に調製したプレ顔料組成物（顔料前駆体）を使用して、顔料の形態を経ることなく、直接印刷インキを製造する印刷インキ組成物の合理化された製造法において、プレ顔料組成物として、予め、ロジン系化合物で表面処理された粗製銅フタロシアニンを乾式粉砕して調製されたプレ顔料組成物であって、該プレ顔料組成物が、上記の表面処理された粗製銅フタロシアニンを体質顔料および／または印刷インキ用樹脂とともに乾式粉砕してなるものを使用することで、乾式粉砕時に混合する印刷インキ用樹脂の使用量を大幅に削減し、従来法の製造上の欠点が改善された優れた品質の印刷インキ組成物の製造方法が提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention is a streamlined printing ink that directly produces printing inks using pre-pigments without going through the form of pigments, which overcomes the disadvantages of conventional methods and allows for the production of improved quality printing inks. It relates to the manufacturing method.
[0002]
[Prior art]
In general, copper phthalocyanine pigments are, for example, urea method (Wiler method) in which phthalic acid or its derivative, urea or its derivative is heated in an organic solvent in the presence of a copper compound and a catalyst, or phthalodinitrile is present in the presence of a copper compound. It is synthesized by a method such as a nitrile method in which a reaction is performed under heating in an organic solvent. The synthesized copper phthalocyanine is called crude copper phthalocyanine, and since the primary particles are very coarse (10 to 100 μm), it cannot be used as it is as a pigment.
[0003]
For this reason, conventionally, when producing printing ink, primary copper particles are finely adjusted (less than 1 μm) by a method of pigmentation represented by dry grinding method and wet grinding method to prepare crude copper phthalocyanine as a pigment. Appropriate properties are used, and the printing ink composition is made of pigmented copper phthalocyanine (copper phthalocyanine pigment) such as a roll mill such as a three-roll mill, a kneader dispersing machine such as a kneader, or a dispersing machine such as a ball mill or a bead mill. Is uniformly dispersed in a printing ink resin or resin solution.
[0004]
Since this process of pigmentation requires a great deal of labor, as a streamlined method for producing printing ink, without using pigments, it is crushed as crude copper phthalocyanine, for example, with a dry attritor (dry pulverization). A method for producing a printing ink simultaneously with pigmentation in a printing ink production process using a pre-prepared (Pre) pigment (pigment precursor) prepared in a fine manner has been proposed (Japanese Patent Publication No. 55-6670, (Kaihei 2-294365, JP-A-9-272833, etc.).
[0005]
In particular, the methods described in JP-A-2-294365 and JP-A-9-272833 in which dry pulverization is carried out in the presence of a resin for printing ink alleviates the aggregation of the pre-pigment and reduces the pre-pigment to the pigment. in that the efficiency of the conversion and inked a method for producing a very good printing inks.
For example, in the method described in JP-A-9-272833, crude copper phthalocyanine is dry-pulverized together with 20 to 80% by weight of a resin for printing ink as a pre-pigment, and this is used as a solvent for printing ink or printing. This is a method for producing printing ink simultaneously with pigmentation of a pre-pigment by heating to 80 to 170 ° C. in an ink varnish.
[0006]
However, in the method using the printing ink resin as described above, a relatively large amount of resin is required to obtain a sufficient effect. However, the use of a large amount of resin has problems for safe operation such as adhesion of the ground material to the inside of the pulverizer due to heat generated during dry pulverization and risk of ignition of the ground material due to heat storage. In addition, the resin may cause structural destruction such as oxidation and breakage (open) cracks due to impact and heat generation during dry pulverization, and the deteriorated resin has not only the hue side of the ink but also viscoelasticity and emulsification characteristics. It may have a significant effect on printability.
[0007]
[Problems to be solved by the invention]
The object of the present invention is to reduce the aggregation of the pre-pigment in a streamlined method of producing a printing ink directly using a copper phthalocyanine pre-pigment without going through the form of the pigment, and to add a large amount of resin in the conventional method. It is an object of the present invention to provide a method for producing an excellent quality printing ink at a low cost without causing various adverse effects on the printing ink and on the production process as generated by using the ink.
[0008]
[Means for Solving the Problems]
When preparing pre-pigments by dry pulverization, the present inventors greatly reduce the amount of printing ink resin used during dry pulverization by using crude copper phthalocyanine surface-treated with a rosin compound in advance. In addition, the inventors have found that the same effect as that obtained by using a large amount of resin can be obtained, and based on this finding, the present invention has been completed.
[0009]
That is, the present invention provides a printing ink containing at least copper phthalocyanine and a printing ink resin using a copper phthalocyanine pre-pigment directly without going through the form of a pigment. A pre-pigment composition prepared by dry pulverizing crude copper phthalocyanine surface-treated with a rosin compound , wherein the pre-pigment composition comprises the above surface-treated crude copper phthalocyanine as an extender pigment and / or A method for producing a printing ink, comprising using a dry pulverized resin together with a printing ink resin .
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in more detail with reference to embodiments of the invention.
The present invention uses a crude copper phthalocyanine that has been surface-treated in advance with a rosin compound in a method for directly producing a printing ink using a pre-precursor (pigment precursor) of copper phthalocyanine that has not undergone a pigmentation step. it is either not used at all for a printing ink resin during dry grinding, it is characterized by the use pre pigment composition made adjustment in very small amount.
[0011]
In general, copper phthalocyanine after completion of the synthesis reaction is obtained by removing the solvent from the reaction slurry under reduced pressure, then removing the reaction impurities by a method such as acid treatment, alkali treatment, washing with warm water, washing with water, filtering and drying, Prepared as crude copper phthalocyanine.
The crude copper phthalocyanine previously surface-treated with the rosin compound used in the present invention is rosin in any step of the copper phthalocyanine synthesis stage, the reaction slurry after the reaction is completed, or the above-mentioned crude copper phthalocyanine preparation stage. Manufactured by mixing and treating system compounds.
[0012]
As a method for treating the rosin compound, a conventionally known treatment method such as adding the rosin compound as an alkaline aqueous solution or a solution dissolved in an organic solvent to a reaction system or a reaction slurry after completion of the reaction can be used. In the above process, the process in the reaction slurry after completion of the reaction and the process in the process of distilling off the solvent are desirable because there are few restrictions on the processing amount and the processing method.
[0013]
Examples of the rosin compound used in the present invention include wood rosin, gum rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin and metal salts thereof, or rosin-modified acrylic resin, rosin-modified alkyd resin, rosin. Examples thereof include various rosin-modified resins such as a modified maleic acid resin, a rosin-modified phenol resin, a rosin-modified fumaric acid resin, a rosin-modified polyamide resin, and a rosin-modified polyester resin. These can be used alone or in combination of two or more. The treatment amount of these rosin compounds is preferably in the range of 1 to 50% by weight based on the crude copper phthalocyanine.
[0014]
Among the above rosin compounds, those having a low melting point are originally mixed with crude copper phthalocyanine and dry pulverized to prepare a pre-pigment composition. Prone to sticking and ignition. However, rosin-based compound, so when it is used in a form that treating the surface of the crude copper phthalocyanine, and at the same time the risk as described above is significantly improved, to uniformly treat the surface of the crude copper phthalocyanine Thus, even when used in a relatively small amount, the aggregation of particles at the preparation stage of the crude copper phthalocyanine composition is alleviated, and the aggregation of particles at the preparation of the pre-pigment composition is effectively alleviated. For this reason, even if it does not use the resin for printing ink again at the time of dry-type grinding | pulverization, the effect similar to having used a lot of resin is acquired by use of a small quantity, and it becomes possible to provide the improved printing ink.
[0015]
In the present invention, dry pulverization can be performed in the presence of extender pigments. Examples of the extender pigment, rather good any one as long as it little affects the hue and transparency of the pigment refractive index less, for example, calcium carbonate or zinc oxide (zinc white), barium sulfate and barite powder, clay, Examples include talc, alumina white, white carbon (fine silica), and mixtures thereof. A preferred extender pigment is calcium carbonate.
[0016]
In the present invention, dry pulverization can also be performed with a printing ink resin that does not interfere with safe driving. The resin for a printing ink to be used, but it may also in general any resin as long as it is used in printing inks. For example, a phenol resin and a modified product thereof, a maleic resin and a modified product thereof, an alkyd resin and a modified product thereof, a petroleum resin, a modified rosin and the like, and a mixture thereof, preferably a rosin modified phenol resin, It is also included in the rosin compound used in the present invention. The extender pigment and / or printing ink resin is preferably used in an amount of 1 to 50% by weight based on the crude copper phthalocyanine.
[0017]
In the dry pulverization of the present invention, in addition to the dry attritor, those using a pulverizing medium such as beads such as a ball mill or a vibration mill, a kneader such as a twin screw extruder or a kneader, a pulverizer such as a jet mill, A strong stirrer such as a Henschel mixer or a type that does not use grinding media can be used, but a type that uses grinding media is preferred in terms of grinding efficiency.
[0018]
In general, dry pulverization in the presence of a resin requires attention to the fixation and ignition of the pulverized material inside the pulverizer due to heat generated during pulverization. Usually, pulverization is performed in the temperature range of 80 to 150 ° C. under cooling. The method of the present invention is also advantageous for sticking and ignition problems, and the pulverization can be performed at a higher temperature. On the other hand, it may be performed at a lower temperature, and the temperature during pulverization is not particularly limited.
[0019]
In general, crude copper phthalocyanine contains about several percent by weight of reaction impurities, but the reaction impurities hinder the conversion of pre-pigments into pigments, which may cause yellowing of printing inks and suitability for printing inks. Also has a significant impact. In the present invention, it is preferable to use high-purity crude copper phthalocyanine having a purity measured by a sulfuric acid method of 97% or more.
[0020]
As the reaction impurities, impurities contained in the crystal of copper phthalocyanine that cannot be removed by ordinary washing are particularly problematic. However, according to the sulfuric acid method, all reaction impurities contained in the crystal can be measured. Purity measurement by the sulfuric acid method follows the following procedure.
(Purity measurement method by sulfuric acid method)
Crude copper phthalocyanine (5.0 g) is dissolved in 50 ml of 98 wt% sulfuric acid by heating (90-100 ° C., 40 minutes), and 150 ml of 15 wt% sulfuric acid is added to this solution for recrystallization. After allowing to cool, peptize in 25 ml of water, add 10 ml of 28 wt% ammonia water and heat (90-100 ° C., 30 minutes). After filtering and washing thoroughly with water, it is dried at 105 to 110 ° C. for 2 hours.
Purity (%) = [mass after treatment (g) / mass before treatment (g)] × 100
[0021]
The crude copper phthalocyanine used in the present invention is preferably copper phthalocyanine synthesized by performing the urea method (Weiler method) under pressure (preferably 0.1 to 0.7 MPa). Copper phthalocyanine synthesized under pressure has an advantage that the amount of reaction impurities incorporated into the copper phthalocyanine crystal is less than copper phthalocyanine synthesized under normal pressure and can be prepared with high purity.
[0022]
When preparing the pre-pigment composition by dry pulverization, if necessary, dry pulverization may be performed by adding a pigment treatment agent or dispersant such as a conventionally known pigment derivative or polymer dispersant, or a surfactant or rosin. Can do. In addition, it is conventionally known that a petroleum-based solvent or an organic solvent generally used for printing ink can be blended as necessary, and that pulverization can be performed in a nitrogen gas atmosphere for the purpose of preventing deterioration of the resin. It is the same as the method.
[0023]
【Example】
Next, the present invention will be described more specifically with reference to pigment production examples, examples and comparative examples. In the text, parts or percentages are based on weight.
[0024]
Pigment production example 1
To a 5 L container, 1000 parts of phthalic anhydride, 2000 parts of urea, 10 parts of ammonium molybdate, 180 parts of cuprous chloride and 2000 parts of Hysol P (manufactured by Nippon Petrochemical Co., Ltd.) were added and reacted at 200 ° C. for 4 hours. .
After completion of the reaction, the solvent was distilled off under reduced pressure, the reaction product was put into 20000 parts of 2% dilute sulfuric acid aqueous solution, stirred at 80 ° C. for 2 hours, filtered, washed with hot water, and washed with water (until the filtrate became neutral). Thus, an aqueous paste of crude copper phthalocyanine was obtained. Next, this aqueous paste was dried at 90 ° C. to obtain 900 parts of crude copper phthalocyanine having a purity measured by a sulfuric acid method of 96.0%.
[0025]
Pigment production example 2
890 parts of crude copper phthalocyanine having a purity of 98.0% as measured by the sulfuric acid method was obtained in the same manner as in Pigment Production Example 1 except that the heating reaction was performed at 200 ° C. for 4 hours under a pressure of 0.3 MPa.
[0026]
Pigment production example 3
100 parts of the crude copper phthalocyanine obtained in Pigment Production Example 1 was added to a dry attritor and ground for 30 minutes. The content of the β-type crystal form of this crude copper phthalocyanine ground product was 43%. Next, 400 parts of isobutyl alcohol and 600 parts of water were added to 100 parts of the obtained ground product, heated to 80 ° C., and mixed with stirring for 5 hours. This mixture was added to 1000 parts of 1.0% dilute sulfuric acid aqueous solution, heated at 80 ° C. for 1 hour, filtered, washed with water, dried and pulverized to obtain a powdered copper phthalocyanine pigment (CIPigment Blue 15: 3) Got.
[0027]
Comparative Example 1
18 parts of the β-type copper phthalocyanine pigment obtained in Pigment Production Example 3 is mixed with 67 parts of a printing ink varnish (rosin-modified phenolic resin varnish, non-volatile content 70%), and the mixture is kneaded 3 times with 3 rolls. An ink was obtained. To this base ink, 19 parts of varnish for printing ink, 6 parts of No. 7 solvent (petroleum solvent manufactured by Nippon Oil Co., Ltd.) and 10 parts of compound (ink adjustment aid) were added to obtain a blue printing ink.
This blue ink was mixed with white ink so that the weight ratio of copper phthalocyanine pigment / titanium oxide was 1/10 to obtain a light-colored ink (coloring power determination).
The blue ink and the light color ink were used as comparative inks according to a conventional method.
[0028]
Example 1
In Pigment Production Example 2, an aqueous paste of crude copper phthalocyanine after sulfuric acid treatment was peptized in 20000 parts of water, 45 parts of hydrogenated rosin was added as an alkaline aqueous solution, and the mixture was stirred at 50 ° C. for 30 minutes. Next, hydrochloric acid was added to adjust the pH to 4.0, and the mixture was stirred at 50 ° C. for 1 hour. Then, the slurry was filtered, washed with water and dried (90 ° C.) to prepare crude copper phthalocyanine having a surface treated with hydrogenated rosin 5%. did.
[0029]
50 parts of the above surface-treated crude copper phthalocyanine and 9.5 parts of calcium carbonate were added to a dry attritor and pulverized for 1 hour. Next, 8.5 parts of a resin for printing ink (rosin-modified phenolic resin) was added and further pulverized for 10 minutes. The β-type crystal content of the obtained pre-pigment composition was 48%.
Next, 50 parts of the obtained pre-pigment composition, 119 parts of varnish for printing ink (rosin-modified phenolic resin: 70% non-volatile content) and 3 parts of No. 7 solvent were stirred at 110 to 120 ° C. for 2 hours in a jacketed dissolver. The mixture was kneaded twice with three rolls to obtain a base ink.
[0030]
To this base ink, 29 parts of printing ink varnish, 14 parts of No. 7 solvent, and 19 parts of compound were added to prepare a blue printing ink.
This blue ink was mixed with white ink so that the weight ratio of copper phthalocyanine pigment / titanium oxide was 1/10 to obtain a light color ink. The obtained blue ink and light color ink have the same hue and coloring power as compared with the respective inks prepared by the conventional method of Comparative Example 1, and also have good performance in ink suitability such as viscoelasticity and emulsification characteristics. showed that.
[0031]
Example 2
178 parts of rosin-modified phenolic resin (weight average molecular weight: 123,000, acid value: 20) was added to the slurry after the heating reaction instead of hydrogenated rosin, and the mixture was stirred at 60 ° C. for 1 hour, and then the reaction solvent was reduced in pressure. Except for distilling off, a crude copper phthalocyanine having a surface treated with 20% rosin-modified phenol resin was prepared in the same manner as in Example 1.
[0032]
60 parts of the above surface-treated crude copper phthalocyanine and 10 parts of calcium carbonate were added to a dry attritor and pulverized for 1 hour. The content of β-type crystals in the obtained pre-pigment composition was 49%.
Next, 50 parts of the obtained pre-pigment composition, 123 parts of varnish for printing ink (rosin-modified phenolic resin: 70% non-volatile content) and 3 parts of No. 7 solvent were stirred at 110 to 120 ° C. for 2 hours in a jacketed dissolver. The mixture was kneaded twice with three rolls to obtain a base ink.
[0033]
In addition to this base ink, 29 parts of printing ink varnish, 14 parts of No. 7 solvent, and 20 parts of compound were added to prepare a blue printing ink.
The following were obtained in the same manner as in Example 1 to obtain the blue ink and the light color ink of the present invention and compared with the respective inks prepared by the conventional method of Comparative Example 1, but with the same hue and coloring power. It also showed good performance with regard to ink suitability such as emulsification characteristics.
[0034]
Example 3
To a dry attritor, add 60 parts of crude copper phthalocyanine and 5 parts of calcium carbonate obtained by surface-treating 20% of the rosin-modified phenolic resin prepared in Example 2 (weight average molecular weight: 123,000, acid value: 20). Milled for hours. Next, this ground product was transferred to a Henschel mixer, and 5 parts of a resin for printing ink (rosin-modified phenol resin) was added and mixed for 30 minutes.
Next, 50 parts of the obtained pre-pigment composition, 118 parts of varnish rosin modified phenolic resin for printing ink: 70% non-volatile content, and 4.5 parts of No. 7 solvent were stirred at 110 to 120 ° C. for 2 hours in a jacketed dissolver. The mixture was kneaded twice with three rolls to obtain a base ink.
[0035]
To this base ink, 33 parts of printing ink varnish, 13 parts of No. 7 solvent, and 20 parts of compound were added to prepare a blue printing ink.
The following are obtained in the same manner as in Example 1 to obtain the blue ink and the light color ink of the present invention, and as a result of comparing these with the respective inks obtained by the conventional method, the hue and coloring power are equivalent, such as viscoelasticity and emulsification characteristics. The ink suitability could withstand practical use.
[0036]
Example 4
Instead of hydrogenated rosin, 267 parts of rosin-modified phenol resin (weight average molecular weight: 123,000, acid value: 20) was added to the slurry after the heating reaction, and the mixture was stirred at 60 ° C. for 1 hour, and then the reaction solvent was reduced in pressure. Except for distilling off, crude copper phthalocyanine was prepared in the same manner as in Example 1 by subjecting 30% by weight of rosin-modified phenolic resin to surface treatment.
[0037]
65 parts of the crude copper phthalocyanine was added to a dry attritor and pulverized for 1 hour. Next, 50 parts of the obtained pre-pigment composition, 127 parts of printing ink varnish (rosin-modified phenolic resin: 70% non-volatile content) and 5 parts of No. 7 solvent were stirred at 110 to 120 ° C. for 2 hours in a jacketed dissolver. The mixture was kneaded twice with three rolls to obtain a base ink.
To this base ink, 40 parts of varnish for printing ink, 13 parts of No. 7 solvent, and 22 parts of compound were added to prepare a blue printing ink.
In the same manner as in Example 1, the blue ink and the light color ink of the present invention were obtained. The obtained blue ink and light color ink had the same hue and coloring power as compared with the respective inks prepared by the conventional method, and showed good ink suitability.
[0038]
【The invention's effect】
The present invention uses a pre-pigment composition (pigment precursor) finely prepared by pulverizing crude copper phthalocyanine with, for example, a dry attritor or the like, and directly producing printing ink without going through the form of pigment. In a streamlined manufacturing method of an ink composition, a pre-pigment composition prepared by dry pulverizing crude copper phthalocyanine previously surface-treated with a rosin compound as a pre-pigment composition , the pre-pigment composition By using a product obtained by dry pulverizing the above surface-treated crude copper phthalocyanine together with extender pigment and / or printing ink resin, the amount of printing ink resin mixed during dry pulverization can be greatly increased. There is provided a process for producing an excellent quality printing ink composition which reduces and improves the manufacturing disadvantages of conventional processes.
Claims (5)
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| JP2002032699A JP3872356B2 (en) | 2002-02-08 | 2002-02-08 | Manufacturing method of printing ink |
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| JP2002032699A JP3872356B2 (en) | 2002-02-08 | 2002-02-08 | Manufacturing method of printing ink |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009081850A1 (en) | 2007-12-21 | 2009-07-02 | Dic Corporation | Pigment composition for printing ink, method for production thereof, and method for production of printing ink |
| CN102363675A (en) * | 2011-10-08 | 2012-02-29 | 孙敬东 | Phthalocyanine blue and manufacturing process |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005154669A (en) * | 2003-11-28 | 2005-06-16 | Toyo Ink Mfg Co Ltd | Pigment composition and printing ink containing the same |
| EP1888692A2 (en) | 2005-05-02 | 2008-02-20 | Ciba Specialty Chemicals Holding, Inc. | Process for preparation of a novel pigmented composition for use in offset inks |
| JP5298272B2 (en) * | 2011-12-05 | 2013-09-25 | 東洋インキＳｃホールディングス株式会社 | Lithographic printing ink composition |
-
2002
- 2002-02-08 JP JP2002032699A patent/JP3872356B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009081850A1 (en) | 2007-12-21 | 2009-07-02 | Dic Corporation | Pigment composition for printing ink, method for production thereof, and method for production of printing ink |
| US8754148B2 (en) | 2007-12-21 | 2014-06-17 | Dic Corporation | Pigment composition for printing ink, method for producing the same and method for producing printing ink |
| CN102363675A (en) * | 2011-10-08 | 2012-02-29 | 孙敬东 | Phthalocyanine blue and manufacturing process |
| CN102363675B (en) * | 2011-10-08 | 2014-05-21 | 吉洵 | Phthalocyanine blue and manufacturing process |
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| JP2003231829A (en) | 2003-08-19 |
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