JP4016624B2

JP4016624B2 - Disazo pigment, process for producing the same and printing ink composition

Info

Publication number: JP4016624B2
Application number: JP2001280885A
Authority: JP
Inventors: 昭生佐藤
Original assignee: Toyo Ink Mfg Co Ltd
Current assignee: Artience Co Ltd
Priority date: 2001-09-17
Filing date: 2001-09-17
Publication date: 2007-12-05
Anticipated expiration: 2021-09-17
Also published as: JP2003082253A

Description

【０００１】
【発明の属する技術分野】
本発明はジスアゾ顔料に関し、詳細には従来のジスアゾ顔料に比較して短時間でフラッシングが可能であり、得られた印刷インキの透明性、流動性に優れたジスアゾ顔料、およびこれを配合した印刷インキに関する。
【０００２】
【従来の技術】
従来、プロセスのオフセットインキはウェットケーキをフラッシングしてインキ化する方法とウェットケーキの乾燥物を３本ロール、サンドミル、ショットミルを用いて分散しインキ化する方法に大別されるが大量生産には前者の方法が優れている。
【０００３】
近年、インキの生産性向上がインキ単価の低減の中でクローズアップされてきた。生産性の向上のためにはウェットケーキをフラッシングする工程での時間の短縮、及びフラッシング後のインキ中の残存水分を完全に除去するための減圧・加熱工程での加熱温度の上昇による時間の短縮が必須条件である。さらにフラッシングする工程での時間の短縮はフラッシングの熱による品質劣化を防ぐ上でも重要である。
【０００４】
しかしながら加熱温度の上昇は品質面で透明性、濃度の著しい劣化の原因になる。従って現実的な対応としてインキ化時の熱による劣化を考慮してウェットケーキをより透明で高濃度にしなくてはならない。
【０００５】
ジスアゾ顔料の透明性、濃度を向上させる方法として、特公昭５５−１０６３０号公報には、２つのカップリング成分すなわちアセトアセトアニリドとその極性基含有アセトアセトアニリドとの混合カップリングが開示されている。この方法によれば、透明性、濃度に優れた黄インキを製造することができるが、極性基を有するカップリング成分を使用したために顔料表面が親水性になってしまいフラッシングする工程での時間の短縮には不利である。
【０００６】
また特開昭６３−７２７６２号公報、特開昭６３−１７８１６９号公報及び特開２０００−７９３１号公報等には、非対称型ジスアゾ顔料化合物を同一反応容器中で効率良く、対称型よりも多くの割合で製造する方法が示されている。この方法によれば、極性のカップリング成分と非極性のカップリング成分を用いることにより、従来のジスアゾ顔料より透明で流動性に優れた顔料がえられるが、極性のカップリング成分を多量に含有するためフラッシング工程での時間の短縮には不利である。さらに極性のカップリング成分は汎用で商業ベースで使用されている非極性のカップリング成分と比較して高価であるため、顔料のコストアップをもたらし、インキの生産性向上によるインキ単価の低減には逆行する。
【０００７】
【発明が解決しようとする課題】
本発明は、従来のジスアゾ顔料に比較して短時間でフラッシングが完了でき、さらに透明で且つ流動性に優れた印刷インキを提供することを目的とする。
【０００８】
【発明が解決しようとする課題】
すなわち本発明は、３，３’−ジクロロベンジジンのテトラゾ化物とアセトアセトアニリド系化合物をカップリングさせてなるジスアゾ顔料において、該アセトアセトアニリド系化合物が、アセトアセトアニリド８０〜９９モル％、式（１）で示される極性基含有アセトアセトアニリド化合物０．５〜１０モル％および式（２）で示されるアルコキシ基含有アセトアセトアニリド化合物０．５〜１０モル％からなることを特徴とするジスアゾ顔料に関する。
【０００９】
式（１）
ＣＨ₃ＣＯＣＨ₂ＣＯＮＨ−Ｘ
（式中、Ｘはカルボン酸基、スルホン酸基およびこれらの金属塩からなる群から選ばれる同一又は異なる１〜４個の置換基を有するフェニル基（該フェニル基は、置換可能な位置がメチル基、メトキシ基、水酸基または塩素原子で置換されていてもよい。）を示す。）
式（２）
ＣＨ₃ＣＯＣＨ₂ＣＯＮＨ−Ｙ
（式中、Ｙは炭素数２〜４のアルコキシ基（該フェニル基は、置換可能な位置がメチル基、メトキシ、水酸基または塩素原子で置換されていてもよい。）を示す。）
更に本発明は、アセトアセトアニリド、極性基含有アセトアセトアニリド化合物およびアルコキシ基含有アセトアセトアニリド化合物の混合物と３，３’−ジクロロベンジジンのテトラゾ液とを反応させることを特徴とする上記ジスアゾ顔料の製造方法に関する。
【００１０】
更に本発明は、同一容器内で、アセトアセトアニリドおよび極性基含有アセトアセトアニリド化合物の混合物と３，３’−ジクロロベンジジンのテトラゾ液とを予め反応させた後、アルコキシ基含有アセトアセトアニリド化合物と３，３’−ジクロロベンジジンのテトラゾ液とを反応させることを特徴とする上記ジスアゾ顔料の製造方法に関する。
【００１１】
更に本発明は、同一容器内で、アセトアセトアニリドおよび極性基含有アセトアセトアニリド化合物の混合物と３，３’−ジクロロベンジジンのテトラゾ液とを予め反応させた後、アセトアセトアニリドおよびアルコキシ基含有アセトアセトアニリド化合物の混合物と３，３’−ジクロロベンジジンのテトラゾ液とを反応させることを特徴とする上記ジスアゾ顔料の製造方法に関する。
【００１２】
更に本発明は、反応が、弱酸性の緩衝溶液中に３，３’−ジクロロベンジジンのテトラゾ溶液とアセトアセトアニリド系化合物のアルカリ性溶液とを連続的に添加する方法で行われる上記ジスアゾ顔料の製造方法に関する。
【００１３】
更に本発明は、上記ジスアゾ顔料がウェットケーキ状態で印刷インキビヒクルによりフラッシングされることを特徴とする印刷インキの製造方法に関する。
【００１４】
更に本発明は、上記ジスアゾ顔料と印刷インキビヒクルとからなることを特徴とする印刷インキに関する。
【００１５】
式（１）で示される極性基含有アセトアセトアニリド化合物の具体例としては、カルボン酸基を持つものとして２−アセトアセチルアミノ安息香酸、４−アセトアセチルアミノ安息香酸、４−アセトアセチルアミノ−２−クロロ安息香酸、４−アセトアセチルアミノ−２ーメチル安息香酸、４−アセアセチルアミノ−２−安息香酸、５−アセトアセチルアミノ−２−ヒドロキシ安息香酸等が、またスルホン酸基としては４−アセトアセチルアミノベンゼンスルホン酸等がある。
【００１６】
これらの極性基含有アセトアセトアニリドにおける極性基の金属塩を構成する金属としては、ナトリウム、カリウム、カルシウム、バリウム、ストロンチウム、マンガン、亜鉛、マグネシウム、アルミニウム等がある。
【００１７】
式（２）で示されるアルコキシ基含有アセトアセトアニリド化合物のアルコキシ基は、エトキシ基、ｎ−プロポキシ基およびその異性体、ｎ−ブトキシ基およびその異性体等であって、具体例としては、アセトアセト−２−フェネチジド、アセトアセト−４−フェネチジド、アセトアセト−２−ヒドロキシ−４−フェネチジド、アセトアセト−２−メチル−４−フェネチジド、アセトアセト−２−クロロ−４−フェネチジド、アセトアセト−２−メトキシ−４−フェネチジド、アセトアセト−４−プロポキシアニリド、アセトアセト−３−イソプロポキシアニリド、アセトアセト−４−ブトキシアニリドがある。
【００１８】
本発明のジスアゾ顔料におけるアセトアセトアニリド系化合物成分相互の割合は、アセトアセトアニリドが９９〜８０モル％、極性基含有アセトアセトアニリド化合物が１０〜０．５モル％、好ましくは１〜５モル％、アルコキシ基含有アセトアセトアニリド化合物が１０．０〜０．５モル％、好ましくは１〜５モル％である。極性基含有アセトアセトアニリド化合物の配合量の下限値は、透明性と濃度により制限を受け、上限値はフラッシング工程の時間短縮において制限を受ける。アルコキシ基含有アセトアセトアニリド化合物の配合量の下限値はフラッシング工程の時間短縮において制限を受け、上限値は透明性過剰による流動性の低下、コストにおいて制限を受ける。
【００１９】
本発明において３，３’−ジクロロベンジジンのテトラゾ液とカップリング成分とのカップリング反応は特に制限されないが、常法により酢酸酸性下、すなわち、ｐＨ６〜３の範囲、温度１０℃〜３０℃、時間３０分〜６０分の間で行う方法がある。また、予め酢酸と苛性ソーダを用いてｐＨを約４．５前後に調整した酸性緩衝溶液を作製し、カップリング成分を苛性ソーダで溶解したカップラー溶液とテトラゾ溶液を同時に等しい反応量で添加する方法であってもよく、この方法によれば、カップリング成分を析出させることなく反応させることができるので好ましい。
【００２０】
本発明のジスアゾ顔料の製造方法は、アセトアセトアニライド系化合物を３成分を混合したものを３，３’−ジクロロベンジジンのテトラゾ液と反応させる方法であってもよいし、アセトアセトアニリドおよび極性基含有アセトアセトアニリド化合物の混合物と３，３’−ジクロロベンジジンのテトラゾ液とを最初に反応させた後、第二段の反応として、アルコキシ基含有アセトアセトアニリド化合物と３，３’−ジクロロベンジジンのテトラゾ液とを反応させるか、アセトアセトアニリドおよびアルコキシ基含有アセトアセトアニリド化合物の混合物と３，３’−ジクロロベンジジンのテトラゾ液とを反応させる方法であってもい。このような二段階のカップリング工程とすることにより、ジスアゾ顔料粒子の表面に疎水性のアルコキシル基含有ジスアゾ化合物が多く生成するので、透明性、流動性を損なうことなくフラッシング工程の時間が短縮化されたジスアゾ顔料が得られる。
【００２１】
又、本発明のジスアゾ顔料は、アセトアセトアニリドおよび極性基含有アセトアセトアニリド化合物の混合物と３，３’−ジクロロベンジジンのテトラゾ化物とから得られるジスアゾ顔料と、アセトアセトアニライドライドおよびアルコキシ基含有アセトアセトアニリド化合物の混合物と３，３’−ジクロロベンジジンのテトラゾ化物とから得られるジスアゾ顔料との混合したものであってもよい。
【００２２】
本発明により得られたジスアゾ顔料の水スラリーはｐＨ９〜１４のアルカリ側に調整後、ロジンのアルカリ塩溶液（添加量は顔料に対して３〜１０重量％）、顔料スラリーを撹拌し均一化し、塩酸を加えてｐＨ６〜４程度の酸性にして顔料表面にロジンを析出させ、その後９０℃まで加熱し、３０分保持してから、濾過、水洗、顔料分２８〜３２％になるように圧搾することによってフラッシング工程に供するジスアゾ顔料のウェットケーキが得られる。
【００２３】
フラッシングは顔料のウェットケーキ８０重量部（乾燥換算）に対してオフセット用印刷インキビヒクル１８０〜２２０重量部を添加しフラッシャーを用いて行われる。
【００２４】
本発明のジスアゾ顔料はプロセス用オフセットインキとして使用される。オフセットインキの組成物は本発明のジスアゾ顔料３〜３５重量％とオフセット用インキビヒクル９７〜４５重量％、その他補助剤（ドライヤー、レベリング改良剤、増粘剤）や体質顔料０〜２０重量％からなる。オフセット用インキビヒクルはロジン変性フェノール樹脂、石油樹脂、アルキッド樹脂、またはこれらの乾性油変性樹脂等の樹脂２０〜５０重量％、アマニ油、桐油、大豆油等の植物油０〜３０重量％、ｎ−パラフィン、イソパラフィン、α−オレフィン等の溶剤１０〜６０重量％からなるものである。
【００２５】
【実施例】
以下実施例をあげて本発明を具体的に説明する。実施例において「部」は全て重量部を示す。
【００２６】
【実施例１】
水４００部に３，３’−ジクロロベンジジン２５．３部と３５％塩酸１６．５部を加えた。この溶液を０℃に冷却後２０％亜硝酸ソーダ溶液を７０部加え、１時間撹拌した。少量のスルファミン酸を加え過剰の亜硝酸ソーダを消失させて、３，３’−ジクロロベンジジンのテトラゾ溶液とした。一方、水４００部にアセトアセトアニリド３４．０部と５−アセトアセチルアミノ−２−ヒドロキシ安息香酸０．９部とアセトアセト−４−フェネチジド０．９部及び苛性ソーダ２０部を加えて溶解した。この溶液に８０％酢酸４５部を少しずつ加えて懸濁液とし、これに前記テトラゾ溶液を約３０分要して加えた。この間の反応温度は約１５℃に保持した。得られたジスアゾ顔料のスラリーを苛性ソーダでｐＨ１０．５に調整後、ロジンの１０％アルカリ塩溶液を６０部添加した。このスラリーを１０分間撹拌後、塩酸を加えてｐＨ５．０に調整して顔料表面にロジンを析出させた。その後９０℃まで加熱し、３０分保持してから、濾過、水洗、圧搾して顔料分３０．０％のウェットケーキを得た。
【００２７】
フラッシングによるインキ化は１Ｌフラッシャーを用いて行った。すなわち上記ウェットケーキを乾燥重量として８０部と予め１００℃に温めたオフセット用インキビヒクル１９０部をフラッシャー中に同時に投入し、フラッシングを行った（オープンフラッシング工程：トータル時間１５分）。次にフラッシングで出てきた水を除去後、減圧（１〜８×１０³Ｐａ）及び混練物の内部温度が１００℃になるまで加熱（熱媒温度１３０℃）を３０分間行い混練物中の水を完全に除去した（バキュームフラッシング工程）。この混練物にオフセット用インキビヒクル３９０部と溶剤４４部を徐々に加えた後フラッシャーから取り出した。その後３本ロールを用いてロール温度６０℃、１０Ｂａrｒの圧力をかけて練肉し粗大粒子を除去し、ベースインキを得た。このベースインキ６２部にオフセット用インキビヒクル２５部、溶剤１０部、補助剤３部加えてタック５．８〜６．０に調整して最終インキを得た。
【００２８】
【実施例２】
テトラゾ溶液の製造法は実施例１と同様に行った。一方、水２００部にアセトアセトアニリド３４．０部と５−アセトアセチルアミノ−２−ヒドロキシ安息香酸０．９部とアセトアセト−４−フェネチジド０．９部及び苛性ソーダ１４部を加え溶解したカップラー溶液を作製した。また８０％酢酸２０部、苛性ソーダ５部のｐＨ４．５に調整した緩衝溶液６００部を作製した。この緩衝溶液に、テトラゾ溶液及びカップラー溶液を同時に、テトラゾが反応中に遊離しないように両溶液の流速を調整しながら約３０分要して加えた。カップリング反応温度は約１５℃に保持した。得られたジスアゾ顔料スラリーは実施例１と同様の操作を行い顔料分３０．０％のウェットケーキを得た。インキ化の方法は実施例１と同様に行い最終インキを得た。
【００２９】
【実施例３】
テトラゾ溶液の製造法は実施例１と同様に行った。一方、水３５０部にアセトアセトアニリド３４．０部と５−アセトアセチルアミノ−２−ヒドロキシ安息香酸０．９部及び苛性ソーダ１９．６部を加えて溶解した。この溶液に８０％酢酸４５部を少しずつ加えて懸濁液とし、これに前記テトラゾ溶液を約３０分要して加えた。この間の反応温度は約１５℃に保持した。得られたジスアゾ顔料のスラリーに、水５０部にアセトアセト−４−フェネチジド０．９部と苛性ソーダ０．４部で溶解した溶液とテトラゾ溶液を同時に、テトラゾが反応中に遊離しないように両溶液の流速を調整しながら、約１０分要して加えた。この間の反応温度も約１５℃に保持した。得られたジスアゾ顔料スラリーは実施例１と同様の操作を行い顔料分３０．０％のウェットケーキを得た。インキ化の方法は実施例１と同様に行い最終インキを得た。
【００３０】
【実施例４】
テトラゾ溶液の製造法は実施例１と同様に行った。一方、水２００部にアセトアセトアニリド１７．０部と５−アセトアセチルアミノ−２−ヒドロキシ安息香酸０．９部及び苛性ソーダ１０部を加えて溶解した。この溶液に８０％酢酸４５部を少しずつ加えて懸濁液とし、これに前記テトラゾ溶液を約２０分要して加えた。この間の反応温度は約１５℃に保持した。得られたジスアゾ顔料のスラリーに、水２００部にアセトアセトアニリド１７．０部とアセトアセト−４−フェネチジド０．９部及び苛性ソーダ１０部で溶解した溶液とテトラゾ溶液を同時に、テトラゾが反応中に遊離しないように両溶液の流速を調整しながら、約２０分要して加えた。この間の反応温度も約１５℃に保持した。得られたジスアゾ顔料スラリーは実施例１と同様の操作を行い顔料分３０．０％のウェットケーキを得た。インキ化の方法は実施例１と同様に行い最終インキを得た。
【００３１】
【実施例５】
テトラゾ溶液の製造法は実施例１と同様に行った。一方、水３５０部にアセトアセトアニリド３４．０部と２−アセトアセチルアミノ安息香酸０．９部及び苛性ソーダ１９．６部を加えて溶解した。この溶液に８０％酢酸４５部を少しずつ加えて懸濁液とし、これに前記テトラゾ溶液を約３０分要して加えた。この間の反応温度は約１５℃に保持した。得られたジスアゾ顔料のスラリーに、水５０部にアセトアセト−２−フェネチジド１．８部及び苛性ソーダ０．４部で溶解した溶液とテトラゾ溶液を同時に、テトラゾが反応中に遊離しないように両溶液の流速を調整しながら約１０分要して加えた。この間の反応温度も約１５℃に保持した。得られたジスアゾ顔料スラリーは実施例１と同様の操作を行い顔料分３０．０％のウェットケーキを得た。インキ化の方法は実施例１と同様に行い最終インキを得た。
【００３２】
【実施例６】
テトラゾ溶液の製造法は実施例１と同様に行った。一方、水３５０部にアセトアセトアニリド３３．６部と４−アセトアセチルアミノベンゼンスルホン酸１．０部及び苛性ソーダ１９．６部を加えて溶解した。この溶液に８０％酢酸４５部を少しずつ加えて懸濁液とし、これに前記テトラゾ溶液を約３０分要して加えた。この間の反応温度は約１５℃に保持した。得られたジスアゾ顔料のスラリーに、水５０部にアセトアセト−４−プロポキシアニリド１．４部及び苛性ソーダ０．４部で溶解した溶液とテトラゾ溶液を同時に、テトラゾが反応中に遊離しないように両溶液の流速を調整しながら約１０分要して加えた。この間の反応温度も約１５℃に保持した。得られたジスアゾ顔料スラリーは実施例１と同様の操作を行い顔料分３０．０％のウェットケーキを得た。インキ化の方法は実施例１と同様に行い最終インキを得た。
【００３３】
【実施例７】
テトラゾ溶液の製造法は実施例１と同様に行った。一方、水３５０部にアセトアセトアニリド３４．０部と４−アセトアセチルアミノベンゼンスルホン酸１．１部及び苛性ソーダ１９．６部を加えて溶解した。この溶液に８０％酢酸４５部を少しずつ加えて懸濁液とし、これに前記テトラゾ溶液を約３０分要して加えた。この間の反応温度は約１５℃に保持した。得られたジスアゾ顔料のスラリーに、水５０部にアセトアセト−４−ブチキシアニリド１．０部及び苛性ソーダ０．４部で溶解した溶液とテトラゾ溶液を同時に、テトラゾが反応中に遊離しないように両溶液の流速を調整しながら約１０分要して加えた。この間の反応温度も約１５℃に保持した。得られたジスアゾ顔料スラリーは実施例１と同様の操作を行い顔料分３０．０％のウェットケーキを得た。インキ化の方法は実施例１と同様に行い最終インキを得た。
【００３４】
【実施例８】
テトラゾ溶液の製造法は実施例１と同様に行った。一方、水３５０部にアセトアセトアニリド３１．９部と４−アセトアセチルアミノ−２ーメチル安息香酸２．４部及び苛性ソーダ１９．６部を加えて溶解した。この溶液に８０％酢酸４５部を少しずつ加えて懸濁液とし、これに前記テトラゾ溶液を約３０分要して加えた。この間の反応温度は約１５℃に保持した。得られたジスアゾ顔料のスラリーに、水５０部にアセトアセト−２−クロロ−４−フェネチジド２．５部及び苛性ソーダ０．４部で溶解した溶液とテトラゾ溶液を同時に、テトラゾが反応中に遊離しないように両溶液の流速を調整しながら、約１０分要して加えた。この間の反応温度も約１５℃に保持した。得られたジスアゾ顔料スラリーは実施例１と同様の操作を行い顔料分３０．０％のウェットケーキを得た。インキ化の方法は実施例１と同様に行い最終インキを得た。
【００３５】
【比較例１】
テトラゾ溶液の製造法は実施例１と同様に行った。一方、水４００部にアセトアセトアニリド３５．４部を苛性ソーダ２０部を加えて溶解した。この溶液に８０％酢酸４５部を少しずつ加えて懸濁液とし、これに前記テトラゾ溶液を約３０分要して加えた。この間の反応温度は約１５℃に保持した。得られたジスアゾ顔料スラリーは実施例１と同様の操作を行い顔料分３０．０％のウェットケーキを得た。インキ化の方法は実施例１と同様に行い最終インキを得た。
【００３６】
【比較例２】
テトラゾ溶液の製造法は実施例１と同様に行った。一方、水４００部にアセトアセトアニリド３４．０部と５−アセトアセチルアミノ−２−ヒドロキシ安息香酸１．８部及び苛性ソーダ２０部を加えて溶解した。この溶液に８０％酢酸４５部を少しずつ加えて懸濁液とし、これに前記テトラゾ溶液を約３０分要して加えた。この間の反応温度は約１５℃に保持した。得られたジスアゾ顔料スラリーは実施例１と同様の操作を行い顔料分３０．０％のウェットケーキを得た。インキ化の方法は実施例１と同様に行い最終インキを得た。
【００３７】
以上の結果を表１にまとめた。L^* はインキの透明性を示しその値が小の方が透明性大、濃度はコーサー値（反射率濃度）で示しその値が大の方が濃度大、流動性はスプレッドメーター測定器での６０秒値（ｍｍ）で示しその値が大の方が流動性大である。水切れ時間はオープンフラッシング工程で水が出てくる時の時間を示しこの値が小さい方がフラッシング性は良好である。
【００３８】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a disazo pigment, and more particularly, a disazo pigment that can be flushed in a short time compared to conventional disazo pigments, and has excellent transparency and fluidity of the obtained printing ink, and a printing blended with the disazo pigment It relates to ink.
[0002]
[Prior art]
Conventionally, process offset inks are roughly classified into a method of flushing wet cake to make ink and a method of dispersing dry cake of wet cake using three rolls, sand mill, and shot mill to make ink, but for mass production. The former method is superior.
[0003]
In recent years, improvement in ink productivity has been highlighted in the reduction of ink unit price. To improve productivity, shorten the time in the process of flushing wet cake, and shorten the time by increasing the heating temperature in the decompression and heating process to completely remove the residual water in the ink after flushing. Is a necessary condition. Further, shortening the time in the flushing process is important for preventing quality deterioration due to the heat of flushing.
[0004]
However, an increase in heating temperature causes significant deterioration in transparency and density in terms of quality. Therefore, as a practical measure, it is necessary to make the wet cake more transparent and highly concentrated in consideration of deterioration due to heat during ink production.
[0005]
As a method for improving the transparency and concentration of a disazo pigment, Japanese Patent Publication No. 55-10630 discloses a mixed coupling of two coupling components, ie, acetoacetanilide and its polar group-containing acetoacetanilide. According to this method, a yellow ink excellent in transparency and density can be produced, but since the coupling component having a polar group is used, the pigment surface becomes hydrophilic and the time for the flushing process is reduced. It is disadvantageous for shortening.
[0006]
In JP-A-63-72762, JP-A-63-178169, JP-A-2000-7931, etc., an asymmetrical disazo pigment compound is efficiently used in the same reaction vessel, and more than the symmetric type. A method of manufacturing in proportion is shown. According to this method, by using a polar coupling component and a non-polar coupling component, a pigment that is more transparent and fluid than conventional disazo pigments can be obtained, but contains a large amount of polar coupling components. Therefore, it is disadvantageous for shortening the time in the flushing process. In addition, polar coupling components are expensive compared to non-polar coupling components that are used in general and on a commercial basis. This increases the cost of pigments and reduces the cost of ink by improving ink productivity. Go backwards.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a printing ink which can complete flushing in a short time as compared with conventional disazo pigments, and is further transparent and excellent in fluidity.
[0008]
[Problems to be solved by the invention]
That is, the present invention relates to a disazo pigment formed by coupling a tetrazotized 3,3′-dichlorobenzidine and an acetoacetanilide compound, wherein the acetoacetanilide compound is 80 to 99 mol% of acetoacetanilide, represented by the formula (1): The present invention relates to a disazo pigment comprising 0.5 to 10 mol% of a polar group-containing acetoacetanilide compound shown and 0.5 to 10 mol% of an alkoxy group-containing acetoacetanilide compound represented by the formula (2).
[0009]
Formula (1)
CH ₃ COCH ₂ CONH-X
(In the formula, X is a phenyl group having 1 to 4 identical or different substituents selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a metal salt thereof. Group, methoxy group, hydroxyl group or chlorine atom may be substituted.)
Formula (2)
CH ₃ COCH ₂ CONH-Y
(In the formula, Y represents an alkoxy group having 2 to 4 carbon atoms (the phenyl group may be substituted at a substitutable position with a methyl group, a methoxy group, a hydroxyl group or a chlorine atom).)
Furthermore, the present invention relates to a method for producing the above disazo pigment, characterized by reacting a mixture of acetoacetanilide, a polar group-containing acetoacetanilide compound and an alkoxy group-containing acetoacetanilide compound with a tetrazo liquid of 3,3′-dichlorobenzidine. .
[0010]
Furthermore, in the present invention, after a mixture of acetoacetanilide and a polar group-containing acetoacetanilide compound and a tetrazo solution of 3,3′-dichlorobenzidine are reacted in advance in the same container, the alkoxy group-containing acetoacetanilide compound and 3,3 It is related with the manufacturing method of the said disazo pigment characterized by making the tetrazo liquid of '-dichlorobenzidine react.
[0011]
Furthermore, in the present invention, in the same container, a mixture of acetoacetanilide and a polar group-containing acetoacetanilide compound and a tetrazo solution of 3,3′-dichlorobenzidine are reacted in advance, and then the acetoacetanilide and alkoxy group-containing acetoacetanilide compound are reacted. The present invention relates to a method for producing the above-mentioned disazo pigment, characterized by reacting a mixture with a tetrazo liquid of 3,3′-dichlorobenzidine.
[0012]
Furthermore, the present invention provides the above method for producing a disazo pigment, wherein the reaction is carried out by continuously adding a tetrazo solution of 3,3′-dichlorobenzidine and an alkaline solution of an acetoacetanilide compound in a weakly acidic buffer solution. About.
[0013]
Furthermore, the present invention relates to a method for producing a printing ink, wherein the disazo pigment is flushed with a printing ink vehicle in a wet cake state.
[0014]
Furthermore, the present invention relates to a printing ink comprising the disazo pigment and a printing ink vehicle.
[0015]
Specific examples of the polar group-containing acetoacetanilide compound represented by the formula (1) include 2-acetoacetylaminobenzoic acid, 4-acetoacetylaminobenzoic acid, 4-acetoacetylamino-2- Chlorobenzoic acid, 4-acetoacetylamino-2-methylbenzoic acid, 4-aceacetylamino-2-benzoic acid, 5-acetoacetylamino-2-hydroxybenzoic acid, etc., and 4-acetoacetyl as the sulfonic acid group Examples include aminobenzene sulfonic acid.
[0016]
Examples of the metal constituting the metal salt of the polar group in these polar group-containing acetoacetanilide include sodium, potassium, calcium, barium, strontium, manganese, zinc, magnesium, and aluminum.
[0017]
The alkoxy group of the alkoxy group-containing acetoacetanilide compound represented by the formula (2) is an ethoxy group, an n-propoxy group and its isomer, an n-butoxy group and its isomer, etc. 2-phenetizide, acetoacet-4-phenetide, acetoacet-2-hydroxy-4-phenetide, acetoacet-2-methyl-4-phenetide, acetoacet-2-chloro-4-phenetide, acetoacet-2-methoxy-4-phenetide, There are acetoacet-4-propoxyanilide, acetoacet-3-isopropoxyanilide, acetoacet-4-butoxyanilide.
[0018]
The ratio of the acetoacetanilide-based compound component in the disazo pigment of the present invention is such that acetoacetanilide is 99 to 80 mol%, polar group-containing acetoacetanilide compound is 10 to 0.5 mol%, preferably 1 to 5 mol%, alkoxy group The content of the acetoacetanilide compound is 10.0 to 0.5 mol%, preferably 1 to 5 mol%. The lower limit of the blending amount of the polar group-containing acetoacetanilide compound is limited by transparency and concentration, and the upper limit is limited in shortening the time of the flushing process. The lower limit of the amount of the alkoxy group-containing acetoacetanilide compound is limited in shortening the time of the flushing process, and the upper limit is limited in fluidity reduction and cost due to excessive transparency.
[0019]
In the present invention, the coupling reaction between the 3,3′-dichlorobenzidine tetrazo solution and the coupling component is not particularly limited, but it is acetic acid by a conventional method, that is, in the range of pH 6 to 3, temperature 10 ° C. to 30 ° C., There is a method of performing between 30 minutes and 60 minutes. In addition, an acidic buffer solution in which the pH is adjusted to about 4.5 using acetic acid and caustic soda in advance is prepared, and a coupler solution in which a coupling component is dissolved in caustic soda and a tetrazo solution are simultaneously added in equal reaction amounts. This method is preferable because the reaction can be performed without precipitating the coupling component.
[0020]
The method for producing the disazo pigment of the present invention may be a method in which a mixture of three components of an acetoacetanilide compound is reacted with a tetrazo solution of 3,3′-dichlorobenzidine, or an acetoacetanilide and a polar group First, the mixture of the acetoacetanilide compound containing 3,3′-dichlorobenzidine and the tetrazo solution of 3,3′-dichlorobenzidine are used as a second stage reaction to form a tetrazo solution of the alkoxy group-containing acetoacetanilide compound and 3,3′-dichlorobenzidine. Or a mixture of an acetoacetanilide and alkoxy group-containing acetoacetanilide compound and a tetrazo liquid of 3,3′-dichlorobenzidine may be used. By adopting such a two-step coupling process, a large amount of hydrophobic alkoxyl group-containing disazo compounds are formed on the surface of the disazo pigment particles, so the time required for the flushing process can be shortened without impairing transparency and fluidity. The resulting disazo pigment is obtained.
[0021]
Further, the disazo pigment of the present invention comprises a disazo pigment obtained from a mixture of acetoacetanilide and a polar group-containing acetoacetanilide compound and a tetrazotized product of 3,3′-dichlorobenzidine, an acetoacetanilide halide and an alkoxy group-containing acetoacetanilide. A mixture of a compound and a disazo pigment obtained from a tetrazotized product of 3,3′-dichlorobenzidine may be used.
[0022]
The aqueous slurry of the disazo pigment obtained according to the present invention is adjusted to an alkali side having a pH of 9 to 14, and then an alkali salt solution of rosin (addition amount is 3 to 10% by weight based on the pigment), and the pigment slurry is stirred and homogenized. Hydrochloric acid is added to acidify the pH to about 6 to 4 to precipitate rosin on the pigment surface, and then heated to 90 ° C., held for 30 minutes, filtered, washed with water, and compressed to a pigment content of 28 to 32%. Thus, a wet cake of a disazo pigment used in the flushing step is obtained.
[0023]
Flushing is performed using a flasher by adding 180 to 220 parts by weight of an offset printing ink vehicle to 80 parts by weight of pigment wet cake (dry conversion).
[0024]
The disazo pigment of the present invention is used as a process offset ink. The composition of the offset ink is 3 to 35% by weight of the disazo pigment of the present invention, 97 to 45% by weight of the offset ink vehicle, other auxiliary agents (dryers, leveling improvers, thickeners) and extender pigments of 0 to 20% by weight. Become. The offset ink vehicle is rosin-modified phenolic resin, petroleum resin, alkyd resin, or resin such as these drying oil-modified resins 20 to 50% by weight, vegetable oil such as linseed oil, tung oil, soybean oil, 0 to 30% by weight, n- It consists of 10 to 60% by weight of a solvent such as paraffin, isoparaffin and α-olefin.
[0025]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples. In the examples, “parts” are all parts by weight.
[0026]
[Example 1]
To 400 parts of water, 25.3 parts of 3,3′-dichlorobenzidine and 16.5 parts of 35% hydrochloric acid were added. After cooling this solution to 0 ° C., 70 parts of a 20% sodium nitrite solution was added and stirred for 1 hour. A small amount of sulfamic acid was added to eliminate excess sodium nitrite, to obtain a tetrazo solution of 3,3′-dichlorobenzidine. On the other hand, 34.0 parts of acetoacetanilide, 0.9 part of 5-acetoacetylamino-2-hydroxybenzoic acid, 0.9 part of acetoacet-4-phenetide and 20 parts of caustic soda were dissolved in 400 parts of water. To this solution, 45 parts of 80% acetic acid was added little by little to make a suspension, and the tetrazo solution was added to this solution in about 30 minutes. During this period, the reaction temperature was maintained at about 15 ° C. The slurry of the obtained disazo pigment was adjusted to pH 10.5 with caustic soda, and 60 parts of a 10% alkaline salt solution of rosin was added. After stirring the slurry for 10 minutes, hydrochloric acid was added to adjust the pH to 5.0 to precipitate rosin on the pigment surface. Thereafter, the mixture was heated to 90 ° C. and held for 30 minutes, followed by filtration, washing with water and pressing to obtain a wet cake having a pigment content of 30.0%.
[0027]
Ink formation by flushing was performed using a 1 L flasher. That is, 80 parts of the wet cake as a dry weight and 190 parts of an offset ink vehicle preliminarily warmed to 100 ° C. were simultaneously charged into the flasher to perform flushing (open flushing process: total time 15 minutes). Next, after removing the water that has come out by flushing, heating until the internal temperature of the kneaded product reaches 100 ° C. under reduced pressure (1 to 8 × 10 ³ Pa) (heating medium temperature 130 ° C.) For 30 minutes to completely remove water in the kneaded product (vacuum flushing step). To this kneaded product, 390 parts of an offset ink vehicle and 44 parts of solvent were gradually added and then taken out from the flasher. Thereafter, using three rolls, a roll temperature of 60 ° C. and a pressure of 10 Barr were applied to knead to remove coarse particles, thereby obtaining a base ink. The final ink was obtained by adjusting the tack to 5.8 to 6.0 by adding 25 parts of the offset ink vehicle, 10 parts of the solvent and 3 parts of the auxiliary agent to 62 parts of the base ink.
[0028]
[Example 2]
The tetrazo solution was produced in the same manner as in Example 1. Meanwhile, a coupler solution was prepared by dissolving 34.0 parts of acetoacetanilide, 0.9 part of 5-acetoacetylamino-2-hydroxybenzoic acid, 0.9 part of acetoacet-4-phenetide and 14 parts of caustic soda in 200 parts of water. did. Moreover, 600 parts of buffer solutions adjusted to pH 4.5 of 20 parts of 80% acetic acid and 5 parts of caustic soda were prepared. To this buffer solution, the tetrazo solution and the coupler solution were added simultaneously at about 30 minutes while adjusting the flow rate of both solutions so that tetrazo was not released during the reaction. The coupling reaction temperature was maintained at about 15 ° C. The obtained disazo pigment slurry was subjected to the same operation as in Example 1 to obtain a wet cake having a pigment content of 30.0%. The final ink was obtained in the same manner as in Example 1 for ink formation.
[0029]
[Example 3]
The tetrazo solution was produced in the same manner as in Example 1. On the other hand, 34.0 parts of acetoacetanilide, 0.9 part of 5-acetoacetylamino-2-hydroxybenzoic acid and 19.6 parts of caustic soda were dissolved in 350 parts of water. To this solution, 45 parts of 80% acetic acid was added little by little to make a suspension, and the tetrazo solution was added to this solution in about 30 minutes. During this period, the reaction temperature was maintained at about 15 ° C. In the slurry of the obtained disazo pigment, a solution prepared by dissolving 0.9 part of acetoacet-4-phenetizide and 0.4 part of caustic soda in 50 parts of water and a tetrazo solution were simultaneously dissolved so that tetrazo was not released during the reaction. It took about 10 minutes while adjusting the flow rate. The reaction temperature during this period was also maintained at about 15 ° C. The obtained disazo pigment slurry was subjected to the same operation as in Example 1 to obtain a wet cake having a pigment content of 30.0%. The final ink was obtained in the same manner as in Example 1 for ink formation.
[0030]
[Example 4]
The tetrazo solution was produced in the same manner as in Example 1. Meanwhile, 17.0 parts of acetoacetanilide, 0.9 part of 5-acetoacetylamino-2-hydroxybenzoic acid and 10 parts of caustic soda were added to 200 parts of water and dissolved. To this solution, 45 parts of 80% acetic acid was added little by little to make a suspension, and the tetrazo solution was added to this solution in about 20 minutes. During this period, the reaction temperature was maintained at about 15 ° C. In the resulting slurry of disazo pigment, a solution of 17.0 parts of acetoacetanilide, 0.9 part of acetoacet-4-phenetizide and 10 parts of caustic soda in 200 parts of water and a tetrazo solution are not released simultaneously during the reaction. It took about 20 minutes while adjusting the flow rate of both solutions. The reaction temperature during this period was also maintained at about 15 ° C. The obtained disazo pigment slurry was subjected to the same operation as in Example 1 to obtain a wet cake having a pigment content of 30.0%. The final ink was obtained in the same manner as in Example 1 for ink formation.
[0031]
[Example 5]
The tetrazo solution was produced in the same manner as in Example 1. On the other hand, 34.0 parts of acetoacetanilide, 0.9 part of 2-acetoacetylaminobenzoic acid and 19.6 parts of caustic soda were dissolved in 350 parts of water. To this solution, 45 parts of 80% acetic acid was added little by little to make a suspension, and the tetrazo solution was added to this solution in about 30 minutes. During this period, the reaction temperature was maintained at about 15 ° C. In the obtained slurry of disazo pigment, a solution of tetrasodium solution and 1.8 parts of acetoacet-2-phenethideide and 0.4 part of caustic soda dissolved in 50 parts of water was simultaneously dissolved so that tetrazo was not released during the reaction. It took about 10 minutes while adjusting the flow rate. The reaction temperature during this period was also maintained at about 15 ° C. The obtained disazo pigment slurry was subjected to the same operation as in Example 1 to obtain a wet cake having a pigment content of 30.0%. The final ink was obtained in the same manner as in Example 1 for ink formation.
[0032]
[Example 6]
The tetrazo solution was produced in the same manner as in Example 1. On the other hand, 33.6 parts of acetoacetanilide, 1.0 part of 4-acetoacetylaminobenzenesulfonic acid and 19.6 parts of caustic soda were dissolved in 350 parts of water. To this solution, 45 parts of 80% acetic acid was added little by little to make a suspension, and the tetrazo solution was added to this solution in about 30 minutes. During this period, the reaction temperature was maintained at about 15 ° C. In the obtained slurry of disazo pigment, a solution prepared by dissolving 1.4 parts of acetoacet-4-propoxyanilide and 0.4 part of caustic soda in 50 parts of water and a tetrazo solution at the same time, both solutions so that tetrazo is not liberated during the reaction. It took about 10 minutes while adjusting the flow rate of. The reaction temperature during this period was also maintained at about 15 ° C. The obtained disazo pigment slurry was subjected to the same operation as in Example 1 to obtain a wet cake having a pigment content of 30.0%. The final ink was obtained in the same manner as in Example 1 for ink formation.
[0033]
[Example 7]
The tetrazo solution was produced in the same manner as in Example 1. On the other hand, 34.0 parts of acetoacetanilide, 1.1 parts of 4-acetoacetylaminobenzenesulfonic acid and 19.6 parts of caustic soda were dissolved in 350 parts of water. To this solution, 45 parts of 80% acetic acid was added little by little to make a suspension, and the tetrazo solution was added to this solution in about 30 minutes. During this period, the reaction temperature was maintained at about 15 ° C. In the slurry of the obtained disazo pigment, a solution prepared by dissolving 1.0 part of acetoacet-4-butoxyanilide and 0.4 part of caustic soda in 50 parts of water and a tetrazo solution are simultaneously dissolved so that tetrazo is not liberated during the reaction. It took about 10 minutes while adjusting the flow rate. The reaction temperature during this period was also maintained at about 15 ° C. The obtained disazo pigment slurry was subjected to the same operation as in Example 1 to obtain a wet cake having a pigment content of 30.0%. The final ink was obtained in the same manner as in Example 1 for ink formation.
[0034]
[Example 8]
The tetrazo solution was produced in the same manner as in Example 1. Meanwhile, 31.9 parts of acetoacetanilide, 2.4 parts of 4-acetoacetylamino-2-methylbenzoic acid and 19.6 parts of caustic soda were added to 350 parts of water and dissolved. To this solution, 45 parts of 80% acetic acid was added little by little to make a suspension, and the tetrazo solution was added to this solution in about 30 minutes. During this period, the reaction temperature was maintained at about 15 ° C. In the slurry of the obtained disazo pigment, a solution of 2.5 parts of acetoacet-2-chloro-4-phenetizide and 0.4 part of caustic soda in 50 parts of water and a tetrazo solution are not released simultaneously during the reaction. It took about 10 minutes while adjusting the flow rate of both solutions. The reaction temperature during this period was also maintained at about 15 ° C. The obtained disazo pigment slurry was subjected to the same operation as in Example 1 to obtain a wet cake having a pigment content of 30.0%. The final ink was obtained in the same manner as in Example 1 for ink formation.
[0035]
[Comparative Example 1]
The tetrazo solution was produced in the same manner as in Example 1. On the other hand, 35.4 parts of acetoacetanilide was dissolved in 400 parts of water by adding 20 parts of caustic soda. To this solution, 45 parts of 80% acetic acid was added little by little to make a suspension, and the tetrazo solution was added to this solution in about 30 minutes. During this period, the reaction temperature was maintained at about 15 ° C. The obtained disazo pigment slurry was subjected to the same operation as in Example 1 to obtain a wet cake having a pigment content of 30.0%. The final ink was obtained in the same manner as in Example 1 for ink formation.
[0036]
[Comparative Example 2]
The tetrazo solution was produced in the same manner as in Example 1. On the other hand, 34.0 parts of acetoacetanilide, 1.8 parts of 5-acetoacetylamino-2-hydroxybenzoic acid and 20 parts of caustic soda were dissolved in 400 parts of water. To this solution, 45 parts of 80% acetic acid was added little by little to make a suspension, and the tetrazo solution was added to this solution in about 30 minutes. During this period, the reaction temperature was maintained at about 15 ° C. The obtained disazo pigment slurry was subjected to the same operation as in Example 1 to obtain a wet cake having a pigment content of 30.0%. The final ink was obtained in the same manner as in Example 1 for ink formation.
[0037]
The above results are summarized in Table 1. L ^* indicates the transparency of the ink. The smaller the value, the greater the transparency. The density is the causer value (reflectance density). The larger the value, the larger the density. The value is shown by a 60 second value (mm). The water draining time indicates the time when water comes out in the open flushing process, and the smaller this value, the better the flushing property.
[0038]

Claims

In a disazo pigment obtained by coupling a tetrazotized 3,3′-dichlorobenzidine and an acetoacetanilide compound, the acetoacetanilide compound is 80 to 99 mol% of acetoacetanilide, a polar group represented by the following formula (1) A disazo pigment comprising 0.5 to 10 mol% of an acetoacetanilide compound and 0.5 to 10 mol% of an alkoxy group-containing acetoacetanilide compound represented by the following formula (2).
Formula (1)
CH ₃ COCH ₂ CONH-X
(In the formula, X is a phenyl group having 1 to 4 identical or different substituents selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a metal salt thereof. Group, methoxy group, hydroxyl group or chlorine atom may be substituted.)
Formula (2)
CH ₃ COCH ₂ CONH-Y
Wherein Y represents a phenyl group having an alkoxy group having 2 to 4 carbon atoms (the phenyl group may be substituted at a substitutable position with a methyl group, a methoxy group, a hydroxyl group or a chlorine atom). .)

The method for producing a disazo pigment according to claim 1, wherein a mixture of acetoacetanilide, a polar group-containing acetoacetanilide compound and an alkoxy group-containing acetoacetanilide compound is reacted with a tetrazo liquid of 3,3'-dichlorobenzidine.

In the same container, a mixture of acetoacetanilide and a polar group-containing acetoacetanilide compound and a tetrazo solution of 3,3′-dichlorobenzidine were reacted in advance, and then an alkoxy group-containing acetoacetanilide compound and 3,3′-dichlorobenzidine were mixed. The method for producing a disazo pigment according to claim 1, wherein the tetrazo liquid is reacted.

In the same container, a mixture of acetoacetanilide and a polar group-containing acetoacetanilide compound and a tetrazo liquid of 3,3′-dichlorobenzidine were reacted in advance, and then a mixture of acetoacetanilide and an alkoxy group-containing acetoacetanilide compound and 3,3 The process for producing a disazo pigment according to claim 1, wherein the tetrazo liquid of '-dichlorobenzidine is reacted.

The disazo pigment according to any one of claims 2 to 4, wherein the reaction is carried out by continuously adding a tetrazo solution of 3,3'-dichlorobenzidine and an alkaline solution of an acetoacetanilide compound in a weakly acidic buffer solution. Manufacturing method.

A method for producing a printing ink, wherein the disazo pigment according to claim 1 is flushed with a printing ink vehicle in a wet cake state.

A printing ink comprising the disazo pigment according to claim 1 and a printing ink vehicle.