JP2004322524A - Dampening water composition for litho printing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To lessen a problem for snapping off or the like even in a printing plate for CTP while occurrence of vapour of a volatile compound is little in printing. <P>SOLUTION: A dampening composition for litho printing comprises a dampening water composition containing (A) compounds of general formulas (1) and/or (2), (B) polypropylene glycol, (C) a polyether structure derivative of adding ethylene oxide and/or propylene oxide to acetylene diol, (D) film-forming water soluble polysaccharides, (E) a dead fat-making agent and (F) a PH buffer. The general formula (1) is given by the formula (1) in [element 1]. In the formula (1), R<SP>1</SP>indicates hydrogen, a 1-12C alkyl group or a 1-12C alkyenyl group. (a) and (c) are an integer of 0 or over, a relation of 3≤a+c≤15 is provided, and b is an integer of 7≤b≤40. The general formula (2) is indicated by the formula in [element 2]. In the formula (2), R<SP>2</SP>and R<SP>3</SP>indicate hydrogen, the 1-12C alkyl group or the 1-12C alkenyl group. (d), (e), (f) and (g) are integers of 0 or over, and relations of 3≤d+f≤15 and 7≤e+g≤40 are provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００１９】
（式（１）において、Ｒ^１は水素、炭素数が１〜１２のアルキル基又は炭素数が１〜１２のアルケニル基を示す。式中のａ及びｃは０以上の整数であって３≦ａ＋ｃ≦１５であり、ｂは７≦ｂ≦４０の整数である。）
【００２０】
【化７】

【００２１】
（式（２）において、Ｒ^２、Ｒ^３は水素、炭素数が１〜１２のアルキル基又は炭素数が１〜１２のアルケニル基を示す。式中のｄ，ｅ，ｆ，ｇは０以上の整数であって、３≦ｄ＋ｆ≦１５及び７≦ｅ＋ｇ≦４０である。）
【００２２】
【発明の実施の形態】
（一）
本発明の上記課題は、１１０℃で１時間加熱しても揮発しない化合物であって、前記一般式（１）又は（２）に示される化合物であって、水酸基又は炭素数が１〜１２のアルキル基または炭素数が１〜１２のアルケニル基のいずれかを有し、これらにエチレンオキサイドが３〜１５モル付加されたか及びまたはプロピレンオキサイドが７〜４０モル付加されたポリエーテル構造の化合物と、ポリプロピレングリコールと、アセチレンジオールにエチレンオキサイド及びまたはプロピレンオキサイドが付加されたエーテル構造の化合物と、皮膜形成性水溶性多糖類、不感脂化剤、ＰＨ緩衝剤を湿し水組成物中に含有させることによって達成され、オフセット印刷において安定的な品質が得ることばかりでなく、紙に浸透した湿し水成分が揮発することのない印刷物を印刷することが出来る。
【００２３】
本発明の平版印刷用湿し水組成物では、湿し水の必要要件である低起泡性や水中での分散性や溶解性が良好であること、及び印刷機上でのインキへの乳化性が適切であることや印刷版の画線部への侵食性が低く耐刷性が良好であり、総合的に印刷適性に優れることを基準に選定された、１１０℃で１時間加熱しても揮発しない化合物として、下記一般式（１）または（２）に示される化合物を少なくとも一種含有する。
【００２４】
【化８】

【００２５】
（式（１）において、Ｒ^１は水素、炭素数が１〜１２のアルキル基又は炭素数が１〜１２のアルケニル基を示す。式中のａ及びｃは０以上の整数であって３≦ａ＋ｃ≦１５であり、ｂは７≦ｂ≦４０の整数である。）
【００２６】
【化９】

【００２７】
（式（２）において、Ｒ^２、Ｒ^３は水素、炭素数が１〜１２のアルキル基又は炭素数が１〜１２のアルケニル基を示す。式中のｄ，ｅ，ｆ，ｇは０以上の整数であって、３≦ｄ＋ｆ≦１５、及び７≦ｅ＋ｇ≦４０の整数である。）
これら化合物（１）及び（２）の平版印刷用湿し水組成物中での合計含有量は０．０１〜１０質量％が好ましい。より好ましくは０．０１〜５質量％の範囲で用いられる。
【００２８】
これらの化合物の使用は単独で用いても、２種類以上を併用しても良い。但し、平版印刷用湿し水材料として含有率は０．０１質量％より少ない場合は、印刷版面非画線部への濡れが悪くなり画線部周辺がインキで汚れやすくなる。又含有量が１０質量％を越えた場合にはコスト的な面で不利であることは言うに及ばず、印刷版面の画線部を侵食しやすくなる。
【００２９】
又、本発明では印刷版に湿し水を供給するローラー上に均一な水膜を形成するために次のような界面活性剤を単独で用いても、２種類以上併用しても良い。アニオン型界面活性剤の具体例としては、アニオン型界面活性剤の具体例としては、例えば、脂肪酸塩類、ヒドロキシアルカンスルホン酸塩類、アルカンスルホン酸塩類、ジアルキルスルホ琥珀酸塩類、ポリオキシエチレンアルキルスルホフェニルエーテル塩類、Ｎ−メチル−Ｎ−オレイルタウリンナトリウム塩類、Ｎ−アルキルスルホ琥珀酸モノアミド二ナトリウム塩類、ポリオキシエチレンアルキルエーテル硫酸エステル塩類、脂肪酸モノグリセリド硫酸エステル塩類、アルキル燐酸エステル塩類、ポリオキシエチレンアルキルエーテル燐酸エステル塩類などが挙げられる。
【００３０】
非イオン型界面活性剤の具体例としては、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンポリスチリルフェニルエーテル類、ポリオキシエチレンポリオキシプロピレンアルキルエーテル類、グリセリン脂肪酸部分エステル化物類、ソルビタン脂肪酸部分エステル化物類、ペンタエリスリトール脂肪酸部分エステル化物類、プロピレングリコールモノ脂肪酸エステル類、ショ糖脂肪酸部分エステル化物類、ポリオキシエチレンソルビタン脂肪酸部分エステル化物類、ポリオキシエチレンソルビトール脂肪酸部分エステル化物類、ポリエチレングリコール脂肪酸エステル類、ポリグリセリン脂肪酸部分エステル化物類、ポリオキシエチレン化ひまし油類、ポリオキシエチレングリセリン脂肪酸部分エステル化物類、脂肪酸ジエタノールアミド類、Ｎ、Ｎ−ビス−２−ヒドロキシアルキルアミン類、ポリオキシエチレンアルキルアミン類、トリエタノールアミン脂肪酸エステル類、トリアルキルアミンオキシド類、ポリオキシエチレン−ポリオキシプロピレンブロックポリマーなどが挙げられる。
【００３１】
その他弗素系界面活性剤、シリコン系界面活性剤も使用することができる。カチオン型界面活性剤の具体例としては、アルキルアミン塩類、第４級アンモニウム塩類、ポリオキシエチレンアルキルアミン塩類、ポリエチレンポリアミン誘導体などが挙げられる。但し、使用する場合にはこれら界面活性剤が平版印刷用湿し水組成物中で１０．０質量％以下とすることが適当である。
【００３２】
更に、本発明の平版印刷用湿し水組成物にはポリプロピレングリコールを０．０２〜１０質量％添加する。この化合物を添加することにより、前記した（Ａ）の化合物の群の中でインキの乳化力が強いものは添加量を減少させて、又、インキの乳化力の弱いものは補強することで、適切な乳化特性を実現し、又印刷版画線部への侵食性を抑制して高耐刷性を実現することが出来る。好ましくは添加量０．０５〜５質量％である。
【００３３】
更に本発明の平版印刷用湿し水組成物には印刷機が高速回転している時でも印刷版面に湿し水を均一に供給するように表面張力を低下させる為、アセチレンジオールにエチレンオキサイド及びまたはプロピレンオキサイドが付加されたポリエーテル構造の化合物を添加する。これら化合物の平版印刷用湿し水組成物中での含有量は０．０１〜６質量％であり、好ましくは０．０２５〜５質量％の範囲で用いられる。
【００３４】
更に本発明の平版印刷用湿し水組成物には、印刷版面の非画線部であるアルミ基板表面における地汚れや、網点の絡み汚れなど印刷物の汚れが発生するのを防止することを目的に、皮膜形成性水溶性多糖類として具体的には、アラビアガム、デキストリン、カルボキシルメチルセルロース（ＣＭＣ）、アセチル化でん粉。ヒドリキシプロピルメチルセルロース（ＨＰＭＣ）、ヒドリキシプロピルセルロース（ＨＰＣ）、ヒドロキシエチルセルロース（ＨＥＣ）、ポリビニルアルコール（ＰＶＡ）、ポリビニルピロリドン（ＰＶＰ）、ポリアクリル酸、アリギン酸ナトリウムを添加する。これら化合物の平版印刷用湿し水組成物中での含有量は０．００２〜０．１質量％で、好ましくは０．００５〜０．０５質量％の範囲で用いられる。
【００３５】
更に、本発明の平版印刷用湿し水組成物には印刷版面の非画線部であるアルミ基板表面における乳化してちり状となったインキの付着や、紙からの溶出物などによる異物の付着を防止することを目的に、不感脂化剤として具体的には、水溶性の有機酸や無機酸を添加する。有機酸として、例えばクエン酸、アスコルビン酸、リンゴ酸、酒石酸、乳酸、グルコン酸、シュウ酸、マロン酸、レブリン酸、フイチン酸、有機ホスホン酸等が挙げられる。無機酸として、例えばリン酸、ピロリン酸及びポリリン酸に代表される縮合リン酸の他、硝酸、硫酸などが挙げられる。これら化合物の平版印刷用湿し水組成物中での含有量は０．００１〜０．１質量％で、好ましくは０．００２〜０．０５質量％の範囲で用いられる。
【００３６】
更に、本発明の平版印刷用湿し水組成物には、湿し水として使用する水道水等の水や、インキや紙からの溶出物によるＰＨの変動を防止することを目的に、ＰＨ緩衝剤として具体的には、水溶性の有機酸や無機酸の塩類を添加する。有機酸として、例えばクエン酸、アスコルビン酸、リンゴ酸、酒石酸、乳酸、グルコン酸、ヒドロキシ酢酸、シュウ酸、マロン酸、レブリン酸、フイチン酸、有機ホスホン酸等であり、無機酸として、例えばリン酸、硝酸、硫酸などが挙げられる。これら有機酸及びまたは無機酸のアルカリ金属塩、アルカリ土類金属塩、あるいはアンモニウム塩、有機アミン酸などを使用する。これら化合物の平版印刷用湿し水組成物中での含有量は０．００５〜０．１質量％で、好ましくは０．０１〜０．１質量％の範囲で用いられる。
【００３７】
この他、本発明では消泡剤として、シリコン系消泡剤及びまたはフッ素系消泡剤が好ましく使用される。その中で、乳化分散型及び可溶化型などいずれも使用できる。これら化合物の平版印刷用湿し水組成物中での含有量は１質量％程度である。
【００３８】
又、本発明では印刷機の湿し水循環装置において長期間使用する際の水の腐敗を防止するための防腐剤として、イミダゾール誘導体、４−イソチアゾリン−３−オン誘導体、ベンズトリアゾール誘導体、アミジンまたはグアジニンの誘導体、４級アンモニウム塩類、ピリジンまたはキノリンの誘導体、ダイアジンまたはトリアゾールの誘導体、オキサゾールまたはオキサジンの誘導体などを使用してもよい。好ましい添加量は、細菌、カビ、酵母などに対して安定に効力を発揮する量であって、細菌、カビ、酵母の種類によっても異なるが、これら化合物の平版印刷用湿し水組成物中での含有量は４質量％以下の範囲が好ましく、また種々の細菌、カビ、酵母に対して効力のあるような２種以上の防腐剤を併用することが好ましい。
【００３９】
又、本発明では着色剤として、水溶性の食品用色素などが好ましく、例えば、黄色色素としてはＣＩＮｏ．１９１４０、１５９８５、赤色色素としてはＣＩＮｏ．１６１８５、４５４３０、１６２５５、４５３８０、４５１００、紫色色素としてはＣＩＮｏ．４２６４０、青色色素としてはＣＩＮｏ．４２０９０、７３０１５、緑色色素としてはＣＩＮｏ．４２０９５などが挙げられる。
【００４０】
本発明の平版印刷用湿し水に使用されるキレート剤としては、エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸、トリエチレンテトラミンヘキサ酢酸、ヒドロキシエチルエチレンジアミントリ酢酸、ニトリロトリ酢酸、１−ヒドロキシエタン−１，１−ジホスホン酸、アミノトリ（メチレンホスホン酸）などやこれらのナトリウム塩類、カリウム塩類、および有機アミン塩類などを挙げることが出来る。これらのキレート剤は濃縮湿し水中に安定に存在し、印刷性を阻害しないものが選ばれる。これら化合物の平版印刷用湿し水組成物中での含有量は１０質量％以下が適当である。
【００４１】
本発明の平版印刷版用湿し水組成物は水道水や井戸水などの水で１０〜１００倍に希釈し、平版印刷機上で使用される。
【００４２】
（二）
本発明の平版印刷用湿し水組成物には、前記した（Ａ）の化合物の中で、インキへの乳化安定性を確保し、印刷版画線部への侵食性が少なく、印刷中に画線が脱落することの無い良好な耐刷性を得るためには、一般式（３）で示される化合物であって、Ｒ^１が水素、炭素数が１〜４のアルキル基又は炭素数が３〜４のアルケニル基であり、ｂは１５〜４０の整数であって、ａおよびｃはそれぞれ１〜５の整数であり、３≦ａ＋ｃ≦１０である化合物でもよい。
【００４３】
【化１０】

【００４４】
好ましくは、Ｒ^１が水素、炭素数が１〜２のアルキル基又は炭素数が３のアルケニル基であり、ｂは２５〜４０の整数で、ａおよびｃはそれぞれ１〜５の整数で、３≦ａ＋ｃ≦１０である。
（三）
更に、本発明の平版印刷用湿し水組成物では、印刷版画線への侵食性を和らげ、且つ湿し水中へのインキのちり汚れ発生や水舟のローラーの汚れがすくなくインキへの乳化特性をより良好とするために、１１０℃で加熱しても揮発しない性質を有し、下記一般式（４）に示される、分子量が２００〜２０００であるポリプロピレングリコールを用いても良い。
【００４５】
【化１１】

【００４６】
この分子量の範囲では水への溶解性が比較的良好で湿し水組成物製造上使用が容易である。より好ましい分子量は２００〜１０００である。
【００４７】
（四）
更に、本発明の平版印刷用湿し水組成物では請求項１の前記（Ｃ）の化合物であって、１１０℃で１時間加熱しても揮発しない、下記一般式（５）に示される、２，４，７，９−テトラメチル−５−デシン−４，７−ジオールの２つの水酸基にエチレンオキサイドが３〜１０モル付加されたか、及びまたはプロピレンオキサイドが０〜５モル付加されたエーテル構造であって、そのＨＬＢが８〜１５の範囲である化合物を用いても良い。
【００４８】
【化１２】

【００４９】
これら化合物の中で、エチレンオキサイドが３モルより少なく付加した化合物では、Ｍｅｔｈｏｄ ２４の条件では揮発する可能性があり、加えて水への溶解性の低下やインキへの乳化安定性が低く本用途に適さない。又、エチレンオキサイドが３より少なく付加したものは１１０℃で１時間加熱した場合に揮発する可能性があり、１０モルを超えて付加した化合物ではインキの乳化性が不充分でありちり汚れ等の印刷物の汚れが発生し、印刷機の水元ローラーに均一な水膜を形成するために必要な表面張力低下能が低く、本用途に適さない。又、これにプロピレンオキサイドが５モルを超えて付加した場合には、添加量が多い場合や、印刷で使用中に濃縮された場合にインキを過剰に乳化する可能性がありインキ着けローラーに湿し水が浸透して所謂ローラーはげとなる可能性が高くなり、更に印刷版画線部への侵食性が強くなり、印刷中に画線が脱落する等耐刷性の低下を招く傾向があり、本用途に適さない。
【００５０】
尚、ＨＬＢとはＨｙｄｒｏｐｈｉｌｅ−Ｌｉｐｏｐｈｉｌｅ Ｂａｌａｎｃｅの略で、界面活性剤が持つ親水性と親油性のバランスを示したものである。すなわち、疎水基の疎水性に比べて親水基の親水性がどれくらい大きいかということを示す一つの尺度である。
【００５１】
又、そのＨＬＢが８〜１５の範囲外である場合には、前述と同様にインキへの乳化性が適切でないか印刷版画線部への侵食性が強くなるので本用途に適さない。好ましくは印刷適性の良好な点からエチレンオキサイドを３〜６モル付加されたか、及びまたはプロピレンオキサイドが０〜３モル付加された化合物であり、そのＨＬＢは８〜１３である。
【００５２】
（五）
更に、本発明の湿し水組成物には皮膜形成性水溶性多糖類として、１１０℃で１時間加熱しても揮発しない、ヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、ヒドロキシプロピルセルロース（ＨＰＣ）、ヒドロキシエチルセルロース（ＨＥＣ）で分子量が１００００〜３５０００であるものから少なくとも１種類以上選んで用いてもよい。
【００５３】
各化合物の分子量が１００００より少ない場合には増粘性が低く、印刷版面を均一に水で濡らして非画線部がインキで汚れないようにする為に必要な粘度が得られ難く、又、分子量が４５０００より大きい場合には増粘性は過剰となり、水への溶解性や分散性の低下や湿し水補充装置の配管での流動性が低下して補充量が不安定となるので本用途に適さない。好ましくは、溶解性及び分散性、増粘性や印刷適性の点を考慮すれば、これら化合物の分子量が１００００〜３５００００である。
【００５４】
（六）
更に、本発明の平版印刷用湿し水には不感脂化剤として、１１０度で１時間加熱しても揮発しない、有機酸ではクエン酸、りんご酸及び酒石酸、無機酸としてはリン酸、ピロリン酸及びポリリン酸に代表される縮合リン酸類を用いてもよい。これらの化合物は印刷版の非画線部の整面効果や水上がり等の印刷適性やインキの乳化特性の面から本用途に適している。尚、これらの化合物は単独でも２種類以上を組み合わせて使用することが出来る。好ましくは、クエン酸、りんご酸、及びリン酸ピロリン酸、ポリリン酸である。
【００５５】
（七）
更に、本発明の平版印刷用湿し水にはＰＨ緩衝剤として、１１０℃で１時間加熱しても揮発しない、有機酸ではクエン酸、アスコルビン酸、リンゴ酸、酒石酸、グルコン酸、シュウ酸、マロン酸、フイチン酸、有機ホスホン酸、無機酸ではリン酸、硝酸、硫酸のアルカリ金属塩、アルカリ土類金属塩、あるいはアンモニウム塩、有機アミン酸塩を用いてもよい。これらの化合物は、インキや汚れ成分の付着を防止して印刷版の非画線部の不感脂化効果を高め、印刷物のいわゆる地汚れの発生を防ぐと同時に、画線部への選択的なインキの付着性を維持することが出来、この他にインキを過剰乳化させにくく湿し水中へのちり汚れを防ぐ効果がある。好ましくはクエン酸、アスコルビン酸、リンゴ酸、酒石酸のアルカリ金属塩、アンモニウム塩である。
【００５６】
【実施例】
本発明を実施例にて更に詳細に説明するが、本発明はこれら実施例に限定されるものではない。尚％は特に指定のない限り質量％を示す。
【００５７】
［実施例１〜４及び比較例１〜５］
本発明による実施例及び比較例では一般式（１）で示される化合物として、ＰＥ−６２（三洋化成（株）製品名、Ｒ^１＝Ｈ、ａ＋ｃ＝１０、ｂ＝３０）、エパン４１０（日本油脂（株）製品名、Ｒ^１＝Ｈ、ａ＋ｃ＝３、ｂ＝２１）、ユニセーフＮＸＳ−４００１（日本油脂（株）製品名、Ｒ^１＝炭素数６〜１０、ａ＋ｃ＝９、ｂ＝２４）、皮膜形成性水溶性多糖類として、６０ＳＨ−０６（信越化学（株）製品名、ヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、平均分子量３５０００）、Ｋｌｕｃｅｌ−Ｌ（三晶（株）製品名、ヒドロキシプロピルセルロース（ＨＰＣ）、平均分子量９５０００）、ＨＰＣ−Ｌ（日本曹達（株）製品名、ヒドロキシプロピルセルロース（ＨＰＣ）、平均分子量２３００００）、消泡剤Ｔ（日光ケミカル製品名）、一般式（３）で示される化合物として、サーフィノール４６５（エアープロダクツ（株）製品名）を使用した。表１の組成に従って、各例の湿し水組成を調製した。単位はグラムであり、表１の組成以外の残部として水を加えてそれぞれの全量を１０００ｇとした。
【００５８】
本発明の湿し水実施例１〜４及び比較例１〜５について、水で５０倍に希釈（濃度２．０％）し、以下に示す測定及びテストを実施した。それらの結果を表２に示す。
【００５９】
（ａ）揮発性有機化合物成分（ＶＯＣ）の測定
揮発性有機化合物成分（ＶＯＣ）の測定方法はアメリカ環境保護局（Ｕｎｉｔｅｄ Ｓｔａｔｅｓ Ｅｎｖｉｒｏｍｅｎｔａｌ Ｐｒｏｔｅｃｔｉｏｎ Ａｇｅｎｃｙ；ＥＰＡ）で定義されたＭｅｔｈｏｄ ２４に基づいて行った。その結果を表２に示す。なお、評価結果の記号の意味は次の通りである；
○・・・ＶＯＣなし、
△・・・ＶＯＣ成分を・・〜５％未満含有する、
×・・・ＶＯＣ成分を５．０％以上含有する。
【００６０】
尚、Ｍｅｔｈｏｄ ２４に基づいた揮発性有機化合物成分（ＶＯＣ）の測定方法とはサンプルを一定量秤量し、１１０℃、１時間オーブンで加熱し、揮発成分量を算出し、更に同じ量のサンプルをＫａｒｌ Ｆｉｓｈｅｒ測定装置により水分量を測定することで揮発成分量から水分量を引いたものを揮発性有機化合物成分（ＶＯＣ）量とする測定方法である。
【００６１】
（ｂ）プレート侵食性テスト
５０％網点とベタの画線のあるＣＴＰ版（ＴＣＣ−６０３；コダックポリクロームグラフィックス（株）製）を作成し、２％に調整した各湿し水に５時間浸漬させ、画線部の侵食性テストを行った。その結果を表２に示す。なお、評価結果の記号の意味は次の通りである；
○・・・画線部侵食性なし、
△・・・液界面に侵食性が見られる、
×・・・５０％網点が侵食され、画線部が取れる。
【００６２】
また、本発明の湿し水１〜４および比較例１〜５について、印刷テストを実施した。印刷条件は以下の通りである；
印刷機：ローランドＲ−７０４（ローランド社製）、
印刷速度：１０，０００枚／１時間、
印刷用紙：十条ダイヤコート５７．５ｋｇ／Ａ全、
湿し水機構：ローランドマチック、
温湿度：２３〜２４℃，５０〜６０％ＲＨ、
インキ：バリウスＧ藍−Ｎ（大日本インキ化学工業（株）製）、
印刷版：ＴＣＣ−６０３（ＣＴＰ版；Ｃｏｍｐｕｔｅｒ ｔｏ Ｐｌａｔｅ；コダックポリクロームグラフィックス（株）製）。
以上の条件で下記の印刷テスト（ｃ）〜（ｆ）を実施した。それらの結果を下記表２に示す。
【００６３】
（ｃ）水幅適性
印刷機の給水量の目盛り（目盛り１〜９９、給水ローラーの回転数の目盛りでもある）で網点の絡みが発生する水目盛りを下限値、紙面のベタ部分の濃度が０．１落ちた水目盛りを上限値とする下限値と上限値の幅を調べた。それらの結果を下記表２に示す。評価結果の記号の意味は次の通りである；
○・・・３５目盛り以上の水幅、
△・・・３０〜２５目盛り以内の水幅、
×・・・２５目盛り以下の水幅。
【００６４】
（ｄ）給水ローラー安定性
印刷１０，０００枚終了後の給水ローラーの汚れ具合を観察した。それらの結果を下記表２に示す。評価結果の記号の意味は次の通りである；
○・・・汚れなし、
△・・・若干汚れがある、
×・・・汚れる。
【００６５】
（ｅ）不感脂化適性
印刷テストにおいて、印刷を停止して、約１時間放置後に再印刷したとき、非画線部の汚れの取れた方を調べた。それらの結果を下記表２に示す。評価結果の記号の意味は次の通りである；
○・・・インキが非画線部からすべて落ちる、
△・・・インキが若干残る、
×・・・インキが残る。
【００６６】
（ｆ）乳化適性
印刷テストにおいて、インキ練ロール及び紙面上のインキの乳化状態を調べた。それらの結果を下記表２に示す。評価結果の記号の意味は次の通りである；
○・・・良い、
△・・・やや悪い、
×・・・悪い。
【００６７】
【表１】

【００６８】
【表２】

【００６９】
表２のＶＯＣ成分測定の結果から、比較例１のような、揮発性有機溶剤のブチルセロソルブやプロピレングリコールや特許文献２８で提案されている蒸発しにくい化合物を添加した湿し水、及び比較例２のようなプロピレングリコール−ｎ−ブチルエーテル、エチレングリコール−ｎ−ブチルエーテル等の低分子アルキルエーテル類が添加された湿し水でもＶＯＣ成分が検出されることがわかる。
【００７０】
プレートの侵食性テストでは本発明の一般式（１）に示す化合物とポリプロピレングリコール（分子量３０００）を併用した比較例３では、分子量の大きいポリプロピレングリコールではプレート画線部への浸透性が高く、画線への侵食性が強くなって好ましくない。
【００７１】
印刷試験では、不感脂化適性についてはシュウ酸では若干劣る。
【００７２】
標準水目盛り適性及び水幅適性については、従来の有機溶剤型の比較例１と実施例１〜４のいずれも同等の適性を有していた。また、サーフィノール４６５を含まない比較例２は実施例より水幅が劣る結果となっている。サーフィノール４６５を添加することにより水幅適性が向上したと考えられる。
【００７３】
給水ローラー安定性については本発明の一般式（１）に示す化合物と分子量が７００のポリプロピレングリコールを添加したものが良好であり、一般式（１）でのＲ^１が炭素数の大きい基を有する化合物や、分子量が３０００と大きいポリプロピレングリコールを添加したものでは比較的給水ローラーが汚れやすくなる。
【００７４】
以上より本発明の湿し水組成物は表２のテスト結果から従来の有機溶剤含有型の湿し水と同等の印刷適性を持ち、良好な性能を有することがわかる。
【００７５】
【発明の効果】
本発明による平版印刷用湿し水材料を含有した平版印刷用湿し水組成物は、ＩＰＡを含有せず液安定性に優れた湿し水組成物であるばかりではなく、従来の有機溶剤含有型の湿し水と同等の印刷適性を持ち、前記のＭｅｔｈｏｄ ２４の基準による揮発成分を含まない、地球環境保全に配慮した湿し水組成物である。本発明による湿し水組成物を希釈して作成した平版印刷用湿し水は、印刷適性に優れた上に印刷版特にＣＴＰ版における版トレ等による品質の低下のない湿し水特性を有した湿し水組成物である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a fountain solution used in lithographic offset printing.
[0002]
[Prior art]
The offset printing method using a lithographic printing plate is a printing method that utilizes the property that water and oil are not essentially mixed.The printing plate surface receives water and repels ink, The former is a non-image area and the latter is an image area. In this method, if dampening water is excessively applied to the ink, the emulsification of the ink becomes excessive, and the ink is deposited on a roller for supplying the ink, resulting in poor transfer. On the other hand, if the amount of the dampening solution is too small, the ink adheres to the non-image area and causes stain.
[0003]
To maintain the balance between the ink and the fountain solution, isopropyl alcohol (hereinafter referred to as IPA) has been added to the fountain solution, and various hydrophilic substances such as gum arabic, carboxymethyl cellulose (CMC), Acids, various surfactants, acids such as phosphoric acid as a surface conditioner for removing plate surface oxides, ammonium bichromate, nitrates, etc. as plate corrosion inhibitors, and organic solvents for adjusting the solubility of various additives. Has been added. Here, the effects of adding IPA include the effect of improving the wetting of the printing plate surface to the hydrophilic non-image area and the effect of increasing the viscosity of the dampening solution to smooth the supply of the dampening solution to the plate surface. The effect is raised.
[0004]
However, IPA falls under the category of Class 4 alcohols, and it is necessary to pay close attention to fire when using it. In addition, it falls under Class 2 Organic Solvents in the Prevention Regulations for Organic Solvents, and is usually added to dampening water at a concentration of about 5 to 20% by mass. was there.
[0005]
For this reason, in recent years, a fountain solution or a fountain solution composition has been proposed in which IPA is not used at all, or even if it is used, the concentration of the fountain solution is 5% by mass or less. For example, Patent Literature 1, Patent Literature 2, Patent Literature 3, Patent Literature 4, Patent Literature 5, Patent Literature 6, and Patent Literature 7 can be cited as examples in which another organic solvent is added as a substitute compound of IPA.
[0006]
It has also been proposed to add a surfactant of an ethylene oxide or propylene oxide adduct of alcohols. For example, Patent Literature 8, Patent Literature 9, Patent Literature 10, Patent Literature 11, Patent Literature 12, Patent Literature 13, Patent Literature 14, Patent Literature 15, Patent Literature 16, Patent Literature 17, Patent Literature 18, Patent Literature 19, Patent Literature 20, Patent Literature 21, Patent Literature 22, Patent Literature 23, Patent Literature 24 and Patent Literature 25 disclose an interface in which ethylene oxide or propylene oxide is added to a monohydric or dihydric alcohol or a trihydric or higher polyhydric alcohol. A fountain solution or fountain solution composition to which an activator has been added has been proposed.
[0007]
However, in recent years, as efforts to improve the working environment have been strengthened, efforts to reduce the amount of organic compounds released into the air due to the increasing momentum of consideration for the global environment have been increasing. In the printing industry, there is increasing interest in the components of raw materials used for printing, and even IPA substitute compounds that are difficult to volatilize, such as high-boiling solvents, can volatilize depending on the operating environment of the printing press. There is also a demand for products using raw materials that are hardly volatilized or non-volatile.
[0008]
While the development of the most suitable for dampening solution is being promoted by focusing on high-boiling solvents and high molecular compounds as raw materials that do not volatilize, it should be noted that volatile organic compounds (VOLATILE ORGANIC COMPOUND; VOC) are worthy of abroad. The definition has been made in the EU and the United States. For example, Non-Patent Document 1 describes a method for measuring VOC components in paints and inks (Method 24). The United States Environmental Protection Agency (United States Environmental Protection Agency; EPA) is a non-volatile organic compound (Non- VOC) is defined as that the organic compound component does not volatilize when heated at 110 ° C. for 1 hour according to the measurement method, and it has been considered that the conventional high boiling point solvent can be regarded as a non-volatile compound. Has become a tough one.
[0009]
Under such an environment, for example, a compound having a boiling point of 150 ° C. or more at 20 ° C. and 1 atm as in Patent Document 26, a compound having a boiling point of 100 ° C. or more and a flash point of 21 ° C. or more as in Patent Document 27 A fountain solution or fountain solution composition containing the same has been proposed, and a fountain solution with less generation of organic solvent vapor is expected to open up a market in the future.
[0010]
However, many of the compounds for substituting IPA disclosed in the above invention contain many volatile components having a low boiling point and cannot be used as fountain solutions containing no volatile components. Further, according to the definition of Method 24, compounds satisfying the boiling point conditions described in the above invention are not only low-boiling point organic solvents but also polyhydric alcohol derivatives such as glycerin, and other compounds. Even in organic solvents which are said to be boiling solvents, there are compounds whose volatile components are slightly confirmed in a test according to Method 24, and do not completely satisfy the requirements of non-volatile solvents.
[0011]
Also, among the surfactants, compounds having a small EO or PO addition mole number such as polyoxyethylene (ethylene oxide; EO) alkyl ethers and polyoxypropylene (propylene oxide; PO) alkyl ethers are volatile components in the test by Method 24. Corresponds to the compound to be confirmed. Furthermore, to use a surfactant satisfying the requirements of Method 24, it is necessary to use a compound having a large number of moles of EO or PO added. However, when a compound having a large number of moles of EO or PO added is used, the former has a high hydrophilicity, so that the emulsification suitability of the ink is inferior, and the latter has a great decrease in solubility in water.
[0012]
Also, to maintain an appropriate surface tension for obtaining the wettability required for printing, the concentration of the surfactant must be considerably increased. As a disadvantage, the dampening solution is concentrated at the time of use and foams in the dampening solution tank.In addition, the ink tends to be excessively emulsified, and the performance such as a decrease in tackiness is changed to change the performance on a printing press. Problems such as reduced transferability between rollers and dirt on a water rod will result. In addition, because of its penetrative nature, the image area of the lithographic printing plate material is easily eroded.In particular, in recent years, using a solid-state laser or semiconductor laser that emits infrared light, an image to be printed on the plate surface is obtained from digital data of a computer or the like. This tendency is remarkable in a so-called CTP (Computer to Plate) printing plate in which a plate is directly recorded and made, and the image portion eroded by the dampening solution swells and drops during printing to deteriorate the printing quality. The problem of having it (also known as a version training) has not yet been completely solved.
[0013]
Patent Document 28 proposes a polyether derivative obtained by adding ethylene oxide and propylene oxide to a monohydric alcohol as a compound that hardly evaporates. However, in these cases, when applied to the above-mentioned Method 24 standard, many organic components evaporate, and furthermore, because of their penetrative properties, the image portions of the lithographic printing plate material are eroded, and the image portions are eroded. Swells and drops during printing, lowering the print quality, such as lowering print quality, which is inferior to the performance of conventional solvent-type fountain solutions. Remaining.
[0014]
[Patent Document 1]
JP-A-52-4301
[Patent Document 2]
JP-A-57-1792
[Patent Document 3]
JP-A-57-19969
[Patent Document 4]
JP-A-2-269094
[Patent Document 5]
JP-A-3-90389
[Patent Document 6]
JP-A-4-1091
[Patent Document 7]
JP-A-5-139068
[Patent Document 8]
JP-A-51-72507
[Patent Document 9]
JP-A-2-48996
[Patent Document 10]
JP-A-2-255386
[Patent Document 11]
JP-A-2-269094 * Double
[Patent Document 12]
JP-A-3-63188
[Patent Document 13]
JP-A-3-155991
[Patent Document 14]
JP-A-5-221180
[Patent Document 15]
JP-A-6-219076
[Patent Document 16]
JP-A-8-337073
[Patent Document 17]
JP-A-9-123635
[Patent Document 18]
JP-A-10-181234
[Patent Document 19]
JP-A-11-99766
[Patent Document 20]
JP-A-1999-5376
[Patent Document 21]
JP-A-2000-94854
[Patent Document 22]
JP 2001-138659 A
[Patent Document 23]
JP 2001-180146 A
[Patent Document 24]
JP-A-5-221179
[Patent Document 25]
JP-A-8-132753
[Patent Document 26]
JP-A-3-135750
[Patent Document 27]
JP-A-6-183171
[Patent Document 28]
JP-A-11-268442
[Non-patent document 1]
Manual Determination of Volatile Organic Compound (VOC) Content in Paints, ink, and Related Coating Products 2nd Edition / ASTM Manual Series
[0015]
[Problems to be solved by the invention]
The present invention uses a compound conforming to the conditions described in Method 24 above (the components do not volatilize when heated at 110 ° C. for 1 hour), and the generation of volatile compound vapor when used during printing is reduced. An object of the present invention is to provide a concentrated fountain solution for lithographic printing which has no liquid stability.
[0016]
Further, in performing the printing operation, the same effect as when IPA is added is obtained, for example, the wettability to the hydrophilic non-image area of the printing plate surface is improved, and the amount of foaming is small, and the supply amount can be easily adjusted. In addition to preventing dirt on printed matter and poor transfer of ink, printing on CTP printing plates with relatively weak image areas on the plate surface can also be performed during printing, such as dropping of image areas during printing. It is an object of the present invention to provide a fountain solution composition for lithographic printing which does not cause a problem of deterioration of the printing quality and can easily obtain a high-quality printed matter.
[0017]
[Means for Solving the Problems]
The fountain solution composition for lithographic printing of the present invention is a compound which does not volatilize even when heated at 110 ° C. for 1 hour, and is a compound represented by the following formula (A) or (2), Or an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 1 to 12 carbon atoms, to which 3 to 15 mol of ethylene oxide has been added and / or 7 to 40 mol of propylene oxide has been added. (B) polypropylene glycol, (C) acetylenic diol to which ethylene oxide and / or propylene oxide are added, (D) film-forming water-soluble polysaccharide, (E) insensitive oil And (F) a PH buffering agent.
[0018]
Embedded image

[0019]
(In the formula (1), R ¹ Represents hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 1 to 12 carbon atoms. A and c in the formula are integers of 0 or more and 3 ≦ a + c ≦ 15, and b is an integer of 7 ≦ b ≦ 40. )
[0020]
Embedded image

[0021]
(In the formula (2), R ² , R ³ Represents hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 1 to 12 carbon atoms. In the formula, d, e, f, and g are integers of 0 or more, and satisfy 3 ≦ d + f ≦ 15 and 7 ≦ e + g ≦ 40. )
[0022]
BEST MODE FOR CARRYING OUT THE INVENTION
(one)
The object of the present invention is a compound which does not volatilize even when heated at 110 ° C. for 1 hour, and is a compound represented by the general formula (1) or (2), wherein the compound has a hydroxyl group or carbon number of 1 to 12. A compound having a polyether structure having an alkyl group or an alkenyl group having 1 to 12 carbon atoms, and having 3 to 15 mol of ethylene oxide added thereto or 7 to 40 mol of propylene oxide added thereto, A dampening water composition containing polypropylene glycol, a compound having an ether structure in which ethylene oxide and / or propylene oxide is added to acetylenic diol, a film-forming water-soluble polysaccharide, a desensitizing agent, and a PH buffering agent. Not only obtains stable quality in offset printing, but also volatilizes the dampening solution components that have permeated the paper. It is possible to print the printed matter never.
[0023]
In the fountain solution composition for lithographic printing of the present invention, low foaming properties and good dispersibility and solubility in water, which are necessary requirements for fountain solution, and emulsification into ink on a printing press Heated at 110 ° C for 1 hour, which was selected on the basis that the printability is appropriate, the erosion to the image area of the printing plate is low and the printing durability is good, and the overall printability is excellent. It contains at least one compound represented by the following general formula (1) or (2) as a compound that does not volatilize.
[0024]
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[0025]
(In the formula (1), R ¹ Represents hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 1 to 12 carbon atoms. A and c in the formula are integers of 0 or more and 3 ≦ a + c ≦ 15, and b is an integer of 7 ≦ b ≦ 40. )
[0026]
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[0027]
(In the formula (2), R ² , R ³ Represents hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 1 to 12 carbon atoms. In the formula, d, e, f, and g are integers of 0 or more, and are integers of 3 ≦ d + f ≦ 15 and 7 ≦ e + g ≦ 40. )
The total content of these compounds (1) and (2) in the fountain solution composition for lithographic printing is preferably from 0.01 to 10% by mass. More preferably, it is used in the range of 0.01 to 5% by mass.
[0028]
These compounds may be used alone or in combination of two or more. However, when the content as a fountain solution material for lithographic printing is less than 0.01% by mass, the wetting of the non-image area of the printing plate surface becomes poor, and the periphery of the image area is easily stained with ink. When the content exceeds 10% by mass, it goes without saying that it is disadvantageous in terms of cost, and the image portion of the printing plate surface is easily eroded.
[0029]
In the present invention, the following surfactants may be used alone or in combination of two or more in order to form a uniform water film on a roller for supplying dampening water to the printing plate. Specific examples of the anionic surfactant include, for example, fatty acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, and polyoxyethylene alkyl sulfophenyl. Ether salts, N-methyl-N-oleyltaurine sodium salts, N-alkylsulfosuccinic acid monoamide disodium salts, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, alkyl phosphates, polyoxyethylene alkyl ethers Phosphate salts and the like.
[0030]
Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, and glycerin fatty acid partial ester. Compounds, sorbitan fatty acid partial esterified products, pentaerythritol fatty acid partial esterified products, propylene glycol monofatty acid esters, sucrose fatty acid partial esterified products, polyoxyethylene sorbitan fatty acid partial esterified products, polyoxyethylene sorbitol fatty acid partial ester Compounds, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esterified compounds, polyoxyethylated castor oils, polyoxyethylene glycol Phosphoric fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, polyoxyethylene-poly Oxypropylene block polymers and the like can be mentioned.
[0031]
Other fluorine-based surfactants and silicon-based surfactants can also be used. Specific examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylenepolyamine derivatives. However, when used, it is appropriate that the content of these surfactants is 10.0% by mass or less in the fountain solution composition for lithographic printing.
[0032]
Furthermore, 0.02 to 10% by mass of polypropylene glycol is added to the fountain solution composition for lithographic printing of the present invention. By adding this compound, among the compounds of the above-mentioned (A), those having a strong emulsifying power of the ink are reduced in the amount added, and those having a weak emulsifying power of the ink are reinforced, Appropriate emulsification characteristics can be realized, and high printing durability can be realized by suppressing erosion of the printing plate image area. Preferably, the addition amount is 0.05 to 5% by mass.
[0033]
Furthermore, the fountain solution composition for lithographic printing of the present invention reduces the surface tension so as to uniformly supply the fountain solution to the printing plate surface even when the printing machine is rotating at high speed. Alternatively, a compound having a polyether structure to which propylene oxide is added is added. The content of these compounds in the fountain solution composition for lithographic printing is from 0.01 to 6% by mass, preferably from 0.025 to 5% by mass.
[0034]
Further, the fountain solution composition for lithographic printing of the present invention prevents the occurrence of stains on printed matter such as background stains on the aluminum substrate surface, which is a non-image area of the printing plate surface, and entanglement stains of halftone dots. For the purpose, as the film-forming water-soluble polysaccharide, specifically, gum arabic, dextrin, carboxymethylcellulose (CMC), and acetylated starch. Add hydridoxypropyl methylcellulose (HPMC), hydroxypropylcellulose (HPC), hydroxyethylcellulose (HEC), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyacrylic acid, sodium alginate. The content of these compounds in the fountain solution composition for lithographic printing is 0.002 to 0.1% by mass, preferably 0.005 to 0.05% by mass.
[0035]
Further, the fountain solution composition for lithographic printing of the present invention has an adhesion of emulsified dusty ink on the surface of the aluminum substrate which is a non-image area of the printing plate surface, and a foreign matter due to eluted substances from paper. For the purpose of preventing adhesion, a water-soluble organic acid or inorganic acid is specifically added as a desensitizing agent. Examples of the organic acid include citric acid, ascorbic acid, malic acid, tartaric acid, lactic acid, gluconic acid, oxalic acid, malonic acid, levulinic acid, phytic acid, and organic phosphonic acid. Examples of the inorganic acid include condensed phosphoric acid typified by phosphoric acid, pyrophosphoric acid, and polyphosphoric acid, as well as nitric acid and sulfuric acid. The content of these compounds in the fountain solution composition for lithographic printing is 0.001 to 0.1% by mass, preferably 0.002 to 0.05% by mass.
[0036]
Further, the fountain solution composition for lithographic printing of the present invention has a pH buffer for the purpose of preventing pH fluctuation due to water such as tap water used as a fountain solution or leaching from ink or paper. Specifically, a salt of a water-soluble organic acid or inorganic acid is added as the agent. Examples of the organic acid include citric acid, ascorbic acid, malic acid, tartaric acid, lactic acid, gluconic acid, hydroxyacetic acid, oxalic acid, malonic acid, levulinic acid, phytic acid, and organic phosphonic acid. , Nitric acid, sulfuric acid and the like. Alkali metal salts, alkaline earth metal salts, or ammonium salts of these organic acids and / or inorganic acids, and organic amine acids are used. The content of these compounds in the fountain solution composition for lithographic printing is 0.005 to 0.1% by mass, and preferably 0.01 to 0.1% by mass.
[0037]
In addition, in the present invention, a silicon-based antifoaming agent and / or a fluorine-based antifoaming agent are preferably used as the antifoaming agent. Among them, any of an emulsified dispersion type and a solubilized type can be used. The content of these compounds in the fountain solution composition for lithographic printing is about 1% by mass.
[0038]
In the present invention, imidazole derivatives, 4-isothiazolin-3-one derivatives, benztriazole derivatives, amidines or guandinines are used as preservatives for preventing water spoilage during long-term use in a fountain solution circulation device of a printing press. , Quaternary ammonium salts, pyridine or quinoline derivatives, diazine or triazole derivatives, oxazole or oxazine derivatives, and the like. The preferred amount of addition is an amount that exerts a stable effect on bacteria, mold, yeast, etc., and varies depending on the type of bacteria, mold, yeast, etc., but in a lithographic printing dampening solution composition of these compounds. Is preferably in the range of 4% by mass or less, and it is preferable to use two or more preservatives which are effective against various bacteria, molds and yeasts.
[0039]
In the present invention, a water-soluble food colorant or the like is preferable as the colorant. For example, as a yellow colorant, CINo. 19140, 15985, and CI Red. 16185, 45430, 16255, 45380, 45100, and as the purple pigment, CINo. 42640, and as a blue pigment, CINo. 42090, 73015 and CINo. 42095 and the like.
[0040]
The chelating agents used in the fountain solution for lithographic printing of the present invention include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1-hydroxyethane-1,1- Examples thereof include diphosphonic acid, aminotri (methylenephosphonic acid) and the like, and sodium salts, potassium salts, and organic amine salts thereof. These chelating agents are selected from those which are stably present in the concentrated fountain solution and do not inhibit printability. The content of these compounds in the fountain solution composition for lithographic printing is suitably 10% by mass or less.
[0041]
The fountain solution composition for a lithographic printing plate of the present invention is diluted 10 to 100 times with water such as tap water or well water and used on a lithographic printing press.
[0042]
(two)
In the fountain solution composition for lithographic printing of the present invention, among the compounds of the above (A), the emulsification stability to ink is ensured, the erosion to the printing plate image portion is small, and the image is formed during printing. In order to obtain good printing durability without the line falling off, the compound represented by the general formula (3) ¹ Is hydrogen, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 3 to 4 carbon atoms, b is an integer of 15 to 40, a and c are each an integer of 1 to 5, A compound satisfying ≦ a + c ≦ 10 may be used.
[0043]
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[0044]
Preferably, R ¹ Is hydrogen, an alkyl group having 1 to 2 carbon atoms or an alkenyl group having 3 carbon atoms, b is an integer of 25 to 40, a and c are each an integer of 1 to 5, and 3 ≦ a + c ≦ 10. is there.
(three)
Further, in the fountain solution composition for lithographic printing of the present invention, the erosion property to the printing plate image is reduced, and the generation of ink dirt in the fountain water and the dirt on the roller of the watercraft are reduced, and the emulsification property to the ink is reduced. In order to further improve the above, polypropylene glycol having a property of not volatilizing even when heated at 110 ° C. and having a molecular weight of 200 to 2,000 represented by the following general formula (4) may be used.
[0045]
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[0046]
Within this molecular weight range, the solubility in water is relatively good, and it is easy to use in producing dampening water compositions. A more preferred molecular weight is from 200 to 1,000.
[0047]
(Four)
Further, in the fountain solution composition for lithographic printing of the present invention, the compound of the above (C) according to claim 1, which does not volatilize even when heated at 110 ° C. for 1 hour, represented by the following general formula (5): Ether structure in which 3 to 10 mol of ethylene oxide is added to two hydroxyl groups of 2,4,7,9-tetramethyl-5-decyne-4,7-diol and / or 0 to 5 mol of propylene oxide is added And a compound having an HLB in the range of 8 to 15 may be used.
[0048]
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[0049]
Among these compounds, compounds to which ethylene oxide is added in less than 3 moles may volatilize under the conditions of Method 24, and in addition, have low solubility in water and low emulsification stability in inks. Not suitable for In addition, those added with less than 3 ethylene oxide may volatilize when heated at 110 ° C. for 1 hour, and compounds added in excess of 10 moles may have insufficient emulsifying properties of the ink and may cause stains and the like. The printed matter is stained, and the ability to lower the surface tension required to form a uniform water film on the head roller of the printing press is low, which is not suitable for this application. Also, if propylene oxide is added in excess of 5 mol, the ink may be excessively emulsified when the amount of addition is large or when the ink is concentrated during use in printing. There is a high possibility that the soaked water penetrates into a so-called roller baldness, and the erosion to the printing plate image portion is further increased, and the printing durability tends to decrease, such as the image falling off during printing. Not suitable for this application.
[0050]
Incidentally, HLB is an abbreviation of Hydrophile-Lipophile Balance and indicates a balance between hydrophilicity and lipophilicity of a surfactant. That is, it is a measure of how much the hydrophilicity of the hydrophilic group is greater than the hydrophobicity of the hydrophobic group.
[0051]
On the other hand, if the HLB is out of the range of 8 to 15, the emulsifying property to the ink is not appropriate or the erosion property to the printing plate image portion becomes strong as described above, so that it is not suitable for this use. Preferably, it is a compound to which 3 to 6 moles of ethylene oxide has been added and / or 0 to 3 moles of propylene oxide has been added from the viewpoint of good printability, and has an HLB of 8 to 13.
[0052]
(5)
Furthermore, the fountain solution composition of the present invention contains, as film-forming water-soluble polysaccharides, hydroxypropylmethylcellulose (HPMC), hydroxypropylcellulose (HPC), and hydroxyethylcellulose (HPMC) which do not volatilize even when heated at 110 ° C. for 1 hour. At least one kind selected from HEC) having a molecular weight of 10,000 to 35,000 may be used.
[0053]
When the molecular weight of each compound is less than 10,000, the viscosity is low, and it is difficult to obtain the viscosity necessary to uniformly wet the printing plate surface with water so that the non-image area is not stained with ink. Is greater than 45,000, the viscosity is excessive, the solubility and dispersibility in water are reduced, the fluidity in the piping of the dampening solution replenisher is reduced, and the replenishment amount becomes unstable. Not suitable. Preferably, these compounds have a molecular weight of 10,000 to 350,000 in consideration of solubility and dispersibility, viscosity increase and printability.
[0054]
(6)
Furthermore, the fountain solution for lithographic printing of the present invention does not volatilize even when heated at 110 ° C. for 1 hour as a desensitizing agent, citric acid, malic acid and tartaric acid as organic acids, and phosphoric acid and pyrroline as inorganic acids. Condensed phosphoric acids represented by acids and polyphosphoric acids may be used. These compounds are suitable for this application from the viewpoint of the surface smoothing effect of the non-image area of the printing plate, the printing suitability such as running up, and the emulsifying properties of the ink. In addition, these compounds can be used alone or in combination of two or more. Preferred are citric acid, malic acid, pyrophosphoric acid, and polyphosphoric acid.
[0055]
(Seven)
Furthermore, the lithographic printing dampening solution of the present invention does not volatilize even when heated at 110 ° C. for 1 hour as a PH buffer. For organic acids, citric acid, ascorbic acid, malic acid, tartaric acid, gluconic acid, oxalic acid, As malonic acid, phytic acid, organic phosphonic acid, or inorganic acid, alkali metal salts, alkaline earth metal salts of phosphoric acid, nitric acid, and sulfuric acid, or ammonium salts or organic amine salts may be used. These compounds prevent the adhesion of ink and dirt components to enhance the desensitization effect of the non-image area of the printing plate, prevent the occurrence of so-called background smear on the printed matter, and at the same time selectively prevent the image area from Ink adhesion can be maintained, and in addition, the ink is less likely to be excessively emulsified, and has the effect of preventing dust stains in the dampening water. Preferred are alkali metal salts and ammonium salts of citric acid, ascorbic acid, malic acid and tartaric acid.
[0056]
【Example】
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition,% indicates mass% unless otherwise specified.
[0057]
[Examples 1 to 4 and Comparative Examples 1 to 5]
In Examples and Comparative Examples according to the present invention, as a compound represented by the general formula (1), PE-62 (product name, R ¹ = H, a + c = 10, b = 30), Epan 410 (product name of Nippon Oil & Fats Co., Ltd., R ¹ = H, a + c = 3, b = 21), Unisafe NXS-4001 (product name of Nippon Oil & Fats Co., Ltd., R ¹ = 6 to 10 carbon atoms, a + c = 9, b = 24), 60SH-06 (Shin-Etsu Chemical Co., Ltd. product name, hydroxypropyl methylcellulose (HPMC), average molecular weight 35,000) as a film-forming water-soluble polysaccharide, Klucel -L (Sansei Corporation product name, hydroxypropyl cellulose (HPC), average molecular weight 95000), HPC-L (Nippon Soda Co., Ltd. product name, hydroxypropyl cellulose (HPC), average molecular weight 230,000), defoaming agent Surfynol 465 (trade name of Air Products Co., Ltd.) was used as the compound represented by T (Nikko Chemical product name) and the general formula (3). According to the composition of Table 1, the fountain solution composition of each example was prepared. The unit is gram, and water was added as the balance other than the composition shown in Table 1 to make the total amount of each of them 1000 g.
[0058]
The dampening solutions of Examples 1 to 4 and Comparative Examples 1 to 5 of the present invention were diluted 50 times with water (concentration: 2.0%), and the following measurements and tests were performed. Table 2 shows the results.
[0059]
(A) Measurement of volatile organic compound component (VOC)
The volatile organic compound component (VOC) was measured based on Method 24 defined by the United States Environmental Protection Agency (EPA) (United States Environmental Protection Agency). Table 2 shows the results. The meanings of the symbols in the evaluation results are as follows:
○ ・ ・ ・ No VOC,
Δ ... contains a VOC component of less than 5%,
X: Contains VOC component of 5.0% or more.
[0060]
The method of measuring volatile organic compound components (VOC) based on Method 24 is as follows. A certain amount of a sample is weighed, heated at 110 ° C. for 1 hour in an oven, the amount of the volatile component is calculated, and the same amount of sample is further analyzed. This is a measurement method in which the amount of water is subtracted from the amount of volatile components by measuring the amount of water with a Karl Fisher measuring device to obtain the amount of volatile organic compound (VOC).
[0061]
(B) Plate erosion test
A CTP plate (TCC-603; manufactured by Kodak Polychrome Graphics Co., Ltd.) having a 50% halftone dot and a solid image was prepared, immersed in each dampening solution adjusted to 2% for 5 hours, and an image area was formed. Was tested for erosion. Table 2 shows the results. The meanings of the symbols in the evaluation results are as follows:
○ ・ ・ ・ No image area erosion,
Δ: Erosion is seen at the liquid interface,
×: 50% halftone dots are eroded, and image areas are removed.
[0062]
In addition, printing tests were performed on the fountain solutions 1 to 4 of the present invention and Comparative Examples 1 to 5. The printing conditions are as follows:
Printing machine: Roland R-704 (Roland)
Printing speed: 10,000 sheets / hour
Printing paper: Jujo diamond coat 57.5kg / A all,
Fountain solution mechanism: Rolandmatic,
Temperature and humidity: 23-24 ° C, 50-60% RH,
Ink: Varius G indigo-N (manufactured by Dainippon Ink and Chemicals, Inc.),
Printing plate: TCC-603 (CTP version; Computer to Plate; manufactured by Kodak Polychrome Graphics Co., Ltd.).
The following printing tests (c) to (f) were performed under the above conditions. The results are shown in Table 2 below.
[0063]
(C) Suitability for water width
The lower limit is the water scale at which the tangling of halftone dots occurs on the scale of the water supply amount of the printing press (scales 1 to 99, also the scale of the number of rotations of the water supply roller), and the water with the density of the solid portion of the paper 0.1 reduced. The range between the lower limit and the upper limit using the scale as the upper limit was examined. The results are shown in Table 2 below. The meanings of the symbols in the evaluation result are as follows:
○ ・ ・ ・ Water width of 35 scales or more,
△ ・ ・ ・ Water width within 30 ~ 25 scale,
×: Water width of 25 scales or less.
[0064]
(D) Water supply roller stability
After 10,000 sheets of printing, the degree of contamination of the water supply roller was observed. The results are shown in Table 2 below. The meanings of the symbols in the evaluation result are as follows:
○ ・ ・ ・ No dirt,
△: There is some dirt,
×: Stained.
[0065]
(E) Desensitization suitability
In the printing test, when printing was stopped and left again for about 1 hour and then reprinted, the non-image area was examined for any stains removed. The results are shown in Table 2 below. The meanings of the symbols in the evaluation result are as follows:
・ ・ ・: All ink drops from non-image areas,
△ ・ ・ ・ Some ink remains,
×: Ink remains.
[0066]
(F) Emulsification suitability
In the printing test, the emulsified state of the ink on the ink kneading roll and the paper surface was examined. The results are shown in Table 2 below. The meanings of the symbols in the evaluation result are as follows:
○ ・ ・ ・ Good,
△ ... Somewhat bad,
×: Bad.
[0067]
[Table 1]

[0068]
[Table 2]

[0069]
From the results of the VOC component measurement in Table 2, the fountain solution to which volatile organic solvents such as butyl cellosolve, propylene glycol, and a compound that is difficult to evaporate as proposed in Patent Document 28 were added, as in Comparative Example 1, and Comparative Example 2 It can be seen that the VOC component can be detected even in a fountain solution to which low molecular alkyl ethers such as propylene glycol-n-butyl ether and ethylene glycol-n-butyl ether are added.
[0070]
In the erosion test of the plate, in Comparative Example 3 in which the compound represented by the general formula (1) of the present invention and polypropylene glycol (molecular weight 3000) were used in combination, polypropylene glycol having a large molecular weight had high permeability to the image portion of the plate. It is not preferable because the erosion of the wire becomes strong.
[0071]
In the printing test, oxalic acid is slightly inferior in desensitization suitability.
[0072]
Regarding the suitability for the standard water scale and the suitability for the water width, the conventional organic solvent type Comparative Example 1 and Examples 1 to 4 all had the same suitability. Further, Comparative Example 2, which did not include Surfynol 465, was inferior in water width to the Example. It is considered that the addition of Surfynol 465 improved the water width suitability.
[0073]
As for the stability of the water supply roller, the one obtained by adding the compound represented by the general formula (1) of the present invention and polypropylene glycol having a molecular weight of 700 is good. ¹ When a compound having a group having a large number of carbon atoms or a polypropylene glycol having a molecular weight as large as 3000 is added, the water supply roller is relatively easily stained.
[0074]
From the above, it can be seen from the test results in Table 2 that the fountain solution of the present invention has printability equivalent to that of a conventional organic solvent-containing fountain solution and has good performance.
[0075]
【The invention's effect】
The fountain solution composition for lithographic printing containing the fountain solution material for lithographic printing according to the present invention is not only a fountain solution composition containing no IPA and having excellent liquid stability, but also containing a conventional organic solvent. A fountain solution composition having printability equivalent to that of a mold fountain solution and containing no volatile components according to the above-mentioned Method 24 standards and taking into consideration global environmental protection. The fountain solution for lithographic printing prepared by diluting the fountain solution composition according to the present invention has excellent printability, and has a fountain solution characteristic that the quality of the printing plate, especially the CTP plate, is not deteriorated by plate tray or the like. Fountain solution composition.

Claims (7)

A fountain solution composition for lithographic printing, comprising the following components (A) to (F), which are compounds that do not volatilize when heated at 110 ° C. for 1 hour.
(A) At least one compound represented by the following general formula (1) or (2).

(In the formula (1), R ¹ represents hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 1 to 12 carbon atoms. In the formula, a and c are integers of 0 or more and 3 ≦ a + c ≦ 15, and b is an integer of 7 ≦ b ≦ 40.)

(In the formula (2), R ² and R ³ represent hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 1 to 12 carbon atoms. In the formula, d, e, f, and g are 0 or more. Where 3 ≦ d + f ≦ 15 and 7 ≦ e + g ≦ 40.)
(B) polypropylene glycol.
(C) A derivative having a polyether structure obtained by adding ethylene oxide and / or propylene oxide to acetylene diol.
(D) a film-forming water-soluble polysaccharide.
(E) Desensitizer.
(F) PH buffer. The fountain solution composition for lithographic printing according to claim 1, wherein the compound (A) is a compound represented by the following general formula (3).

(In the formula (3), R ¹ represents hydrogen, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 3 to 4 carbon atoms, b represents an integer of 15 to 40, and a and c each represent 1 Represents an integer of 5 to 3, and 3 ≦ a + c ≦ 10.) The fountain solution composition for lithographic printing according to claim 1, wherein the component (B) is polypropylene glycol (PPG) represented by the following general formula (4), and has a molecular weight of 200 to 2,000.

The above-mentioned (C) is represented by the following general formula (5), and ethylene oxide (EO) is added to two hydroxyl groups of 2,4,7,9-tetramethyl-5-decyne-4,7-diol by 3 to The fountain solution composition for lithographic printing according to claim 1, wherein the compound has a polyether structure to which 10 mol is added and / or 0 to 5 mol of propylene oxide (PO) is added, and HLB is 8 to 15. object.

(In the formula (5), w + y = 0 to 5 and v + x = 3 to 10.) The above film-forming water-soluble polysaccharide (D) is one or more selected from the group consisting of hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC) and hydroxypropylmethylcellulose (HPMC), and the average The fountain solution composition for lithographic printing according to claim 1, having a molecular weight of 10,000 to 450,000. The desensitizing agent of (E) is at least one selected from citric acid, malic acid and tartaric acid as organic acids and phosphoric acid and condensed phosphoric acids as inorganic acids. 4. A fountain solution composition for lithographic printing according to claim 1. The fountain solution composition for lithographic printing according to claim 1, wherein the PH buffer (F) is an organic acid or a salt thereof.