JP2004285255A - Resin for printing ink, and printing ink using the same - Google Patents
Resin for printing ink, and printing ink using the same Download PDFInfo
- Publication number
- JP2004285255A JP2004285255A JP2003080558A JP2003080558A JP2004285255A JP 2004285255 A JP2004285255 A JP 2004285255A JP 2003080558 A JP2003080558 A JP 2003080558A JP 2003080558 A JP2003080558 A JP 2003080558A JP 2004285255 A JP2004285255 A JP 2004285255A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- printing ink
- rosin
- parts
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、印刷インキ用樹脂及び該印刷インキ用樹脂を使用した印刷インキに関し、具体的には、フェノール樹脂を一切含まない樹脂であって、印刷インキに使用した場合、非芳香族系溶剤に対する溶解性に優れ、オフセット印刷において要求される優れたインキ性能を与える印刷インキ用樹脂、及び該印刷インキ用樹脂を使用した印刷インキに関するものである。
【０００２】
【従来の技術】
従来から、高分子量、高粘度、高軟化点、インキ用溶剤に対する優れた溶解性等の諸性質を有し、オフセット印刷インキに用いた場合には印刷適性に優れることから、オフセット印刷インキに使用するインキ用樹脂としては、ロジン類をレゾール型フェノール樹脂で変性したロジン変性フェノール樹脂が広く使用されている（例えば、特許文献１、特許文献２参照）。ロジン変性フェノール樹脂は、顔料への濡れが良く、顔料が均一分散しやすいという特長を有するとともに、ゲル化剤との反応によって印刷インキに適した物性の樹脂ワニスを得られるため、オフセット印刷インキ用樹脂として、重用されており、高速印刷・高光沢を支える樹脂として、現在、国内では年間約数万トンが消費されている。このロジン変性フェノール樹脂は、ロジン類、アルキルフェノールホルムアルデヒド縮合物、及び多価アルコールの反応生成物から構成される。
【０００３】
ロジン変性フェノール樹脂は、アルキルフェノールホルムアルデヒド縮合物をその主原料の一つとしており、アルキルフェノールホルムアルデヒド縮合物の合成には、アルキルフェノールとホルムアルデヒドとを、アルカリまたは酸触媒を用いて反応させる方法が用いられている。しかし、この合成過程では、有害な揮発性有機化合物（ＶＯＣ）であるホルムアルデヒドを含有する廃水が発生するため、近年、ロジン変性フェノール樹脂に由来する大気汚染などの環境問題や作業環境上の問題が指摘されている。また、ロジン変性フェノール樹脂からなるインキを用いる印刷工程においては、インキの加熱乾燥時にホルムアルデヒドが発生することも以前から指摘されていた。さらに、アルキルフェノールは近年内分泌攪乱物質（いわゆる環境ホルモン）として疑われてきており、我が国や合衆国、欧州においても内分泌攪乱作用を調査する優先物質に指定されている。我が国においては、２００１年にノニルフェノールが、２００２年にはオクチルフェノールが内分泌攪乱作用を有する物質として結論付けられた。
【０００４】
そこで、ロジン変性フェノール樹脂の諸問題を軽減するために従来から種々の試みがなされてきた。例えば、石油樹脂、不飽和カルボン酸又はその無水物、脂肪族多塩基酸、多価アルコールとを加熱反応させて得られる樹脂（例えば、特許文献３参照）、樹脂酸とα，β−エチレン性不飽和カルボン酸またはその無水物及びＣ４〜Ｃ５のトリメチロールアルカン又はアルケンを反応させてなることを特徴とする樹脂（例えば、特許文献４参照）、ロジン類（ａ）、極性基含有石油樹脂（ｂ）、脂肪族モノアルコール類、脂肪族ジアルコール類、脂肪族モノアミン類及び脂肪族モノエポキシ類からなる群より選択される少なくとも１種（ｃ）、並びにポリオール類（ｄ）を反応させてなるポリエステル樹脂（例えば、特許文献５参照）、重合性石油樹脂（ａ）と不飽和カルボン酸類（ｂ）を共重合させてなるポリマー（Ａ）、並びに▲１▼脂肪族モノアルコール類、▲２▼脂肪族モノアミン類及び▲３▼脂肪酸類からなる群より選択される少なくとも一種（ｃ）を反応させてなる印刷インキ用樹脂（例えば、特許文献６参照）などが提案されている。
【０００５】
これらの各公報に開示されている印刷インキ用樹脂は、いずれもアルキルフェノールホルムアルデヒド縮合物を原料とせず、しかもロジン変性フェノール樹脂に匹敵する特性（高分子量、高粘度、高軟化点、高溶解性）を有するものであると記載されている。しかしながら、オフセット印刷インキ用樹脂に対する要求性能の中で、特に非芳香族系溶剤に対する溶解性に関して、前記各公報記載の印刷インキ用樹脂は充分満足するものではない。更に、最近は印刷インキの低コスト化、印刷の高速化等、印刷インキ用樹脂に対する要求は多岐に亘っているため、今までのところロジン変性フェノール樹脂以外には、前述の要求される諸性能をすべて満足することは困難であり、したがって脱フェノール樹脂の技術は未だ完成されてはいないといえる。
【０００６】
上記の理由により、人体に有害なフェノール類やホルムアルデヒドを合成過程で使用せず、しかもロジン変性フェノール樹脂に匹敵する特性を備えた印刷インキ用樹脂の開発が望まれている。
【特許文献１】
特開平９−２６８２１１号公報
【特許文献２】
特開２００１−１０６７５４号公報
【特許文献３】
特開２００１−３１７１８号公報
【特許文献４】
特開２０００−１４３７８５号公報
【特許文献５】
特開２００１−２３３９４７号公報
【特許文献６】
特開２００２−９７２３２号公報
【０００７】
【発明が解決しようとする課題】
本発明は、合成過程でフェノール類、ホルムアルデヒドを使用せず、オフセット印刷インキ用樹脂として好適な程度に樹脂粘度が高く、非芳香族系溶剤に対する優れた溶解性を示す、新規な印刷インキ用樹脂、及び該印刷インキ用樹脂を使用した印刷インキを提供することを課題とする。
【０００８】
【課題を解決するための手段】
本発明は、アクリル酸１モル付加ロジン（Ａ）、重合ロジン（Ｂ）、アルケニル置換コハク酸又はその無水物（Ｃ）、多価アルコール（Ｄ）、及び必要に応じて、さらにα，β−不飽和カルボン酸付加石油樹脂（Ｅ）からなる混合物を、加熱反応させて得られる樹脂であって、アルケニル置換コハク酸又はその無水物（Ｃ）を、アクリル酸１モル付加ロジン（Ａ）及び重合ロジン（Ｂ）の総量１００重量部に対して、５〜２０重量部使用することを特徴とする樹脂からなる印刷インキ用樹脂に関するものである。
【０００９】
また、本発明は、前記印刷インキ用樹脂、石油系溶剤、乾性油及び顔料を必須成分とする印刷インキに関するものである。
【００１０】
以下に、本発明の構成をより詳しく説明する。
【００１１】
【発明の実施の形態】
アクリル酸１モル付加ロジン（Ａ）は、ロジン類とアクリル酸とを加熱付加反応して得ることができる。本発明のロジン類とは、ガムロジン、トール油ロジン、ウッドロジン、又はこれらの混合物が挙げられる。本発明は、アビエチン酸及びその類縁体を主成分とする樹脂酸から構成されるロジン類と、アクリル酸とを加熱反応して得られるアクリル酸１モル付加ロジン（Ａ）を使用することを特徴としている。ロジン類とアクリル酸との反応はディールスアルダー反応であり、この反応は、例えば、反応温度は１２０〜３００℃、好ましくは１５０〜２６０℃、反応時間は３〜８時間で行うことができる。なお、未反応のアクリル酸が残留すると得られる印刷インキ用樹脂の溶剤に対する溶解性が低下するため、アクリル酸１モルに対してロジン類１モル以上、好ましくは、アクリル酸：ロジン類＝１：１（モル比）を使用してアクリル酸１モル付加ロジン（Ａ）を得るのが良い。
【００１２】
また、アクリル酸１モル付加ロジン（Ａ）の使用量としては、使用する原料の総量１００重量部に対して、２５〜７０重量部が好ましい。アクリル酸１モル付加ロジン（Ａ）の使用量が２５重量部に満たない場合は、分子量の高い樹脂が得られない。また７０重量部を超える場合は樹脂の分子量の制御が難しくなる。
【００１３】
重合ロジン（Ｂ）は、ロジン類を硫酸触媒により重合したもので、２量体ロジンを主成分として、他に単量体、場合によっては３量体以上のものを含む混合物である。重合ロジン（Ｂ）は本発明の印刷インキ用樹脂に適正な分子量と溶解性とを付与するはたらきがあり、その使用量は、アクリル酸１モル付加ロジン（Ａ）及び重合ロジン（Ｂ）の総量１００重量部に対して２５〜６０重量部であり、好ましくは３０〜５０重量部である。重合ロジン（Ｂ）の使用量が、２５重量部に満たない場合は樹脂の分子量の制御が難しくなり、６０重量部を超える場合にはコスト高となり、好ましくない。
【００１４】
アルケニル置換コハク酸又はその無水物（Ｃ）は、直鎖又は分岐状の、α−オレフィン又は内部オレフィンに、（無水）マレイン酸を付加することで得られ、炭素数１２〜１８のオレフィンと（無水）マレイン酸との付加物が好ましく使用できる。本発明ではアルケニル置換コハク酸又はその無水物（Ｃ）を印刷インキ用溶剤に対する溶解性付与剤として使用する。アルケニル置換コハク酸又はその無水物（Ｃ）の添加量は、アクリル酸１モル付加ロジン（Ａ）及び重合ロジン（Ｂ）の総量１００重量部に対して、５〜２０重量部である。アルケニル置換コハク酸又はその無水物（Ｃ）の添加量が、５重量部に満たない場合は樹脂の溶解性の向上効果が低く、又２０重量部を超える場合には樹脂の融点が下がり、好ましくない。
【００１５】
多価アルコール（Ｄ）は、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール、ブタンジオール、ヘキサンジオール、オクタンジオール、ノナンジオール、ネオペンチルグリコール等の２価アルコール；グリセリン、トリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、ソルビトール等の３価以上のアルコール；が挙げられる。これらの中でも、樹脂の分子量、融点等を適正に調整する面から、グリセリン又はペンタエリスリトールが好ましい。多価アルコール（Ｄ）は、他の成分とエステル化反応することにより印刷インキ用樹脂の分子量及び粘度を上げるはたらきがあり、その添加量はアクリル酸１モル付加ロジン（Ａ）、重合ロジン（Ｂ）、およびα，β−不飽和カルボン酸付加石油樹脂（Ｅ）の総カルボキシル基１当量に対して、０．８〜１．２当量である。多価アルコール（Ｄ）の添加量が、０．８当量に満たない場合、また１．２当量を超える場合は、得られる印刷インキの乳化性、耐水性が悪くなり好ましくない。
【００１６】
α，β−不飽和カルボン酸付加石油樹脂（Ｅ）は、例えばビニルトルエン、α−メチルスチレン、シクロペンタジエン、ジシクロペンタジエン、メチルブテン、イソプレン、ペンテン、シクロペンテン、ペンタジエン等を主成分とする公知の石油樹脂に、α，β−不飽和カルボン酸を加熱付加反応させることによって得られる。α，β−不飽和カルボン酸としては公知のものが使用出来、具体的には、フマル酸、マレイン酸、イタコン酸、クロトン酸；またはこれらの無水物；などが挙げられる。これらのα，β−不飽和カルボン酸付加石油樹脂（Ｅ）の中でも、ジシクロペンタジエンを主成分とする石油樹脂に、マレイン酸又はその無水物を付加させたものが好ましい。α，β−不飽和カルボン酸付加石油樹脂（Ｅ）は、印刷インキを調製する際、石油系溶剤に対する溶解性を向上させるはたらきがある。α，β−不飽和カルボン酸付加石油樹脂（Ｅ）は、使用する原料全量に対して、２０〜４０重量部使用するのが好ましい。α，β−不飽和カルボン酸付加石油樹脂（Ｅ）の使用量が２０重量部に満たない場合は、溶解性の向上効果が低く、４０重量部を超える場合は顔料の分散性が悪くなり、インキにした場合、ミスチングが発生しやすくなる。
【００１７】
本発明に係る印刷インキ用樹脂は、前記（Ａ）〜（Ｄ）成分、及び必要に応じてさらに（Ｅ）成分を混合・加熱することによりエステル化反応を行って製造する。加熱する温度は、１５０〜２８０℃が好ましく、２００〜２６０℃であればより好ましい。混合・加熱方法は、特に限定されず、（Ａ）〜（Ｅ）成分を混合した後に加熱し反応させる方法、多価アルコール（Ｄ）成分以外をあらかじめ溶融可能温度まで加熱して混合した後、多価アルコール（Ｄ）成分を添加して、反応温度まで加熱して行う方法などを適用することができる。
【００１８】
本発明においては前記（Ａ）〜（Ｅ）成分の他に、本発明の効果を損なわない範囲で、他の成分を併用することが出来、具体的には分子量調整などの目的で、ロジン類、アクリル酸以外のα，β−不飽和カルボン酸とロジン類とを加熱付加反応して得られるα，β−不飽和カルボン酸付加ロジン、脂肪酸等を使用することができる。
【００１９】
本発明に係る印刷インキ用樹脂の物性は、酸価が２５以下、重量平均分子量が１〜１５万、融点が１２０℃以上、印刷インキ用溶剤との溶解性（トレランス）は、２（ｇ／ｇ）以上が望ましい。ここで印刷インキ溶剤との溶解性は次の方法で求められる。
溶解性（トレランス）：樹脂２ｇと溶剤（０号ソルベント）２ｇを１９０〜２００℃で１５分間溶解し、２５℃で同じ溶剤を滴下しつつ白濁するまでの、樹脂１ｇ当たりの全溶剤量（ｇ）。
したがってこの数値は大きいほど良好な溶解性を示す。
【００２０】
本発明に係る印刷用インキを調製する方法を以下に説明する。
【００２１】
本発明に係る印刷インキは、オフセット印刷に使用されるものであり、前述のようにして得られた本発明の印刷インキ用樹脂、石油系溶剤、乾性油及び顔料を必須成分とし、具体的には次の組成を混錬して得るのが好ましい。
印刷インキの組成：（重量％）
顔料 １０〜２５
樹脂ワニス ４０〜８０
乾性油 ０〜１０
石油系溶剤 ５〜４０
乾燥促進剤 ０〜 ２
顔料としては公知のものが使用出来、例えばカーボンブラック、フタロシアニンブルー、カーミン６Ｂ、レーキレッドＣ、ベンジジンイエローなどが挙げられる。これらの顔料は被印刷物に色付けをするためのものであり、必要に応じて、黒色、黄色、紅色、藍色等の顔料が選択される。
【００２２】
樹脂ワニスを調製する方法は次の通りである。攪拌機、水分離冷却器、及び温度計付セパラブルフラスコに、本発明の印刷インキ用樹脂３０〜６０重量％、乾性油１０〜３０重量％、石油系溶剤２０〜６０重量％を仕込み、窒素気流下で１８０〜２００℃で１時間溶解して元ワニスを得る。得られた元ワニスを１００℃まで冷却した後、ゲル化剤０．５〜２重量％を添加する。更に、１８０℃まで昇温し、３０分保温して樹脂ワニスを調製する。
【００２３】
乾性油としては、亜麻仁油、桐油等が挙げられ、亜麻仁油が好適に使用される。
【００２４】
石油系溶剤は、インキ粘度の調整や印刷後の乾燥性を促進するために添加され、主に沸点が２００〜４００℃の炭化水素系の溶剤が使用できる。具体的には０号ソルベント、０号ソルベントＨ、３〜７号ソルベント、ＡＦ４〜７号ソルベント［いずれも新日本石油化学（株）製］等が使用される。
【００２５】
乾燥促進剤は、印刷後に乾性油が重合して皮膜を硬化させる触媒のはたらきをするものであり、例えばナフテン酸マンガン溶液などが挙げられる。
【００２６】
【実施例】
次に具体例により、本発明の印刷インキ用樹脂、その合成方法、及び印刷インキ用樹脂を用いた印刷インキの印刷適性についてより詳しく説明する。なお、例中「部」とは重量部を表わす。
【００２７】
［実施例１］
（１）印刷インキ用樹脂の製造
攪拌機、リービッヒ冷却器、温度計付セパラブルフラスコに、ガムロジン４０００部、アクリル酸８４７部を仕込み、１３５℃で３時間、１４０℃で２時間、２１０℃で２時間反応した後、更に１０ｍｍＨｇ以下で１時間減圧を行い、アクリル酸１モル付加ロジンを得た。
攪拌機、リービッヒ冷却器、温度計付セパラブルフラスコに、上記で得られたアクリル酸１モル付加ロジン６７５部、重合ロジン［（株）理化ファインテク製：リカロジンＤＸ］６７５部、アルケニル置換コハク酸無水物（Ｃ１８直鎖内部オレフィンと無水マレイン酸の付加物）１６９部を仕込んだ後２１０℃まで昇温し、ペンタエリスリトール１０９．１部、グリセリン４９．２部を添加した。この後、２５５℃まで昇温して１０時間反応を行った後、更に１０ｍｍＨｇ以下で１時間減圧を行い、印刷インキ用樹脂であるＳ１を得た。
【００２８】
（２）印刷インキの製造方法
攪拌機、水分離冷却器、及び温度計付セパラブルフラスコに、前記（１）で得られた印刷インキ用樹脂（Ｓ１）４０部、亜麻仁油２０部、及びＡＦ５号ソルベント［新日本石油化学（株）製の非芳香族石油系溶剤］４０部を仕込み、窒素気流下で２００℃で１時間溶解して元ワニスを得た。得られた元ワニスを１００℃まで冷却した後、ＡＬＣＨ［川研ファインケミカル（株）製アルミキレート］１．０部を添加した。更に、１８０℃まで昇温し、３０分保温してそれぞれのインキ用ゲルワニスを調製した。
前記インキ用ゲルワニスを用いて以下に示す配合割合で３本ロールで練肉して印刷インキ、Ｉ１を得た。なお、インキのタック値は９〜１０になるように調整した。
カーミン６Ｂ（紅顔料） １８部
ワニス ７０〜７９部
日石ＡＦ５号ソルベント ２〜１１部
ナフテン酸マンガン １部
【００２９】
［実施例２〜４］
表１に記載したように原料の種類と使用量を代えた以外は実施例１と同じ操作を行い、印刷インキ用樹脂であるＳ２〜Ｓ４、及び印刷インキＩ２〜Ｉ４を得た。
【００３０】
［比較例１〜５］
表１に記載したように原料の種類と使用量を代えた以外は実施例１と同じ操作を行い、比較印刷インキ用樹脂であるＲＳ１〜ＲＳ５、及び比較印刷インキＲＩ１〜ＲＩ５を得た。
【００３１】
［比較例６］
（１）比較印刷インキ用樹脂の製造
攪拌機、還流冷却器、温度計付セパラブルフラスコに、トルエン１５００部、パラオクチルフェノール２０６０部、パラホルムアルデヒド６５２．２部からなる混合物を５２〜５７℃に加熱し、４８％水酸化ナトリウム水溶液５０部を添加した。発熱反応で昇温するが、７５℃で保温とし、水浴及び湯浴にて６時間反応を続けた。反応終了後、濃塩酸６３部、水２００部を加えて攪拌し、冷却後静置させ、上澄層を分液ロートで分離し、不揮発分６４％のレゾール型フェノール樹脂を得た。
攪拌機、リービッヒ冷却器、温度計付セパラブルフラスコに、ガムロジン１０００部と、上記で得られたレゾール型フェノール樹脂７８７部との混合物をトルエンを留去させながら２１０〜２２０℃まで昇温し、グリセリン９６部を添加した後２４５〜２５０℃で８時間反応し、酸価が２７以下になったことを確認後、更に１０ｍｍＨｇ以下で１時間減圧を行い、比較印刷インキ用樹脂、ＲＩ６を得た。
【００３２】
【表１】
前記実施例及び比較例で得られた印刷インキ用樹脂について、色相、酸価、融点、重量平均分子量（Ｍｗ）、亜麻仁油粘度、溶剤への溶解性（トレランス）を評価した。なお、その評価方法は以下のように行い、結果を表２に示した。
・色相：ＡＳＴＭによるＵＳロジンカラーグレード。
・酸価：ＪＩＳ Ｋ−５９０２ ロジン酸価測定法による。
・融点：ＪＩＳ Ｋ−００６４ 化学薬品の融点測定法による。
・重量平均分子量：ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算の分子量を測定。
・亜麻仁油粘度（Ｐｓ）：亜麻仁油と樹脂とを重量比６５：３５の割合で配合し、加熱溶解させたものを、落球粘度計で測定。
・溶解性（トレランス）：樹脂２ｇと溶剤（０号ソルベント）２ｇを１９０〜２００℃で１５分間溶解し、２５℃で同じ溶剤を滴下しつつ白濁するまでの、樹脂１ｇ当たりの全溶剤量（ｇ）。
【００３４】
【表２】
前記実施例及び比較例で得られた印刷インキの性能評価を次のように行い、その結果を表３に示した。
・光沢：インキ０．４ｍｌをＲＩテスター［（株）明製作所製］全面ロールでアート紙に展色した後、２０℃、相対湿度６５％で２４時間調湿し、６０°〜６０°光沢計で測定した。
・タック：インコメーター４００ｒｐｍ、室温２５℃、ロール温度３２℃、規格のインキ量で１分後の値を測定した。
・セット：インキ０．１７５ｍｌをＲＩテスター［（株）明製作所製］４分割ロールで展色した後、展色物を時間毎に分割し、別のアート紙に貼り合わせた。この試料についてＲＩテスターのロールを用いて展色物から別のアート紙上へのインキの付着度を観察し、インキが付着しなくなるまでの時間（分）を測定した。
・ミスチング：インキ４ｍｌをインコメーターにチャージし、４００ｒｐｍで１分間、更に１２００ｒｐｍで３分間回転させ、ロール直下に置いて白色紙上へのインキの飛散度を観察し、下記の判定基準に準じて評価を行った。
◎：インキの飛散の発生がなかった。
○：インキの飛散がやや発生していた。
△：インキの飛散が目立つ程度に発生していた。
・フロー：規格平行板粘度計（スプレッドメーター）で２５℃、１分後のインキの広がり（直径）（ｍｍ）を測定した。
【００３６】
【表３】
以上の結果より、（Ａ）〜（Ｄ）成分よりなる本願発明の印刷インキ用樹脂は、重量平均分子量が高く、溶解性に優れており、該印刷インキ用樹脂を用いた印刷インキにおいては、ミスチングの発生がないことがわかった。また、（Ａ）〜（Ｄ）成分に加えて（Ｅ）成分を使用した印刷インキ用樹脂は、溶解性がさらに改善されることが分かった。
【００３８】
従来のアルキルフェノールホルムアルデヒド縮合物を使用した印刷インキ用樹脂および印刷インキ（比較例６）に対し、本願発明に係る印刷インキ用樹脂および印刷インキの性能は同等であることが分かった。
【００３９】
【発明の効果】
本発明の印刷インキ用樹脂はアクリル酸１モル付加ロジン（Ａ）、重合ロジン（Ｂ）、アルケニル置換コハク酸又はその無水物（Ｃ）、及び多価アルコール（Ｄ）及び必要に応じて、さらにα，β−不飽和カルボン酸付加石油樹脂（Ｅ）からなる混合物を加熱反応して得られる樹脂であり、アルキルフェノールやホルムアルデヒド等人体に有害とされる物質を含まないため、作業環境の面で優れており、しかも、オフセット印刷に使用されるインキの調製に適した物性を示す。また、従来から使用されてきたロジン変性フェノール樹脂と比較して遜色のない印刷適性を有している。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a printing ink resin and a printing ink using the printing ink resin, specifically, a resin containing no phenolic resin, and when used in a printing ink, a non-aromatic solvent. The present invention relates to a printing ink resin having excellent solubility and providing excellent ink performance required in offset printing, and a printing ink using the printing ink resin.
[0002]
[Prior art]
It has been used in offset printing inks because it has various properties such as high molecular weight, high viscosity, high softening point, and excellent solubility in solvents for inks, and has excellent printability when used in offset printing inks. A rosin-modified phenol resin obtained by modifying a rosin with a resole-type phenol resin is widely used as an ink resin (see, for example, Patent Documents 1 and 2). Rosin-modified phenolic resins have good wettability to pigments and are easy to disperse evenly.In addition, a resin varnish suitable for printing inks can be obtained by reaction with a gelling agent. Currently, about tens of thousands of tons are consumed annually in Japan as a resin that is heavily used as a resin and supports high-speed printing and high gloss. This rosin-modified phenol resin is composed of a reaction product of a rosin, an alkylphenol formaldehyde condensate, and a polyhydric alcohol.
[0003]
Rosin-modified phenolic resins use an alkylphenol formaldehyde condensate as one of its main raw materials, and a method of reacting an alkylphenol with formaldehyde using an alkali or acid catalyst is used for the synthesis of the alkylphenol formaldehyde condensate. . However, in this synthesis process, wastewater containing formaldehyde, which is a harmful volatile organic compound (VOC), is generated, and in recent years, environmental problems such as air pollution derived from rosin-modified phenol resin and work environment problems have been raised. It is pointed out. It has also been pointed out that in a printing process using an ink composed of a rosin-modified phenol resin, formaldehyde is generated when the ink is heated and dried. Furthermore, alkylphenols have recently been suspected as endocrine disrupting substances (so-called environmental hormones), and are designated as priority substances for investigating endocrine disrupting effects in Japan, the United States and Europe. In Japan, it was concluded in 2001 that nonylphenol and octylphenol had endocrine disrupting effects in 2002.
[0004]
Therefore, various attempts have been made in the past to reduce the problems of the rosin-modified phenol resin. For example, a resin obtained by heating and reacting a petroleum resin, an unsaturated carboxylic acid or its anhydride, an aliphatic polybasic acid, and a polyhydric alcohol (for example, see Patent Document 3), a resin acid and α, β-ethylenic Resin characterized by reacting unsaturated carboxylic acid or its anhydride and C 4 -C 5 trimethylolalkane or alkene (for example, see Patent Document 4), rosins (a), and polar group-containing petroleum Reacting at least one resin (b) selected from the group consisting of a resin (b), an aliphatic monoalcohol, an aliphatic dialcohol, an aliphatic monoamine and an aliphatic monoepoxy, and a polyol (d); Polyester resin (for example, see Patent Document 5), polymer (A) obtained by copolymerizing polymerizable petroleum resin (a) and unsaturated carboxylic acid (b), and (1) fat Resins for printing inks obtained by reacting at least one type (c) selected from the group consisting of aliphatic monoalcohols, (2) aliphatic monoamines and (3) fatty acids (for example, see Patent Document 6). Have been.
[0005]
The resins for printing inks disclosed in each of these publications do not use alkylphenol formaldehyde condensate as a raw material and have properties comparable to rosin-modified phenolic resins (high molecular weight, high viscosity, high softening point, high solubility). It is described that it has. However, among the required performances for the offset printing ink resin, the resins for printing inks described in the above publications are not sufficiently satisfactory, particularly with respect to solubility in non-aromatic solvents. Furthermore, recently, there has been a wide variety of demands for resin for printing ink, such as low cost of printing ink and high-speed printing. It is difficult to satisfy all of the above, and it can be said that the technology of dephenolic resin has not been completed yet.
[0006]
For the above reasons, development of a resin for a printing ink which does not use phenols or formaldehyde which are harmful to the human body in the synthesis process and has properties comparable to rosin-modified phenolic resins is desired.
[Patent Document 1]
Japanese Patent Application Laid-Open No. 9-268211 [Patent Document 2]
JP 2001-106754 A [Patent Document 3]
JP 2001-31718 A [Patent Document 4]
Japanese Patent Application Laid-Open No. 2000-143785 [Patent Document 5]
JP 2001-233947 A [Patent Document 6]
JP-A-2002-97232
[Problems to be solved by the invention]
The present invention provides a novel printing ink resin that does not use phenols or formaldehyde in the synthesis process, has a high resin viscosity suitable for an offset printing ink resin, and exhibits excellent solubility in non-aromatic solvents. An object of the present invention is to provide a printing ink using the printing ink resin.
[0008]
[Means for Solving the Problems]
The present invention relates to a 1-mol acrylic acid-added rosin (A), a polymerized rosin (B), an alkenyl-substituted succinic acid or its anhydride (C), a polyhydric alcohol (D), and, if necessary, α, β- A resin obtained by subjecting a mixture consisting of an unsaturated carboxylic acid-added petroleum resin (E) to a heat reaction, wherein alkenyl-substituted succinic acid or its anhydride (C) is obtained by adding 1 mol of acrylic acid-added rosin (A) and polymerizing The present invention relates to a resin for printing ink, comprising 5 to 20 parts by weight based on 100 parts by weight of the total amount of rosin (B).
[0009]
The present invention also relates to a printing ink comprising the printing resin, a petroleum solvent, a drying oil and a pigment as essential components.
[0010]
Hereinafter, the configuration of the present invention will be described in more detail.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
Acrylic acid 1 mol addition rosin (A) can be obtained by heat addition reaction of rosins and acrylic acid. The rosins of the present invention include gum rosin, tall oil rosin, wood rosin, and mixtures thereof. The present invention is characterized in that a rosin composed of a resin acid having abietic acid and its analog as a main component, and a 1-mol addition rosin (A) obtained by heating and reacting acrylic acid with acrylic acid are used. And The reaction between rosin and acrylic acid is a Diels-Alder reaction, and this reaction can be performed, for example, at a reaction temperature of 120 to 300 ° C, preferably 150 to 260 ° C, and a reaction time of 3 to 8 hours. In addition, if the unreacted acrylic acid remains, the solubility of the obtained resin for printing ink in a solvent decreases, so that 1 mol or more of rosins relative to 1 mol of acrylic acid, preferably acrylic acid: rosin = 1: 1. It is preferred to use 1 (molar ratio) to obtain 1 mol of acrylic acid-added rosin (A).
[0012]
The amount of the rosin (A) added with 1 mol of acrylic acid is preferably 25 to 70 parts by weight based on 100 parts by weight of the total amount of the raw materials used. If the amount of rosin (A) added with 1 mol of acrylic acid is less than 25 parts by weight, a resin having a high molecular weight cannot be obtained. If it exceeds 70 parts by weight, it becomes difficult to control the molecular weight of the resin.
[0013]
The polymerized rosin (B) is obtained by polymerizing rosins with a sulfuric acid catalyst, and is a mixture containing a dimer rosin as a main component, a monomer, and in some cases, a trimer or more. The polymerized rosin (B) has a function of imparting an appropriate molecular weight and solubility to the resin for a printing ink of the present invention, and the amount used is the total amount of the rosin (A) added with 1 mol of acrylic acid and the polymerized rosin (B). It is 25 to 60 parts by weight, preferably 30 to 50 parts by weight, per 100 parts by weight. If the amount of the polymerized rosin (B) is less than 25 parts by weight, it becomes difficult to control the molecular weight of the resin, and if it exceeds 60 parts by weight, the cost increases, which is not preferable.
[0014]
The alkenyl-substituted succinic acid or its anhydride (C) is obtained by adding (anhydride) maleic acid to a linear or branched α-olefin or an internal olefin. An adduct with maleic anhydride) can be preferably used. In the present invention, the alkenyl-substituted succinic acid or its anhydride (C) is used as a solubility-imparting agent in a solvent for printing ink. The amount of the alkenyl-substituted succinic acid or its anhydride (C) to be added is 5 to 20 parts by weight based on 100 parts by weight of the total amount of the rosin (A) and the polymerized rosin (B). When the amount of the alkenyl-substituted succinic acid or its anhydride (C) is less than 5 parts by weight, the effect of improving the solubility of the resin is low, and when it exceeds 20 parts by weight, the melting point of the resin is lowered. Absent.
[0015]
Polyhydric alcohols (D) include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, hexanediol, octanediol, nonanediol, neopentyl glycol, etc. And trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. Among them, glycerin or pentaerythritol is preferred from the viewpoint of appropriately adjusting the molecular weight, melting point, and the like of the resin. The polyhydric alcohol (D) has a function of increasing the molecular weight and viscosity of the resin for printing ink by esterification reaction with other components, and the addition amount thereof is 1 mol of rosin added with acrylic acid (A) and polymerized rosin (B). ), And 0.8 to 1.2 equivalents to 1 equivalent of the total carboxyl groups of the α, β-unsaturated carboxylic acid-added petroleum resin (E). If the amount of the polyhydric alcohol (D) is less than 0.8 equivalents or more than 1.2 equivalents, the emulsifiability and water resistance of the obtained printing ink are undesirably deteriorated.
[0016]
The α, β-unsaturated carboxylic acid-added petroleum resin (E) is, for example, a known petroleum containing, as a main component, vinyltoluene, α-methylstyrene, cyclopentadiene, dicyclopentadiene, methylbutene, isoprene, pentene, cyclopentene, pentadiene and the like. It can be obtained by heating and adding an α, β-unsaturated carboxylic acid to a resin. Known α, β-unsaturated carboxylic acids can be used, and specific examples thereof include fumaric acid, maleic acid, itaconic acid, crotonic acid; and anhydrides thereof. Among these α, β-unsaturated carboxylic acid-added petroleum resins (E), those obtained by adding maleic acid or an anhydride thereof to a petroleum resin containing dicyclopentadiene as a main component are preferable. The α, β-unsaturated carboxylic acid-added petroleum resin (E) has a function of improving the solubility in petroleum solvents when preparing a printing ink. The α, β-unsaturated carboxylic acid-added petroleum resin (E) is preferably used in an amount of 20 to 40 parts by weight based on the total amount of the raw materials used. When the amount of the α, β-unsaturated carboxylic acid-added petroleum resin (E) is less than 20 parts by weight, the effect of improving the solubility is low, and when it exceeds 40 parts by weight, the dispersibility of the pigment becomes poor. When ink is used, misting tends to occur.
[0017]
The resin for a printing ink according to the present invention is produced by carrying out an esterification reaction by mixing and heating the components (A) to (D) and, if necessary, the component (E). The heating temperature is preferably from 150 to 280 ° C, more preferably from 200 to 260 ° C. The method of mixing and heating is not particularly limited, and a method in which the components (A) to (E) are mixed and then heated and reacted, after the components other than the polyhydric alcohol (D) are heated to a meltable temperature in advance and mixed, A method of adding a polyhydric alcohol (D) component and heating to a reaction temperature, for example, can be applied.
[0018]
In the present invention, in addition to the components (A) to (E), other components can be used in combination as long as the effects of the present invention are not impaired. Specifically, rosins are used for the purpose of adjusting the molecular weight and the like. Α, β-unsaturated carboxylic acid-added rosin, fatty acid, etc. obtained by heating addition reaction of α, β-unsaturated carboxylic acid other than acrylic acid with rosins can be used.
[0019]
The physical properties of the resin for printing ink according to the present invention include an acid value of 25 or less, a weight average molecular weight of 150,000 to 150,000, a melting point of 120 ° C. or more, and a solubility (tolerance) with a solvent for printing ink of 2 (g / g). g) or more is desirable. Here, the solubility in the printing ink solvent is determined by the following method.
Solubility (tolerance): 2 g of the resin and 2 g of the solvent (No. 0 solvent) were dissolved at 190 to 200 ° C. for 15 minutes, and the total amount of the solvent per 1 g of the resin (g) until the solution became cloudy while dropping the same solvent at 25 ° C. ).
Therefore, the larger the value, the better the solubility.
[0020]
The method for preparing the printing ink according to the present invention will be described below.
[0021]
The printing ink according to the present invention is used for offset printing, and the resin for a printing ink of the present invention obtained as described above, a petroleum solvent, a drying oil and a pigment as essential components, and specifically, Is preferably obtained by kneading the following composition.
Composition of printing ink: (% by weight)
Pigment 10-25
Resin varnish 40-80
Dry oil 0-10
Petroleum solvent 5-40
Drying accelerator 0-2
Known pigments can be used, and examples thereof include carbon black, phthalocyanine blue, carmine 6B, lake red C, and benzidine yellow. These pigments are used to color the printing substrate, and black, yellow, red, indigo and other pigments are selected as necessary.
[0022]
The method for preparing the resin varnish is as follows. A stirrer, a water separation cooler, and a separable flask equipped with a thermometer were charged with 30 to 60% by weight of the resin for a printing ink of the present invention, 10 to 30% by weight of a drying oil, and 20 to 60% by weight of a petroleum-based solvent. Dissolve at 180 to 200 ° C. for 1 hour to obtain the original varnish. After cooling the obtained varnish to 100 ° C., 0.5 to 2% by weight of a gelling agent is added. Further, the temperature is raised to 180 ° C. and kept for 30 minutes to prepare a resin varnish.
[0023]
Examples of the drying oil include linseed oil and tung oil, and linseed oil is preferably used.
[0024]
The petroleum-based solvent is added to adjust the viscosity of the ink and promote the drying property after printing, and a hydrocarbon-based solvent having a boiling point of 200 to 400 ° C can be mainly used. Specifically, No. 0 solvent, No. 0 solvent H, No. 3 to No. 7 solvent, AF No. 4 to No. 7 solvent (all manufactured by Nippon Petrochemical Co., Ltd.) and the like are used.
[0025]
The drying accelerator functions as a catalyst for curing the film by the polymerization of the drying oil after printing, and examples thereof include a manganese naphthenate solution.
[0026]
【Example】
Next, with reference to specific examples, the printing ink resin of the present invention, a method for synthesizing the same, and the printability of the printing ink using the printing ink resin will be described in more detail. In the examples, "parts" represents parts by weight.
[0027]
[Example 1]
(1) Production of resin for printing ink In a separable flask equipped with a stirrer, a Liebig condenser, and a thermometer, 4,000 parts of gum rosin and 847 parts of acrylic acid were charged, at 135 ° C for 3 hours, at 140 ° C for 2 hours, and at 210 ° C for 2 hours. After reacting for an hour, the pressure was further reduced at 10 mmHg or less for 1 hour to obtain rosin with 1 mol of acrylic acid.
In a separable flask equipped with a stirrer, a Liebig condenser and a thermometer, 675 parts of the rosin added with 1 mol of acrylic acid obtained above, 675 parts of a polymerized rosin [manufactured by Rika Finetech Co., Ltd .: Licarodine DX], alkenyl-substituted succinic anhydride After charging 169 parts of a product (an adduct of a C18 linear internal olefin and maleic anhydride), the temperature was raised to 210 ° C., and 109.1 parts of pentaerythritol and 49.2 parts of glycerin were added. Thereafter, the temperature was raised to 255 ° C., and the reaction was carried out for 10 hours. Then, the pressure was further reduced at 10 mmHg or less for 1 hour to obtain S1 as a printing ink resin.
[0028]
(2) Production method of printing ink In a separable flask equipped with a stirrer, a water separation cooler and a thermometer, 40 parts of the resin for printing ink (S1) obtained in the above (1), 20 parts of linseed oil, and AF5 A solvent [non-aromatic petroleum-based solvent manufactured by Nippon Petrochemical Co., Ltd.] (40 parts) was charged and dissolved at 200 ° C. for 1 hour in a nitrogen stream to obtain an original varnish. After cooling the obtained varnish to 100 ° C., 1.0 part of ALCH [aluminum chelate manufactured by Kawaken Fine Chemical Co., Ltd.] was added. Further, the temperature was raised to 180 ° C., and the temperature was kept for 30 minutes to prepare each gel varnish for ink.
Using the above gel varnish for ink, the mixture was kneaded with three rolls in the mixing ratio shown below to obtain a printing ink, I1. In addition, the tack value of the ink was adjusted so as to be 9 to 10.
Carmine 6B (Red Pigment) 18 parts Varnish 70-79 parts Nisseki AF5 Solvent 2-11 parts Manganese naphthenate 1 part
[Examples 2 to 4]
The same operation as in Example 1 was performed except that the types and amounts of the raw materials were changed as described in Table 1, to obtain printing ink resins S2 to S4 and printing inks I2 to I4.
[0030]
[Comparative Examples 1 to 5]
The same operation as in Example 1 was performed except that the types and amounts of the raw materials were changed as described in Table 1, to obtain resins RS1 to RS5 for comparative printing inks and comparative printing inks RI1 to RI5.
[0031]
[Comparative Example 6]
(1) Production of resin for comparative printing ink A mixture composed of 1500 parts of toluene, 2060 parts of paraoctylphenol, and 652.2 parts of paraformaldehyde was heated to 52 to 57 ° C in a separable flask equipped with a stirrer, a reflux condenser, and a thermometer. And 50 parts of a 48% aqueous sodium hydroxide solution were added. The temperature was raised by an exothermic reaction, but kept at 75 ° C., and the reaction was continued for 6 hours in a water bath and a hot water bath. After the completion of the reaction, 63 parts of concentrated hydrochloric acid and 200 parts of water were added, and the mixture was stirred, allowed to stand after cooling, and the supernatant layer was separated with a separating funnel to obtain a resol type phenol resin having a nonvolatile content of 64%.
In a separable flask equipped with a stirrer, a Liebig condenser and a thermometer, a mixture of 1000 parts of gum rosin and 787 parts of the resole-type phenol resin obtained above was heated to 210 to 220 ° C. while distilling off toluene, and glycerin was added. After 96 parts were added, the mixture was reacted at 245 to 250 ° C. for 8 hours. After confirming that the acid value was 27 or less, the pressure was further reduced to 10 mmHg or less for 1 hour to obtain a resin for comparative printing ink, RI6.
[0032]
[Table 1]
The resins for printing inks obtained in the above Examples and Comparative Examples were evaluated for hue, acid value, melting point, weight average molecular weight (Mw), linseed oil viscosity, and solubility (tolerance) in solvents. In addition, the evaluation method was performed as follows, and the result was shown in Table 2.
Hue: US rosin color grade according to ASTM.
-Acid value: According to JIS K-5902 rosin acid value measuring method.
Melting point: JIS K-0064 Determined by melting point method of chemicals.
Weight average molecular weight: The molecular weight in terms of polystyrene was measured by gel permeation chromatography (GPC).
Flaxseed oil viscosity (Ps): Flaxseed oil and resin were blended at a weight ratio of 65:35, and the mixture was heated and dissolved, and measured with a falling ball viscometer.
-Solubility (tolerance): 2 g of the resin and 2 g of the solvent (No. 0 solvent) were dissolved at 190 to 200 ° C for 15 minutes, and the total amount of the solvent per 1 g of the resin until the solution became cloudy while dropping the same solvent at 25 ° C ( g).
[0034]
[Table 2]
The performance of the printing inks obtained in the above Examples and Comparative Examples was evaluated as follows, and the results are shown in Table 3.
・ Gloss: 0.4 ml of ink was spread on art paper with a roll of RI tester [manufactured by Akira Seisakusho Co., Ltd.], and then humidified at 20 ° C. and 65% relative humidity for 24 hours. Was measured.
Tack: The value after 1 minute was measured with an incometer at 400 rpm, a room temperature of 25 ° C., a roll temperature of 32 ° C., and a standard ink amount.
-Set: 0.175 ml of ink was spread with a RI tester (manufactured by Akira Seisakusho Co., Ltd.) by four-split rolls, and then the spread was divided every hour and bonded to another art paper. Using a roll of an RI tester, the degree of adhesion of the ink from the developed material to another art paper was observed for this sample, and the time (minute) until the ink did not adhere was measured.
-Misting: 4 ml of ink is charged into an incometer, rotated at 400 rpm for 1 minute, and further rotated at 1200 rpm for 3 minutes, placed immediately under a roll, observed for the degree of ink scattering on white paper, and evaluated according to the following criteria. Was done.
A: No ink scattering occurred.
：: Some scattering of ink occurred.
C: Scattering of the ink occurred to a remarkable degree.
Flow: The spread (diameter) (mm) of the ink after 1 minute at 25 ° C. was measured with a standard parallel plate viscometer (spread meter).
[0036]
[Table 3]
From the above results, the printing ink resin of the present invention comprising the components (A) to (D) has a high weight average molecular weight and excellent solubility, and in the printing ink using the printing ink resin, No misting occurred. Further, it was found that the solubility for the printing ink resin using the component (E) in addition to the components (A) to (D) was further improved.
[0038]
It was found that the performance of the printing ink resin and the printing ink according to the present invention is equivalent to that of the conventional printing ink resin and printing ink using the alkylphenol formaldehyde condensate (Comparative Example 6).
[0039]
【The invention's effect】
The resin for a printing ink of the present invention comprises acrylic acid 1 mol-added rosin (A), polymerized rosin (B), alkenyl-substituted succinic acid or its anhydride (C), and polyhydric alcohol (D) and, if necessary, further. It is a resin obtained by heating and reacting a mixture consisting of an α, β-unsaturated carboxylic acid-added petroleum resin (E). It does not contain substances harmful to the human body, such as alkylphenol and formaldehyde, and is excellent in work environment. And exhibits physical properties suitable for preparing an ink used for offset printing. Further, it has printability comparable to that of rosin-modified phenolic resin that has been used conventionally.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003080558A JP4702590B2 (en) | 2003-03-24 | 2003-03-24 | Printing ink resin and printing ink using the printing ink resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003080558A JP4702590B2 (en) | 2003-03-24 | 2003-03-24 | Printing ink resin and printing ink using the printing ink resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004285255A true JP2004285255A (en) | 2004-10-14 |
| JP4702590B2 JP4702590B2 (en) | 2011-06-15 |
Family
ID=33294380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003080558A Expired - Fee Related JP4702590B2 (en) | 2003-03-24 | 2003-03-24 | Printing ink resin and printing ink using the printing ink resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4702590B2 (en) |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007204677A (en) * | 2006-02-03 | 2007-08-16 | Arakawa Chem Ind Co Ltd | Pigment-coating agent, coating pigment and printing ink composition |
| JP2007292869A (en) * | 2006-04-21 | 2007-11-08 | Ricoh Co Ltd | Image forming apparatus, image forming method and process cartridge |
| JP2007292816A (en) * | 2006-04-21 | 2007-11-08 | Kao Corp | Polyester for toner |
| JP2007292862A (en) * | 2006-04-21 | 2007-11-08 | Ricoh Co Ltd | Image forming apparatus and method, and process cartridge |
| JP2007292818A (en) * | 2006-04-21 | 2007-11-08 | Kao Corp | Polyester for toner |
| JP2007292820A (en) * | 2006-04-21 | 2007-11-08 | Kao Corp | Polyester for toner |
| JP2007292817A (en) * | 2006-04-21 | 2007-11-08 | Kao Corp | Polyester for toner |
| JP2007292819A (en) * | 2006-04-21 | 2007-11-08 | Kao Corp | Polyester for toner |
| JP2007292860A (en) * | 2006-04-21 | 2007-11-08 | Ricoh Co Ltd | Image forming apparatus, image forming method and process cartridge |
| JP2007292873A (en) * | 2006-04-21 | 2007-11-08 | Ricoh Co Ltd | Image forming apparatus, image forming method and process cartridge |
| JP2007292863A (en) * | 2006-04-21 | 2007-11-08 | Ricoh Co Ltd | Image forming apparatus method, and process cartridge |
| JP2007292858A (en) * | 2006-04-21 | 2007-11-08 | Ricoh Co Ltd | Image forming apparatus, image forming method and process cartridge |
| JP2007292815A (en) * | 2006-04-21 | 2007-11-08 | Kao Corp | Polyester for toner |
| JP2007322926A (en) * | 2006-06-02 | 2007-12-13 | Ricoh Co Ltd | Image forming apparatus, image forming method, and process cartridge |
| WO2007142094A1 (en) * | 2006-06-02 | 2007-12-13 | Kao Corporation | Toner for electrophotography |
| JP2007322931A (en) * | 2006-06-02 | 2007-12-13 | Kao Corp | Electrophotographic toner |
| JP2007322928A (en) * | 2006-06-02 | 2007-12-13 | Ricoh Co Ltd | Image forming apparatus, image forming method and process cartridge |
| JP2007322930A (en) * | 2006-06-02 | 2007-12-13 | Kao Corp | Electrophotographic toner |
| JP2007322927A (en) * | 2006-06-02 | 2007-12-13 | Ricoh Co Ltd | Image forming apparatus, image forming method and process cartridge |
| JP2007322932A (en) * | 2006-06-02 | 2007-12-13 | Kao Corp | Electrophotographic toner |
| JP2007322842A (en) * | 2006-06-02 | 2007-12-13 | Kao Corp | Electrophotographic toner |
| JP2007322925A (en) * | 2006-06-02 | 2007-12-13 | Ricoh Co Ltd | Image forming apparatus, image forming method, and process cartridge |
| JP2007333976A (en) * | 2006-06-14 | 2007-12-27 | Kao Corp | Binder resin for toner |
| US7892718B2 (en) | 2006-04-21 | 2011-02-22 | Ricoh Company, Ltd. | Image forming apparatus, image forming method and process cartridge |
| US8309291B2 (en) | 2006-04-21 | 2012-11-13 | Kao Corporation | Polyester for toner |
| JP2016188273A (en) * | 2015-03-30 | 2016-11-04 | 東洋インキＳｃホールディングス株式会社 | Permeation-drying type offset printing ink composition |
| US11999920B2 (en) | 2020-09-14 | 2024-06-04 | Ecolab Usa Inc. | Cold flow additives for plastic-derived synthetic feedstock |
| US12031097B2 (en) | 2021-10-14 | 2024-07-09 | Ecolab Usa Inc. | Antifouling agents for plastic-derived synthetic feedstocks |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233435A (en) * | 2018-07-28 | 2019-01-18 | 广东绿之彩印刷科技股份有限公司 | A kind of ink and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000029455A1 (en) * | 1998-11-16 | 2000-05-25 | Toyo Ink Mfg. Co., Ltd. | Resin for printing ink and printing ink |
| JP2002363446A (en) * | 2001-06-04 | 2002-12-18 | Toyo Ink Mfg Co Ltd | Curable covering composition, printing ink, printing method by the same and printed product by the same |
| JP2004099860A (en) * | 2002-07-19 | 2004-04-02 | Arakawa Chem Ind Co Ltd | Polyester resin, method for producing the same, binder for printing ink and printing ink |
| JP2004203975A (en) * | 2002-12-24 | 2004-07-22 | Arakawa Chem Ind Co Ltd | Method for manufacturing resin varnish for printing ink |
-
2003
- 2003-03-24 JP JP2003080558A patent/JP4702590B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000029455A1 (en) * | 1998-11-16 | 2000-05-25 | Toyo Ink Mfg. Co., Ltd. | Resin for printing ink and printing ink |
| JP2002363446A (en) * | 2001-06-04 | 2002-12-18 | Toyo Ink Mfg Co Ltd | Curable covering composition, printing ink, printing method by the same and printed product by the same |
| JP2004099860A (en) * | 2002-07-19 | 2004-04-02 | Arakawa Chem Ind Co Ltd | Polyester resin, method for producing the same, binder for printing ink and printing ink |
| JP2004203975A (en) * | 2002-12-24 | 2004-07-22 | Arakawa Chem Ind Co Ltd | Method for manufacturing resin varnish for printing ink |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007204677A (en) * | 2006-02-03 | 2007-08-16 | Arakawa Chem Ind Co Ltd | Pigment-coating agent, coating pigment and printing ink composition |
| JP2007292817A (en) * | 2006-04-21 | 2007-11-08 | Kao Corp | Polyester for toner |
| JP2007292860A (en) * | 2006-04-21 | 2007-11-08 | Ricoh Co Ltd | Image forming apparatus, image forming method and process cartridge |
| JP2007292862A (en) * | 2006-04-21 | 2007-11-08 | Ricoh Co Ltd | Image forming apparatus and method, and process cartridge |
| JP2007292818A (en) * | 2006-04-21 | 2007-11-08 | Kao Corp | Polyester for toner |
| JP2007292820A (en) * | 2006-04-21 | 2007-11-08 | Kao Corp | Polyester for toner |
| US7892718B2 (en) | 2006-04-21 | 2011-02-22 | Ricoh Company, Ltd. | Image forming apparatus, image forming method and process cartridge |
| JP2007292819A (en) * | 2006-04-21 | 2007-11-08 | Kao Corp | Polyester for toner |
| JP2007292816A (en) * | 2006-04-21 | 2007-11-08 | Kao Corp | Polyester for toner |
| JP2007292873A (en) * | 2006-04-21 | 2007-11-08 | Ricoh Co Ltd | Image forming apparatus, image forming method and process cartridge |
| JP2007292863A (en) * | 2006-04-21 | 2007-11-08 | Ricoh Co Ltd | Image forming apparatus method, and process cartridge |
| JP2007292858A (en) * | 2006-04-21 | 2007-11-08 | Ricoh Co Ltd | Image forming apparatus, image forming method and process cartridge |
| JP2007292815A (en) * | 2006-04-21 | 2007-11-08 | Kao Corp | Polyester for toner |
| US8309291B2 (en) | 2006-04-21 | 2012-11-13 | Kao Corporation | Polyester for toner |
| JP2007292869A (en) * | 2006-04-21 | 2007-11-08 | Ricoh Co Ltd | Image forming apparatus, image forming method and process cartridge |
| WO2007142094A1 (en) * | 2006-06-02 | 2007-12-13 | Kao Corporation | Toner for electrophotography |
| JP2007322926A (en) * | 2006-06-02 | 2007-12-13 | Ricoh Co Ltd | Image forming apparatus, image forming method, and process cartridge |
| JP2007322930A (en) * | 2006-06-02 | 2007-12-13 | Kao Corp | Electrophotographic toner |
| JP2007322927A (en) * | 2006-06-02 | 2007-12-13 | Ricoh Co Ltd | Image forming apparatus, image forming method and process cartridge |
| JP2007322932A (en) * | 2006-06-02 | 2007-12-13 | Kao Corp | Electrophotographic toner |
| JP2007322842A (en) * | 2006-06-02 | 2007-12-13 | Kao Corp | Electrophotographic toner |
| JP2007322925A (en) * | 2006-06-02 | 2007-12-13 | Ricoh Co Ltd | Image forming apparatus, image forming method, and process cartridge |
| JP2007322928A (en) * | 2006-06-02 | 2007-12-13 | Ricoh Co Ltd | Image forming apparatus, image forming method and process cartridge |
| US7824832B2 (en) | 2006-06-02 | 2010-11-02 | Kao Corporation | Toner for electrophotography |
| JP2007322931A (en) * | 2006-06-02 | 2007-12-13 | Kao Corp | Electrophotographic toner |
| JP2007333976A (en) * | 2006-06-14 | 2007-12-27 | Kao Corp | Binder resin for toner |
| JP2016188273A (en) * | 2015-03-30 | 2016-11-04 | 東洋インキＳｃホールディングス株式会社 | Permeation-drying type offset printing ink composition |
| US11999920B2 (en) | 2020-09-14 | 2024-06-04 | Ecolab Usa Inc. | Cold flow additives for plastic-derived synthetic feedstock |
| US12031097B2 (en) | 2021-10-14 | 2024-07-09 | Ecolab Usa Inc. | Antifouling agents for plastic-derived synthetic feedstocks |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4702590B2 (en) | 2011-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4702590B2 (en) | Printing ink resin and printing ink using the printing ink resin | |
| JP4867119B2 (en) | Polyester resin, its production method, binder for printing ink and printing ink | |
| JP4812049B2 (en) | Polyester resin, its production method, binder for printing ink and printing ink | |
| JP5582419B2 (en) | Rosin-modified phenolic resin, its production method and printing ink | |
| WO2005103173A1 (en) | Method for producing modified rosin ester resin composition for lithographic ink varnish and method for producing lithographic ink varnish | |
| US5969071A (en) | Method for preparing phenolic rosin resins | |
| JP4550045B2 (en) | Rosin phenolic resin and related uses | |
| JP4662093B2 (en) | Printing ink binder and printing ink | |
| JP4639448B2 (en) | Polyester resin, its production method, binder for printing ink and printing ink | |
| JP5796274B2 (en) | Rosin-modified phenolic resin, its production method and printing ink | |
| JP5050338B2 (en) | New petroleum resin-containing rosin-modified phenolic resin | |
| JP4326074B2 (en) | Resin for printing ink | |
| JP4677075B2 (en) | Method for producing resin varnish for printing ink | |
| JP3298268B2 (en) | Method for producing rosin phenol resin | |
| JP4596199B2 (en) | Polyester resin, its production method, binder for printing ink and printing ink | |
| JP2004307698A (en) | Preparation method of high viscoelastic gel varnish for printing ink | |
| JP2005133049A (en) | Resin for offset ink | |
| JP2004300399A (en) | Rosin-modified phenol resin | |
| JP3971594B2 (en) | Varnish and printing ink | |
| JP2001262032A (en) | Printing ink varnish | |
| JPH01292080A (en) | Printing ink | |
| JP5082348B2 (en) | Novel resin composition and method for producing the same | |
| JP2003268283A (en) | Ink varnish and ink | |
| JP2023143757A (en) | Rosin-modified phenol resin, varnish for printing ink, printing ink and printed matter | |
| JPS59191776A (en) | Printing ink resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060323 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060517 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20061207 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20061215 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090617 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090630 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090806 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100420 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100608 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110210 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110223 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |