JP3821476B2 - Resin for paper coating - Google Patents
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- JP3821476B2 JP3821476B2 JP2002258595A JP2002258595A JP3821476B2 JP 3821476 B2 JP3821476 B2 JP 3821476B2 JP 2002258595 A JP2002258595 A JP 2002258595A JP 2002258595 A JP2002258595 A JP 2002258595A JP 3821476 B2 JP3821476 B2 JP 3821476B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、紙に対して優れた印刷効果を与える紙塗工用樹脂に関する。
【０００２】
【従来の技術】
顔料、水性バインダーおよび紙塗工用樹脂を主体とした塗工組成物を紙に塗布し、乾燥、カレンダー処理などの必要な処理を施して得られる塗工紙は、商業印刷物や雑誌・書籍などに広く用いられている。そして、インキ受理性および耐水性に優れた塗工紙を与える紙塗工用樹脂として、（a）ポリアミン類、（b）脂環式多価カルボン酸類とグリコール類との反応で得られる遊離カルボキシル基を有する反応生成物、および／または、脂環式多価カルボン酸類、（c）アルキル化剤、ならびに（d）尿素類を反応せしめてなる樹脂が、例えば特許文献１などに報告され、該樹脂の具体的な製造方法としては、（a）、（b）および（d）成分を順次、反応せしめたのち、（c）成分を反応せしめてなる紙塗工用樹脂が開示されている。
【０００３】
【特許文献１】
特開昭６２−１１６６１９号公報
【０００４】
【発明が解決しようとする課題】
最近、塗工紙として印刷品質の高度化、高速化が図られていることから、本発明の目的としては、さらに向上されたインキ受理性および耐水性を有する塗工紙を与える紙塗工用樹脂を提供することである。
【０００５】
【課題を解決するための手段】
本発明は、下記（a）成分、（b）成分および（c）成分を反応させて得られた樹脂に、（d）成分を反応せしめてなることを特徴とする紙塗工用樹脂である。
（a）ポリアミン類
（b）脂環式多価カルボン酸類とグリコール類との反応で得られる
遊離カルボキシル基を有する反応生成物、および／または、
脂環式多価カルボン酸類
（c）一般式（４）〜（６）からなる群から選ばれる少なくとも１種のアルキル化剤
で表されるエピハロヒドリン、
ＨＯＣＨ ２ （ＣＨ ２ ） Ｗ Ｘ （５）
（式中、Ｘはハロゲン原子等を表し、ｗは１〜３程度の数を表す。）
で表されるモノハロヒドリン、
で表されるジハロヒドリン
（d）尿素類
【０００６】
【発明の実施の形態】
以下、本発明について詳細に説明する。
本発明における（a）ポリアミン類としては、分子中に１級又は２級アミノ基を少なくとも２個有する脂肪族アミンであり、例えば、エチレンイミンを重合して得られるポリエチレンイミン；エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン等の炭素数１〜１０程度のアルキレン基を含有するアルキレンジアミン；ジエチレントリアミン、トリエチレンテトラミン、ペンタエチレンヘキサミン、テトラエチレンペンタミン、イミノビスプロピルアミン、３−アザヘキサン−１，６−ジアミン、４，７−ジアザデカン−１，１０−ジアミン等のポリアルキレンポリアミン；イソホロンジアミン、ビス（アミノメチル）シクロヘキサンなどの脂環式アミン；複素環ポリアミン等が挙げられる。
【０００７】
ここで複素環ポリアミンとは、通常、窒素原子、酸素原子、硫黄原子などのヘテロ原子を少なくとも１個含有する脂環式炭化水素基である複素環を含み、１級又は２級アミノ基を少なくとも２個有するアミンのことである。具体的には、ピペラジン、ホモピペラジン等のような複素環ジアミン類；Ｎ−アミノエチルピペラジン、Ｎ−アミノプロピルピペラジン、及び１，４−ビス（アミノプロピル）ピペラジンのようなアミノアルキルを含有した複素環ポリアミンなどが挙げられる。
複素環ポリアミンとしては、複素環のヘテロ原子として窒素原子を含有する複素環ポリアミンが好ましい。
【０００８】
（a）成分として、異なる２種類以上のポリアミン類を用いてもよい。
（a）成分としては、中でも、ポリアルキレンポリアミンが好ましく、とりわけ、ジエチレントリアミン、トリエチレンテトラミンが好適である。
【０００９】
本発明の（b）脂環式多価カルボン酸類とは、分子中に２個以上のカルボキシル基を有し、分子中に二重結合を有していてもよい脂環式多価カルボン酸、該カルボン酸と炭素数１〜４程度のアルコールとからなるエステル類、あるいは該カルボン酸の無水物である。
具体的にはテトラヒドロフタル酸、ヘキサヒドロフタル酸、シクロヘキサン−１，４−ジカルボン酸、３−メチルテトラヒドロフタル酸、４−メチルテトラヒドロフタル酸、シクロヘキサン−１，２，４−トリカルボン酸等の脂環式多価カルボン酸；前記脂環式多価カルボン酸のメチル基、エチル基などの低級エステル類：テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、３−メチルテトラヒドロ無水フタル酸、４−メチルテトラヒドロ無水フタル酸、シクロヘキサン−１，２，４−トリカルボン酸一無水物などの脂環式多価カルボン酸無水物等が挙げられる。
【００１０】
（b）成分の脂環式多価カルボン酸類として、２種類以上の脂環式多価カルボン酸類を使用してもよい。脂環式多価カルボン酸類の（b）成分としては、中でもテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、３−メチルテトラヒドロ無水フタル酸及び４−メチルテトラヒドロ無水フタル酸から選ばれる少なくとも１種類の脂環式多価カルボン酸類およびそれらの酸無水物等が好適である。
【００１１】
また、（b）成分として、前記脂環式多価カルボン酸類とグリコール類を、脂環式多価カルボン酸類を過剰モル比で反応させて得られ、分子末端に遊離カルボキシル基を有する反応生成物を使用することができる。
ここで、グリコール類としては、エチレングリコール、プロピレングリコール、ブタンジオール等のアルキレングリコール類、シクロペンタンジオール、シクロヘキサンジオール等のシクロアルキレングリコール類、ブテンジオール、オクテンジオール等のアルケニレングリコール類、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、ポリエチレングリコール、ポリテトラメチレンリコール等のポリアルキレングリコール類、ビスフェノールＡのエチレンオキサイド付加物、水素化ビスフェノールＡのエチレンオキサイド付加物等が例示される。これらグリコール類は単独で使用しても、あるいは異なる２種類以上を併用してもよい。グリコール類として、中でもエチレングリコール、ジエチレングリコールが好ましい。
【００１２】
分子末端に遊離カルボキシル基を有する反応生成物における脂環式多価カルボン酸類とグリコール類の比率としては、通常、グリコール類のヒドロキシル基１モルに対して脂環式多価カルボン酸類が１〜２モル程度であり、好ましくは１〜１．５モル程度である。
分子末端に遊離カルボキシル基を有する反応生成物は、必要に応じて生成する水を留去しながら、通常、温度１００〜２００℃、好ましくは１２０〜１８０℃程度で２〜１０時間程度、好ましくは３〜８時間程度攪拌することによって得ることができる。
【００１３】
分子末端に遊離カルボキシル基を有する反応生成物の（b）成分としては、中でも、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、３−メチルテトラヒドロ無水フタル酸及び４−メチルテトラヒドロ無水フタル酸から選ばれる少なくとも１種類の脂環式多価カルボン酸の無水物とエチレングリコール又はジエチレングリコールの反応物である、分子末端に遊離カルボキシル基を有する反応生成物が好適である。
【００１４】
本発明の（c）成分は、下記一般式（４）〜（６）で表されるからなる群から選ばれる少なくとも１種のアルキル化剤である。
【００１５】
一般式（４）は下記式（４）
で表されるエピハロヒドリンである。
エピハロヒドリンとしては、例えば、エピクロルヒドリン、エピブロモヒドリン等が挙げられる。
【００１６】
一般式（５）は下記式（５）
ＨＯＣＨ２（ＣＨ２）ＷＸ （５）
（式中、Ｘはハロゲン原子等を表し、ｗは１〜３程度の数を表す。）
で表されるモノハロヒドリンである。
モノハロヒドリンとしては、例えば、エチレンクロロヒドリン、エチレンブロモヒドリン等が挙げられる。
【００１７】
一般式（６）は下記式（６）
で表されるジハロヒドリンである。
ジハロヒドリンとしては、例えば、１，３−ジクロロ−２−プロパノール、２，３−ジクロロ−１−プロパノール等が挙げられる。
【００１８】
成分（c）として、一般式（４）〜（６）で表される群から選ばれる２種以上アルキル化剤を併用してもよい。
成分（c）としては、中でも、一般式（４）で表されるエピハロヒドリンが好ましく、とりわけ、エピクロロヒドリンが好適である。
【００１９】
本発明の（d）成分は、例えば、尿素、メチル尿素、ジメチル尿素、チオ尿素、４，５−ジヒドロキシ−２−イミダゾリジノン、１−（２−アミノエチル）−２−イミダゾリジノン等の尿素類であり、中でも尿素が好適である。
【００２０】
本発明の紙塗工用樹脂は、（a）〜（c）成分の反応生成物に（d）成分を反応せしめたものである。
該樹脂に含有される単量体単位の比率は、通常、（a）成分に含有される１級アミノ基及び２級アミノ基の合計量（以下、アミノ基量という）１モル比に対して、（b）成分は０．１〜０．５モル比程度であり、（c）成分は０．１〜０．９モル比程度であり、（d）成分が０．１〜０．５モル比程度である。
【００２１】
本発明の紙塗工用樹脂の製造方法としては、（a）〜（c）成分を任意の順番で反応し、続いて（d）成分を反応する製造方法である。中でも（a）成分と（b）成分を反応したのち、（c）成分を反応し、続いて（d）成分を反応する製造方法が好ましく、具体的には（ア）グリコール類と脂環式多価カルボン酸類とをエステル化反応せしめた（b）分子末端に遊離カルボキシル基を有する反応生成物と、（a）成分をアミド化反応せしめ、続いて（c）成分を反応せしめた後、（d）成分と脱アンモニア反応せしめる方法、（イ）（a）および（b）成分を（ア）と同様にアミド化反応せしめたのち、さらに脂環式多価カルボン酸類の（b）成分を（a）成分由来のアミノ残基にアミド化反応させ、続いて（c）成分を反応せしめた後、（d）成分と脱アンモニア反応せしめる方法、（ウ）（a）成分と脂環式多価カルボン酸類の（b）成分をアミド化反応せしめ、続いて（c）成分を反応せしめた後、（d）成分と脱アンモニア反応せしめる方法などが例示される。
【００２２】
（a）成分と（b）成分との反応は（b）成分の種類によって、反応温度および反応時間が異なるが、例えば、（b）分子末端に遊離カルボキシル基を有する反応生成物および／または脂環式多価カルボン酸と、（a）成分とをアミド化反応させる場合、通常、１３０〜２５０℃程度で、水等を留去しながら、２〜１０時間程度反応させる方法；
（b）脂環式多価カルボン酸無水物と（a）成分とをアミド化反応させる場合、通常、５０〜２００℃程度で、水等を留去しながら、１〜１０時間程度反応させる方法；
（b）脂環式多価カルボン酸エステルと（a）成分とをアミド化反応させる場合、通常、８０〜２５０℃程度で、水またはアルコール等を留去しながら、２〜１０時間程度反応させる方法等が挙げられる。
【００２３】
アミノ基と（c）成分との反応は、通常、３０〜１２０℃程度、好ましくは５０〜１００℃程度にて１〜２０時間程度、好ましくは２〜１０時間程度反応させる。
得られた水溶液を５０重量％水溶液の２５℃における粘度は、通常、１０〜３，０００mPa・s程度、好ましくは、１０〜２００mPa・s程度 、とりわけ好ましくは３０〜１００mPa・s程度である。
【００２４】
（a）〜（c）成分の反応生成物と（d）成分との脱アンモニア反応は、通常、８０〜１８０℃程度、好ましくは９０〜１６０℃程度で、発生するアンモニアを留去しながら４〜３０時間程度、好ましくは５〜２０時間度反応させる方法等が挙げられる。
【００２５】
このようにして得られた紙塗工用樹脂は、必要に応じて、リン酸、硫酸、塩酸、硝酸などの無機酸や、蟻酸、酢酸、プロピオン酸、アジピン酸などの有機酸を用いて、通常、ｐＨ６〜１０程度、好ましくは中性程度に調整する。
【００２６】
かくして得られた紙塗工用樹脂は、顔料および水性バインダーとともに紙用塗工組成物として調整される。
ここで、顔料としては、例えば、白色無機顔料、白色有機顔料などが挙げられる。白色無機顔料の具体例としては、カオリン、タルク、炭酸カルシウム（重質又は軽質）、水酸化アルミニウム、サチンホワイト、酸化チタンなどが挙げられる。また白色有機顔料の具体例としては、例えば、ポリスチレン、メラミン−ホルムアルデヒド樹脂、尿素−ホルムアルデヒド樹脂などが挙げられる。
顔料として、２種類以上の顔料を使用してもよい。
【００２７】
水性バインダーとしては、例えば、水溶性バインダー、水乳化系バインダーなどが挙げられる。水溶性バインダーの具体例としては、酸化でんぷん、無変性でんぷん、リン酸エステルなどで変性されたでんぷん等のでんぷん類；カゼイン、ゼラチンなどの水溶性プロテイン；カルボキシメチルセルロースなどの変性セルロース類；部分または完全けん化されたポリビニルアルコール、変性ポリビニルアルコール等が挙げられる。水乳化系バインダーの具体例としては、カルボキシル基やニトリル基を有することもあるスチレン−ブタジエン系樹脂（ＳＢＲラテックス）、アクリロニトリル−ブタジエン系樹脂（ＮＢＲラテックス）、クロロプレン系樹脂（ＣＲラテックス）、メチルメタクリレート−ブタジエン系樹脂（ＭＢＲラテックス）、アクリル系モノマー２種以上の共重合樹脂、アクリル系モノマーと酢酸ビニルとの共重合樹脂、アクリル系モノマーとスチレンとの共重合樹脂、酢酸ビニル樹脂、スチレン−酢酸ビニル樹脂、エチレン−酢酸ビニル樹脂などが挙げられる。
水性バインダーとして、２種類以上の異なる水性バインダーを使用しても良い。
【００２８】
本発明の紙用塗工組成物における顔料、水性バインダー（固形分）および紙塗工用樹脂（固形分）の重量比率としては、通常、顔料１００重量部に対して、水性バインダーが１〜２００重量部程度、とりわけ好ましくは５〜５０重量部程度であり、紙塗工用樹脂が０.０５〜５重量部程度、とりわけ好ましくは、０.１〜２重量部程度である。
【００２９】
紙用塗工組成物を調製するにあたり、顔料、水性バインダー及び樹脂組成物の添加混合順序は任意であり、特に制限されない。例えば、樹脂組成物を顔料及び水性バインダーの混合物に添加混合する方法、樹脂組成物を予め顔料又は水性バインダーに添加混合しておき、これを残りの成分と配合する方法などが採用できる。
【００３０】
さらに、塗工組成物に、例えば、アロンＴ−４０（東亞合成社製）、スミレーズレジン DS-10（住友化学社製）などの分散剤、粘度・流動性調整剤、消泡剤、防腐剤、潤滑剤、保水剤、染料・有色顔料等の着色剤、ならびに、本発明の紙塗工用樹脂とは異なる印刷適性向上剤および耐水化剤などを含有せしめてもよい。
【００３１】
本発明の塗工紙とは、前記紙塗工用組成物を片面または両面に含有する紙である。紙の製造方法としては、例えば、製紙科学（中外産業調査会発行（１９８２））、Pulp and Paper：Chemistry and Chemical Technology, Vol.II, John Wiley & Sons (1980)などに記載の方法により、化学パルプ、機械パルプ、故紙パルプなどを抄紙する方法などが挙げられる。
本発明に用いられる紙に、必要により、填料、サイジング剤、バンド剤、紙力増強剤、染料などの添加剤を含有せしめた紙であってもよい。
なお、本発明の紙とは広義の意味であって、狭義の意味でいう紙のほか、いわゆる板紙をも包含する。
【００３２】
本発明の塗工紙の製造方法としては、例えば、紙に塗工組成物を１回塗工する方法、塗工組成物の配合比率が同じまたは異なる塗工組成物を複数回塗工する方法などが挙げられる。
ここで、塗工方法としては、例えば、ブレードコーター、エアーナイフコーター、バーコーター、サイズプレスコーター、ゲートロールコーター、キャストコーターなどのコーターを用いて塗工組成物を塗工原紙に塗布し、その後、必要な乾燥を行い、さらに必要に応じてスーパーカレンダーなどで平滑化処理を施す方法などが挙げられる。
【００３３】
【発明の効果】
本発明の紙塗工用樹脂は、耐水性およびインク受理性に優れた塗工紙を与える。また、本発明の樹脂は印刷適性向上剤および耐水化剤にも使用し得る。
【００３４】
【実施例】
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれらによって限定される物ではない。例中、部および％は、特に断わらないかぎり重量基準である。また、固形分は、ＪＩＳ Ｋ６８２８の４．９に準じて乾燥することにより求めた蒸発残分であり、粘度及びｐＨは、２５℃において測定した値である。
【００３５】
（実施例１）
＜（b）成分の製造例１：樹脂１-１の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、３−メチルテトラヒドロ無水フタル酸および４−メチルテトラヒドロ無水フタル酸の混合物４５８．０部（２．７６モル比、HN-2000 日立化成工業（株）製）及びテトラヒドロ無水フタル酸１６７７．５部（１１．０３モル比）を仕込み、内温を１２０℃に昇温した。次に、内温１２０〜１４０℃に保温しながら、エチレングリコール４２７．７部（６．８９モル比）をゆっくりと滴下し、滴下終了後、内温１４０〜１５５℃でさらに１時間攪拌し、末端に遊離カルボキシル基を有する反応生成物２５６３．０部を得た。該反応生成物は、エチレングリコールがすべて反応したとして、６．８９モル比とみなした。その後、このポリエステルを冷却せずにステンレスのトレイに回収し、冷却して固化させ、樹脂（１-１）を得た。
【００３６】
＜（a）成分と（b）成分との生成物の製造例１：樹脂１-２の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂（１-１）を１２０８．４部（３．２５モル比）添加し、内温を１１０℃まで昇温させたのち、トリエチレンテトラミン９５０．５部（６．５０モル比、アミノ基として２６．０モル比）を１１０〜１３５℃でゆっくりと滴下した。次いで、生成する水を留去しながら内温を１４５℃まで昇温させ、発生する水を留去しながら、さらに内温１４５〜１５５℃で４時間反応させた。このとき、留去した水の重量は３９．０部であった。その後、水６３４．７部を加えて固形分濃度７３．６％のポリエステルポリアミド樹脂水溶液（樹脂１-２）２７６６．４部（アミノ基として１９．５モル比）を得た。
【００３７】
＜（a）〜（c）成分から得られる生成物の製造例１：樹脂１-３の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂（１-２）を１９０．７部（アミノ基として１．３４モル比）と水２４．３部を添加し、６５〜７５℃に内温を保持しながら、テトラヒドロ無水フタル酸１７．０部（０．１１モル比）を添加し、さらに内温６５〜７５℃で２時間攪拌した。次に、内温６５〜７５℃でエピクロルヒドリン１６．８部（０．１８モル比）を２時間かけて滴下し、さらに内温６５〜７５℃で４時間攪拌した。その後、室温に冷却し、固形分濃度７０％のエピクロルヒドリン変性ポリエステルポリアミド樹脂水溶液（樹脂１-３）２４８．４部（アミノ基として１．２３モル比）を得た。
【００３８】
＜紙塗工用樹脂の製造例１：紙塗工用樹脂１の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂（１-３）を２４８．４部（アミノ基として１．２３モル比）添加し、８０℃まで内温を昇温させた。次に、尿素３３．０部（０．５５モル比）を添加した後、内温を９０℃まで昇温させた。続いて、発生するアンモニアを系外に留去しながら、内温１０５℃まで２時間かけて昇温させ、さらに、発生するアンモニアを反応器から留去しながら、内温１０５℃程度で１０時間反応させた。その後、水９９．０部を徐々に加えながら冷却して、不揮発分５３．０％、ｐＨ７．９６、粘度８０．０mPa・sの水溶液（紙塗工用樹脂樹脂１）３６６．０部を得た。
【００３９】
（実施例２）
＜（b）成分の製造例２：樹脂２-１の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、３−メチルテトラヒドロ無水フタル酸および４−メチルテトラヒドロ無水フタル酸の混合物４２４．８部（２．５６モル比）及びテトラヒドロ無水フタル酸１５５５．６部（１０．２２モル比）を仕込み、内温を１２０℃に昇温した。次に、内温１２０〜１４０℃に保温しながら、エチレングリコール３９６．７部（６．３９モル比）をゆっくりと滴下し、滴下終了後、内温１４０〜１５５℃でさらに１時間攪拌し、末端に遊離カルボキシル基を有するポリエステル２３７６．７部（６．３９モル比とみなす）を得た。その後、このポリエステルを冷却せずにステンレスのトレイに回収し、冷却・固化させ、樹脂（２-１）を得た。
【００４０】
＜（a）成分と（b）成分との生成物の製造例２：樹脂２-２の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂（２-１）を１０５９．６部（２．８５モル比）添加し、内温を１１０℃まで昇温させ、トリエチレンテトラミン８３３．２部（５．７０モル比、アミノ基として２２．８モル比）を内温１１０〜１３５℃でゆっくりと滴下した。次いで、生成する水を留去しながら内温を１４５℃まで昇温させ、発生する水を留去しながら、さらに内温１４５〜１５５℃で４時間攪拌した。このとき、留去した水の重量は３７．１部であった。続いて、水８１１．２部を加えて固形分濃度６７．３％のポリエステルポリアミド樹脂水溶液（樹脂２-２）２６６２．０部（アミノ基として１７．１モル比）を得た。
【００４１】
＜（a）〜（c）成分から得られる生成物の製造例２：樹脂２-３の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂（２-２）を７３０．１部（アミノ基として２．３４モル比）と水８６．６部を添加し、内温を７０℃に昇温させた。次に、内温６５〜７５℃に保持しながら、テトラヒドロ無水フタル酸５９．２部（０．３９モル比）を添加し、さらに内温６５〜７５℃にて２時間攪拌した。続いて、内温６５〜７５℃にてエピクロルヒドリン５７．６部（０．６２モル比）を２時間かけて滴下し、さらに内温６５〜７５℃にて４時間攪拌した。その後、室温に冷却し、固形分濃度６６．２％のエピクロルヒドリン変性ポリエステルポリアミド樹脂水溶液（樹脂２-３）８９４．７部（アミノ基として４．３０モル比）を得た。
【００４２】
＜紙塗工用樹脂の製造例２：紙塗工用樹脂２の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂（２-３）を２８３．２部（アミノ基として０．６２モル比）添加し、内温を８０℃まで昇温させ、尿素３１．１部（０．５２モル比）を添加した後、さらに内温を９０℃まで昇温させた。次いで、生成するアンモニアを反応器から留去しながら、内温１０５℃まで２時間かけて昇温させ、さらに、発生するアンモニアを反応器から留去しながら、内温１０４〜１０６℃で１０時間攪拌した。その後、水４３．３部を徐々に加えながら冷却して、不揮発分５８．９％、ｐＨ７．９２、粘度２２１mPa・sの水溶液（紙塗工用樹脂２）３６３．１部を得た。
【００４３】
（実施例３）
＜（b）成分の製造例３：樹脂３-１の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、３−メチルテトラヒドロ無水フタル酸および４−メチルテトラヒドロ無水フタル酸の混合物４３２．０部（２．６０モル比）及びテトラヒドロ無水フタル酸１５８２．３部（１０．４０モル比）を添加し、内温を１２０℃に昇温した。次に、内温１２０〜１４０℃を保持しながら、エチレングリコール４０３．５部（６．５０モル比）をゆっくりと滴下し、滴下終了後、内温１４０〜１５５℃にて、さらに１時間攪拌させ、末端に遊離カルボキシル基を有する生成物２４１８．３部（６．５０モル比とみなす）を得た。その後、この生成物を冷却せずにステンレスのトレイに回収し、冷却・固化させ、樹脂（３-１）を得た。
【００４４】
＜（a）成分と（b）成分との生成物の製造例３：樹脂３-２の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂（３-１）を４９９．０部（１．３４モル比）添加し、内温を１１０℃まで昇温させたのち、トリエチレンテトラミン２９４．２部（２．０１モル比、アミノ基として８．０５モル比）及び２−アミノエチルピペラジン８６．６部（０．６７モル比、アミノ基として１．３４モル比）を内温１１０〜１３５℃でゆっくりと滴下した。次いで、生成する水を留去しながら内温を１４５℃まで昇温させ、発生する水を留去しながら、さらに内温１４５〜１５５℃にて４時間攪拌した。このとき、留去した水の重量は１９．７部であった。その後、水１５７．５部を加えて固形分濃度８０％のポリエステルポリアミド樹脂水溶液（樹脂３-２）１０１３．１部（アミノ基として６．７０モル比）を得た。
【００４５】
＜（a）〜（c）成分から得られる生成物の製造例３：樹脂３-３の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂（３-２）を２５１．１部（アミノ基として１．６６モル比）と水１８１．４部を添加し、内温を７０℃に昇温させた。そこへ、内温６５〜７５℃にてエピクロルヒドリン３０．８部（０．３３モル比）を１時間かけて滴下し、さらに内温６５〜７５℃で４時間攪拌した。その後、室温に冷却し、固形分濃度５０％のエピクロルヒドリン変性ポリエステルポリアミド樹脂水溶液（樹脂３-３）４６２．３部（アミノ基として１．６６モル比）を得た。
【００４６】
＜紙塗工用樹脂の製造例３：紙塗工用樹脂３の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂（３-３）を１５７．６部（０．１１部、アミノ基として０．５７モル比）添加し、内温を８０℃まで昇温させ、尿素２０．４部（０．３４モル比）を添加した後、内温を９０℃へ昇温させた。次いで、生成するアンモニア及び水を留去しながら内温を１１０℃まで２時間かけて昇温させ、さらに、発生成するアンモニア及び水を留去しながら、内温１１０℃にて８時間攪拌させた。このとき、留去した水の重量は５７．８部であった。その後、水４２．８部を徐々に加えながら冷却して、不揮発分６０．０％、ｐＨ７．９７、粘度２１０mPa・sの水溶液（紙塗工用樹脂３）１６０．８ｇを得た。
【００４７】
（実施例４）
＜（a）成分と（b）成分との生成物の製造例４：樹脂４-２の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、トリエチレンテトラミン１３５．８部（０．９３モル比、アミノ基として３．７１モル比）を添加し、内温を７０℃に昇温し、内温６５〜７５℃で、テトラヒドロ無水フタル酸７０．６部（０．４６モル比）を仕込み、さらに内温６５〜７５℃で８時間攪拌させた。その後、水８０．１部を加えながら室温に冷却し、固形分濃度７０％のポリアミド樹脂水溶液（樹脂４-２）２８６．３部（アミノ基として３．２５モル比）を得た。
【００４８】
＜（a）〜（c）成分から得られる生成物の製造例４：樹脂４-３の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂（４−２）を２８６．３部（アミノ基として３．２５モル比）と水２５．８部を添加し、内温を７０℃に昇温させ、内温６５〜７５℃でエピクロルヒドリン６０．１部（０．６５モル比）を３．５時間かけて滴下し、さらに内温６５〜７５℃で４時間攪拌した。その後、室温に冷却し、固形分濃度７０％のエピクロルヒドリン変性ポリアミド樹脂水溶液（樹脂４-３）３７２．１部（アミノ基として３．２５モル比）を得た。
【００４９】
＜紙塗工用樹脂の製造例４：紙塗工用樹脂４の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂（４-３）を１１０．９部（アミノ基として０．９７モル比）添加し、内温を８０℃へ昇温させた。次に、尿素３４．９部（０．５８モル）を添加した後、内温を９０℃へ昇温させ、生成するアンモニアを反応器から留去しながら、内温１１０℃まで０．５時間かけて昇温させた。続いて、生成するアンモニアを反応器から留去しながら、内温１１０℃にて８時間攪拌した。その後、水３８．７部を徐々に加えながら冷却して、不揮発分６０．４％、ｐＨ８．０９、粘度１７８mPa・sの水溶液（紙塗工用樹脂４）１７５．６部を得た。
【００５０】
（比較例１）
＜（b）成分の製造例５：樹脂５-１の合成＞
温度計、還流冷却器及び攪拌棒を備えた四つ口フラスコに、３−メチルテトラヒドロ無水フタル酸および４−メチルテトラヒドロ無水フタル酸の混合物４２４．２部（２．５５モル比）及びテトラヒドロ無水フタル酸１５５３．４部（１０．２１モル比）を、内温を１２０℃に昇温した。そして、内温１２０〜１４０℃にて、エチレングリコール３９６．１部（６．３８モル比）をゆっくりと滴下し、滴下終了後、内温１４０〜１５５℃でさらに１時間攪拌し、末端に遊離カルボキシル基を有する生成物（樹脂５-１）２３７３．３部（６．３８モル比とみなす）を得た。その後、このポリエステルを冷却せずにステンレスのトレイに回収し、冷却して固化させ樹脂５-１を得た。
【００５１】
＜（a）成分と（b）成分との生成物の製造例５：樹脂５-２の合成＞
温度計、還流冷却器及び攪拌棒を備えた四つ口フラスコに、樹脂５-１を１６０．０部（０．４３モル比）仕込み、内温を１１０℃まで昇温させ、そこへトリエチレンテトラミン１２５．９部（０．８６モル比、アミノ基として３．４４モル比）を内温１１０〜１３５℃でゆっくりと滴下した。次いで、生成する水を留去しながら内温を１４５℃まで昇温させ、生成する水を留去しながら、さらに内温１４５〜１５５℃にて４時間攪拌した。このとき、留去された水の重量は４．８部であった。その後、水６０．９部を加えて固形分濃度８０％のポリエステルポリアミド樹脂水溶液（樹脂５-２）３４２．０部（０．４３モル比、アミノ基として２．５８モル比）を得た。
【００５２】
＜（a）成分と（b）成分との生成物に（d）成分を反応せしめて得られる生成物の製造例１：樹脂５-３の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂（５-２）を３４２．０部（０．４３モル比、アミノ基として２．５８モル比）添加し、内温を８０℃へ昇温させ、尿素６２．０部（１．０３モル比）を添加した後、内温を９０℃へ昇温させた。次いで、生成するアンモニアを反応器から留去しながら、内温を１１０℃まで１．５時間かけて昇温し、さらに、内温１１０℃にて８時間攪拌した。その後、水１３９．４部を徐々に加えながら２５℃に冷却し、２８％苛性ソーダを用いてｐＨを１１．０に調整し、不揮発分５７．２％のポリエステルポリアミドポリ尿素樹脂水溶液（樹脂５-３）５９２．８部（０．４３モル比、アミノ基として１．５５モル比）を得た。
【００５３】
＜（a）、（b）および（d）成分の反応生成物に、（c）成分を反応せしめて得られる紙塗工用樹脂の製造例１：樹脂５の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂５-３を１５０．２部（０．１１モル比、アミノ基として０．３９モル比）添加し、内温を７０℃に昇温させた。次に、内温６５〜７５℃にてエピクロルヒドリン１０．１部（０．１１モル比）を３時間かけて滴下し、さらに内温６５〜７５℃で４時間攪拌した。続いて、内温６５〜７５℃で２時間攪拌した。その後、水２．７部を加えてから室温に冷却し、不揮発分５９．９％、ｐＨ６．７９、粘度２７２mPa・sの水溶液（紙塗工用樹脂５）１７０．５部を得た。
【００５４】
（比較例２）
塗工用組成物に紙塗工用樹脂を使用しなかった。
【００５５】
＜塗工組成物の製造例＞
実施例１〜４および比較例１で得られた紙塗工用樹脂１〜５を、表１に記載の重量比率で混合し、すべての固形分が６４％となるように水と１０％苛性ソーダ水溶液で調整して、塗工組成物とした。得られたそれぞれの塗工組成物について、以下の方法で物性値を測定し、その結果を表２に示した。
【００５６】
＜ｐＨ＞
ガラス電極式水素イオン濃度計〔東亜電波工業（株）製〕を用い、調製直後の塗工組成物のｐＨを２５℃にて測定した。
【００５７】
＜粘度＞
Ｂ型粘度計〔（株）東京計器製、ＢＬ型〕を用い、６０rpm 、２５℃で、調製直後の塗工組成物の粘度を測定した。
【００５８】
【表１】
（塗工組成物）
＜塗工紙の製造例＞
塗工組成物を、米坪量８０ｇ／m2の上質紙の片面に、ワイヤーロッドを用いて塗工量が１４ｇ／m2となるように塗布した。塗布後ただちに、１２０℃にて３０秒間熱風乾燥し、次いで温度２３℃、相対湿度５０％にて１６時間調湿し、さらに温度６０℃、線圧６０kg／cmの条件で２回スーパーカレンダー処理を施して、塗工紙を得た。こうして得た塗工紙を耐水性及びインキ受理性の試験に供し、試験結果を表２にまとめた。なお、試験方法は以下のとおりである。
【００６０】
＜耐水性：ウェットピック法（ＷＰ法）＞
ＲＩ試験機（明製作所製）を使用し、塗工面を給水ロールで湿潤させた後に印刷し、紙むけ状態を肉眼で観察して判定した。判定基準は次のように行った。
耐水性 （劣）１〜５（優）
【００６１】
＜インキ受理性＞
＜Ａ 法＞
ＲＩ試験機を使用して、塗工面を給水ロールで湿潤させた後に印刷し、インキの受理性を肉眼で観察して判定した。判定基準は次のように行った。
インキ受理性 （劣）１〜５（優）
【００６２】
＜Ｂ 法＞
ＲＩ試験機を使用して、金属ロールとゴムロールの間にわずかな間隙をあけ、その間隙に水を注いだ後速やかに印刷し、インキの受理性を肉眼で観察して判定した。判定基準は次のように行った。
インキ受理性 （劣）１〜５（優）
【００６３】
【表２】
（塗工組成物および塗工紙の物性）
──────────────────────────────
実施例 比較例
1 2 3 4 1 2
──────────────────────────────
紙塗工用樹脂 1 2 3 4 5 −
──────────────────────────────
尿素の反応順序*1 後 後 後 後 前 −
──────────────────────────────
塗工組成物の物性
ｐＨ 9.1 9.1 9.1 9.1 9.1 9.3
粘度（mPa・s） 1790 1840 1800 1940 1940 1840
──────────────────────────────
塗工紙物性
耐水性 ：WP法 4.7 4.5 4.6 4.4 3.5 1.2
インキ受理性：A法 4.6 4.7 4.4 4.7 2.7 1.5
〃 ：B法 4.7 4.8 4.4 5.0 2.7 1.3
──────────────────────────────
*1：(c)エピクロルヒドリンと(d)尿素の反応順序。表中の「前」は(d)尿素の反応をエピクロルヒドリンの反応の前に行ったことを示し、「後」は(d)尿素の反応をエピクロルヒドリンの反応の後に行ったことを示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a paper coating resin that gives an excellent printing effect to paper.
[0002]
[Prior art]
Coated papers obtained by applying a coating composition mainly composed of pigments, water-based binders and paper coating resins to paper, and performing necessary treatments such as drying and calendering are commercial prints, magazines, books, etc. Widely used in As a paper coating resin that gives coated paper with excellent ink acceptability and water resistance, (a) polyamines, (b) free carboxyls obtained by reaction of alicyclic polycarboxylic acids with glycols A reaction product having a group and / or a resin obtained by reacting an alicyclic polyvalent carboxylic acid, (c) an alkylating agent, and (d) urea is reported in, for example, Patent Document 1 and the like. As a specific method for producing the resin, a paper coating resin is disclosed in which the components (a), (b), and (d) are reacted sequentially, and then the component (c) is reacted.
[0003]
[Patent Document 1]
Japanese Patent Laid-Open No. 62-116619
[0004]
[Problems to be solved by the invention]
Recently, as the coated paper has been improved in printing quality and speed, the object of the present invention is to provide a coated paper having further improved ink acceptability and water resistance. It is to provide a resin.
[0005]
[Means for Solving the Problems]
The present invention is a paper coating resin characterized by reacting the component (d) with a resin obtained by reacting the following components (a), (b) and (c): .
(A) Polyamines
(B) Obtained by reaction of alicyclic polycarboxylic acids with glycols
A reaction product having a free carboxyl group, and / or
Alicyclic polycarboxylic acids
(C)At least one alkylating agent selected from the group consisting of general formulas (4) to (6)
An epihalohydrin represented by
HOCH 2 (CH 2 ) W X (5)
(In the formula, X represents a halogen atom or the like, and w represents a number of about 1 to 3.)
A monohalohydrin represented by
Dihalohydrin represented by
(D) Urea
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The (a) polyamines in the present invention are aliphatic amines having at least two primary or secondary amino groups in the molecule, such as polyethyleneimine obtained by polymerizing ethyleneimine; ethylenediamine, propylenediamine, Alkylenediamine containing an alkylene group of about 1 to 10 carbon atoms such as hexamethylenediamine; diethylenetriamine, triethylenetetramine, pentaethylenehexamine, tetraethylenepentamine, iminobispropylamine, 3-azahexane-1,6-diamine, Examples include polyalkylene polyamines such as 4,7-diazadecane-1,10-diamine; alicyclic amines such as isophorone diamine and bis (aminomethyl) cyclohexane; and heterocyclic polyamines.
[0007]
Here, the heterocyclic polyamine usually includes a heterocyclic ring that is an alicyclic hydrocarbon group containing at least one heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom, and includes at least a primary or secondary amino group. It is an amine having two. Specifically, heterocyclic diamines such as piperazine, homopiperazine and the like; heterocycles containing aminoalkyl such as N-aminoethylpiperazine, N-aminopropylpiperazine, and 1,4-bis (aminopropyl) piperazine Examples thereof include cyclic polyamines.
The heterocyclic polyamine is preferably a heterocyclic polyamine containing a nitrogen atom as a hetero atom of the heterocyclic ring.
[0008]
As the component (a), two or more different polyamines may be used.
As the component (a), polyalkylene polyamine is preferable, and diethylenetriamine and triethylenetetramine are particularly preferable.
[0009]
The (b) alicyclic polyvalent carboxylic acid of the present invention has an alicyclic polyvalent carboxylic acid which has two or more carboxyl groups in the molecule and may have a double bond in the molecule, An ester composed of the carboxylic acid and an alcohol having about 1 to 4 carbon atoms, or an anhydride of the carboxylic acid.
Specifically, alicyclic rings such as tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane-1,4-dicarboxylic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, cyclohexane-1,2,4-tricarboxylic acid Lower polyesters such as methyl group and ethyl group of the alicyclic polycarboxylic acid: tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride Examples thereof include alicyclic polycarboxylic acid anhydrides such as acid and cyclohexane-1,2,4-tricarboxylic acid monoanhydride.
[0010]
As the (b) component alicyclic polycarboxylic acid, two or more kinds of alicyclic polycarboxylic acid may be used. The component (b) of the alicyclic polycarboxylic acid is at least one alicyclic selected from tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride and 4-methyltetrahydrophthalic anhydride. Formula polycarboxylic acids and their acid anhydrides are preferred.
[0011]
Also, as the component (b), a reaction product obtained by reacting the alicyclic polyvalent carboxylic acids and glycols with an alicyclic polyvalent carboxylic acid in an excess molar ratio and having a free carboxyl group at the molecular end. Can be used.
Here, the glycols include alkylene glycols such as ethylene glycol, propylene glycol and butanediol, cycloalkylene glycols such as cyclopentanediol and cyclohexanediol, alkenylene glycols such as butenediol and octenediol, diethylene glycol and dipropylene. Examples thereof include polyalkylene glycols such as glycol, triethylene glycol, polyethylene glycol, and polytetramethylene glycol, ethylene oxide adducts of bisphenol A, ethylene oxide adducts of hydrogenated bisphenol A, and the like. These glycols may be used alone or in combination of two or more different types. As glycols, ethylene glycol and diethylene glycol are particularly preferable.
[0012]
As a ratio of the alicyclic polyvalent carboxylic acid and the glycol in the reaction product having a free carboxyl group at the molecular end, the alicyclic polyvalent carboxylic acid is usually 1 to 2 per 1 mol of the hydroxyl group of the glycol. About 1 mol, preferably about 1 to 1.5 mol.
The reaction product having a free carboxyl group at the molecular terminal is usually at a temperature of 100 to 200 ° C., preferably about 120 to 180 ° C. for about 2 to 10 hours, preferably while distilling off the water produced as needed. It can be obtained by stirring for about 3 to 8 hours.
[0013]
The component (b) of the reaction product having a free carboxyl group at the molecular end is, among others, at least selected from tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride and 4-methyltetrahydrophthalic anhydride A reaction product having a free carboxyl group at the molecular end, which is a reaction product of one type of alicyclic polycarboxylic acid anhydride and ethylene glycol or diethylene glycol, is preferred.
[0014]
The component (c) of the present invention isIt is at least one alkylating agent selected from the group consisting of the following general formulas (4) to (6).
[0015]
General formula (4) is the following formula (4)
It is an epihalohydrin represented by
Examples of epihalohydrin include epichlorohydrin and epibromohydrin.
[0016]
General formula (5) is the following formula (5)
HOCH2(CH2)WX (5)
(In the formula, X represents a halogen atom or the like, and w represents a number of about 1 to 3.)
It is a monohalohydrin represented by
Examples of the monohalohydrin include ethylene chlorohydrin and ethylene bromohydrin.
[0017]
General formula (6) is the following formula (6)
It is a dihalohydrin represented by
Examples of the dihalohydrin include 1,3-dichloro-2-propanol and 2,3-dichloro-1-propanol.
[0018]
As component (c)Two or more alkylating agents selected from the group represented by the general formulas (4) to (6)May be used in combination.
As the component (c), epihalohydrin represented by the general formula (4) is preferable, and epichlorohydrin is particularly preferable.
[0019]
Component (d) of the present invention includes, for example, urea, methylurea, dimethylurea, thiourea, 4,5-dihydroxy-2-imidazolidinone, 1- (2-aminoethyl) -2-imidazolidinone and the like. Ureas, among which urea is preferred.
[0020]
The resin for paper coating of the present invention is obtained by reacting the component (d) with the reaction product of the components (a) to (c).
The ratio of monomer units contained in the resin is usually 1 mol ratio of the total amount of primary amino groups and secondary amino groups (hereinafter referred to as amino group amounts) contained in component (a). (B) component is about 0.1-0.5 mol ratio, (c) component is about 0.1-0.9 mol ratio, (d) component is 0.1-0.5 mol ratio. It is about the ratio.
[0021]
The paper coating resin production method of the present invention is a production method in which the components (a) to (c) are reacted in an arbitrary order and the component (d) is subsequently reacted. Among them, a production method in which (a) component and (b) component are reacted, (c) component is reacted, and then (d) component is preferably reacted. Specifically, (a) glycol and alicyclic (B) A reaction product having a free carboxyl group at the molecular end and an amidation reaction of component (a) followed by reaction of component (c) d) Method of deammonia reaction with the component, (a) After the components (a) and (b) are amidated in the same manner as (a), the component (b) of the alicyclic polycarboxylic acid is further converted to ( a) Amidation reaction to the amino residue derived from the component, followed by reacting the component (c), followed by deammonia reaction with the component (c) (c) Component (a) and the alicyclic polyvalent Carry out the amidation reaction of component (b) of the carboxylic acid, and then react the component (c). After it is illustrated and method in which deammoniation and component (d).
[0022]
The reaction between component (a) and component (b) varies depending on the type of component (b), and the reaction temperature and reaction time vary. For example, (b) a reaction product and / or fat having a free carboxyl group at the molecular end. When the acyclic polycarboxylic acid and the component (a) are subjected to an amidation reaction, the reaction is usually performed at about 130 to 250 ° C. for about 2 to 10 hours while distilling off water and the like;
(B) When an alicyclic polycarboxylic acid anhydride and the component (a) are subjected to an amidation reaction, the reaction is usually performed at about 50 to 200 ° C. for about 1 to 10 hours while distilling off water and the like. ;
(B) When an alicyclic polyvalent carboxylic acid ester and the component (a) are subjected to an amidation reaction, the reaction is usually performed at about 80 to 250 ° C. for about 2 to 10 hours while distilling off water or alcohol. Methods and the like.
[0023]
The reaction between the amino group and the component (c) is usually about 30 to 120 ° C., preferably about 50 to 100 ° C. for about 1 to 20 hours, preferably about 2 to 10 hours.
The viscosity of the obtained aqueous solution at 25 ° C. in a 50% by weight aqueous solution is usually about 10 to 3,000 mPa · s, preferably about 10 to 200 mPa · s, particularly preferably about 30 to 100 mPa · s.
[0024]
The deammonia reaction between the reaction products (a) to (c) and the component (d) is usually about 80 to 180 ° C., preferably about 90 to 160 ° C., while distilling off the generated ammonia. The method of making it react for about -30 hours, Preferably about 5 to 20 hours etc. are mentioned.
[0025]
The resin for paper coating obtained in this way, if necessary, using inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and organic acids such as formic acid, acetic acid, propionic acid, adipic acid, Usually, the pH is adjusted to about 6 to 10, preferably neutral.
[0026]
The paper coating resin thus obtained is prepared as a paper coating composition together with a pigment and an aqueous binder.
Here, examples of the pigment include white inorganic pigments and white organic pigments. Specific examples of the white inorganic pigment include kaolin, talc, calcium carbonate (heavy or light), aluminum hydroxide, satin white, titanium oxide, and the like. Specific examples of the white organic pigment include polystyrene, melamine-formaldehyde resin, urea-formaldehyde resin, and the like.
Two or more types of pigments may be used as the pigment.
[0027]
Examples of the aqueous binder include a water-soluble binder and a water-emulsified binder. Specific examples of the water-soluble binder include starches such as starch modified with oxidized starch, non-denatured starch, and phosphate ester; water-soluble proteins such as casein and gelatin; modified celluloses such as carboxymethyl cellulose; partially or completely Examples thereof include saponified polyvinyl alcohol and modified polyvinyl alcohol. Specific examples of water-emulsified binders include styrene-butadiene resins (SBR latex), acrylonitrile-butadiene resins (NBR latex), chloroprene resins (CR latex), and methyl methacrylate, which may have carboxyl groups or nitrile groups. -Butadiene resin (MBR latex), copolymer resin of two or more acrylic monomers, copolymer resin of acrylic monomers and vinyl acetate, copolymer resin of acrylic monomers and styrene, vinyl acetate resin, styrene-acetic acid Examples thereof include vinyl resins and ethylene-vinyl acetate resins.
Two or more different aqueous binders may be used as the aqueous binder.
[0028]
The weight ratio of the pigment, the aqueous binder (solid content) and the paper coating resin (solid content) in the paper coating composition of the present invention is usually 1 to 200 based on 100 parts by weight of the pigment. About 5 parts by weight, particularly preferably about 5 to 50 parts by weight, and the resin for paper coating is about 0.05 to 5 parts by weight, and particularly preferably about 0.1 to 2 parts by weight.
[0029]
In preparing the paper coating composition, the order of addition and mixing of the pigment, the aqueous binder and the resin composition is arbitrary and is not particularly limited. For example, a method of adding and mixing a resin composition to a mixture of a pigment and an aqueous binder, a method of adding and mixing a resin composition in advance to a pigment or an aqueous binder, and blending it with the remaining components can be employed.
[0030]
In addition, for example, dispersants such as Aron T-40 (manufactured by Toagosei Co., Ltd.), Sumirez Resin DS-10 (manufactured by Sumitomo Chemical Co., Ltd.), viscosity / fluidity modifiers, antifoaming agents, antiseptics, etc. A colorant such as an agent, a lubricant, a water retention agent, a dye or a colored pigment, and a printability improver and a water resistance agent different from the paper coating resin of the present invention may be contained.
[0031]
The coated paper of the present invention is paper containing the paper coating composition on one side or both sides. As a method for producing paper, for example, paper science (published by Chugai Industry Research Council (1982)), Pulp and Paper: Chemistry and Chemical Technology, Vol. II, John Wiley & Sons (1980) can be used. Examples of the method include paper making of pulp, mechanical pulp, waste paper pulp, and the like.
The paper used in the present invention may be paper in which additives such as a filler, a sizing agent, a banding agent, a paper strength enhancer, and a dye are added as necessary.
In addition, the paper of the present invention has a broad meaning, and includes so-called paperboard in addition to paper in a narrow sense.
[0032]
Examples of the method for producing the coated paper of the present invention include, for example, a method in which a coating composition is applied to paper once, and a method in which a coating composition having the same or different blending ratio is applied multiple times. Etc.
Here, as a coating method, for example, a coating composition is applied to a coating base paper using a coater such as a blade coater, an air knife coater, a bar coater, a size press coater, a gate roll coater, or a cast coater, and then And a method of performing necessary drying and further performing a smoothing treatment with a super calender or the like, if necessary.
[0033]
【The invention's effect】
The resin for paper coating of the present invention gives a coated paper excellent in water resistance and ink acceptability. The resin of the present invention can also be used as a printability improver and a water resistance-imparting agent.
[0034]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not a thing limited by these. In the examples, parts and% are based on weight unless otherwise specified. Moreover, solid content is the evaporation residue calculated | required by drying according to 4.9 of JISK6828, and a viscosity and pH are the values measured at 25 degreeC.
[0035]
(Example 1)
<Production Example of Component (b) 1: Synthesis of Resin 1-1>
A reactor equipped with a thermometer, a reflux condenser and a stir bar was charged with 458.0 parts of a mixture of 3-methyltetrahydrophthalic anhydride and 4-methyltetrahydrophthalic anhydride (2.76 mole ratio, HN-2000 Hitachi Chemical) And 1677.5 parts (11.03 molar ratio) of tetrahydrophthalic anhydride were charged, and the internal temperature was raised to 120 ° C. Next, while maintaining the internal temperature at 120 to 140 ° C., 427.7 parts (6.89 mole ratio) of ethylene glycol was slowly added dropwise, and after completion of the dropwise addition, the mixture was further stirred at an internal temperature of 140 to 155 ° C. for 1 hour, 2563.0 parts of a reaction product having a free carboxyl group at the end was obtained. The reaction product was regarded as a 6.89 molar ratio, assuming all the ethylene glycol had reacted. Thereafter, this polyester was recovered in a stainless steel tray without being cooled, and cooled and solidified to obtain a resin (1-1).
[0036]
<Production Example 1 of Component (a) and Component (b) 1: Synthesis of Resin 1-2>
1208.4 parts (3.25 mole ratio) of the resin (1-1) was added to a reactor equipped with a thermometer, a reflux condenser and a stirring rod, and the internal temperature was raised to 110 ° C. 950.5 parts of ethylenetetramine (6.50 molar ratio, 26.0 molar ratio as an amino group) was slowly added dropwise at 110 to 135 ° C. Next, the internal temperature was raised to 145 ° C. while distilling off the generated water, and the reaction was further carried out for 4 hours at an internal temperature of 145 to 155 ° C. while distilling off the generated water. At this time, the weight of distilled water was 39.0 parts. Thereafter, 634.7 parts of water was added to obtain 2766.4 parts of an aqueous polyester polyamide resin solution (resin 1-2) having a solid content concentration of 73.6% (19.5 molar ratio as an amino group).
[0037]
<Production Example 1 of Products Obtained from Components (a) to (c) 1: Synthesis of Resin 1-3>
In a reactor equipped with a thermometer, a reflux condenser, and a stirring rod, 190.7 parts of resin (1-2) (1.34 mole ratio as amino group) and 24.3 parts of water were added, and 65-75 17.0 parts (0.11 molar ratio) of tetrahydrophthalic anhydride was added while maintaining the internal temperature at 0 ° C., and the mixture was further stirred at an internal temperature of 65 to 75 ° C. for 2 hours. Next, 16.8 parts (0.18 mole ratio) of epichlorohydrin was added dropwise at an internal temperature of 65 to 75 ° C. over 2 hours, and the mixture was further stirred at an internal temperature of 65 to 75 ° C. for 4 hours. Then, it cooled to room temperature and obtained 248.4 parts (1.23 molar ratio as an amino group) of epichlorohydrin modified polyester polyamide resin aqueous solution (resin 1-3) with a solid content concentration of 70%.
[0038]
<Production Example of Resin for Paper Coating 1: Synthesis of Resin 1 for Paper Coating>
248.4 parts of resin (1-3) (1.23 molar ratio as an amino group) was added to a reactor equipped with a thermometer, a reflux condenser and a stirring rod, and the internal temperature was raised to 80 ° C. . Next, after adding 33.0 parts of urea (0.55 molar ratio), the internal temperature was raised to 90 ° C. Subsequently, while distilling off the generated ammonia to the outside of the system, the temperature is raised to an internal temperature of 105 ° C. over 2 hours. Further, while distilling off the generated ammonia from the reactor, the internal temperature is about 105 ° C. for 10 hours. Reacted. Thereafter, cooling was performed while gradually adding 99.0 parts of water to obtain 366.0 parts of an aqueous solution (resin resin 1 for paper coating) having a non-volatile content of 53.0%, pH of 7.96, and a viscosity of 80.0 mPa · s. It was.
[0039]
(Example 2)
<Production Example 2 of Component (b): Synthesis of Resin 2-1>
A reactor equipped with a thermometer, reflux condenser and stir bar was charged with 424.8 parts (2.56 molar ratio) of 3-methyltetrahydrophthalic anhydride and 4-methyltetrahydrophthalic anhydride and 1555 tetrahydrophthalic anhydride. .6 parts (10.22 molar ratio) was charged, and the internal temperature was raised to 120 ° C. Next, while maintaining the internal temperature at 120 to 140 ° C., 396.7 parts (6.39 mole ratio) of ethylene glycol was slowly added dropwise, and after completion of the dropwise addition, the mixture was further stirred at an internal temperature of 140 to 155 ° C. for 1 hour, 2376.7 parts of polyester having a free carboxyl group at the end (considered as 6.39 molar ratio) was obtained. Thereafter, the polyester was recovered in a stainless steel tray without cooling, and cooled and solidified to obtain a resin (2-1).
[0040]
<Production Example 2: Product of Component (a) and Component (b): Synthesis of Resin 2-2>
To a reactor equipped with a thermometer, a reflux condenser, and a stirring rod, 1059.6 parts (2.85 mole ratio) of resin (2-1) was added, the internal temperature was raised to 110 ° C., and triethylenetetramine was added. 833.2 parts (5.70 molar ratio, 22.8 molar ratio as an amino group) was slowly added dropwise at an internal temperature of 110 to 135 ° C. Next, the internal temperature was raised to 145 ° C. while distilling off the generated water, and the mixture was further stirred for 4 hours at an internal temperature of 145 to 155 ° C. while distilling off the generated water. At this time, the weight of distilled water was 37.1 parts. Subsequently, 811.2 parts of water was added to obtain 2662.0 parts (17.1 molar ratio as amino groups) of a polyester polyamide resin aqueous solution (resin 2-2) having a solid content concentration of 67.3%.
[0041]
<Production Example 2 of Product Obtained from Components (a) to (c): Synthesis of Resin 2-3>
To a reactor equipped with a thermometer, a reflux condenser and a stirring rod, 730.1 parts of resin (2-2) (2.34 mole ratio as amino group) and 86.6 parts of water were added, and the internal temperature was adjusted. The temperature was raised to 70 ° C. Next, 59.2 parts (0.39 mole ratio) of tetrahydrophthalic anhydride was added while maintaining the internal temperature at 65 to 75 ° C, and the mixture was further stirred at an internal temperature of 65 to 75 ° C for 2 hours. Subsequently, 57.6 parts (0.62 mole ratio) of epichlorohydrin was added dropwise at an internal temperature of 65 to 75 ° C. over 2 hours, and the mixture was further stirred at an internal temperature of 65 to 75 ° C. for 4 hours. Then, it cooled to room temperature and obtained 894.7 parts (4.30 mol ratio as an amino group) of epichlorohydrin modified polyester polyamide resin aqueous solution (resin 2-3) with a solid content concentration of 66.2%.
[0042]
<Production Example 2 of Paper Coating Resin: Synthesis of Resin 2 for Paper Coating>
To a reactor equipped with a thermometer, a reflux condenser and a stirring rod, 283.2 parts of resin (2-3) (0.62 mole ratio as amino group) was added, and the internal temperature was raised to 80 ° C., After adding 31.1 parts of urea (0.52 molar ratio), the internal temperature was further raised to 90 ° C. Next, while distilling off the generated ammonia from the reactor, the temperature is raised to an internal temperature of 105 ° C. over 2 hours. Further, while distilling off the generated ammonia from the reactor, the internal temperature is 104 to 106 ° C. for 10 hours. Stir. Thereafter, cooling was performed while gradually adding 43.3 parts of water to obtain 363.1 parts of an aqueous solution (resin 2 for paper coating) having a non-volatile content of 58.9%, a pH of 7.92, and a viscosity of 221 mPa · s.
[0043]
(Example 3)
<Production Example 3 of Component (b): Synthesis of Resin 3-1>
A reactor equipped with a thermometer, reflux condenser and stir bar was charged with 432.0 parts (2.60 molar ratio) of 3-methyltetrahydrophthalic anhydride and 4-methyltetrahydrophthalic anhydride and 1582 tetrahydrophthalic anhydride. .3 parts (10.40 molar ratio) was added, and the internal temperature was raised to 120 ° C. Next, while maintaining the internal temperature of 120 to 140 ° C., 403.5 parts (6.50 molar ratio) of ethylene glycol was slowly added dropwise, and after completion of the addition, the mixture was further stirred at an internal temperature of 140 to 155 ° C. for 1 hour. To give 2418.3 parts of a product having a free carboxyl group at the end (taken as 6.50 molar ratio). Thereafter, the product was recovered in a stainless steel tray without cooling, and cooled and solidified to obtain a resin (3-1).
[0044]
<Production Example 3 of Product of Component (a) and Component (b) 3: Synthesis of Resin 3-2>
After adding 499.0 parts (1.34 mole ratio) of resin (3-1) to a reactor equipped with a thermometer, a reflux condenser, and a stirring rod, and raising the internal temperature to 110 ° C., Including 294.2 parts of ethylenetetramine (2.01 mole ratio, 8.05 mole ratio as amino group) and 86.6 parts of 2-aminoethylpiperazine (0.67 mole ratio, 1.34 mole ratio as amino group) The solution was slowly added dropwise at a temperature of 110 to 135 ° C. Next, the internal temperature was raised to 145 ° C. while distilling off the generated water, and the mixture was further stirred for 4 hours at an internal temperature of 145 to 155 ° C. while distilling off the generated water. At this time, the weight of distilled water was 19.7 parts. Thereafter, 157.5 parts of water was added to obtain 1013.1 parts of an aqueous polyester polyamide resin solution (resin 3-2) having a solid content concentration of 80% (6.70 mole ratio as amino groups).
[0045]
<Production Example 3 of Product Obtained from Components (a) to (c): Synthesis of Resin 3-3>
To a reactor equipped with a thermometer, a reflux condenser and a stirring rod, 251.1 parts of resin (3-2) (1.66 molar ratio as amino group) and 181.4 parts of water were added, and the internal temperature was adjusted. The temperature was raised to 70 ° C. There, 30.8 parts (0.33 molar ratio) of epichlorohydrin was dripped over 1 hour at the internal temperature of 65-75 degreeC, and also it stirred at the internal temperature of 65-75 degreeC for 4 hours. Then, it cooled to room temperature and obtained 462.3 parts (1.66 molar ratio as an amino group) of epichlorohydrin modified polyester polyamide resin aqueous solution (resin 3-3) with a solid content concentration of 50%.
[0046]
<Production Example 3 of Paper Coating Resin: Synthesis of Resin 3 for Paper Coating>
157.6 parts of resin (3-3) (0.11 part, 0.57 molar ratio as amino group) was added to a reactor equipped with a thermometer, a reflux condenser and a stirring rod, and the internal temperature was 80 ° C. And 20.4 parts (0.34 molar ratio) of urea was added, and then the internal temperature was raised to 90 ° C. Then, the internal temperature is raised to 110 ° C. over 2 hours while distilling off the generated ammonia and water, and further stirred for 8 hours at 110 ° C. while distilling off the generated ammonia and water. It was. At this time, the weight of distilled water was 57.8 parts. Thereafter, the mixture was cooled while gradually adding 42.8 parts of water to obtain 160.8 g of an aqueous solution (resin 3 for paper coating) having a nonvolatile content of 60.0%, pH of 7.97, and a viscosity of 210 mPa · s.
[0047]
(Example 4)
<Production Example 4 of Product of (a) Component and (b) Component: Synthesis of Resin 4-2>
To a reactor equipped with a thermometer, a reflux condenser and a stir bar, 135.8 parts of triethylenetetramine (0.93 mole ratio, 3.71 mole ratio as an amino group) was added, and the internal temperature was raised to 70 ° C. Then, 70.6 parts (0.46 mole ratio) of tetrahydrophthalic anhydride was charged at an internal temperature of 65 to 75 ° C., and further stirred at an internal temperature of 65 to 75 ° C. for 8 hours. Then, it cooled to room temperature, adding 80.1 parts of water, and obtained 286.3 parts (3.25 molar ratio as an amino group) of polyamide resin aqueous solution (resin 4-2) of 70% of solid content concentration.
[0048]
<Production Example 4 of Product Obtained from Components (a) to (c): Synthesis of Resin 4-3>
To a reactor equipped with a thermometer, a reflux condenser, and a stirring rod, 286.3 parts (3.25 mole ratio as an amino group) of resin (4-2) and 25.8 parts of water were added, and the internal temperature was adjusted. The temperature was raised to 70 ° C., 60.1 parts (0.65 mole ratio) of epichlorohydrin was added dropwise over 3.5 hours at an internal temperature of 65 to 75 ° C., and the mixture was further stirred at an internal temperature of 65 to 75 ° C. for 4 hours. Then, it cooled to room temperature and obtained 372.1 parts (3.25 molar ratio as an amino group) of epichlorohydrin modified polyamide resin aqueous solution (resin 4-3) with a solid content concentration of 70%.
[0049]
<Production Example 4 of Paper Coating Resin: Synthesis of Paper Coating Resin 4>
110.9 parts of resin (4-3) (0.97 mole ratio as amino group) was added to a reactor equipped with a thermometer, a reflux condenser and a stirring rod, and the internal temperature was raised to 80 ° C. . Next, after 34.9 parts (0.58 mol) of urea was added, the internal temperature was raised to 90 ° C., and the generated ammonia was distilled off from the reactor, and the internal temperature was raised to 110 ° C. for 0.5 hour. The temperature was raised over time. Subsequently, the resulting ammonia was stirred from the reactor for 8 hours at an internal temperature of 110 ° C. Thereafter, cooling was performed while gradually adding 38.7 parts of water to obtain 175.6 parts of an aqueous solution (resin 4 for paper coating) having a nonvolatile content of 60.4%, pH 8.09, and a viscosity of 178 mPa · s.
[0050]
(Comparative Example 1)
<Production Example 5 of Component (b): Synthesis of Resin 5-1>
A four-necked flask equipped with a thermometer, a reflux condenser and a stir bar was charged with 424.2 parts (2.55 mole ratio) of a mixture of 3-methyltetrahydrophthalic anhydride and 4-methyltetrahydrophthalic anhydride and tetrahydrophthalic anhydride. 1553.4 parts of acid (10.21 molar ratio) was heated to an internal temperature of 120 ° C. Then, 396.1 parts (6.38 mole ratio) of ethylene glycol was slowly added dropwise at an internal temperature of 120 to 140 ° C., and after completion of the dropwise addition, the mixture was further stirred for 1 hour at an internal temperature of 140 to 155 ° C. and released to the end. 2333.3 parts of a product having a carboxyl group (resin 5-1) (considered to be 6.38 molar ratio) was obtained. Thereafter, the polyester was recovered in a stainless steel tray without being cooled, and cooled and solidified to obtain a resin 5-1.
[0051]
<Production Example 5 of Product of Component (a) and Component (b): Synthesis of Resin 5-2>
A four-necked flask equipped with a thermometer, a reflux condenser and a stirring rod was charged with 160.0 parts (0.43 mole ratio) of resin 5-1, the internal temperature was raised to 110 ° C., and triethylene was added there. 125.9 parts of tetramine (0.86 molar ratio, 3.44 molar ratio as amino group) was slowly added dropwise at an internal temperature of 110 to 135 ° C. Next, the internal temperature was raised to 145 ° C. while distilling off the produced water, and the mixture was further stirred for 4 hours at an internal temperature of 145 to 155 ° C. while distilling off the produced water. At this time, the weight of distilled water was 4.8 parts. Thereafter, 60.9 parts of water was added to obtain 342.0 parts (0.43 mole ratio, 2.58 mole ratio as amino groups) of a polyester polyamide resin aqueous solution (resin 5-2) having a solid concentration of 80%.
[0052]
<Production Example 1 of Product Obtained by Reaction of Component (d) with Product of Component (a) and Component (b) 1: Synthesis of Resin 5-3>
342.0 parts (0.43 mole ratio, 2.58 mole ratio as amino group) of resin (5-2) was added to a reactor equipped with a thermometer, a reflux condenser and a stirring rod, and the internal temperature was 80. The temperature was raised to 0 ° C., 62.0 parts (1.03 molar ratio) of urea was added, and then the internal temperature was raised to 90 ° C. Next, while distilling off the produced ammonia from the reactor, the internal temperature was raised to 110 ° C. over 1.5 hours and further stirred at the internal temperature 110 ° C. for 8 hours. Thereafter, the mixture was cooled to 25 ° C. while gradually adding 139.4 parts of water, the pH was adjusted to 11.0 using 28% caustic soda, and an aqueous polyester polyamide polyurea resin solution (resin 5- 3) 592.8 parts (0.43 molar ratio, 1.55 molar ratio as an amino group) were obtained.
[0053]
<Production Example 1 of Paper Coating Resin Obtained by Reacting Component (c) to Reaction Product of Components (a), (b) and (d) 1: Synthesis of Resin 5>
150.2 parts of resin 5-3 (0.11 mole ratio, 0.39 mole ratio as amino group) was added to a reactor equipped with a thermometer, a reflux condenser and a stirring rod, and the internal temperature was adjusted to 70 ° C. The temperature was raised. Next, 10.1 parts (0.11 molar ratio) of epichlorohydrin was added dropwise at an internal temperature of 65 to 75 ° C. over 3 hours, and the mixture was further stirred at an internal temperature of 65 to 75 ° C. for 4 hours. Then, it stirred at internal temperature 65-75 degreeC for 2 hours. Thereafter, 2.7 parts of water was added and then cooled to room temperature to obtain 170.5 parts of an aqueous solution (resin 5 for paper coating) having a nonvolatile content of 59.9%, pH 6.79, and a viscosity of 272 mPa · s.
[0054]
(Comparative Example 2)
No paper coating resin was used in the coating composition.
[0055]
<Production example of coating composition>
The paper coating resins 1 to 5 obtained in Examples 1 to 4 and Comparative Example 1 were mixed at a weight ratio shown in Table 1, and water and 10% caustic soda so that the total solid content was 64%. A coating composition was prepared by adjusting with an aqueous solution. About each obtained coating composition, the physical-property value was measured with the following method, and the result was shown in Table 2.
[0056]
<PH>
Using a glass electrode type hydrogen ion concentration meter (manufactured by Toa Denpa Kogyo Co., Ltd.), the pH of the coating composition immediately after preparation was measured at 25 ° C.
[0057]
<Viscosity>
Using a B-type viscometer [manufactured by Tokyo Keiki Co., Ltd., BL type], the viscosity of the coating composition immediately after preparation was measured at 60 rpm and 25 ° C.
[0058]
[Table 1]
(Coating composition)
<Examples of coated paper production>
The coating composition has a rice basis weight of 80 g / m.2Using a wire rod on one side of high-quality paper, the coating amount is 14g / m2It applied so that it might become. Immediately after the application, it is dried with hot air at 120 ° C. for 30 seconds, then conditioned for 16 hours at a temperature of 23 ° C. and a relative humidity of 50%, and further subjected to supercalender treatment twice under the conditions of a temperature of 60 ° C. and a linear pressure of 60 kg / cm. And coated paper was obtained. The coated paper thus obtained was subjected to water resistance and ink acceptability tests, and the test results are summarized in Table 2. The test method is as follows.
[0060]
<Water resistance: Wet pick method (WP method)>
Using an RI testing machine (manufactured by Meisei Seisakusho), the coated surface was wetted with a water supply roll and then printed, and the peeled state was visually observed and judged. The judgment criteria were as follows.
Water resistance (poor) 1-5 (excellent)
[0061]
<Ink acceptability>
<Method A>
Using an RI testing machine, the coated surface was wetted with a water supply roll and then printed, and the acceptability of the ink was determined by visual observation. The judgment criteria were as follows.
Ink acceptability (poor) 1 to 5 (excellent)
[0062]
<Method B>
Using a RI tester, a slight gap was formed between the metal roll and the rubber roll, water was poured into the gap, printing was performed immediately, and the acceptability of the ink was determined by visual observation. The judgment criteria were as follows.
Ink acceptability (poor) 1 to 5 (excellent)
[0063]
[Table 2]
(Physical properties of coating composition and coated paper)
──────────────────────────────
Example Comparative example
1 2 3 4 1 2
──────────────────────────────
Resin for paper coating 1 2 3 4 5 −
──────────────────────────────
Urea reaction sequence * 1 After After After After Before −
──────────────────────────────
Physical properties of coating composition
pH 9.1 9.1 9.1 9.1 9.1 9.3
Viscosity (mPa · s) 1790 1840 1800 1940 1940 1840
──────────────────────────────
Physical properties of coated paper
Water resistance: WP method 4.7 4.5 4.6 4.4 3.5 1.2
Ink acceptability: Method A 4.6 4.7 4.4 4.7 2.7 1.5
法: Method B 4.7 4.8 4.4 5.0 2.7 1.3
──────────────────────────────
* 1: Reaction sequence of (c) epichlorohydrin and (d) urea. “Before” in the table indicates that (d) the reaction of urea was performed before the reaction of epichlorohydrin, and “after” indicates that the reaction of (d) urea was performed after the reaction of epichlorohydrin.
Claims (4)
（a）ポリアミン類
（b）脂環式多価カルボン酸類とグリコール類との反応で得られる
遊離カルボキシル基を有する反応生成物、および／または、
脂環式多価カルボン酸類
（c）一般式（４）〜（６）からなる群から選ばれる少なくとも１種のアルキル化剤
で表されるエピハロヒドリン、
ＨＯＣＨ ２ （ＣＨ ２ ） Ｗ Ｘ （５）
（式中、Ｘはハロゲン原子等を表し、ｗは１〜３程度の数を表す。）
で表されるモノハロヒドリン、
で表されるジハロヒドリン
（d）尿素類A resin for paper coating, which is obtained by reacting the component (d) with a resin obtained by reacting the following components (a), (b) and (c).
(A) polyamines (b) reaction products having free carboxyl groups obtained by reaction of alicyclic polyvalent carboxylic acids with glycols, and / or
Alicyclic polycarboxylic acid (c) At least one alkylating agent selected from the group consisting of general formulas (4) to (6)
An epihalohydrin represented by
HOCH 2 (CH 2 ) W X (5)
(In the formula, X represents a halogen atom or the like, and w represents a number of about 1 to 3.)
A monohalohydrin represented by
Dihalohydrin (d) ureas represented by
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