JPS6158599B2

JPS6158599B2 -

Info

Publication number: JPS6158599B2
Application number: JP51127048A
Authority: JP
Inventors: Masato Nakamura; Shuji Takemura; Kenji Endo; Susumu Kikawa
Original assignee: Honshu Paper Co Ltd
Current assignee: Honshu Paper Co Ltd
Priority date: 1976-10-22
Filing date: 1976-10-22
Publication date: 1986-12-12
Also published as: JPS5351234A

Description

[Detailed description of the invention]

本発明は塗被用組成物に関する。さらに詳しく
言えば、本発明は少なくとも１種のスチレン系モ
ノマーと少なくとも１種のエチレン性不飽和酸成
分との共重合体の採用を特徴とし、特定のカチオ
ン性有機化合物をその成分として含むことのでき
る塗被用組成物に関する。本発明者等は、先にエピハロヒドリンと脂肪族
アミンとのカチオン性縮合物を顔料および結合剤
と混合したものからなる組成物を紙および板紙等
に塗工することにより塗工紙および塗工板紙等の
白色度、オフセツト印刷適性、インキ乾燥速度、
耐光性等の特性を大巾に向上させることができる
ことを見出した。しかしながら、一般にカチオン
性有機化合物を塗被用組成物等の組成物に添加す
る場合、組成物の流動特性が著しく悪くなり、そ
の粘度が大巾に上昇してしまうという欠点があ
る。このため従来は、そのような欠点を免れた特
定の限られた種類のカチオン性有機化合物しか使
用することができなかつた。したがつて、もし、
あらゆるカチオン性有機化合物のうちから目的に
応じて所望のものを使用して上述のような欠点の
ない塗被用組成物をつくることができれば、当該
分野における非常に大きな技術的貢献であること
は明らかである。本発明者等は、このような観点
に立つて鋭意研究を行なつた結果、特定のアニオ
ン性共重合体をカチオン性有機化合物と共に塗被
用組成物に添加することにより、これまでカチオ
ン性有機化合物のみを添加した場合には困難であ
つた塗料顔料のランダム配向と塗料流動性の両立
が可能となり、白色度、不透明度、オフセツト印
刷適性およびインキ乾燥等にすぐれた塗被紙が工
業的に得られることを見出し、本発明を完成する
に至つた。本発明の組成物は少なくとも１種のスチレン系
モノマーと少なくとも１種のエチレン性不飽和酸
成分との共重合体を含むことを特徴とする。ここ
で、エチレン性不飽和酸成分とは、エチレン性不
飽和結合を少なくとも１つ分子内に含む有機酸お
よびその塩、およびその無水物のほか、そのよう
な酸のエステルを包括するものである。上述の共
重合体は、これをそのまま所望のカチオン性有機
化合物および顔料、結合剤その他の添加剤と混合
して塗被用組成物とすることもできるし、あるい
は上述の共重合体をさらに少なくとも１種の重合
性モノマーと重合触媒の存在下に反応させて得ら
れる共重合体−重合性モノマー反応生成物をカチ
オン性有機化合物、顔料、結合剤およびその他の
添加剤と混合して所望の組成物をつくることもで
きる。また、この場合、共重合体と反応させるた
めに重合性モノマーとしてその一部または全部を
カチオン性モノマーで置きかえることもでき、そ
のようにして得られた処理済み共重合体を用いる
場合には、カチオン性有機化合物を別透に使用し
なくても所望の塗被用組成物をつくることができ
る。スチレン系モノマーをエチレン性不飽和酸成
分と反応させて得られる最初の共重合体と、これ
をさらに重合性モノマーと反応させて得られる処
料済み共重合体とを区別するため、後者の共重合
体を共重合体−重合性モノマー反応生成物と呼ん
だが、この共重合体−重合性モノマー反応生成物
は最初の共重合体を重合触媒の存在下に少なくと
も１種の重合性モノマーと反応させて得られたも
のであるから、用いられる重合性モノマーの少な
くとも一部は最初の共重合体にグラフトしている
ものと考えられる。スチレン系モノマーとエチレン性不飽和酸成分
との共重合体は任意の通常の共重合法を用いてつ
くることができる。たとえば、少なくとも１種の
スチレン系モノマーを、過酸化ベンゾイル等の重
合触媒およびｎ―ドデシルメルカプタン等の重合
調節剤または酸化防止剤の存在下に室温でエチレ
ン性不飽和酸成分と反応させて共重合体をつくる
ことができる。得られた共重合体を加熱キユアリ
ングしたものを用いればさらに好ましい組成物が
得られる。スチレン系モノマーとエチレン性不飽
和酸成分との共重合比は特に制限はないが、一般
にスチレン系モノマー：エチレン性不飽和酸成分
の比が１：１〜２：１の共重合体が得られるよう
にすることが好ましい。該共重合体の重合度は広
い範囲内で採用できるが、一般に、分子量10000
〜100000の共重合体とすることが好ましい。このようにして得られたスチレン系モノマーと
エチレン性不飽和重合体との共重合体をさらに重
合性モノマーと反応させる方法としては、当業者
ならば容易に思いつく種々の方法があるが、たと
えば上述の共重合体を粉砕して水性分散液をつく
り、重合触媒および重合性モノマーをこの分散液
中に加え、加熱撹拌して重合を行なわせることが
できる。この場合、先にも述べたごとく、重合性
モノマーの少なくとも一部は前記共重合体にグラ
フトするものと考えられる。また加えられた重合
性モノマーのホモポリマーが形成されて、上記の
共重合体と絡み合つているものもあると考えられ
る。重合性モノマーの使用量は任意に決定するこ
とができるが、共存せしめられる共重合体対重合
性モノマーのモル比が１：９〜９：１あることが
一般に好ましい。このようにして得られる共重合
体−重合性モノマー反応生成物の水性分散液は、
そのまま他の成分と混合して本発明の組成物をつ
くるために用いることができる。本発明の組成物は(イ)スチレン系モノマーとエチ
レン性不飽和酸成分との共重合体またはその共重
合体をさらに重合性モノマーと反応させて得られ
た共重合体−重合性モノマー反応生成物、(ロ)カチ
オン性有機化合物、(ハ)顔料、(ニ)結合剤を必須成分
とする液性分散体である。各必須成分の重量比は
任意に選ぶことができる。しかしながら、塗布用
組成物として好ましい結果が得られるのは、組成
物の合計重量を100重量部とした場合、(イ)前記共
重合体または共重合体−重合性モノマー反応生成
物0.1〜10重量部（乾量基準）および(ロ)カチオン
性有機化合物0.05〜10重量部（乾量基準）を含む
場合である。顔料、結合剤および分散媒は、この
種の組成物において通常採用される任意の量を用
いることができるが、一般的には顔料40〜90重量
部、結合剤10〜60重量部が用いられ、残りの部分
が分散媒およびその他の必要な添加剤である。分散媒としては通常は水が用いられるが、水に
代えてまたは水と共に、種々の有機溶媒を用いる
こともできる。前記重合性モノマーとしてカチオ
ン性モノマーを用いた場合には、前記カチオン性
有機化合物の使用を省略することもできる。本発明の塗被用組成物中の各成分物質の混合比
は任意に決定することができるが、共重合体また
は共重合体−重合性モノマー反応生成物とカチオ
ン性有機化合物との合計量をモル基準で100とし
た場合：前者対後者の比を50：50〜99：１とする
ことが好ましい。重合性モノマーの一部または全
部をカチオン性モノマーで置きかえた場合は、置
きかえたカチオン性モノマーの量に見合う量だけ
共重合体成分の量を増し、それに見合う量だけカ
チオン性有機化合物の量を減らすことができる。本発明の塗被用組成物は、(イ)共重合体または共
重合体−重合性モノマー反応生成物0.1〜25重量
％；(ロ)有機カチオン性化合物0.05〜25重量％；(ハ)
顔料40〜90重量％；(ニ)結合剤５〜60重量％を水そ
の他の分散液に分散させて用いることが好まし
い。上記の組成物には、その他の添加剤を必要に
応じて添加することができる。重合性モノマーの
一部又は全てをカチオン性モノマーで置きかえた
場合は、用いたカチオン性モノマーの量に見合う
量だけ共重合体−重合性モノマー反応生成物の量
を増し、それに見合う量だけカチオン性有機化合
物の量を減らすことができる。重合性モノマーと
して重合可能なカチオン性モノマーを含んで用い
た場合塗被用組成物調製に際して有機カチオン性
化合物の使用を省略することもできるが、この場
合の塗被用組成物の各成分物質の混合比は(イ)共重
合体−カチオン性モノマー反応生成物１〜55重量
％；(ロ)顔料40〜90重量％；および(ハ)結合剤５〜55
重量％とし残りの部分を分散媒およびその他の添
加剤とすることが好ましい。本発明の実施において使用できるスチレン系モ
ノマーとしては、スチレン、ビニルトルエン、α
−メチルスチレン等を代表的なものとして挙げる
ことができる。本発明の実施例において、スチレン系モノマー
と共重合させる目的で使用することのできるエチ
レン性不飽和酸およびそのエステルとしては、ア
クリル酸、メタクリル酸、クロトン酸、イタコン
酸、マレイン酸、フマール酸等のアルケンモノま
たはジカルボン酸およびそれらのエステルを代表
的なものとして挙げることができる。また上記の
酸の塩および無水物を使用することもできる。マ
レイン酸モノメチルエステル、イタコン酸モノブ
チルエステル等のジカルボン酸のモノアルキルエ
ステル類ももちろん有効に使用することができ
る。これらの酸およびその塩およびその無水物並
びにそれらの酸のエステルを総括して本明細書中
でエチレン性不飽和酸成分ということもある。前記スチレン系モノマー対前記エチレン系不飽
和酸成分の割合は特に制限はなく、必要に応じて
任意に選ぶことができるが、スチレン系モノマ
ー：エチレン性不飽和酸成分のモル比が１：１〜
２：１である場合に一般によい結果が得られる。本発明の実施において、スチレン系モノマーと
エチレン性不飽和酸成分との共重合体と共にさら
に処理する目的で使用することのできる重合性モ
ノマーの代表的なものとしては、アクリル酸メチ
ル、アクリル酸エチル、アクリル酸ｎ―プロピ
ル、アクリル酸イソプロピル、アクリル酸ｎ―ブ
チル、アクリル酸第２級ブチル、アクリル酸第３
級ブチル、アクリル酸２−エチルヘキシル等のア
クリル酸エステル類；メタクリル酸メチル、メタ
クリル酸エチル、メタクリル酸ｎ−プロピル、メ
タクリル酸イソプロピル、メタクリル酸ｎ−ブチ
ル、メタクリル酸第２級ブチル、メタクリル酸第
３級ブチル、メタクリル酸２−エチルヘキシル等
のメタクリル酸エステル類；スチレン、ビニルト
ルエン、α−メチルスチレン、β−クロルスチレ
ン、ジビニルベンゼン等のスチレン系モノマー
類；蟻酸ビニル、酢酸ビニル、プロピオン酸ビニ
ル等の有機酸ビニルエステル類；アクリロニトリ
ル、メタアクリロニトリル、エタアクリロニトリ
ル等のニトリル類；エチレン、プロピレン等のα
−オレフイン類；１，３−ブタジエン、イソブチ
レン、クロロプレン、イソプレン等の共役ジエン
モノマー類；塩化ビニル、弗化ビニル、塩化ビニ
リデン等のハロゲン化オレフイン類；アクリル
酸、メタアクリル酸、クロトン酸、イタコン酸、
マレイン酸、フマール酸、シトラコン酸、センシ
オン酸等のアルケンモノまたはジカルボン酸；お
よびこれらの酸の塩または無水物；マレイン酸モ
ノメチルエステル、イタコン酸モノブチルエステ
ル等のジカルボン酸のモノアルキルエステル類；
イタコン酸ジメチルエステル、マレイン酸ジエチ
ルエステル等のジカルボン酸のジアルキルエステ
ル類；アクリルアミド、メタアクリルアミド、マ
レイン酸アミド、マレイン酸イミド、Ｎ−ヒドロ
キシアクリルアミド、Ｎ−ヒドロキシメタアクリ
ルアミド、Ｎ−メチロールアクリルアミド、Ｎ−
イソプロピルアクリルアミド、ジアセトンアクリ
ルアミド、スチレン−ｐ−スルホン酸またはその
アルカリ塩、アクリル酸グリシジル、メタアクリ
ル酸グリシジル、アクリル酸２−ヒドロキシエチ
ル、アクリル酸α−シアノメチル、アクロレイン
のアクリル酸アリル等の各種化合物を挙げること
ができる。前記共重合体と、これと共に重合触媒の存在下
に反応させる重合性モノマーとの割合は任意に決
定することができるが、前者対後者の重量比を
１：９ないし９：１とすることが好ましい。本発明の実施例において、前記共重合体または
共重合体―重合性モノマー反応生成物と混合して
本発明の塗被用組成物をつくるために使用するこ
とのできるカチオン性有機化合物の代表的なもの
としては、エチレンジアミン、ヘキサメチレンジ
アミン、ジエチレントリアミン、トリエチレンテ
トラミン、テトラエチレンペンタミン等の１分子
中に少なくとも２つのＮ原子を含むアミン類およ
びその塩；ポリアクリル酸ジメチルアミノエチ
ル、ポリアクリル酸ジエチルアミノエチル等のカ
チオン性含窒素ポリアクリル酸エステル及びその
塩；ポリメタクリル酸ジエチルアミノエチル、ポ
リメタクリル酸ｎ−ブチルアミノエチル等のカチ
オン性含窒素ポリメタクリル酸エステル及びその
塩；エピハロヒドリンとアミンの縮合物；モノア
ミノジカルボン酸と多塩基アミンの縮合物及びそ
の塩；カチオン変性ポリアクリルアミド、カチオ
ン変性尿素樹脂、カチオン変性エポキシ樹脂及び
それらの塩；ポリビニルベンジルトリメチルアン
モニウムクロライド；ポリアミドエピクロルヒド
リン；ポリビニルピリジン、ポリビニルイミダゾ
ール等のカチオン性ポリ含窒素複素環式化合物及
びその塩；ポリエチレンイミンを挙げることがで
きる。本発明の実施において、単独でまたは前記重合
性モノマーと混合して前記共重合体と反応させる
目的で使用することのできるカチオン性モノマー
の代表的なものとしては、アクリル酸ジメチルア
ミノエチル、アクリル酸ジエチルアミノエチル等
のカチオン性含窒素アクリル酸エステル及びその
塩；メタクリル酸ジエチルアミノエチル、メタク
リル酸ｎ―ブチルアミノエチル等のカチオン性含
窒素メタクリル酸エステル及びその塩；ビニルピ
リジン、ビニルイミダゾール等のカチオン性含窒
素複素環式化合物及びその塩、カチオン性Ｎビニ
ルアミド及びその塩、ジメチルアリルアミン、ジ
アリルアミン等のアリルアミン化合物及びその塩
を挙げることができる。本発明の実施において、前記共重合体または共
重合体―重合性モノマー反応生成物およびカチオ
ン性有機化合物と混合して本発明の塗被用組成物
をつくるために使用することのできる顔料結合剤
としては、この種の塗被用組成物に通常使用され
る顔料結合剤の任意のものを用いることができる
が、代表的なものを例示すれば、カゼイン、殿
粉、大豆タンパクなどの天然物およびPVA、ス
チレン―ブタジエン系エマルジヨン、アクリル系
エマルジヨン、酢ビ系エマルジヨンなどの合成物
を挙げることができる。本発明の実施において、前記共重合体または共
重合体―重合性モノマー反応生成物、カチオン性
有機化合物および顔料結合剤と共に用いて本発明
の塗被用組成物をつくるために使用することので
きる顔料の代表的なものを例示すれば、クレー、
炭酸カルシウム、タルクなどの無機顔料、ポリス
チレンエマルジヨン粒子などの有機顔料等を挙げ
ることができる。本発明の組成物は一般に塗被用として広範の目
的に使用することができるが、特に紙および板紙
の塗被用組成物として適している。本発明の組成
物を塗被した紙および板紙は、白色度、不透明
度、オフセツト印刷適性、インキ乾燥速度、およ
び耐光性のすべての特性において優れた塗工紙お
よび塗工紙板とすることができる。このような効
果は、本発明の塗被用組成物以外の組成物を用い
た場合には容易に得られない効果である。したが
つて、本発明の新規な塗被用組成物を塗被してな
る紙材はそれ自体新規な紙材であつて従来存在し
得なかつたものである。以下実施例により説明するが、これらの実施例
は本発明を例示するものであつて制限するもので
はない。実施例１ (a) スチレン系モノマーと、エチレン性不飽和酸
および／またはそのエステルとの共重合体の合
成：スチレンモノマー117重量部、マレイン酸モ
ノメチルエステル97.5重量部、過酸化ベンゾイ
ル1.72重量部、ｎ―ドデシルメルカプタン2.15
重量部を室温で撹拌混合し、得られた混合物を
表面が平滑なステンレス板の間に、最終的に得
られる注形重合体の厚さが約５mmとなるように
注入した。その後60℃〜100℃で３時間、次い
で徐々に昇温し、130℃〜140℃で10時間反応し
た後室温に冷却し、無色透明なスチレン―マレ
イン酸モノメチルエステル共重合体よりなる重
合板を得た。次にこの重合板を粉砕し、希アン
モニア水に溶解した。 (b) 上記共重合体をその水性分散液中で重合触媒
の存在下に重合性モノマーと反応させることに
よる共重合体―重合性モノマー反応生成物の製
造：還流冷却器付きの４つ口フラスコに、上記(a)
のごとくしてつくつたスチレン―マレイン酸モ
ノメチルエステル共重合体のアンモニウム塩を
15重量％含む水溶液267重量部を仕込み、これ
にアクリルアミド60重量部、蒸留水150重量部
を加え、撹拌しながら溶解した。これを恒温槽
中で60℃に昇温し、10％過硫酸アンモニウム水
溶液20重量部および10％ジメチルアミノプロピ
オニトリル水溶液２重量部を重合触媒として加
え、チツ素気流中で60℃の温度にて４時間撹拌
を続けて重合し、共重合体―重合性モノマー反
応生成物の水性分散液（）を得た。 (c) 塗被用組成物の調製および塗工紙の製造：ミキサーに水60重量部、分散剤１重量部（固
形物で0.4重量部）および28％アンモニア水1.1
重量部を入れ、撹拌しながらクレー100重量部
を加えてよく分散させ、クレースラリーを得
た。次いで撹拌を続けながら前記共重合体―重
合性モノマー反応生成物の水性分散液（）30
重量部（固形物で６重量部）、ポリエチレンイ
ミン1.67重量部（固形物で0.5重量部）を加
え、さらにスチレン―ブタジエン系ラテツクス
28重量部（固形物で14重量部）を添加し、最後
に全固形分濃度45％となるように水を加え、
100メツシユの金鋼で過して塗被用組成物
（）を調製した。この塗被用組成物（）を40℃に加温しＢ型
粘度計で60rpmの粘度を測定した。次にこの塗被用組成物を実験用エアナイフ塗布
機で塗工量が約15ｇ／m²となるようにメートル坪
量350ｇ／m²の原紙に塗工した。塗工紙は、25
℃、65％RHの恒温恒湿の室内に一晩放置した
後、60℃、85Kg／cmの条件でスパーカレンダー掛
けを施してから、以下の各試験に供した。試験結
果は第１表に示す通りであつた。白色度、不透明
度、オフセツト印刷適性、インキ乾燥速度および
耐光性の各測定は次の方法に従つて行なつたもの
である。 (1) 白色度：GE白色度計 (2) 不透明度：不透明度85％の用紙に塗工量が約
15ｇ／m²になるように手塗りし、ホトボルト計
で測定した。 (3) オフセツト印刷適性：塗工紙に水を一定量付
着させ、すぐに印刷した場合のインキの乗り具
合の程度を視覚的に優、良、可、不可の４段階
で評価した。 (4) インキ乾燥速度：オフセツトインキ0.5c.c.を
RIテスターによつて塗工紙に印刷した後、一
定時間間隔で印刷を白紙に転写し、被転写紙に
インキが付着しなくなつたときの時間（分）で
示した。 (5) 耐光性：紫外線カーボンアークを温度40℃で
20時間照射後の白色度の照射前の白色度に対す
る低下率。実施例２ α―メチルスチレン117重量部、アクリル酸
47.2重量部、過酸化ベンゾイル1.31重量部、ｎ―
ドデシルメルカプタン1.64重量部を用いたこと以
外は、実施例１(a)に記載したと同様にして共重合
体水性分散液をつくつた。これを共重合体水性分
散液（）とする。次にこの共重合体水性分散液
（）20重量部（固形物で３重量部）と、カチオ
ン性有機化合物であるエピクロルヒドリン―とジ
メチルアミンとの縮合物1.0重量部（固形物で0.5
重量部）とをホモミキサーで高速撹拌し、組成物
（）をつくつた。次に、この組成物（）25.1
重量部（固形物で4.2重量部）およびアクリル系
ラテツクス31重量部（固形物で15.5重量部）を使
用したこと以外は実施例１(c)の場合と同様にし
て、塗被用組成物（）をつくつた。塗被用組成
物（）の粘度を測定した後、この組成物を紙に
塗工し、実施例１(c)に記載した方法に従つて各試
験項目に関する測定を行なつた。これらの試験結
果は第１表に示す通りであつた。実施例３スチレン83.2重量部、ビニルトルエン94.4重量
部、マレイン酸モノエチル72重量部、フマール酸
モノブチル86重量部、過酸化ベンゾイル、2.68重
量部およびｎ―ドデシルメルカプタン3.36重量部
を使用したこと以外は実施例１(a)の場合と同様に
して、共重合体水性分散液（）をつくつた。次
いでこの共重合体水性分散液（）20重量部（固
形物で３重量部）、カチオン型変性尿素樹脂1.3重
量部（固形物で0.5重量部）エピプロムヒドリン
とメチルアミンの縮合物１重量部（固形物で0.5
重量部）、殿粉−PVAの混合物〔殿粉／PVA＝
１／１（重量比）〕66.6重量部（固形物で10重量
部）、および酢ビ系ラテツクス24重量部（固形物
で12重量部）を加えたこと以外は実施例１(c)に記
載したのと同様にして、塗被用組成物（）を調
製した。この塗被用組成物（）の粘度を測定し
た後、これを紙に塗工し、実施例１(c)に列挙した
試験項目についての測定を行なつた。これらの結
果は第１表に示す通りであつた。実施例４ α―メチルスチレン147.5重量部、メタクリル
酸86重量部、過酸化ベンゾイル1.87重量部および
ｎ―ドデシルメルカプタン2.33重量部を使用した
こと以外は実施例１(a)に記載したのと同様にし
て、共重合体水性分散液（）をつくつた。次い
でこの共重合体水性分散液（）400重量部（固
形物で60重量部）、アクリルアミド20重量部、ア
クリル酸ジメチルアミノエチル10重量部、アクリ
ル酸ジメチルアミノエチル10重量部、10％過硫酸
アンモニウム水溶液24重量部、10％ジメチルアミ
ノプロピオニトリル水溶液、2.4重量部、および
蒸留水34.6重量部を使用したこと以外は、実施例
１(b)の場合と同様にして、共重合体―重合性モノ
マー反応生成物の水性分散液（）をつくつた。
さらに、この共重合体―重合性モノマー反応生成
物の水性分散液（）35重量部（固形物で７重量
部）、およびスチレン―ブタジエン系ラテツクス
24重量部（固形物で12重量部）を使用したこと以
外は実施例１(c)の場合と同様にして、塗被用組成
物（）をつくつた。この塗被用組成物（）に
ついて粘度を測定した後、これを紙に塗工し、実
施例１(c)に列挙した各試験項目についての測定を
行なつた。これらの結果は第１表に示す通りであ
つた。実施例５スチレン104重量部、イタコン酸112重量部、過
酸化ベンゾイル1.30重量部、ｎ―ドデシルメルカ
プタン0.65重量部を使用する以外は、実施例１(a)
に記載した方法と同様の方法で共重合体水性分散
液を得た。次いで上記共重合体水性分散液（）
40重量部（固形物で６重量部）、ジエチレントリ
アミン0.5重量部、酢酸ビニル系ラテツクス32重
量部（固形物で16重量部）を使用する以外は、実
施例１(c)に記載した方法と同様の方法に従つて
（紙用）塗被組成物を調整粘度を測定し塗工後実
施例１(c)に記載した試験項目を測定した。得られ
た結果は、第１表に示す。実施例６スチレン187重量部、マレイン酸モノプロピル
エステル158重量部、過酸化ベンゾイル2.76重量
部およびｎ―ドデシルメルカプタン3.45重量部を
使用したこと以外は、実施例１(a)に記載したと同
様にして、共重合体水性分散液（）をつくつ
た。次いで、上記共重合体水性分散液（）333
重量部（固形物で50重量部）、メタアクリルアミ
ド30.8重量部、アクリロニトリル19.2重量部、10
％過硫酸アンモニウム水溶液25重量部、10％ジエ
チルアミノプロピオニトリル水溶液2.5重量部、
および蒸留水89.5重量部を使用したこと以外は実
施例１(b)の場合と同様にして、共重合体―重合性
モノマー反応生成物の水性分散液（）をつくつ
た。次に、この共重合体―重合性モノマー反応生
成物の水性分散液（）37.5重量部（固形物で
7.5重量部）、ポリビニルベンジルトリメチルアン
モニウムクロライド1.3重量部（固形物で0.4重量
部）およびスチレン―ブタジエン系ラテツクス30
重量部（固形物で15重量部）を用いたこと以外
は、実施例１(c)の場合と同様にして、塗被用組成
物（）を調製した。この塗被用組成物（）に
ついて粘度を測定した後、これを紙に塗工し、実
施例１(c)に列挙した試験項目についての測定を行
なつた。実施例７スチレン104重量部、マレイン酸モノブチルエ
ステル172重量部、過酸化ベンゾイル2.21重量
部、およびｎ―ドデシルメルカプタン2.76重量部
を使用したこと以外は実施例１(a)の場合と同様に
して、共重合体水性分散液（）をつくつた。次
いで、この共重合体水性分散液（）267重量部
（固形物で40重量部）、アクリルアミド36.7重量
部、アクリル酸メチル18.3重量部、ジビニルベン
ゼン５重量部、10％過硫酸アンモニウム水溶液30
重量部、10％ジメチルアミノプロピオニトリル水
溶液３重量部、および蒸留水140重量部を使用し
たこと以外は、実施例１(b)の場合と同様として、
共重合体―重合性モノマー反応生成物の水性分散
液（）をつくつた。次に、この共重合体―重合
性モノマー反応生成物の水性分散液（）33.3重
量部（固形物で５重量部）、エチレンジアミン２
重量部（固形物で0.6重量部）、カゼイン水溶液30
重量部（固形物で4.5重量部）およびスチレン―
ブタジエン系ラテツクス24重量部（固形物で12重
量部）を使用したこと以外は、実施例１(c)の場合
と同様にして、塗被用組成物（）を調製した。
この塗被用組成物（）について粘度を測定した
後、これを紙に塗工し、実施例１(c)に列挙した試
験項目についての測定を行なつた。これらの結果
は第１表に示す通りであつた。比較例１共重合体―重合性モノマー反応生成物の水性分
散液（）を使用しないこと以外は、実施例１(c)
と全く同様のことを行なつた。結果は第１表に示
す通りであつた。比較例２カチオン型変性尿素樹脂を用いないこと以外は
実施例３と全く同様のことを行なつた。結果は第
１表に示す通りであつた。比較例３ポリビニルベンジルトリメチルアンモニウムク
ロライドを用いないこと以外は、実施例６と全く
同様のことを行なつた。結果は第１表に示す通り
であつた。比較例４共重合体―重合性モノマー反応生成物の水性分
散液（）を用いない以外は実施例７と全く同様
のことを行なつた。結果は第１表に示す通りであ
つた。 The present invention relates to coating compositions. More specifically, the present invention is characterized by the employment of a copolymer of at least one styrenic monomer and at least one ethylenically unsaturated acid component, which contains a specific cationic organic compound as a component. The present invention relates to a coating composition that can be applied. The present inventors have previously applied a composition consisting of a cationic condensate of epihalohydrin and an aliphatic amine mixed with a pigment and a binder to paper, paperboard, etc., thereby producing coated paper and paperboard. whiteness, offset printing suitability, ink drying speed, etc.
It has been found that properties such as light resistance can be greatly improved. However, in general, when a cationic organic compound is added to a composition such as a coating composition, the flow characteristics of the composition are significantly deteriorated and the viscosity thereof is significantly increased. For this reason, in the past, only certain limited types of cationic organic compounds that were free from such drawbacks could be used. Therefore, if
If it were possible to create a coating composition free of the above-mentioned drawbacks by using a desired cationic organic compound depending on the purpose, it would be a huge technical contribution to the field. it is obvious. As a result of intensive research from this perspective, the present inventors have discovered that by adding a specific anionic copolymer to a coating composition together with a cationic organic compound, the present inventors have succeeded in It is now possible to achieve both random orientation of paint pigments and paint fluidity, which was difficult to achieve when only compounds are added, and coated paper with excellent whiteness, opacity, offset printing suitability, and ink drying properties has become commercially available. The present inventors have discovered that the present invention can be obtained, and have completed the present invention. The composition of the present invention is characterized in that it contains a copolymer of at least one styrenic monomer and at least one ethylenically unsaturated acid component. Here, the ethylenically unsaturated acid component includes organic acids containing at least one ethylenically unsaturated bond in the molecule, their salts, and their anhydrides, as well as esters of such acids. . The above-mentioned copolymer can be mixed as it is with a desired cationic organic compound, pigment, binder and other additives to form a coating composition, or the above-mentioned copolymer can be further mixed with at least one additive. A copolymer-polymerizable monomer reaction product obtained by reacting one type of polymerizable monomer with a polymerization catalyst in the presence of a polymerization catalyst is mixed with a cationic organic compound, a pigment, a binder, and other additives to obtain a desired composition. You can also make things. In addition, in this case, part or all of the polymerizable monomer can be replaced with a cationic monomer in order to react with the copolymer, and when the treated copolymer obtained in this way is used, A desired coating composition can be prepared without separately using a cationic organic compound. To distinguish between the initial copolymer obtained by reacting a styrenic monomer with an ethylenically unsaturated acid component and the treated copolymer obtained by further reacting this with a polymerizable monomer, the latter copolymer is Although the polymer was referred to as a copolymer-polymerizable monomer reaction product, the copolymer-polymerizable monomer reaction product is obtained by reacting the initial copolymer with at least one polymerizable monomer in the presence of a polymerization catalyst. It is considered that at least a part of the polymerizable monomer used is grafted onto the initial copolymer. Copolymers of styrenic monomers and ethylenically unsaturated acid components can be made using any conventional copolymerization method. For example, at least one styrenic monomer is copolymerized by reacting it with an ethylenically unsaturated acid component at room temperature in the presence of a polymerization catalyst such as benzoyl peroxide and a polymerization regulator or antioxidant such as n-dodecyl mercaptan. You can create a union. A more preferable composition can be obtained by heat-curing the obtained copolymer. There is no particular restriction on the copolymerization ratio of the styrene monomer and ethylenically unsaturated acid component, but generally a copolymer with a styrenic monomer:ethylenic unsaturated acid component ratio of 1:1 to 2:1 can be obtained. It is preferable to do so. The degree of polymerization of the copolymer can be adopted within a wide range, but generally the molecular weight is 10,000.
It is preferable to set it as a copolymer of 100,000 to 100,000. As a method for further reacting the thus obtained copolymer of a styrenic monomer and an ethylenically unsaturated polymer with a polymerizable monomer, there are various methods that can be easily thought of by those skilled in the art. An aqueous dispersion is prepared by pulverizing the copolymer, a polymerization catalyst and a polymerizable monomer are added to this dispersion, and the polymerization is carried out by heating and stirring. In this case, as mentioned above, at least a portion of the polymerizable monomer is considered to be grafted onto the copolymer. It is also believed that some homopolymers of the added polymerizable monomers are formed and are entangled with the above-mentioned copolymers. Although the amount of the polymerizable monomer to be used can be arbitrarily determined, it is generally preferable that the molar ratio of the copolymer to the polymerizable monomer to be coexisting is 1:9 to 9:1. The aqueous dispersion of the copolymer-polymerizable monomer reaction product thus obtained is
It can be used as is to prepare the composition of the present invention by mixing with other components. The composition of the present invention is (a) a copolymer of a styrene monomer and an ethylenically unsaturated acid component, or a copolymer-polymerizable monomer reaction product obtained by further reacting the copolymer with a polymerizable monomer. It is a liquid dispersion whose essential components are (b) a cationic organic compound, (c) a pigment, and (d) a binder. The weight ratio of each essential component can be arbitrarily selected. However, when the total weight of the composition is 100 parts by weight, preferable results can be obtained as a coating composition using (a) 0.1 to 10 parts by weight of the copolymer or copolymer-polymerizable monomer reaction product; (on a dry basis) and (b) 0.05 to 10 parts by weight (on a dry basis) of a cationic organic compound. The pigment, binder and dispersion medium can be used in any amounts normally employed in this type of composition, but generally 40 to 90 parts by weight of pigment and 10 to 60 parts by weight of binder are used. , the remaining part is the dispersion medium and other necessary additives. Water is usually used as the dispersion medium, but various organic solvents can also be used instead of or together with water. When a cationic monomer is used as the polymerizable monomer, the use of the cationic organic compound can also be omitted. The mixing ratio of each component in the coating composition of the present invention can be arbitrarily determined, but the total amount of the copolymer or copolymer-polymerizable monomer reaction product and cationic organic compound When expressed as 100 on a molar basis, the ratio of the former to the latter is preferably 50:50 to 99:1. When some or all of the polymerizable monomers are replaced with cationic monomers, increase the amount of the copolymer component by an amount commensurate with the amount of the replaced cationic monomer, and reduce the amount of the cationic organic compound by an amount commensurate with the amount of the replaced cationic monomer. be able to. The coating composition of the present invention comprises (a) 0.1 to 25% by weight of a copolymer or copolymer-polymerizable monomer reaction product; (b) 0.05 to 25% by weight of an organic cationic compound; (c)
It is preferable to use the pigment by dispersing 40 to 90% by weight of the pigment and 5 to 60% by weight of the binder (d) in water or other dispersion liquid. Other additives can be added to the above composition as necessary. When some or all of the polymerizable monomers are replaced with cationic monomers, the amount of copolymer-polymerizable monomer reaction product is increased by an amount commensurate with the amount of cationic monomer used, and the amount of cationic monomer is increased by an amount commensurate with the amount of cationic monomer used. The amount of organic compounds can be reduced. When a polymerizable cationic monomer is used as a polymerizable monomer, it is possible to omit the use of an organic cationic compound when preparing a coating composition. The mixing ratio is (a) 1 to 55% by weight of copolymer-cationic monomer reaction product; (b) 40 to 90% by weight of pigment; and (c) 5 to 55% by weight of binder.
It is preferable that the remaining portion be used as a dispersion medium and other additives. Styrenic monomers that can be used in the practice of this invention include styrene, vinyltoluene, α
-Methylstyrene etc. can be mentioned as a typical example. In the examples of the present invention, examples of ethylenically unsaturated acids and esters thereof that can be used for copolymerization with styrenic monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. Typical examples include alkene mono- or dicarboxylic acids and esters thereof. It is also possible to use salts and anhydrides of the acids mentioned above. Of course, monoalkyl esters of dicarboxylic acids such as monomethyl maleate and monobutyl itaconate can also be used effectively. These acids, their salts, their anhydrides, and esters of these acids may be collectively referred to herein as ethylenically unsaturated acid components. The ratio of the styrene monomer to the ethylenically unsaturated acid component is not particularly limited and can be arbitrarily selected as necessary, but the molar ratio of the styrenic monomer to the ethylenically unsaturated acid component is 1:1 to 1:1.
Good results are generally obtained when the ratio is 2:1. In the practice of this invention, representative polymerizable monomers that can be used for further processing with the copolymer of styrenic monomer and ethylenically unsaturated acid component include methyl acrylate, ethyl acrylate, , n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, secondary butyl acrylate, tertiary acrylate
Acrylic acid esters such as butyl methacrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, secondary butyl methacrylate, tertiary methacrylate Methacrylic acid esters such as butyl and 2-ethylhexyl methacrylate; Styrenic monomers such as styrene, vinyltoluene, α-methylstyrene, β-chlorostyrene, and divinylbenzene; Vinyl formate, vinyl acetate, vinyl propionate, etc. Organic acid vinyl esters; Nitriles such as acrylonitrile, methacrylonitrile, and etaacrylonitrile;
-Olefins; Conjugated diene monomers such as 1,3-butadiene, isobutylene, chloroprene, isoprene; Halogenated olefins such as vinyl chloride, vinyl fluoride, vinylidene chloride; Acrylic acid, methacrylic acid, crotonic acid, itaconic acid ,
Alkene mono- or dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and cencionic acid; and salts or anhydrides of these acids; monoalkyl esters of dicarboxylic acids such as maleic acid monomethyl ester and itaconic acid monobutyl ester;
Dialkyl esters of dicarboxylic acids such as dimethyl itaconate and diethyl maleate; acrylamide, methacrylamide, maleic amide, maleic imide, N-hydroxyacrylamide, N-hydroxymethacrylamide, N-methylolacrylamide, N-
Various compounds such as isopropylacrylamide, diacetone acrylamide, styrene-p-sulfonic acid or its alkali salt, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, α-cyanomethyl acrylate, allyl acrylate of acrolein, etc. can be mentioned. The ratio of the copolymer to the polymerizable monomer reacted with it in the presence of a polymerization catalyst can be arbitrarily determined, but the weight ratio of the former to the latter may be 1:9 to 9:1. preferable. In the examples of the present invention, representative cationic organic compounds that can be used to mix with the copolymer or copolymer-polymerizable monomer reaction product to form the coating composition of the present invention are described. Examples include amines containing at least two N atoms in one molecule, such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, and their salts; dimethylaminoethyl polyacrylate, polyacrylic acid Cationic nitrogen-containing polyacrylic esters and their salts such as diethylaminoethyl; Cationic nitrogen-containing polymethacrylic esters and their salts such as diethylaminoethyl polymethacrylate and n-butylaminoethyl polymethacrylate; Condensates of epihalohydrin and amines ; Condensates of monoaminodicarboxylic acids and polybasic amines and their salts; Cation-modified polyacrylamide, cation-modified urea resins, cation-modified epoxy resins and their salts; Polyvinylbenzyltrimethylammonium chloride; Polyamide epichlorohydrin; Polyvinylpyridine, polyvinylimidazole, etc. Cationic polynitrogen-containing heterocyclic compounds and salts thereof; polyethyleneimine can be mentioned. In the practice of the present invention, representative cationic monomers that can be used alone or in combination with the polymerizable monomer for the purpose of reacting with the copolymer include dimethylaminoethyl acrylate, acrylic acid Cationic nitrogen-containing acrylic esters and their salts such as diethylaminoethyl; cationic nitrogen-containing methacrylic esters and their salts such as diethylaminoethyl methacrylate and n-butylaminoethyl methacrylate; cationic nitrogen-containing acrylic esters and their salts such as vinylpyridine and vinylimidazole; Examples include nitrogen heterocyclic compounds and salts thereof, cationic N-vinylamide and salts thereof, and allylamine compounds such as dimethylallylamine and diallylamine and salts thereof. A pigment binder that can be used in the practice of the invention to form a coating composition of the invention by mixing with the copolymer or copolymer-polymerizable monomer reaction product and a cationic organic compound. As a pigment binder, any pigment binder commonly used in this type of coating composition can be used, but representative examples include natural products such as casein, starch, and soybean protein. and synthetic products such as PVA, styrene-butadiene emulsion, acrylic emulsion, and vinyl acetate emulsion. In the practice of the present invention, the copolymer or copolymer-polymerizable monomer reaction product, cationic organic compound, and pigment binder can be used to form the coating composition of the present invention. Typical examples of pigments include clay,
Examples include inorganic pigments such as calcium carbonate and talc, and organic pigments such as polystyrene emulsion particles. Although the compositions of the present invention can be used for a wide variety of purposes as coatings in general, they are particularly suitable as coating compositions for paper and paperboard. Paper and paperboard coated with the composition of the present invention can be coated papers and paperboards that are excellent in all properties: whiteness, opacity, offset printability, ink drying speed, and light fastness. . Such an effect is not easily obtained when a composition other than the coating composition of the present invention is used. Therefore, the paper material coated with the novel coating composition of the present invention is itself a new paper material that could not exist before. The present invention will be explained below with reference to examples, but these examples are intended to illustrate the present invention and not to limit it. Example 1 (a) Synthesis of copolymer of styrenic monomer and ethylenically unsaturated acid and/or its ester: 117 parts by weight of styrene monomer, 97.5 parts by weight of monomethyl maleate, 1.72 parts by weight of benzoyl peroxide, n-dodecyl mercaptan 2.15
Parts by weight were stirred and mixed at room temperature, and the resulting mixture was poured between stainless steel plates with smooth surfaces so that the thickness of the final cast polymer would be about 5 mm. Thereafter, the temperature was gradually raised to 60°C to 100°C for 3 hours, and the reaction was carried out at 130°C to 140°C for 10 hours, then cooled to room temperature to form a colorless and transparent polymer plate made of styrene-maleic acid monomethyl ester copolymer. Obtained. Next, this polymer plate was crushed and dissolved in dilute ammonia water. (b) Production of a copolymer-polymerizable monomer reaction product by reacting the above copolymer with a polymerizable monomer in its aqueous dispersion in the presence of a polymerization catalyst: a four-necked flask equipped with a reflux condenser. In (a) above
The ammonium salt of the styrene-maleic acid monomethyl ester copolymer prepared as follows.
267 parts by weight of an aqueous solution containing 15% by weight was charged, and 60 parts by weight of acrylamide and 150 parts by weight of distilled water were added thereto and dissolved with stirring. This was heated to 60°C in a constant temperature bath, 20 parts by weight of 10% ammonium persulfate aqueous solution and 2 parts by weight of 10% dimethylaminopropionitrile aqueous solution were added as polymerization catalysts, and heated at 60°C in a nitrogen stream. Stirring was continued for 4 hours for polymerization to obtain an aqueous dispersion () of a copolymer-polymerizable monomer reaction product. (c) Preparation of coating composition and production of coated paper: In a mixer, add 60 parts by weight of water, 1 part by weight of dispersant (0.4 parts by weight of solids) and 1.1 parts by weight of 28% ammonia water.
100 parts by weight of clay was added and dispersed well with stirring to obtain a clay slurry. Next, while continuing to stir, the aqueous dispersion ()30 of the copolymer-polymerizable monomer reaction product was added.
parts by weight (6 parts by weight of solid matter), 1.67 parts by weight of polyethyleneimine (0.5 parts by weight of solid matter), and further styrene-butadiene latex.
Add 28 parts by weight (14 parts by weight of solids), and finally add water to make a total solids concentration of 45%.
A coating composition () was prepared by passing it through 100 mesh gold steel. This coating composition (2) was heated to 40° C. and its viscosity at 60 rpm was measured using a B-type viscometer. Next, this coating composition was applied to a base paper having a metric basis weight of 350 g/m ² using an experimental air knife coater at a coating weight of approximately 15 g/m ² . Coated paper is 25
After being left in a constant temperature and humidity room at 65% RH overnight, it was subjected to super calendering at 60°C and 85 kg/cm, and then subjected to the following tests. The test results were as shown in Table 1. Measurements of whiteness, opacity, offset printing suitability, ink drying speed and light fastness were carried out according to the following methods. (1) Whiteness: GE whiteness meter (2) Opacity: Approximate coating amount on paper with 85% opacity
It was hand-coated to a density of 15 g/m ² and measured using a photovoltmeter. (3) Offset printing suitability: A certain amount of water was applied to coated paper, and immediately after printing, the degree of ink coverage was visually evaluated in four grades: excellent, good, fair, and poor. (4) Ink drying speed: 0.5cc of offset ink
After printing on coated paper using an RI tester, the print was transferred to white paper at regular intervals, and the time (minutes) was expressed as the time when ink stopped adhering to the transferred paper. (5) Light resistance: UV carbon arc at a temperature of 40℃
Decrease rate of whiteness after 20 hours of irradiation compared to whiteness before irradiation. Example 2 117 parts by weight of α-methylstyrene, acrylic acid
47.2 parts by weight, benzoyl peroxide 1.31 parts by weight, n-
An aqueous copolymer dispersion was prepared as described in Example 1(a) except that 1.64 parts by weight of dodecyl mercaptan was used. This is referred to as a copolymer aqueous dispersion (). Next, 20 parts by weight of this copolymer aqueous dispersion (3 parts by weight in solid matter) and 1.0 parts by weight (0.5 parts by weight in solid matter) of a condensate of epichlorohydrin, which is a cationic organic compound, and dimethylamine.
parts by weight) were stirred at high speed in a homomixer to prepare a composition (). Then this composition () 25.1
The coating composition ( ) was created. After measuring the viscosity of the coating composition (2), this composition was applied to paper, and measurements regarding each test item were performed according to the method described in Example 1(c). The results of these tests are shown in Table 1. Example 3 Implemented except that 83.2 parts by weight of styrene, 94.4 parts by weight of vinyltoluene, 72 parts by weight of monoethyl maleate, 86 parts by weight of monobutyl fumarate, 2.68 parts by weight of benzoyl peroxide and 3.36 parts by weight of n-dodecylmercaptan were used. An aqueous copolymer dispersion () was prepared in the same manner as in Example 1(a). Next, 20 parts by weight of this copolymer aqueous dispersion (3 parts by weight as a solid), 1.3 parts by weight of a cationic modified urea resin (0.5 parts by weight as a solid), and 1 weight of a condensate of epipromhydrin and methylamine were added. parts (0.5 parts in solids)
parts by weight), starch-PVA mixture [starch/PVA=
1/1 (weight ratio)] as described in Example 1(c) except that 66.6 parts by weight (10 parts by weight of solid matter) and 24 parts by weight of vinyl acetate latex (12 parts by weight of solid matter) were added. A coating composition () was prepared in the same manner as described above. After measuring the viscosity of this coating composition (2), it was applied to paper and the test items listed in Example 1(c) were measured. These results were as shown in Table 1. Example 4 Same as described in Example 1(a) except that 147.5 parts by weight of α-methylstyrene, 86 parts by weight of methacrylic acid, 1.87 parts by weight of benzoyl peroxide and 2.33 parts by weight of n-dodecylmercaptan were used. Then, an aqueous copolymer dispersion () was prepared. Next, 400 parts by weight of this copolymer aqueous dispersion (60 parts by weight as a solid), 20 parts by weight of acrylamide, 10 parts by weight of dimethylaminoethyl acrylate, 10 parts by weight of dimethylaminoethyl acrylate, and 10% aqueous ammonium persulfate solution. A copolymer-polymerizable monomer was prepared in the same manner as in Example 1(b) except that 24 parts by weight, 2.4 parts by weight of 10% aqueous dimethylaminopropionitrile solution, and 34.6 parts by weight of distilled water were used. An aqueous dispersion () of the reaction product was prepared.
Furthermore, 35 parts by weight (7 parts by weight of solid matter) of an aqueous dispersion of this copolymer-polymerizable monomer reaction product, and a styrene-butadiene latex.
A coating composition (2) was prepared in the same manner as in Example 1(c) except that 24 parts by weight (12 parts by weight of solid matter) was used. After measuring the viscosity of this coating composition (2), it was applied to paper and measurements were made for each test item listed in Example 1(c). These results were as shown in Table 1. Example 5 Example 1(a) except that 104 parts by weight of styrene, 112 parts by weight of itaconic acid, 1.30 parts by weight of benzoyl peroxide, and 0.65 parts by weight of n-dodecyl mercaptan were used.
An aqueous copolymer dispersion was obtained in the same manner as described in . Next, the above copolymer aqueous dispersion ()
Same as the method described in Example 1(c) except that 40 parts by weight (6 parts by weight of solid matter), 0.5 parts by weight of diethylenetriamine, and 32 parts by weight of vinyl acetate latex (16 parts by weight of solid matter) were used. The coating composition (for paper) was adjusted and its viscosity was measured according to the method described in 1. After coating, the test items described in Example 1(c) were measured. The results obtained are shown in Table 1. Example 6 Same as described in Example 1(a) except that 187 parts by weight of styrene, 158 parts by weight of maleic acid monopropyl ester, 2.76 parts by weight of benzoyl peroxide and 3.45 parts by weight of n-dodecyl mercaptan were used. Then, an aqueous copolymer dispersion () was prepared. Next, the above copolymer aqueous dispersion () 333
Parts by weight (50 parts by weight in solid form), 30.8 parts by weight of methacrylamide, 19.2 parts by weight of acrylonitrile, 10 parts by weight
% ammonium persulfate aqueous solution 25 parts by weight, 10% diethylaminopropionitrile aqueous solution 2.5 parts by weight,
An aqueous dispersion () of the copolymer-polymerizable monomer reaction product was prepared in the same manner as in Example 1(b) except that 89.5 parts by weight of distilled water was used. Next, 37.5 parts by weight (solid matter) of the aqueous dispersion () of this copolymer-polymerizable monomer reaction product
7.5 parts by weight), 1.3 parts by weight of polyvinylbenzyltrimethylammonium chloride (0.4 parts by weight in solid matter), and styrene-butadiene latex 30
A coating composition (2) was prepared in the same manner as in Example 1(c), except that parts by weight (15 parts by weight of solid matter) were used. After measuring the viscosity of this coating composition (2), it was applied to paper and the test items listed in Example 1(c) were measured. Example 7 The same procedure as in Example 1(a) was carried out except that 104 parts by weight of styrene, 172 parts by weight of maleic acid monobutyl ester, 2.21 parts by weight of benzoyl peroxide, and 2.76 parts by weight of n-dodecyl mercaptan were used. , an aqueous copolymer dispersion () was prepared. Next, 267 parts by weight of this copolymer aqueous dispersion (40 parts by weight as a solid), 36.7 parts by weight of acrylamide, 18.3 parts by weight of methyl acrylate, 5 parts by weight of divinylbenzene, and 30 parts by weight of a 10% ammonium persulfate aqueous solution.
Same as in Example 1(b) except that parts by weight, 3 parts by weight of 10% aqueous dimethylaminopropionitrile solution, and 140 parts by weight of distilled water were used.
An aqueous dispersion of the copolymer-polymerizable monomer reaction product was prepared. Next, 33.3 parts by weight (5 parts by weight of solid matter) of an aqueous dispersion of this copolymer-polymerizable monomer reaction product, 2 parts by weight of ethylenediamine
Parts by weight (0.6 parts by weight of solid matter), casein aqueous solution 30
Parts by weight (4.5 parts by weight in solid form) and styrene
A coating composition (2) was prepared in the same manner as in Example 1(c), except that 24 parts by weight of butadiene latex (12 parts by weight in solid matter) was used.
After measuring the viscosity of this coating composition (2), it was applied to paper and the test items listed in Example 1(c) were measured. These results were as shown in Table 1. Comparative Example 1 Example 1(c) except that the aqueous dispersion ( ) of the copolymer-polymerizable monomer reaction product was not used.
I did exactly the same thing. The results were as shown in Table 1. Comparative Example 2 The same procedure as in Example 3 was carried out except that the cationic modified urea resin was not used. The results were as shown in Table 1. Comparative Example 3 The same procedure as in Example 6 was carried out except that polyvinylbenzyltrimethylammonium chloride was not used. The results were as shown in Table 1. Comparative Example 4 The same procedure as in Example 7 was carried out except that the aqueous dispersion () of the copolymer-polymerizable monomer reaction product was not used. The results were as shown in Table 1.

【表】実施例１から７および比較例１から４により得
られた第１表の測定結果を比較すれば、本発明に
よる紙用塗被組成物は粘度が低く、かつこれを塗
工した紙および板紙は白色度、不透明度、オフセ
ツト印刷適性、インキ乾燥速度、耐光性のすべて
が優れた塗工紙及び塗工板紙となることが明らか
である。[Table] Comparing the measurement results in Table 1 obtained from Examples 1 to 7 and Comparative Examples 1 to 4, it is found that the paper coating composition according to the present invention has a low viscosity, and the paper coated with it has a low viscosity. It is clear that the coated paper and paperboard are excellent in whiteness, opacity, offset printing suitability, ink drying speed, and light resistance.

Claims

[Scope of Claims] 1 (a) an alkali-soluble copolymer consisting of at least one styrene monomer and at least one ethylenically unsaturated acid component; (b) two or more nitrogen atoms in one molecule 1. A coating composition for paper and paperboard, comprising at least one cationic organic compound containing: (c) a pigment containing clay; and (d) a binder. 2. The composition according to claim 1, wherein the copolymerization ratio of styrenic monomer to ethylenically unsaturated acid component is 1:1 to 2:1 in molar ratio. 3. The composition according to any one of claims 1 to 2, wherein the copolymer has a molecular weight of 10,000 to 100,000. 4. The composition according to any one of claims 1 to 3, characterized in that the molar ratio of copolymer to cationic organic compound is 50:50 to 99:1. 5 (a) 0.1 to 10% by weight of the copolymer; (b) 0.05 to 10% by weight of the organic cationic compound; (c) 40 to 90% by weight of the clay-containing pigment; and (d) 10 to 60% by weight of the binder. % by weight, with the remainder being a dispersion medium and other additives.
The composition according to any one of Item 4. 6 (a) Reacting an alkali-soluble copolymer consisting of at least one styrenic monomer and at least one ethylenically unsaturated acid component with at least one other polymerizable monomer in the presence of a polymerization catalyst. The obtained copolymer-polymerizable monomer reaction product; (b) at least one cationic organic compound containing two or more nitrogen atoms in one molecule; (c) a pigment containing clay; and (d) A coating composition for paper and paperboard, characterized in that it contains a binder. 7 The copolymerization ratio of styrene monomer to ethylenically unsaturated acid component is 1:1 to 2:1 in molar ratio,
The mixing ratio of copolymer to polymerizable monomer is 1:9 or more
Composition according to claim 6, characterized in that the ratio is 9:1. 8. The composition according to any one of claims 6 to 7, wherein the copolymer has a molecular weight of 10,000 to 100,000. 9. The ratio of copolymer-polymerizable monomer reaction product to cationic organic compound is 50:50 to 99:
Claim 6, characterized in that: 1
The composition according to any one of items 1 to 8. 10 (a) The content of the copolymer-polymerizable monomer reaction product is 0.1 to 25% by weight; (b) the content of the organic cationic compound is 0.05 to 25% by weight; (c)
The content of the clay-containing pigment is 40 to 90% by weight; and (d) the content of the binder is 5 to 60% by weight.
The composition according to any one of claims 6 to 9, wherein the remainder is a dispersion medium and other additives. 11 1 to 100 mol% of the polymerizable monomers
11. The composition according to any one of claims 6 to 10, characterized in that cationic monomer is substituted for cationic monomer. 12 (a) Reacting an alkali-soluble copolymer of at least one styrenic monomer and at least one ethylenically unsaturated acid component with at least one polymerizable cationic monomer in the presence of a polymerization catalyst. Obtained product; (b) Pigment containing clay;
and (iii) a coating composition for paper and paperboard, comprising a binder. 13 The copolymerization ratio of styrene monomer to ethylenically unsaturated acid component is 1:1 to 2:1 in molar ratio, and the mixing ratio of copolymer to cationic monomer is 1:9 to 9:1. 13. A composition according to claim 12, characterized in that: 14. The composition according to any one of claims 12 to 13, wherein the copolymer has a molecular weight of 10,000 to 100,000. 15 (a) the content of the copolymer-cationic monomer reaction product is 1 to 55% by weight; (b) the content of the clay-containing pigment is 40 to 90% by weight; and (c) The content of the binder is 5 to 55% by weight,
15. The composition according to claim 12, wherein the remainder is a dispersion medium and other additives. 16 (a) At least one polymerizable cationic monomer and at least one alkali-soluble copolymer of at least one styrenic monomer and at least one ethylenically unsaturated acid component in the presence of a polymerization catalyst A coating composition for paper and paperboard, comprising: a product obtained by reacting with another polymerizable monomer; (b) a pigment containing clay; and (c) a binder. 17 The copolymerization ratio of styrene monomer to ethylenically unsaturated acid component is 1:1 to 2:1 in molar ratio, and the mixing ratio of copolymer to polymerizable monomer and cationic monomer is 1:9 to 9: 17. The composition according to claim 16, characterized in that: 1. 18 Claims 16 to 17, characterized in that the copolymer has a molecular weight of 10,000 to 100,000.
The composition according to any of paragraphs. 19 (a) The content of the copolymer-polymerizable monomer and cationic monomer reaction product is 1 to 55% by weight; (b) The content of the clay-containing pigment is 40% by weight.
and (c) the content of the binder is 5 to 55% by weight, with the remainder being a dispersion medium and other additives. 19. The composition according to any one of Item 18. 20. The composition according to any one of claims 1 to 19, wherein the styrenic monomer is at least one member selected from the group consisting of styrene, vinyltoluene, and α-methylstyrene. 21 The ethylenically unsaturated acid component is at least one selected from the group consisting of ethylenically unsaturated acids, salts of ethylenically unsaturated acids, anhydrides of ethylenically unsaturated acids, and esters of ethylenically unsaturated acids.
21. The composition according to any one of claims 1 to 20, which is a member. 22. The composition according to claim 21, wherein the ethylenically unsaturated acid component is at least one member selected from the group consisting of alkene mono- and dicarboxylic acids, and salts, anhydrides and esters thereof. 23 The other polymerizable monomers include acrylic esters, methacrylic esters, styrene monomers, organic acid vinyl esters, nitriles, α-olefins, conjugated diene monomers,
Halogenated olefins, alkene mono- or dicarboxylic acids and their salts and anhydrides, dicarboxylic acid monoalkyl esters, dicarboxylic acid dialkyl esters, amides, styrene-p
- At least one member selected from the group consisting of sulfonic acids and their alkali salts, glycidyls, and unsaturated aldehydes.
The composition according to any one of items 2 to 19. 24 The cationic organic compound is ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and salts thereof, and other amines containing two or more nitrogen atoms in one molecule and salts thereof; polyacrylic Cationic nitrogen-containing polyacrylic esters and their salts such as dimethylaminoethyl acid and diethylaminoethyl polyacrylate; cationic nitrogen-containing methacrylic esters and their salts such as diethylaminoethyl polymethacrylate and n-butylaminoethyl polymethacrylate; ;
Condensates of epihalohydrin and amines; condensates of monoaminodicarboxylic acids and polybasic amines and their salts; cation-modified polyacrylamide, cation-modified urea resins, cation-modified epoxy resins and their salts; polyvinylbenzyltrimethylammonium chloride; polyamide epichlorohydrin; Cationic polynitrogen-containing heterocyclic compounds such as polyvinylpyridine and polyvinylimidazole and salts thereof; at least one member selected from the group consisting of polyethyleneimine; Claim 1
The composition according to any one of Items 11 and 20 to 22. 25 The cationic monomer is a cationic nitrogen-containing acrylic ester and its salt such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate; diethylaminoethyl methacrylate;
Cationic nitrogen-containing methacrylic esters and their salts such as n-butylaminoethyl methacrylate; cationic nitrogen-containing heterocyclic compounds and their salts such as vinylpyridine and vinylimidazole; cationic N-vinylamide and its salts; dimethylallylamine; The composition according to any one of claims 12 to 19, which is at least one member selected from the group consisting of allylamine compounds such as diallylamine and salts thereof.