JP4332979B2 - Coated paper for printing - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、原紙に顔料と接着剤を主成分とする塗工層を設ける印刷用塗工紙に関するものである。
【０００２】
【従来の技術】
近年、印刷物のビジュアル化、カラー化及び高級化に伴い、特に印刷用塗工紙の塗工面の光沢度、白色度の改良要望が高まっている。即ち、印刷技術の進歩と共に高速印刷が行われるようになり、そのような印刷技術に付随して印刷品質に優れた印刷用塗工紙が要望されている。
【０００３】
例えば印刷用塗工紙の塗工組成物に関しては、超微粒子重質炭酸カルシウム、微細立方形軽質炭酸カルシウム、デラミカオリン、焼成カオリン、微粒子タルク、プラスチックピグメント等の微細顔料の使用及びこれらの顔料を用いた塗工液濃度が６５％以上の高濃度塗工法等数多くの方法が提案されており、これらの方法はいずれも微粒子顔料を使用する方法では共通しているが、印刷表面強度に難点を残している。その対策として接着剤であるラテックスをより多く配合することになり、結果として印刷時の吸水性が低下し、インキ着肉不良を招き高品質の印刷が出来ないうえに、製造原価も割高になる。また、製紙用顔料としては低価格であることからカオリンが用いられているが、高い白紙光沢度は達成できるものの白色度やインク受理性に難があるという欠点がある。
【０００４】
また、形状を有する微粒軽質炭酸カルシウム（針状、柱状、紡錘状等）を高配合化することで得られる塗工紙は白紙光沢度、白色度に優れる。しかしながら、塗工液中に針状あるいは柱状の軽質炭酸カルシウムを高配合すると、塗工液の粘度が高くなりすぎてしまうために、例えばブレード方式の塗工装置で塗工液を原紙に塗工する場合、塗工速度を高くし過ぎるとブレード刃先にスタラクタイトやブリーディング（ブレードの刃先に塗工液の凝集物が付着する現象）が発生し、紙面上にストリークなどの欠陥を発生させるため、塗工速度には限界があり高速操業性や生産性の低下などを招いてしまうのが現状である。また、塗工液の動的保水性が大きく低下してしまうため、塗工液が原紙にしみ込みすぎて原紙被覆性が劣る結果、カレンダー処理時の白紙光沢度発現性が低下する問題や、バインダー不足によって印刷表面強度が低下する問題を同時に招いてしまう。
【０００５】
針状あるいは柱状の炭酸カルシウムを塗工液用顔料として用いる既存技術としては、例えば長径が３μｍ以上、１００μｍ以下で、短径がの０．３μｍ以上、４μｍ以下の針状炭酸カルシウムを塗工液中に顔料として１０重量％以上含有する方法（特開平７−７０９８６号公報）、アラゴナイト型軽質炭酸カルシウムを顔料として５〜７０重量％以上含有した塗工液を、カーテン塗布装置によって塗布する方法（特開平７−１６６４９３号公報）、長径／短径＝５〜１０である針状炭酸カルシウムを全顔料に対して１０〜４０重量％含有した塗工液をベントブレード塗布方式によって塗布する方法（特開平７−２１６７９１号公報）などが挙げられるが、これらの技術を用いても、高速操業性が劣るのみならず、白紙光沢度や印刷表面強度の低下を十分なレベルまで改善することはできなかった。また、特開平１０−２２６９７４号報においては、硫酸塩法またはソーダ法によるパルプ製造工程の苛性化工程で、生石灰を白液で消和後、緑液で苛性化反応することにより針状の軽質炭酸カルシウムを製造し、前記針状軽質炭酸カルシウムを填料あるいは顔料として使用することによって、塗工紙の不透明度や印刷後光沢等の印刷適性を改善する方法を提供しているが、印刷表面強度や高速操業性の改善に対しては十分な効果は得られなかった。
【０００６】
【発明が解決しようとする課題】
以上のような状況に鑑み、本発明の課題は、原紙に顔料と接着剤を主成分とする塗工層を設ける印刷用塗工紙において、白紙光沢度、不透明度、白色度が高く、印刷表面強度および高速操業性に優れた印刷用塗工紙を提供するものである。
【０００７】
【課題を解決するための手段】
本発明者らはこの課題について鋭意検討した結果、原紙上に顔料と接着剤を主成分とする塗工層を有する印刷用塗工紙及びその製造方法において、顔料としていがぐり状軽質炭酸カルシウムを湿式粉砕により得られた軽質炭酸カルシウムを特定量含有し、且つ、接着剤として特定の粒子径範囲をもつラテックスを含有する塗工液を塗工することによって本発明を成すに至った。
【０００８】
以下、発明の詳細を示す。
【０００９】
一般に、形状を有する微粒軽質炭酸カルシウム（針状、柱状、紡錘状等）を高配合化することで得られる塗工紙は白紙光沢度や白色度、さらには不透明度等の発現に対して優れた効果を与えるが、その一方で、塗工液の高速せん断下での粘度が高くなるため、塗工速度を高くし過ぎるとブレード刃先にスタラクタイト（ブレードの刃先に塗工液が乾燥状態で鐘乳石状に堆積する現象）やブリーディング（ブレードの刃先に塗工液がウエット状態で付着する現象）が発生し、紙面上にストリークなどの欠陥を発生させるため、塗工速度には限界があり高速操業性や生産性の低下などを招いてしまう問題があった。また、塗工液の動的保水性が大きく低下してしまうため、塗工液が原紙にしみ込みすぎて原紙被覆性が劣る結果、カレンダー処理時の白紙光沢度発現性の低下やバインダー不足による印刷表面強度の低下を同時に招いてしまう問題があった。
【００１０】
以上のような状況において、本発明者等は、いがぐり状軽質炭酸カルシウムを湿式粉砕することにより得られた軽質炭酸カルシウムを全顔料中に６０〜９５重量％、平均粒子径が５０〜９０ｎｍである共重合体ラテックスを含有した塗工液を塗工することによってこれらの問題を解決した。この理由については十分に解明されていないが、粉砕により炭酸カルシウムの凝集体或いは擬似凝集体が一次粒子となることや新たな結晶面が出るとこで粒子の表面電荷が変化することによって、顔料の流動性が大幅に改善されたものと考えられる。また、粉砕することによって顔料の比表面積が適度に増大し、顔料の保水性が大幅に改善された結果、原紙への塗工液の浸透が抑制され印刷表面強度が大幅に改善されたと考えられる。本発明においては、いがぐり状の軽質炭酸カルシウムの湿式粉砕後の平均粒子径が０．２５〜０．９０μｍのものを使用することが好ましい。また、上記記載のラテックスを併用すると、顔料と共重合体ラテックスによるバイモーダル効果によって塗工液の高せん断速度下での粘度を著しく低下させることができるため、高速操業性を飛躍的に向上させることができると考えられる。また、上記記載のラテックスは単位重量当たりの粒子数が多いために顔料との接着点が増大し、印刷表面強度も飛躍的に向上すると考えられる。
【００１１】
但し、粉砕後の軽質炭酸カルシウムの配合量が６０重量％未満の場合には、白色度、白紙光沢度、不透明度が劣る。これは白色度や白紙光沢度、不透明度の発現効果に優れた粉砕後の軽質炭酸カルシウムの配合量が十分でないためと考えられる。一方、配合量が９５重量％を越えると、印刷表面強度が劣る。これは粉砕によって比表面積の増大した粉砕後の軽質炭酸カルシウムを過度に配合することによって、接着剤不足が引き起こされるためと考えられる。ただし、顔料の粉砕の度合によっては９５重量部を越えても問題とはならない場合もある。
【００１２】
また、共重合体ラテックスの平均粒子径が５０ｎｍ未満の場合、白紙光沢度の発現性が低下する。これは、塗工層が極度に緻密化するためにカレンダー処理を行っても塗工層の平滑化が十分に促進されないためと考えられる。一方、平均粒子径が９０ｎｍを越える場合は、高速操業性と印刷表面強度が低下する。これは、ラテックスの平均粒子径が大きすぎるために、顔料とラテックスによるバイモーダル効果が十分に発現されないだけでなく、顔料との接着点が減少することに起因しているものと考えられる。
【００１３】
また、本発明で使用されるいがぐり状軽質炭酸カルシウムは、短径０．２〜０．４μｍ、長径１．５〜４．０μｍの一次粒子の凝集体であり、該凝集体の平均粒子径が２．５〜１２．０μｍであることが好ましい。一次粒子の短径が０．２μmに満たない場合、あるいは長径が１．５μｍに満たない場合、あるいは該凝集体の粒子径が２．５μｍに満たない場合は、粉砕後の軽質炭酸カルシウムが小さくなりすぎるために顔料の比表面積が増大し、高速操業性や印刷表面強度が低下する傾向にある。また、一次粒子の短径が０．４μmを越える場合、あるいは長径が４．０μｍを越える場合は、あるいは該凝集体の粒子径が１２．０μｍを越える場合は、粉砕後の軽質炭酸カルシウム中に粗粒子が含まれ易くなるため、白紙光沢度と不透明度が低下する傾向にある。
【００１４】
また、本発明の共重合体ラテックスの配合量は５〜１５重量％が好ましく、配合量が５重量％未満の場合には印刷表面強度が低下しやすい傾向にある。一方、１５重量％を越える場合には塗工層が緻密化するために白紙光沢度が低下する傾向にある。
【００１５】
【発明の実施の形態】
本発明で使用されるいがぐり状の軽質炭酸カルシウムは、炭酸ガス法（消石灰スラリーに炭酸ガスを吹き込んで製造）や苛性化法（硫酸塩法またはソーダ法によるパルプ製造工程の苛性化工程で製造）で製造されたものを粉砕して使用するが、その形状は、短径が０．２〜０．４μｍ、長径が１．５〜４．０μｍの一次粒子の凝集体で、該凝集体の平均粒子径が２．５〜１２．０μｍであることが好ましい。また、いがぐり状の苛性化軽質炭酸カルシウムを使用する場合は以下の製造法に従って得ることができる。（１）苛性化工程外から導入した生石灰を用い、（２）消石灰生成時の生石灰と水のモル比が、生石灰：水＝１：１〜１：５であり、かつ消石灰の重量の基準として０．０５〜８重量％の炭酸カルシウムを含有する前記消石灰に対して、前記消石灰濃度が１０〜６０重量％になるように白液を添加し、撹拌あるいは混和しながら消和させて石灰乳及び／又は石灰泥を生成する第一段工程、次いで該石灰乳及び／又は石灰泥に、前記苛性化工程で発生し、白液を製造するのに必要な所定量の緑液を該石灰乳及び／又は石灰泥に対して特定の範囲の添加速度で逐次添加し、反応温度２５〜７５℃にて苛性化反応を行うことによって製造するものである。この方法で得たいがぐり状苛性化軽質炭酸カルシウムは、パルプ製造工程の苛性工程で得られる主産物の水酸化ナトリウムを製造する際の副産物であるため、従来の石灰乳と炭酸ガスとの反応による方法で得られる軽質炭酸カルシウムに比べて非常に低コストで製品を製造し得る。
本発明では、いがぐり状の軽質炭酸カルシウムをビーズミル等の粉砕機により適度に湿式粉砕して使用するが、湿式粉砕して得られた軽質炭酸カルシウムは、いがぐり状軽質炭酸カルシウムから放射状に突き出ている針の先端が折れることでできる針状または柱状の軽質炭酸カルシウムであるが、先端部が折れた後に残る比較的球状に近い針状または柱状軽質炭酸カルシウムの凝集体を含んでいてもかまわない。
【００１６】
また、粉砕機としては製紙用顔料の湿式粉砕にごく一般に使用されるアトライター、振動ミル、ボールミル、竪型サンドミル、横型サンドミル、ジェットミル等が挙げられる。また、粉砕メディアとしてはガラス、セラミック、アルミナ、ジルコニア等の硬質原料で製造された球状のボールが挙げられ、粒子径は０．１〜１０ｍｍであることが好ましい。粉砕効率を考慮すると、メディアの充填率はできる限り高い方が好ましいが、充填率が高すぎる場合は粉砕室内でのメディアの動きが制限され、逆に粉砕効率を低下させることもあり、使用する粉砕機に応じて適宜調節する。
【００１７】
また、本発明で使用する顔料は、前記記載の軽質炭酸カルシウム以外に特に規定するものではなく、製紙用としてごく一般に使用される重質炭酸カルシウム、軽質炭酸カルシウム、カオリン、クレー、デラミネーテッドクレー、タルク、サチンホワイト、シリカ、プラスチックピグメント、二酸化チタン等の無機顔料やポリスチレンや尿素樹脂等の有機顔料が挙げられ、これらの顔料のなかから１種以上を前記記載の軽質炭酸カルシウムと併用する。
【００１８】
また、本発明で使用する接着剤は前記記載のラテックス以外に特に規定するものではなく、製紙用としてごく一般に使用されるスチレン・ブタジエン共重合体、スチレン・ブタジエン・アクリル共重合体あるいはその変性物等が使用され、これら重合体のモノマーとしては、スチレン、ブタジエンの他、メチルメタクリレート他ビニル系不飽和カルボン酸エステル化合物やアクリロニトリル等その他ビニル化合物、あるいはアクリル酸、マレイン酸等ビニル系不飽和カルボン酸等が挙げられる。また、酸化デンプン、リン酸エステル化デンプン、エーテル化デンプン、酵素変性デンプンや冷水可溶性デンプン、カゼイン、カルボキシメチルセルロース等の水溶性天然高分子系の接着剤を併用しても良い。接着剤の使用量は、顔料１００重量部に対して５〜３０重量部が好ましい。
【００１９】
また、塗工液には分散剤、増粘剤、消泡剤、耐水化剤、保水剤など製紙用としてごく一般に使用される各種助剤を使用してもかまわない。これらの中でも、保水剤としてカルボキシメチル基の置換度が０．５〜１．０であるカルボキシメチルセルロースを添加することで、塗工液の動的保水性がさらに良好となり塗工紙品質を向上することができる。添加量は、顔料１００重量部に対して０．１〜０．３重量部であることが好ましい。塗工液濃度は４０〜７０％が好ましく、特に６５％以上の高濃度塗工においては高速流動性の改善効果が一層顕著に現われる。
【００２０】
かくして調製された塗工液は原紙に塗工されるが、塗工方法は特に限定されるものではなく、各種ブレードコータ、ロールコータ、エアーナイフコータ、バーコータ、ロッドブレードコータ、ショートドウェルコータ等の各種塗工装置をオンマシン或いはオフマシンで原紙用に単層或いは多層塗工される。また、２層塗工される場合は、上塗り塗工液と下塗り塗工液の両方か、あるいは上塗り塗工液と下塗り塗工液のどちらか一方が前記記載の塗工液組成を満たしていれば、それ以外の塗工液組成については特に規定されるものではない。塗工量は両面で５〜５０ｇ／ｍ２の範囲で調節されるが、下塗り塗工層を設ける場合、下塗り塗工量は両面で５〜２０ｇ／ｍ２であることが望ましい。
【００２１】
本発明で使用される原紙としては、メカニカルパルプ、ケミカルパルプ及び古紙回収パルプ等を任意の比率で混合して用いられ、必要に応じて通常の製紙用填料、紙力増強剤、歩留まり向上剤及びサイズ剤等を添加した製紙原料をシングルワイヤーあるいはツインワイヤーを有する通常の抄紙機によって抄造され、坪量は３０〜４００ｇ／ｍ２であることが好ましい。
【００２２】
また、本発明の塗工組成物を塗工して得られる塗工紙は、スーパーカレンダー、グロスカレンダー、ソフトカレンダー等の表面仕上げ装置を用いて印刷用塗工紙を得るが、軽い仕上げ処理を行うか無処理で光沢の低いマット調の印刷用塗工紙を得ることもできる。また、本発明の印刷用塗工紙は、枚葉または巻取りのいずれでもオフセット印刷が可能である。
【００２３】
【実施例】
以下に、実施例を挙げて本発明をより具体的に説明するが、もちろんその範囲に限定されるものではない。なお、例中の部及び％は特に断らない限り、それぞれ重量部及び重量％を示す。
＜品質評価方法＞
（１）軽質炭酸カルシウムの平均粒子径
島津遠心沈降式粒度分布測定装置ＳＡ−ＣＰ２形（島津製作所製）で測定し、累積重量分布の５０％点を平均粒子径とした。
（２）軽質炭酸カルシウムの長径及び短径
走査電子顕微鏡（日本電子ＪＳＭ−５３００）で長径・短径平均値を測定した。
（３）ラテックスの平均粒子径
０．０５〜０．２％濃度に希釈した試料を調製し、波長５２５ｎｍの吸光度を測定して、あらかじめ作成した検量線により求めた。
（４）白色度
デジタルハンター白色度計（東洋精機製作所製）を用いてＪＩＳ Ｐ−８１２３に従い測定した。
（５）白紙光沢度
ＪＩＳ Ｐ−８１４２に従い、角度７５度で測定した。
（６）不透明度
デジタルハンター白色度計（東洋精機製作所製）を用いてＪＩＳ Ｐ−８１３８、Ａ法に従い測定した。
（７）ドライ強度
ＲＩ−Ｉ型印刷機（明製作所製）を用い、東洋インキ製ＴＶ−２４を使用し、インキ量０．３５ｍｌ一定で印刷し、印刷面のピッキングの程度を目視で相対評価した。
◎＝全く発生しない、○＝ほとんど発生しない、△＝発生する、×＝発生が著しい
（８）スタラクタイト発生状況
ブレードの刃先に発生するスタラクタイトの発生状況を目視で評価した。
◎＝全く発生しない、○＝ほとんど発生しない、△＝発生する、×＝発生が著しい
［実施例１］
苛性化法で製造された短径０．２９μｍ、長径１．７μｍの一次粒子よりなる平均粒子径５．３μｍのいがぐり状軽質炭酸カルシウム１００部に、ポリアクリル酸ソーダ系分散剤を０．５部添加して得られた濃度７０％の粗スラリーを、ビーズ径１．５〜２．０ｍｍであるガラスビーズ（東芝バロティーニ社製）を２０ｋｇ充填したベッセル容量８ガロンのサンドミル（アイメックス社製）を用いて粉砕した。粉砕後の平均粒子径は０．４３μｍであった。
【００２４】
このようにして得られた粉砕後の軽質炭酸カルシウム８０部に、重質炭酸カルシウム１０部、カオリン１０部、接着剤として全顔料に対して平均粒子径６０ｎｍのスチレン・ブタジエン系共重合体ラテックスを１２部、さらに保水剤としてカルボキシメチル基の置換度が０．７であるカルボキシメチルセルロースを全顔料に対して固形分で０．２部添加して、固形分濃度６８％の塗工液を調製した。かくして調製された塗工液を、坪量５０ｇ／ｍ２の上質原紙に対して、ブレードコータを用いて塗工速度１２００ｍ／分の条件で塗工量が片面当たり１２．０ｇ／ｍ２となるように両面塗工した。さらに、２スタックのソフトカレンダーを用いて、ニップ数2回、処理速度１０００ｍ／分、処理温度１５０℃、処理線圧２００ｋｇｆ／ｃｍの条件で表面処理して印刷用塗工紙を得た。
［実施例２］
粉砕後の軽質炭酸カルシウム８０部、重質炭酸カルシウム１０部、カオリン１０部の代わりに、粉砕後の軽質炭酸カルシウム６２部、重質炭酸カルシウム２８部、カオリン１０部を配合した以外は、実施例１と全く同一の方法で印刷用塗工紙を得た。
［実施例３］
粉砕後の軽質炭酸カルシウム８０部、重質炭酸カルシウム１０部、カオリン１０部の代わりに、粉砕後の軽質炭酸カルシウム９３部、カオリン７部を配合した以外は、実施例１と全く同一の方法で印刷用塗工紙を得た。
［実施例４］
平均粒子径６０ｎｍの代わりに平均粒子径７８ｎｍのスチレン・ブタジエン系共重合体ラテックスを配合した以外は、実施例１と全く同一の方法で印刷用塗工紙を得た。
［実施例５］
平均粒子径６０ｎｍの代わりに平均粒子径５２ｎｍのスチレン・ブタジエン系共重合体ラテックスを配合した以外は、実施例１と全く同一の方法で印刷用塗工紙を得た。
［実施例６］
カルボキシメチル基の置換度が０．７であるカルボキシメチルセルロースの代わりに、りん酸エステル化澱粉を２部配合した以外は、実施例１と全く同一の方法で印刷用塗工紙を得た。
［実施例7］
苛性化法で製造された短径０．２９μｍ、長径１．７μｍの一次粒子よりなる平均粒子径５．３μｍのいがぐり状軽質炭酸カルシウムの代わりに、苛性化法で製造された短径０．２８μｍ、長径１．７μｍの一次粒子よりなる平均粒子径１４．０μｍのいがぐり状軽質炭酸カルシウムを使用した以外は、実施例１と全く同一の方法で印刷用塗工紙を得た。
［実施例８］
苛性化法で製造された短径０．２９μｍ、長径１．７μｍの一次粒子よりなる平均粒子径５．３μｍのいがぐり状軽質炭酸カルシウムの代わりに、苛性化法で製造された短径０．４５μｍ、長径３．７μｍの一次粒子よりなる平均粒子径１１．２μｍのいがぐり状軽質炭酸カルシウムを使用した以外は、実施例１と全く同一の方法で印刷用塗工紙を得た。
［比較例１］
粉砕後の軽質炭酸カルシウム８０部、重質炭酸カルシウム１０部、カオリン１０部の代わりに、粉砕後の軽質炭酸カルシウム５０部、重質炭酸カルシウム４０部、カオリン１０部を配合した以外は、実施例１と全く同一の方法で印刷用塗工紙を得た。
［比較例２］
粉砕後の軽質炭酸カルシウム８０部、重質炭酸カルシウム１０部、カオリン１０部の代わりに、粉砕後の軽質炭酸カルシウム１００部を配合した以外は、実施例１と全く同一の方法で印刷用塗工紙を得た。
［比較例３］
平均粒子径６０ｎｍの代わりに平均粒子径４１ｎｍのスチレン・ブタジエン系共重合体ラテックスを配合した以外は、実施例１と全く同一の方法で印刷用塗工紙を得た。
［比較例４］
平均粒子径６０ｎｍの代わりに平均粒子径９７ｎｍのスチレン・ブタジエン系共重合体ラテックスを配合した以外は、実施例１と全く同一の方法で印刷用塗工紙を得た。
［比較例５］
いがぐり状軽質炭酸カルシウムを粉砕したものの代わりに、短径０．２５μｍ、長径２．８μｍの針状軽質炭酸カルシウムを未粉砕で使用した以外は実施例１と全く同一の方法で印刷用塗工紙を得た。
［比較例６］
いがぐり状軽質炭酸カルシウムを粉砕したものの代わりに、いがぐり状軽質炭酸カルシウムを未粉砕で使用した以外は、実施例１と全く同一の方法で印刷用塗工紙を得た。
【００２５】
以上の評価結果を表１に示した。
【００２６】
【表１】
【発明の効果】
本発明により、白紙光沢度、不透明度、白色度が高く、印刷表面強度および高速操業性に優れた印刷用塗工紙を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a coated paper for printing in which a base paper is provided with a coating layer mainly composed of a pigment and an adhesive.
[0002]
[Prior art]
In recent years, with the visualization, colorization, and upgrading of printed matter, there is a growing demand for improving the glossiness and whiteness of the coated surface of coated paper for printing. That is, high-speed printing has been performed with the advancement of printing technology, and there is a demand for a coated paper for printing excellent in print quality accompanying such printing technology.
[0003]
For example, with respect to the coating composition of coated paper for printing, the use of fine pigments such as ultrafine heavy calcium carbonate, fine cubic light calcium carbonate, deramikaolin, calcined kaolin, fine particle talc, plastic pigment and the like. Many methods such as a high concentration coating method in which the concentration of the coating solution used is 65% or more have been proposed, and these methods are all common in the method using fine particle pigments, but the printing surface strength is difficult. I'm leaving. As a countermeasure, more latex, an adhesive, is added, resulting in a decrease in water absorption during printing, resulting in poor ink deposition and high quality printing, and higher manufacturing costs. . In addition, kaolin is used as a papermaking pigment because of its low cost. However, it has a drawback that whiteness and ink acceptability are difficult although high glossiness can be achieved.
[0004]
Moreover, the coated paper obtained by highly blending fine light calcium carbonate having a shape (such as needles, columns, spindles, etc.) is excellent in white paper glossiness and whiteness. However, if a high amount of needle-like or columnar light calcium carbonate is added to the coating liquid, the viscosity of the coating liquid becomes too high. For example, the coating liquid is applied to the base paper with a blade-type coating device. If the coating speed is too high, stalactite and bleeding (a phenomenon in which agglomerates of coating liquid adhere to the blade edge) occur on the blade edge, causing defects such as streaks on the paper surface. The present situation is that there is a limit to the coating speed, resulting in a decrease in high-speed operability and productivity. In addition, since the dynamic water retention of the coating liquid is greatly reduced, the coating liquid is soaked into the base paper, resulting in poor base paper coverage, resulting in a problem that the glossiness of white paper during calendar processing is reduced, At the same time, it causes a problem that the printing surface strength is lowered due to insufficient binder.
[0005]
As an existing technique using acicular or columnar calcium carbonate as a coating liquid pigment, for example, acicular calcium carbonate having a major axis of 3 μm to 100 μm and a minor axis of 0.3 μm to 4 μm is applied. A method of containing 10% by weight or more as a pigment (Japanese Patent Laid-Open No. 7-70986), and a method of applying a coating liquid containing 5 to 70% by weight or more of aragonite type light calcium carbonate as a pigment ( JP-A-7-166493), a method of applying a coating solution containing 10 to 40% by weight of acicular calcium carbonate having a major axis / minor axis = 5 to 10% based on the total pigment by a vent blade coating method (special (Kaihei 7-216791) and the like, but even if these techniques are used, not only the high-speed operability is inferior, but also the glossiness of the white paper and the printing surface strength are low. The could not be improved to a sufficient level. In JP-A-10-226974, in the causticizing step of the pulp manufacturing process by the sulfate method or the soda method, the quick lime is dehydrated with white liquor and then causticized with green liquor to produce acicular light While producing calcium carbonate and using the acicular light calcium carbonate as a filler or pigment, it provides a method for improving printability such as opacity of coated paper and gloss after printing. In addition, sufficient effects were not obtained for improving high-speed operability.
[0006]
[Problems to be solved by the invention]
In view of the situation as described above, the problem of the present invention is that the coated paper for printing provided with a coating layer mainly composed of a pigment and an adhesive on the base paper has high white paper glossiness, opacity, whiteness, and printing. The present invention provides a coated paper for printing excellent in surface strength and high-speed operability.
[0007]
[Means for Solving the Problems]
As a result of intensive studies on this problem, the inventors of the present invention applied wet garlic light calcium carbonate as a pigment in a coated paper for printing having a coating layer mainly composed of a pigment and an adhesive on a base paper. The present invention has been achieved by applying a coating solution containing a specific amount of light calcium carbonate obtained by pulverization and a latex having a specific particle size range as an adhesive.
[0008]
Details of the invention will be described below.
[0009]
In general, coated paper obtained by highly blending fine light calcium carbonate with a shape (needle shape, columnar shape, spindle shape, etc.) is excellent in the expression of white paper glossiness, whiteness, and even opacity. On the other hand, the viscosity of the coating liquid under high-speed shearing increases, so if the coating speed is increased too much, stalactinite (the coating liquid is dry on the blade edge) (Phenomenon that accumulates in the form of stalactites) and bleeding (a phenomenon in which the coating liquid adheres to the blade tip in a wet state) occurs, causing defects such as streaks on the paper surface, so the coating speed is limited and high speed There was a problem that caused a decrease in operability and productivity. In addition, since the dynamic water retention of the coating liquid is greatly reduced, the coating liquid is soaked into the base paper and the base paper is inferior, resulting in a decrease in white paper glossiness during calendar processing and insufficient binder. There has been a problem in that the printing surface strength is lowered at the same time.
[0010]
In the situation as described above, the present inventors have 60 to 95% by weight of light calcium carbonate obtained by wet-grinding garlic light calcium carbonate in the total pigment, and an average particle size of 50 to 90 nm. These problems were solved by applying a coating solution containing a copolymer latex. The reason for this has not been fully elucidated, but the aggregate of calcium carbonate or pseudo-aggregate becomes primary particles by pulverization or the surface charge of the particles changes due to the appearance of a new crystal plane, thereby It is thought that the liquidity has been greatly improved. In addition, the specific surface area of the pigment was increased moderately by grinding, and the water retention of the pigment was greatly improved. As a result, the penetration of the coating liquid into the base paper was suppressed and the printing surface strength was greatly improved. . In the present invention, it is preferable to use garlic light calcium carbonate having an average particle size of 0.25 to 0.90 μm after wet pulverization. In addition, when the latex described above is used in combination, the viscosity at a high shear rate of the coating liquid can be remarkably reduced due to the bimodal effect of the pigment and the copolymer latex, thereby dramatically improving the high-speed operability. It is considered possible. Further, since the latex described above has a large number of particles per unit weight, it is considered that the adhesion point with the pigment is increased and the printing surface strength is greatly improved.
[0011]
However, when the blended amount of light calcium carbonate after pulverization is less than 60% by weight, the whiteness, white paper glossiness, and opacity are inferior. This is presumably because the amount of light calcium carbonate after pulverization, which is excellent in whiteness, white paper glossiness, and opacity, is not sufficient. On the other hand, when the blending amount exceeds 95% by weight, the printing surface strength is inferior. This is presumably because an insufficient adhesive is caused by excessively blending the light calcium carbonate after pulverization whose specific surface area is increased by pulverization. However, depending on the degree of pulverization of the pigment, there may be no problem even if it exceeds 95 parts by weight.
[0012]
In addition, when the average particle size of the copolymer latex is less than 50 nm, the white paper glossiness is reduced. This is presumably because smoothing of the coating layer is not sufficiently promoted even if a calendar treatment is performed in order for the coating layer to become extremely dense. On the other hand, when the average particle diameter exceeds 90 nm, high-speed operability and printing surface strength are reduced. This is considered to be due to the fact that the bimodal effect due to the pigment and latex is not sufficiently exhibited because the average particle diameter of the latex is too large, and the adhesion point between the pigment and the pigment is reduced.
[0013]
Moreover, the garlic light calcium carbonate used in the present invention is an aggregate of primary particles having a minor axis of 0.2 to 0.4 μm and a major axis of 1.5 to 4.0 μm, and the average particle diameter of the aggregate is It is preferable that it is 2.5-12.0 micrometers. When the short diameter of the primary particles is less than 0.2 μm, the long diameter is less than 1.5 μm, or the particle diameter of the aggregate is less than 2.5 μm, the light calcium carbonate after pulverization is small. Therefore, the specific surface area of the pigment increases, and high-speed operability and printing surface strength tend to decrease. Further, when the short diameter of the primary particles exceeds 0.4 μm, the long diameter exceeds 4.0 μm, or the particle diameter of the aggregate exceeds 12.0 μm, the light calcium carbonate after pulverization Since coarse particles are easily contained, the glossiness and opacity of blank paper tend to be reduced.
[0014]
Further, the blending amount of the copolymer latex of the present invention is preferably 5 to 15% by weight, and when the blending amount is less than 5% by weight, the printing surface strength tends to be lowered. On the other hand, when it exceeds 15% by weight, the gloss of the white paper tends to decrease because the coating layer becomes dense.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The garlic light calcium carbonate used in the present invention is produced by a carbon dioxide method (manufactured by blowing carbon dioxide into a slaked lime slurry) or a causticizing method (manufactured in a causticizing step of a pulp producing step by a sulfate method or a soda method). However, the shape is an aggregate of primary particles having a minor axis of 0.2 to 0.4 μm and a major axis of 1.5 to 4.0 μm. The particle diameter is preferably 2.5 to 12.0 μm. Moreover, when using a corrugated caustic light calcium carbonate, it can obtain according to the following manufacturing methods. (1) Using quick lime introduced from outside the causticization process, (2) The molar ratio of quick lime and water at the time of slaked lime production is quick lime: water = 1: 1 to 1: 5, and as a reference for the weight of slaked lime White liquor is added to the slaked lime containing 0.05 to 8% by weight of calcium carbonate so that the slaked lime concentration is 10 to 60% by weight, and the mixture is hydrated with stirring or mixing, and lime milk and The first stage step of producing lime mud, and then the lime milk and / or lime mud are generated in the causticizing step, and a predetermined amount of green liquor necessary for producing white liquor is added to the lime milk and It is manufactured by sequentially adding to the lime mud at an addition rate in a specific range and performing a causticizing reaction at a reaction temperature of 25 to 75 ° C. Sagly causticized light calcium carbonate obtained by this method is a by-product in producing sodium hydroxide, the main product obtained in the caustic process of the pulp manufacturing process, and therefore, by the conventional reaction between lime milk and carbon dioxide. The product can be produced at a very low cost compared to the light calcium carbonate obtained by the method.
In the present invention, the light calcium carbonate in the form of a garlic is used after being appropriately wet pulverized by a pulverizer such as a bead mill, but the light calcium carbonate obtained by wet pulverization protrudes radially from the garlic light calcium carbonate. Although it is needle-like or columnar light calcium carbonate formed by breaking the tip of the needle, it may contain an aggregate of needle-like or columnar light calcium carbonate that is relatively spherical and remains after the tip is broken.
[0016]
Examples of the pulverizer include attritors, vibration mills, ball mills, vertical sand mills, horizontal sand mills, jet mills and the like that are generally used for wet pulverization of papermaking pigments. Examples of the grinding media include spherical balls made of hard raw materials such as glass, ceramic, alumina, and zirconia, and the particle diameter is preferably 0.1 to 10 mm. Considering the grinding efficiency, the media filling rate is preferably as high as possible. However, if the filling rate is too high, the movement of the media in the grinding chamber is limited, and conversely, the grinding efficiency may be lowered and used. Adjust appropriately according to the pulverizer.
[0017]
In addition, the pigment used in the present invention is not particularly defined other than the light calcium carbonate described above, and is generally used as heavy calcium carbonate, light calcium carbonate, kaolin, clay, and delaminated clay. Inorganic pigments such as talc, satin white, silica, plastic pigment, and titanium dioxide, and organic pigments such as polystyrene and urea resin are used. One or more of these pigments are used in combination with the light calcium carbonate described above.
[0018]
The adhesive used in the present invention is not particularly defined other than the latex described above, and is a styrene / butadiene copolymer, a styrene / butadiene / acrylic copolymer or a modified product thereof, which is generally used for papermaking. As the monomer of these polymers, styrene, butadiene, methyl methacrylate, other vinyl unsaturated carboxylic acid ester compounds, acrylonitrile and other vinyl compounds, and acrylic unsaturated acid, maleic acid and other vinyl unsaturated carboxylic acids Etc. In addition, a water-soluble natural polymer adhesive such as oxidized starch, phosphate esterified starch, etherified starch, enzyme-modified starch, cold water soluble starch, casein, carboxymethylcellulose, etc. may be used in combination. As for the usage-amount of an adhesive agent, 5-30 weight part is preferable with respect to 100 weight part of pigments.
[0019]
In the coating liquid, various auxiliary agents generally used for papermaking, such as a dispersant, a thickener, an antifoaming agent, a water-resistant agent, and a water retention agent, may be used. Among these, by adding carboxymethylcellulose having a carboxymethyl group substitution degree of 0.5 to 1.0 as a water retention agent, the dynamic water retention of the coating liquid is further improved, and the coated paper quality is improved. be able to. The addition amount is preferably 0.1 to 0.3 parts by weight with respect to 100 parts by weight of the pigment. The coating solution concentration is preferably 40 to 70%, and particularly in high concentration coating of 65% or more, the effect of improving high-speed fluidity appears more remarkably.
[0020]
The coating solution thus prepared is applied to the base paper, but the coating method is not particularly limited, and various blade coaters, roll coaters, air knife coaters, bar coaters, rod blade coaters, short dwell coaters, etc. Various coating apparatuses are applied on a single layer or multiple layers on a base paper by an on machine or an off machine. In the case of two-layer coating, both the topcoat coating solution and the undercoat coating solution, or either the topcoat coating solution or the undercoat coating solution satisfy the above-described coating solution composition. For example, the composition of the other coating liquid is not particularly defined. The coating amount is adjusted in the range of 5 to 50 g / m 2 on both sides, but when an undercoat coating layer is provided, the undercoat coating amount is preferably 5 to 20 g / m 2 on both sides.
[0021]
As the base paper used in the present invention, mechanical pulp, chemical pulp, waste paper recovered pulp and the like are mixed and used at an arbitrary ratio, and if necessary, normal paper filler, paper strength enhancer, yield improver and The papermaking raw material to which the sizing agent and the like are added is made by a normal paper machine having a single wire or a twin wire, and the basis weight is preferably 30 to 400 g / m 2 .
[0022]
In addition, the coated paper obtained by coating the coating composition of the present invention is obtained by using a surface finishing device such as a super calendar, gloss calendar, soft calendar, etc. It is possible to obtain a matte printing coated paper having a low gloss with or without treatment. Moreover, the printing coated paper of the present invention can be offset printed by either sheet feeding or winding.
[0023]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the scope. In addition, unless otherwise indicated, the part and% in an example show a weight part and weight%, respectively.
<Quality evaluation method>
(1) Average particle size of light calcium carbonate Measured with Shimadzu centrifugal sedimentation type particle size distribution analyzer SA-CP2 (manufactured by Shimadzu Corporation), and the 50% point of the cumulative weight distribution was defined as the average particle size.
(2) The major axis and minor axis average value of light calcium carbonate was measured with a scanning electron microscope (JEOL JSM-5300).
(3) A sample diluted to an average particle diameter of 0.05 to 0.2% of latex was prepared, and the absorbance at a wavelength of 525 nm was measured, and obtained with a calibration curve prepared in advance.
(4) Whiteness Measured according to JIS P-8123 using a digital hunter whiteness meter (manufactured by Toyo Seiki Seisakusho).
(5) Blank paper glossiness Measured at an angle of 75 degrees according to JIS P-8142.
(6) Opacity Measured according to JIS P-8138, method A using a digital hunter whiteness meter (manufactured by Toyo Seiki Seisakusho).
(7) Using a dry-strength RI-I type printer (manufactured by Meisei Seisakusho), using Toyo Ink TV-24, printing with a constant ink amount of 0.35 ml, and visually evaluating the degree of picking on the printed surface did.
◎ = Not generated at all, ○ = Not generated at all, Δ = Generated, X = Significantly generated (8) Staractite generation status The generation status of stratactite generated at the blade edge of the blade was visually evaluated.
◎ = Not generated at all, ○ = Not generated at all, Δ = Generated, × = Significantly generated [Example 1]
0.5 parts of a polyacrylic acid soda-based dispersant is added to 100 parts of an irrigated light calcium carbonate having an average particle diameter of 5.3 μm composed of primary particles having a minor axis of 0.29 μm and a major axis of 1.7 μm produced by a causticizing method Add a crude slurry of 70% concentration obtained by adding 20 kg of glass beads having a bead diameter of 1.5 to 2.0 mm (manufactured by Toshiba Barotini) and a sand mill having a vessel capacity of 8 gallon (manufactured by IMEX). And crushed. The average particle size after pulverization was 0.43 μm.
[0024]
To 80 parts of the light calcium carbonate after pulverization thus obtained, 10 parts of heavy calcium carbonate, 10 parts of kaolin, and styrene / butadiene copolymer latex having an average particle diameter of 60 nm as an adhesive with respect to all pigments. 12 parts of carboxymethyl cellulose having a carboxymethyl group substitution degree of 0.7 as a water retention agent was added in a solid content of 0.2 parts to the total pigment to prepare a coating solution having a solid content concentration of 68%. . The coating amount of the coating solution thus prepared is 12.0 g / m 2 per one surface of a high-quality base paper having a basis weight of 50 g / m 2 using a blade coater at a coating speed of 1200 m / min. So that both sides were coated. Further, using a two-stack soft calender, surface treatment was carried out under the conditions of nip number 2 times, processing speed 1000 m / min, processing temperature 150 ° C., processing linear pressure 200 kgf / cm to obtain a coated paper for printing.
[Example 2]
Example except that 80 parts of light calcium carbonate after pulverization, 10 parts of heavy calcium carbonate, and 10 parts of kaolin were mixed with 62 parts of light calcium carbonate after pulverization, 28 parts of heavy calcium carbonate and 10 parts of kaolin. A coated paper for printing was obtained in exactly the same manner as in Example 1.
[Example 3]
Except for blending 80 parts of light calcium carbonate after pulverization, 10 parts of heavy calcium carbonate and 10 parts of kaolin, 93 parts of light calcium carbonate after pulverization and 7 parts of kaolin were used in exactly the same manner as in Example 1. A coated paper for printing was obtained.
[Example 4]
A coated paper for printing was obtained in exactly the same manner as in Example 1, except that a styrene / butadiene copolymer latex having an average particle size of 78 nm was blended instead of the average particle size of 60 nm.
[Example 5]
A coated paper for printing was obtained in exactly the same manner as in Example 1, except that a styrene / butadiene copolymer latex having an average particle size of 52 nm was blended instead of the average particle size of 60 nm.
[Example 6]
A coated paper for printing was obtained in exactly the same manner as in Example 1 except that 2 parts of phosphate esterified starch was blended in place of carboxymethylcellulose having a carboxymethyl group substitution degree of 0.7.
[Example 7]
A short diameter of 0.28 μm manufactured by the causticizing method is used instead of the light-cored light calcium carbonate having an average particle diameter of 5.3 μm composed of primary particles having a short diameter of 0.29 μm and a long diameter of 1.7 μm manufactured by the causticizing method. A coated paper for printing was obtained in exactly the same manner as in Example 1, except that a light-spotted light calcium carbonate having an average particle size of 14.0 μm composed of primary particles having a major axis of 1.7 μm was used.
[Example 8]
Instead of the corrugated light calcium carbonate with a mean particle size of 5.3 μm consisting of primary particles with a minor axis of 0.29 μm and a major axis of 1.7 μm produced by the causticizing method, a minor axis of 0.45 μm produced by the causticizing method. A coated paper for printing was obtained in exactly the same manner as in Example 1, except that a light-spotted light calcium carbonate having an average particle size of 11.2 μm composed of primary particles having a major axis of 3.7 μm was used.
[Comparative Example 1]
Example except that 80 parts of light calcium carbonate after pulverization, 10 parts of heavy calcium carbonate, and 10 parts of kaolin were mixed with 50 parts of light calcium carbonate after pulverization, 40 parts of heavy calcium carbonate and 10 parts of kaolin. A coated paper for printing was obtained in exactly the same manner as in Example 1.
[Comparative Example 2]
Coating for printing in exactly the same manner as in Example 1 except that 80 parts of light calcium carbonate after grinding, 10 parts of heavy calcium carbonate and 10 parts of kaolin were blended in 100 parts of light calcium carbonate after grinding. I got paper.
[Comparative Example 3]
A coated paper for printing was obtained in exactly the same manner as in Example 1, except that a styrene / butadiene copolymer latex having an average particle size of 41 nm was blended instead of the average particle size of 60 nm.
[Comparative Example 4]
A coated paper for printing was obtained in exactly the same manner as in Example 1, except that a styrene / butadiene copolymer latex having an average particle size of 97 nm was blended instead of the average particle size of 60 nm.
[Comparative Example 5]
Coated paper for printing in exactly the same manner as in Example 1 except that needle-shaped light calcium carbonate having a short diameter of 0.25 μm and a long diameter of 2.8 μm was used in place of the pulverized light calcium carbonate that was not pulverized. Got.
[Comparative Example 6]
A coated paper for printing was obtained in exactly the same manner as in Example 1, except that the garlic light calcium carbonate was used unpulverized instead of the pulverized light calcium carbonate.
[0025]
The above evaluation results are shown in Table 1.
[0026]
[Table 1]
【The invention's effect】
According to the present invention, it is possible to obtain a coated paper for printing having high white paper glossiness, opacity and whiteness, and excellent print surface strength and high-speed operability.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000073367A JP4332979B2 (en) | 2000-03-16 | 2000-03-16 | Coated paper for printing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000073367A JP4332979B2 (en) | 2000-03-16 | 2000-03-16 | Coated paper for printing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001262492A JP2001262492A (en) | 2001-09-26 |
| JP4332979B2 true JP4332979B2 (en) | 2009-09-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000073367A Expired - Fee Related JP4332979B2 (en) | 2000-03-16 | 2000-03-16 | Coated paper for printing |
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| Country | Link |
|---|---|
| JP (1) | JP4332979B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5203776B2 (en) * | 2008-03-31 | 2013-06-05 | 日本製紙株式会社 | Method for producing light calcium carbonate slurry produced in causticizing process and paper coated with coating liquid containing said slurry |
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| Publication number | Publication date |
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| JP2001262492A (en) | 2001-09-26 |
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