JP2004339639A - Coated paper for printing use - Google Patents
Coated paper for printing use Download PDFInfo
- Publication number
- JP2004339639A JP2004339639A JP2003136991A JP2003136991A JP2004339639A JP 2004339639 A JP2004339639 A JP 2004339639A JP 2003136991 A JP2003136991 A JP 2003136991A JP 2003136991 A JP2003136991 A JP 2003136991A JP 2004339639 A JP2004339639 A JP 2004339639A
- Authority
- JP
- Japan
- Prior art keywords
- paper
- printing
- average particle
- parts
- manufactured
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Paper (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は印刷用塗被紙に関し、表面強度、塗工適性に優れ、特に優れた白色度、白紙光沢度、印刷光沢度、不透明度を備えた印刷用塗被紙に関する。
【０００２】
【従来の技術】
近年、印刷物に対し、写真や図案を多用し、更にカラー化するなどにより、視覚的に内容を強力に伝達しようとする（以下視覚化という）強い要望がある。一方、省資源、輸送コストなどの点から印刷物の軽量化に対しても強い要望がある。この二つの要望は相反するものであって、視覚化に適する高級グレードの印刷用塗被紙は原紙坪量、塗工量とも多く、高価であって、軽量、低価格の要望にそぐわない。そこで、いわゆる低級グレードの印刷用塗被紙で、より上のグレードの品質を実現する技術が求められている。
【０００３】
印刷用塗被紙の品質のうち、重要なものは、白色度、不透明度、白紙光沢度及び印刷光沢度である。そのうち白色度はコントラストに、不透明度は裏抜けに、光沢度は印刷物の高級感に関係し、これらが全て良いバランスで満足されることが重要である。
【０００４】
前述のごとく、軽量化は原紙を低坪量にするとともに低塗工量の塗被層とすることが必要である。しかし、紙料配合を変えないで、単に低坪量の紙とすれば、軽量化に比例して紙厚が薄くなり不透明度が不足する。低坪量原紙の上に厚い塗工層を設ければ、印刷適性は低坪量化前の水準を維持することができるが、不透明度はむしろ低下するので実用的でない。逆に高坪量原紙上に低塗工量の塗工層を設けると、不透明度は十分であるが、低坪量化には必要以上に塗工量を減らさざるをえなくなるため、印刷品質が不十分となり、やはり実用的でない。
【０００５】
従って、原紙の坪量と塗工量は一定のバランスが必要であり、低坪量原紙には低塗工量塗被層、高坪量原紙には高塗工量塗被層の印刷用塗被紙ということになり、一般的に低坪量品は高坪量品と比較して白色度、不透明度、白紙光沢度及び印刷光沢度は劣る。一般に不透明度は坪量が８０ｇ／ｍ２以下になると急激に低下する。
【０００６】
低坪量にも関わらず、特に優れた白紙外観と印刷適性を備えた塗工紙について、製紙用パルプとして機械パルプをある一定量以上使用し、填料として無定型シリカを含有した原紙上に塗工層を設けることが記載されている（特許文献１参照）。しかし、表面強度や白色度等、満足のいくものが得られていないのが現状である。
【０００７】
【特許文献１】
特開２００１−２１４３８５号公報
【０００８】
【発明が解決しようとする課題】
本発明は、グレードの壁を越えた品質の印刷用塗被紙の提供にあり、具体的には、原紙の坪量と塗被層の塗工量が同レベルの従来の印刷用塗被紙に比べ、白色度、不透明度、白紙光沢度、印刷光沢度が改善され、印刷作業性に適した表面強度を有する印刷用塗被紙を提供することにある。
【０００９】
【課題を解決するための手段】
本発明は、原紙の少なくとも片面に、顔料と接着剤を主成分とする塗被層を設けた印刷用塗被紙において、前記塗被層中の全顔料に対し、平均粒子径が０．３〜１．０μｍの有機顔料を５〜１５質量％及び平均粒子径が０．５μｍ以下の軽質炭酸カルシウムを２０〜４０質量％含有させ、白紙光沢度が７２％以上、白色度が８３％以上であることを特徴とする。
前記塗被層中にさらに前記塗被層中の全顔料に対し、平均粒子径が０．５μｍ以下の重質炭酸カルシウムを１０質量％以上含有させたものが好ましい。
前記原紙が化学パルプ１００％からなることが好ましい。
前記印刷用塗被紙の不透明度が８８％以上であることが好ましい。
【００１０】
【発明の実施の形態】
印刷用塗被紙の白紙光沢度が７２％以上、白色度が８３％以上を得るために、本発明においては、塗被層中の全顔料に対し、平均粒子径が０．３〜１．０μｍの有機顔料を５〜１５質量％及び平均粒子径が０．５μｍ以下の軽質炭酸カルシウムを２０〜４０質量％含有させることが重要である。
【００１１】
有機顔料のみの配合では光沢度の発現性は十分であるが、白色度、不透明度の発現性への寄与率が低く、軽質炭酸カルシウムのみの配合では、光沢度の発現性への寄与率が低い。また、有機顔料の含有量が５質量％未満では光沢度発現効果が低く、１５質量％を越えると光沢度発現効果は高いが、表面強度が低くなりオフセット印刷時にブランケットからインクが転写される際に塗被層の表面剥けトラブルが発生しやすい。有機顔料の平均粒子径が０．３μｍ未満では、白紙光沢度が出にくく、１．０μｍを超えると塗工液の流動性に劣り、塗工面の乱れを生じさせ白紙外観等に悪影響を及ぼす。また、軽質炭酸カルシウムの含有量が２０質量％未満では白色度、不透明度発現効果が低く、４０質量％を越えると塗被層を形成する塗工液の流動性が悪化し、ストリークなど操業上のトラブルが発生しやすく好ましくない。また、軽質炭酸カルシウムの平均粒子径が０．５μｍを超えると、白紙光沢度、不透明度が出にくくなる。
【００１２】
また、本発明においては、前記塗被層中にさらに前記塗被層中の全顔料に対し、平均粒子径が０．５μｍ以下の重質炭酸カルシウムを１０質量％以上含有させることが好ましい。より好ましくは１０〜３０質量％である。前記重質炭酸カルシウムを１０質量％以上含む塗被層を設けた場合、印刷用塗被紙の白色度、光沢度発現性を高位に維持することが可能であり、併せて塗被層を形成する塗工液の流動性をそこなわずに塗工しやすい。なお、３０質量％を超えると白紙光沢度、印刷光沢度または不透明度が出にくくなる傾向にある。前記重質炭酸カルシウムが１０質量％未満では、塗工液の流動性改善効果が低い傾向にある。また、重質炭酸カルシウムの平均粒子径が０．５μｍを超えると、白紙光沢度が出にくくなる。
【００１３】
前記塗被層に用いられる他の顔料としては、支障のない範囲でカオリン、クレー、デラミネーテッドクレー、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、コロイダルシリカ、サチンホワイトなどの無機顔料などが使用できるが、なかでも平均粒子径が０．３μｍ以下の微粒カオリンは、白紙光沢度や印刷光沢度の向上のため、好ましく用いられる。なお、前記微粒カオリンの使用量は、塗被層中の全顔料に対し３０〜６０質量％程度である。
【００１４】
前記塗被層に用いられる接着剤としては、印刷用塗被紙用塗被層に従来から用いられている、スチレン・ブタジエン系、スチレン・アクリル系、エチレン・酢酸ビニル系、ブタジエン・メチルメタクリレート系、酢酸ビニル・ブチルアクリレート系、等の各種共重合体ラテックス、ポリビニルアルコール、無水マレイン酸共重合体、アクリル酸・メチルメタクリレート系共重合体等の合成接着剤、カゼイン、大豆蛋白、合成蛋白などの蛋白質類、酸化澱粉、陽性澱粉、尿素燐酸エステル化澱粉、ヒドロキシエチルエーテル化澱粉などのエーテル化澱粉、デキストリンなどの澱粉類、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース等のセルロース誘導体などが挙げられる。これらの接着剤は顔料１００質量部あたり５〜２５質量部、より好ましくは６〜１５質量部程度の範囲で使用される。
【００１５】
また、必要に応じて配合する添加剤としては、分散剤、増粘剤、保水剤、消泡剤、耐水化剤、着色剤等、通常の塗被層用塗工液に配合される各種助剤が適宜使用される。
【００１６】
本発明に使用する原紙は、バージンケミカルパルプ１００質量％配合品が好ましく、針葉樹林系化学パルプ５０質量％以下と広葉樹林系化学パルプ５０質量％以上で構成されており、それらを叩解してパルプスラリーとし、これに軽質炭酸カルシウムを原紙重量当たり１０〜１３質量％となるよう添加して紙料とする。針葉樹林系化学パルプは主に紙力と関係し、広葉樹林系化学パルプは表面性に関係する。従って、広葉樹林系化学パルプが針葉樹林系化学パルプより高配合であることは、原紙表面性の低質による塗工ムラ、塗被紙表面性への悪化を防止する事が出来る為、好ましい配合である。また、填料は紙料スラリーの抄紙適性や強度特性を調節する目的で、軽質炭酸カルシュウム以外に少量のタルク、カオリン、クレー、重質炭酸カルシウム、酸化チタン、無定形シリケートを混合しても良い。
【００１７】
これらの紙料に必要に応じて通常抄紙工程で使用される薬品類、例えば紙力増強剤、サイズ剤、消泡剤、着色剤などを添加し、抄紙する。抄紙方法は特に限定されるものではなく、トップワイヤーなどを含む長網マシン、丸網マシン、この両者の併用マシン、ヤンキードライヤーマシンなどを用いて、酸性抄紙、中性抄紙、アルカリ性抄紙方式で抄紙する。また、サイズプレス、ゲートロールコーター、プレメタリングサイズプレスを使用して、澱粉、ポリビニルアルコールなどを予備塗工した原紙や、 顔料と接着剤を含む塗工液を一層以上予備塗工した原紙も使用することができる。塗工原紙としては、一般の塗工紙に用いられる坪量が４０〜６０ｇ／ｍ２程度の原紙を用いることができる。
【００１８】
調成された塗工液は、バーコーター、ロールコーター、エアナイフコーター、リバースロールコーター、カーテンコーター、サイズプレスコーター、ゲートロールコーター等を用いて、一層もしくは二層以上を原紙上に両面塗工する。塗工量は、所望の特性に応じて決定されるが、本発明の場合およそ原紙坪量が４３〜５７ｇ／ｍ２で、片面当たり９〜１２ｇ／ｍ２の塗工量で、十分な被覆性と印刷面光沢度を得ることができる。
【００１９】
湿潤塗工層を乾燥させる方法としては、例えば蒸気加熱シリンダ、加熱熱風エアドライヤ、ガスヒータードライヤ、電気ヒータードライヤ、赤外線ヒータードライヤ等の各種方式のドライヤを単独あるいは組み合わせて用いる。
【００２０】
本発明においては、上述した塗工原紙に塗工液を塗工、乾燥して得られた印刷用塗被紙は、弾性ロールと６０〜１００℃に加熱した剛性ロールからなる通常のスーパーカレンダーで表面仕上げを行う。一般に、剛性ロール温度が高いほど低いニップ圧あるいは短いニップ滞留時間で原紙あるいは塗工層を平滑化することができる。本発明において、スーパーカレンダー処理後に得られる印刷用塗被紙の密度は１．１５〜１．２２程度であり、１．１６〜１．２０がより好ましい。
【００２１】
【実施例】
以下に、実施例を挙げて本発明を具体的に説明するが、勿論、本発明はしれらに限定されるものではない。なお、特に断らない限り、例中の部および％はそれぞれ質量部および質量％を示す。
【００２２】
尚、実施例や比較例で使用した顔料の粒子径は以下の方法で測定した。
（顔料の平均粒子径）
ピロリン酸ソーダの０．１％液中に顔料を超音波で５分間分散処理し、セディグラフ（マイクロメリティクス社製）を用いて沈降法により測定した。平均粒子径は粗粒子分からの累積質量が５０％に相当する点での粒子径で示した。
【００２３】
（実施例１）
▲１▼ 原紙の製造
ＬＢＫＰ６０部（フリーネス４５０ｍｌ／ｃｓｆ）、ＮＢＫＰ４０部（フリーネス４５０ｍｌ／ｃｓｆ）からなるパルプスラリー中に、パルプ固形分に対して填料として軽質炭酸カルシウムを紙灰分で１０％となるように添加し、さらに内添サイズ剤としてＡＫＤサイズ剤（商品名：サイズパインＫ−９０２、荒川化学工業社製）０．０５％、硫酸アルミニウム０．５％、内添紙力剤（商品名：エースＫ、王子コーンスターチ社製）０．６％をそれぞれ添加して紙料を調成した。このように調成された紙料を用いて、ハイブリッドタイプのツインワイヤ抄紙機で抄紙、乾燥を行って成紙（基紙）を得た。次いで、このようにして得られた基紙の両面に２本ロールサイズプレス装置を介して、６％濃度の酸化澱粉糊液（商品名：エースＡ、王子コーンスターチ社製）を両面固形分換算で１．４ｇ／ｍ２となるように塗布、乾燥して米坪が４３ｇ／ｍ２の原紙を得た。
【００２４】
▲２▼ 塗被層用塗工液の調製
微粒カオリン（商品名：カオファイン、シール社製、平均粒子径０．２５μｍ）４０部、軽質炭酸カルシウム（商品名：コーラルブライトＦＤ、矢橋工業社製、平均粒子径０．５μｍ）３０部、重質炭酸カルシウム（商品名：セタカーブＨＧ、備北粉化社製、平均粒子径０．５μｍ）２０部、有機顔料（商品名：Ｖ−１００４、日本ゼオン社製、平均粒子径０．３μｍ）１０部からなる顔料１００部に、分散剤としてポリアクリル酸ソーダ（商品名：アロンＴ−４０、東亜合成社製）０．０５部を添加してミキサーで分散し、固形分濃度が６７％の顔料スラリーを調成した。このようにして得られた顔料スラリーに、非増粘型のスチレン・ブタジエン共重合体ラテックス（商品名：２５４０Ａ、ＪＳＲ社製）８．５部、および酸化澱粉（商品名：エースＡ、王子コーンスターチ社製）２部を加え、さらに水を加えて固形分濃度６１％の塗被層用塗工液を調製した。
【００２５】
▲３▼ 印刷用塗被紙の製造
上記の原紙に、前記塗被層用塗工液を乾燥後の塗工量が、片面で１０ｇ／ｍ２、両面で２０ｇ／ｍ２になるように、１０００ｍ／分の塗工速度のブレードコーターで両面塗工を行い、紙水分が６％になるようにシリンダードライヤーにて乾燥した。次いで、通紙速度６００ｍ／分、線圧２２．５ＭＰａ・ｃｍ、カレンダーニップ数１１ニップの条件でスーパーカレンダー処理を行い印刷用塗被紙を得た。
【００２６】
（実施例２）
微粒カオリン（商品名：カオファイン、シール社製、平均粒子径０．２５μｍ）４５部、軽質炭酸カルシウム（商品名：コーラルブライトＦＤ、矢橋工業社製、平均粒子径０．５μｍ）４０部、重質炭酸カルシウム（商品名：セタカーブＨＧ、備北粉化社製、平均粒子径０．５μｍ）１０部、有機顔料（商品名：Ｖ−１００４、日本ゼオン社製、平均粒子径０．３μｍ）５部とした以外は、実施例１と同様にして印刷用塗被紙を得た。
【００２７】
（実施例３）
微粒カオリン（商品名：カオファイン、シール社製、平均粒子径０．２５μｍ）４５部、軽質炭酸カルシウム（商品名：コーラルブライトＦＤ、矢橋工業社製、平均粒子径０．５μｍ）２０部、重質炭酸カルシウム（商品名：セタカーブＨＧ、備北粉化社製、平均粒子径０．５μｍ）２０部，有機顔料（商品名：Ｖ−１００４、日本ゼオン社製、平均粒子径０．３μｍ）１５部とした以外は、実施例１と同様にして印刷用塗被紙を得た。
【００２８】
（実施例４）
微粒カオリン（商品名：カオファイン、シール社製、平均粒子径０．２５μｍ）４４部、軽質炭酸カルシウム（商品名：コーラルブライトＦＤ、矢橋工業社製、平均粒子径０．５μｍ）３０部、重質炭酸カルシウム（商品名：セタカーブＨＧ、備北粉化社製、平均粒子径０．５μｍ）２０部，有機顔料（商品名：Ｖ−１００４、日本ゼオン社製、平均粒子径０．３μｍ）６部とした以外は、実施例１と同様にして印刷用塗被紙を得た。
【００２９】
（実施例５）
微粒カオリン（商品名：カオファイン、シール社製、平均粒子径０．２５μｍ）５５部、軽質炭酸カルシウム（商品名：コーラルブライトＦＤ、矢橋工業社製、平均粒子径０．５μｍ）３５部、重質炭酸カルシウム（商品名：セタカーブＨＧ、備北粉化社製、平均粒子径０．５μｍ）５部，有機顔料（商品名：Ｖ−１００４、日本ゼオン社製、平均粒子径０．３μｍ）５部とした以外は、実施例１と同様にして印刷用塗被紙を得た。
【００３０】
（実施例６）
▲４▼ 原紙の製造
実施例１において、ＬＢＫＰ４０部、ＮＢＫＰ３０部、機械パルプ３０部とした以外は、実施例１と同様にして米坪が４３ｇ／ｍ２の原紙を得た。
【００３１】
上記原紙を使用した以外は，実施例１と同様にして印刷用塗被紙を得た。
【００３２】
（比較例１）
微粒カオリン（商品名：カオファイン、シール社製、平均粒子径０．２５μｍ）４７部、軽質炭酸カルシウム（商品名：コーラルブライトＦＤ、矢橋工業社製、平均粒子径０．５μｍ）３０部、重質炭酸カルシウム（商品名：セタカーブＨＧ、備北粉化社製、平均粒子径０．５μｍ）２０部，有機顔料（商品名：Ｖ−１００４、日本ゼオン社製、平均粒子径０．３μｍ）３部とした以外は、実施例１と同様にして印刷用塗被紙を得た。
【００３３】
（比較例２）
微粒カオリン（商品名：カオファイン、シール社製、平均粒子径０．２５μｍ）３０部、軽質炭酸カルシウム（商品名：コーラルブライトＦＤ、矢橋工業社製、平均粒子径０．５μｍ）３０部、重質炭酸カルシウム（商品名：セタカーブＨＧ、備北粉化社製、平均粒子径０．５μｍ）２０部，有機顔料（商品名：Ｖ−１００４、日本ゼオン社製、平均粒子径０．３μｍ）２０部とした以外は、実施例１と同様にして印刷用塗被紙を得た。
【００３４】
（比較例３）
微粒カオリン（商品名：カオファイン、シール社製、平均粒子径０．２５μｍ）６０部、軽質炭酸カルシウム（商品名：コーラルブライトＦＤ、矢橋工業社製、平均粒子径０．５μｍ）１０部、重質炭酸カルシウム（商品名：セタカーブＨＧ、備北粉化社製、平均粒子径０．５μｍ）２０部，有機顔料（商品名：Ｖ−１００４、日本ゼオン社製、平均粒子径０．３μｍ）１０部とした以外は、実施例１と同様にして印刷用塗被紙を得た。
【００３５】
（比較例４）
微粒カオリン（商品名：カオファイン、シール社製、平均粒子径０．２５μｍ）３０部、軽質炭酸カルシウム（商品名：コーラルブライトＦＤ、矢橋工業社製、平均粒子径０．５μｍ）５０部、重質炭酸カルシウム（商品名：セタカーブＨＧ、備北粉化社製、平均粒子径０．５μｍ）１０部，有機顔料（商品名：Ｖ−１００４、日本ゼオン社製、平均粒子径０．３μｍ）１０部とした以外は、実施例１と同様にして印刷用塗被紙を得た。
【００３６】
（比較例５）
微粒カオリン（商品名：カオファイン、シール社製、平均粒子径０．２５μｍ）４０部、軽質炭酸カルシウム（商品名：ＴＰ−１２１−７Ｋ、奥多摩工業社、平均粒子径０．８μｍ）３０部、重質炭酸カルシウム（商品名：セタカーブＨＧ、備北粉化社製、平均粒子径０．５μｍ）２０部，有機顔料（商品名：Ｖ−１００４、日本ゼオン社製、平均粒子径０．３μｍ）１０部とした以外は、実施例１と同様にして印刷用塗被紙を得た。
【００３７】
かくして得られた１１種類の印刷用塗被紙について、下記の評価をおこない得られた結果を表１に示した。なお、本発明における印刷用塗被紙の測定および評価については、特に記載ない限り、２３℃、５０ＲＨ％の環境下でおこなった。
【００３８】
・白色度
ＪＩＳ Ｐ ８１４８−１９９３に準拠し、分光白色度測定計（スガ試験機社製）を用いて、Ｃ／２光源で測定した。
【００３９】
・白紙光沢度
光沢度計（商品名：ＧＭ−２６Ｄ、村上色彩技術研究所製）を用いて，７５°光沢度を測定した。
【００４０】
・不透明度
ＪＩＳ Ｐ ８１４９−２０００に準拠し、分光白色度測定計（スガ試験機社製）を用いて、Ｃ／２光源で測定した。
【００４１】
・印刷光沢度
小森リスロン４色印刷後、光沢度計（商品名：ＧＭ−２６Ｄ、村上色彩技術研究所製）を用いて，６０°光沢度を測定した。
【００４２】
・密度
ＪＩＳ Ｐ ８１１８に基づいて測定した。
【００４３】
・表面強度
ＲＩ−Ｉ型印刷試験器を用い、特殊インキ（商品名：ＰＲＩＮＴＩＮＧ ＩＮＫ、東洋インキ製造社製）を０．７０ｇ使用して印刷を行った後、裏取りを行い、剥け状態を以下の基準で目視評価した。
◎：極めて良好。
○：良好。
△：やや劣る。
×：劣る。
【００４４】
・塗工適性
塗工時の塗工面、ブレードの状態を目視で観察し判定した。
○：ストリーク、ブリーディングの発生が認められず高速での塗工が可能。
△：ストリーク、ブリーディングの発生がわずかに認められる。
×：ストリーク、ブリーディングの発生が認められ、高速での塗工が困難。
【００４５】
【表１】
【発明の効果】
表１より明らかなように、本発明に係る印刷用塗被紙は、白色度、白紙光沢度および不透明度が高い優れた白紙外観と、高い印刷光沢度を示した。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a coated paper for printing, and more particularly, to a coated paper having excellent whiteness, white paper gloss, print gloss, and opacity having excellent surface strength and coating suitability.
[0002]
[Prior art]
2. Description of the Related Art In recent years, there has been a strong demand for visual transmission of content (hereinafter referred to as visualization) by using a lot of photographs and designs on printed matter and further coloring the printed matter. On the other hand, there is a strong demand for reducing the weight of printed materials in terms of resource saving and transportation costs. These two demands are contradictory, and high-grade printing coated paper suitable for visualization has a large base paper basis weight and a large coating amount, and is expensive, and does not meet the demand for light weight and low cost. Therefore, there is a need for a technique for realizing higher quality grades of so-called low grade printing coated paper.
[0003]
Among the qualities of the printing coated paper, important ones are whiteness, opacity, blank gloss and printing gloss. Among them, the whiteness relates to the contrast, the opacity relates to the strikethrough, and the glossiness relates to the sense of quality of the printed matter, and it is important that all of them are satisfied in a good balance.
[0004]
As described above, to reduce the weight, it is necessary to make the base paper a low basis weight and a coating layer having a low coating amount. However, if the paper is simply made of a low basis weight without changing the composition of the stock, the paper thickness becomes thinner in proportion to the weight reduction and the opacity becomes insufficient. If a thick coating layer is provided on the low basis weight base paper, the printability can be maintained at the level before the reduction in the basis weight, but the opacity is rather lowered, so that it is not practical. Conversely, if a low coating weight coating layer is provided on a high basis weight base paper, the opacity will be sufficient, but the printing quality will be reduced because the coating weight must be reduced more than necessary to reduce the weight. Insufficient, again not practical.
[0005]
Therefore, the basis weight of the base paper and the coating amount need to be in a certain balance, and a low coating weight coating layer is applied to a low basis weight base paper and a high coating amount coating layer is applied to a high basis weight base paper. In other words, a low basis weight product is generally inferior in whiteness, opacity, white paper glossiness, and print glossiness to a high basis weight product. In general, the opacity sharply decreases when the basis weight is 80 g / m 2 or less.
[0006]
Regarding coated paper that has particularly excellent white paper appearance and printability in spite of its low basis weight, use mechanical pulp as a papermaking pulp in a certain amount or more and coat it on base paper containing amorphous silica as a filler. It is described that a working layer is provided (see Patent Document 1). However, at present, satisfactory products such as surface strength and whiteness have not been obtained.
[0007]
[Patent Document 1]
JP 2001-214385 A
[Problems to be solved by the invention]
The present invention is to provide a coated printing paper having a quality that exceeds the grade wall. Specifically, a conventional coated printing paper having the same level of the basis weight of the base paper and the coating amount of the coating layer is provided. An object of the present invention is to provide a coated paper for printing which has improved whiteness, opacity, glossiness of white paper and glossiness of printing as compared with the above, and has a surface strength suitable for printing workability.
[0009]
[Means for Solving the Problems]
The present invention relates to a printing coated paper in which a coating layer containing a pigment and an adhesive as main components is provided on at least one side of the base paper, wherein an average particle diameter of all pigments in the coating layer is 0.3. 5 to 15% by mass of an organic pigment having a particle size of 1.0 to 1.0 μm and 20 to 40% by mass of light calcium carbonate having an average particle size of 0.5 μm or less, a glossiness of white paper of 72% or more, and a whiteness of 83% or more. There is a feature.
Preferably, the coating layer further contains 10% by mass or more of heavy calcium carbonate having an average particle diameter of 0.5 μm or less with respect to all the pigments in the coating layer.
Preferably, the base paper is made of 100% chemical pulp.
It is preferable that the opacity of the printing coated paper is 88% or more.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
In order to obtain a white paper gloss of 72% or more and a whiteness of 83% or more of the coated paper for printing, in the present invention, the average particle diameter of all the pigments in the coated layer is 0.3 to 1. It is important to contain 5 to 15% by mass of an organic pigment of 0 μm and 20 to 40% by mass of light calcium carbonate having an average particle size of 0.5 μm or less.
[0011]
When only organic pigments are used, the expression of gloss is sufficient, but the contribution to whiteness and opacity is low.When only calcium carbonate is used, the contribution to expression of gloss is low. Low. When the content of the organic pigment is less than 5% by mass, the effect of developing glossiness is low, and when the content exceeds 15% by mass, the effect of expressing glossiness is high, but the surface strength is low and the ink is transferred from the blanket during offset printing. In addition, a trouble of peeling the surface of the coating layer easily occurs. If the average particle size of the organic pigment is less than 0.3 μm, the glossiness of white paper is difficult to be obtained, and if it exceeds 1.0 μm, the fluidity of the coating liquid is poor, and the coating surface is disturbed to adversely affect the appearance of the white paper. If the content of light calcium carbonate is less than 20% by mass, the effect of expressing whiteness and opacity is low, and if it exceeds 40% by mass, the fluidity of the coating solution forming the coating layer is deteriorated, and operation such as streak is deteriorated. This is not preferred because troubles tend to occur. On the other hand, when the average particle size of the light calcium carbonate exceeds 0.5 μm, it is difficult to obtain glossiness and opacity of white paper.
[0012]
In the present invention, it is preferable that the coating layer further contains 10% by mass or more of heavy calcium carbonate having an average particle diameter of 0.5 μm or less with respect to all the pigments in the coating layer. More preferably, it is 10 to 30% by mass. When a coating layer containing 10% by mass or more of the heavy calcium carbonate is provided, the whiteness and glossiness of the coated paper for printing can be maintained at a high level, and the coating layer is also formed. It is easy to apply without impairing the fluidity of the coating liquid. If the content exceeds 30% by mass, the glossiness of white paper, the glossiness of printing, or the opacity tends to be difficult to be obtained. If the amount of the heavy calcium carbonate is less than 10% by mass, the effect of improving the fluidity of the coating liquid tends to be low. On the other hand, if the average particle size of the heavy calcium carbonate exceeds 0.5 μm, the glossiness of white paper becomes difficult to appear.
[0013]
Other pigments used in the coating layer include inorganic pigments such as kaolin, clay, delaminated clay, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, colloidal silica, and satin white as long as they do not interfere. Among them, fine kaolin having an average particle diameter of 0.3 μm or less is preferably used for improving white paper glossiness and printing glossiness. The amount of the fine kaolin used is about 30 to 60% by mass based on all the pigments in the coating layer.
[0014]
As the adhesive used for the coating layer, styrene-butadiene-based, styrene-acrylic, ethylene-vinyl acetate-based, butadiene-methyl methacrylate-based, which is conventionally used for coating layers for printing coated paper. , Vinyl acetate / butyl acrylate copolymer latex, polyvinyl alcohol, maleic anhydride copolymer, acrylic acid / methyl methacrylate copolymer, etc., synthetic adhesives, casein, soy protein, synthetic protein, etc. Examples include proteins, oxidized starch, positive starch, etherified starch such as urea phosphate esterified starch and hydroxyethyl etherified starch, starches such as dextrin, and cellulose derivatives such as carboxymethyl cellulose, hydroxymethyl cellulose, and hydroxyethyl cellulose. These adhesives are used in an amount of 5 to 25 parts by mass, more preferably about 6 to 15 parts by mass, per 100 parts by mass of the pigment.
[0015]
Additives to be added as needed include various dispersants, thickeners, water-retaining agents, defoamers, water-proofing agents, coloring agents, etc., which are used in general coating liquids for coating layers. Agents are used as appropriate.
[0016]
The base paper used in the present invention is preferably 100% by mass of virgin chemical pulp, and is composed of 50% by mass or less of coniferous forest chemical pulp and 50% by mass or more of broadleaf forest chemical pulp. A slurry is prepared, and light calcium carbonate is added to the slurry in an amount of 10 to 13% by mass based on the weight of the base paper to obtain a stock. Coniferous chemical pulp is mainly related to paper strength, while broadleaf chemical pulp is related to surface properties. Therefore, it is preferable that the broad-leaved forest chemical pulp has a higher blending than the coniferous forest chemical pulp because it can prevent coating unevenness due to poor quality of the base paper surface and deterioration of the coated paper surface. is there. The filler may be mixed with a small amount of talc, kaolin, clay, heavy calcium carbonate, titanium oxide, or amorphous silicate besides light calcium carbonate for the purpose of adjusting the papermaking suitability and strength characteristics of the stock slurry.
[0017]
If necessary, chemicals usually used in the papermaking process, for example, a paper strength enhancer, a sizing agent, an antifoaming agent, a coloring agent, and the like are added to these stocks, and papermaking is performed. The papermaking method is not particularly limited, and the papermaking is performed by an acid papermaking, a neutral papermaking, or an alkaline papermaking method using a fourdrinier machine including a top wire, a round netting machine, a combination machine of both, a Yankee dryer machine, and the like. I do. Base paper pre-coated with starch, polyvinyl alcohol, etc. using a size press, gate roll coater, or pre-metalling size press, or base paper pre-coated with a coating liquid containing one or more pigments and adhesives Can be used. As the base paper for coating, base paper having a basis weight of about 40 to 60 g / m 2 used for general coated paper can be used.
[0018]
The prepared coating liquid is coated on one side or two or more layers on base paper using a bar coater, roll coater, air knife coater, reverse roll coater, curtain coater, size press coater, gate roll coater, or the like. . The amount of coating is determined according to the desired properties. In the case of the present invention, the basis weight of the base paper is approximately 43 to 57 g / m 2 , and the coating amount of 9 to 12 g / m 2 per side is sufficient. And printing surface glossiness.
[0019]
As a method of drying the wet coating layer, various types of dryers such as a steam heating cylinder, a heated hot air dryer, a gas heater dryer, an electric heater dryer, and an infrared heater dryer are used alone or in combination.
[0020]
In the present invention, a coating liquid for printing obtained by applying a coating liquid to the above-mentioned coating base paper and drying is obtained by a normal super calender comprising an elastic roll and a rigid roll heated to 60 to 100 ° C. Finish the surface. In general, the higher the rigid roll temperature, the lower the nip pressure or the shorter the nip residence time, the smoother the base paper or coating layer. In the present invention, the density of the coated printing paper obtained after the super calendering treatment is about 1.15 to 1.22, and more preferably 1.16 to 1.20.
[0021]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but it is a matter of course that the present invention is not limited thereto. Unless otherwise specified, parts and% in the examples indicate parts by mass and% by mass, respectively.
[0022]
The particle size of the pigment used in Examples and Comparative Examples was measured by the following method.
(Average particle diameter of pigment)
The pigment was dispersed in a 0.1% solution of sodium pyrophosphate by ultrasonic waves for 5 minutes, and measured by a sedimentation method using a Sedigraph (manufactured by Micromeritics). The average particle size was indicated by the particle size at the point where the cumulative mass from the coarse particles was equivalent to 50%.
[0023]
(Example 1)
{Circle around (1)} Production of base paper In a pulp slurry consisting of 60 parts of LBKP (450 ml / csf freeness) and 40 parts of NBKP (450 ml / csf free), light calcium carbonate is used as a filler at 10% of paper ash content based on pulp solid content. And AKD sizing agent (trade name: Size Pine K-902, manufactured by Arakawa Chemical Industry Co., Ltd.) 0.05%, aluminum sulfate 0.5%, internal paper strengthening agent (trade name: Ace K, manufactured by Oji Cornstarch Co., Ltd.) was added to prepare a stock. Using the thus prepared stock, papermaking and drying were performed with a hybrid type twin-wire paper machine to obtain a commercial paper (base paper). Then, a 6% -concentrated oxidized starch paste solution (trade name: Ace A, manufactured by Oji Cornstarch Co., Ltd.) was converted into a solid content on both sides of both sides of the base paper thus obtained through a two-roll size press. It was applied to 1.4 g / m 2 and dried to obtain a base paper having a rice area of 43 g / m 2 .
[0024]
{Circle around (2)} Preparation of Coating Liquid for Coating Layer 40 parts of fine kaolin (trade name: Kao Fine, manufactured by SEAL Co., average particle size 0.25 μm), light calcium carbonate (trade name: Coral Bright FD, manufactured by Yabashi Kogyo Co., Ltd.) , Average particle size 0.5 μm), 30 parts of heavy calcium carbonate (trade name: Setacarb HG, manufactured by Bihoku Powder Chemical Co., Ltd., average particle size 0.5 μm), 20 parts, organic pigment (trade name: V-1004, Zeon Corporation) 100 parts of a pigment consisting of 10 parts of an average particle diameter of 0.3 μm) and 0.05 part of sodium polyacrylate (trade name: ARON T-40, manufactured by Toagosei Co., Ltd.) as a dispersant, and adding the resulting mixture with a mixer. The dispersion was dispersed to prepare a pigment slurry having a solid content of 67%. 8.5 parts of a non-thickening styrene-butadiene copolymer latex (trade name: 2540A, manufactured by JSR) and 8.5 parts of oxidized starch (trade name: Ace A, Oji corn starch) are added to the pigment slurry thus obtained. Was added, and water was further added to prepare a coating liquid for a coating layer having a solid content concentration of 61%.
[0025]
{Circle around (3)} Production of coated paper for printing On the above-mentioned base paper, the coating amount after drying the coating liquid for coating layer is 10 g / m 2 on one side and 20 g / m 2 on both sides. Coating was performed on both sides with a blade coater at a coating speed of 1000 m / min, and dried with a cylinder dryer so that the paper moisture content was 6%. Next, a super calendering process was performed under the conditions of a paper passing speed of 600 m / min, a linear pressure of 22.5 MPa · cm, and a number of calendar nips of 11 to obtain coated paper for printing.
[0026]
(Example 2)
45 parts of fine kaolin (trade name: Kao Fine, manufactured by Seal Co., average particle diameter 0.25 μm), 40 parts of light calcium carbonate (trade name: Coral Bright FD, manufactured by Yabashi Kogyo Co., average particle diameter 0.5 μm), heavy 10 parts of high-quality calcium carbonate (trade name: Setacarb HG, manufactured by Bihoku Powder Chemical Co., Ltd., average particle diameter 0.5 μm), 5 parts of organic pigment (trade name: V-1004, manufactured by Zeon Corporation, average particle diameter 0.3 μm) A coated paper for printing was obtained in the same manner as in Example 1 except that the above conditions were satisfied.
[0027]
(Example 3)
45 parts of fine kaolin (trade name: Kao Fine, manufactured by Seal Co., average particle diameter 0.25 μm), 20 parts of light calcium carbonate (trade name: Coral Bright FD, manufactured by Yabashi Kogyo Co., average particle diameter 0.5 μm), heavy Quality calcium carbonate (trade name: Setacarb HG, manufactured by Bihoku Powder Chemical Co., Ltd., average particle size 0.5 μm), 20 parts, organic pigment (trade name: V-1004, manufactured by Nippon Zeon Co., average particle size 0.3 μm) 15 parts A coated paper for printing was obtained in the same manner as in Example 1 except that the above conditions were satisfied.
[0028]
(Example 4)
44 parts of fine kaolin (trade name: Kao Fine, manufactured by Seal Co., average particle diameter 0.25 μm), 30 parts of light calcium carbonate (trade name: Coral Bright FD, manufactured by Yabashi Kogyo Co., average particle diameter 0.5 μm), heavy 20 parts of high quality calcium carbonate (trade name: Setacarb HG, manufactured by Bihoku Powder Chemical Co., Ltd., average particle diameter 0.5 μm), 6 parts of organic pigments (trade name: V-1004, manufactured by Zeon Corporation, average particle diameter 0.3 μm) A coated paper for printing was obtained in the same manner as in Example 1 except that the above conditions were satisfied.
[0029]
(Example 5)
55 parts of fine kaolin (trade name: Kao Fine, manufactured by Seal Co., average particle diameter 0.25 μm), 35 parts of light calcium carbonate (trade name: Coral Bright FD, manufactured by Yabashi Kogyo Co., average particle diameter 0.5 μm), heavy 5 parts of porous calcium carbonate (trade name: Setacarb HG, manufactured by Bihoku Powder Chemical Co., Ltd., average particle diameter 0.5 μm), 5 parts of organic pigment (trade name: V-1004, manufactured by Zeon Corporation, average particle diameter 0.3 μm) A coated paper for printing was obtained in the same manner as in Example 1 except that the above conditions were satisfied.
[0030]
(Example 6)
{Circle around (4)} Base paper production A base paper having a rice tsubo of 43 g / m 2 was obtained in the same manner as in Example 1 except that LBKP was 40 parts, NBKP was 30 parts, and mechanical pulp was 30 parts.
[0031]
A coated paper for printing was obtained in the same manner as in Example 1 except that the above base paper was used.
[0032]
(Comparative Example 1)
47 parts of fine kaolin (trade name: Kao Fine, manufactured by Seal Co., average particle size 0.25 μm), 30 parts of light calcium carbonate (trade name: Coral Bright FD, manufactured by Yabashi Kogyo Co., average particle size 0.5 μm), heavy Quality calcium carbonate (trade name: Setacarb HG, manufactured by Bihoku Powder Chemical Co., Ltd., average particle diameter 0.5 μm), 20 parts, organic pigment (trade name: V-1004, manufactured by Zeon Corporation, average particle diameter 0.3 μm) 3 parts A coated paper for printing was obtained in the same manner as in Example 1 except that the above conditions were satisfied.
[0033]
(Comparative Example 2)
30 parts of fine kaolin (trade name: Kao Fine, manufactured by SEAL Co., average particle diameter 0.25 μm), 30 parts of light calcium carbonate (trade name: Coral Bright FD, manufactured by Yabashi Kogyo Co., average particle diameter 0.5 μm), heavy 20 parts of high-quality calcium carbonate (trade name: Setacarb HG, manufactured by Bihoku Powder Chemical Co., Ltd., average particle size: 0.5 μm), 20 parts of organic pigments (trade name: V-1004, manufactured by Zeon Corporation, average particle size: 0.3 μm) A coated paper for printing was obtained in the same manner as in Example 1 except that the above conditions were satisfied.
[0034]
(Comparative Example 3)
60 parts of fine kaolin (trade name: Kao Fine, manufactured by SEAL Co., average particle size 0.25 μm), 10 parts of light calcium carbonate (trade name: Coral Bright FD, manufactured by Yabashi Kogyo Co., average particle size 0.5 μm), heavy 20 parts of porous calcium carbonate (trade name: Setacarb HG, manufactured by Bihoku Powder Chemical Co., Ltd., average particle diameter 0.5 μm), 10 parts of organic pigments (trade name: V-1004, manufactured by Zeon Corporation, average particle diameter 0.3 μm) A coated paper for printing was obtained in the same manner as in Example 1 except that the above conditions were satisfied.
[0035]
(Comparative Example 4)
30 parts of fine kaolin (trade name: Kao Fine, manufactured by SEAL Co., average particle diameter 0.25 μm), 50 parts of light calcium carbonate (trade name: Coral Bright FD, manufactured by Yabashi Kogyo Co., average particle diameter 0.5 μm), heavy 10 parts of high quality calcium carbonate (trade name: Setacarb HG, manufactured by Bihoku Powder Chemical Co., Ltd., average particle diameter 0.5 μm), 10 parts of organic pigment (trade name: V-1004, manufactured by Zeon Corporation, average particle diameter 0.3 μm) A coated paper for printing was obtained in the same manner as in Example 1 except that the above conditions were satisfied.
[0036]
(Comparative Example 5)
40 parts of fine kaolin (trade name: Kao Fine, manufactured by SEAL Co., Ltd., average particle diameter 0.25 μm), 30 parts of light calcium carbonate (trade name: TP-121-7K, Okutama Industry Co., average particle diameter 0.8 μm), 20 parts of heavy calcium carbonate (trade name: Setacarb HG, manufactured by Bihoku Powder Chemical Co., Ltd., average particle size 0.5 μm), organic pigment (trade name: V-1004, manufactured by Zeon Corporation, average particle size 0.3 μm) 10 Coating paper for printing was obtained in the same manner as in Example 1 except that the above parts were used.
[0037]
The following evaluations were performed on the 11 coated printing papers thus obtained, and the results obtained are shown in Table 1. In addition, the measurement and evaluation of the coated paper for printing in the present invention were performed in an environment of 23 ° C. and 50 RH% unless otherwise specified.
[0038]
-Whiteness Measured with a C / 2 light source using a spectral whiteness meter (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS P 8148-1993.
[0039]
Gloss at 75 ° was measured using a blank gloss meter (trade name: GM-26D, manufactured by Murakami Color Research Laboratory).
[0040]
Opacity Measured with a C / 2 light source using a spectral whiteness meter (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS P 8149-2000.
[0041]
Print Gloss After printing four colors of Komori Lithrone, 60 ° gloss was measured using a gloss meter (trade name: GM-26D, manufactured by Murakami Color Research Laboratory).
[0042]
-Density: Measured based on JIS P 8118.
[0043]
・ Using a surface strength RI-I type printing tester, printing was performed using 0.70 g of special ink (product name: PRINTING INK, manufactured by Toyo Ink Mfg. Co., Ltd.), and then backing was performed. Was visually evaluated based on the following criteria.
：: extremely good.
：: good.
Δ: Slightly inferior.
×: Poor.
[0044]
Coating aptitude The coating surface and the state of the blade at the time of coating were visually observed and judged.
：: High-speed coating is possible without generation of streaks and bleeding.
Δ: Streak and bleeding are slightly observed.
X: Streaks and bleeding were observed, and high-speed coating was difficult.
[0045]
[Table 1]
【The invention's effect】
As is clear from Table 1, the coated paper for printing according to the present invention exhibited excellent white paper appearance having high whiteness, blank gloss and opacity, and high print gloss.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003136991A JP2004339639A (en) | 2003-05-15 | 2003-05-15 | Coated paper for printing use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003136991A JP2004339639A (en) | 2003-05-15 | 2003-05-15 | Coated paper for printing use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004339639A true JP2004339639A (en) | 2004-12-02 |
Family
ID=33526763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003136991A Pending JP2004339639A (en) | 2003-05-15 | 2003-05-15 | Coated paper for printing use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2004339639A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007270375A (en) * | 2006-03-31 | 2007-10-18 | Nippon Paper Industries Co Ltd | Coated paper for printing |
| JP2011026754A (en) * | 2009-06-26 | 2011-02-10 | Nippon Paper Industries Co Ltd | Printing paper |
| JP2013501157A (en) * | 2009-07-29 | 2013-01-10 | ビー・エイ・エス・エフ、コーポレーション | A new glossing system for paper and paperboard coatings |
| JP2018178314A (en) * | 2017-04-14 | 2018-11-15 | 大王製紙株式会社 | Printing paper and production method thereof |
-
2003
- 2003-05-15 JP JP2003136991A patent/JP2004339639A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007270375A (en) * | 2006-03-31 | 2007-10-18 | Nippon Paper Industries Co Ltd | Coated paper for printing |
| JP2011026754A (en) * | 2009-06-26 | 2011-02-10 | Nippon Paper Industries Co Ltd | Printing paper |
| JP2011196010A (en) * | 2009-06-26 | 2011-10-06 | Nippon Paper Industries Co Ltd | Printing paper |
| JP2013501157A (en) * | 2009-07-29 | 2013-01-10 | ビー・エイ・エス・エフ、コーポレーション | A new glossing system for paper and paperboard coatings |
| JP2018178314A (en) * | 2017-04-14 | 2018-11-15 | 大王製紙株式会社 | Printing paper and production method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2007270377A (en) | Lightweight coated paper for printing | |
| JP2000226791A (en) | Coated paper | |
| JP3371422B2 (en) | Matte coated paper | |
| JP4333026B2 (en) | Matte coated paper for offset printing | |
| JP4619328B2 (en) | Single glossy kraft paper and manufacturing method thereof | |
| JP2007262643A (en) | Coated paper | |
| JP2008274464A (en) | Coated paper for printing and method for producing the same | |
| JP5615578B2 (en) | Matte coated paper for printing and method for producing the same | |
| JP4333109B2 (en) | Fine coated paper | |
| JP2003213595A (en) | Matted coated paper | |
| JP4999253B2 (en) | Fine coated paper | |
| JP2002173892A (en) | Coated paper for gravure printing | |
| JP4918746B2 (en) | Manufacturing method of coated paper for offset printing and coated paper | |
| JP4380049B2 (en) | Matte coated paper for offset printing | |
| JP2004339639A (en) | Coated paper for printing use | |
| JP3458896B2 (en) | Coated paper for printing | |
| JP2000336593A (en) | Coated paper for printing | |
| JPH0593392A (en) | Mechanical paper for printing | |
| JP4385629B2 (en) | Coated paper for printing | |
| JP2001214395A (en) | Coated paper for printing | |
| JP2002088679A (en) | Coated paper for gravure printing | |
| JP6633251B2 (en) | Coated paper for printing | |
| JP5841552B2 (en) | Coated paper for printing | |
| JP4919574B2 (en) | Manufacturing method of coated paper for printing and coated paper. | |
| JP4288293B2 (en) | Manufacturing method of coated paper |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Effective date: 20050801 Free format text: JAPANESE INTERMEDIATE CODE: A621 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20071115 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20071127 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080124 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080708 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20090310 |