JP5577878B2 - Pigment-coated paper for printing and method for producing pigment-coated paper for printing - Google Patents
Pigment-coated paper for printing and method for producing pigment-coated paper for printing Download PDFInfo
- Publication number
- JP5577878B2 JP5577878B2 JP2010137731A JP2010137731A JP5577878B2 JP 5577878 B2 JP5577878 B2 JP 5577878B2 JP 2010137731 A JP2010137731 A JP 2010137731A JP 2010137731 A JP2010137731 A JP 2010137731A JP 5577878 B2 JP5577878 B2 JP 5577878B2
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- pigment
- parts
- mass
- printing
- coating layer
- Prior art date
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- 238000007639 printing Methods 0.000 title claims description 80
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Landscapes
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Paper (AREA)
Description
本発明は、印刷用顔料塗被紙に関するものである。詳しくは、オフセット印刷適性に優れ、且つ水性顔料インクを用いた高速インクジェットプリンターによる印刷適性も備えたハイブリッド印刷に適したグロス系印刷用顔料塗被紙に関するものである。 The present invention relates to a pigment-coated paper for printing. More specifically, the present invention relates to a pigment-coated paper for gloss printing suitable for hybrid printing, which is excellent in offset printing suitability and has print suitability by a high-speed ink jet printer using aqueous pigment ink.
オフセット印刷は、高速かつ大量印刷が可能であることから、印刷物製造方法の主流となっている。一方、近年インクジェット記録技術の発展に伴い、固定データをフルカラーオフセット印刷方式でプレプリントした印刷物に、クーポン券、ラッキーナンバー、バーコード、ＱＲコードなどの可変データをモノクロインクジェットプリンターで追い刷りする、いわゆるハイブリッド印刷が行われる場合も増えている。
その一例として、パッケージ分野においても、たとえば食品用箱などで、キャンペーン期間中に塗工板紙（所謂コートボール）に固定データをオフセット印刷したのちにシリアルナンバーやＱＲコードを追い刷り、製函を行う場合もある。
Offset printing has become the mainstream of printed matter manufacturing methods because high-speed and large-volume printing is possible. On the other hand, with the development of inkjet recording technology in recent years, variable data such as coupons, lucky numbers, barcodes, QR codes, etc. are additionally printed on a printed matter obtained by pre-printing fixed data by a full-color offset printing method with a monochrome inkjet printer. The number of cases where hybrid printing is performed is increasing.
As an example, in the packaging field, for example, in a food box, after fixed data is offset printed on a coated paperboard (so-called coated ball) during the campaign period, the serial number and QR code are additionally printed, and box making is performed. In some cases.
また、物流分野においては、メール便が安価な配送料金を背景に大きく成長している。通常メール便は、封筒表面に宛名やバーコードを印字し、出荷、荷受確認は、バーコード読み取りにより行っている。非塗工紙を用いた封筒では、インクジェットでダイレクト記録できるが、より高品位なオフセット印刷画像を得るためには、顔料塗被紙を用いた封筒を使用することになる。この場合は、オフセット印刷画像を印刷した封筒に、宛名やバーコード等の必要データを印刷したラベルを封筒表面に貼付する方法が採用されている。このことは、ラベル自身はもとより、粘着剤面を保護する剥離紙が必要であり、貼付作業も発生する。顔料塗被紙をベースとする封筒上に直接インクジェット記録ができれば、コスト面、省資源、省エネルギーの観点、作業時間面からも有利となる。 In the physical distribution field, mail services are growing greatly on the back of inexpensive delivery charges. Usually, mail is printed with an address and barcode on the envelope surface, and shipment and receipt confirmation are performed by reading the barcode. An envelope using non-coated paper can be directly recorded by inkjet, but an envelope using pigment-coated paper is used to obtain a higher-quality offset print image. In this case, a method is adopted in which a label on which necessary data such as an address and a barcode is printed is attached to the envelope surface on which the offset print image is printed. This requires not only the label itself, but also a release paper that protects the pressure-sensitive adhesive surface, and a sticking operation also occurs. If ink jet recording can be performed directly on an envelope based on pigment coated paper, it is advantageous from the viewpoint of cost, resource saving, energy saving, and working time.
これらの用途では、天候により高温高湿環境に曝されたり、降雨等水分と接触する場合が考えられるため、水性染料インクによる記録では信頼性に欠ける場合が考えられるため、顔料インクの使用が望まれている。
また、これらの用途では製函工程や郵便局等の自動仕分け装置を通過する場合に、部材と接触し、インクジェット印字部分が擦られるため、耐擦過性の改善が望まれている。
In these applications, it may be exposed to high-temperature and high-humidity environments depending on the weather, or it may come into contact with moisture such as rain, so it may be unreliable in recording with water-based dye ink. It is rare.
Further, in these applications, when passing through an automatic sorting apparatus such as a box making process or a post office, contact with a member and an ink jet printing portion are rubbed, and therefore, improvement in scratch resistance is desired.
オフセット印刷で使用されている印刷用顔料塗被紙としては、通常、特開平７−１８９１７９号公報（特許文献１）記載のようなものが挙げられる。前記塗工紙は、通常各種コーターを用いて、顔料、バインダー等を含む塗被層用塗被液を基紙の片面あたり１０ｇ／ｍ２以上塗布し、その後、カレンダ処理して表面を平滑化して製造されている。これら一般的な塗工紙は印刷加工適性を主眼においているため、オフセット印刷におけるピッキングやブリスターなどが発生しない顔料塗被層強度は有しているが、インクジェットインク吸収性は乏しいものであった。 As the pigment-coated paper for printing used in offset printing, there are usually those described in JP-A-7-189179 (Patent Document 1). The coated paper is usually coated with a coating layer coating solution containing pigments, binders, etc. at least 10 g / m 2 per side of the base paper using various coaters, and then calendered to smooth the surface. Manufactured. Since these general coated papers mainly focus on printing process suitability, they have a pigment coating layer strength that does not generate picking or blistering in offset printing, but have poor ink-jet ink absorbability.
オフセット印刷、インクジェット印刷の両方式に適する印刷用紙としては、基紙上にシリカを主体とした顔料を含む層を設ける方法（特開２００２−１２７５８７号公報、特許文献２）が提案されている。顔料塗被層にシリカを用いることによって、インクジェットインクの吸収性は向上するものの、オフセット印刷時にピッキングを起こさないために、バインダー成分を多用する必要があるため、顔料塗被紙表面の光沢は低下して、グロス系印刷用紙の質感は得られず、また、シリカを用いることにより、製造コストも上昇し、一般のグロス系印刷用紙のコストを大きく上回ってしまうため、市場には受け入れられていない。 As a printing paper suitable for both offset printing and inkjet printing, a method of providing a layer containing a pigment mainly composed of silica on a base paper (Japanese Patent Laid-Open No. 2002-127487, Patent Document 2) has been proposed. By using silica in the pigment coating layer, the ink-jet ink absorbability is improved, but since it does not cause picking during offset printing, it is necessary to use a large amount of binder components, so the gloss of the pigment coated paper surface is reduced. In addition, the texture of gloss printing paper cannot be obtained, and the use of silica increases the manufacturing cost and greatly exceeds the cost of general gloss printing paper, so it is not accepted by the market. .
また、基紙に予め特定の構造のカチオン樹脂を塗被し、さらに軽質炭酸カルシウムを主体とする顔料塗被層を設け、その表面のブリストー法（Ｊ．ＴＡＰＰＩ Ｎｏ．５１−８７）による特定の吸収時間でのインク転移量を規定した印刷用塗工紙（特開２００４−８４１４１号公報、特許文献３）が提案されている。しかしながらこの方法でも顔料塗被紙表面は高光沢度が得られず、グロス系印刷用紙の質感は得られない。 In addition, a cationic resin having a specific structure is coated on the base paper in advance, and a pigment coating layer mainly composed of light calcium carbonate is provided, and a specific surface by the Bristow method (J. TAPPI No. 51-87) on the surface is provided. There has been proposed a coated paper for printing (Japanese Patent Application Laid-Open No. 2004-84141, Patent Document 3) in which the amount of ink transfer in the absorption time is defined. However, even with this method, the surface of the pigment-coated paper cannot obtain a high glossiness, and the texture of the gloss printing paper cannot be obtained.
また、基紙上に、少なくとも２層の塗被層を設け、基紙隣接層には特定の形状の顔料を含有させ、表面層には特定のガラス転移温度を有する熱可塑性有機微粒子を含有させることにより、表面にクラックを発生させて塗被層の透気性を高めることにより、オフセット印刷、電子写真記録時のブリスターを防止し、またインクジェット用紙としての使用（特開２００５−３６３７９号公報、特許文献４）も提案されている。しかしながら、オフセット印刷用インキの粘度や電子写真用トナーの熱溶融粘度に比べて、インクジェットインクの粘度ははるかに低いため、用紙表面にクラックが多数存在すると、そのクラックに沿ってインクがにじむ、所謂フェザリング現象が発生し、満足な印刷画質が得られない。
さらに、顔料塗被層表面の王研式平滑度、基紙のステキヒトサイズ度、顔料塗被紙の密度等を特定の範囲に規定した感圧接着シート用塗工紙（特開２００９−２２８１７１号公報、特許文献５）が提案されている。しかしながら、この場合も水性染料インクでは満足なモノクロインクジェットによる印刷適性が得られるものの、水性顔料インクの定着性（耐擦過性）には乏しい。従って、オフセット印刷可能な表面強度と水性顔料インクジェットによる印刷適性を備え、かつ表面光沢度が高い印刷用顔料塗被紙は得られていないのが現状である。
Further, at least two coating layers are provided on the base paper, the base paper adjacent layer contains a pigment having a specific shape, and the surface layer contains thermoplastic organic fine particles having a specific glass transition temperature. Prevents cracks during offset printing and electrophotographic recording by generating cracks on the surface and improving the air permeability of the coating layer, and is also used as inkjet paper (Japanese Patent Laid-Open No. 2005-36379, Patent Documents) 4) has also been proposed. However, since the viscosity of inkjet ink is much lower than the viscosity of offset printing ink and the heat melting viscosity of electrophotographic toner, if there are many cracks on the paper surface, the ink bleeds along the cracks. A feathering phenomenon occurs and satisfactory print image quality cannot be obtained.
Furthermore, the coated paper for pressure-sensitive adhesive sheets in which the Oken-type smoothness on the surface of the pigment coating layer, the steecht sizing degree of the base paper, the density of the pigment coated paper, etc. are specified in a specific range (Japanese Patent Application Laid-Open No. 2009-228171). No. 5, Patent Document 5) has been proposed. However, in this case as well, although satisfactory printability by monochrome ink jet can be obtained with the aqueous dye ink, the fixability (abrasion resistance) of the aqueous pigment ink is poor. Accordingly, the present situation is that a pigment-coated paper for printing having surface strength capable of offset printing, printability by aqueous pigment inkjet, and high surface gloss has not been obtained.
本発明の目的は、オフセット印刷適性に優れ、且つ水性顔料インクを用いた高速インクジェットプリンターによる印刷適性も備えたハイブリッド印刷に適したグロス系印刷用顔料塗被紙を提供するものである。 An object of the present invention is to provide a gloss-coated pigment-coated paper suitable for hybrid printing, which is excellent in offset printability and also has printability by a high-speed ink jet printer using an aqueous pigment ink.
本発明者は、上記課題を解決すべく鋭意研究を行なった結果、顔料塗被層を内側顔料塗被層と最表顔料塗被層の少なくとも二層構成を採用し、各層にそれぞれの機能を分担させることにより解決できることを見出したのである。本発明は、以下のとおりである。 As a result of earnest research to solve the above problems, the present inventor adopted at least a two-layer configuration of the pigment coating layer of the inner pigment coating layer and the outermost pigment coating layer, and each layer has a function. It was found that it can be solved by sharing. The present invention is as follows.
（１）基紙の片面に、少なくとも内側顔料塗被層と、最表顔料塗被層を有する印刷用顔料塗被紙において、内側顔料塗被層は、顔料１００質量部中、軽質炭酸カルシウムを５０質量部以上含有し、バインダーとしてスチレン・ブタジエン共重合体ラテックスを顔料１００質量部に対して８〜１５質量部含有し、最表顔料塗被層は、顔料１００質量部中、平均粒子径（短径）が０．８μｍ以下の軽質炭酸カルシウムを５０質量部以上含有し、バインダーとしてスチレン・ブタジエン共重合体ラテックスを顔料１００質量部に対して４〜３０質量部含有する乾燥された塗被層に、水溶性多価金属塩の水溶液を塗布し、乾燥された層であることを特徴とする印刷用顔料塗被紙である。
（２）水溶性多価金属塩がギ酸カルシウムであるである（１）に記載の印刷用顔料塗被紙である。
（３）前記最表顔料塗被層に用いられる軽質炭酸カルシウムが柱状または紡錘状の軽質炭酸カルシウムである（１）又は（２）記載の印刷用顔料塗被紙である。
（４）前記最表顔料塗被層にカゼインを顔料１００質量部に対して１〜１０質量部含有する（１）〜（３）のいずれか一に記載の印刷用顔料塗被紙である。
（５）前記最表顔料塗被層中に、スチレンアクリル共重合体ラテックスを顔料１００質量部に対して１〜３０質量部含有する（１）〜（４）のいずれか一に記載の印刷用顔料塗被紙である。
（６）前記最表顔料塗被層中に、中空プラスチックピグメントを顔料１００質量部に対して３〜１５質量部含有する（１）〜（５）のいずれか一に記載の印刷用顔料塗被紙である。
（７）基紙の片面に、少なくとも２層の顔料塗被層を形成する印刷用顔料塗被紙の製造方法において、基紙に、顔料１００質量部中、軽質炭酸カルシウムを５０質量部以上含有し、バインダーとしてスチレン・ブタジエン共重合体ラテックスを顔料１００質量部に対して８〜１５質量部含有する内側顔料塗被層用塗液を塗布し、次いで、顔料１００質量部中、平均粒子径（短径）が０．８μｍ以下の軽質炭酸カルシウムを５０質量部以上含有し、バインダーとしてスチレン・ブタジエン共重合体ラテックスを顔料１００質量部に対して４〜３０質量部含有する最表顔料塗被層用塗液を塗布し、乾燥後、水溶性多価金属塩の水溶液を塗布し、乾燥することを特徴とする印刷用顔料塗被紙の製造方法である。
(1) In a printing pigment coated paper having at least an inner pigment coating layer and an outermost pigment coating layer on one side of the base paper, the inner pigment coating layer contains light calcium carbonate in 100 parts by mass of pigment. 50 parts by mass or more, 8-15 parts by mass of styrene / butadiene copolymer latex as a binder with respect to 100 parts by mass of the pigment, and the outermost pigment coating layer has an average particle diameter ( A dried coating layer containing 50 parts by mass or more of light calcium carbonate having a minor axis of 0.8 μm or less and 4 to 30 parts by mass of styrene / butadiene copolymer latex as a binder with respect to 100 parts by mass of pigment. A pigment-coated paper for printing, which is a layer coated with an aqueous solution of a water-soluble polyvalent metal salt and dried.
(2) The printing pigment-coated paper according to (1), wherein the water-soluble polyvalent metal salt is calcium formate.
(3) The printing pigment-coated paper according to (1) or (2), wherein the light calcium carbonate used in the outermost pigment-coated layer is a columnar or spindle-shaped light calcium carbonate.
(4) The pigment coated paper for printing according to any one of (1) to (3), wherein the outermost pigment coated layer contains 1 to 10 parts by mass of casein with respect to 100 parts by mass of the pigment.
(5) The outermost pigment coating layer contains 1 to 30 parts by mass of a styrene acrylic copolymer latex with respect to 100 parts by mass of the pigment, for printing according to any one of (1) to (4). It is pigment coated paper.
(6) The pigment coating for printing according to any one of (1) to (5), wherein the outermost pigment coating layer contains 3 to 15 parts by mass of a hollow plastic pigment with respect to 100 parts by mass of the pigment. Paper.
(7) In a method for producing a pigment coated paper for printing, in which at least two pigment coated layers are formed on one side of a base paper, the base paper contains 50 parts by mass or more of light calcium carbonate in 100 parts by mass of pigment. Then, an inner pigment coating layer coating solution containing 8 to 15 parts by mass of styrene / butadiene copolymer latex as a binder with respect to 100 parts by mass of the pigment is applied, and then the average particle diameter ( The outermost pigment coating layer containing 50 parts by mass or more of light calcium carbonate having a minor axis of 0.8 μm or less and 4 to 30 parts by mass of styrene / butadiene copolymer latex as a binder with respect to 100 parts by mass of pigment. A method for producing a pigment-coated paper for printing, which comprises applying a coating liquid for coating, drying, coating an aqueous solution of a water-soluble polyvalent metal salt, and drying.
本発明により、オフセット印刷適性に優れ、且つ水性顔料インクを用いた高速インクジェットプリンターによる印刷適性も備えたハイブリッド印刷に適したグロス系印刷用顔料塗被紙が得られる。 According to the present invention, it is possible to obtain a gloss-based pigment-coated paper suitable for hybrid printing, which is excellent in offset printability and also has printability by a high-speed ink jet printer using an aqueous pigment ink.
以下、本発明について詳しく説明する。本発明の印刷用顔料塗被紙は、基紙の片面に、少なくとも内側顔料塗被層と、最表顔料塗被層を有する印刷用顔料塗被紙であって、内側顔料塗被層は、顔料１００質量部中、軽質炭酸カルシウムを５０質量部以上含有し、バインダーとしてスチレン・ブタジエン共重合体ラテックスを顔料１００質量部に対して８〜１５質量部含有し、最表顔料塗被層は、顔料１００質量部中、平均粒子径（短径）が０．８μｍ以下の軽質炭酸カルシウムを５０質量部以上含有し、バインダーとしてスチレン・ブタジエン共重合体ラテックスを顔料１００質量部に対して４〜３０質量部含有する乾燥された塗被層に、水溶性多価金属塩の水溶液を塗布し、乾燥された層であることを特徴とする。 The present invention will be described in detail below. The printing pigment coated paper of the present invention is a printing pigment coated paper having at least an inner pigment coating layer and an outermost pigment coating layer on one side of a base paper, and the inner pigment coating layer is: In 100 parts by mass of pigment, 50 parts by mass or more of light calcium carbonate, 8-15 parts by mass of styrene / butadiene copolymer latex as a binder with respect to 100 parts by mass of pigment, and the outermost pigment coating layer, In 100 parts by mass of the pigment, 50 parts by mass or more of light calcium carbonate having an average particle size (minor axis) of 0.8 μm or less is contained, and 4 to 30 styrene / butadiene copolymer latex is used as a binder with respect to 100 parts by mass of the pigment. An aqueous layer of a water-soluble polyvalent metal salt is applied to a dried coating layer containing parts by mass, and the layer is a dried layer.
内側顔料塗被層は、顔料１００質量部中、軽質炭酸カルシウムを５０質量部以上含有し、バインダーとしてスチレン・ブタジエン共重合体ラテックスを顔料１００質量部に対して、８〜１５質量部含有させることにより、顔料粒子間空隙が増大し、高いインクジェットインクの溶媒吸収速度とオフセット印刷に必要な表面強度を両立させることができる。 The inner pigment coating layer contains 50 parts by mass or more of light calcium carbonate in 100 parts by mass of the pigment, and 8 to 15 parts by mass of styrene / butadiene copolymer latex as a binder with respect to 100 parts by mass of the pigment. As a result, the space between the pigment particles is increased, and both the high solvent absorption speed of the inkjet ink and the surface strength necessary for offset printing can be achieved.
軽質炭酸カルシウムの使用量は、顔料１００質量部中の軽質炭酸カルシウムを５０質量部以上含有する必要があるが、７０質量部以上含有することが好ましく、８０質量部以上含有することがより好ましい。なお、５０質量部未満の場合、十分なインクジェットインクの溶媒吸収性が得られない。 The light calcium carbonate is used in an amount of 50 parts by mass or more of light calcium carbonate in 100 parts by mass of the pigment, preferably 70 parts by mass or more, and more preferably 80 parts by mass or more. In addition, when it is less than 50 parts by mass, sufficient solvent absorbability of the inkjet ink cannot be obtained.
内側顔料塗被層は、軽質炭酸カルシウム以外の顔料を併用することも可能である。その具体例としては、例えば、カオリン、重質炭酸カルシウム、凝集炭酸カルシウム、平均粒子径（短径）が０．８μｍを超える軽質炭酸カルシウム、タルク、硫酸カルシウム、硫酸バリウム、二酸化チタン、酸化亜鉛、アルミナ、炭酸マグネシウム、酸化マグネシウム、シリカ、微粒子シリカ、コロイダルシリカ、アルミノ珪酸マグネシウム、微粒子状珪酸カルシウム、微粒子状炭酸マグネシウム、ホワイトカーボン、サチンホワイト、ベントナイト、ゼオライト、セリサイト、スメクタイト等の鉱物材料からなる顔料や、ポリスチレン樹脂、スチレン・アクリル共重合樹脂、尿素樹脂、メラミン樹脂、アクリル樹脂、塩化ビニリデン樹脂、ベンゾグアナミン樹脂、並びにこれらの微小中空粒子や貫通孔型の有機材料からなる有機顔料等が挙げられる。 The inner pigment coating layer may be used in combination with a pigment other than light calcium carbonate. Specific examples thereof include, for example, kaolin, heavy calcium carbonate, agglomerated calcium carbonate, light calcium carbonate having an average particle diameter (short axis) exceeding 0.8 μm, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, Made of mineral materials such as alumina, magnesium carbonate, magnesium oxide, silica, particulate silica, colloidal silica, magnesium aluminosilicate, particulate calcium silicate, particulate magnesium carbonate, white carbon, satin white, bentonite, zeolite, sericite, smectite Pigments, polystyrene resins, styrene / acrylic copolymer resins, urea resins, melamine resins, acrylic resins, vinylidene chloride resins, benzoguanamine resins, and organic pigments made of these micro hollow particles or through-hole organic materials It is below.
内側顔料塗被層は、バインダーとしてスチレン・ブタジエン共重合体ラテックスを顔料１００質量部に対して、８〜１５質量部含有させるものである。スチレン・ブタジエン共重合体ラテックスの含有量が８質量部未満の場合は、十分な表面強度が得られず、オフセット印刷適性に支障を来たすことがある。また１５質量部を超える場合は、インクジェットインクの溶媒吸収性が低下することがある。 The inner pigment coating layer contains 8 to 15 parts by mass of styrene / butadiene copolymer latex as a binder with respect to 100 parts by mass of the pigment. When the content of the styrene / butadiene copolymer latex is less than 8 parts by mass, sufficient surface strength cannot be obtained, and the offset printability may be hindered. Moreover, when it exceeds 15 mass parts, the solvent absorptivity of an inkjet ink may fall.
またスチレン・ブタジエン共重合体以外のバインダーも併用することができ、具体例としては、デンプン類、ヒドロキシエチルセルロース、メチルセルロース、カルボキシメチルセルロース、ゼラチン、カゼイン、アラビアガム、ジイソブチレン・無水マレイン酸共重合体塩、スチレン・無水マレイン酸共重合体塩、エチレン・アクリル酸共重合体塩、スチレン・アクリル酸共重合体塩、尿素樹脂、メラミン樹脂、アミド樹脂、スチレンアクリル共重合体ラテックス、ポリウレタン系ラテックス、スチレン、アクリル酸、メタクリル酸、アクリル酸エステル、メタクリル酸エステル、アクリルアミド、メタクリルアミド、メチルビニルエーテル等のビニル系重合体や共重合体類、メチルメタクリレート・ブタジエン樹脂系等の合成ゴムラテックス、ポリウレタン樹脂、ポリエステル樹脂、ポリアミド樹脂、オレフィン・無水マレイン酸樹脂、メラミン樹脂等が挙げられる。 Binders other than styrene / butadiene copolymers can also be used in combination. Specific examples include starches, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, gum arabic, diisobutylene / maleic anhydride copolymer salts. , Styrene / maleic anhydride copolymer salt, ethylene / acrylic acid copolymer salt, styrene / acrylic acid copolymer salt, urea resin, melamine resin, amide resin, styrene acrylic copolymer latex, polyurethane latex, styrene Synthetic rubber latex such as acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, methyl vinyl ether and other vinyl polymers and copolymers, methyl methacrylate and butadiene resin Scan, polyurethane resins, polyester resins, polyamide resins, olefin-maleic anhydride resins, melamine resins, and the like.
内側顔料塗被層中には、各種助剤、例えば界面活性剤、ｐＨ調節剤、粘度調節剤、柔軟剤、光沢付与剤、ワックス類、分散剤、流動変性剤、安定化剤、帯電防止剤、架橋剤、サイズ剤、蛍光増白剤、着色剤、紫外線吸収剤、消泡剤、耐水化剤、可塑剤、滑剤、防腐剤及び香料等の少なくとも１種が必要に応じて適宜含まれていてもよい。 In the inner pigment coating layer, various auxiliary agents such as surfactants, pH adjusters, viscosity modifiers, softeners, gloss imparting agents, waxes, dispersants, flow modifiers, stabilizers, antistatic agents , A crosslinking agent, a sizing agent, a fluorescent brightening agent, a colorant, an ultraviolet absorber, an antifoaming agent, a water-resistant agent, a plasticizer, a lubricant, an antiseptic, and a fragrance are appropriately included as necessary. May be.
内側顔料塗被層の塗工量は、３〜３０ｇ／ｍ２が好ましい。特に、基紙と接する内側顔料塗被層の場合、塗工量が６ｇ／ｍ２未満では基紙の凹凸を埋めることが困難で、光沢発現性も低下することがある。３０ｇ／ｍ２より多い場合では、塗工の際の乾燥性が悪くなるなど、操業性が低下し、製造原価も高くなり、また、パッケージ分野や物流分野で箱や封筒などに加工する場合、折り曲げ部分や折り畳み部分で内側塗被層の欠落を生じる虞もある。より好ましい塗工量は３〜１５ｇ／ｍ２、特に好ましい塗工量は６〜１２ｇ／ｍ２である。 The coating amount of the inner pigment coating layer is preferably 3 to 30 g / m 2 . In particular, in the case of the inner pigment coating layer in contact with the base paper, if the coating amount is less than 6 g / m 2 , it is difficult to fill the unevenness of the base paper, and gloss development may be reduced. When the amount is more than 30 g / m 2 , the operability is lowered such as poor drying during coating, and the production cost is increased. In addition, when processing into a box or envelope in the packaging field or the logistics field, There is also a possibility that the inner coating layer may be lost in the folded portion or the folded portion. A more preferable coating amount is 3 to 15 g / m 2 , and a particularly preferable coating amount is 6 to 12 g / m 2 .
内側顔料塗被層を形成する塗工方法としては、一般に従来の塗工装置、例えばブレードコーター、エアーナイフコーター、ロールコーター、リバースロールコーター、バーコーター、カーテンコーター、スロットダイコーター、グラビアコーター、チャンプレックスコーター、ブラシコーター、ツーロール、並びにメータリングブレード式のサイズプレスコーター、ビルブレードコーター、ショートドウェルコーター、ゲートロールコーター等の塗工装置を適宜に用いることができる。なかでも、高濃度塗被液を高速塗工できるブレードコーターは、内側顔料塗被層のバインダー樹脂の基紙へのしみこみが小さく抑えられるため、前記バインダー樹脂の使用量で、インクジェットインク吸収性と表面強度の両立した層が得られ易く、また優れた表面性が得られるため高光沢性が得られやすいため、好ましく用いられる。 The coating method for forming the inner pigment coating layer is generally a conventional coating apparatus such as a blade coater, air knife coater, roll coater, reverse roll coater, bar coater, curtain coater, slot die coater, gravure coater, channel. Coating apparatuses such as a plex coater, a brush coater, a two roll, a metering blade type size press coater, a bill blade coater, a short dwell coater, and a gate roll coater can be appropriately used. Among these, the blade coater that can apply a high-concentration coating solution at high speed suppresses the penetration of the binder resin of the inner pigment coating layer into the base paper, so that the amount of the binder resin used can be reduced. A layer having a high surface strength can be easily obtained, and an excellent surface property can be obtained.
最表顔料塗被層で主成分として使用する軽質炭酸カルシウムは、平均粒子径（短径）が０．８μｍ以下であれば、特に限定するものではない。軽質炭酸カルシウムの形状としては、例えば柱状、紡錘状のものが好ましい。平均粒子径（短径）が０．８μｍを超えると、白紙光沢が低下し、さらにはオフセット印刷後のインキグロスが低下し、印刷物の質感が損なわれる。さらには水性顔料インクの色素粒子が顔料粒子間空隙に沈みこみ、印刷濃度を低下させる虞がある。ここでいう主成分とは、顔料１００質量部中の軽質炭酸カルシウムを５０質量部以上含有することであり、７０質量部以上含有することが好ましく、８０質量部以上含有することがより好ましい。なお、平均粒子径（短径）は、使用する製品のカタログに記載された値を採用するが、記載がない場合は、ＳＥＭ写真（倍率×１０，０００）よりデジマチックノギスで測定した値を採用するとよい。 The light calcium carbonate used as the main component in the outermost pigment coating layer is not particularly limited as long as the average particle diameter (short diameter) is 0.8 μm or less. As the shape of the light calcium carbonate, for example, a columnar shape or a spindle shape is preferable. When the average particle diameter (minor axis) exceeds 0.8 μm, the glossiness of white paper is lowered, and further, the ink gloss after offset printing is lowered, and the texture of the printed matter is impaired. Furthermore, the pigment particles of the aqueous pigment ink may sink into the gaps between the pigment particles, and the print density may be reduced. The main component here means containing 50 parts by mass or more of light calcium carbonate in 100 parts by mass of the pigment, preferably 70 parts by mass or more, and more preferably 80 parts by mass or more. In addition, although the value described in the catalog of the product to use is employ | adopted for an average particle diameter (short axis), when there is no description, the value measured with the Digimatic caliper from a SEM photograph (magnification x10,000) is used. Adopt it.
最表顔料塗被層では、特定の軽質炭酸カルシウム以外の顔料を併用することも可能である。その具体例としては、例えば、カオリン、重質炭酸カルシウム、凝集炭酸カルシウム、平均粒子径（短径）が０．８μｍを超える軽質炭酸カルシウム、タルク、硫酸カルシウム、硫酸バリウム、二酸化チタン、酸化亜鉛、アルミナ、炭酸マグネシウム、酸化マグネシウム、シリカ、微粒子シリカ、コロイダルシリカ、アルミノ珪酸マグネシウム、微粒子状珪酸カルシウム、微粒子状炭酸マグネシウム、ホワイトカーボン、サチンホワイト、ベントナイト、ゼオライト、セリサイト、スメクタイト等の鉱物材料からなる顔料や、ポリスチレン樹脂、スチレン・アクリル共重合樹脂、尿素樹脂、メラミン樹脂、アクリル樹脂、塩化ビニリデン樹脂、ベンゾグアナミン樹脂、並びにこれらの微小中空粒子や貫通孔型の有機材料からなる有機顔料等が挙げられる。 In the outermost pigment coating layer, a pigment other than a specific light calcium carbonate can be used in combination. Specific examples thereof include, for example, kaolin, heavy calcium carbonate, agglomerated calcium carbonate, light calcium carbonate having an average particle diameter (short axis) exceeding 0.8 μm, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, Made of mineral materials such as alumina, magnesium carbonate, magnesium oxide, silica, particulate silica, colloidal silica, magnesium aluminosilicate, particulate calcium silicate, particulate magnesium carbonate, white carbon, satin white, bentonite, zeolite, sericite, smectite Pigments, polystyrene resins, styrene / acrylic copolymer resins, urea resins, melamine resins, acrylic resins, vinylidene chloride resins, benzoguanamine resins, and organic pigments made of these micro hollow particles or through-hole organic materials It is below.
中でも、カオリンは、オフセット印刷適性は優れるが、水性顔料インクの定着を阻害する虞があるため、併用する場合においても顔料１００質量部に対して３０部以下での使用が好ましい。また、微小中空粒子や貫通孔型の有機材料からなる有機顔料（中空プラスチックピグメントともいう）を顔料１００質量部中、３〜１５質量部併用することが好ましい。３質量部以上使用すると、光沢向上効果が発現し、１５質量部以下の配合にとどめることにより、表面強度の低下を防ぎ、オフセット印刷適性を両立する。 Of these, kaolin is excellent in offset printability but may hinder the fixing of the aqueous pigment ink. Therefore, kaolin is preferably used in an amount of 30 parts or less with respect to 100 parts by mass of the pigment. Further, it is preferable to use 3 to 15 parts by mass of an organic pigment (also referred to as a hollow plastic pigment) made of fine hollow particles or a through-hole type organic material in 100 parts by mass of the pigment. When it is used in an amount of 3 parts by mass or more, a gloss improvement effect is exhibited, and by reducing the blending to 15 parts by mass or less, a decrease in surface strength is prevented and both offset printing suitability is achieved.
最表顔料塗被層中にはバインダーとしてスチレン・ブタジエン共重合体ラテックスを顔料１００質量部に対して４〜３０質量部含有させるものである。より好ましくは８〜２０質量部である。含有量が４質量部未満の場合、十分な表面強度が得られず、オフセット印刷に支障を来たすことがある。一方、３０質量部を超える場合は、インクジェットインクの溶媒通過性が低下することはもとより、光沢発現性も低下してしまう。 In the outermost pigment coating layer, 4 to 30 parts by mass of a styrene / butadiene copolymer latex is contained as a binder with respect to 100 parts by mass of the pigment. More preferably, it is 8-20 mass parts. When the content is less than 4 parts by mass, sufficient surface strength cannot be obtained, and offset printing may be hindered. On the other hand, when it exceeds 30 parts by mass, not only the solvent permeability of the ink-jet ink is lowered but also the glossiness is lowered.
最表顔料塗被層中には、スチレン・ブタジエン共重合体ラテックス以外のバインダーを併用することも可能である。併用されるバインダーとしては、例えばデンプン類、ヒドロキシエチルセルロース、メチルセルロース、カルボキシメチルセルロース、ゼラチン、カゼイン、アラビアガム、ジイソブチレン・無水マレイン酸共重合体塩、スチレン・無水マレイン酸共重合体塩、エチレン・アクリル酸共重合体塩、スチレン・アクリル酸共重合体塩、尿素樹脂、メラミン樹脂、アミド樹脂、スチレンアクリル共重合体ラテックス、ポリウレタン系ラテックス、スチレン、アクリル酸、メタクリル酸、アクリル酸エステル、メタクリル酸エステル、アクリルアミド、メタクリルアミド、メチルビニルエーテル等のビニル系重合体や共重合体類、メチルメタクリレート・ブタジエン樹脂系等の合成ゴムラテックス、ポリウレタン樹脂、ポリエステル樹脂、ポリアミド樹脂、オレフィン・無水マレイン酸樹脂、メラミン樹脂等が挙げられる。 In the outermost pigment coating layer, a binder other than styrene / butadiene copolymer latex can be used in combination. Examples of binders used in combination include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, diisobutylene / maleic anhydride copolymer salt, styrene / maleic anhydride copolymer salt, ethylene / acrylic. Acid copolymer salt, styrene / acrylic acid copolymer salt, urea resin, melamine resin, amide resin, styrene acrylic copolymer latex, polyurethane latex, styrene, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester , Acrylamide, methacrylamide, methyl vinyl ether and other vinyl polymers and copolymers, methyl methacrylate / butadiene resin synthetic rubber latex, polyurethane resin, polyester resin, polyamid Resins, olefin-maleic anhydride resins, melamine resins, and the like.
中でも、カゼインは、光沢発現性の低下が小さく、水溶性多価金属塩との反応により、特に湿潤時の表面強度が向上するので併用することが好ましいバインダーである。カゼインの添加量としては、最表層顔料１００質量部に対して１〜１０質量部程度が好ましい。１質量部以上とすることにより顕著な添加効果を得、１０質量部以下とすることによりインクジェットインクの溶媒通過性の低下を防ぐことができる。 Among them, casein is a binder that is preferably used in combination because it has a small decrease in glossiness and improves the surface strength particularly when wet by reaction with a water-soluble polyvalent metal salt. As addition amount of casein, about 1-10 mass parts is preferable with respect to 100 mass parts of outermost layer pigments. When the amount is 1 part by mass or more, a remarkable effect of addition can be obtained, and when the amount is 10 parts by mass or less, it is possible to prevent a decrease in solvent permeability of the inkjet ink.
また、スチレンアクリル共重合体ラテックスは、インクジェット印刷直後の耐擦過性が向上するので併用することが好ましいバインダーである。スチレンアクリル共重合体ラテックスの添加量としては、最表層顔料１００質量部に対して１〜３０質量部が好ましい。より好ましくは３〜２０質量部である。１質量部以上とすることにより顕著な添加効果を得、３０質量部以下とすることによりインクジェットインクの溶媒通過性の低下を防ぐことができる。スチレンアクリル共重合体ラテックスを用いることにより、インクジェット印刷直後の耐擦過性が改善される理由は定かではないが、おそらく、水性顔料インク中に配合されている成分との相性がよいためではないかと考えられる。 Styrene acrylic copolymer latex is a binder that is preferably used in combination because it improves the scratch resistance immediately after ink jet printing. As addition amount of styrene acrylic copolymer latex, 1-30 mass parts is preferable with respect to 100 mass parts of outermost layer pigments. More preferably, it is 3-20 mass parts. When the amount is 1 part by mass or more, a remarkable effect of addition can be obtained, and when the amount is 30 parts by mass or less, a decrease in solvent permeability of the inkjet ink can be prevented. The reason why the scratch resistance immediately after ink jet printing is improved by using the styrene acrylic copolymer latex is not clear, but probably because it is compatible with the components blended in the aqueous pigment ink. Conceivable.
また各顔料塗被層中には、各種助剤、例えば界面活性剤、ｐＨ調節剤、粘度調節剤、柔軟剤、光沢付与剤、ワックス類、分散剤、流動変性剤、安定化剤、帯電防止剤、架橋剤、サイズ剤、蛍光増白剤、着色剤、紫外線吸収剤、消泡剤、耐水化剤、可塑剤、滑剤、防腐剤及び香料等の少なくとも１種が必要に応じて適宜含まれていてもよい。 In each pigment coating layer, various auxiliary agents such as surfactants, pH regulators, viscosity modifiers, softeners, gloss imparting agents, waxes, dispersants, flow modifiers, stabilizers, antistatic agents As appropriate, at least one of an agent, a crosslinking agent, a sizing agent, a fluorescent brightening agent, a coloring agent, an ultraviolet absorber, an antifoaming agent, a water-proofing agent, a plasticizer, a lubricant, a preservative, and a fragrance is included as necessary. It may be.
最表顔料塗被層の塗工量は、３〜３０ｇ／ｍ２が好ましい。塗工量が３ｇ／ｍ２より少ない場合は、十分な被覆ができないため、光沢度を適正化できないことがある。また３０ｇ／ｍ２より多い場合では、塗工の際の乾燥性が悪くなるなど、操業性が低下し、製造原価も高くなり、また、パッケージ分野や物流分野で箱や封筒などに加工する場合、折り曲げ部分や折り畳み部分で最表層の欠落を生じる虞もある。より好ましい塗工量は３〜２０ｇ／ｍ２、特に好ましい塗工量は４〜１５ｇ／ｍ２である。 The coating amount of the outermost pigment coating layer is preferably 3 to 30 g / m 2 . When the coating amount is less than 3 g / m 2 , the glossiness may not be optimized because sufficient coating cannot be performed. Also, when the amount is more than 30 g / m 2 , the operability is lowered and the manufacturing cost is increased, for example, the drying property at the time of coating is deteriorated, and when processing into a box or an envelope in the packaging field or the logistics field. There is also a possibility that the outermost layer may be lost at the bent portion or the folded portion. A more preferable coating amount is 3 to 20 g / m 2 , and a particularly preferable coating amount is 4 to 15 g / m 2 .
最表顔料塗被層を形成する塗工方法としては、一般に従来の塗工装置、例えばブレードコーター、エヤーナイフコーター、ロールコーター、リバースロールコーター、バーコーター、カーテンコーター、スロットダイコーター、グラビアコーター、チャンプレックスコーター、ブラシコーター、ツーロール、並びにメータリングブレード式のサイズプレスコーター、ビルブレードコーター、ショートドウェルコーター、ゲートロールコーター等の塗工装置を適宜に用いることができる。なかでも、高濃度塗被液を高速塗工できるブレードコーターは、最表顔料塗被層で使用するバインダー成分の内側顔料塗被層へのしみこみが小さく抑えられるため、前記バインダー樹脂の使用量で、インクジェットインク吸収性と表面強度の両立した層が得られ易く、また優れた表面性が得られるため高光沢性が得られやすいため、好ましく用いられる。また、内側顔料塗被層と外側顔料塗被層を同時多層コーティングしてもよく、内側顔料塗被層を完全に乾かさない状態で最表顔料塗被層を塗布する、所謂Ｗｅｔ ｏｎ Ｗｅｔ法で積層しても構わない。 As a coating method for forming the outermost pigment coating layer, generally a conventional coating apparatus such as a blade coater, an air knife coater, a roll coater, a reverse roll coater, a bar coater, a curtain coater, a slot die coater, a gravure coater, Coating apparatuses such as a Champlex coater, a brush coater, a two roll, a metering blade type size press coater, a bill blade coater, a short dwell coater, and a gate roll coater can be used as appropriate. Among these, the blade coater that can apply high-concentration coating liquid at high speed can suppress the penetration of the binder component used in the outermost pigment coating layer into the inner pigment coating layer. A layer having both ink jet ink absorbability and surface strength can be easily obtained, and since excellent surface properties can be obtained, high glossiness is easily obtained. Also, the inner pigment coating layer and the outer pigment coating layer may be coated simultaneously in multiple layers, and the outermost pigment coating layer is applied in a state where the inner pigment coating layer is not completely dried, so-called Wet on Wet method. You may laminate.
本発明では最表顔料塗被層用の塗液を塗布・乾燥して層を形成した後、水溶性多価金属塩の水溶液を塗布することにより、良好なオフセット印刷適性と水性顔料インクジェットインクの溶媒通過性を得るものである。
かかる水溶性多価金属塩の具体例としては、ギ酸、酢酸、クエン酸、酒石酸、乳酸、マロン酸、マレイン酸、グリコール酸、リンゴ酸、アクリル酸、塩酸、硫酸、硝酸、リン酸等のカルシウム、亜鉛、マグネシウム、アルミニウムの各塩等が挙げられる。なかでもギ酸カルシウムは、優れたオフセット印刷適性と水性顔料インクジェットインク溶媒通過性を付与するため好ましく用いられる。
In the present invention, a coating solution for the outermost pigment coating layer is applied and dried to form a layer, and then an aqueous solution of a water-soluble polyvalent metal salt is applied to obtain a good offset printability and an aqueous pigment inkjet ink. The solvent passage is obtained.
Specific examples of such water-soluble polyvalent metal salts include calcium such as formic acid, acetic acid, citric acid, tartaric acid, lactic acid, malonic acid, maleic acid, glycolic acid, malic acid, acrylic acid, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. , Zinc, magnesium, aluminum salts and the like. Among these, calcium formate is preferably used because it imparts excellent offset printability and aqueous pigment inkjet ink solvent passage.
多価金属塩の塗布量としては特に限定するものではないが、例えば０．００１〜２ｇ／ｍ２程度、よりこのましくは０．０２〜０．５ｇ／ｍ２である。顕著な塗布効果を得るためには０．００１ｇ／ｍ２以上の塗工が必要であり、２ｇ／ｍ２以下とすることにより顔料インク定着性が低下することを防ぐことが出来る。
水溶性多価金属塩の塗工方法としては、上記塗被層と同様の塗工装置が用いられる。また平滑化処理工程において、キャレンダーを用いたニップ塗工も可能である。
The application amount of the polyvalent metal salt is not particularly limited, but is, for example, about 0.001 to 2 g / m 2 , more preferably 0.02 to 0.5 g / m 2 . In order to obtain a remarkable coating effect, it is necessary to apply 0.001 g / m 2 or more, and by setting it to 2 g / m 2 or less, it is possible to prevent the pigment ink fixability from being lowered.
As a coating method for the water-soluble polyvalent metal salt, the same coating apparatus as that for the coating layer is used . In or smoothing step, nip coating using calender is also possible.
上記のように、本発明は、顔料塗被層を少なくとも内側顔料塗被層と水溶性多価金属塩の水溶液で処理した最表顔料塗被層の積層状態で形成するものであるが、内側顔料塗被層には、インクジェットインクの溶媒吸収性付与機能を、また、最表顔料塗被層には、水性顔料インクの定着性、インク溶媒通過性付与機能というように、機能を分担することにより、オフセット印刷適性に優れ、且つ水性顔料インクを用いた高速インクジェットプリンターによる印刷適性も備えたハイブリッド印刷に適したグロス系印刷用顔料塗被紙となる。 As described above, the present invention forms the pigment coating layer in a laminated state of at least the inner pigment coating layer and the outermost pigment coating layer treated with an aqueous solution of a water-soluble polyvalent metal salt. The pigment coating layer has the function of imparting the solvent absorbability of the ink-jet ink, and the outermost pigment coating layer has the functions of fixing the aqueous pigment ink and imparting the ink solvent permeability. Thus, a gloss-based pigment-coated paper suitable for hybrid printing having excellent offset printing suitability and printing suitability by a high-speed inkjet printer using aqueous pigment ink is obtained.
上記顔料塗被層を有する顔料塗被紙は、オフセット印刷適性に優れ、且つ水性顔料インクを用いた高速インクジェットプリンターによる印刷適性も優れるものである。また、パッケージ分野の製函工程や、物流分野の郵便局等の自動仕分け装置を通過する場合等に必要なインクジェット印字部分の耐擦過性も優れるため、パッケージ分野や物流分野における箱や封筒等の用途にも適した顔料塗被紙である。また、従来の塗被層に主成分としてシリカを用いた印刷用紙（例えば、特許文献２等）に比べ、塗被層の強度が優れるため、パッケージ分野や物流分野における箱や封筒等の加工適性も適した顔料塗被紙といえる。 The pigment-coated paper having the pigment coating layer is excellent in offset printing suitability and excellent in printability by a high-speed ink jet printer using an aqueous pigment ink. In addition, because it has excellent scratch resistance of the ink-jet printing part required when passing through the box making process in the package field and the automatic sorting device such as the post office in the logistic field, it can be used for boxes and envelopes in the package field and the logistic field. It is a pigment-coated paper suitable for applications. In addition, since the strength of the coating layer is superior to conventional printing paper using silica as the main component in the coating layer (for example, Patent Document 2), it is suitable for processing boxes and envelopes in the packaging and logistics fields. Is also a suitable pigment coated paper.
上記顔料塗被層は、基紙の片面に設けてもよく、両面に形成してもよい。以下に、基紙について説明する。 The pigment coating layer may be provided on one side of the base paper or may be formed on both sides. The base paper will be described below.
本発明における基紙を構成するパルプについて、本発明の効果を損なわない範囲において、その製法及び種類等に特に限定はない。例えばＫＰのような化学パルプ、ＳＧＰ、ＲＧＰ、ＢＣＴＭＰ及びＣＴＭＰ等の機械パルプ、脱墨パルプのような古紙パルプ、並びにケナフ、竹、藁、麻等のような非木材パルプであってもよく、またポリアミド繊維、ポリエステル繊維等の有機合成繊維、再生繊維、例えばポリノジック繊維、並びにガラス繊維、セラミック繊維、カーボン繊維等の無機質繊維も混用することができる。なお、基紙に用いるパルプとして、ＥＣＦパルプ、ＴＣＦパルプ等の塩素フリーパルプを用いることが好ましい。 About the pulp which comprises the base paper in this invention, in the range which does not impair the effect of this invention, there is no limitation in the manufacturing method, a kind, etc. in particular. For example, chemical pulp such as KP, mechanical pulp such as SGP, RGP, BCTMP and CTMP, waste paper pulp such as deinked pulp, and non-wood pulp such as kenaf, bamboo, straw, hemp, etc. Organic synthetic fibers such as polyamide fibers and polyester fibers, recycled fibers such as polynosic fibers, and inorganic fibers such as glass fibers, ceramic fibers, and carbon fibers can also be used in combination. In addition, it is preferable to use chlorine free pulp, such as ECF pulp and TCF pulp, as the pulp used for the base paper.
基紙を構成するパルプの叩解度については、特に限定するものではないが、例えば３００〜５５０ｃｃ（ＣＳＦ）の範囲で調整されることが好ましい。叩解度が５５０ｃｃを超える場合は、繊維の絡み合いや接着力が不十分なため、満足な内部強度が得られず、オフセット印刷時にブリスターが発生する虞がある。また３００ｃｃ未満の場合は、繊維の絡み合いによる接着改善効果は飽和しており、逆に単繊維強度低下の影響により印刷強度が低下してしまうおそれがある。より好ましくは３５０〜５２０ｃｃである。 The beating degree of the pulp constituting the base paper is not particularly limited, but is preferably adjusted in the range of 300 to 550 cc (CSF), for example. When the beating degree exceeds 550 cc, the entanglement and adhesive strength of the fibers are insufficient, so that satisfactory internal strength cannot be obtained, and blisters may occur during offset printing. On the other hand, if it is less than 300 cc, the effect of improving the adhesion due to the entanglement of the fibers is saturated, and conversely, the printing strength may be reduced due to the influence of the single fiber strength reduction. More preferably, it is 350-520cc.
基紙中には、本発明の効果を損なわない範囲において、バインダー、乾燥紙力増強剤、湿潤紙力増強剤も併用可能である。バインダーとしては、例えば各種デンプン、ポリビニルアルコール、カルボキシメチルセルロース等の水溶性高分子が挙げられる。乾燥紙力増強剤としては、アニオン性、カチオン性、または両性のポリアクリルアミド樹脂が挙げられる。また湿潤紙力増強剤としては、例えばポリアミド樹脂、メラミン・ホルムアルデヒド樹脂、尿素・ホルムアルデヒド樹脂、ポリアミド・ポリアミン・エピクロルヒドリン樹脂、ポリエチレンイミン樹脂等が挙げられる。 In the base paper, a binder, a dry paper strength enhancer, and a wet paper strength enhancer can be used in combination as long as the effects of the present invention are not impaired. Examples of the binder include water-soluble polymers such as various starches, polyvinyl alcohol, and carboxymethyl cellulose. Examples of the dry paper strength enhancer include anionic, cationic, or amphoteric polyacrylamide resins. Examples of the wet paper strength enhancer include polyamide resins, melamine / formaldehyde resins, urea / formaldehyde resins, polyamide / polyamine / epichlorohydrin resins, and polyethyleneimine resins.
本発明では、基紙のサイズ度については、特に限定するものではないが、一般にステキヒトサイズ度で、１００秒以下程度に調整される。サイズ度の調整方法としては、原料中に含有される内添サイズ剤や、サイズプレス塗工機で塗工される表面サイズ剤をそれぞれ単独または組み合わせて所定のサイズ度に調整される。内添サイズ剤としては、ロジン系サイズ剤、合成サイズ剤、石油樹脂系サイズ剤、アルキルケテンダイマー、アルケニル無水コハク酸系の中性サイズ剤等のサイズ剤が使用でき、硫酸バンド、カチオン化デンプン等、適当なサイズ剤と定着剤を組み合わせて使用する。表面サイズ剤としては、上記内添サイズで使用したものの他、スチレン・マレイン酸共重合体、スチレン・アクリル酸共重合体、スチレン・メタクリル酸共重合体等が挙げられるが、もちろんこれらに限定されるものではない。 In the present invention, the sizing degree of the base paper is not particularly limited, but is generally adjusted to a Steecht sizing degree of about 100 seconds or less. As a method for adjusting the sizing degree, the internal sizing agent contained in the raw material and the surface sizing agent applied by a size press coating machine are adjusted to a predetermined sizing degree, either singly or in combination. As internal sizing agents, sizing agents such as rosin sizing agents, synthetic sizing agents, petroleum resin sizing agents, alkyl ketene dimers, and alkenyl succinic anhydride neutral sizing agents can be used. A suitable sizing agent and fixing agent are used in combination. Examples of the surface sizing agent include styrene / maleic acid copolymer, styrene / acrylic acid copolymer, styrene / methacrylic acid copolymer, etc. in addition to those used in the above-mentioned internal sizes. It is not something.
また基紙中には必要に応じて、填料が配合されていてもよい。填料としては、一般に上質紙に用いられる各種の顔料を用いることができ、例えばカオリン、焼成カオリン、炭酸カルシウム、硫酸カルシウム、硫酸バリウム、二酸化チタン、タルク、酸化亜鉛、アルミナ、炭酸マグネシウム、酸化マグネシウム、シリカ、ホワイトカーボン、ベントナイト、ゼオライト、セリサイト及びスメクタイト等の鉱物質顔料、並びにポリスチレン系樹脂、尿素系樹脂、メラミン系樹脂、アクリル系樹脂及び塩化ビニリデン系樹脂の微小中空粒子、密実型粒子および貫通孔型粒子などの有機顔料が挙げられる。 Moreover, a filler may be blended in the base paper as necessary. As the filler, various pigments generally used for fine paper can be used, such as kaolin, calcined kaolin, calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, talc, zinc oxide, alumina, magnesium carbonate, magnesium oxide, Mineral pigments such as silica, white carbon, bentonite, zeolite, sericite and smectite, as well as fine hollow particles, solid particles and polystyrene resins, urea resins, melamine resins, acrylic resins and vinylidene chloride resins Examples thereof include organic pigments such as through-hole particles.
なお、基紙の抄紙時に、その紙料中に、本発明の所望の効果を損なわない範囲で、パルプ繊維や填料の他に、従来から使用されている各種のアニオン性、ノニオン性、カチオン性あるいは両性の歩留向上剤、濾水性向上剤等の各種抄紙用内添助剤を必要に応じて適宜選択して使用することができる。さらに染料、蛍光増白剤、ｐＨ調整剤、消泡剤、ピッチコントロール剤、スライムコントロール剤等の抄紙用内添助剤も必要に応じて適宜添加することができる。 In addition to the pulp fiber and filler, various anionic, nonionic, and cationic properties that have been used in the past are included in the stock when the base paper is made, as long as the desired effects of the present invention are not impaired. Alternatively, various papermaking internal additives such as amphoteric yield improver and freeness improver can be appropriately selected and used as necessary. Furthermore, internal additives for papermaking such as dyes, fluorescent brighteners, pH adjusters, antifoaming agents, pitch control agents, slime control agents and the like can be added as necessary.
基紙の抄紙方法については特に限定はなく、例えば抄紙ｐＨが４．５付近で行われる酸性抄紙法、炭酸カルシウム等のアルカリ性填料を主成分として含み、抄紙ｐＨ約６の弱酸性から抄紙ｐＨ約９の弱アルカリ性で行われる中性抄紙法等の、全ての抄紙方法を適用することができ、抄紙機も長網抄紙機、ツインワイヤー抄紙機、丸網抄紙機、ヤンキー抄紙機等を適宜使用することができる。 There is no particular limitation on the paper making method of the base paper. For example, an acidic paper making method in which the paper making pH is around 4.5, an alkaline filler such as calcium carbonate is contained as a main component, and the paper making pH is from about 6 to about the paper making pH. All paper making methods such as neutral paper making method with 9 weak alkalinity can be applied, and long paper machine, twin wire paper machine, round net paper machine, Yankee paper machine etc. are used as appropriate can do.
本発明で使用される基紙が板紙の場合も、構成されるパルプについては特に限定されない。例えば、晒ないしは未晒の化学パルプ、機械パルプ、さらには脱墨ないしは未脱墨パルプの古紙パルプ等の一種または二種以上を適宜混合して使用される。その他、原紙には必要に応じて、サイズ剤、紙力剤、薬品安定剤、濾水剤、填料、染料等を適宜添加することもできる。なお、原紙の米坪は通常１５０〜６５０ｇ／ｍ２程度である。
板紙基紙の場合も上記の填料を使用することが可能である。
板紙基紙を得るための抄紙機としては、長網式抄紙機、短網式抄紙機、円網式抄紙機、オントップフォーマー、ギャップフォーマー等の抄紙機が使用でき、２層以上を抄き合わせて原紙抄造を行う。基紙が板紙である場合、強度に優れるため、特にパッケージ分野や物流分野において使用される箱や封筒等の用途に適した印刷用顔料塗被板紙となる。
Even when the base paper used in the present invention is a paperboard, the constituted pulp is not particularly limited. For example, one or two or more of bleached or unbleached chemical pulp, mechanical pulp, deinked or undeinked pulp waste paper pulp, and the like are used as appropriate. In addition, a sizing agent, a paper strength agent, a chemical stabilizer, a filtering agent, a filler, a dye, and the like can be appropriately added to the base paper as necessary. The base weight of the base paper is usually about 150 to 650 g / m 2 .
In the case of paperboard base paper, it is possible to use the above filler.
As a paper machine for obtaining a paperboard base paper, a paper machine such as a long net paper machine, a short net paper machine, a circular net paper machine, an on-top former or a gap former can be used. The base paper is made by combining them. When the base paper is a paperboard, it is excellent in strength, so that it becomes a pigment-coated paperboard for printing particularly suitable for applications such as boxes and envelopes used in the packaging field and the logistics field.
本発明の印刷用顔料塗被紙は、各顔料塗被層を設けた後、平滑化処理を施して、表面の光沢を発現させるものである。平滑化処理方法としては、スーパーカレンダ、グロスカレンダ、ソフトカレンダ等、通常の平滑化処理装置を用いて行われる。前記平滑化処理はオンマシンやオフマシンで適宜施されてもよく、加圧装置の形態、加圧ニップの数、加温等も通常の平滑化処理装置に応じて適宜調節される。平滑化処理後の印刷用顔料塗被紙の各種物性としては、表面の７５度における白紙光沢度（ＪＩＳ−Ｐ８１４２）は、特に限定するものではないが、例えば４０％以上あればオフセット印刷後のインキグロスの高い印刷物が得られるため好ましい。 The pigment-coated paper for printing of the present invention is one in which each pigment-coated layer is provided and then subjected to a smoothing treatment to develop surface gloss. As a smoothing processing method, a normal smoothing processing device such as a super calendar, a gloss calendar, a soft calendar, or the like is used. The smoothing process may be appropriately performed on-machine or off-machine, and the form of the pressure device, the number of pressure nips, heating, and the like are appropriately adjusted according to a normal smoothing device. As various physical properties of the pigment coated paper for printing after the smoothing treatment, the white paper glossiness (JIS-P8142) at 75 degrees on the surface is not particularly limited. This is preferable because a printed matter with high ink gloss can be obtained.
また印刷用顔料塗被紙としての密度については特に限定するものではないが、０．９５〜１．１５ｇ／ｃｍ３であることが好ましい。密度が０．９５ｇ／ｃｍ３を下回る場合は、十分な印刷強度が得られないことがあり、また１．１５ｇ／ｃｍ３を超える場合は、インクジェットインク吸収容量が確保できないために、満足なインクジェットインク吸収性が得られなくなることがある。ただし、基紙に板紙を用いる場合の密度は、０．７５〜１．００程度が好ましい。 Moreover, although it does not specifically limit about the density as a pigment coated paper for printing, It is preferable that it is 0.95-1.15 g / cm < 3 >. If the density is less than 0.95 g / cm 3 , sufficient printing strength may not be obtained, and if it exceeds 1.15 g / cm 3 , the ink-jet ink absorption capacity cannot be secured, so Ink absorbability may not be obtained. However, the density when using paperboard as the base paper is preferably about 0.75 to 1.00.
本発明において、ハイブリッド印刷物の作成方法については、特に限定するものではない。例えば、固定情報をオフセット印刷機で印刷後にインクジェットプリンターで可変情報を印刷して作成できるが、先にインクジェットプリンターで可変情報を印刷した後にオフセット印刷することもできる。両者は、オンライン、オフラインのどちらでもよく、用紙形態も平判、巻取りのどちらでも作成可能である。なお、パッケージ分野や物流分野で用いる場合、製函前或いは製袋前にハイブリッド印刷してもよく、オフセット印刷後に製函或いは製袋を行い、インクジェットプリンターで可変情報を印刷してもよい。 In the present invention, the method for producing a hybrid printed material is not particularly limited. For example, the fixed information can be created by printing the variable information with an inkjet printer after printing it with an offset printer, but it can also be offset printed after the variable information is printed with the inkjet printer first. Both of them can be online or offline, and the paper form can be created by either plain or winding. When used in the packaging field or the physical distribution field, hybrid printing may be performed before box making or bag making, or variable information may be printed by an ink jet printer after box printing or bag making.
以下に実施例を挙げて本発明を詳細に説明するが、勿論本発明はこれに限定されるものではない。実施例において示す「部」および「％」は、特に明示の無い限り、質量部および質量％である。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In the examples, “parts” and “%” are parts by mass and mass% unless otherwise specified.
実施例１
［基紙の製造］
ＬＢＫＰ（ＣＳＦフリーネス４５０ｍｌ）９０質量部、ＮＢＫＰ（ＣＳＦフリーネス４５０ｍｌ）１０質量部のパルプスラリーに、内添サイズ剤としてアルケニル無水コハク酸（商品名：ファイブラン８１、ナショナルスターチ社製）０．０５質量部、紙力増強剤としてポリアクリルアミド系樹脂（商品名：ＰＳ１９４−７、荒川化学工業社製）０．２質量部、硫酸バンド０．６質量部を添加し、これらの混合物を白水で希釈してｐＨ５．３、固形分濃度１．１％の紙料を調製した。この紙料を、長網抄紙機に供して抄紙し、得られた湿紙に、スチレン・マレイン酸共重合体（商品名：ポリマロン３８５、荒川化学工業社製）０．２部、酸化澱粉（商品名：エースＡ、王子コーンスターチ社製）を濃度５．５％で含むサイズプレス液を、サイズプレス装置で塗布量が乾燥質量で２ｇ／ｍ２となるように塗布し、乾燥して、さらにマシンカレンダを用いて平滑化処理を施して、坪量９４ｇ／ｍ２の基紙を得た。
Example 1
[Manufacture of base paper]
A pulp slurry of 90 parts by weight of LBKP (CSF freeness 450 ml) and 10 parts by weight of NBKP (CSF freeness 450 ml), alkenyl succinic anhydride (trade name: Fibran 81, manufactured by National Starch Co., Ltd.) 0.05 mass as an internal sizing agent Part, 0.2 part by mass of polyacrylamide resin (trade name: PS194-7, manufactured by Arakawa Chemical Industries) and 0.6 part by mass of sulfuric acid band are added as a paper strength enhancer, and these mixtures are diluted with white water. A paper stock having a pH of 5.3 and a solid content concentration of 1.1% was prepared. This stock is subjected to a papermaking machine to make a paper, and the obtained wet paper has 0.2 parts of a styrene / maleic acid copolymer (trade name: Polymeralon 385, manufactured by Arakawa Chemical Industries), oxidized starch ( A size press liquid containing 5.5% concentration of product name: Ace A (manufactured by Oji Cornstarch Co., Ltd.) is applied with a size press apparatus so that the applied amount is 2 g / m 2 in terms of dry mass, dried, and further A smoothing process was performed using a machine calendar to obtain a base paper having a basis weight of 94 g / m 2 .
［内側顔料塗被層用塗被液の調製］
紡錘状軽質炭酸カルシウムの６３％分散液（商品名：タマパールＴＰ２２１ＧＳ、平均粒子径（短径）０．３μｍ、奥多摩工業社製）１５９質量部、酸化澱粉（商品名：エースＡ、王子コーンスターチ社製）の２０％水溶液１０質量部およびスチレン・ブタジエン共重合体ラテックスの５０％分散液（商品名：Ｔ−２５３１Ｈ、ＪＳＲ社製）２４質量部を添加攪拌し、さらに水を加えて、固形分濃度５０％の塗被液を調製した。
[Preparation of coating solution for inner pigment coating layer]
Spindle-like light calcium carbonate 63% dispersion (trade name: Tamapearl TP221GS, average particle size (minor axis) 0.3 μm, manufactured by Okutama Kogyo Co., Ltd.) 159 parts by mass, oxidized starch (trade name: Ace A, manufactured by Oji Cornstarch) ) And 20 parts by weight of a 20% aqueous solution of styrene / butadiene copolymer latex (trade name: T-2531H, manufactured by JSR) 24 parts by weight were added and stirred. A 50% coating solution was prepared.
［カゼインの溶解］
水、尿素１０質量部、ニュージーランドカゼイン１００質量部を混合撹拌し、昇温を開始する。次に２５％アンモニア液を７．７質量部加えて６０℃まで昇温したのち２０分保持した後冷却し、１０％のカゼイン水溶液を得た。
［最表顔料塗被層用塗被液の調製］
水、上記で得られたカゼインの１０％水溶液３６質量部に紡錘状軽質炭酸カルシウムの６３％分散液（商品名：タマパールＴＰ２２１ＧＳ、平均粒子径（短径）０．３μｍ、奥多摩工業社製）１５９質量部およびスチレン・ブタジエン共重合体ラテックスの５０％分散液（商品名：Ｔ−２５３１Ｈ、ＪＳＲ社製）３７質量部を添加攪拌し、固形分濃度５０％の塗被液を調製した。
[Dissolution of casein]
Water, 10 parts by mass of urea, and 100 parts by mass of New Zealand casein are mixed and stirred, and the temperature rise is started. Next, 7.7 parts by mass of 25% ammonia solution was added, the temperature was raised to 60 ° C., held for 20 minutes, and then cooled to obtain a 10% casein aqueous solution.
[Preparation of coating solution for outermost pigment coating layer]
Water, 63% dispersion of spindle-shaped light calcium carbonate in 36 parts by mass of the 10% aqueous solution of casein obtained above (trade name: Tamapearl TP221GS, average particle size (minor axis) 0.3 μm, manufactured by Okutama Kogyo Co., Ltd.) 159 Mass parts and 37 parts by mass of a 50% dispersion of styrene / butadiene copolymer latex (trade name: T-2531H, manufactured by JSR) were added and stirred to prepare a coating solution having a solid content concentration of 50%.
［内側顔料塗被層の形成］
前記内側顔料塗被層用塗被液を、前記基紙の両面に、ブレードコーターを用いて片面当たり乾燥塗布量が７ｇ／ｍ２なるように塗工し、内側顔料塗被層を形成した。
［最表顔料塗被層の形成］
前記最表顔料塗被層用塗被液を、上記基紙の両面に形成された内側顔料塗被層上に、ブレードコーターを用いて片面当たり乾燥塗布量が１０ｇ／ｍ２なるように塗工し、最表顔料塗被層を形成した。
［多価金属塩水溶液の塗布］
ギ酸カルシウムの４％水溶液を上記基紙の両面に形成された最表顔料塗被層上に、ロールコーターを用いて片面当たり０．１２ｇ／ｍ２付着するように塗布した後、スーパーカレンダを用いて、線圧６０ｋｇ／ｃｍ、２ニップの条件で平滑化処理を施して、坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
[Formation of inner pigment coating layer]
The inner pigment coating layer coating solution was applied to both sides of the base paper using a blade coater so that the dry coating amount per side was 7 g / m 2 to form an inner pigment coating layer.
[Formation of outermost pigment coating layer]
Coating the outermost pigment coating layer coating solution on the inner pigment coating layer formed on both sides of the base paper using a blade coater so that the dry coating amount per side is 10 g / m 2. Then, the outermost pigment coating layer was formed.
[Application of polyvalent metal salt aqueous solution]
After applying a 4% aqueous solution of calcium formate onto the outermost pigment coating layer formed on both sides of the above base paper using a roll coater so as to adhere 0.12 g / m 2 per side, use a super calender. Then, a smoothing process was performed under the conditions of a linear pressure of 60 kg / cm and 2 nips, and a pigment-coated paper for printing having a basis weight of 128 g / m 2 was obtained.
実施例２
実施例１の最表顔料塗被層用塗被液の調製において、紡錘状軽質炭酸カルシウムの６３％分散液（商品名：タマパールＴＰ２２１ＧＳ、平均粒子径（短径）０．３μｍ、奥多摩工業社製）１５９質量部の代わりに、柱状軽質炭酸カルシウムの６０％分散液（商品名：タマパールＴＰ−１２３ＣＳ、平均粒子径（短径）０．４４μｍ、奥多摩工業社製）１６７質量部を使用した以外は実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Example 2
In the preparation of the coating solution for the outermost pigment coating layer of Example 1, a 63% dispersion of spindle-shaped light calcium carbonate (trade name: Tamapearl TP221GS, average particle size (minor axis) 0.3 μm, manufactured by Okutama Kogyo Co., Ltd. ) Instead of 159 parts by mass, 167 parts by mass of a columnar light calcium carbonate 60% dispersion (trade name: Tamapearl TP-123CS, average particle size (minor axis) 0.44 μm, manufactured by Okutama Kogyo Co., Ltd.) was used. In the same manner as in Example 1, a pigment-coated paper for printing having a basis weight of 128 g / m 2 was obtained.
実施例３
実施例１の最表顔料塗被層用塗被液の調製において、紡錘状軽質炭酸カルシウムの６３％分散液（商品名：タマパールＴＰ２２１ＧＳ、平均粒子径（短径）０．３μｍ、奥多摩工業社製）１５９質量部の代わりに、柱状軽質炭酸カルシウムの６２％分散液（商品名：タマパールＴＰ−１２３ＨＧ、平均粒子径（短径）０．２μｍ、奥多摩工業社製）１６１質量部を使用した以外は実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Example 3
In the preparation of the coating solution for the outermost pigment coating layer of Example 1, a 63% dispersion of spindle-shaped light calcium carbonate (trade name: Tamapearl TP221GS, average particle size (minor axis) 0.3 μm, manufactured by Okutama Kogyo Co., Ltd. ) Instead of 159 parts by mass, a 62% dispersion of columnar light calcium carbonate (trade name: Tama Pearl TP-123HG, average particle diameter (minor axis) 0.2 μm, manufactured by Okutama Kogyo Co., Ltd.) was used except that 161 parts by mass was used. In the same manner as in Example 1, a pigment-coated paper for printing having a basis weight of 128 g / m 2 was obtained.
実施例４
実施例１の最表顔料塗被層用塗被液の調製において、紡錘状軽質炭酸カルシウムの６３％分散液（商品名：タマパールＴＰ２２１ＧＳ、平均粒子径（短径）０．３μｍ、奥多摩工業社製）１５９質量部の代わりに、紡錘状軽質炭酸カルシウムの６５％分散液（商品名：ＹＣＣ−ＦＤ、平均粒子径（短径）０．６μｍ、矢橋工業社製）１５４質量部を使用した以外は実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Example 4
In the preparation of the coating solution for the outermost pigment coating layer of Example 1, a 63% dispersion of spindle-shaped light calcium carbonate (trade name: Tamapearl TP221GS, average particle size (minor axis) 0.3 μm, manufactured by Okutama Kogyo Co., Ltd. ) Instead of 159 parts by mass, 154 parts by mass of a spindle-shaped light calcium carbonate 65% dispersion (trade name: YCC-FD, average particle diameter (minor axis) 0.6 μm, manufactured by Yabashi Kogyo Co., Ltd.) was used. In the same manner as in Example 1, a pigment-coated paper for printing having a basis weight of 128 g / m 2 was obtained.
実施例５
実施例１の最表顔料塗被層用塗被液の調製において、カゼインの１０％水溶液３６質量部の代わりに、酸化澱粉（商品名：エースＡ、王子コーンスターチ社製）の２０％水溶液１８質量部を使用した以外は実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Example 5
In the preparation of the coating solution for the outermost pigment coating layer of Example 1, 18 mass of 20% aqueous solution of oxidized starch (trade name: Ace A, manufactured by Oji Cornstarch) instead of 36 mass parts of 10% aqueous solution of casein. A pigment-coated paper for printing having a basis weight of 128 g / m 2 was obtained in the same manner as in Example 1 except that the parts were used.
実施例６
実施例１の最表顔料塗被層用塗被液の調製において、スチレン・ブタジエン共重合体ラテックスの５０％分散液（商品名：Ｔ−２５３１Ｈ、ＪＳＲ社製）の使用量を２７質量部に減らし、さらにスチレンアクリル共重合体ラテックス（商品名：ＰＤＸ７２３６、ＢＡＳＦジャパン社製）の４０％分散液１２．５質量部を加えた以外は実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Example 6
In the preparation of the coating solution for the outermost pigment coating layer of Example 1, the amount of the 50% dispersion of styrene / butadiene copolymer latex (trade name: T-2531H, manufactured by JSR) was 27 parts by mass. Printing with a basis weight of 128 g / m 2 was carried out in the same manner as in Example 1 except that 12.5 parts by weight of a 40% dispersion of styrene acrylic copolymer latex (trade name: PDX7236, manufactured by BASF Japan) was added. Pigment coated paper was obtained.
実施例７
実施例１の最表顔料塗被層用塗被液の調製において、さらに中空プラスチックピグメントの２６％分散液（商品名：ＡＥ−８５２、ＪＳＲ社製）を２０質量部添加した以外は、実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Example 7
In the preparation of the coating solution for the outermost pigment coating layer of Example 1, the example except that 20 parts by mass of a 26% dispersion of a hollow plastic pigment (trade name: AE-852, manufactured by JSR) was further added. In the same manner as in Example 1, a pigment-coated paper for printing having a basis weight of 128 g / m 2 was obtained.
実施例８
実施例１の多価金属塩水溶液の塗布において、ギ酸カルシウムの４％水溶液の代わりに、硫酸亜鉛の４％水溶液を使用した以外は、実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Example 8
Printing with a basis weight of 128 g / m 2 in the same manner as in Example 1 except that a 4% aqueous solution of zinc sulfate was used in place of the 4% aqueous solution of calcium formate in the application of the aqueous polyvalent metal salt solution of Example 1. Pigment coated paper was obtained.
実施例９
実施例１の多価金属塩水溶液の塗布において、ギ酸カルシウム水溶液の濃度を４％から１％に下げ、０．０３ｇ／ｍ２付着するように塗布した以外は、実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Example 9
In the application of the polyvalent metal salt aqueous solution of Example 1, the concentration of the calcium formate aqueous solution was reduced from 4% to 1%, and it was applied in the same manner as in Example 1 except that it was applied so as to adhere 0.03 g / m 2. A pigment-coated paper for printing with an amount of 128 g / m 2 was obtained.
実施例１０
実施例１の多価金属塩水溶液の塗布において、ギ酸カルシウム水溶液の濃度を４％から１０％に上げ、０．３ｇ／ｍ２付着するように塗布した以外は、実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Example 10
In the application of the polyvalent metal salt aqueous solution of Example 1, the basis weight was the same as in Example 1 except that the concentration of the calcium formate aqueous solution was increased from 4% to 10% and applied so as to adhere 0.3 g / m 2. A pigment-coated paper for printing with an amount of 128 g / m 2 was obtained.
実施例１１
実施例１の最表顔料塗被層用塗被液の調製において、スチレン・ブタジエン共重合体ラテックスの５０％分散液の使用量を３７質量部から３０質量部に減らした以外は実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Example 11
In the preparation of the coating solution for the outermost pigment coating layer of Example 1, the amount of the 50% dispersion of styrene / butadiene copolymer latex was reduced from 37 parts by mass to 30 parts by mass, and Example 1 Similarly, a pigment-coated paper for printing having a basis weight of 128 g / m 2 was obtained.
実施例１２
実施例１の印刷用顔料塗被紙の製造において、基紙に坪量３５０ｇ／ｍ２の非塗工板紙（商品名：コラボファイン−Ｗ、王子特殊紙社製）を使用した以外は実施例１と同様にして坪量３８４ｇ／ｍ２の印刷用顔料塗被板紙を得た。
Example 12
In the production of the pigment-coated paper for printing of Example 1, the example was used except that non-coated paperboard (trade name: Collaboration Fine-W, manufactured by Oji Specialty Paper Co., Ltd.) having a basis weight of 350 g / m 2 was used as the base paper. In the same manner as in Example 1, a pigment-coated board for printing having a basis weight of 384 g / m 2 was obtained.
比較例１
実施例１の最表顔料塗被層用塗被液の調製において、紡錘状軽質炭酸カルシウムの６３％分散液（商品名：タマパールＴＰ２２１ＧＳ、平均粒子径（短径）０．３μｍ、奥多摩工業社製）の使用量を１５９質量部から４８質量部に減らし、且つカオリン（商品名：ウルトラホワイト９０、ＢＡＳＦジャパン社製）の７０％分散液１００質量部を使用した以外は、実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Comparative Example 1
In the preparation of the coating solution for the outermost pigment coating layer of Example 1, a 63% dispersion of spindle-shaped light calcium carbonate (trade name: Tamapearl TP221GS, average particle size (minor axis) 0.3 μm, manufactured by Okutama Kogyo Co., Ltd. ) Was reduced from 159 parts by mass to 48 parts by mass, and 100 parts by mass of kaolin (trade name: Ultra White 90, manufactured by BASF Japan) was used in the same manner as in Example 1. Thus, a pigment-coated paper for printing having a basis weight of 128 g / m 2 was obtained.
比較例２
実施例１の最表顔料塗被層用塗被液の調製において、スチレン・ブタジエン共重合体ラテックスの５０％分散液の使用量を３７質量部から７４質量部に増やした以外は実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Comparative Example 2
In the preparation of the coating solution for the outermost pigment coating layer in Example 1, the amount of the 50% dispersion of the styrene / butadiene copolymer latex was increased from 37 parts by mass to 74 parts by mass, and Example 1 Similarly, a pigment-coated paper for printing having a basis weight of 128 g / m 2 was obtained.
比較例３
実施例１の最表顔料塗被層用塗被液の調製において、紡錘状軽質炭酸カルシウムの６３％分散液（商品名：タマパールＴＰ２２１ＧＳ、平均粒子径（短径）０．３μｍ、奥多摩工業社製）１５９質量部の代わりに平均粒子径１．７μｍの軽質炭酸カルシウムの６３％分散液１５９質量部を使用した以外は実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Comparative Example 3
In the preparation of the coating solution for the outermost pigment coating layer of Example 1, a 63% dispersion of spindle-shaped light calcium carbonate (trade name: Tamapearl TP221GS, average particle size (minor axis) 0.3 μm, manufactured by Okutama Kogyo Co., Ltd. ) A pigment-coated paper for printing having a basis weight of 128 g / m 2 in the same manner as in Example 1 except that 159 parts by mass of a 63% dispersion of light calcium carbonate having an average particle size of 1.7 μm was used instead of 159 parts by mass. Got.
比較例４
実施例１の内側顔料塗被層用塗被液の調製において、紡錘状軽質炭酸カルシウムの６３％分散液（商品名：タマパールＴＰ２２１ＧＳ、平均粒子径（短径）０．３μｍ、奥多摩工業社製）の使用量を１５９質量部から４８質量部に減らし、且つカオリン（商品名：ウルトラホワイト９０、ＢＡＳＦジャパン社製）の７０％分散液１００質量部を使用した以外は、実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Comparative Example 4
In the preparation of the coating solution for the inner pigment coating layer of Example 1, a 63% dispersion of spindle-shaped light calcium carbonate (trade name: Tama Pearl TP221GS, average particle size (minor axis) 0.3 μm, manufactured by Okutama Kogyo Co., Ltd.) In the same manner as in Example 1, except that 100 parts by weight of a 70% dispersion of kaolin (trade name: Ultra White 90, manufactured by BASF Japan Ltd.) was used. A pigment-coated paper for printing having a basis weight of 128 g / m 2 was obtained.
比較例５
実施例１の内側顔料塗被層用塗被液の調製において、スチレン・ブタジエン共重合体ラテックスの５０％分散液の使用量を２４質量部から４８質量部に増やした以外は実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Comparative Example 5
In the preparation of the coating solution for the inner pigment coating layer of Example 1, the same as Example 1 except that the amount of the 50% dispersion of styrene / butadiene copolymer latex was increased from 24 parts by mass to 48 parts by mass. Thus, a pigment-coated paper for printing having a basis weight of 128 g / m 2 was obtained.
比較例６
実施例１の印刷用顔料塗被紙の製造において、多価金属塩を塗布しなかった以外は実施例１と同様にして坪量１２８ｇ／ｍ２の印刷用顔料塗被紙を得た。
Comparative Example 6
In the production of the printing pigment-coated paper of Example 1, a printing pigment-coated paper having a basis weight of 128 g / m 2 was obtained in the same manner as in Example 1 except that the polyvalent metal salt was not applied.
得られた印刷用顔料塗被紙について以下の評価を行い、結果を表１に示した。 The following evaluation was performed on the obtained pigment-coated paper for printing, and the results are shown in Table 1.
「評価方法」
［塗被層表面の光沢度の測定］
得られた顔料塗被紙の表面光沢を、光沢度計（ＪＩＳ−Ｚ８７４１記載）を用い、ＪＩＳ Ｐ８１４２に従って、入射角７５度で測定した。
"Evaluation method"
[Measurement of surface gloss of coating layer]
The surface gloss of the obtained pigment-coated paper was measured at an incident angle of 75 degrees according to JIS P8142 using a gloss meter (described in JIS-Z8741).
［塗被層表面のオフセット印刷適性の評価］
（ドライピック強度）
ＲＩ印刷機（ＲＩ−１、石川島産業機械株式会社製）を用いて、試験用インキ（ベストワン紙試験用ＳＤ５０紅ＢＴ−１３、Ｔ＆Ｋ ＴＯＫＡ社製）により、ベタ印刷を行い、印刷面のピッキングの程度を目視判定した。５段階評価で５が最もよく、１が最も悪い水準であり、３が許容限度である。
[Evaluation of offset printability on the coating layer surface]
(Dry pick strength)
Using a RI printing machine (RI-1, manufactured by Ishikawajima Industrial Machinery Co., Ltd.), solid printing is performed using a test ink (SD50 Red BT-13 for Best One Paper Test, manufactured by T & K TOKA), and the printed surface is picked. The degree of was visually determined. 5 is the best in the 5-level evaluation, 1 is the worst level, and 3 is the allowable limit.
（ウェットピック強度）
上記ドライピック強度試験方法において、印刷前に水付着ロールで各印刷用顔料塗被紙表面に水を付着させた以外はドライピック強度試験方法と同様にしてウェットピック強度を評価した。
(Wet pick strength)
In the dry pick strength test method, wet pick strength was evaluated in the same manner as in the dry pick strength test method, except that water was adhered to the surface of each coated pigment-coated paper with a water adhesion roll before printing.
［塗被層表面のインクジェット印刷適性の評価］
（インク吸収性の評価）
（１）得られた顔料塗被紙を油吸収メーター自動式（ＪＩＳ Ｐ−８１３０、熊谷理機工業株式会社製）にセットする。
（２）セットした試験片上部にセロハンテープを貼付し、そのセロハンテープ上に、水性顔料インクジェットインク（大日本スクリーン社トゥループレスジェット５２０用黒インクを、マイクロシリンジを用いて、５μｌのせる。
（３）インク上に金属ローラーを通過させた後、伸ばされたインク表面の光沢感が消えるまでの時間を目視判定して、インクジェットインク吸収速度を評価した。
おおむね、５秒以内で乾燥するものが、実機プリンター適性を有すると判定した。
[Evaluation of ink-jet printability on coating layer surface]
(Evaluation of ink absorbency)
(1) The obtained pigment coated paper is set in an oil absorption meter automatic type (JIS P-8130, manufactured by Kumagaya Riki Kogyo Co., Ltd.).
(2) A cellophane tape is affixed to the upper part of the set test piece, and 5 μl of aqueous pigment inkjet ink (black ink for True Press Jet 520, Dainippon Screen Co., Ltd.) is put on the cellophane tape using a microsyringe.
(3) After passing the metal roller over the ink, the time until the glossiness of the stretched ink surface disappeared was visually judged to evaluate the ink jet ink absorption speed.
In general, it was determined that what dried within 5 seconds had suitability for an actual printer.
（初期定着性の評価）
上記インク吸収性の評価と同様にして、得られた顔料塗被紙上にインクジェットインクを塗布し、直後に指で擦り、擦らない部分との光学濃度差に対する割合でインク初期定着性を評価した。
(Evaluation of initial fixability)
In the same manner as the evaluation of the ink absorptivity, an ink-jet ink was applied onto the obtained pigment-coated paper, and immediately after rubbing with a finger, the initial ink fixability was evaluated based on the ratio to the optical density difference from the non-rubbed portion.
（耐擦過性の評価）
上記インク吸収性の評価と同様にして、得られた顔料塗被紙上にインクジェットインクを塗布し、２３℃５０％ＲＨ環境下に１日放置した後に指で擦り、擦らない部分との光学濃度差に対する割合でインク耐擦過性を評価した。
(Evaluation of scratch resistance)
In the same manner as the ink absorption evaluation described above, an inkjet ink was applied on the obtained pigment-coated paper, left for one day in an environment of 23 ° C. and 50% RH, and rubbed with a finger. The ink scratch resistance was evaluated based on the ratio of
表１が明らかに示しているように、本発明に係る印刷用顔料塗被紙は、ドライピック強度、ウェットピック強度とも優れた強度を保持し、オフセット印刷適性を有している。また高い水性顔料インクジェットインク適性も兼ね備えており、ハイブリッド印刷用紙としての適性に優れる印刷用顔料塗被紙が得られた（実施例１〜１２）。一方、最表顔料塗被層用処方、内側顔料塗被層用処方が本発明の規定からはずれる場合および最表顔料塗被層上に多価金属塩を塗布しなかった場合、ハイブリッド印刷用途に適した顔料塗被紙は得られなかった（比較例１〜６）。 As Table 1 clearly shows, the printing pigment-coated paper according to the present invention has excellent dry pick strength and wet pick strength, and has offset printing suitability. Moreover, it also has high water-based pigment inkjet ink suitability, and a pigment-coated paper for printing excellent in suitability as hybrid printing paper was obtained (Examples 1 to 12). On the other hand, when the formulation for the outermost pigment coating layer and the formulation for the inner pigment coating layer deviate from the provisions of the present invention and when the polyvalent metal salt is not applied on the outermost pigment coating layer, it is suitable for hybrid printing applications. No suitable pigment coated paper was obtained (Comparative Examples 1-6).
本発明は、オフセット印刷適性に優れ、且つ水性顔料インクを用いた高速インクジェットプリンター記録適性も備えた、ハイブリッド印刷に適したグロス系印刷用顔料塗被紙が得られるものであり、特にパッケージ分野や物流分野で実用上極めて有用なものである。 The present invention provides a gloss-coated pigment-coated paper suitable for hybrid printing, which is excellent in offset printing suitability and also has high-speed inkjet printer recording suitability using aqueous pigment ink. It is extremely useful in practice in the logistics field.
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