JP4897848B2 - Semi-gloss oil-based inkjet recording sheet - Google Patents
Semi-gloss oil-based inkjet recording sheet Download PDFInfo
- Publication number
- JP4897848B2 JP4897848B2 JP2009085822A JP2009085822A JP4897848B2 JP 4897848 B2 JP4897848 B2 JP 4897848B2 JP 2009085822 A JP2009085822 A JP 2009085822A JP 2009085822 A JP2009085822 A JP 2009085822A JP 4897848 B2 JP4897848 B2 JP 4897848B2
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- Prior art keywords
- oil
- based ink
- layer
- receiving
- ink
- 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.)
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Landscapes
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Description
本発明は、油性インクジェット記録方式に好適であり、表面の光沢度が抑制されたセミグロスタイプの油性インク用記録シートに関する。 The present invention relates to a semi-gloss type recording sheet for oil-based ink that is suitable for an oil-based ink jet recording system and has a suppressed surface glossiness.
インクジェット記録方式は、ディフレクション方式、キャビティ方式、サーモジェット方式、バブルジェット方式、サーマルインクジェット方式、スリットジェット方式、スパークジェット方式などがある。作動原理は、インクの微小液滴を飛翔させて紙などのインクジェット記録シートに付着させ、画像・文字などの記録を行うものであり、高速、低騒音、多色化が容易、記録パターンの融通性が大きいなどの特徴がある。さらに、現像−定着が不要などの長所もあり、漢字を含め各種図形、カラー画像などの記録装置として種々の用途において急速に普及している。 Examples of the ink jet recording method include a deflection method, a cavity method, a thermo jet method, a bubble jet method, a thermal ink jet method, a slit jet method, and a spark jet method. The principle of operation is that ink droplets are ejected and deposited on an ink jet recording sheet such as paper to record images and characters. High speed, low noise, easy multi-coloring, versatility of recording patterns There are features such as large nature. In addition, there is an advantage that development-fixing is unnecessary, and it is rapidly spreading in various applications as a recording apparatus for various figures including Kanji and color images.
特に、溶媒中にイエロー、マゼンタ、シアン、ブラックなどの色材を各々含有させた多色インクを用いるインクジェット記録方式によって記録された画像は、製版方式による多色印刷と比較しても遜色のない記録画像を得ることが可能である。また、安価であることから、作成部数が少ない用途においては、フルカラー画像記録分野にまで広く応用されている。 In particular, an image recorded by an ink jet recording method using multicolor inks each containing a color material such as yellow, magenta, cyan, and black in a solvent is comparable to multicolor printing by a plate making method. It is possible to obtain a recorded image. In addition, since it is inexpensive, it is widely applied to the field of full-color image recording in applications where the number of created copies is small.
このようなインクジェット記録方式の大半は、水性又は親水性溶剤との混合溶媒中に各種の水溶性染料を溶解し、必要によって各種の添加剤を配合した水性インクを使用している。水性インクは、印字後の色調が鮮やかで明るく、インクドットのコントラストが大きく、またインク粘度の調整が容易であり、安全性が高いなどの利点を有する。しかしながら、色材として水溶性染料を選択していることから、(1)インク溶媒に対する色材の溶解濃度を高めることが困難であること、(2)水への溶解性や画像の発色性と画像の保存安定性とを両立できる水性染料の設計が困難であること、などの欠点を有している。 Most of such ink jet recording methods use water-based inks in which various water-soluble dyes are dissolved in a mixed solvent with an aqueous or hydrophilic solvent and various additives are blended as necessary. Water-based ink has advantages such as vivid and bright color tone after printing, large ink dot contrast, easy adjustment of ink viscosity, and high safety. However, since a water-soluble dye is selected as the color material, (1) it is difficult to increase the concentration of the color material dissolved in the ink solvent, and (2) the solubility in water and the color development of the image It has drawbacks such as difficulty in designing an aqueous dye that can achieve both the storage stability of an image.
そこで、これらを解決する手段として、色材として、例えば、染料系として分散染料、ナフトール染料、建染染料、硫化染料を用い、顔料系としてはカーボンブラック、各種色顔料を用い、かつ、インク溶媒として、例えば、イソパラフィン類、エーテル類、可塑剤などの溶剤を用いた、油性インクが非常に有効であり、実用化されている。 Therefore, as means for solving these problems, as a color material, for example, a disperse dye, a naphthol dye, a vat dye, or a sulfur dye is used as a dye system, carbon black, various color pigments are used as a pigment system, and an ink solvent is used. For example, oil-based inks using solvents such as isoparaffins, ethers, and plasticizers are very effective and are in practical use.
一方、油性インクは、(a)油溶性染料を溶剤中に高濃度に溶解又は分散することが容易であり、銀塩写真に匹敵する高い画像濃度を実現することが可能である。(b)基本的に、水性インクに比べて耐水性が良好である、(c)水溶性染料と比較して、耐光性、耐オゾン性を考慮した染料の分子設計に自由度があるなどに、優れるのみならず、(d)インクジェット装置のヘッドノズルの目詰まりが起こり難くいなどの利点も備えている。特に耐光性、耐オゾン性が優れることから近年では大判のPOPアート、広告・ディスプレイ用途で壁紙などにも多用されている。 On the other hand, the oil-based ink (a) can easily dissolve or disperse the oil-soluble dye in a solvent at a high concentration, and can achieve a high image density comparable to a silver salt photograph. (B) Basically, water resistance is better than water-based inks, (c) compared to water-soluble dyes, there is a degree of freedom in molecular design of dyes considering light resistance and ozone resistance, etc. Not only is it excellent, but it also has the advantage that (d) clogging of the head nozzles of the ink jet apparatus is less likely to occur. In particular, since it has excellent light resistance and ozone resistance, it has been widely used in recent years as wallpaper for large-format POP art and advertising / display applications.
広告・ディスプレイ用途で壁に貼って使用される場合には、古い広告の上に新しい広告を重ねて貼って使用されるために、下層の図柄が透けないように薄い支持体を用いた場合でも、白色度を維持しつつ高い不透明度が必要とされる。 When using it on a wall for advertising / display applications, it is used by overlaying a new advertisement on top of an old advertisement, so even if a thin support is used so that the underlying pattern is not transparent High opacity is required while maintaining whiteness.
また、コックリングとは、インクジェット記録シートの支持体として用いられる上質紙、コーテッド紙の天然パルプ同士の水素結合が、水性インクの溶媒(水)によって切断されて部分的に伸延するために波打つ現象を指す。また、油性インクであっても記録シートに支持体としてプラスチックフィルムを用いた場合及び/又はインクの受容層に油溶性の樹脂を用いた場合は、印字を行った部分が膨潤し、コックリングを生じる場合がある。コックリングは、プリンターの搬送性及び/又はハンドリング性が低下するのみならず、インクジェット記録方式のプロッターで出力される図面などの精密な記録が必要な場合、特に近年における高画質な記録画像を得る場合には、好ましい現象ではない。 Cockling is a phenomenon in which hydrogen bonds between natural pulp of high-quality paper and coated paper used as a support for an ink jet recording sheet are cut by a solvent (water) of water-based ink and partially stretched. Point to. Even when oil-based ink is used, when a plastic film is used as the support for the recording sheet and / or when an oil-soluble resin is used for the ink receiving layer, the printed portion swells and cockling occurs. May occur. Cockling not only reduces the transportability and / or handling of the printer, but also obtains high-quality recorded images in recent years, especially when precise recording such as drawings output by an inkjet recording type plotter is required. In some cases, this is not a favorable phenomenon.
一方、インクジェット記録方式に用いられるインクジェット記録用紙は、(イ)印字ドットの濃度が高く色調が明るく鮮やかであること、(ロ)インクの吸収が速く印字ドットが重なった場合でもインクが流れ出したり滲んだりしないこと、(ハ)印字ドットの横方向への拡散が必要以上に大きくならないこと、(ニ)インクドットの形状が真円に近く、かつ、その周辺が滑らかでぼやけないこと、(ホ)白色度が高いことなどの要求を満たす必要がある。これらの要求を満たすために、インクジェット記録用紙は、支持体上にインク受理層を形成して、インクの定着性と画像の鮮明性を向上させたものが一般的である。前記インク受理層は、印字した後に、多量の水又は水と親水性溶剤との混合溶媒を即座に吸収し、微量な水溶性染料を効率よく定着させることが主な目的となっており、低濃度で溶解された水性インクに対して効果を発揮するように設計されている。 On the other hand, the inkjet recording paper used for the inkjet recording method is (a) the density of the printed dots is high and the color tone is bright and vivid, and (b) the ink absorbs quickly and even if the printed dots overlap. (D) The ink dots do not spread more than necessary, (d) The shape of the ink dots is close to a perfect circle, and the surrounding area is smooth and unblurred. It is necessary to satisfy requirements such as high whiteness. In order to satisfy these requirements, an ink jet recording sheet generally has an ink receiving layer formed on a support to improve ink fixability and image sharpness. The ink receiving layer mainly absorbs a large amount of water or a mixed solvent of water and a hydrophilic solvent after printing, and is mainly intended to fix a small amount of water-soluble dye efficiently. It is designed to exert an effect on aqueous ink dissolved at a concentration.
しかし、この種のインク受理層は、油溶性染料を用いた油性インクには適していない。一方、油性インクについては、前記の要求を満たすために親油性であり、また疎水性である合成非晶質シリカ又はその塩、これらを併用し、必要に応じてバインダーと共に支持体上に塗工した、油性インクに適したインク受理層を形成したインクジェット記録紙が開示されている(例えば、特許文献1及び特許文献2参照。)。これらの特許文献に開示された油性インクジェット記録紙は、シリカの親油性を利用して、シリカ表面の細孔に油性インクの油性溶媒を取り込むことで記録画像の滲みを防止している。しかし、従来の水性インク用のインクジェット記録用紙とは異なり、油性インク用の記録シートに親油性、吸油性の高い合成非晶質シリカを表層に用いた場合、インクのドット径が小さくなり過ぎ、滲みは無く高精細な画像を得ることができても、非常に画像の記録濃度が薄く、鮮明性・コントラストの劣るものとなってしまう。 However, this type of ink receiving layer is not suitable for oil-based inks using oil-soluble dyes. On the other hand, for oil-based inks, synthetic amorphous silica or a salt thereof, which is oleophilic and hydrophobic to satisfy the above requirements, is used in combination, and if necessary, coated on a support together with a binder. Ink jet recording paper having an ink receiving layer suitable for oil-based ink is disclosed (see, for example, Patent Document 1 and Patent Document 2). The oil-based ink jet recording paper disclosed in these patent documents uses the lipophilicity of silica to prevent bleeding of recorded images by incorporating an oily solvent of oil-based ink into pores on the silica surface. However, unlike conventional water-based ink-jet recording paper, when the surface of the recording layer for oil-based ink is made of synthetic amorphous silica having high lipophilicity and oil-absorbing property, the dot diameter of the ink becomes too small. Even if a high-definition image without blurring can be obtained, the recording density of the image is very thin and the sharpness and contrast are inferior.
また、近年では記録される画像に高級感、又は写真類似の品質を付与するために、その表面を平滑にして光沢層を設けることが行われているが、一方で、その光沢層の光沢度はその用途や見るものの嗜好によって変化する。すなわち、光沢度が高い記録媒体だけで無く、表面の光沢がある程度抑制されたセミグロスタイプと呼ばれる記録媒体が望まれる。特に屋外や屋内でも照明の強い状態で使用されるディスプレイ、ポスター用途で用いた場合に、光沢度が高いと、観賞する角度によって光が散乱し、見づらくなってしまうことがある。記録画像の鮮明性を得るために、インク受理層に比表面積が大きく、吸油量を抑えたシリカを用いることによって、印字された油性インクのドット径を大きくし、所定の画像濃度を得る方法が開示されている(例えば、特許文献3参照。)。しかし、光を散乱しないマット調の油性インクジェット用の記録媒体では、やはり画像の鮮明性が低く、鮮やかさに劣り、特にディスプレイ用途では採用できない。このような理由からセミグロスタイプの記録媒体が切望されている。 In recent years, in order to give a recorded image a high-class feeling or a photographic-like quality, a glossy layer is provided by smoothing the surface. Changes depending on its use and preference of what it sees. That is, not only a recording medium having a high glossiness but also a recording medium called a semi-gloss type in which the surface gloss is suppressed to some extent is desired. In particular, when used in displays or posters that are used outdoors or indoors with strong illumination, if the glossiness is high, light may be scattered depending on the viewing angle, making it difficult to see. In order to obtain the clearness of the recorded image, there is a method for obtaining a predetermined image density by increasing the dot diameter of the printed oil-based ink by using silica having a large specific surface area and a reduced oil absorption amount in the ink receiving layer. (For example, refer to Patent Document 3). However, a matte oil-based ink jet recording medium that does not scatter light still has low image clarity and inferior vividness, and cannot be used particularly for display applications. For these reasons, a semi-gloss type recording medium is desired.
本発明の目的は、溶媒としてイソパラフィン類、エーテル類、いわゆる可塑剤と呼ばれているような油性溶剤を用い、かつ、油性インク特有の色材を用いた油性インクに対して、画像濃度が高く、インク吸収性に優れ、かつ、ディスプレイ、広告ポスター、壁紙用途に適した光沢感を有するセミグロスタイプの油性インク用インクジェット記録シートを提供することにある。 An object of the present invention is to use an oil-based solvent as a solvent called isoparaffins, ethers, so-called plasticizers, and has a higher image density than an oil-based ink using a color material peculiar to oil-based inks. Another object of the present invention is to provide a semi-gloss type ink jet recording sheet for oil-based inks that has excellent ink absorbability and has a glossiness suitable for displays, advertisement posters, and wallpaper applications.
この油性インクに用いられる色材として、例えば、油溶性染料としてナフトール染料、アゾ染料、金属錯塩染料、アントラキノン染料、キノイミン染料、インジゴ染料、シアニン染料、キノリン染料、ニトロ染料、ニトロソ染料、ベンゾキノン染料、カーボニウム染料、ナフトキノン染料、ナフタルイミド染料、フタロシアニン染料、ペリニン染料などを挙げることができる。また、顔料としてはカーボンブラック、各種色顔料が使用されており、また有機顔料として不溶性アゾ顔料、縮合アゾ顔料、キレートアゾ顔料、ペリノン顔料、ニトロ顔料、ニトロソ顔料、ペリレン顔料、アニリンブラックを挙げることができる。 Coloring materials used in this oil-based ink include, for example, naphthol dyes, azo dyes, metal complex dyes, anthraquinone dyes, quinoimine dyes, indigo dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes as oil-soluble dyes, Examples thereof include carbonium dyes, naphthoquinone dyes, naphthalimide dyes, phthalocyanine dyes, and perinine dyes. In addition, carbon black and various color pigments are used as pigments, and examples of organic pigments include insoluble azo pigments, condensed azo pigments, chelate azo pigments, perinone pigments, nitro pigments, nitroso pigments, perylene pigments, and aniline black. it can.
本発明者等は、セミグロス油性インクジェット用記録シートの前記問題点について鋭意研究を重ねた結果、支持体表面上に特定のガラス転移温度をもつ塩化ビニル−アクリル共重合体を主体とする油性インク受容光沢層を形成することで従来の油性インク用記録シートに要求される品質を有しつつ、高い印字濃度と光沢感による画像の高い鮮明性を達成できることを見出した。しかも支持体と油性インク受容光沢層との間に非晶質シリカを含有するインク受容層を設けることで、更に良好なインク吸収性を得られることを見出した。 As a result of earnest research on the above-mentioned problems of the semi-gloss oil-based ink jet recording sheet, the present inventors have received an oil-based ink mainly composed of a vinyl chloride-acrylic copolymer having a specific glass transition temperature on the support surface. It has been found that by forming a glossy layer, it is possible to achieve high image density and high image clarity due to glossiness while maintaining the quality required for conventional recording sheets for oil-based inks. Furthermore, it has been found that by providing an ink receiving layer containing amorphous silica between the support and the oil-based ink receiving glossy layer, even better ink absorbability can be obtained.
第1の解決手段は、支持体の少なくとも一方の面に形成される油性インク受容光沢層にガラス転移温度が20〜55℃の塩化ビニル−アクリル共重合体樹脂を用いたものである。この構成によって、光沢感を有し、表面に無数のヒビ割れを発生させることによって、良好な油性インクの吸収を得ることができ、更に印字後は油性インクの溶媒を吸収、膨潤した塩化ビニル−アクリル共重合樹脂層のひび割れの隙間が小さくなることで、印字光沢も損なうことのないセミグロス油性インクジェット記録シートである。また、塩化ビニル−アクリル共重合体樹脂が膨潤した場合も、このひび割れが埋まるだけであるため、油性インク受容光沢層が油性インクで膨潤してもコックリングを抑えることができるセミグロス油性インクジェット記録シートである。 In the first solution, a vinyl chloride-acrylic copolymer resin having a glass transition temperature of 20 to 55 ° C. is used for the oil-based ink-receiving glossy layer formed on at least one surface of the support. With this configuration, it is possible to obtain good oil-based ink absorption by generating countless cracks on the surface, and after printing, the vinyl chloride that has absorbed and swollen the solvent of the oil-based ink can be obtained. This is a semi-gloss oil-based ink jet recording sheet in which the cracks in the acrylic copolymer resin layer are reduced and the print gloss is not impaired. Further, even when the vinyl chloride-acrylic copolymer resin swells, only the cracks are filled, so that the semi-gloss oil-based ink jet recording sheet that can suppress cockling even if the oil-based ink receiving glossy layer swells with the oil-based ink. It is.
第2の解決手段は、支持体と油性インク受容光沢層との間に少なくとも非晶質シリカ、水溶性高分子接着剤を含有するインク吸収層を設けたものである。 In the second solution, an ink absorbing layer containing at least amorphous silica and a water-soluble polymer adhesive is provided between the support and the oil-based ink receiving glossy layer.
第3の解決手段は、更に水溶性高分子樹脂を主体とする油性インク浸透防止層を支持体と油性インク受容光沢層の間、又は支持体とインク受容層との間に設けたものである。 In the third solution, an oil-based ink permeation preventive layer mainly composed of a water-soluble polymer resin is provided between the support and the oil-based ink receiving glossy layer or between the support and the ink receiving layer. .
第4の解決手段は、支持体上の油性インク受容光沢層と反対の面に、少なくともノニオン性直接着色色顔料又は染料と非水溶性樹脂とを含有するバックコート液を塗布し、JIS P 8149:2005「紙及び板紙−不透明度試験方法」に規定する不透明度が97%以上で、かつ、油性インク受容光沢層面がJIS P 8148:2001「紙、板紙及びパルプ−ISO白色度の測定方法」に規定する白色度が83%以上としたものである。 A fourth solution is to apply a backcoat solution containing at least a nonionic directly colored color pigment or dye and a water-insoluble resin to the surface of the support opposite to the oil-based ink-receiving glossy layer. JIS P 8149 : 2005 “Paper and paperboard—Opacity test method” has an opacity of 97% or more, and the oil-based ink receptive gloss layer surface is JIS P 8148: 2001 “Paper, paperboard and pulp—ISO whiteness measurement method” The whiteness specified in the above is 83% or more.
本発明に係わるセミグロス油性インクジェット記録シートは、このような構成によって油性インクを用いたインクジェットプリンターの油性インクの吸収性と発色性、光沢感に優れ高画質な記録が可能である。油性インク受容光沢層は、多数のヒビ割れを有していることからインク吸収性に優れるだけでなく、印字後に油性インクの溶媒を吸収し、油性インク受容光沢層が膨潤した場合にも、ひび割れが小さくなることによってコックリングの発生を抑制し、かつ、印字後についても光沢感を損なうことのない印字画像を得ることができる。また、支持体と油性インク受容光沢層との間に少なくとも非晶質シリカ、水溶性高分子を含有するインク吸収層を設けることで、より良好な溶剤インク吸収性が得ることができ、かつ、支持体にプラスチックフィルム、合成繊維シートを用いた場合でもコックリングを抑制することが可能となる。さらに、水溶性高分子樹脂を主体とする油性インク浸透防止層を支持体と油性インク受容光沢層の間、又は支持体とインク受容層の間に設けることでコックリングを完全に抑えることかできる。さらに、支持体上の油性インク受容光沢層と反対の面にノニオン性直接染色色顔料又は染料と非水溶性樹脂とを用いたバックコート層を設けることで、壁紙、ポスター用途で重ねて使用した場合の下層の図柄が透けるのを防止することができる。 With such a configuration, the semi-gloss oil-based ink jet recording sheet according to the present invention is excellent in absorbability, color developability, and glossiness of an oil-based ink of an ink-jet printer using oil-based ink, and enables high-quality recording. The oil-based ink receptive glossy layer not only has excellent ink absorbability because it has a large number of cracks, but it also absorbs the solvent of the oil-based ink after printing and causes the oil-based ink receptive glossy layer to swell. As a result of the decrease, the occurrence of cockling can be suppressed, and a printed image that does not impair the gloss after printing can be obtained. Further, by providing an ink absorbing layer containing at least amorphous silica and a water-soluble polymer between the support and the oil-based ink receiving glossy layer, better solvent ink absorbability can be obtained, and Cockling can be suppressed even when a plastic film or a synthetic fiber sheet is used for the support. Further, cockling can be completely suppressed by providing an oil-based ink permeation preventive layer mainly composed of a water-soluble polymer resin between the support and the oil-based ink receiving glossy layer or between the support and the ink receiving layer. . Furthermore, a back coat layer using a nonionic direct dyeing color pigment or dye and a water-insoluble resin was provided on the surface opposite to the oil-based ink-receptive glossy layer on the support, which was used repeatedly for wallpaper and poster applications. It is possible to prevent the lower layer of the case from being seen through.
次に本発明を詳細に説明するが、本発明はこれら実施形態に限定されるものではない。 Next, the present invention will be described in detail, but the present invention is not limited to these embodiments.
本発明の油性インク受容光沢層に使用される樹脂は、塩化ビニル−アクリル共重合体であり、ガラス転移温度が20〜55℃であり、好ましくは25〜50℃であり、より好ましくは30〜50℃である。塗工・乾燥時に塩化ビニル−アクリル共重合体粒子が溶融・増膜化し、表面にヒビ割れが形成されるように乾燥を行う。ガラス転移温度が20℃未満では、塗布・乾燥後にもタック感が有り、巻き取ったときなどにブロッキングが発生するほか、加工工程でも扱いづらい。55℃を超える場合では、塗工・乾燥の熱で塩化ビニル−アクリル共重合体粒子が増膜、ヒビ割れし難く、粒子状のまま乾燥されるためインク吸収性に劣り、インク量が少ないパターンででは比較的問題にならないが、インク量の多い画像パターンでは画像境界部に滲みや吸収ムラを生じたり、インクの乾燥性が悪く、巻き取ったときに裏面に転写を生じたりしてしまう。また、乾燥温度を上げた場合には、ポリオレフィン系プラスチックフィルム、合成繊維など低融点樹脂シートへの塗布が困難となる。 The resin used for the oil-based ink receptive gloss layer of the present invention is a vinyl chloride-acrylic copolymer, and has a glass transition temperature of 20 to 55 ° C, preferably 25 to 50 ° C, more preferably 30 to 30 ° C. 50 ° C. Drying is performed so that the vinyl chloride-acrylic copolymer particles melt and increase in thickness during coating and drying, and cracks are formed on the surface. When the glass transition temperature is less than 20 ° C., there is a feeling of tack even after coating and drying, blocking occurs when wound up, and it is difficult to handle even in the processing step. When the temperature exceeds 55 ° C., the vinyl chloride-acrylic copolymer particles are not thickened or cracked by the heat of coating and drying, and are dried in the form of particles, resulting in poor ink absorbability and a small amount of ink. However, in an image pattern with a large amount of ink, bleeding or uneven absorption occurs in the image boundary portion, or the drying property of the ink is poor, and transfer is generated on the back surface when wound up. In addition, when the drying temperature is raised, it becomes difficult to apply to a low melting point resin sheet such as a polyolefin-based plastic film or synthetic fiber.
本発明で使用される塩化ビニル−アクリル共重合体は、ブロック共重合体でも交互共重合体でもよい。塩化ビニル−アクリル共重合体を構成する塩化ビニルモノマー単位又は塩化ビニル重合体ブロックの塩化ビニルモノマー単位とアクリルモノマー単位又はアクリル重合体ブロックのアクリルモノマーとの組成質量比率は90:10〜60:40、特に85:15〜65:35、中でも80:20〜70:30であるのが好ましい。塩化ビニル−アクリル共重合樹脂中の塩化ビニル単位とアクリルモノマー単位との組成質量比率が90:10〜60:40の範囲から外れて、>90:10である場合では、油性インクに対する膨潤性は良好となり、樹脂への染着性は高いものの、印字後に膨潤した樹脂層の固化が遅く、結果的にインク吸収不良のように巻き取ったときに支持体裏面への画像転写、ブロッキングなどを発生し易い。<60:40の場合には、油性インクに対する樹脂の膨潤性が悪く、インク吸収不良や滲みを生じて鮮明画像を得られない。 The vinyl chloride-acrylic copolymer used in the present invention may be a block copolymer or an alternating copolymer. The composition mass ratio of the vinyl chloride monomer unit constituting the vinyl chloride-acrylic copolymer or the vinyl chloride monomer unit of the vinyl chloride polymer block and the acrylic monomer unit or the acrylic monomer of the acrylic polymer block is 90:10 to 60:40. In particular, 85:15 to 65:35, particularly 80:20 to 70:30 is preferable. In the case where the composition mass ratio of the vinyl chloride unit and the acrylic monomer unit in the vinyl chloride-acrylic copolymer resin is out of the range of 90:10 to 60:40 and> 90:10, the swelling property with respect to the oil-based ink is Although it is good and dyeability to the resin is high, solidification of the swollen resin layer after printing is slow, resulting in image transfer to the back of the support, blocking, etc. when wound up like poor ink absorption Easy to do. In the case of <60:40, the swelling property of the resin with respect to the oil-based ink is poor, and ink absorption failure or bleeding occurs, so that a clear image cannot be obtained.
アクリルモノマー又はアクリル重合体ブロックを構成するアクリルモノマーは、アクリル酸、アルキル基中炭素原子数1〜14の(メタ)アクリル酸アルキルエステル、例えば、次に挙げるものに限定しないが、例にはメチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、プロピルアクリレート、プロピルメタクリレート、n−ブチルアクリレート、n−ブチルメタクリレート、n−ペンチルアクリレート、n−ヘキシルアクリレート、n−ヘキシルメタクリレート、n−ヘプチルアクリレート、n−オクチルアクリレート、n−ノニルアクリレート、ラウリルアクリレート、ステアリルアクリレート、ステアリルメタクリレート、ベヘニルアクリレート及びそれらの分岐した異性体、例えば2−エチルヘキシルアクリレートがある。 The acrylic monomer or the acrylic monomer constituting the acrylic polymer block is not limited to acrylic acid, alkyl group (meth) acrylic acid alkyl ester having 1 to 14 carbon atoms in the alkyl group, for example, but examples include methyl Acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-hexyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-octyl Acrylate, n-nonyl acrylate, lauryl acrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate and their branched isomers, such as 2-ethyl There is hexyl acrylate.
塩化ビニル−アクリル共重合体に代えて、塩化ビニル−酢酸ビニル共重合体樹脂を用いた場合には、塩化ビニル−アクリル共重合体を使用した場合の前記組成質量比が>90:10である場合と同様な欠点が生じる。さらに、塩化ビニル−アクリル共重合体に代えて、従来、公知のポリビニルアルコール、ポリビニルピロリドン等の水溶性高分子及び/又はブタジエン系ラテックスを用いた場合も、油性インクの吸収不良及び/又は画像濃度の低下が見られた。これは、これらの樹脂が基本的に油性インクとの親和性に欠けるために満足な膨潤、染着が行われなかったためと推測される。 When a vinyl chloride-vinyl acetate copolymer resin is used instead of the vinyl chloride-acrylic copolymer, the composition mass ratio when the vinyl chloride-acrylic copolymer is used is> 90:10. The same disadvantages occur. Furthermore, in place of a vinyl chloride-acrylic copolymer, conventionally known water-soluble polymers such as polyvinyl alcohol and polyvinyl pyrrolidone and / or butadiene-based latex may also be used to cause poor absorption of oil-based ink and / or image density. Decrease was observed. This is presumably because satisfactory swelling and dyeing were not performed because these resins basically lacked affinity with oil-based inks.
本発明における油性インク受容光沢層は、発明を損なわない範囲であればスーパーカレンダー、グロスカレンダーなどのカレンダー装置を用い光沢感を高めることができる。 The oil-based ink-receiving glossy layer in the present invention can enhance glossiness by using a calendar device such as a super calender or a gloss calender as long as the invention is not impaired.
本発明における油性インク受容光沢層には、発明を損なわない範囲で必要に応じて、架橋剤、増粘剤、流動性改良剤、消泡剤、抑泡剤、分散剤、酸化防止剤、pH調整剤等を添加できる。さらに、色調を調整する着色顔料、染料、蛍光染料なども添加することが可能である。ただし、非晶質シリカ、炭酸カルシウム等の無機顔料を油性インク受容光沢層に配合した場合は、光沢感を損なうばかりでなく、油性インクが浸透したときに塩化ビニル−アクリル共重合体が膨潤するのを阻害するため、配合には光沢感とインク吸収性への注意が必要である。 In the oil-based ink receptive glossy layer of the present invention, a crosslinking agent, a thickener, a fluidity improver, an antifoaming agent, a defoaming agent, a dispersing agent, an antioxidant, pH are added as necessary without departing from the scope of the invention. A regulator or the like can be added. Furthermore, it is possible to add coloring pigments, dyes, fluorescent dyes and the like for adjusting the color tone. However, when an inorganic pigment such as amorphous silica or calcium carbonate is added to the oil-based ink-receiving glossy layer, not only the glossiness is impaired, but also the vinyl chloride-acrylic copolymer swells when the oil-based ink penetrates. In order to prevent this, it is necessary to pay attention to glossiness and ink absorbency when blending.
本発明のインク受容層に使用される非晶質シリカとしては、一般的に沈降法又はゲル法シリカが挙げられ、多孔性でインクの吸収性が高く、鮮明な発色を可能とする。平均粒子径としてはレーザー回折・散乱法による平均粒子径で1〜25μmが用いられるが、好ましくは3〜20μm、より好ましくは5〜12μmである。平均粒子径が1μm未満の場合は、塗工層の強度が大きく低下し、また塗工液の粘度も大きく上昇し製造工程での負担となる。また25μmを超える平均粒子径の場合は、インク受容層上に油性インク受容光沢層を設けた場合にも光沢感を得られないばかりでなく、用途によっては印字後に表面にラミネート処理を行うときに、平滑性が低いために記録シートとラミネートフィルムの間に空隙が生じるなどのトラブルが発生する。また、必要に応じてシリカ以外の微粒子も併用することが可能である。これらの微粒子としては、カオリナイト、タルク、軽質炭酸カルシウム、重質炭酸カルシウム、ゼオライト、アルミナ、硫酸バリウム、カーボンブラック、酸化亜鉛、硫酸亜鉛、炭酸亜鉛、二酸化チタン、サチンホワイト、珪酸アルミニウム、ケイソウ土、珪酸カルシウム、水酸化アルミニウム、炭酸マグネシウム、水酸化マグネシウム等の無機系微粒子など、アクリル又はメタアクリル系、塩化ビニル系、酢酸ビニル系、ナイロン、スチレン−アクリル系、スチレン−ブタジエン系、ポリスチレン−アクリル系、ポリスチレン系、ウレタン系、ポリエステル系等の有機系微粒子など、一般に紙塗工に用いられている微粒子が挙げられる。 As the amorphous silica used in the ink receiving layer of the present invention, precipitation method or gel method silica is generally used, and it is porous, has high ink absorbability, and enables clear color development. As an average particle diameter, 1-25 micrometers is used by the average particle diameter by a laser diffraction and a scattering method, Preferably it is 3-20 micrometers, More preferably, it is 5-12 micrometers. When the average particle diameter is less than 1 μm, the strength of the coating layer is greatly reduced, and the viscosity of the coating solution is also greatly increased, which is a burden in the production process. Further, in the case of an average particle diameter exceeding 25 μm, not only glossiness is not obtained even when an oil-based ink receptive gloss layer is provided on the ink receptive layer. Moreover, troubles such as a gap between the recording sheet and the laminate film occur due to low smoothness. Further, fine particles other than silica can be used in combination as required. These fine particles include kaolinite, talc, light calcium carbonate, heavy calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, titanium dioxide, satin white, aluminum silicate, diatomaceous earth. , Inorganic fine particles such as calcium silicate, aluminum hydroxide, magnesium carbonate, magnesium hydroxide, acrylic or methacrylic, vinyl chloride, vinyl acetate, nylon, styrene-acrylic, styrene-butadiene, polystyrene-acrylic Fine particles generally used for paper coating, such as organic fine particles such as polyethylene, polystyrene, urethane, and polyester.
インク受容層に用いられる非水溶性高分子樹脂としては、例えば塩化ビニル及びその共重合体、スチレン−ブタジエン共重合体、メチルメタクリレート−ブタジエン共重合体等の共役ジエン系重合体ラテックス、アクリル酸エステル若しくはメタクリル酸エステルの重合体若しくは共重合体等のアクリル系重合体ラテックス、エチレン−酢酸ビニル共重合体等のビニル系重合体ラテックス、又はこれらの各種重合体のカルボキシル基、カチオン性基等の官能基含有変性重合体ラテックス、更にそれらのブレンド等が適用可能である。 Examples of the water-insoluble polymer resin used in the ink-receiving layer include conjugated diene polymer latexes such as vinyl chloride and copolymers thereof, styrene-butadiene copolymers, methyl methacrylate-butadiene copolymers, and acrylate esters. Or acrylic polymer latex such as polymer or copolymer of methacrylic acid ester, vinyl polymer latex such as ethylene-vinyl acetate copolymer, or functionalities such as carboxyl group and cationic group of these various polymers Group-containing modified polymer latexes and blends thereof can be applied.
インク受容層に用いられる水溶性高分子樹脂としては、ポリビニルアルコール、澱粉、ゼラチン、カゼイン、ポリビニルピロリドン、その各種変性体などが挙げられるが価格の面からポリビニルアルコールが好ましい。鹸化度90モル%未満のいわゆる部分鹸化タイプは、塗膜耐水性に劣る他、非常に泡立ち易く、通常の塗工装置では連続して美麗な塗工面を得難い。このことから鹸化度としては、90モル%以上のものが好ましい。配合量としては、インク受容層に占める割合として5〜25質量%が好ましく、より好ましくは7〜20質量%である。 Examples of the water-soluble polymer resin used in the ink receiving layer include polyvinyl alcohol, starch, gelatin, casein, polyvinyl pyrrolidone, and various modified products thereof, but polyvinyl alcohol is preferable from the viewpoint of price. The so-called partial saponification type having a saponification degree of less than 90 mol% is inferior in water resistance of the coating film and is very easy to foam, and it is difficult to obtain a beautiful coating surface continuously with a normal coating apparatus. Therefore, the saponification degree is preferably 90 mol% or more. The blending amount is preferably 5 to 25% by mass, more preferably 7 to 20% by mass as a proportion of the ink receiving layer.
インク受容層には、本発明を損なわない範囲で必要に応じて、架橋剤、カチオン性樹脂、増粘剤、流動性改良剤、消泡剤、抑泡剤、分散剤、酸化防止剤、pH調整剤等を添加できる。 In the ink-receiving layer, a crosslinking agent, a cationic resin, a thickener, a fluidity improver, an antifoaming agent, a foam suppressor, a dispersant, an antioxidant, pH, as necessary, as long as the present invention is not impaired. A regulator or the like can be added.
インク受容層における非晶質シリカの役割としては、油性インク及びその溶媒の吸収である。そして、非水溶性高分子樹脂と水溶性樹脂の役割としては、非晶質シリカ及び無機顔料の結着させるものである。このとき、水溶性高分子樹脂は、油性インクの溶媒によって非水溶性高分子樹脂が膨潤し、記録シート全体がコックリングするのを抑制するものである。 The role of amorphous silica in the ink receiving layer is absorption of oil-based ink and its solvent. The role of the water-insoluble polymer resin and the water-soluble resin is to bind amorphous silica and an inorganic pigment. At this time, the water-soluble polymer resin prevents the water-insoluble polymer resin from swelling due to the solvent of the oil-based ink and causing the entire recording sheet to cock.
本発明は、プラスチックフィルムや合成繊維を支持体に用いた場合に油性インクの溶媒が、支持体を膨潤させコックリングするのを防ぐために、水溶性高分子樹脂を主体とした油性インク浸透防止層を設けることができる。油性インク浸透防止層に用いられる水溶性高分子としては、ポリビニルアルコール、澱粉、ゼラチン、カゼイン、ポリビニルピロリドン、その各種変性体などが挙げられるが、価格及び増膜性の面からポリビニルアルコールが好ましい。鹸化度90モル%未満のいわゆる部分鹸化タイプは、塗膜耐水性に劣る他、非常に泡立ち易く、通常の塗工装置では連続して美麗な塗工面を得難い。このことから鹸化度としては、90モル%以上のものが好ましい。 The present invention relates to an oil-based ink permeation preventive layer mainly composed of a water-soluble polymer resin in order to prevent the solvent of an oil-based ink from swelling and cockling when a plastic film or synthetic fiber is used for the support. Can be provided. Examples of the water-soluble polymer used in the oil-based ink permeation preventive layer include polyvinyl alcohol, starch, gelatin, casein, polyvinyl pyrrolidone, and various modified products thereof. Polyvinyl alcohol is preferred from the viewpoint of price and film-thickness. The so-called partial saponification type having a saponification degree of less than 90 mol% is inferior in water resistance of the coating film and is very easy to foam, and it is difficult to obtain a beautiful coating surface continuously with a normal coating apparatus. Therefore, the saponification degree is preferably 90 mol% or more.
油性インク浸透防止層には本発明を損なわない範囲で必要に応じて、架橋剤、増粘剤、流動性改良剤、消泡剤、抑泡剤、分散剤、酸化防止剤、pH調整剤等を添加できる。また、ブロッキング防止のために各種微粒子を配合することも可能である。さらに、色調を調整する着色顔料、染料、蛍光染料なども添加することが可能である。 In the oil-based ink permeation preventive layer, a crosslinking agent, a thickener, a fluidity improver, an antifoaming agent, an antifoaming agent, a dispersant, an antioxidant, a pH adjusting agent, etc. Can be added. It is also possible to mix various fine particles to prevent blocking. Furthermore, it is possible to add coloring pigments, dyes, fluorescent dyes and the like for adjusting the color tone.
本発明の支持体は、特に限定されるものではなく、天然紙、プラスチックフィルム、合成紙、不織布、布、木材、金属薄膜等が挙げられ、用途に応じて選定される。用途によって支持体にも耐水性を求める場合には、プラスチックフィルム又は合成繊維からなる合成紙、不織布などのシートの方が好ましい。プラスチックフィルムとしては、例えばポリエステルフィルム、ポリプロピレンフィルム、ポリエチレンフィルム、ナイロン、ビニロン、アクリル等のプラスチックフィルム又はシートの貼り合わせたものが挙げられる。プラスチックフィルムは、強度の点から一軸乃至二軸延伸されていることが好ましい。不織布としては、ポリエチレン繊維をシート状に散布し、熱圧着させてシート状に形成したものなどが上げられる。 The support of the present invention is not particularly limited, and examples thereof include natural paper, plastic film, synthetic paper, non-woven fabric, cloth, wood, metal thin film, and the like, and are selected according to use. When water resistance is also required for the support depending on the application, a sheet such as a synthetic paper or nonwoven fabric made of a plastic film or synthetic fiber is preferred. Examples of the plastic film include a polyester film, a polypropylene film, a polyethylene film, a plastic film such as nylon, vinylon, and acrylic, or a laminate of sheets. The plastic film is preferably uniaxially or biaxially stretched from the viewpoint of strength. Examples of the non-woven fabric include those formed by spreading polyethylene fibers in a sheet shape and thermocompression bonding to form a sheet shape.
本発明の支持体裏面に設けるバックコート層に用いる着色顔料は、ノニオン性に限定される。イオン性のある着色顔料は、凝集し易く色斑の原因となる。本発明における着色顔料を配合したバック層は、広告ポスターや壁紙用途などで重ね貼りしたときの下層の図柄が透けて見えるのを防止するためである。重ね貼りするときには、主に水溶性の接着剤が裏面に塗布されるため、着色顔料を支持体に固着する樹脂としては、非水溶性樹脂が好ましい。非水溶性樹脂としては、スチレン−ブタジエン共重合体、メチルメタクリレート−ブタジエン共重合体等の共役ジエン系重合体ラテックス、アクリル酸エステル若しくはメタクリル酸エステルの重合体又は共重合体等のアクリル系重合体ラテックス、エチレン−酢酸ビニル共重合体等のビニル系重合体ラテックスが挙げられる。 The color pigment used for the back coat layer provided on the back surface of the support of the present invention is limited to nonionic properties. An ionic coloring pigment easily aggregates and causes color spots. The back layer containing the color pigment in the present invention is to prevent the lower layer pattern from being seen through when it is overlaid for advertisement posters or wallpaper applications. When overlaying, a water-soluble adhesive is mainly applied to the back surface, and therefore a water-insoluble resin is preferable as the resin for fixing the color pigment to the support. Examples of water-insoluble resins include conjugated diene polymer latex such as styrene-butadiene copolymer and methyl methacrylate-butadiene copolymer, acrylic polymer such as acrylate ester or methacrylate ester polymer, or copolymer. Examples thereof include latex polymer and vinyl polymer latex such as ethylene-vinyl acetate copolymer.
また、先に記した着色顔料を配合したバックコート層を設けない場合であっても、一般的に公知でカール防止や浸透防止、摩擦適性改善等の目的に応じてバックコート層を設けることができる。 Further, even when the back coat layer containing the color pigment described above is not provided, it is generally known that a back coat layer may be provided for the purpose of preventing curling, preventing penetration, improving frictional properties, etc. it can.
支持体上に構成される油性インク受容光沢層、インク受容層、油性インク浸透防止層の各塗工量は、本発明における層構成、使用する支持体及びその用途によって異なるが、経済的にも不必要に多くする必要は無く、好適な例を挙げれば、乾燥後の質量で油性インク受容光沢層が3〜30g/m2、好ましくは5〜25g/m2である。3g/m2未満の場合は、光沢度に劣り、また均一な光沢面が得られない、30g/m2を超える場合には均一な光沢面を得ることができるが、コスト的に不経済である。インク受容層は、3〜20g/m2、好ましくは5〜15g/m2である。インク受容層が3g/m2未満の場合には、工程数の増加に比してインク吸収性の改善効果が低く、またプラスチックフィルムや樹脂繊維を用いた不織布を用いた場合に、印字時にコックリングを生じ易い。20g/m2を超える場合には、受容層の強度が低下してしまうという問題が生じる。油性インク浸透防止層は、0.5〜10g/m2、好ましくは1〜5g/m2である。油性インク浸透防止層が0.5g/m2未満の場合は、プラスチックフィルムや樹脂繊維を用いた不織布を用いたときに、印字時のコックリング防止効果に劣る。10g/m2を超える場合には、品質上に大きな問題とはならないが、コスト的に不経済である。 The coating amounts of the oil-based ink-receiving glossy layer, ink-receiving layer, and oil-based ink permeation-preventing layer formed on the support vary depending on the layer structure in the present invention, the support to be used and its use, but also economically. unnecessarily need to increase without, by way of preferred example, oil-based ink receptive glossy layer is 3 to 30 g / m 2 in weight after drying is preferably 5 to 25 g / m 2. If it is less than 3 g / m 2 , the glossiness is inferior and a uniform glossy surface cannot be obtained. If it exceeds 30 g / m 2 , a uniform glossy surface can be obtained, but this is uneconomical in terms of cost. is there. The ink receiving layer is 3 to 20 g / m 2 , preferably 5 to 15 g / m 2 . When the ink receiving layer is less than 3 g / m 2 , the effect of improving ink absorbency is low as compared with the increase in the number of steps, and when a non-woven fabric using a plastic film or resin fiber is used, the ink absorption layer is reduced during printing. It is easy to produce a ring. When it exceeds 20 g / m 2 , there arises a problem that the strength of the receiving layer is lowered. Oil ink permeation preventing layer, 0.5~10g / m 2, preferably from 1 to 5 g / m 2. When the oil-based ink penetration preventing layer is less than 0.5 g / m 2 , the effect of preventing cockling during printing is inferior when a non-woven fabric using a plastic film or resin fiber is used. If it exceeds 10 g / m 2 , it will not be a major problem in quality, but it is uneconomical in terms of cost.
支持体上に油性インク受容光沢層、インク受容層、油性インク浸透防止層、バックコート層を設ける方法としては、特に限定されるものではなく、従来から公知のグラビアコート方式、キスコート方式、ディップ方式、スプレイコート方式、カーテンコート方式、エアナイフコート方式、ブレードコート方式、リバースロールコート方式、バーコート方式などの塗工機によって設けることができる。
[実施例]
The method for providing the oil-based ink receiving glossy layer, the ink receiving layer, the oil-based ink permeation preventing layer, and the backcoat layer on the support is not particularly limited, and conventionally known gravure coating method, kiss coating method, dip method. , Spray coating method, curtain coating method, air knife coating method, blade coating method, reverse roll coating method, bar coating method and the like.
[Example]
実施例を挙げて本発明をより具体的に説明するが、本発明はこれによって限定されるものではない。なお、実施例、比較例において部、%及び質量%とあるのは、すべて乾燥後の固形分換算での数値を示す。 The present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “part”, “%”, and “mass%” all indicate numerical values in terms of solid content after drying.
<紙支持体の作成>
LBKP(広葉樹晒クラフトパルプ)100部(カナディアンスタンダードフリーネス:CSF=500ml)のパルプスラリーに、パルプに対し、カチオン澱粉1.0部、タルク5.0部、酸性ロジンサイズ剤0.2部、液体硫酸バンド1部を添加し調製した紙料を長網式抄紙機で抄紙し、坪量110g/m2の原紙に酸化澱粉(商品名:王子エースA、王子コーンスターチ社製)6%をサイズプレスによって乾燥塗布量が片面当たり1.5g/m2となるようにオンマシンで塗布し、シリンダードライヤーで乾燥し紙支持体を得た。
<Creation of paper support>
To 100 parts of LBKP (hardwood bleached kraft pulp) (Canadian Standard Freeness: CSF = 500 ml) pulp slurry, 1.0 part of cationic starch, 5.0 parts of talc, 0.2 part of acidic rosin sizing agent, liquid Paper stock prepared by adding 1 part of sulfuric acid band is made with a long net paper machine, and 6% of oxidized starch (trade name: Oji Ace A, manufactured by Oji Cornstarch) is size-pressed on a base paper with a basis weight of 110 g / m 2 Was applied on-machine so that the dry coating amount was 1.5 g / m 2 per side, and dried with a cylinder dryer to obtain a paper support.
<油性インク受容光沢層の形成>
紙支持体上に次に示す油性インク受容光沢層の組成物を乾燥質量で15g/m2となるように塗工・乾燥させて形成し、セミグロス油性インクジェット記録シートを得た。得られたセミグロス油性インクジェット記録シートの表面の電子顕微鏡写真を図1に示す。
<Formation of oil-based ink receiving glossy layer>
The composition of the oil-based ink-receiving glossy layer shown below was formed on a paper support by coating and drying to a dry mass of 15 g / m 2 to obtain a semi-gloss oil-based inkjet recording sheet. An electron micrograph of the surface of the obtained semi-gloss oil-based ink jet recording sheet is shown in FIG.
<油性インク受容光沢層の組成物>
以下、ガラス転移温度は、「Tg」と記す。
塩化ビニル−アクリル共重合樹脂(日信化学製ビニブラン278 Tg33℃、
塩化ビニル/アクリル組成比=80/20) 100質量%
消泡剤(サンノプコ製SNデフォーマー777) 0.60質量%
蛍光染料(日本曹達製ケーコールBXNL) 0.5質量%
増粘剤(サンノプコ製SNシックナー929S) 1.5質量%
<Composition of oil-based ink receiving glossy layer>
Hereinafter, the glass transition temperature is described as “Tg”.
Vinyl chloride-acrylic copolymer resin (Nippon Chemical's Vinibrand 278 Tg 33 ° C,
Vinyl chloride / acrylic composition ratio = 80/20) 100% by mass
Defoamer (San Nopco SN deformer 777) 0.60% by mass
Fluorescent dye (Nippon Soda Kakeru BXNL) 0.5 mass%
Thickener (San Nopco SN thickener 929S) 1.5% by mass
実施例1において、塩化ビニル−アクリル共重合樹脂(日信化学製ビニブラン278 Tg33℃)を塩化ビニル−アクリル共重合樹脂(日信化学製ビニブラン690 Tg46℃、塩化ビニル/アクリル組成比=80/20)に変更した以外は、実施例1と同様にしてセミグロス油性インクジェット記録シートを得た。得られたセミグロス油性インクジェット記録シートの表面の電子顕微鏡写真を図2に示す。 In Example 1, a vinyl chloride-acrylic copolymer resin (Nisshin Chemical Viniblanc 278 Tg33 ° C.) was replaced with a vinyl chloride-acrylic copolymer resin (Nisshin Chemical Viniblanc 690 Tg 46 ° C., vinyl chloride / acrylic composition ratio = 80/20. A semi-gloss oil-based ink jet recording sheet was obtained in the same manner as in Example 1 except that the above was changed. An electron micrograph of the surface of the obtained semi-gloss oil-based ink jet recording sheet is shown in FIG.
<インク受容層及び油性インク受容光沢層の形成>
実施例1において、支持体上にインク受容層の組成物を乾燥質量で10g/m2となるように塗工・乾燥させて形成した後、実施例1と同様の油性インク受容光沢層を設けてセミグロス油性インクジェット記録シートを得た。
<Formation of ink receiving layer and oil-based ink receiving glossy layer>
In Example 1, the composition of the ink receiving layer was formed on the support by coating and drying so that the dry mass was 10 g / m 2, and then the same oil-based ink receiving glossy layer as in Example 1 was provided. Thus, a semi-gloss oil-based ink jet recording sheet was obtained.
<インク受容層の組成物>
非晶質シリカ(グレース製74x4500) 100質量%
ポリビニルアルコール(クラレ製PVA−117) 20質量%
エチレン−酢酸ビニル共重合体(住友化学製スミカフレックス450) 20質量%
青味顔料(大日精化製TB520Blue2B) 0.06質量%
蛍光染料(日本曹達製ケーコールBXNL) 0.5質量%
カチオン樹脂(センカ製パピオゲンP−105) 10質量%
消泡剤(サンノプコ製SNデフォーマー777) 0.60質量%
<Composition of ink receiving layer>
Amorphous silica (Grace 74x4500) 100% by mass
Polyvinyl alcohol (Kuraray PVA-117) 20% by mass
Ethylene-vinyl acetate copolymer (Sumitomo Chemical Sumikaflex 450) 20% by mass
Ao pigment (TB520Blue2B manufactured by Dainichi Seika) 0.06 mass%
Fluorescent dye (Nippon Soda Kakeru BXNL) 0.5% by mass
Cationic resin (Senka Papiogen P-105) 10% by mass
Defoamer (San Nopco SN deformer 777) 0.60% by mass
実施例3において、油性インク受容光沢層の塩化ビニル−アクリル共重合樹脂を日信化学製ビニブラン690(Tg46℃、塩化ビニル/アクリル組成比=80/20)に変更した以外は、実施例3と同様にしてセミグロス油性インクジェット記録シートを得た。 Example 3 is the same as Example 3 except that the vinyl chloride-acrylic copolymer resin of the oil-based ink receptive glossy layer is changed to Nishin Chemical's Viniblanc 690 (Tg 46 ° C., vinyl chloride / acrylic composition ratio = 80/20). Similarly, a semi-gloss oil-based ink jet recording sheet was obtained.
実施例3において、ソフトカレンダーを用いて線圧30kg/cm、25℃、2ニップ1パスの条件で表面処理を行った以外は、実施例3と同様にしてセミグロス油性インクジェット記録シートを得た。 In Example 3, a semi-gloss oil-based ink jet recording sheet was obtained in the same manner as in Example 3 except that the surface treatment was performed using a soft calender under the conditions of a linear pressure of 30 kg / cm, 25 ° C., and 2 nips and 1 pass.
実施例3において、紙支持体を空洞及び酸化チタン含有のポリプロピレンフィルム(南亜製PI−80)にした以外は、実施例3と同様にしてセミグロス油性インクジェット記録シートを得た。 In Example 3, a semi-gloss oil-based inkjet recording sheet was obtained in the same manner as in Example 3 except that the paper support was a hollow and titanium oxide-containing polypropylene film (PI-80 manufactured by Nanya).
<油性インク浸透防止層及び油性インク受容光沢層の形成>
実施例6に用いたフィルム支持体上に、次に示す油性インク浸透防止層の組成物を乾燥質量で2g/m2となるように塗工・乾燥させて形成した後、実施例1と同様の油性インク受容光沢層を設けてセミグロス油性インクジェット記録シートを得た。
<Formation of oil-based ink permeation prevention layer and oil-based ink receiving glossy layer>
On the film support used in Example 6, the composition of the oil-based ink permeation preventive layer shown below was applied and dried to a dry mass of 2 g / m 2 , and then the same as in Example 1. A semi-gloss oil-based ink jet recording sheet was obtained by providing an oil-based ink-receiving glossy layer.
<油性インク浸透防止層の組成物>
非晶質シリカ(グレース製74x4500) 20質量%
ポリビニルアルコール(クラレ製PVA−117) 100質量%
酢酸ジルコニル(第一希元素化学製ジルコゾールZA−30) 5質量%
消泡剤(サンノプコ製SNデフォーマー777) 0.50質量%
<Composition of oil-based ink penetration preventing layer>
Amorphous silica (Grace 74x4500) 20% by mass
Polyvinyl alcohol (Kuraray PVA-117) 100% by mass
Zirconyl acetate (Zircozol ZA-30, manufactured by Daiichi Elemental Chemistry) 5% by mass
Antifoaming agent (San Nopco SN deformer 777) 0.50% by mass
<油性インク浸透防止層、インク受容層及び油性インク受容光沢層の形成>
実施例6で用いたフィルム支持体上に実施例7と同様の油性インク浸透防止層を設けた後、実施例3と同様のインク受容層、油性インク受容光沢層を設けてセミグロス油性インクジェット記録シートを得た。
<Formation of oil-based ink permeation preventive layer, ink receiving layer and oil-based ink receiving glossy layer>
After providing the same oil-based ink permeation preventive layer as that of Example 7 on the film support used in Example 6, the same ink-receiving layer and oil-based ink-receiving glossy layer as those of Example 3 are provided, and a semi-gloss oil-based inkjet recording sheet Got.
実施例8において、フィルム支持体をポリエチレン繊維からなる不織布(旭デュポン製AR1082)とした以外は、実施例8と同様にしてセミグロス油性インクジェット記録シートを得た。 In Example 8, a semi-gloss oil-based inkjet recording sheet was obtained in the same manner as in Example 8 except that the film support was a non-woven fabric made of polyethylene fibers (AR1082 manufactured by Asahi DuPont).
<バックコート層Aの形成>
実施例1において、紙支持体の裏面に次に示すバックコート層Aの組成物を乾燥質量で1g/m2塗工した以外は、実施例1と同様にしてセミグロス油性インクジェット記録シートを得た。
<Formation of back coat layer A>
In Example 1, a semi-gloss oil-based ink jet recording sheet was obtained in the same manner as in Example 1, except that the composition of the back coat layer A shown below was applied at a dry mass of 1 g / m 2 on the back surface of the paper support. .
<バックコート層組成物A>
色顔料(大日精化製TB708ブルー:ノニオン性) 20質量%
スチレン−ブタジエン系ラテックス(旭化成製P6030) 100質量%
消泡剤(サンノプコ製SNデフォーマー777) 0.20質量%
<Backcoat layer composition A>
Color pigment (TB708 Blue manufactured by Dainichi Seika: nonionic) 20% by mass
Styrene-butadiene latex (P6030 manufactured by Asahi Kasei) 100% by mass
Defoamer (San Nopco SN deformer 777) 0.20% by mass
実施例10において、紙支持体の裏面のバックコート層組成物Aを次に示すバックコート層組成物Bに変更した以外は、実施例10と同様にしてミグロス油性インクジェット記録シートを得た。 In Example 10, a migros oil-based inkjet recording sheet was obtained in the same manner as in Example 10 except that the backcoat layer composition A on the back surface of the paper support was changed to the backcoat layer composition B shown below.
<バックコート層組成物B>
色顔料(御国色素製C−12021:ノニオン性) 70質量%
色顔料(御国色素性Black C:ノニオン性) 7質量%
スチレン−ブタジエン系ラテックス(旭化成製P6030) 100質量%
消泡剤(サンノプコ製SNデフォーマー777) 0.20質量%
<Backcoat layer composition B>
70% by mass of color pigment (C-12021 made by Gokoku Dye, nonionic)
Color pigment (Okuni Dye Black C: Nonionic) 7% by mass
Styrene-butadiene latex (P6030 manufactured by Asahi Kasei) 100% by mass
Defoamer (San Nopco SN deformer 777) 0.20% by mass
実施例1において塩化ビニル−アクリル共重合樹脂(日信化学製ビニブラン278 Tg33℃)を塩化ビニル−アクリル共重合樹脂(日信化学製ビニブラン271 Tg−3℃、塩化ビニル/アクリル組成比=80/20)に変更した以外は、実施例1と同様にして記録シートを得た。 In Example 1, a vinyl chloride-acrylic copolymer resin (Nishin Chemical Co., Ltd. vinibran 278 Tg33 ° C.) was replaced with a vinyl chloride-acrylic copolymer resin (Nisshin Chemical Co., Ltd. vinibran 271 Tg-3 ° C., vinyl chloride / acrylic composition ratio = 80 / A recording sheet was obtained in the same manner as in Example 1 except for changing to 20).
実施例1において、塩化ビニル−アクリル共重合樹脂(日信化学製ビニブラン278 Tg33℃)を塩化ビニル−アクリル共重合樹脂(日信化学製ビニブラン900 Tg70℃、塩化ビニル/アクリル組成比=90/10)に変更した以外は、実施例1と同様にして記録シートを得た。得られた記録シートの表面の電子顕微鏡写真を図3に示す。 In Example 1, a vinyl chloride-acrylic copolymer resin (Nisshin Chemical Vinibrand 278 Tg 33 ° C.) was replaced with a vinyl chloride-acrylic copolymer resin (Nisshin Chemical Vinibrand 900 Tg 70 ° C., vinyl chloride / acrylic composition ratio = 90/10. The recording sheet was obtained in the same manner as in Example 1 except that the above was changed. An electron micrograph of the surface of the obtained recording sheet is shown in FIG.
実施例1において、塩化ビニル−アクリル共重合樹脂(日信化学製ビニブラン278 Tg33℃)を塩化ビニル−アクリル共重合樹脂(日信化学製ビニブラン902 Tg60℃、塩化ビニル/アクリル組成比=80/20)に変更した以外は、実施例1と同様にして記録シートを得た。得られた記録シートの表面の電子顕微鏡写真を図4に示す。 In Example 1, a vinyl chloride-acrylic copolymer resin (Nisshin Chemical ViniBran 278 Tg33 ° C.) was replaced with a vinyl chloride-acrylic copolymer resin (Nisshin Chemical ViniBran 902 Tg 60 ° C., vinyl chloride / acrylic composition ratio = 80/20. The recording sheet was obtained in the same manner as in Example 1 except that the above was changed. An electron micrograph of the surface of the obtained recording sheet is shown in FIG.
実施例1において、塩化ビニル−アクリル共重合樹脂(日信化学製ビニブラン278 Tg33℃)を塩化ビニル樹脂(日信化学製ビニブラン985 Tg80℃、塩化ビニル/アクリル組成比=100/0)に変更した以外は、実施例1と同様にして記録シートを得た。 In Example 1, vinyl chloride-acrylic copolymer resin (Nisshin Chemical Vinibrand 278 Tg33 ° C.) was changed to vinyl chloride resin (Nisshin Chemical ViniBran 985 Tg 80 ° C., vinyl chloride / acrylic composition ratio = 100/0). A recording sheet was obtained in the same manner as Example 1 except for the above.
実施例1において、塩化ビニル−アクリル共重合樹脂(日信化学製ビニブラン278 Tg33℃)を塩化ビニル−酢酸ビニル共重合樹脂(日信化学製ビニブラン603 Tg63℃、塩化ビニル/酢酸ビニル組成比=80/20)に変更した以外は、実施例1と同様にして記録シートを得た。 In Example 1, a vinyl chloride-acrylic copolymer resin (Nishin Chemical Vinibrand 278 Tg33 ° C.) was replaced with a vinyl chloride-vinyl acetate copolymer resin (Nishin Chemical Vinibrand 603 Tg 63 ° C., vinyl chloride / vinyl acetate composition ratio = 80. / 20) A recording sheet was obtained in the same manner as in Example 1 except that the recording sheet was changed.
実施例3において、油性インク受容光沢層を設けなかった以外は、実施例3と同様にして記録シートを得た。 In Example 3, a recording sheet was obtained in the same manner as in Example 3 except that the oil-based ink receiving gloss layer was not provided.
実施例3において、塩化ビニル−アクリル共重合樹脂(日信化学製ビニブラン278 Tg33℃)を塩化ビニル−アクリル共重合樹脂(日信化学製ビニブラン902 Tg60℃、塩化ビニル/アクリル組成比=80/20)に変更した以外は、実施例3と同様にして記録シートを得た。 In Example 3, a vinyl chloride-acrylic copolymer resin (Nishin Chemical's Vinibrand 278 Tg33 ° C) was replaced with a vinyl chloride-acrylic copolymer resin (Nisshin Chemical's Vinibrand 902 Tg 60 ° C, vinyl chloride / acrylic composition ratio = 80/20. A recording sheet was obtained in the same manner as in Example 3 except that the above was changed.
実施例で得られたセミグロス油性インクジェット記録シート及び比較例で得られた記録シートを、次の方法で性能評価を行った。 The semi-gloss oil-based ink jet recording sheets obtained in the examples and the recording sheets obtained in the comparative examples were evaluated by the following methods.
(1)インク吸収性の評価
油性インクを使用したインクジェットプリンター(ミマキエンジニアリング製 JV−3)を用い、「高精彩カラーディジタル標準画像データ ISO/JIS−SCID JIS X 9201:1995準拠」における画像サンプルN2A「カフェテリア」を出力し、画像の乾燥具合・滲み具合からインクの吸収性を評価した。画像に滲みやインク吸収ムラが無く、鮮明で乾燥性に優れるものを◎、実用上問題の無いものを○、実用上に不安があるものを△、インクの吸収性が劣り、及び/又は画像に滲み、ムラなど欠陥を生じ、実使用に問題があるものを×とした。
(1) Evaluation of ink absorptivity Image sample N2A in “High-definition color digital standard image data ISO / JIS-SCID JIS X 9201: 1995 compliant” using an ink-jet printer (Mimaki Engineering JV-3) using oil-based ink. "Cafeteria" was output, and the ink absorbency was evaluated from the degree of image drying and bleeding. An image having no blur or ink absorption unevenness, crisp and excellent in drying property ◎, practically no problem ◯, practically uneasy △, ink absorption is inferior, and / or image The case where defects such as bleeding and unevenness were found and there was a problem in actual use was rated as x.
(2)発色濃度の評価
油性インクを使用したインクジェットプリンター(ミマキエンジニアリング製 JV−3)を用い、「高精彩カラーディジタル標準画像データ ISO/JIS−SCID JIS X 9201:1995準拠」における画像サンプルN6A「カラーチャート」を出力し、濃色部、ブラックの発色濃度を印字濃度計マクベス社製RD−19Iで測定した。印字濃度の数値が高い程、濃度が濃く、鮮やかであることを示す。
(2) Evaluation of color density Image sample N6A in “High-definition color digital standard image data ISO / JIS-SCID JIS X 9201: 1995 compliant” using an ink jet printer using oil-based ink (JV-3, manufactured by Mimaki Engineering) The color chart "was output, and the dark color portion and black color density were measured with a printing densitometer Macbeth RD-19I. The higher the print density value, the darker and darker the print density.
(3)コックリングの評価
油性インクを使用したインクジェットプリンター(ミマキエンジニアリング製 JV−3)を用い、「高精彩カラーディジタル標準画像データ ISO/JIS−SCID JIS X 9201:1995準拠」における画像サンプルN2A「カフェテリア」を出力した後、23℃、50%RH条件下に24時間放置した後、印字画像部のボコツキ状態を観察した。目視にて殆どボコツキの発生しなかったものを◎、若干ボコツキが発生したが実用上問題の無いものを○、ボコツキが発生し、実用上問題があるものを×とした。
(3) Evaluation of cockling An image sample N2A in “High-definition color digital standard image data ISO / JIS-SCID JIS X 9201: 1995 compliant” using an inkjet printer using oil-based ink (JV-3, manufactured by Mimaki Engineering) After outputting “Cafeteria”, it was left under conditions of 23 ° C. and 50% RH for 24 hours, and then the blurred state of the printed image portion was observed. The case where there was almost no blurring visually was rated as ◎, the case where slight blurring occurred but no problem in practical use was marked as ◯, the case where blurring occurred, and a problem in practical use was marked as x.
(4)白紙部の75度鏡面光沢度の評価
作成したセミグロス溶剤インクジェット記録シートの白紙部について「GLOSS METER GM−26D」を用いてJIS P 8142:2005「75度鏡面光沢度試験方法」に従い、75度鏡面光沢度を測定した。
(4) Evaluation of 75-degree specular gloss of white paper portion According to JIS P 8142: 2005 “75-degree specular gloss test method” using “GLOSS METER GM-26D” for the white paper portion of the prepared semi-gloss solvent inkjet recording sheet, The 75 degree specular gloss was measured.
(5)印字画像形成部の75度鏡面光沢度の評価
インク吸収性の評価で出力した「高精彩カラーディジタル標準画像データ ISO/JIS−SCID JIS X 9201:1995準拠」における画像サンプルN2A「カフェテリア」画像部の左上、空部について「GLOSS METER GM−26D」を用いてJIS P 8142:2005「75度鏡面光沢度試験方法」に従い、75度鏡面光沢度を測定した。
(5) Evaluation of 75 degree specular gloss of printed image forming part Image sample N2A “cafeteria” in “High-definition color digital standard image data ISO / JIS-SCID JIS X 9201: 1995 compliant” output in the evaluation of ink absorbency The 75 degree specular glossiness was measured according to JIS P 8142: 2005 "75 degree specular gloss test method" using "GLOSS METER GM-26D" for the upper left part of the image part.
(6)白色度
油性インク受容光沢層面について、日本電色工業製PF−10を用いてJIS P 8148:2001「紙、板紙及びパルプ−ISO白色度の測定方法」に従い、白色度を測定した。
(6) Whiteness The whiteness of the oil-based ink-receiving glossy layer surface was measured using PF-10 manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS P 8148: 2001 “Paper, paperboard and pulp—ISO whiteness measurement method”.
(7)不透明度
油性インク受容光沢層面について、日本電色工業製PF−10を用いてJIS P 8149:2005「紙及び板紙−不透明度試験方法」に従い、不透明度を測定した。
(7) Opacity The opacity of the oil-based ink-receiving glossy layer surface was measured using PF-10 manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS P 8149: 2005 “Paper and paperboard—Opacity test method”.
セミグロス油性インクジェット記録シートの評価結果を表1に示す。実施例1〜10で得られたセミグロス油性インクジェット記録シートは、表1に示すように本発明に合致する物性値を有し、鮮明な発色性と広告・ポスター用途に適した光沢感を有し、印字後のボコツキ・コックリングもなく良好であった。また、例として図1〜2に実施例1及び実施例2の塗工・乾燥後の表面写真を示すが、油性インク受容光沢層は無数のヒビを生じることによって良好なインク吸収性を示した。 Table 1 shows the evaluation results of the semi-gloss oil-based ink jet recording sheet. The semi-gloss oil-based ink jet recording sheets obtained in Examples 1 to 10 have physical property values consistent with the present invention as shown in Table 1, have clear color development properties and glossiness suitable for advertising / poster applications. The film was good without any unevenness or cockling after printing. As an example, FIGS. 1 and 2 show surface photographs after coating and drying in Examples 1 and 2, and the oil-based ink-receiving glossy layer showed good ink absorbency by generating innumerable cracks. .
一方、油性インク受容光沢層に所定の樹脂を用いなかったもの及び比較例6のように油性インク受容光沢層を設けなかったものは、インク吸収性、発色濃度、コックリング、光沢度のいずれかに欠点が生じた。特に、所定のガラス転移温度未満の樹脂を用いた比較例1は、塗工・乾燥後も表面にベタツキ・タック感を生じ、プリンターでの印字、ロール状に巻き取ることができなかった。また、例として所定のガラス転移温度を超えた塩化ビニル−アクリル共重合樹脂を用いたものとして図3〜4に比較例2及び3の塗工・乾燥後の表面写真を示すが、油性インク受容光沢層はひび割れの数が少なく、また小さいため、油性インクの吸収性に劣った。 On the other hand, the oil-based ink receptive gloss layer that does not use a predetermined resin and the oil-based ink receptive gloss layer that does not have an oil-based ink receptive gloss layer as in Comparative Example 6 are any of ink absorbency, color density, cockling, and glossiness. There was a drawback. In particular, Comparative Example 1 using a resin having a temperature lower than the predetermined glass transition temperature produced a sticky / tacky surface on the surface even after coating and drying, and could not be printed on a printer or wound into a roll. In addition, as examples using vinyl chloride-acrylic copolymer resin exceeding a predetermined glass transition temperature, FIGS. 3 to 4 show surface photographs after coating and drying in Comparative Examples 2 and 3, but the oil-based ink acceptance Since the glossy layer has a small number of cracks and is small , the oil-based ink has poor absorbability.
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