JP5639358B2 - Inkjet recording material for non-aqueous ink - Google Patents
Inkjet recording material for non-aqueous ink Download PDFInfo
- Publication number
- JP5639358B2 JP5639358B2 JP2009279268A JP2009279268A JP5639358B2 JP 5639358 B2 JP5639358 B2 JP 5639358B2 JP 2009279268 A JP2009279268 A JP 2009279268A JP 2009279268 A JP2009279268 A JP 2009279268A JP 5639358 B2 JP5639358 B2 JP 5639358B2
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- ink
- receiving layer
- recording material
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- 239000000463 material Substances 0.000 title claims description 66
- 239000000976 ink Substances 0.000 claims description 163
- 239000002245 particle Substances 0.000 claims description 91
- 239000008199 coating composition Substances 0.000 claims description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 49
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- 230000009477 glass transition Effects 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000010410 layer Substances 0.000 description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 238000001035 drying Methods 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 24
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 3
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- 239000000975 dye Substances 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Description
本発明は、非水系インク用インクジェット記録材料に関して、特に良好なインク乾燥性と高い発色性を有し、且つ印刷品質及び耐水性に優れた非水系インク用インクジェット記録材料に関するものである。 The present invention relates to an inkjet recording material for non-aqueous inks, and particularly to an inkjet recording material for non-aqueous inks that has good ink drying properties and high color developability and is excellent in print quality and water resistance.
現在、インクジェットプリンターやプロッターの目ざましい進歩により、フルカラーでしかも高精細な画像が容易に得られるようになってきている。 At present, due to remarkable progress in inkjet printers and plotters, full-color and high-definition images can be easily obtained.
インクジェット記録方式は、種々の作動原理によりインクの微小液滴を飛翔させて紙等の記録材料に付着させ、画像・文字等の記録を行うものである。インクジェットプリンターやプロッターはコンピューターにより作成した文字や各種図形等の画像情報のハードコピー作成装置として、種々の用途で近年急速に普及している。特に多色インクジェット記録方式により形成されるカラー画像は製版方式による多色印刷やカラー写真方式による印画に比較しても遜色のない記録を得ることが可能であり、更に作成部数が少ない用途においては、印刷技術や写真技術よりも安価で済むことから広く応用されている。特にプリンター技術の進歩により、Ａ０やＢ０サイズまたはそれより大きな広幅用紙への高解像度印刷が高速で行えるようになったことから、屋内外の展示、広告用途に広く用いられるようになってきた。そのため従来以上に用紙及び画像の耐候性、保存性が求められるようになっている。 The ink jet recording system records images, characters, and the like by causing micro droplets of ink to fly and adhere to a recording material such as paper according to various operating principles. Inkjet printers and plotters are rapidly spreading in various applications in recent years as hard copy creation apparatuses for image information such as letters and various graphics created by a computer. In particular, color images formed by the multicolor ink jet recording method can obtain recordings that are inferior to those of multicolor printing by the plate making method and printing by the color photographic method. It is widely applied because it is cheaper than printing technology and photographic technology. In particular, the advancement of printer technology has enabled high-resolution printing on A0, B0 size or larger wide paper at high speed, and it has become widely used for indoor and outdoor exhibitions and advertising purposes. Therefore, the weather resistance and storability of paper and images are required more than ever.
このために、最近では顔料タイプのインクが使用されるようになってきている。顔料インクは光劣化も少なく、水によって再溶解しないため、染料タイプのインクよりも耐候性、画像保存性が向上することが知られている。これら顔料インクは、インク溶媒の種類から水系（水性）と非水系（溶剤系）に大別される。 For this reason, pigment-type inks have recently been used. It is known that the pigment ink has little light deterioration and does not re-dissolve with water, so that the weather resistance and the image storage stability are improved as compared with the dye type ink. These pigment inks are roughly classified into water-based (aqueous) and non-aqueous (solvent-based) types depending on the type of ink solvent.
水系顔料インクは、臭気がなく、メンテナンスの容易さ等から広く用いられている。しかし、水系顔料インクは、顔料の分散濃度を高くできず、印字濃度や色の鮮鋭性が劣る。また、水系顔料インク用の記録材料は、無機顔料を主体とした速乾、浸透性の空隙タイプが大半である。これらは多孔質のインク受理層を形成するため、インク乾燥性は良好であるものの、溶媒である水が用紙繊維を膨潤させて生じるコックリング（用紙表面の波打ち）により、印刷時にインクドットがずれて印刷ムラを発生する場合がある。 Water-based pigment inks are widely used because they have no odor and are easy to maintain. However, the water-based pigment ink cannot increase the pigment dispersion concentration, and is inferior in print density and color sharpness. Also, most of the recording materials for water-based pigment inks are quick-drying and penetrating void types mainly composed of inorganic pigments. Since these form a porous ink-receiving layer, the ink drying property is good, but the ink dots are displaced during printing due to cockling (waving on the paper surface) generated by the water as the solvent swelling the paper fibers. Printing unevenness may occur.
一方、非水系顔料インクは、シクロヘキサノンやメチルエチルケトンを溶媒とする強溶剤系、油溶性染料や無機／有機顔料等をパラフィン類、エーテル類、アルコール類等の溶媒に溶解した油性系、そしてグリコールエーテルを主体とした溶媒に顔料を分散させたグリコール系（弱溶剤系）インク等がある。中でもグリコール系インクは、インクの乾燥性が良好でありつつ、作業環境への負荷が少ないため、現在主流となりつつある。これら非水系インクは、顔料の分散濃度を高めることで、印字濃度や鮮鋭性を向上させることができ、またコックリングも発生しないことから、良好な印刷物の作製が可能である。 On the other hand, non-aqueous pigment inks are strong solvent systems using cyclohexanone and methyl ethyl ketone as solvents, oil-based systems in which oil-soluble dyes and inorganic / organic pigments are dissolved in solvents such as paraffins, ethers and alcohols, and glycol ethers. There are glycol-based (weak solvent-based) inks in which pigments are dispersed in a main solvent. Among these, glycol-based inks are currently becoming mainstream because they have good ink drying properties and a low load on the work environment. These non-aqueous inks can improve the print density and sharpness by increasing the dispersion density of the pigment, and can produce good printed matter because no cockling occurs.
非水系インクを受理する記録材料としては、水系顔料インク同様、シリカ及び接着剤からなる記録材料が提案されている（例えば、特許文献１参照）。しかしながらこのような空隙タイプの記録材料では、インクの顔料成分が溶媒とともにインク受理層に浸透してしまい、印字濃度が十分に発現しない。また、顔料成分のインク受理層への落ち込みを抑え、表面近傍に留めるべく、インク受理層に微粒顔料を使用した記録材料も提案されている（例えば、特許文献２参照）が、顔料成分のみがインク受理層表面に残り、印字部擦過性に劣る傾向がある。また展示、広告用途として必要な特性である耐水性に劣る傾向がある。 As a recording material that accepts a non-aqueous ink, a recording material made of silica and an adhesive has been proposed as in the case of an aqueous pigment ink (see, for example, Patent Document 1). However, in such a void type recording material, the pigment component of the ink penetrates into the ink receiving layer together with the solvent, and the printing density is not sufficiently developed. In addition, a recording material using a fine pigment in the ink receiving layer has been proposed in order to suppress the drop of the pigment component to the ink receiving layer and keep it in the vicinity of the surface (see, for example, Patent Document 2). It remains on the surface of the ink receiving layer and tends to be inferior in printed portion scratching. In addition, there is a tendency to be inferior in water resistance, which is a necessary characteristic for display and advertising purposes.
空隙タイプとは異なり、支持体上に溶剤に可溶あるいは膨潤する成分を主体とするインク受理層を塗設し、インクを受理する所謂膨潤タイプの記録材料も提案されている（例えば、特許文献３、４参照）。これら膨潤タイプの記録材料は、空隙タイプのような細孔をほとんど有しておらず、また水に不溶な成分で構成されているため、耐水性に優れる。そして、インク中の溶媒によりインク受理層が溶解または膨潤し、インクの顔料成分をインク受理層表面に留めるため、高い印字濃度を発現し、且つインク乾燥後には良好な印字部擦過性を付与できる。しかしながら空隙タイプと異なり、インク受理層が溶媒により溶解、膨潤することからインク乾燥性が遅い。また、インク受理層のべとつき感が強くブロッキングが発生しやすい等、結果として作業効率が著しく低下してしまう。
このように、特に良好なインク乾燥性と高い発色性を有し、べとつきが少なく、耐水性に優れた非水系インク用インクジェット記録材料を得ることが非常に困難であった。
Unlike the void type, a so-called swelling type recording material in which an ink receiving layer mainly composed of a component that is soluble or swelled in a solvent is coated on a support to receive ink has been proposed (for example, Patent Documents). 3 and 4). These swelling type recording materials have almost no pores as in the void type and are composed of water-insoluble components, and thus have excellent water resistance. Then, the ink receiving layer is dissolved or swollen by the solvent in the ink, and the pigment component of the ink is retained on the surface of the ink receiving layer, so that a high printing density is exhibited and good printed part scratchability can be imparted after drying the ink. . However, unlike the void type, the ink receiving layer dissolves and swells with the solvent, so that the ink drying property is slow. In addition, the stickiness of the ink receiving layer is strong and blocking is likely to occur. As a result, the working efficiency is significantly reduced.
Thus, it has been very difficult to obtain an ink jet recording material for non-aqueous inks that has particularly good ink drying properties and high color developability, little stickiness, and excellent water resistance.
本発明の目的は、実現が従来困難であった、特に良好なインク乾燥性と高い発色性を有し、べとつきが少なく、且つ耐水性に優れた非水系インク用インクジェット記録材料を提供することにある。 The object of the present invention is to provide an ink jet recording material for non-aqueous inks that has been difficult to realize in the past, has particularly good ink drying properties and high color developability, is less sticky, and has excellent water resistance. is there.
この課題に対し検討を行った結果、本発明のインクジェット記録材料、すなわち支持体上に１層のインク受理層のみを設けてなる非水系インク用インクジェット記録材料において、インク受理層が熱可塑性樹脂、無機微粒子、有機中空粒子を少なくとも含有し、無機微粒子が平均粒子径０．３〜６μｍのシリカ微粒子であり、有機中空粒子の平均粒子径が０．４〜１．０μｍであり、熱可塑性樹脂１００質量部に対する無機微粒子及び有機中空粒子の比率が、それぞれ１０〜２５質量部、１０〜７５質量部とすることで、特に良好なインク乾燥性と高い発色性を有し、べとつきが少なく、且つ耐水性に優れた非水系インク用インクジェット記録材料を提供することが可能になった。 As a result of studying this problem, the inkjet recording material of the present invention, that is, the inkjet recording material for non-aqueous ink in which only one ink-receiving layer is provided on the support, the ink-receiving layer is a thermoplastic resin, Thermoplastic resin 100 containing at least inorganic fine particles and organic hollow particles, wherein the inorganic fine particles are silica fine particles having an average particle size of 0.3 to 6 μm, and the organic hollow particles have an average particle size of 0.4 to 1.0 μm. When the ratio of the inorganic fine particles and the organic hollow particles to 10 parts by mass is 10 to 25 parts by mass and 10 to 75 parts by mass, respectively, the ink has particularly good ink drying properties and high color development, less stickiness, and water resistance. It has become possible to provide an ink jet recording material for non-aqueous inks having excellent properties.
特に有機中空粒子の空隙率が、３０％以上であることで、特に良好なインク乾燥性を得ることが可能になった。 In particular, when the porosity of the organic hollow particles is 30% or more, particularly good ink drying properties can be obtained.
また、熱可塑性樹脂のガラス転移温度が、−２０℃〜６０℃であることで、特に良好なインク乾燥性と耐水性を得ることが可能となった。 In addition, when the glass transition temperature of the thermoplastic resin is −20 ° C. to 60 ° C., particularly good ink drying properties and water resistance can be obtained.
本発明により、従来得られなかった特に良好なインク乾燥性と高い発色性を有し、べとつきが少なく、且つ耐水性に優れた非水系インク用インクジェット記録材料が得られる。 According to the present invention, an ink jet recording material for non-aqueous ink that has a particularly good ink drying property and high colorability, which has not been obtained so far, is less sticky and has excellent water resistance.
以下、本発明の非水系インク用インクジェット記録材料を詳細に説明する。 Hereinafter, the inkjet recording material for non-aqueous ink of the present invention will be described in detail.
本発明者は、特に良好なインク乾燥性と高い発色性を有し、且つ良好な印刷品質と優れた耐水性を有する非水系インク用インクジェット記録材料を得るべく鋭意検討した。その結果、支持体上に少なくとも１層のインク受理層を設けてなる非水系インク用インクジェット記録材料において、インク受理層が熱可塑性樹脂、無機微粒子、有機中空粒子を少なくとも含有し、且つ有機中空粒子の平均粒子径が０．４〜１．０μｍであることで、非水系インク溶媒の吸収性の改善により、高い発色性を保ちつつ、インク乾燥性を向上することができることを見出した。 The inventor has intensively studied to obtain an ink jet recording material for non-aqueous inks that has particularly good ink drying properties and high color developability, as well as good print quality and excellent water resistance. As a result, in the inkjet recording material for non-aqueous ink in which at least one ink receiving layer is provided on the support, the ink receiving layer contains at least a thermoplastic resin, inorganic fine particles, and organic hollow particles, and the organic hollow particles It has been found that when the average particle size of the ink is 0.4 to 1.0 μm, it is possible to improve the ink drying property while maintaining high color developability by improving the absorbability of the non-aqueous ink solvent.
更に本発明者は、発色性に影響を及ぼさずに、より良好なインク乾燥性を目指すべく鋭意検討した。その結果、熱可塑性樹脂１００質量部に対する無機微粒子及び有機中空粒子の比率が、それぞれ５〜５０質量部、１０〜７５質量部とすることで、インク受理層のべとつきを抑えつつ、優れたインク乾燥性を付与できることを見出した。 Furthermore, the present inventor has intensively studied to achieve better ink drying properties without affecting the color developability. As a result, the ratio of the inorganic fine particles and the organic hollow particles to 100 parts by mass of the thermoplastic resin is 5 to 50 parts by mass and 10 to 75 parts by mass, respectively, and excellent ink drying while suppressing stickiness of the ink receiving layer. It has been found that sex can be imparted.
本発明において支持体とは、紙基材等の吸水性支持体、またポリエチレン、ポリプロピレン、ポリ塩化ビニル、ジアセテート樹脂、トリアセテート樹脂、セロファン、アクリル樹脂、ポリエチレンテレフタレート、ポリエチレンナフタレート等のフィルム、更にポリオレフィン樹脂被覆紙等の非吸水性支持体等を用いることができる。加えて、各種不織布や合成紙を支持体として用いることもできる。本発明で使用される紙基材としては、ＬＢＫＰ、ＮＢＫＰ等の化学パルプ、ＧＰ、ＰＧＷ、ＲＭＰ、ＴＭＰ、ＣＴＭＰ、ＣＭＰ、ＣＧＰ等の機械パルプ、ＤＩＰ等の古紙パルプ等の木材パルプと従来公知の顔料を主成分として、バインダー及びサイズ剤や定着剤、歩留まり向上剤、カチオン化剤、紙力増強剤等の各種添加剤を１種以上用いて混合し、長網抄紙機、円網抄紙機、ツインワイヤー抄紙機等の各種装置で製造された原紙、更に原紙に、澱粉、ポリビニルアルコール等でのサイズプレスやアンカーコート層を設けた原紙や、それらの上にコート層を設けたアート紙、コート紙、キャストコート紙、バライタ紙等の塗工紙も含まれる。このような原紙及び塗工紙に、そのまま本発明にかかる塗層を設けても良いし、平坦化をコントロールする目的で、マシンカレンダー、ＴＧカレンダー、ソフトカレンダー等のカレンダー装置を使用しても良い。 In the present invention, the support means a water-absorbing support such as a paper base material, a film of polyethylene, polypropylene, polyvinyl chloride, diacetate resin, triacetate resin, cellophane, acrylic resin, polyethylene terephthalate, polyethylene naphthalate, and the like. Non-water-absorbing supports such as polyolefin resin-coated paper can be used. In addition, various nonwoven fabrics and synthetic paper can be used as the support. Examples of the paper base material used in the present invention include chemical pulps such as LBKP and NBKP, mechanical pulps such as GP, PGW, RMP, TMP, CTMP, CMP, and CGP, and wood pulp such as waste paper pulp such as DIP and the like. The main component is a pigment, a binder, a sizing agent, a fixing agent, a yield improver, a cationizing agent, a paper strength enhancer, etc. , Base paper manufactured by various devices such as twin wire paper machines, base paper provided with size press and anchor coat layer with starch, polyvinyl alcohol etc. on base paper, art paper provided with coat layer on them, Coated paper such as coated paper, cast coated paper and baryta paper is also included. Such a base paper and coated paper may be provided with the coating layer according to the present invention as they are, or a calendar device such as a machine calendar, a TG calendar, or a soft calendar may be used for the purpose of controlling flattening. .
また、支持体を挟んだインク受理層の反対面には、カール適性、糊付け時の紙伸びや糊の支持体への浸透を防止する適性を付与するために、バックコート層を塗工することも可能であり、その際の顔料としては、軽質炭酸カルシウム、重質炭酸カルシウム、炭酸マグネシウム、カオリン、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、硫化亜鉛、炭酸亜鉛、サチンホワイト、ケイ酸アルミニウム、ケイソウ土、ケイ酸カルシウム、ケイ酸マグネシウム、水酸化アルミニウム、リトポン、ゼオライト、加水ハロイサイト、水酸化マグネシウム等の白色無機顔料、スチレン系プラスチックピグメント、アクリル系プラスチックピグメント、ポリエチレン微粒子、マイクロカプセル、尿素樹脂微粒子、メラミン樹脂微粒子等の有機顔料等が挙げられるが、特に平板状顔料や加水ハロイサイトが好ましい。 Also, on the opposite side of the ink receiving layer with the support interposed between them, a backcoat layer should be applied in order to provide curl suitability, paper stretch during gluing, and suitability to prevent the penetration of glue into the support. The following pigments are available: light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, silica White inorganic pigments such as aluminum oxide, diatomaceous earth, calcium silicate, magnesium silicate, aluminum hydroxide, lithopone, zeolite, hydrous halloysite, magnesium hydroxide, styrene plastic pigment, acrylic plastic pigment, polyethylene fine particles, microcapsule, Urea resin fine particles, melamine resin fine particles, etc. Although machine pigments, and the like, in particular plate-like pigment and hydrated halloysite preferred.
バックコート層のバインダーとしては、酸化澱粉、エーテル化澱粉、リン酸エステル化澱粉等の澱粉誘導体、カルボキシメチルセルロース、ヒドロキシエチルセルロース等のセルロース誘導体、カゼイン、ゼラチン、大豆蛋白、ポリビニルアルコールまたはその誘導体、ポリビニルピロリドン、無水マレイン酸樹脂、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共重合体ラテックス、アクリル酸エステル及びメタクリル酸エステルの重合体または共重合体等のアクリル系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、あるいはこれら各種重合体の中にカルボキシ基等の官能基含有単量体を導入した官能基変性重合体ラテックス、メラミン樹脂、尿素樹脂等の熱硬化性合成樹脂、ポリメチルメタクリレート等のアクリル酸エステル、メタクリル酸エステルの重合体または共重合体樹脂、ポリウレタン樹脂、不飽和ポリエステル樹脂、塩化ビニル−酢酸ビニル共重合体、ポリビニルブチラール、アルキッド樹脂等の合成樹脂系接着剤等を挙げることができる。 As a binder for the back coat layer, starch derivatives such as oxidized starch, etherified starch and phosphate esterified starch, cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, casein, gelatin, soybean protein, polyvinyl alcohol or derivatives thereof, polyvinylpyrrolidone , Conjugated diene copolymer latex such as maleic anhydride resin, styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, acrylic polymer such as acrylate ester and methacrylate ester polymer or copolymer Acrylic polymer latex such as ethylene-vinyl acetate copolymer such as ethylene-vinyl acetate copolymer, or functional group-modified polymer latex in which a functional group-containing monomer such as carboxy group is introduced into these various polymers , Me Thermosetting synthetic resins such as min resin and urea resin, acrylic acid ester such as polymethyl methacrylate, methacrylic acid ester polymer or copolymer resin, polyurethane resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer And synthetic resin adhesives such as polyvinyl butyral and alkyd resin.
本発明の非水系インク用インクジェット記録材料は、経師貼り等の壁面装飾やポスター等の展示物に使用され、古い展示物の上に新しいものを貼り付けることが多い。そのため、重ね貼りした際に下地の色や柄が透過しないような高い不透明度が必要である。そこで、バックコート層は高い不透明度を得るため、色味調整剤等により着色してあることが好ましい。特に青、黄、グレー等の色は、不透明度向上効果が高いため、好ましい。 The ink-jet recording material for non-aqueous ink of the present invention is used for wall decorations such as pastoral pasting and exhibits such as posters, and a new one is often pasted on an old exhibit. For this reason, high opacity is required so that the base color and pattern do not pass through when they are overlaid. Therefore, the back coat layer is preferably colored with a color adjusting agent or the like in order to obtain high opacity. In particular, colors such as blue, yellow, and gray are preferable because the effect of improving opacity is high.
バックコート層にはまた、必要に応じて、界面活性剤、消泡剤、増粘剤、蛍光増白剤、酸化防止剤、紫外線吸収剤等の各種添加剤を添加することもできる。 In addition, various additives such as a surfactant, an antifoaming agent, a thickening agent, a fluorescent whitening agent, an antioxidant, and an ultraviolet absorber can be added to the backcoat layer as necessary.
本発明において熱可塑性樹脂とは、実質的に非水溶性の熱可塑性樹脂であり、例えば熱可塑性樹脂が水中に分散した液状物から、一旦乾燥した後は熱水にも実質的に溶解しない点で水溶性樹脂と区別される。その例としては、酢酸ビニル重合体、エチレン−酢酸ビニル共重合体、塩化ビニル重合体、塩化ビニル−酢酸ビニル共重合体、塩化ビニル−（メタ）アクリル酸エステル共重合体、（メタ）アクリル酸エステルの重合体、スチレン−（メタ）アクリル酸エステル共重合体、スチレン−ブタジエン共重合体、アクリロニトリル−ブタジエン共重合体、イソプレン共重合体、クロロプレン共重合体、ウレタン系重合体、及びこれらの重合体を構成する単量体の２種以上をランダム的、グラフト的、ブロック的に組み合わせた共重合体等の合成樹脂であり、水性分散液やエマルジョンを含む。また、天然ゴムラテックス等を挙げることができる。これらは、その１種を単独で用いても良く、またそれらの２種以上を組み合わせて用いても良い。 In the present invention, the thermoplastic resin is a substantially water-insoluble thermoplastic resin, for example, a liquid material in which the thermoplastic resin is dispersed in water, and it does not substantially dissolve in hot water once dried. Is distinguished from water-soluble resin. Examples thereof include vinyl acetate polymer, ethylene-vinyl acetate copolymer, vinyl chloride polymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride- (meth) acrylic acid ester copolymer, (meth) acrylic acid. Ester polymers, styrene- (meth) acrylic acid ester copolymers, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, isoprene copolymers, chloroprene copolymers, urethane polymers, and their polymers It is a synthetic resin such as a copolymer in which two or more monomers constituting the coalescence are combined in a random, graft or block manner, and includes an aqueous dispersion or emulsion. Moreover, natural rubber latex etc. can be mentioned. One of these may be used alone, or two or more of these may be used in combination.
本発明において、熱可塑性樹脂のガラス転移温度は、低すぎるとインク受理層のべとつきによるブロッキング発生や、インク受理層の強度低下に繋がる。また高すぎると乾燥工程での皮膜形成が不十分となり、印字品質の低下や記録材料としての耐水性の低下を招くことから、−２０℃〜６０℃であることが好ましく、０℃〜４０℃であることが更に好ましい。 In the present invention, if the glass transition temperature of the thermoplastic resin is too low, blocking due to stickiness of the ink receiving layer and strength reduction of the ink receiving layer are caused. On the other hand, if it is too high, film formation in the drying process becomes insufficient, leading to a decrease in printing quality and a decrease in water resistance as a recording material. Therefore, the temperature is preferably -20 ° C to 60 ° C, preferably 0 ° C to 40 ° C. More preferably.
本発明において無機微粒子とは、平均粒子径が１０μｍ以下の一次あるいは凝集粒子を指し、その例としては、重質炭酸カルシウム、軽質炭酸カルシウム、湿式合成シリカ、乾式合成シリカ、コロイダルシリカ、ケイソウ土、ケイ酸カルシウム、タルク、水酸化マグネシウム、ハロイサイト、活性白土、酸性白土、ハイドロタルサイト、アルミナ水和物、水酸化アルミニウム、ベントナイトクレー、ゼオライト、カオリン、焼成カオリン、セッコウ、酸化チタン、硫酸バリウム等を挙げることができる。これらの顔料は、その１種を単独で用いても良く、またはそれらの２種以上を組み合わせて用いても良い。 In the present invention, the inorganic fine particles refer to primary or agglomerated particles having an average particle diameter of 10 μm or less, and examples thereof include heavy calcium carbonate, light calcium carbonate, wet synthetic silica, dry synthetic silica, colloidal silica, diatomaceous earth, Calcium silicate, talc, magnesium hydroxide, halloysite, activated clay, acid clay, hydrotalcite, alumina hydrate, aluminum hydroxide, bentonite clay, zeolite, kaolin, calcined kaolin, gypsum, titanium oxide, barium sulfate, etc. Can be mentioned. One of these pigments may be used alone, or two or more thereof may be used in combination.
本発明において無機微粒子の平均粒子径とは、凝集構造を有する粒子についてはその凝集粒子径を、凝集構造をとらない粒子についてはその一次粒子径を指す。これら無機微粒子の平均粒子径の測定法としては、レーザー回折法、細孔電気抵抗法、動的光散乱法、遠心沈降法等が知られている。通常、コロイダルシリカ等サブミクロン以下の微粒子の測定には動的光散乱法が用いられ、ミクロンオーダーの微粒子に関してはレーザー回折法や細孔電気抵抗法が用いられることが多い。本発明における平均粒子径の測定は、サブミクロン以下に関しては動的光散乱法、ミクロンオーダーに関してはレーザー回折法の値を用いる。 In the present invention, the average particle size of the inorganic fine particles refers to the aggregated particle size for particles having an aggregated structure, and the primary particle size for particles not having an aggregated structure. Known methods for measuring the average particle size of these inorganic fine particles include laser diffraction, pore electrical resistance, dynamic light scattering, and centrifugal sedimentation. Usually, the dynamic light scattering method is used to measure fine particles of submicron or less such as colloidal silica, and the laser diffraction method or the pore electrical resistance method is often used for fine particles of micron order. In the measurement of the average particle diameter in the present invention, the value of the dynamic light scattering method is used for submicron or less, and the value of the laser diffraction method is used for the micron order.
本発明におけるこれら無機微粒子の添加量は、少なすぎるとインク受理層のべとつき及びインク乾燥性改善効果が得られず、多すぎると発色性や耐水性等の品質の著しい低下を招くことから、熱可塑性樹脂１００質量部に対して５〜５０質量部が好ましく、１０〜２５質量部が更に好ましい。 If the addition amount of these inorganic fine particles in the present invention is too small, the stickiness of the ink receiving layer and the ink drying property cannot be improved, and if too large, the quality such as color developability and water resistance will be significantly lowered. 5-50 mass parts is preferable with respect to 100 mass parts of plastic resins, and 10-25 mass parts is still more preferable.
かかる無機微粒子の中でもシリカ微粒子は、とりわけ印字部の発色性を向上しつつ、インク受理層のべとつきやインク乾燥性を改善できることから好ましい。本発明においてシリカ微粒子とは、ケイ酸ナトリウム等のケイ酸塩と、硫酸等の酸を混和し、洗浄、熟成、粉砕等の工程を経る、沈降法及びゲル法としてその製造法が知られている所謂湿式法シリカ、または気化させた四塩化ケイ素と水素の混合物を１６００℃以上の高温で空気中において燃焼させることにより製造する所謂乾式法シリカ等の多孔質の二酸化ケイ素を指す。本発明の塗工組成物には、そのいずれをも好ましく用いることができる。 Among these inorganic fine particles, silica fine particles are particularly preferable because they can improve the stickiness of the ink receiving layer and the ink drying property while improving the color developability of the printing portion. In the present invention, silica fine particles are mixed with a silicate such as sodium silicate and an acid such as sulfuric acid, and are subjected to steps such as washing, aging, and pulverization, and their production methods are known as precipitation methods and gel methods. It refers to porous silicon dioxide such as so-called wet process silica or so-called dry process silica produced by burning a mixture of vaporized silicon tetrachloride and hydrogen in air at a high temperature of 1600 ° C. or higher. Any of them can be preferably used in the coating composition of the present invention.
本発明に用いるシリカ微粒子としては、その平均粒子径が大きすぎるものを用いた場合、印字部の発色性が発現しにくくなることがあり、また平均粒子径が小さすぎると、インク乾燥性に対する効果が低くなることから、シリカ微粒子の平均粒子径は０．３〜６μｍのものが好ましく用いられ、０．５〜３μｍのものがより好ましく用いられる。 As the silica fine particles used in the present invention, when the particles having an average particle size that is too large are used, it may be difficult to develop the color developability of the printed portion. If the average particle size is too small, the effect on the ink drying property may be obtained. Therefore, the average particle size of the silica fine particles is preferably 0.3 to 6 μm, more preferably 0.5 to 3 μm.
本発明における有機中空粒子とは、通常は水分散体として提供され、粒子内部には水が充填されている。これら粒子は、乾燥により粒子内部の水が粒子の殻部分を拡散、通過して空気と置換され、空隙を有する構造になる。このような有機中空粒子は市販されており、具体的な商品名としては、ニポールＭＨ５０５５（日本ゼオン株式会社製）、ローペイクＨＰ−１０５５、ローペイクＨＰ−９１、ローペイクＨＰ−４３３、ローペイクＯＰ−８４Ｊ、ローペイクＡＦ−１３５３、ローペイクＳＮ−１０５５、ローペイクＳＥ、ローペイクＳＴ（ローム・アンド・ハース・ジャパン株式会社製）、ＳＸ８６６（Ａ）、ＳＸ８６６（Ｂ）、ＳＸ８７８２（Ａ）、ＳＸ８７８２（Ｄ）、ＳＸ８７８２（Ｐ）（ＪＳＲ株式会社製）等が挙げられる。これらの粒子は、その１種を単独で用いても良く、またはそれらの２種以上を組み合わせて用いても良い。 The organic hollow particles in the present invention are usually provided as an aqueous dispersion, and the inside of the particles is filled with water. These particles have a structure having voids because water inside the particles diffuses and passes through the shells of the particles and is replaced with air by drying. Such organic hollow particles are commercially available, and specific trade names include Nipol MH5055 (manufactured by Zeon Corporation), Ropaque HP-1055, Ropaque HP-91, Ropaque HP-433, Ropaque OP-84J, Ropaque AF-1353, Ropaque SN-1055, Ropaque SE, Ropaque ST (manufactured by Rohm and Haas Japan Co., Ltd.), SX866 (A), SX866 (B), SX8782 (A), SX8782 (D), SX8782 ( P) (manufactured by JSR Corporation) and the like. One kind of these particles may be used alone, or two or more kinds thereof may be used in combination.
本発明において有機中空粒子の平均粒子径とは、凝集構造を有する粒子についてはその凝集粒子径を、凝集構造をとらない粒子についてはその一次粒子径を指す。これら有機中空粒子の平均粒子径の測定法としては、レーザー回折法、細孔電気抵抗法、動的光散乱法、遠心沈降法等が知られている。通常、サブミクロン以下の粒子の測定には動的光散乱法が用いられ、ミクロンオーダーの粒子に関してはレーザー回折法や細孔電気抵抗法が用いられることが多い。本発明における平均粒子径の測定は、サブミクロン以下に関しては動的光散乱法、ミクロンオーダーに関してはレーザー回折法の値を用いる。 In the present invention, the average particle size of the organic hollow particles refers to the aggregated particle size for particles having an aggregated structure, and the primary particle size for particles not having an aggregated structure. Known methods for measuring the average particle size of these organic hollow particles include laser diffraction, pore electrical resistance, dynamic light scattering, and centrifugal sedimentation. Usually, the dynamic light scattering method is used to measure particles of submicron or less, and the laser diffraction method or the pore electrical resistance method is often used for particles of micron order. In the measurement of the average particle diameter in the present invention, the value of the dynamic light scattering method is used for submicron or less, and the value of the laser diffraction method is used for the micron order.
本発明に用いる有機中空粒子の平均粒子径は、０．４〜１．０μｍの範囲である。ここで有機中空粒子の平均粒子径が０．４μｍ未満の場合、インク乾燥性やインク受理層表面のべとつき悪化を招き、また、平均粒子径が１．０μｍを超えると、発色性や耐水性の低下を招くため、好ましくない。 The average particle diameter of the organic hollow particles used in the present invention is in the range of 0.4 to 1.0 μm. Here, when the average particle diameter of the organic hollow particles is less than 0.4 μm, the ink drying property and the stickiness of the surface of the ink receiving layer are deteriorated, and when the average particle diameter exceeds 1.0 μm, the color developability and water resistance are deteriorated. Since it causes a decrease, it is not preferable.
本発明における有機中空粒子の添加量は、少なすぎるとインク乾燥性改善効果が得られず、多すぎると塗層強度の低下を招くことから、熱可塑性樹脂１００質量部に対して、１０〜７５質量部が好ましく、２０〜６５質量部が更に好ましい。 If the addition amount of the organic hollow particles in the present invention is too small, the effect of improving the ink drying property cannot be obtained, and if it is too large, the coating layer strength is lowered. A mass part is preferable and 20-65 mass parts is still more preferable.
かかる有機中空粒子の中でも、その空隙率が３０％以上の粒子を使用することで、より良好なインク乾燥性を得ることができるため好ましい。 Among these organic hollow particles, it is preferable to use particles having a porosity of 30% or more because better ink drying properties can be obtained.
本発明においてインク受理層とは、支持体上に形成される塗工層を言う。この塗工層を形成する塗工組成物は通常、水中に各材料を溶解ないし分散せしめた水性液の形で用いられる。 In the present invention, the ink receiving layer refers to a coating layer formed on a support. The coating composition for forming this coating layer is usually used in the form of an aqueous liquid in which each material is dissolved or dispersed in water .
本発明のインク受理層には、本発明の効果を損なわない程度に、ビニルピロリドン重合体、（メタ）アクリル酸重合体、（メタ）アクリルアミド重合体、ポリビニルアルコール、カルボキシメチルセルロース、ヒドロキシエチルセルロース、澱粉等の水溶性高分子化合物を添加することもできる。また必要に応じて、界面活性剤、消泡剤、増粘剤、色味調整剤、蛍光増白剤、酸化防止剤、紫外線吸収剤等各種の添加剤を添加することもできる。 In the ink receiving layer of the present invention, vinyl pyrrolidone polymer, (meth) acrylic acid polymer, (meth) acrylamide polymer, polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, starch, etc. The water-soluble polymer compound can also be added. If necessary, various additives such as a surfactant, an antifoaming agent, a thickening agent, a color adjusting agent, a fluorescent brightening agent, an antioxidant, and an ultraviolet absorber can be added.
本発明において、塗工組成物を塗工する方法に特に制限はなく、エアナイフコーター、ブレードコーター、ロッドブレードコーター、バーコーター、リバースロールコーター、ロールナイフコーター、ゲートロールコーター、フィルムトランスファーコーター、リップコーター、ダイコーター、カーテンコーター等各種の塗工方式を用いることができる。 In the present invention, the method for coating the coating composition is not particularly limited, and an air knife coater, blade coater, rod blade coater, bar coater, reverse roll coater, roll knife coater, gate roll coater, film transfer coater, lip coater. Various coating methods such as a die coater and a curtain coater can be used.
本発明において、塗工組成物を支持体上に塗工する量に特に制限はないが、インク乾燥性と経済性を両立させるためには通常、固形分として５〜３０ｇ／ｍ２が好ましく、１０〜２５ｇ／ｍ２が更に好ましい。また本発明の塗工組成物を支持体上に塗設する場合、本発明の効果を損なわない範囲で、目的とする量を２回以上に分けて塗設しても構わない。 In the present invention, the amount of the coating composition to be coated on the support is not particularly limited, but usually 5 to 30 g / m 2 is preferable as a solid content in order to achieve both ink drying properties and economy. 10-25 g / m < 2 > is still more preferable. Moreover, when coating the coating composition of this invention on a support body, in the range which does not impair the effect of this invention, you may divide and make the target quantity into 2 times or more.
また、塗工組成物を塗工・乾燥させた後で、ソフトカレンダー、スーパーカレンダー等のカレンダー装置により処理を行うことも可能である。 In addition, after the coating composition is applied and dried, it can be processed by a calendar device such as a soft calendar or a super calendar.
以下本発明の実施例を示す。なお、本実施例中で、特に明示しない限り部は質量部、％は質量％を示すものとする。 Examples of the present invention will be described below. In the examples, unless otherwise specified, parts are parts by mass, and% is mass%.
［実施例１］
［インク受理層塗工組成物１の調製］
固形分濃度５５％のエチレン−酢酸ビニル共重合物（住化ケムテックス株式会社製スミカフレックス４０１ＨＱ：ガラス転移温度−１８℃）１８１．８部（不揮発分として１００部）に、固形分濃度２７％の有機中空粒子（ローム・アンド・ハース・ジャパン株式会社製ローペイクＨＰ−９１：平均粒子径１．０μｍ、空隙率５０％）を１６６．７部（不揮発分として４５部）添加、次いで固形分濃度８％で溶解したポリビニルアルコール（クラレ株式会社製ＰＶＡ２３５）を１８．７５部（不揮発分として１．５部）添加、攪拌した。更に、平均粒子径３μｍの非晶質シリカ（水澤化学工業株式会社製ミズカシルＰ−７０５）を２０部（不揮発分として２０部）添加し、最終固形分濃度が３４％となるように水を添加・混合してインク受理層塗工組成物１を得た。
[Example 1]
[Preparation of Ink Receiving Layer Coating Composition 1]
181.8 parts (100 parts as a non-volatile content) of ethylene-vinyl acetate copolymer (Sumitomo Chemtex Co., Ltd., Sumikaflex 401HQ: glass transition temperature—18 ° C.) having a solid content concentration of 55% and a solid content concentration of 27% 166.7 parts (45 parts as non-volatile content) of organic hollow particles (Rohm and Haas Japan Co., Ltd. Ropeke HP-91: average particle size 1.0 μm, porosity 50%) were added, and then solid content concentration 8 % Of polyvinyl alcohol (PVA235 manufactured by Kuraray Co., Ltd.) dissolved in% was added and stirred. Furthermore, 20 parts of amorphous silica (Mizusawa Chemical Co., Ltd. Mizukasil P-705) with an average particle diameter of 3 μm was added, and water was added so that the final solid content concentration was 34%. -The ink receiving layer coating composition 1 was obtained by mixing.
［インクジェット記録材料の作製］
坪量１０４．７ｇ／ｍ２の原紙（三菱製紙株式会社製ダイヤフォーム）上に、インク受理層塗工組成物１を、乾燥後の塗工量が２０ｇ／ｍ２となるようにエアナイフコーターを用いて塗工し、熱風型乾燥機を用いて乾燥させ、得られた塗工紙をソフトカレンダーにて処理することで実施例１のインクジェット記録材料を作製した。
[Preparation of inkjet recording material]
On a base paper having a basis weight of 104.7 g / m 2 (Diafoam manufactured by Mitsubishi Paper Industries Co., Ltd.), apply an air knife coater so that the ink receiving layer coating composition 1 is 20 g / m 2 after drying. The inkjet recording material of Example 1 was produced by processing using the soft calender, and drying with the hot air type dryer.
［実施例２］
実施例１のインク受理層塗工組成物１における熱可塑性樹脂を、固形分濃度４６％のアクリル酸エステル共重合物（ニチゴー・モビニール株式会社製モビニールＤＭ７７４：ガラス転移温度１３℃）２１７．４部（不揮発分として１００部）に変更したインク受理層塗工組成物２を使用した以外は実施例１と同様にして実施例２のインクジェット記録材料を得た。
[Example 2]
217.4 parts of a thermoplastic resin in the ink-receiving layer coating composition 1 of Example 1 having an acrylic acid ester copolymer having a solid content concentration of 46% (Minvinyl DM774, glass transition temperature 13 ° C., manufactured by Nichigo Movinyl Co., Ltd.) An ink jet recording material of Example 2 was obtained in the same manner as in Example 1 except that the ink receiving layer coating composition 2 changed to (nonvolatile content of 100 parts) was used.
［実施例３］
実施例１のインク受理層塗工組成物１における熱可塑性樹脂を、固形分濃度５０％の塩化ビニル−アクリル系共重合物（日信化学工業株式会社製ビニブラン９０２：ガラス転移温度６０℃）２００部（不揮発分として１００部）に変更したインク受理層塗工組成物３を使用した以外は実施例１と同様にして実施例３のインクジェット記録材料を得た。
[Example 3]
The thermoplastic resin in the ink-receiving layer coating composition 1 of Example 1 was replaced with a vinyl chloride-acrylic copolymer having a solid content of 50% (Vinyl Blanc 902 manufactured by Nissin Chemical Industry Co., Ltd .: glass transition temperature 60 ° C.) 200. An ink jet recording material of Example 3 was obtained in the same manner as in Example 1 except that the ink receiving layer coating composition 3 changed to 100 parts (nonvolatile content) was used.
［実施例４］
実施例１のインク受理層塗工組成物１における熱可塑性樹脂を、固形分濃度４４％のスチレン−アクリル系共重合物（ヘンケルテクノロジーズジャパン株式会社製ヨドゾールＧＤ９３：ガラス転移温度３５℃）２２７．３部（不揮発分として１００部）に変更したインク受理層塗工組成物４を使用した以外は実施例１と同様にして実施例４のインクジェット記録材料を得た。
[Example 4]
The thermoplastic resin in the ink-receiving layer coating composition 1 of Example 1 was converted into a styrene-acrylic copolymer having a solid content of 44% (Yodosol GD93 manufactured by Henkel Technologies Japan Co., Ltd .: glass transition temperature 35 ° C.) 227.3. An ink jet recording material of Example 4 was obtained in the same manner as in Example 1 except that the ink-receiving layer coating composition 4 changed to 100 parts (nonvolatile content) was used.
［実施例５］
実施例１のインク受理層塗工組成物１における熱可塑性樹脂を、固形分濃度４０％の塩化ビニル−アクリル系共重合物（日信化学工業株式会社製ビニブラン９００：ガラス転移温度７０℃）２５０部（不揮発分として１００部）に変更したインク受理層塗工組成物５を使用した以外は実施例１と同様にして実施例５のインクジェット記録材料を得た。
[Example 5]
The thermoplastic resin in the ink-receiving layer coating composition 1 of Example 1 was replaced with a vinyl chloride-acrylic copolymer having a solid content of 40% (Vinyl Blanc 900 manufactured by Nissin Chemical Industry Co., Ltd .: glass transition temperature 70 ° C.) 250. An ink jet recording material of Example 5 was obtained in the same manner as in Example 1 except that the ink receiving layer coating composition 5 changed to 100 parts (nonvolatile content) was used.
［実施例６］
実施例１のインク受理層塗工組成物１における熱可塑性樹脂を、固形分濃度４５％のアクリル酸エステル共重合物（日本ゼオン株式会社製Ｎｉｐｏｌ ＬＸ８７４：ガラス転移温度−３１℃）２２２．２部（不揮発分として１００部）に変更したインク受理層塗工組成物６を使用した以外は実施例１と同様にして実施例６のインクジェット記録材料を得た。
[Example 6]
222.2 parts of an acrylic ester copolymer (Nipol LX874, manufactured by Nippon Zeon Co., Ltd .: glass transition temperature -31 ° C.) having a solid content concentration of 45% was used as the thermoplastic resin in the ink receiving layer coating composition 1 of Example 1. An ink jet recording material of Example 6 was obtained in the same manner as in Example 1 except that the ink receiving layer coating composition 6 changed to (nonvolatile content of 100 parts) was used.
［実施例７］
実施例４のインク受理層塗工組成物４における熱可塑性樹脂を、固形分濃度５５％のエチレン−酢酸ビニル共重合物（住化ケムテックス株式会社製スミカフレックス４０１ＨＱ：ガラス転移温度−１８℃）９０．９部（不揮発分として５０部）、及び固形分濃度４４％のスチレン−アクリル系共重合物（ヘンケルテクノロジーズジャパン株式会社製ヨドゾールＧＤ９３：ガラス転移温度３５℃）１１３．７部（不揮発分として５０部）に変更したインク受理層塗工組成物７を使用した以外は実施例４と同様にして実施例７のインクジェット記録材料を得た。
[Example 7]
The thermoplastic resin in the ink-receiving layer coating composition 4 of Example 4 was replaced with an ethylene-vinyl acetate copolymer having a solid content concentration of 55% (Sumikaflex 401HQ manufactured by Sumika Chemtex Co., Ltd .: glass transition temperature-18 ° C.) 90. 9 parts (50 parts as non-volatile content) and a styrene-acrylic copolymer having a solid content concentration of 44% (Yodosol GD93 manufactured by Henkel Technologies Japan Co., Ltd .: glass transition temperature 35 ° C.) 113.7 parts (50% as non-volatile content) The ink-jet recording material of Example 7 was obtained in the same manner as in Example 4 except that the ink-receiving layer coating composition 7 was used.
［実施例８］
実施例７のインク受理層塗工組成物７における非晶質シリカの量を、５部（不揮発分で５部）に変更したインク受理層塗工組成物８を使用した以外は実施例７と同様にして実施例８のインクジェット記録材料を得た。
[Example 8]
Example 7 is the same as Example 7 except that the amount of amorphous silica in the ink-receiving layer coating composition 7 of Example 7 is changed to 5 parts (5 parts in nonvolatile content). In the same manner, an ink jet recording material of Example 8 was obtained.
［参考例１］
実施例７のインク受理層塗工組成物７における非晶質シリカの量を、５０部（不揮発分で５０部）に変更したインク受理層塗工組成物９を使用した以外は実施例７と同様にして参考例１のインクジェット記録材料を得た。
[ Reference Example 1 ]
Example 7 and Example 7 were used except that the amount of amorphous silica in the ink-receiving layer coating composition 7 of Example 7 was changed to 50 parts (50 parts in nonvolatile content). In the same manner, the ink jet recording material of Reference Example 1 was obtained.
［実施例９］
実施例７のインク受理層塗工組成物７における有機中空粒子の量を、３７．０４部（不揮発分で１０部）に変更したインク受理層塗工組成物１０を使用した以外は実施例７と同様にして実施例９のインクジェット記録材料を得た。
[Example 9 ]
Example 7 except that the ink receiving layer coating composition 10 in which the amount of the organic hollow particles in the ink receiving layer coating composition 7 of Example 7 was changed to 37.04 parts (10 parts in terms of nonvolatile content) was used. In the same manner, an ink jet recording material of Example 9 was obtained.
［実施例１０］
実施例７のインク受理層塗工組成物７における有機中空粒子の量を、２７７．８部（不揮発分で７５部）に変更したインク受理層塗工組成物１１を使用した以外は実施例７と同様にして実施例１０のインクジェット記録材料を得た。
[Example 10 ]
Example 7 except that the ink receiving layer coating composition 11 was used in which the amount of the organic hollow particles in the ink receiving layer coating composition 7 of Example 7 was changed to 277.8 parts (75 parts in nonvolatile content). In the same manner as described above, an ink jet recording material of Example 10 was obtained.
［実施例１１］
実施例７のインク受理層塗工組成物７における有機中空粒子を、平均粒子径１．０μｍ、空隙率５５％のローペイクＨＰ−１０５５（ローム・アンド・ハース・ジャパン株式会社製）に変更したインク受理層塗工組成物１２を使用した以外は実施例７と同様にして実施例１１のインクジェット記録材料を得た。
[Example 11 ]
Ink obtained by changing the organic hollow particles in the ink-receiving layer coating composition 7 of Example 7 to Ropeke HP-1055 (Rohm and Haas Japan Co., Ltd.) having an average particle size of 1.0 μm and a porosity of 55%. An inkjet recording material of Example 11 was obtained in the same manner as Example 7 except that the receiving layer coating composition 12 was used.
［実施例１２］
実施例７のインク受理層塗工組成物７における有機中空粒子を、平均粒子径０．５５μｍ、空隙率２５％のローペイクＯＰ−８４Ｊ（ローム・アンド・ハース・ジャパン株式会社製）に変更したインク受理層塗工組成物１３を使用した以外は実施例７と同様にして実施例１２のインクジェット記録材料を得た。
[Example 12 ]
Ink obtained by changing the organic hollow particles in the ink receiving layer coating composition 7 of Example 7 to Ropeke OP-84J (Rohm and Haas Japan Co., Ltd.) having an average particle size of 0.55 μm and a porosity of 25%. An inkjet recording material of Example 12 was obtained in the same manner as in Example 7 except that the receiving layer coating composition 13 was used.
［実施例１３］
実施例７のインク受理層塗工組成物７における有機中空粒子を、平均粒子径０．４５μｍ、空隙率３３％のローペイクＨＰ−４３３（ローム・アンド・ハース・ジャパン株式会社製）に変更したインク受理層塗工組成物１４を使用した以外は実施例７と同様にして実施例１３のインクジェット記録材料を得た。
[Example 13 ]
Ink obtained by changing the organic hollow particles in the ink-receiving layer coating composition 7 of Example 7 to Ropeke HP-433 (Rohm and Haas Japan Co., Ltd.) having an average particle diameter of 0.45 μm and a porosity of 33%. An ink jet recording material of Example 13 was obtained in the same manner as in Example 7 except that the receiving layer coating composition 14 was used.
［実施例１４］
実施例７のインク受理層塗工組成物７における非晶質シリカを、平均粒子径６μｍの非晶質シリカ（水澤化学工業株式会社製ミズカシルＰ−７８Ａ）に変更したインク受理層塗工組成物１５を使用した以外は実施例７と同様にして実施例１４のインクジェット記録材料を得た。
[Example 14 ]
Ink-receiving layer coating composition obtained by changing the amorphous silica in the ink-receiving layer coating composition 7 of Example 7 to amorphous silica having an average particle diameter of 6 μm (Mizukasil P-78A manufactured by Mizusawa Chemical Co., Ltd.). An inkjet recording material of Example 14 was obtained in the same manner as Example 7 except that 15 was used.
［参考例２］
実施例７のインク受理層塗工組成物７における非晶質シリカを、平均粒子径２５ｎｍ、固形分濃度５０％のコロイダルシリカ（日産化学工業株式会社製スノーテックス５０）４０部（不揮発分として２０部）に変更したインク受理層塗工組成物１６を使用した以外は実施例７と同様にして参考例２のインクジェット記録材料を得た。
[Reference Example 2 ]
The amorphous silica in the ink-receiving layer coating composition 7 of Example 7 is 40 parts of colloidal silica (Snowtex 50 manufactured by Nissan Chemical Industries, Ltd.) having an average particle size of 25 nm and a solid content concentration of 50% (nonvolatile content of 20 parts). The ink-jet recording material of Reference Example 2 was obtained in the same manner as in Example 7 except that the ink receiving layer coating composition 16 changed to (Part) was used.
［実施例１５］
実施例７のインク受理層塗工組成物７における非晶質シリカを、平均粒子径０．３μｍの非晶質シリカ（グレースデビソン社製サイロジェットＤＡＺＬ７０３Ａ）に変更したインク受理層塗工組成物１７を使用した以外は実施例７と同様にして実施例１５のインクジェット記録材料を得た。
[Example 15 ]
Ink-receiving layer coating composition 17 in which the amorphous silica in ink-receiving layer coating composition 7 of Example 7 was changed to amorphous silica having an average particle size of 0.3 μm (Silojet DAZL703A manufactured by Grace Devison). An ink jet recording material of Example 15 was obtained in the same manner as Example 7 except that was used.
［実施例１６］
実施例７のインク受理層塗工組成物７における非晶質シリカを、平均粒子径１μｍの非晶質シリカ（グレースデビソン社製サイロジェットＤＡＺＬ７１０Ａ）に変更したインク受理層塗工組成物１８を使用した以外は実施例７と同様にして実施例１６のインクジェット記録材料を得た。
[Example 16 ]
The ink receiving layer coating composition 18 obtained by changing the amorphous silica in the ink receiving layer coating composition 7 of Example 7 to amorphous silica having an average particle diameter of 1 μm (Silojet DAZL710A manufactured by Grace Devison) is used. An ink jet recording material of Example 16 was obtained in the same manner as Example 7 except that.
［参考例３］
実施例７のインク受理層塗工組成物７における非晶質シリカを、平均粒子径８μｍの非晶質シリカ（東ソーシリカ株式会社製ニップジェルＡＺ−６Ａ０）に変更したインク受理層塗工組成物１９を使用した以外は実施例７と同様にして参考例３のインクジェット記録材料を得た。
[Reference Example 3 ]
Ink-receiving layer coating composition 19 obtained by changing the amorphous silica in the ink-receiving layer coating composition 7 of Example 7 to amorphous silica having an average particle diameter of 8 μm (Nipgel AZ-6A0 manufactured by Tosoh Silica Co., Ltd.) The ink jet recording material of Reference Example 3 was obtained in the same manner as Example 7 except that was used.
［比較例１］
実施例１のインク受理層塗工組成物１を、下記インク受理層塗工組成物２０に変更した以外は実施例１と同様にして比較例１のインクジェット記録材料を得た。
［インク受理層塗工組成物２０の調製］
固形分濃度５５％のエチレン−酢酸ビニル共重合物（住化ケムテックス株式会社製スミカフレックス４０１ＨＱ：ガラス転移温度−１８℃）９０．９部（不揮発分として５０部）に、固形分濃度４４％のスチレン−アクリル系共重合物（ヘンケルテクノロジーズジャパン株式会社製ヨドゾールＧＤ９３：ガラス転移温度３５℃）１１３．７部（不揮発分として５０部）を添加、次いで固形分濃度８％で溶解したポリビニルアルコール（クラレ株式会社製ＰＶＡ２３５）を１８．７５部（不揮発分として１．５部）添加、攪拌し、最終固形分濃度が３４％となるように水を添加・混合してインク受理層塗工組成物２０を得た。
[Comparative Example 1]
An inkjet recording material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the ink receiving layer coating composition 1 of Example 1 was changed to the following ink receiving layer coating composition 20.
[Preparation of Ink Receiving Layer Coating Composition 20]
An ethylene-vinyl acetate copolymer having a solid content concentration of 55% (Sumikaflex 401HQ manufactured by Sumika Chemtex Co., Ltd .: glass transition temperature—18 ° C.) 90.9 parts (50 parts as non-volatile content) with a solid content concentration of 44% Styrene-acrylic copolymer (Yendol GD93 manufactured by Henkel Technologies Japan Co., Ltd .: glass transition temperature 35 ° C.) 113.7 parts (50 parts as non-volatile content) was added, and then polyvinyl alcohol (Kuraray) dissolved at a solid content concentration of 8%. 18.75 parts (1.5 parts as a non-volatile content) of PVA235) manufactured by Co., Ltd. was added and stirred, and water was added and mixed so that the final solid content concentration would be 34%. The ink receiving layer coating composition 20 Got.
［比較例２］
実施例７のインク受理層塗工組成物７から、有機中空粒子を除いたインク受理層塗工組成物２１を使用した以外は実施例７と同様にして比較例２のインクジェット記録材料を得た。
[Comparative Example 2]
An ink jet recording material of Comparative Example 2 was obtained in the same manner as in Example 7 except that the ink receiving layer coating composition 21 excluding the organic hollow particles was used from the ink receiving layer coating composition 7 of Example 7. .
［比較例３］
実施例７のインク受理層塗工組成物７から、非晶質シリカを除いたインク受理層塗工組成物２２を使用した以外は実施例７と同様にして比較例３のインクジェット記録材料を得た。
[Comparative Example 3]
An ink jet recording material of Comparative Example 3 was obtained in the same manner as in Example 7 except that the ink receiving layer coating composition 22 excluding amorphous silica was used from the ink receiving layer coating composition 7 of Example 7. It was.
［比較例４］
実施例７のインク受理層塗工組成物７における非晶質シリカの量を、６０部（不揮発分として６０部）に変更したインク受理層塗工組成物２３を使用した以外は実施例７と同様にして比較例４のインクジェット記録材料を得た。
[Comparative Example 4]
Example 7 and Example 7 were used except that the amount of amorphous silica in the ink-receiving layer coating composition 7 of Example 7 was changed to 60 parts (60 parts as a non-volatile content). Similarly, an inkjet recording material of Comparative Example 4 was obtained.
［比較例５］
実施例７のインク受理層塗工組成物７における有機中空粒子の量を、３３３．３部（不揮発分として９０部）に変更したインク受理層塗工組成物２４を使用した以外は実施例７と同様にして比較例５のインクジェット記録材料を得た。
[Comparative Example 5]
Example 7 except that the ink receiving layer coating composition 24 in which the amount of the organic hollow particles in the ink receiving layer coating composition 7 of Example 7 was changed to 333.3 parts (90 parts as a non-volatile content) was used. In the same manner, an ink jet recording material of Comparative Example 5 was obtained.
［比較例６］
実施例７のインク受理層塗工組成物７における有機中空粒子を、平均粒子径０．３μｍ、空隙率３０％のＳＸ８６６（Ｂ）（ＪＳＲ株式会社製）に変更し、最終固形分濃度を３２％としたインク受理層塗工組成物２５に変更した以外は実施例７と同様にして比較例６のインクジェット記録材料を得た。
[Comparative Example 6]
The organic hollow particles in the ink receiving layer coating composition 7 of Example 7 were changed to SX866 (B) (manufactured by JSR Corporation) having an average particle diameter of 0.3 μm and a porosity of 30%, and the final solid content concentration was 32. The ink jet recording material of Comparative Example 6 was obtained in the same manner as in Example 7, except that the composition was changed to the ink receiving layer coating composition 25.
［比較例７］
実施例７のインク受理層塗工組成物７における有機中空粒子を、平均粒子径１．３μｍ、空隙率５３％のローペイクＡＦ−１３５３（ローム・アンド・ハース・ジャパン株式会社製）に変更したインク受理層塗工組成物２６に変更した以外は実施例７と同様にして比較例７のインクジェット記録材料を得た。
[Comparative Example 7]
Ink obtained by changing the organic hollow particles in the ink-receiving layer coating composition 7 of Example 7 to Ropeke AF-1353 (Rohm and Haas Japan Co., Ltd.) having an average particle size of 1.3 μm and a porosity of 53%. An inkjet recording material of Comparative Example 7 was obtained in the same manner as in Example 7 except that the receiving layer coating composition 26 was changed.
［比較例８］
実施例７のインク受理層塗工組成物７における有機中空粒子を、平均粒子径０．５μｍ、空隙率０％の有機密実粒子（三井化学株式会社製グロスデール２０１Ｓ）に変更したインク受理層塗工組成物２７に変更した以外は実施例７と同様にして比較例８のインクジェット記録材料を得た。
[Comparative Example 8]
The ink receiving layer obtained by changing the organic hollow particles in the ink receiving layer coating composition 7 of Example 7 to organic solid particles (Grossdale 201S manufactured by Mitsui Chemicals, Inc.) having an average particle diameter of 0.5 μm and a porosity of 0%. An inkjet recording material of Comparative Example 8 was obtained in the same manner as Example 7 except that the coating composition 27 was changed.
［比較例９］
実施例１のインク受理層塗工組成物１を、下記インク受理層塗工組成物２８に変更し、乾燥後の塗工量を１２ｇ／ｍ２とした以外は実施例１と同様にして比較例９のインクジェット記録材料を得た。
［インク受理層塗工組成物２８の調製］
水３５０部に水酸化ナトリウム２部を溶解し、ここに平均粒子径６μｍの非晶質シリカ（水澤化学工業株式会社製ミズカシルＰ−７８Ａ）１００部を添加した後、ノコギリ型ブレードを有する分散機を用いて十分に分散した。次いでケン化度９８．５ｍｏｌ％のシリル変性ポリビニルアルコール（クラレ社製Ｒポリマー１１３０）の１２％水溶液２００部（不揮発分として２４部）を添加・混合してインク受理層塗工組成物２８を得た。
[Comparative Example 9]
Comparison was made in the same manner as in Example 1 except that the ink receiving layer coating composition 1 of Example 1 was changed to the following ink receiving layer coating composition 28 and the coating amount after drying was changed to 12 g / m 2. The ink jet recording material of Example 9 was obtained.
[Preparation of Ink Receiving Layer Coating Composition 28]
Disperser having a saw blade after dissolving 2 parts of sodium hydroxide in 350 parts of water and adding 100 parts of amorphous silica (Mizukasil P-78A manufactured by Mizusawa Chemical Co., Ltd.) having an average particle size of 6 μm. Was sufficiently dispersed. Next, 200 parts of a 12% aqueous solution of silyl-modified polyvinyl alcohol (R polymer 1130 manufactured by Kuraray Co., Ltd.) having a saponification degree of 98.5 mol% was added and mixed to obtain an ink receiving layer coating composition 28. It was.
［印刷品質の評価］
ローランド．ディー．ジー．株式会社製インクジェットプリンター（ＳＯＬＪＥＴ ＰＲＯIIＶ）により、Ｃ、Ｍ、Ｙ、Ｋ、Ｒ、Ｇ、Ｂを隣接配置したベタ画像及びＩＳＯ／ＪＩＳ−ＳＣＩＤ Ｎ５（自転車）の評価画像を印刷し、各記録材料の印刷品質を、画像の発色性及び細部の判読性を基準とし次の４段階に分類した。ここで、Ｄは実用上問題があるレベルである。
Ａ；発色性が高い、もしくは印画部にムラや滲みがなく、非常に良好
Ｂ；発色性がやや低い、もしくは印画部に若干の滲みやムラが確認される
Ｃ；発色性が低い、もしくは境界部の滲みが顕著で、ベタ部に吸収ムラが若干確認される
Ｄ；発色性が著しく低い、もしくは全般に色の境界部での滲み、ベタ部吸収ムラが顕著
[Evaluation of print quality]
Roland. Dee. Gee. Printed solid images with C, M, Y, K, R, G, and B adjacent and evaluation images of ISO / JIS-SCID N5 (bicycle) using an inkjet printer (SOLJET PROIIV) manufactured by Co., Ltd. The print quality was classified into the following four stages based on the color development of the image and the legibility of details. Here, D is a practically problematic level.
A: High color developability or very good with no unevenness or blurring in the print area B: Slightly low color developability or slight blurring or unevenness in the print area C: Low color developability or border Dyeing is noticeable in the solid part and some uneven absorption is observed in the solid part D: The color developability is remarkably low, or the bleeding in the color boundary part and the solid part absorption unevenness are remarkable in general.
［インク乾燥性の評価］
ローランド．ディー．ジー．株式会社製インクジェットプリンター（ＳＯＬＪＥＴ ＰＲＯIIＶ）により、Ｃ、Ｍ、Ｙ、Ｋ、Ｒ、Ｇ、Ｂのベタ画像を印刷し、５分後に市販のＰＰＣ用紙を印刷部に載せて、ゴムローラーで５往復擦った際の該ＰＰＣ用紙の汚れ具合を基準として、各記録材料のインク乾燥性を次の４段階に分類した。ここで、Ｄは実用上問題があるレベルである。
Ａ；ＰＰＣ用紙へのインク転写は全くない
Ｂ；若干のインク転写が見られるものの、印画部の乱れはなく良好
Ｃ；ＲＧＢ等の二次色部でインク転写が顕著に見られる
Ｄ；インク転写が顕著に発生している
[Evaluation of ink drying properties]
Roland. Dee. Gee. A solid image of C, M, Y, K, R, G, and B is printed by an inkjet printer (SOLJET PROIIV), and a commercially available PPC paper is placed on the printing unit after 5 minutes, and the rubber roller makes 5 round trips. Based on the degree of soiling of the PPC paper when rubbed, the ink drying property of each recording material was classified into the following four stages. Here, D is a practically problematic level.
A: No ink transfer to PPC paper B: Slight ink transfer is observed, but there is no disturbance in the printed part C: Ink transfer is noticeable in secondary color parts such as RGB D: Ink transfer Is noticeably occurring
［記録材料の耐水性評価］
１０ｃｍ×１０ｃｍに裁断した各記録材料の裏面に、防水のためセロハンテープを全面貼付し、温度２０℃の水を満たしたバット中に１時間浸漬後、インク受理層表面を指で擦り、各記録材料の耐水性を目視評価した。ここで、Ｄは実用上問題があるレベルである。
Ａ；インク受理層への水の浸透及び剥離等は全くない
Ｂ；インク受理層に水が部分的に浸透するが、塗層剥離は確認されない
Ｃ；インク受理層に水が浸透し、部分的に塗層剥離を生じる
Ｄ；浸透した水が支持体まで到達し、擦過により支持体から剥離を生じる
[Water resistance evaluation of recording materials]
A cellophane tape is affixed to the back of each recording material cut to 10 cm × 10 cm for waterproofing, immersed in a vat filled with water at a temperature of 20 ° C. for 1 hour, and then the surface of the ink receiving layer is rubbed with a finger to record each recording material. The water resistance of the material was visually evaluated. Here, D is a practically problematic level.
A: No penetration or peeling of water into the ink receiving layer B; Water partially penetrates into the ink receiving layer but no coating layer peeling is confirmed C; Water penetrates into the ink receiving layer and partially D which causes peeling of the coating layer in the coating; D which penetrated water reaches the support and peels off from the support by rubbing
［インク受理層のべとつき評価］
Ａ４サイズに裁断した各記録材料の表面にＰＰＣ用紙を重ねた評価用サンプルを、ロール温度４０℃、５０ｋｇ／ｃｍ２のゲージ圧に調整したスーパーカレンダーに１回通紙し、その後、ＰＰＣ用紙と各記録材料を剥離することで、インク受理層のべとつきを評価した。ここで、Ｄは実用上問題があるレベルである。
Ａ；ＰＰＣ用紙への貼りつきは全くない
Ｂ；ＰＰＣ用紙への貼りつきが若干あるが、紙層剥離等の発生はなく、良好
Ｃ；ＰＰＣ用紙への貼りつきが顕著で、一部剥離が生じている
Ｄ；ＰＰＣ用紙が完全に貼りつき、剥がすことが困難
[Sticking evaluation of ink receiving layer]
An evaluation sample in which PPC paper is stacked on the surface of each recording material cut to A4 size is passed once through a super calendar adjusted to a roll temperature of 40 ° C. and a gauge pressure of 50 kg / cm 2. The stickiness of the ink receiving layer was evaluated by peeling off each recording material. Here, D is a practically problematic level.
A: There is no sticking to PPC paper B: There is some sticking to PPC paper, but there is no occurrence of paper layer peeling, etc. Good C: Sticking to PPC paper is remarkable, part peeling Generated D: PPC paper is completely stuck and difficult to remove
各実施例、各比較例で得られた記録材料のインク乾燥性、印刷品質、耐水性、べとつきを表１に示す。 Table 1 shows the ink drying properties, print quality, water resistance, and tackiness of the recording materials obtained in each Example and each Comparative Example.
表１より、支持体に熱可塑性樹脂、無機微粒子、有機中空粒子を少なくとも含有する塗工組成物からなるインク受理層を形成し、有機中空粒子の平均粒子径が０．４〜１．０μｍの範囲であり、熱可塑性樹脂１００質量部に対する無機微粒子及び有機中空粒子の比率が、それぞれ５〜５０質量部、１０〜７５質量部である実施例１〜１６並びに参考例１〜３は、良好なインク乾燥性を有しつつ、優れた印字品質とインク受理層の耐水性を有し、べとつきが少ないことがわかる。 From Table 1, an ink receiving layer made of a coating composition containing at least a thermoplastic resin, inorganic fine particles, and organic hollow particles is formed on the support, and the average particle size of the organic hollow particles is 0.4 to 1.0 μm. Examples 1 to 16 and Reference Examples 1 to 3 in which the ratio of the inorganic fine particles and the organic hollow particles to 100 parts by mass of the thermoplastic resin is 5 to 50 parts by mass and 10 to 75 parts by mass, respectively, are good. It can be seen that while having ink drying properties, it has excellent print quality and water resistance of the ink receiving layer, and is less sticky.
無機微粒子及び有機中空粒子の一方または両方を含まない比較例１、２及び３、有機中空粒子の平均粒子径が特定範囲未満の比較例６、有機中空粒子を有機密実粒子に置換した比較例８は、インク乾燥性及びべとつきが悪化する。無機微粒子及び有機中空粒子が特定の比率以上含まれる比較例４及び５は、耐水性及び印刷品質の悪化が顕著に現れる。有機中空粒子の平均粒子径が特定範囲を超える比較例７は、印刷品質が顕著に悪化する。シリカとポリビニルアルコールを主体とした比較例９は、顔料インクが塗層に浸透し、鮮明な画像が得られず、且つ塗層への水の浸透が顕著であり、耐水性が悪化する。 Comparative Examples 1, 2, and 3 not including one or both of inorganic fine particles and organic hollow particles, Comparative Example 6 in which the average particle diameter of organic hollow particles is less than a specific range, and Comparative Example in which organic hollow particles are replaced with organic dense particles In No. 8, ink drying property and stickiness deteriorate. In Comparative Examples 4 and 5 in which the inorganic fine particles and the organic hollow particles are contained in a specific ratio or more, the water resistance and the print quality are significantly deteriorated. In Comparative Example 7 in which the average particle diameter of the organic hollow particles exceeds the specific range, the print quality is significantly deteriorated. In Comparative Example 9 mainly composed of silica and polyvinyl alcohol, the pigment ink penetrates into the coating layer, a clear image cannot be obtained, and the penetration of water into the coating layer is remarkable, resulting in poor water resistance.
Claims (3)
In the inkjet recording material for non-aqueous ink in which only one ink receiving layer is provided on the support, the ink receiving layer is formed from a coating composition containing at least a thermoplastic resin, inorganic fine particles, and organic hollow particles, The inorganic fine particles are silica fine particles having an average particle diameter of 0.3 to 6 μm, the average particle diameter of the organic hollow particles is 0.4 to 1.0 μm, and the ratio of the inorganic fine particles and the organic hollow particles to 100 parts by mass of the thermoplastic resin. Are 10-25 mass parts and 10-75 mass parts, respectively, The inkjet recording material for non-aqueous inks characterized by the above-mentioned.
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| JP2013158938A (en) * | 2012-02-02 | 2013-08-19 | Riso Kagaku Corp | Oil-based inkjet printing method, and ink set |
| JP6544906B2 (en) * | 2014-09-30 | 2019-07-17 | セーレン株式会社 | Ink jet printed matter and method of manufacturing ink jet printed matter |
| JP2017217768A (en) * | 2016-06-03 | 2017-12-14 | 北越紀州製紙株式会社 | Medium for inkjet recording and method for producing the same |
| CN106117586A (en) * | 2016-08-19 | 2016-11-16 | 上海谷奇数码科技有限公司 | Mirror image multi-functional Weak solvent printed material, the preparation method of printed material and card |
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