JP3809671B2 - Inkjet recording paper - Google Patents

Description

【００２１】
このようなホウ素高分子化合物は、その極性に起因して支持体１として用いられるポリエステル等の極性部を有するフィルムや、パルプを構成するセルロース類に対する接着性に優れる。一方で、このホウ素高分子化合物は、水系インクに用いられる極性有機溶剤に対する膨潤性にも優れる。
【００２２】
このように、中間層２に、吸水性及び接着性に優れるホウ素高分子化合物を用いるとよい。このホウ素高分子化合物の中間層２中の含有量は、２０重量部％以上が好ましい。このホウ素高分子化合物の含有量が２０重量部未満になると、添加効果が少なくなる。
【００２３】
また、中間層２の厚みは、０．５〜３０μｍであることが好ましい。中間層２の厚みが０．５μｍ未満である場合には、吸水容量が小さくなって上述した効果が少なくなる。３０μｍを越えると、上述した効果にそれ以上の差異が無くなり、かえって剛性が大きくなって成膜性が悪くなり経済性が悪くなる。
【００２４】
中間層２には、染料受容層３を成膜する際に染料受容層３側に溶出して定着性を阻害しない限り、ガラス転移温点（Ｔｇ）を制御するために可塑剤を添加してもよいし、それ以外の目的で例えば吸水性制御のために補助的添加剤、耐光性改善のために紫外線吸収剤、あるいは品質改善のために蛍光増白剤などの種々の添加剤を含有させてもよい。
【００２５】
なお、本発明において染料受容層３形成用組成物に使用する層間化合物としては、交換性陽イオンまたは交換性陰イオンを有する層状無機高分子を使用することができる。
【００２６】
交換性陽イオンを有する層状無機高分子としては、天然もしくは合成層状珪酸塩またはそれらの焼成体を例示することができ、代表的には、３−八面体スメクタイト構造を有する以下の式（１）で示されるモンモリロナイト群を使用することができる。
【００２７】
（Ｘ，Ｙ）_２−３Ｚ_４Ｏ_１０（ＯＨ）_２・ｍＨ_２Ｏ・（Ｗ_１／３） ・・・（１）
（但し、式（１）中、ＸはＡｌ、Ｆｅ（ＩＩＩ）、Ｍｎ（ＩＩＩ）、またはＣｏ（ＩＩＩ）であり、ＹはＭｇ、Ｆｅ（ＩＩ）、Ｎｉ、ＺｎまたはＬｉであり、Ｚは、ＳｉまたはＡｌであり、ＷはＫ、Ｎａ、またはＣａであり、Ｈ_２Ｏは層間水であり、ｍは整数を表す。）
【００２８】
交換性陰イオンを有する層状無機高分子としては、０：１型粘土鉱物の一種であり、ＡｌＯ_６八面体シートからなる層状のハイドロタルサイト群鉱物を好ましく例示することができる。このようなハイドロタルサイト群鉱物の代表的なものとしては、式（２）で表されるハイドロタルサイトを例示することができる。
【００２９】
Ｍｇ_６Ａｌ_２（ＯＨ）_１６・ＣＯ_３・４Ｈ_２Ｏ ・・・（２）
上述した層間化合物は、バインダー樹脂中に分散保持される。このようなバインダー樹脂としては、一般の熱可塑性樹脂を使用することができるが、層間化合物が分散し易く、しかも水溶性インク組成物の溶媒である水やアルコール等が浸透する親水性樹脂を使用することが好ましく、例えば、ポリビニルブチラール樹脂、ヒドロキシプロピルセルロース樹脂、ビニルピロリドン−酢酸ビニル共重合体樹脂、ポリビニルアルコール樹脂、ポリビニルアセタール樹脂等を使用できる。
【００３０】
このような層間化合物やバインダー樹脂の含有量は、染料受容層３の定着効果、柔軟性を考慮して、適宜選択されるものである。
【００３１】
また、本発明において使用される支持体１としては、紙、合成紙、プラスチックペーパー、金属板、金属箔、アルミニウム等を蒸着したプラスチックフィルム等から任意に選択できる。
【００３２】
本発明において使用されるインク組成物は、少なくとも水と、染料受容層３中の層間化合物にイオン交換作用に基づくインターカレーション反応により定着保持されるような水溶性染料とを含有する。ここでは、染料受容層３中の層間化合物が交換性陽イオンを有する層状無機高分子である場合には、水溶性カチオン染料（水溶性塩基性染料）を使用でき、染料受容層３中の層間化合物が交換性陰イオンを有する層状無機高分子である場合には、交換性水溶性アニオン染料（水溶性直接染料または水溶性酸性染料）を使用できる。
【００３３】
水溶性カチオン染料としては、アミン塩または第４級アンモニウム基を有するアゾ染料、トリフェニルメタン染料、アゾン染料、オキサジン染料、チアジン染料などが挙げられる。
【００３４】
水溶性アニオン染料としては、発色団としてモノアゾ基、ジズアゾ基、アントラキノン骨格、トリフェニルメタン骨格などを有し、さらに分子中に１〜３個のスルホン酸基またはカルボキシル基等の陰イオン性の水溶性基を有するもの等が挙げられる。
【００３５】
ところで、上述した画像を実際に形成する場合には、バブル駆動ジェットノズルやピエゾ素子駆動ジェットノズル等を備えた通常のインクジェット記録装置を用い、画像信号に応じて選択的にインク組成物を染料受容層３上に吐出させればよい。
【００３６】
【実施例】
以下、本発明を適用したインクジェット記録用印画紙に画像形成を行って、インク乾燥性、定着性、解像性を調べた。
【００３７】
実施例１
先ず始めに、１００μｍ厚の中性紙の片面上に、水系ボロン樹脂（商品名：ＭＣＢ３００、ボロンインターナショナル社製）をワイヤーバーを用いて、乾燥時塗布量が３ｇ／ｍ^２になるよう塗布成膜し、中間層２を形成した。
【００３８】
次に、層間化合物として、合成ハイドロタルサイト（商品名：ＫＷ２２００、協和化学工業（株）製）にリンゴ酸を交換容量の５０％吸着させた粉体１００ｇを用意した。そして、ポリビニルブチラール（商品名：ＢＬ−１、積水化学（株）製）を５重量％含むエタノール水溶液１ｋｇに上記粉体を投入し、１週間ロールミルによる分散を行って懸濁液を得た。この懸濁液を先の中性紙の中間層２上にドクターブレードを用いて塗布、含浸させ、１１０℃の熱風にて１分間乾燥して染料受容層３を形成し、インクジェット記録用印画紙（実施例１）を得た。
【００３９】
一方、組成（１）で示されるインク溶液と、インク溶液の組成から染料を除いた希釈液とを定量混合し、与えられた濃度データに基づいて所定の濃度のインク液滴をインクジェット記録用印画紙上に付着させるソニー製キャリアジェット式インクジェットプリンタを用意した。そして、この給紙トレイに上記インクジェット記録用印画紙を装着し、２液混合方式のフルカラー印画を行った。なお、混合吐出液滴の径から液量の多い部位の液適量は、６０ピコリットルと見積もられた。
【００４０】
（組成１）
染料 ２重量部
イエロー：Ｃ．Ｉ．アシッドイエロー２３
マゼンダ：Ｃ．Ｉ．アシッドマゼンダ５２
シアン ：Ｃ．Ｉ．アシッドシアン９
ブラック：Ｃ．Ｉ．ダイレクトブラック１５４
イソプロピルアルコール ２重量部
ジエチレングリコール ３重量部
水 ３０重量部
非イオン性界面活性剤 ０．０５重量部
（商品名：ノイゲンＥＡ１２０、第１工業製薬（株）製）
【００４１】
実施例２〜実施例４
先ず始めに、１１０μｍ厚の白色ポリエステルフィルムの片面上に、水系ボロン樹脂（商品名：ＭＣＢ３００、ボロンインターナショナル社製）とポリエステル系エマルジョン（商品名：バイロナールＭＤ−１２００、東洋紡社製）との重量比が４：１、２：３、１：４、１：５である混合物をそれぞれワイヤーバーを用いて、乾燥時塗布厚が１５μｍ（湿潤時塗布厚が５０μｍ）になるよう塗布成膜し、中間層２を形成した。
【００４２】
次に、層間化合物として、合成ハイドロタルサイト（商品名：ＫＷ２２００、協和化学工業（株）製）にリンゴ酸を交換容量の４０％吸着させた粉体１００ｇを用意した。そして、ヒドロキシプロピルセルロース（商品名：ＨＰＣ−Ｍ、日本曹達製）を１０重量％含むエタノール水溶液１ｋｇに上記粉体を投入し、６０時間ロールミルによる分散を行って懸濁液を得た。
【００４３】
この懸濁液を先のポリエステルフィルムの中間層２上にドクターブレードを用いて塗布、含浸させ、１１０℃の熱風にて１分間乾燥して染料受容層３を形成し、インクジェット記録用印画紙（実施例２〜実施例４）を得た。
【００４４】
そして、実施例１と同様のソニー製キャリアジェット式インクジェットプリンタを用いて、それぞれ２液混合方式のフルカラー印画を行った。
【００４５】
実施例５〜実施例８
１１０μｍ厚の白色ポリエステルフィルムの片面上に、水系ボロン樹脂（商品名：ＭＣＢ３００、ボロンインターナショナル社製）とポリエステル系エマルジョン（商品名：バイロナールＭＤ−１２００、東洋紡社製）との重量比が４：１の混合物をワイヤーバーを用いて、乾燥時塗布厚が０．５、１．０、５．０、３０μｍになるようそれぞれ塗布成膜し、中間層２を形成した。これ以外は、実施例２と同様に印画紙（実施例５〜実施例８）を得て、ソニー製キャリアジェット式インクジェットプリンタを用いて、それぞれ２液混合方式のフルカラー印画を行った。
【００４６】
比較例１
実施例１のインクジェット記録用印画紙の構成から中間層２を除いて作製した以外は、同様にしてインクジェット記録用印画紙（比較例１）を作製し、ソニー製キャリアジェット式インクジェットプリンタを用いて、２液混合方式のフルカラー印画を行った。
【００４７】
比較例２
実施例２のインクジェット記録用印画紙の構成から中間層２を除いて作製した以外は、同様にしてインクジェット記録用印画紙（比較例２）を作製し、ソニー製キャリアジェット式インクジェットプリンタを用いて、２液混合方式のフルカラー印画を行った。
【００４８】
比較例３
実施例２のインクジェット記録用印画紙の構成において、中間層のボロン樹脂の含有量を１７％とした以外は、同様にしてインクジェット記録用印画紙（比較例３）を作製し、ソニー製キャリアジェット式インクジェットプリンタを用いて、２液混合方式のフルカラー印画を行った。
【００４９】
画像の評価
実施例１〜実施例８においては、インクの乾燥性（浸透性）もよく、低濃度部から高濃度部の全域にかけて真円状のドット形状を有し、毛羽立ちや滲みのない解像性の良い画像を得ることができた。それに対し、中間層２を設けず直接ポリエステルフィルムに印画した比較例２においては、全濃度領域においてインクの溢れによるドットの凝集が認められ、指で触ると染料受容層３に吸収されなかったインクが指に付着した。
【００５０】
次に、画像の定着性を調べるために、実施例１、比較例１で得られた印画直後の画像上に中性紙を重ねて２０ｇ／ｃｍ^２の圧力を加えて１０秒間押圧した。その結果、実施例１においては画像の移行が殆どみられなかったのに対し、比較例１においては最大で反射濃度０．４に至る画像の移行が生じた。
【００５１】
次に、実施例２〜実施例８、及び比較例２で得られた画像を画像出力後から５分間放置し、記録された画像上に粘着テープを張り付けた。その結果、実施例２〜実施例８においては、記録画像が支持体１に残存したままであったのに対し、比較例２においては、記録画像が支持体１から剥離して粘着テープに移った。
【００５２】
次に、実施例１〜実施例８及び比較例１、比較例２で得られた画像を水中に１分間浸漬した。その結果、実施例１〜実施例８で得られた画像においてはインクの溶出が見られなかったのに対し、比較例１、比較例２においては顕著なインクの溶出が見られた。
【００５３】
以上の結果を実験条件と共にまとめて表１に示す。表１中の画像評価は、それぞれの実験結果を総合評価したものであり、◎印は、たいへん良好な記録画像が得られたもの、○印は良好な記録画像が得られたもの、△印は、○印に少し劣るもの、×印は滲みのある記録画像が得られたものを示す。なお、支持体が中性紙である場合には中性紙に含有されるインクの量が多いため、中間層の厚みの表示は塗布量（単位：ｇ／ｍ^２）で示している。
【００５４】
【表１】

【００５５】
表１からわかるように、中間層２が設けられた実施例１〜実施例８のインクジェット記録用印画紙は、実用的な乾燥性を有するとともに、定着性、解像性に優れ、高品位な記録画像を形成することができる。但し、表１の結果からわかるように、中間層２に占める水系ボロン樹脂の含有量は、２０重量％以上であることが好ましく、４０重量％以上がより好ましい。
【００５６】
さらに、実施例５〜実施例８の結果からわかるように、中間層２の厚みは、乾燥厚にして０．５μｍ以上が好ましく、５μｍ以上がより好ましい。３０μｍ以上になると、中間層２による改善効果にそれ以上の差異が認められず、インクジェット記録用印画紙自体の剛性が強くなって好ましくない。
【００５７】
なお、インクジェット記録用印画紙（比較例１）に、市販のインクジェットプリンタ（商品名：１２００Ｃ、ヒュレットパッカード社製）を用いて、組成（２）からなるインク溶液によりフルカラー印画を行った。この場合には、画像の品位にそれほど問題がないことから、中間層２の設置による改善効果は、支持体１がポリエステルフィルムのような非パルプ素材の場合において、より顕著に現れることがわかる。
【００５８】
以上の実施例からわかるように、本発明を適用したインクジェット記録用印画紙においては、染料受容層３と支持体１との間に水系ボロン樹脂よりなる中間層２が設けることにより、定着性、乾燥性、解像性に優れた高品位な記録画像を得ることができる。
【００５９】
【発明の効果】
以上の説明からも明らかなように、本発明に係るインクジェット記録用印画紙は、支持体と染料受容層との間に中間層が設けられてなることから、中間層が印画時において染料受容層から浸透拡散してくるインク成分中の染料以外の成分を受容し、インクの乾燥速度、浸透速度を増大させる。したがって、本発明に係るインクジェット記録用印画紙においては、インクジェット形式においても実用的なインク乾燥性を示し、銀塩系写真像に匹敵する定着性を有するとともに、解像性、色再現性に優れた高品位画像を形成することができる。
【図面の簡単な説明】
【図１】 本発明を適用したインクジェット記録用印画紙の構成を示す断面図である。
要部断面図である。
【符号の説明】
１ 支持体、２ 中間層、３ 染料受容層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photographic paper that can form a dye image having excellent fixability by using an ink composition containing a water-soluble dye, and is particularly suitable for ink jet recording.
[0002]
[Prior art]
As a method for fixing image information produced by a personal computer or the like on a photographic paper, a method of forming a dye image on a photographic paper by using an ink composition by an ink jet recording method is promising.
[0003]
In such an ink jet recording system, a solution-like ink is ejected from a nozzle using an electric field, heat, pressure, or the like as a driving source, and the dye is transferred to the dye receiving layer of the photographic paper.
[0004]
Here, as the dye used in the ink, a water-soluble direct dye or an acid dye is mainly used. The dye-receiving layer of photographic paper uses water-soluble polymers with excellent affinity for dyes, organic or inorganic fillers, and other auxiliary substances, which are skillfully controlled to control dye penetration and image bleeding. It is blended.
[0005]
By the way, dyes used in this method are dyes due to interactions such as van der Waals forces and hydrogen bonds with the components of the dye receiving layer after moving to the dye receiving layer, as represented by direct dyeing theory. Retained in the receiving layer. However, if other objects such as solvents or resins with higher affinity for these dyes come into contact with the dye after image formation, the outflow and transfer of the dye from the dye receiving layer to other objects will occur. There is a problem in that the image is blurred and does not show perfect fixing properties like a so-called silver salt photographic image.
[0006]
In order to be able to use images formed by the conventional ink jet recording method in fields where high image durability is required, for example, for proof photographs and printed materials for outdoor exhibitions, improvement of dye image fixability is required. There is a strong demand. In addition to paper products using cellulose, there is a strong demand for inkjet recording on a support such as a non-absorbing plastic film such as an OHP sheet.
[0007]
Japanese Patent Application Laid-Open No. 7-69925 proposes to fix and hold the dye in the dye-receiving layer by an intercalation reaction based on an ion exchange action as a means for solving such a problem. This dye receiving layer contains an intercalation compound having ion exchange ability, and firmly holds the dye by an intercalation reaction based on an ion exchange action.
[0008]
[Problems to be solved by the invention]
However, in the above-described photographic paper, when the amount of ink discharged is larger than before (40 picoliters per dot or more), or when the swelling capacity of the dye receiving layer with respect to the ink solvent composition is insufficient, Decrease in the penetration rate of the dye, resulting in extremely poor image drying, enlargement of the dots that make up the image more than necessary, or failure in superimposition, resulting in greatly improved resolution and color reproducibility There was a problem of deterioration.
[0009]
Furthermore, when a non-water-absorbing plastic film is used as the support, or when ink exceeding 100 microliters is applied per dot, the solvent of the water-soluble ink exceeding the permeation capacity causes image bleeding. There have been problems such as causing ink transfer due to contact with the image and the hand.
[0010]
The present invention is intended to solve the above-described problems. When an image is formed on a photographic paper by an ink jet recording method, it is comparable to a silver salt photographic image while showing practical ink drying properties. An object of the present invention is to provide a photographic printing paper for ink-jet recording which has a fixing property and is capable of obtaining a high-quality image having excellent resolution and color reproducibility.
[0011]
[Means for Solving the Problems]
As a result of intensive studies with the inventors that have achieved the above-mentioned object, the above-mentioned problems are caused by providing an intermediate layer having excellent water absorption and adhesion between the dye-receiving layer and the support. I found out that it was solved.
[0012]
The photographic paper for inkjet recording according to the present invention has been completed based on such knowledge, and is an intermediate made of a resin having water absorption and adhesion between the support and the dye receiving layer thereon. A layer is formed, and the dye-receiving layer contains synthetic hydrotalcite as an intercalation compound that fixes and holds the dye by an intercalation reaction based on an ion exchange action, and the intermediate layer has B-O in the main chain. the water-soluble boron polymer compound containing a bond in a proportion of more than 20 wt% in the intermediate layer, the thickness of the intermediate layer is characterized in that it is a 0.5 to 30 m.
[0013]
In the photographic paper in which an intermediate layer is provided between the dye receiving layer and the support, the intermediate layer receives components other than the dye in the ink component that penetrates and diffuses from the dye receiving layer at the time of printing. In addition, the absorption capacity of the aqueous solvent can be increased. In addition to increasing the apparent drying speed, the ink permeation speed is also increased, so that it is possible to eliminate degradation in resolution and poor color reproduction at the pixel level due to ink leakage on the landing surface. .
[0014]
In particular, boron polymer compounds containing a B—O bond composed of a semipolar bond in the main chain are celluloses that constitute a film or pulp having a polar part such as polyester used as a support due to its polarity. On the other hand, it also has excellent swellability to polar organic solvents used in water-based inks.
[0015]
As described above, since the photographic paper for ink jet recording according to the present invention includes an intermediate layer excellent in water absorption and adhesiveness, the intermediate layer other than the dye that penetrates and diffuses from the dye receiving layer at the time of printing. The ink component is received, and the drying speed and penetration speed of the ink are increased. Therefore, the inkjet recording photographic paper according to the present invention can provide a high-quality image excellent in resolution and color reproducibility.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
As shown in FIG. 1, the photographic paper for inkjet recording according to the present invention has a support 1, an intermediate layer 2, and a dye receiving layer 3 formed in this order. In the dye receiving layer 3, the water-soluble cationic dye or the water-soluble anionic dye is fixed and held between the hydrophilic layers of the intercalation compound having the cation exchange ability or the anion exchange ability by the intercalation reaction based on the ion exchange action.
[0017]
The intermediate layer 2 in contact with both the support 1 and the dye receiving layer 3 is composed of a resin having water absorption and adhesiveness, and the dye in the ink component that penetrates and diffuses from the dye receiving layer 3 at the time of printing. Accept other ingredients. As a result, the photographic paper for ink-jet recording provided with the intermediate layer 2 can increase the absorption capacity of the aqueous solvent and not only increase the apparent drying speed but also increase the ink penetration speed. It is possible to eliminate degradation of resolution and color reproduction failure at the pixel level due to ink leakage.
[0018]
As described above, the photographic paper for ink jet recording to which the present invention is applied has the intermediate layer 2 excellent in water absorption and adhesiveness, and thus has fixing ability comparable to a silver salt photographic image and ink drying. Therefore, it is possible to obtain a high-quality image having excellent resolution and color reproducibility.
[0019]
By the way, a resin having water absorbability and adhesiveness is used for the intermediate layer 2, and in particular, a boron polymer compound containing a B—O bond in the main chain is preferable. Such boron polymer compounds are preferred.
[0020]
[Chemical 1]

[0021]
Such a boron polymer compound is excellent in adhesiveness to a film having a polar part such as polyester used as the support 1 or cellulose constituting the pulp due to its polarity. On the other hand, this boron polymer compound is also excellent in swelling property with respect to a polar organic solvent used in water-based ink.
[0022]
Thus, it is preferable to use a boron polymer compound that is excellent in water absorption and adhesiveness for the intermediate layer 2. The content of the boron polymer compound in the intermediate layer 2 is preferably 20 parts by weight or more. When the content of the boron polymer compound is less than 20 parts by weight, the effect of addition decreases.
[0023]
Moreover, it is preferable that the thickness of the intermediate | middle layer 2 is 0.5-30 micrometers. When the thickness of the intermediate layer 2 is less than 0.5 μm, the water absorption capacity is reduced and the above-described effects are reduced. If it exceeds 30 μm, there will be no further difference in the above-described effects, and on the contrary, the rigidity will increase and the film formability will deteriorate and the economic efficiency will deteriorate.
[0024]
A plasticizer is added to the intermediate layer 2 in order to control the glass transition temperature point (Tg) as long as the dye receiving layer 3 is not eluted and hindered by fixing when the dye receiving layer 3 is formed. For other purposes, various additives such as an auxiliary additive for controlling water absorption, an ultraviolet absorber for improving light resistance, or an optical brightener for improving quality may be included. May be.
[0025]
In the present invention, a layered inorganic polymer having an exchangeable cation or an exchangeable anion can be used as the intercalation compound used in the composition for forming the dye-receiving layer 3.
[0026]
As the layered inorganic polymer having an exchangeable cation, natural or synthetic layered silicates or fired bodies thereof can be exemplified, and typically, the following formula (1) having a 3-octahedral smectite structure: The montmorillonite group shown by can be used.
[0027]
(X, Y) _2-3 Z ₄ O ₁₀ (OH) ₂ .mH ₂ O. (W _1/3 ) (1)
(In the formula (1), X is Al, Fe (III), Mn (III), or Co (III), Y is Mg, Fe (II), Ni, Zn, or Li, and Z is , Si or Al, W is K, Na, or Ca, H ₂ O is interlayer water, and m represents an integer.)
[0028]
The layered inorganic polymer having an exchangeable anion is a kind of 0: 1 type clay mineral, and a layered hydrotalcite group mineral composed of an AlO ₆ octahedron sheet can be preferably exemplified. A typical example of such a hydrotalcite group mineral is a hydrotalcite represented by the formula (2).
[0029]
Mg ₆ Al ₂ (OH) ₁₆ · CO ₃ · 4H ₂ O (2)
The above-mentioned intercalation compound is dispersed and held in the binder resin. As such a binder resin, a general thermoplastic resin can be used, but a hydrophilic resin in which an intercalation compound is easily dispersed and water or alcohol that is a solvent of the water-soluble ink composition penetrates is used. For example, polyvinyl butyral resin, hydroxypropyl cellulose resin, vinyl pyrrolidone-vinyl acetate copolymer resin, polyvinyl alcohol resin, polyvinyl acetal resin and the like can be used.
[0030]
The content of such an intercalation compound and binder resin is appropriately selected in consideration of the fixing effect and flexibility of the dye receiving layer 3.
[0031]
In addition, the support 1 used in the present invention can be arbitrarily selected from paper, synthetic paper, plastic paper, metal plate, metal foil, plastic film on which aluminum or the like is deposited, and the like.
[0032]
The ink composition used in the present invention contains at least water and a water-soluble dye that can be fixed and held by the intercalation reaction based on the ion exchange action on the intercalation compound in the dye receiving layer 3. Here, when the intercalation compound in the dye-receiving layer 3 is a layered inorganic polymer having an exchangeable cation, a water-soluble cationic dye (water-soluble basic dye) can be used, and the interlayer in the dye-receiving layer 3 can be used. When the compound is a layered inorganic polymer having exchangeable anions, exchangeable water-soluble anionic dyes (water-soluble direct dyes or water-soluble acid dyes) can be used.
[0033]
Examples of water-soluble cationic dyes include amine salts or azo dyes having a quaternary ammonium group, triphenylmethane dyes, azone dyes, oxazine dyes, thiazine dyes, and the like.
[0034]
The water-soluble anionic dye has a monoazo group, a disazo group, an anthraquinone skeleton, a triphenylmethane skeleton, etc. as a chromophore, and an anionic water-soluble one such as 1 to 3 sulfonic acid groups or carboxyl groups in the molecule. And the like having a functional group.
[0035]
By the way, when the above-described image is actually formed, a normal ink jet recording apparatus equipped with a bubble driving jet nozzle, a piezo element driving jet nozzle, or the like is used, and the ink composition is selectively received according to the image signal. What is necessary is just to discharge on the layer 3.
[0036]
【Example】
Hereinafter, an image was formed on an inkjet recording photographic paper to which the present invention was applied, and the ink drying property, fixing property, and resolution were examined.
[0037]
Example 1
First, an aqueous boron resin (trade name: MCB300, manufactured by Boron International Co., Ltd.) is coated on one side of neutral paper with a thickness of 100 μm using a wire bar so that the coating amount when dried is 3 g / m ^2. The intermediate layer 2 was formed.
[0038]
Next, 100 g of powder in which malic acid was adsorbed to 50% of the exchange capacity on a synthetic hydrotalcite (trade name: KW2200, manufactured by Kyowa Chemical Industry Co., Ltd.) was prepared as an interlayer compound. And the said powder was thrown into 1 kg of ethanol aqueous solution containing 5 weight% of polyvinyl butyral (Brand name: BL-1, product made from Sekisui Chemical Co., Ltd.), and it disperse | distributed with a roll mill for 1 week, and obtained suspension. This suspension is applied and impregnated on the intermediate layer 2 of the neutral paper using a doctor blade, and dried with hot air at 110 ° C. for 1 minute to form the dye-receiving layer 3. (Example 1) was obtained.
[0039]
On the other hand, the ink solution represented by the composition (1) and the diluted solution obtained by removing the dye from the composition of the ink solution are quantitatively mixed, and ink droplets having a predetermined concentration are printed on the basis of the given concentration data. Sony carrier jet inkjet printers were prepared to be attached on paper. Then, the ink jet recording printing paper was mounted on the paper feed tray, and a two-component mixed type full color printing was performed. From the diameter of the mixed discharge droplets, the appropriate amount of liquid at the portion with a large amount of liquid was estimated to be 60 picoliters.
[0040]
(Composition 1)
Dye 2 parts by weight Yellow: C.I. I. Acid Yellow 23
Magenta: C.I. I. Acid Magenta 52
Cyan: C.I. I. Acid Cyan 9
Black: C.I. I. Direct black 154
Isopropyl alcohol 2 parts by weight Diethylene glycol 3 parts by weight Water 30 parts by weight Nonionic surfactant 0.05 part by weight (trade name: Neugen EA120, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
[0041]
Example 2 to Example 4
First, a weight ratio of a water-based boron resin (trade name: MCB300, manufactured by Boron International) and a polyester-based emulsion (trade name: Vylonal MD-1200, manufactured by Toyobo Co., Ltd.) on one side of a 110 μm thick white polyester film. : 1, 2: 3, 1: 4, 1: 5 using wire bars to form a coating film with a coating thickness of 15 μm when dried (50 μm when wet). Layer 2 was formed.
[0042]
Next, 100 g of powder in which malic acid was adsorbed to 40% of the exchange capacity on a synthetic hydrotalcite (trade name: KW2200, manufactured by Kyowa Chemical Industry Co., Ltd.) was prepared as an interlayer compound. And the said powder was thrown into 1 kg of ethanol aqueous solution which contains 10 weight% of hydroxypropyl cellulose (brand name: HPC-M, Nippon Soda Co., Ltd.), and dispersion | distribution by a roll mill was performed for 60 hours, and suspension was obtained.
[0043]
This suspension is applied and impregnated on the intermediate layer 2 of the polyester film using a doctor blade, and dried with hot air at 110 ° C. for 1 minute to form the dye-receiving layer 3. Examples 2 to 4 ) were obtained.
[0044]
Then, using a Sony carrier jet type ink jet printer similar to that in Example 1, two-component mixed type full color printing was performed.
[0045]
Examples 5 to 8
A weight ratio of water-based boron resin (trade name: MCB300, manufactured by Boron International) and polyester emulsion (trade name: Vylonal MD-1200, manufactured by Toyobo Co., Ltd.) is 4: 1 on one side of a 110 μm thick white polyester film. The intermediate layer 2 was formed by coating each of the above mixtures using a wire bar so that the coating thickness during drying was 0.5, 1.0, 5.0, and 30 μm. Except for this, photographic paper (Examples 5 to 8 ) was obtained in the same manner as in Example 2, and full-color printing by a two-component mixing method was performed using a Sony carrier jet ink jet printer.
[0046]
Comparative Example 1
An inkjet recording photographic paper (Comparative Example 1) was produced in the same manner except that the intermediate layer 2 was excluded from the configuration of the photographic paper for inkjet recording of Example 1, and a Sony carrier jet inkjet printer was used. A two-component mixed-type full color printing was performed.
[0047]
Comparative Example 2
An inkjet recording photographic paper (Comparative Example 2) was prepared in the same manner except that the intermediate layer 2 was removed from the configuration of the inkjet recording photographic paper of Example 2, and a Sony carrier jet inkjet printer was used. A two-component mixed-type full color printing was performed.
[0048]
Comparative Example 3
An inkjet recording photographic paper (Comparative Example 3) was prepared in the same manner as in the configuration of the photographic paper for inkjet recording of Example 2, except that the content of boron resin in the intermediate layer was 17%. A two-component mixed-type full-color printing was performed using an ink jet printer.
[0049]
In image evaluation examples 1 to 8 , the ink has good drying properties (penetration), has a round dot shape from the low density portion to the high density portion, and has no fuzz or bleeding. An image with good image quality could be obtained. On the other hand, in Comparative Example 2 in which the intermediate layer 2 was not provided and the polyester film was directly printed, dot aggregation due to ink overflow was observed in all density regions, and ink that was not absorbed by the dye receiving layer 3 when touched with a finger. Stuck to the finger.
[0050]
Next, in order to examine the fixability of the image, neutral paper was superimposed on the image immediately after printing obtained in Example 1 and Comparative Example 1, and a pressure of 20 g / cm ² was applied and pressed for 10 seconds. As a result, almost no image transfer was observed in Example 1, whereas in Comparative Example 1, an image transfer that reached a maximum reflection density of 0.4 occurred.
[0051]
Next, the images obtained in Examples 2 to 8 and Comparative Example 2 were allowed to stand for 5 minutes after the image was output, and an adhesive tape was attached to the recorded image. As a result, in Examples 2 to 8 , the recorded image remained on the support 1, whereas in Comparative Example 2, the recorded image peeled off from the support 1 and transferred to the adhesive tape. It was.
[0052]
Next, the images obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were immersed in water for 1 minute. As a result, in the images obtained in Examples 1 to 8 , no ink elution was observed, whereas in Comparative Examples 1 and 2, remarkable ink elution was observed.
[0053]
The above results are summarized in Table 1 together with the experimental conditions. The image evaluation in Table 1 is a comprehensive evaluation of the results of each experiment. The mark ◎ indicates that a very good recorded image was obtained, the mark ◯ indicates that a good recorded image was obtained, and the mark △. Is a little inferior to the mark ◯, and the mark x indicates that a recorded image with bleeding was obtained. When the support is neutral paper, the amount of ink contained in the neutral paper is large, and therefore the thickness of the intermediate layer is indicated by the coating amount (unit: g / m ² ).
[0054]
[Table 1]

[0055]
As can be seen from Table 1, the ink-jet recording photographic papers of Examples 1 to 8 provided with the intermediate layer 2 have practical drying properties, excellent fixability and resolution, and high quality. A recorded image can be formed. However, as can be seen from the results in Table 1 , the content of the aqueous boron resin in the intermediate layer 2 is preferably 20% by weight or more, and more preferably 40% by weight or more.
[0056]
Furthermore, as can be seen from the results of Example 5 to Example 8 , the thickness of the intermediate layer 2 is preferably 0.5 μm or more, more preferably 5 μm or more in terms of dry thickness. When the thickness is 30 μm or more, no further difference is recognized in the improvement effect by the intermediate layer 2, and the rigidity of the photographic paper for inkjet recording itself is increased, which is not preferable.
[0057]
Inkjet recording paper (Comparative Example 1) was subjected to full-color printing with an ink solution comprising the composition (2) using a commercially available inkjet printer (trade name: 1200C, manufactured by Hewlett Packard). In this case, since there is no problem in the quality of the image, it can be seen that the improvement effect due to the installation of the intermediate layer 2 appears more prominently when the support 1 is a non-pulp material such as a polyester film.
[0058]
As can be seen from the above examples, in the photographic paper for ink jet recording to which the present invention is applied, the intermediate layer 2 made of a water-based boron resin is provided between the dye receiving layer 3 and the support 1, thereby fixing ability, A high-quality recorded image having excellent drying properties and resolution can be obtained.
[0059]
【The invention's effect】
As is clear from the above description, the photographic paper for ink jet recording according to the present invention is provided with an intermediate layer between the support and the dye receiving layer, and therefore the intermediate layer is a dye receiving layer during printing. Ingredients other than the dye in the ink component penetrating and diffusing from the ink are received, and the drying speed and penetration speed of the ink are increased. Therefore, the photographic paper for ink jet recording according to the present invention exhibits practical ink drying properties even in an ink jet format, has fixing properties comparable to silver salt photographic images, and is excellent in resolution and color reproducibility. High-quality images can be formed.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing the configuration of an inkjet recording photographic paper to which the present invention is applied.
It is principal part sectional drawing.
[Explanation of symbols]
1 support, 2 intermediate layer, 3 dye receiving layer

Claims (1)

An intermediate layer made of a resin having water absorption and adhesiveness is formed between the support and the dye receiving layer thereon,
The dye receiving layer contains synthetic hydrotalcite as an intercalation compound that fixes and holds the dye by an intercalation reaction based on an ion exchange action,
The intermediate layer contains a proportion of more than 20 wt% of a water-soluble boron polymer compound in the intermediate layer containing a B-O bond in the main chain, the thickness of the intermediate layer is 0.5~30μm Inkjet recording photographic paper characterized by

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