JP3904120B2 - Reaction liquid used in inkjet recording method using two liquids and inkjet recording method using the same - Google Patents

Description

（式中、０≦ｍ＋ｎ≦５０、Ｒ¹ 、Ｒ² 、Ｒ³ 、およびＲ⁴ は独立してアルキル基である）
上記式（Ｉ）で表される化合物の代表的なものとして具体的にはオルフィンＹ、サーフィノール８２、サーフィノール４４０、サーフィノール４６５、サーフィノール４８５（いずれも製造：Ａｉｒ Ｐｒｏｄｕｃｔｓ ａｎｄ Ｃｈｅｍｉｃａｌｓ．Ｉｎｃ．）等がある。これらは単独でまたは２種類以上添加しても良い。
【００５６】
本発明の好ましい態様によれば、反応液はｐＨ調整のためにトリエタノールアミンを含んでなる。トリエタノールアミンが添加される場合、その添加量は、０〜２．０重量％程度が好ましい。
【００５７】
インク組成物
本発明においてインク組成物とは、モノクロ印字を行う場合にはブラックインク組成物を意味し、さらにカラー印字を行う場合にはカラーインク組成物、具体的にはイエローインク組成物、マゼンタインク組成物、およびシアンインク組成物、更に場合によってブラックインク組成物を意味するものとする。
【００５８】
本発明において用いられるインク組成物は、少なくとも着色剤と水とを含んでなる。
【００５９】
本発明において用いられるインク組成物に含まれる着色剤としては、染料、顔料のいずれであってもよいが、インク組成物の不溶化あるいは増粘等の作用によって、インク中の着色成分の浸透を抑制する場合は、水性媒体中に溶解している染料よりも分散している顔料の方が有利である。
【００６０】
染料としては、直接染料、酸性染料、食用染料、塩基性染料、反応性染料、分散染料、建染染料、可溶性建染染料、反応分散染料、など通常インクジェット記録に使用する各種染料を使用することができる。
【００６１】
顔料としては、特別な制限なしに無機顔料、有機顔料を使用することができる。無機顔料としては、酸化チタンおよび酸化鉄に加え、コンタクト法、ファーネス法、サーマル法などの公知の方法によって製造されたカーボンブラックを使用することができる。また、有機顔料としては、アゾ顔料（アゾレーキ、不溶性アゾ顔料、縮合アゾ顔料、キレートアゾ顔料などを含む）、多環式顔料（例えば、フタロシアニン顔料、ペリレン顔料、ペリノン顔料、アントラキノン顔料、キナクリドン顔料、ジオキサジン顔料、チオインジゴ顔料、イソインドリノン顔料、キノフラロン顔料など）、染料キレート（例えば、塩基性染料型キレート、酸性染料型キレートなど）、ニトロ顔料、ニトロソ顔料、アニリンブラックなどを使用できる。
【００６２】
本発明の好ましい態様によれば、これらの顔料は、分散剤または界面活性剤で水性媒体中に分散させて得られた顔料分散液としてインクに添加されるのが好ましい。好ましい分散剤としては、顔料分散液を調製するのに慣用されている分散剤、例えば高分子分散剤を使用することができる。
【００６３】
分散剤または界面活性剤の好ましい例としては、ポリアクリル酸、ポリメタクリル酸、アクリル酸−アクリロニトリル共重合体、酢酸ビニル−アクリル酸エステル共重合体、アクリル酸−アクリル酸アルキルエステル共重合体、スチレン−アクリル酸共重合体、スチレン−メタクリル酸共重合体、スチレン−アクリル酸−アクリル酸アルキルエステル共重合体、スチレン−メタクリル酸−アクリル酸アルキルエステル共重合体、スチレン−α−メチルスチレン−アクリル酸共重合体、スチレン−α−メチルスチレン−アクリル酸−アクリル酸アルキルエステル共重合体、スチレン−マレイン酸共重合体、ビニルナフタレン−マレイン酸共重合体、酢酸ビニル−エチレン共重合体、酢酸ビニル−脂肪酸ビニルエチレン共重合体、酢酸ビニル−マレイン酸エステル共重合体、酢酸ビニル−クロトン酸共重合体、酢酸ビニル−アクリル酸共重合体が挙げられる。
【００６４】
本発明の好ましい態様によれば、これらの共重合体は重量平均分子量が３，０００〜５０，０００程度であるのが好ましく、より好ましくは５，０００〜３０，０００程度、最も好ましくは７，０００〜１５，０００程度である。
【００６５】
分散剤の添加量は、顔料を安定に分散させ、本発明による他の効果を失わない範囲で適宜添加されて良い。本発明の好ましい態様によれば、その使用量は顔料：分散剤として１：０．０６〜１：３程度の範囲が好ましく、より好ましくは１：０．１２５〜１：３程度の範囲である。
【００６６】
インクへの顔料の添加量は、０．５〜２５重量％程度が好ましく、より好ましくは２〜１５重量％程度である。
【００６７】
本発明の好ましい態様によれば、インク組成物は樹脂エマルジョンを含んでなるのが好ましい。ここで、樹脂エマルジョンとは、連続相が水であり、分散相が次のような樹脂成分であるエマルジョンを意味する。分散相の樹脂成分としては、アクリル系樹脂、酢酸ビニル系樹脂、スチレン−ブタジエン系樹脂、塩化ビニル系樹脂、アクリル−スチレン系樹脂、ブタジエン系樹脂、スチレン系樹脂、架橋アクリル樹脂、架橋スチレン樹脂、ベンゾグアナミン樹脂、フェノール樹脂、シリコーン樹脂、エポキシ樹脂、などがあげられる。
【００６８】
本発明の好ましい態様によれば、この樹脂は親水性部分と疎水性部分とを併せ持つ重合体であるのが好ましい。また、これらの樹脂成分の粒子径はエマルジョンを形成する限り特に限定されないが、１５０ｎｍ程度以下が好ましく、より好ましくは５〜１００ｎｍ程度である。
【００６９】
これらの樹脂エマルジョンは、樹脂モノマーを、場合によって界面活性剤とともに水中で分散重合することによって得ることができる。例えば、アクリル系樹脂またはスチレン−アクリル系樹脂のエマルジョンは、（メタ）アクリル酸エステル、または（メタ）アクリル酸エステルおよびスチレンを、界面活性剤とともに水中で分散重合させることによって得ることができる。樹脂成分と界面活性剤との混合の割合は、通常１０：１〜５：１程度とするのが好ましい。界面活性剤の使用量が前記範囲にあることでより良好なインクの耐水性、浸透性が得られる。界面活性剤は特に限定されないが、好ましい例としてはアニオン性界面活性剤（例えばドデシルベンゼルスルホン酸ナトリウム、ラウリル酸ナトリウム、ポリオキシエチレンアルキルエーテルサルフェートのアンモニウム塩など）、非イオン性界面活性剤（例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルエステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルアミン、ポリオキシエチレンアルキルアミドなど）があげられ、これらを単独または二種以上を混合して用いることができる。また、アセチレングリコール（オレフィンＹ、ならびにサーフィノール８２、１０４、４４０、４６５、および４８５（いずれもAir Products and Chemicals Inc. 製））を用いることも可能である。
【００７０】
また、分散相成分としての樹脂と水との割合は、樹脂１００重量部に対して水６０〜４００重量部、好ましくは１００〜２００の範囲が適当である。
【００７１】
また、市販の樹脂エマルジョンを使用することも可能であり、例えばマイクロジェルＥ−１００２、Ｅ−５００２（スチレン−アクリル系樹脂エマルジョン、日本ペイント株式会社製）、ボンコート４００１（アクリル系樹脂エマルジョン、大日本インキ化学工業株式会社製）ボンコート５４５４（スチレン−アクリル系樹脂エマルジョン、大日本インキ化学工業株式会社製）、ＳＡＥ−１０１４（スチレン−アクリル系樹脂エマルジョン、日本ゼオン株式会社製）、サイビノールＳＫ−２００（アクリル系樹脂エマルジョン、サイデン化学株式会社製）、などがあげられる。
【００７２】
本発明に使用するインクは、樹脂エマルジョンを、その樹脂成分がインクの０．１〜４０重量％となるよう含有するのが好ましく、より好ましくは１〜２５重量％の範囲である。
【００７３】
樹脂エマルジョンは、多価金属イオンとの相互作用により、着色成分の浸透を抑制し、さらに記録媒体への定着を促進する効果を有する。また、樹脂エマルジョンの種類によっては記録媒体上で皮膜を形成し、印刷物の耐擦性をも向上させる効果も有する。
【００７４】
本発明の好ましい態様によれば、インク組成物は樹脂エマルジョン形態の熱可塑性樹脂を含むことができる。ここで、熱可塑性樹脂とは、軟化温度が５０℃〜２５０℃、好ましくは６０℃〜２００℃、のものである。ここで、軟化温度という語は、熱可塑性樹脂のガラス転移点、融点、粘性率が１０¹¹〜１０¹²ポアズになる温度、流動点、樹脂エマルジョンの形態にある場合その最低造膜温度（ＭＦＴ）のうち最も低い温度を意味するものとする。このような樹脂エマルジョンを含んでなるインク組成物を用いた場合、記録後記録媒体を熱可塑性樹脂の軟化温度以上の温度で加熱する加熱工程を実施するのが好ましい。
【００７５】
また、これらの樹脂としては、軟化または溶融温度以上に加熱され冷却された際に強固な耐水性、耐擦性のある膜を形成するものを選択するのが好ましい。
【００７６】
水不溶性の熱可塑性樹脂の具体例としては、ポリアクリル酸、ポリメタアクリル酸、ポリメタアクリル酸エステル、ポリエチルアクリル酸、スチレン‐ブタジエン共重合体、ポリブタジエン、アクリロニトリル‐ブタジエン共重合体、クロロプレン共重合体、フッ素樹脂、フッ化ビニリデン、ポリオレフィン樹脂、セルロース、スチレン‐アクリル酸共重合体、スチレン‐メタアクリル酸共重合体、ポリスチレン、スチレン‐アクリルアミド共重合体、ポリイソブチルアクリレート、ポリアクリロニトリル、ポリ酢酸ビニル、ポリビニルアセタール、ポリアミド、ロジン系樹脂、ポリエチレン、ポリカーボネート、塩化ビニリデン樹脂、セルロース系樹脂、酢酸ビニル樹脂、エチレン‐酢酸ビニル共重合体、酢酸ビニル‐アクリル共重合体、塩化ビニル樹脂、ポリウレタン、ロジンエステル等が挙げられるがこれらに限定されるものではない。
【００７７】
低分子量の熱可塑性樹脂の具体例としては、ポリエチレンワックス、モンタンワックス、アルコールワックス、合成酸化ワックス、αオレフィン‐無水マレイン酸共重合体、カルナバワックス等の動植物系ワックス、ラノリン、パラフィンワックス、マイクロクリスタリンワックス等が挙げられる。
【００７８】
このような樹脂エマルジョンとして、公知の樹脂エマルジョンを用いることも可能であり、例えば特公昭６２−１４２６号、特開平３−５６５７３号、特開平３−７９６７８号、特開平３−１６００６８号、特開平４−１８４６２号などに記載の樹脂エマルジョンをそのまま用いることができる。
【００７９】
本発明の好ましい態様によれば、インク組成物はアルギン酸誘導体を含むことができる。アルギン酸誘導体の好ましい例としては、アルギン酸アルカリ金属塩（例えば、ナトリウム塩、カリウム塩）アルギン酸有機塩（例えば、トリエタノールアミン塩）、アルギン酸アンモニウム塩、等が挙げられる。
【００８０】
このアルギン酸誘導体のインク組成物への添加量は、好ましくは０．０１〜１重量％程度であり、より好ましくは０．０５〜０．５重量％程度である。
【００８１】
アルギン酸誘導体の添加により良好な画像が得られる理由は確定できないが、反応液に存在する多価金属塩が、インク組成物中のアルギン酸誘導体と反応し、着色剤の分散状態を変化させ、着色剤の記録媒体への定着が促進されることに起因するものと考えられる。
【００８２】
また、本発明に用いられるインク組成物は、無機酸化物コロイドを含んでいてもよい。無機酸化物コロイドの好ましい例としては、コロイダルシリカ、アルミナコロイドがあげられる。これらは、一般的には、ＳｉＯ₂ 、Ａｌ₂ ０₃ 等の超微粒子を水または有機溶媒中に分散したコロイド溶液である。市販されている無機酸化物コロイドとしては、分散媒が水、メタノール、２−プロパノール、ｎ−プロパノール、キシレンなどであり、ＳｉＯ₂ 、Ａｌ₂ ０₃ 等の粒子の粒径が５〜１００ｎｍであるものが一般的である。また、無機酸化物コロイド溶液のｐＨは中性領域ではなく酸性またはアルカリ性に調製されているものが多い。これは、無機酸化物コロイドの安定分散領域が酸性側かアルカリ性側に存在するためであり、インク組成物に添加する場合には、無機酸化物コロイドの安定分散領域のｐＨとインクのｐＨとを考慮して添加する必要がある。
【００８３】
インク組成物中の無機酸化物コロイドの添加量は、０．１〜１５重量％となるよう添加するのが好ましく、二種以上の添加も可能である。
【００８４】
本発明の好ましい態様によれば、インク組成物は有機溶媒を含んでなるのが好ましい。この有機溶媒は、好ましくは低沸点有機溶剤であり、その好ましい例としては、メタノール、エタノール、ｎ−プロピルアルコール、ｉｓｏ−プロピルアルコール、ｎ−ブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール、ｉｓｏ−ブタノール、ｎ−ペンタノールなどがあげられる。特に一価アルコールが好ましい。低沸点有機溶剤は、インクの乾燥時間を短くする効果がある。
【００８５】
また、本発明の好ましい態様によれば、本発明に使用するインク組成物は、さらに高沸点有機溶媒からなる湿潤剤を含んでなることが好ましい。高沸点有機溶媒剤の好ましい例としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、プロピレングリコール、ブチレングリコール、１，２，６−ヘキサントリオール、チオグリコール、ヘキシレングリコール、グリセリン、トリメチロールエタン、トリメチロールプロパンなどの多価アルコール類、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチエレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテルなどの多価アルコールのアルキルエーテル類、尿素、２−ピロリドン、Ｎ−メチル−２−ピロリドン、１，３−ジメチル−２−イミダゾリジノン、トリエタノールアミンなどがあげられる。
【００８６】
これら湿潤剤の添加量は、インクの０．５〜４０重量％が好ましく、より好ましくは２〜２０重量％の範囲である。また、低沸点有機溶剤の添加量はインクの０．５〜１０重量％が好ましく、より好ましくは１．５〜６重量％の範囲である。
【００８７】
本発明の好ましい態様によれば、インク組成物は糖を含有してなるのが好ましい。糖類の例としては、単糖類、二糖類、オリゴ糖類（三糖類および四糖類を含む）および多糖類があげられ、好ましくはグルコース、マンノース、フルクトース、リボース、キシロース、アラビノース、ガラクトース、アルドン酸、グルシシール、（ソルビット）、マルトース、セロビオース、ラクトース、スクロース、トレハロース、マルトトリオース、などがあげられる。ここで、多糖類とは広義の糖を意味し、アルギン酸、α−シクロデキストリン、セルロースなど自然界に広く存在する物質を含む意味に用いることとする。
【００８８】
また、これらの糖類の誘導体としては、前記した糖類の還元糖（例えば、糖アルコール（一般式ＨＯＣＨ₂ （ＣＨＯＨ）n ＣＨ₂ ＯＨ（ここで、ｎ＝２〜５の整数を表す）で表される）、酸化糖（例えば、アルドン酸、ウロン酸など）、アミノ酸、チオ糖などがあげられる。特に糖アルコールが好ましく、具体例としてはマルチトール、ソルビットなどがあげられる。
【００８９】
これら糖類の含有量は、インクの０．１〜４０重量％、好ましくは０．５〜３０重量％の範囲が適当である。
【００９０】
その他、必要に応じて、ｐＨ調整剤、防腐剤、防かび剤等を添加しても良い。
【００９１】
インクジェット記録装置
本発明によるインクジェット記録方法を実施するインクジェット記録装置につて以下、図面を用いて説明する。
【００９２】
図１のインクジェット記録装置は、インク組成物および反応液をタンクに収納し、インク組成物および反応液がインクチューブを介して記録ヘッドに供給される態様である。すなわち、記録ヘッド１とインクタンク２とがインクチューブ３で連通される。ここで、インクタンク２は内部が区切られてなり、インク組成物、場合によって複数のカラーインク組成物の部屋と、反応液の部屋とが設けられてなる。
【００９３】
記録ヘッド１は、キャリッジ４に沿って、モータ５で駆動されるタイミングベルト６によって移動する。一方、記録媒体である紙７はプラテン８およびガイド９によって記録ヘッド１と対面する位置に置かれる。なお、この態様においては、キャップ１０が設けられてなる。このキャップ１０には吸引ポンプ１１が連結され、いわゆるクリーニング操作を行う。吸引されたインク組成物はチューブ１２を介して廃インクタンク１３に溜め置かれる。
【００９４】
記録ヘッド１のノズル面の拡大図を図２に示す。１ｂで示される部分が反応液のノズル面であって、反応液が吐出されるノズル２１が縦方向に設けられてなる。一方、１ｃで示される部分がインク組成物のノズル面であって、ノズル２２、２３、２４、２５からはそれぞれイエローインク組成物、マゼンタインク組成物、シアンインク組成物、そしてブラックインク組成物が吐出される。
【００９５】
さらにこの図２に記載の記録ヘッドを用いたインクジェット記録方法を図３を用いて説明する。記録ヘッド１は矢印Ａ方向に移動する。その移動の間に、ノズル面１ｂより反応液が吐出され、記録媒体７上に帯状の反応液付着領域３１を形成する。次に記録媒体７が紙送り方向矢印Ｂに所定量移送される。その間記録ヘッド１は図中で矢印Ａと逆方向に移動し、記録媒体７の左端の位置に戻る。そして、既に反応液が付着している反応液付着領域にインク組成物を印字し、印字領域３２を形成する。
【００９６】
また、図４に記載のように記録ヘッド１において、ノズルを全て横方向に並べて構成することも可能である。図中で、４１ａおよび４１ｂは反応液の吐出ノズルであり、ノズル４２、４３、４４、４５からはぞれぞれイエローインク組成物、マゼンタインク組成物、シアンインク組成物、そしてブラックインク組成物が吐出される。このような態様の記録ヘッドにおいては、記録ヘッド１がキャリッジ上を往復する往路、復路いずれにおいても印字が可能である点で、図２に示される記録ヘッドを用いた場合よりも速い速度での印字が期待できる。
【００９７】
さらに反応液とインク組成物の表面張力を調節することにより、これらの付着順序にかかわらず、高品質の印字がより一定して得られる。この場合反応液の吐出ノズルを１つとすることもでき（例えば図中で４１ｂのノズルを省くことができる）、さらなるヘッドの小型化と印字の高速化が達成できる。
【００９８】
さらに、インクジェット記録装置には、インク組成物の補充がインクタンクであるカートリッジを取り替えることで行われるものがある。また、このインクタンクは記録ヘッドと一体化されたものであってもよい。
【００９９】
このようなインクタンクを利用したインクジェット記録装置の好ましい例を図５に示す。図中で図１の装置と同一の部材については同一の参照番号を付した。図５の態様において、記録ヘッド１ａおよび１ｂは、インクタンク２ａおよび２ｂと一体化されてなる。記録ヘッド１ａまたは１ｂをそれぞれインク組成物および反応液を吐出するものとする。印字方法は基本的に図１の装置と同様であってよい。そして、この態様において、記録ヘッド１ａとインクタンク２ａおよび記録ヘッド１ａおよびインクタンク２ｂは、キャリッジ４上をともに移動する。
【０１００】
さらに、印字がなされた記録媒体を加熱するヒータが設けられてなる、インクジェット記録装置の好ましい例を図６に示す。図６は、ヒータ１４を設けた点以外は図１に示したものと同様なものである。このヒータ１４は、記録媒体に接触してそれを加熱するものであっても、赤外線などを照射しまたは熱風を吹き付けるなど記録媒体に接触せずに加熱するものであってもよい。
【０１０１】
また、本発明の好ましい態様によれば、インクジェット記録装置は、さらに反応液とインク組成物とを収納し、かつインク組成物および反応液の量が、インク組成物が先に消費し尽くされるものとされたものが好ましい。
【０１０２】
また、別の好ましい態様によれば、インクジェット記録装置に用いられるインクタンクが提供される。このインクタンクは、好適には取り替え可能なカートリッジ式であってもよく、さらに好適には記録ヘッドと一体化されたものであってもよい。いずれの態様によっても、反応液とインク組成物とを収納し、かつインク組成物および反応液の量がインク組成物が先に消費し尽くされるものとされたものとするのが好ましい。
【０１０３】
なお、この態様とは逆に、反応液がインク組成物よりも先に消費し尽くされるようなものとされると、反応液は透明であることが一般的であるので、消費し尽された時点を知ることが難しくなる。すなわち、反応液が消費し尽くされたことを、印字を観察し、その印字品質が劣化していることで初めて知ることとなり、印字品質の観察を常に使用者に課すこととなる。
【０１０４】
一方、この態様によるインクジェット記録装置にあっては、インク組成物はそれ自体有色であることから、その消尽を容易に知ることができる。さらに、インク組成物が消費し尽くされる前に反応液がなくなることがないので、安定して二液を印字するインクジェット記録方法を行うことが可能となる。一方、インク組成物および反応液を収納するタンク部分にセンサー手段などを設けその消費を観察することも考えられるが、この態様にあってはそのような複雑な機構を極めて簡便な仕組みで代替できる点でも価値のあるものといえる。
【０１０５】
なお、この態様において、複数のインク組成物を用いた場合に、「反応液よりもインク組成物の方が先に消費し尽くされる」とは、いずれか一つのインク組成物が消費し尽くされた時点で依然として反応液が残っている限り、複数のインク組成物の全てが消費し尽くされた時においても反応液が残っていなければならないことを必ずしも意味する物ではないが、複数のインク組成物の全てが消費し尽くされた場合においても反応液が残っているようなものとされるのが好ましい。
【０１０６】
【実施例】
以下本発明を以下の実施例によって詳細に説明するが、本発明はこれらに限定されるれものではない。
【０１０７】
実施例Ａ
反応液の調製
以下の成分を混合することにより反応液Ａ１〜１０を調製した。
【０１０８】
反応液Ａ１
硝酸マグネシウム・六水和物 ５重量％
グリセリン ２０重量％
トリエチレングリコール
モノブチルエーテル １０重量％
２−ピロリドン ５重量％
トリエタノールアミン ０．２重量％
純水 残量
【０１０９】
反応液Ａ２
硝酸マグネシウム・六水和物 ５重量％
グリセリン ２０重量％
トリエチレングリコール
モノブチルエーテル １０重量％
２−ピロリドン １０重量％
トリエタノールアミン ０．２重量％
純水 残量
【０１１０】
反応液Ａ３
硝酸マグネシウム・六水和物 ５重量％
グリセリン ２０重量％
ジエチレングリコール
モノブチルエーテル １０重量％
１，３−ジメチル
−２−イミダゾリジノン １０重量％
トリエタノールアミン ０．２重量％
純水 残量
【０１１１】
反応液Ａ４
硝酸マグネシウム・六水和物 ５重量％
グリセリン ２０重量％
サーフィノール４６５ ０．７重量％
チオジグリコール ５重量％
トリエタノールアミン ０．２重量％
純水 残量
【０１１２】
反応液Ａ５
硝酸カルシウム・四水和物 ５重量％
グリセリン ２０重量％
トリエチレングリコール
モノブチルエーテル １０重量％
２−ピロリドン ５重量％
トリエタノールアミン ０．２重量％
純水 残量
【０１１３】
反応液Ａ６
アシッド・イエロー２３ ３．２重量％
硝酸マグネシウム・六水和物 ５重量％
グリセリン １２重量％
ジエチレングリコール
モノブチルエーテル ３重量％
サーフィノール４６５ ０．７重量％
シエチレングリコール ４重量％
２−ピロリドン ５重量％
トリエタノールアミン ０．１重量％
純水 残量
【０１１４】
反応液Ａ７
リアクティブ・レッド１８０ ４．２重量％
硝酸マグネシウム・六水和物 ５重量％
グリセリン １７重量％
シエチレングリコール
モノブチルエーテル ３重量％
サーフィノール４６５ ０．７重量％
ジエチレングリコール ４重量％
２−ピロリドン ５重量％
トリエタノールアミン ０．９重量％
純水 残量
【０１１５】
反応液Ａ８
アシッド・ブルー９ １．５重量％
ダイレクト・ブルー１９９ ３．５重量％
硝酸マグネシウム・六水和物 ５重量％
グリセリン １２重量％
シエチレングリコール
モノブチルエーテル ３重量％
サーフィノール４６５ ０．７重量％
ジエチレングリコール ４重量％
２−ピロリドン ５重量％
トリエタノールアミン ０．１重量％
純水 残量
【０１１６】
反応液Ａ９
硝酸マグネシウム・六水和物 ５重量％
グリセリン ２０重量％
トリエチレングリコール
モノブチルエーテル １０重量％
トリエタノールアミン ０．２重量％
純水 残量
【０１１７】
反応液Ａ１０
硝酸カルシウム・四水和物 ５重量％
グリセリン ２０重量％
トリエチレングリコール
モノブチルエーテル １０重量％
トリエタノールアミン ０．２重量％
純水 残量
【０１１８】
インク組成物の調製
ブラックインクＡ１
カーボンブラックＭＡ７ ５重量％
（三菱化成株式会社製）
スチレンーアクリル酸共重合体 １重量％
（分散剤）
スクロース ０．７重量％
マルチトール ６．３重量％
グリセリン １０重量％
２−ピロリドン ２重量％
エタノール ４重量％
純水 残量
【０１１９】
カーポンブラックと分散剤とを混合し、サンドミル（安川製作所製）中でガラスピーズ（直径１．７ｍｍ、混合物の１．５倍量（重量））とともに２時間分散させた。その後、ガラスピーズを取り除き、他の成分を加え常温で２０分間攪拌した。５μｍのメンブランフルターでろ過して、インクジェット記録用ブラックインクを得た。
【０１２０】
反応液Ａの評価
評価Ａ１：異物の発生量
反応液をテフロンビンに入れて密封し、７０℃で１週間放置した。放置後、反応液１０ｍｌを１０μｍのメッシュフィルターを通し、異物をろ集した。その結果は第１表に示される通りであった。表中、
ろ集された異物の数が２０個未満−Ａ
ろ集された異物の数が２０個以上１００個未満−Ｂ
ろ集された異物の数が１００個以上−Ｃ
とした。
【０１２１】
評価Ａ２：印刷安定性
反応液をＭＪ−５００Ｃ（セイコーエプソン株式会社製）のインクカートリッジに充填し、プリンターに装着した。キャラクター、グラフィックが混在するパターンをＡ４紙に１００００枚印刷し、途中で「飛行曲がり」や、「抜け」が生じないか観察した。
【０１２２】
なお、反応液１〜５は透明であるため、アシッド・ブルー９（染料）を０．５重量％添加し、曲がり、抜けが容易に確認できるよう着色した。
【０１２３】
その結果は、第１表に示される通りであった。表中、
曲りや抜けの発生回数が２０回未満−Ａ
曲りや抜けの発生回数が２０回以上５０回未満−Ｂ
曲りや抜けの発生回数が５０回以上−Ｃ
とした。
【０１２４】
評価Ａ３：印字品質（にじみ）
インクジェトプリンタＭＪ−５００Ｃを用いて、以下の各紙に印刷を行った。印刷は、反応液を１００％ｄｕｔｙで印刷した後、ブラックインクＡ１で文字を印刷した。乾燥後、文字におけるにじみの発生の有無を調べた。
【０１２５】
▲１▼ＸｅｒｏｘＰ紙（ゼロックス株式会社製）
▲２▼Ｒｉｃｏｐｙ６２００紙（リコー株式会社製）
▲３▼Ｘｅｒｏｘ４０２４紙（ゼロックス株式会社製）
▲４▼Ｎｅｅｎａｈ Ｂｏｎｄ紙（キンバリークラーク社製）
▲５▼Ｘｅｒｏｘ Ｒ紙（ゼロックス株式会社製・再生紙）
▲６▼やまゆり紙（本州製紙株式会社製・再生紙）
【０１２６】
その結果は、第１表に示される通りであった。表中、
にじみがなく鮮明な印刷の場合−Ａ、
ひげ状のにじみが発生した場合−Ｂ、
文字の輪郭がはっきりしないほどにじみが発生した場合−Ｃ
とした。
【０１２７】

【０１２８】
実施例Ｂ
反応液の調製
以下の成分を混合することにより反応液Ｂ１〜１０を調製した。
反応液Ｂ１
硝酸マグネシウム・六水和物 ２５重量％
トリエチレングリコール
モノブチルエーテル １０重量％
グリセリン ２０重量％
アンモニア水（２９％水溶液） ０．０５重量％
純水 残量
以上の成分を混合し、室温で１時間攪袢を行い、その後５μｍのメンブランフルターで組成物を吸引ろ過して、反応液を得た。
【０１２９】
反応液Ｂ２
硝酸マグネシウム・六水和物 ２５重量％
トリエチレングリコール
モノブチルエーテル １０重量％
グリセリン ２０重量％
アンモニア水（２９％水溶液） ０．２重量％
純水 残量
【０１３０】
反応液Ｂ３
硝酸マグネシウム・六水和物 ２５重量％
トリエチレングリコール
モノブチルエーテル １０重量％
グリセリン ２０重量％
シクロヘキシルアミン ０．１重量％
純水 残量
【０１３１】
反応液Ｂ４
硝酸マグネシウム・六水和物 ２５重量％
トリエチレングリコール
モノブチルエーテル １０重量％
グリセリン ２０重量％
Ｎ−シクロヘキシル−
Ｎ−ドデシルアミン ０．１重量％
純水 残量
【０１３２】
反応液Ｂ５
硝酸マグネシウム・六水和物 ２５重量％
トリエチレングリコール
モノブチルエーテル １０重量％
グリセリン ２０重量％
デカメチレンイミン ０．１重量％
純水 残量
【０１３３】
反応液Ｂ６
硝酸マグネシウム・六水和物 ２５重量％
トリエチレングリコール
モノブチルエーテル １０重量％
グリセリン ２０重量％
ジシクロヘキシルアミン亜硝酸塩 ０．１重量％
純水 残量
【０１３４】
反応液Ｂ７
硝酸マグネシウム・六水和物 ２５重量％
トリエチレングリコール
モノブチルエーテル １０重量％
グリセリン ２０重量％
ジオクチルアミン ０．１重量％
ヘプタン酸 ０．１重量％
純水 残量
【０１３５】
反応液Ｂ８
硝酸カルシウム・四水和物 ２０重量％
トリエチレングリコール
モノブチルエーテル １０重量％
グリセリン ２０重量％
アンモニア水（２９％） ０．２重量％
純水 残量
【０１３６】
反応液Ｂ９
硝酸マグネシウム・六水和物 ２５重量％
トリエチレングリコール
モノブチルエーテル １０重量％
グリセリン ２０重量％
純水 残量
【０１３７】
反応液Ｂ１０
硝酸カルシウム・四水和物 ２０重量％
トリエチレングリコール
モノブチルエーテル １０重量％
グリセリン ２０重量％
純水 残量
【０１３８】
インク組成物の調製
ブラックインクＢ１
カーボンブラックＭＡ７ ５重量％
（三菱化成株式会社製）
スチレンアクリル酸共重合体 １重量％
（分散剤）
ボンコート４００１ ３重量％
（アクリル系樹脂エマルジョン、樹脂成分５０％、ＭＦＴ５℃、大日本インキ株式会社製）
スクロース ０．７重量％
マルチトール ６．３重量％
グリセリン １０重量％
２−ピロリドン ２重量％
エタノール ４重量％
純水 残量
【０１３９】
カーボンブラックと分散剤とを混合し、サンドミル（安川製作所製）中でガラスビーズ（直径１．７ｍｍ、混合物の１．５倍量（重量））とともに２時間分散させた。その後、ガラスビーズを取り除き、他の成分を加え常温で２０分間攪袢した。５μｍのメンブランフルターでろ過して、インクジェット記録用インクを得た。
【０１４０】
反応液の評価
評価Ｂ１：印字品質（にじみ）
インクジェトプリンタＭＪ−５００Ｃ（セイコーエプソン株式会社製）を用いて、以下の各紙に印刷を行った。印刷は、まず反応液を１００％ｄｕｔｙで印刷した後、ブラックインクＢ１で文字を印刷した。乾燥後、文字におけるにじみの発生の有無を調べた。
【０１４１】
▲１▼Ｘｅｒｏｘ Ｐ紙（ゼロックス株式会社製）
▲２▼Ｒｉｃｏｐｙ ６２００紙（リコー株式会社製）
▲３▼Ｘｅｒｏｘ ４０２４紙（ゼロックス株式会社製）
▲４▼Ｎｅｅｎａｈ Ｂｏｎｄ紙（キンバリークラーク社製）
▲５▼Ｘｅｒｏｘ Ｒ紙（ゼロックス株式会社製・再生紙）
▲６▼やまゆり紙（本州製紙株式会社製・再生紙）
【０１４２】
その結果は、第２表に示される通りであった。表中、
にじみがなく鮮明な印刷の場合−Ａ
ひげ状のにじみが発生した場合−Ｂ
文字の輪郭がはっきりしないほどにじみが発生した場合−Ｃ。
【０１４３】
評価Ｂ２：目詰まり特性
インクジェットプリンタＭＪ−５００Ｃのヘッドに反応液を充填し、１０分間連続して英数文字を印刷した。その後プリンタを停止し、キャップをせずに４０℃、２５Ｒｈの環境下で１月間放置した。放置後再び英数文字を印刷し、放置前と同等の印字が得られるまでに要した目詰まり復帰動作の回数を調べた。その結果は、第２表に示される通りであった。表中、
０〜２回の復帰動作で初期と同等の印刷が可能−Ａ
３〜５回の復帰動作で初期と同等の印刷が可能−Ｂ
６回以上の復帰動作でも初期と同等の印刷が不可能−Ｃ。
【０１４４】
評価Ｂ３： 吐出安定性
インクジェットプリンタＭＪ−５００Ｃのヘッドに反応液を充填し、Ａ４サイズの紙に連続して英数文字を印字した。印字中に飛行曲がり（インク小滴がまっすぐ飛ばなくなることをいう）が発生した場合、復帰動作を行う。復帰動作を行なっても飛行曲がりが直らない場合、それまでに印刷した枚数を吐出安定性を表わすパラメータとした。
【０１４５】
その結果は第２表の通りであった。
【０１４６】
飛行曲がりが復帰しなくなるまでの印刷枚数が１００００枚以上−Ａ
飛行曲がりが復帰しなくなるまでの印刷枚数が１００００枚以下−Ｂ
飛行曲がりが復帰しなくなるまでの印刷枚数が５０００枚以下−Ｃ
【０１４７】

【０１４８】
参考例
反応液の調製
以下の成分を混合することにより反応液Ｃ１〜５を調製した。
【０１４９】
反応液Ｃ１
スワノール ＣＡ−２１５０ １０重量％
（塩化ラウリルトリメチルアンモニウム、固形分50％、日光ケミカルズ（株）製）
硝酸マグネシウム・六水和物 ５重量％
グリセリン １０重量％
トリエタノールアミン ０．２重量％
純水 残量
【０１５０】
反応液Ｃ２
スワノール ＣＡ−２３５０ １０重量％
（塩化セチルトリメチルアンモニウム、固形分50％、日光ケミカルズ（株）製）
硝酸カルシウム・四水和物 ５重量％
グリセリン １０重量％
トリエタノールアミン ０．２重量％
純水 残量
【０１５１】
反応液Ｃ３
スワノール ＣＡ−３０８０ ３重量％
（塩化ジオクチルジメチルアンモニウム、固形分80％、日光ケミカルズ（株）製）
酢酸マグネシウム・四水和物 ５重量％
グリセリン １０重量％
トリエタノールアミン ０．２重量％
純水 残量
【０１５２】
反応液Ｃ４
カチオン Ｍ２−１００ ５重量％
（塩化オクタデシルジメチルベンジルアンモニウム、日本油脂（株）製）
酢酸カルシウム・一水和物 ５重量％
グリセリン １０重量％
トリエタノールアミン ０．２重量％
純水 残量
【０１５３】
反応液Ｃ５
カチオン ＳＡ ５重量％
（オクタデシルアミン酢酸塩、日本油脂（株）製）
蟻酸カルシウム（無水） ５重量％
グリセリン １０重量％
トリエタノールアミン ０．２重量％
純水 残量
【０１５４】
インク組成物の調製
ブラックインクＣ１
カーボンブラックＲａｖｅｎ１０８０ ５重量％
（コロンビヤン・カーボン製）
スチレン−アクリル酸共重合体 １重量％
（分散剤）
ボンコート ４００１ ５重量％
（アクリル系樹脂エマルジョン、樹脂成分50％、大日本インキ化学工業（株）製）
スクロース ０．７重量％
マルチトール ６．３重量％
グリセリン １０重量％
２−ピロリドン ２重量％
エタノール ４重量％
純水 残量
【０１５５】
カーボンブラックと分散剤を混合し、サンドミル（安川製作所製）内でガラスビーズ（直径１．７ｍｍ、混合物の１．５倍量（重量））と共に２時間分散させた。その後ガラスビーズを取り除き、他の成分を加え、常温で２０分間攪拌した。５μｍのメンブランフィルターで濾過し、インクジェット記録用インク組成物を得た。
【０１５６】
以下のブラックインクＣ２およびイエロー、シアン、マゼンタの各インク組成物からなるカラーインクセットＣ１の調製は、上記ブラックインクＣ１の方法に準じて行った。
【０１５７】
ブラックインクＣ２
カーボンブラック ＭＡ７ ５重量％
（三菱化学（株）製）
スチレン−アクリル酸共重合体 １重量％
（分散剤）
ボンコート ５４５４ ５重量％
（スチレン−アクリル系樹脂エマルジョン、樹脂成分45％、大日本インキ化学工業（株）製）
スクロース ０．７重量％
マルチトール ６．３重量％
グリセリン １０重量％
２−ピロリドン ２重量％
エタノール ４重量％
純水 残量
【０１５８】
カラーインクセットＣ１
下記の着色剤（顔料）と液媒体とから、それぞれイエローインク、マゼンタインク、シアンインクを調製した。
【０１５９】
＜顔料＞
イエローインク
顔料ＫＥＴＹＥＬＬＯＷ４０３ ２重量％
（大日本インキ化学工業株式会社製）
マゼンタインク
顔料ＫＥＴＲＥＤ３０９ ２重量％
（大日本インキ化学工業株式会社製）
シアンインク
顔料ＫＥＴＢＬＵＥＥＸ−１ ２重量％
（大日本インキ化学工業株式会社製）
＜液媒体＞
スチレン−アクリル酸共重合体 ０．４重量％
（分散剤）
ボンコート４００１ ２重量％
スクロース ０．７重量％
マルチトール ６．３重量％
グリセリン １０重量％
２−ピロリドン ２重量％
エタノール ４重量％
純水 （残量）
【０１６０】
印字評価試験
以上示したインク組成物および反応液を、下記の第３表に示されるように組み合わせ、インクジェットプリンタで実際に印刷を行って印字品質等を評価した。
【０１６１】
評価Ｃ１：印字品質（にじみ）
評価Ａ３に準じて実施した。結果は下記の第３表に示されるとおりであった。
【０１６２】
評価Ｃ２：印字品質（ＯＤ値）
インクジェットプリンターＭＪ−７００Ｖ２Ｃを用いて上記評価Ｃ１で使用した紙に、１００％ｄｕｔｙで反応液を印刷した後、ブラックインクで文字を印刷した。乾燥後、印刷物の反射ＯＤ値をＭａｃｂｅｔｈ ＰＣＭＩＩ（マクベス社製）で測定した。
【０１６３】
その結果は下記の第３表に示される通りであった。
【０１６４】
評価Ｃ３：印刷ムラ
インクジェットプリンタＭＪ−７００Ｖ２Ｃで、以下の各紙に１００％ｄｕｔｙで印刷を行った。
【０１６５】
▲１▼Ｒｉｃｏｐｙ ６２００紙（リコー（株）製）
▲２▼Ｃａｎｏｎ ＰＢ ＰＡＰＥＲ紙（キャノン（株）製）
得られた印刷物の任意の５点のＯＤ値をＭａｃｈｂｅｔｈ ＰＣＭＩＩを用いて測定し、その平均値を求めた。この手順を５回繰り返し、５つの平均値の最大値と最小値を求めた。この差が０．５未満であると実用上問題なく、さらには０．４未満が好ましい。
【０１６６】
その結果は、下記の第３表に示される通りであった。表中、
Ａ：ＯＤ値の差が０．２未満
Ｂ：ＯＤ値の差が０．２以上０．４未満
Ｃ：ＯＤ値の差が０．４以上。
【０１６７】
評価Ｃ４：カラーブリード
インクジェットプリンタＭＪ−７００Ｖ２Ｃを用いて上記評価Ａ３で使用した紙に、１００％ｄｕｔｙ反応液を印刷した後、カラーインクセットＣ１の各色インク組成物により１００％ｄｕｔｙの印刷を行い、同時にブラックインクＣ１またはＣ２により文字を印刷した。得られた印刷物の、文字の境界部分での不均一な色の混じりの有無を調べた。印字を目視により観察した。
【０１６８】
その結果は、下記の第３表に示される通りであった。表中、
Ａ：色の混じりがなく境界が鮮明
Ｂ：ひげ状の色の混じりが発生した
Ｃ：文字も輪郭もはっきりしないほど色が混じる。
【０１６９】
第３表
反応液 ブラックインク 評価 C1 評価 C2 評価 C3 評価 C4
参考例１ Ｃ１ １ Ａ 1.41 Ａ −
２ Ｃ１ ２ Ａ 1.43 Ａ −
３ Ｃ２ ２ Ａ 1.43 Ａ −
４ Ｃ３ ２ Ａ 1.45 Ａ −
５ Ｃ４ １ Ａ 1.45 Ａ −
６ Ｃ４ ２ Ａ 1.48 Ａ Ａ
７ Ｃ５ ２ Ａ 1.46 Ａ Ａ
８ − ２ Ｂ 1.33 Ｂ Ｃ
【図面の簡単な説明】
【図１】本発明による方法を実施するインクジェット記録装置を示す図であって、この態様においては記録ヘッドとインクタンクがそれぞれ独立してなり、インク組成物および第一液はインクチューブによって記録ヘッドに供給される。
【図２】記録ヘッドのノズル面の拡大図であって、１ｂが第一液のノズル面であり、１ｃがインク組成物のノズル面である。
【図３】図２の記録ヘッドを用いたインクジェット記録を説明する図である。図中で、３１は第一液付着領域であり、３２は第一液が付着されてた上にインク組成物が印字された印字領域である。
【図４】記録ヘッドの別の態様を示す図であって、吐出ノズルが全て横方向に並べて構成されたものである。
【図５】本発明による方法を実施するインクジェット記録装置を示す図であって、この態様においては記録ヘッドとインクタンクが一体化されてなる。
【図６】本発明による方法を実施するインクジェット記録装置を示す図であって、この態様において画像が記録された後の記録媒体を加熱する加熱手段１４が設けられてなる。
【符号の説明】
１ 記録ヘッド
２ インクタンク
３ インクチューブ
２１ 第一液吐出ノズル
２２、２３、２４、２５ インク組成物吐出ノズル
３１ 第一液付着領域
３２ 印字領域[0001]
BACKGROUND OF THE INVENTION
Field of Invention
The present invention relates to an ink jet recording method for performing printing by attaching a reaction liquid and an ink composition to a recording medium, and a reaction liquid used therefor.
[0002]
Background art
The ink jet recording method is a printing method in which printing is performed by causing a droplet of an ink composition to fly and adhere to a recording medium such as paper. This method has a feature that a high-resolution and high-quality image can be printed at a high speed with a relatively inexpensive apparatus. In general, an ink composition that is usually used for ink jet recording contains water as a main component and contains a coloring component and a wetting agent such as glycerin for the purpose of preventing clogging.
[0003]
On the other hand, as an ink jet recording method, a new method has recently been proposed in which a polyvalent metal salt solution is applied to a recording medium and then an ink composition containing a dye having at least one carboxyl group is applied (for example, a special feature). Kaihei 5-202328). In this method, an insoluble complex is formed from a polyvalent metal ion and a dye, and the presence of this complex is said to provide a high-quality image having water resistance and no color bleeding.
[0004]
Further, by using a combination of a color ink containing a surfactant or a penetrating solvent and a salt that imparts at least permeability and a black ink that thickens or aggregates due to the action of this salt, the image density is increased. A proposal has also been made that a high-quality color image without color bleeding can be obtained (Japanese Patent Laid-Open No. 6-106735). That is, an ink jet recording method has been proposed in which a good image can be obtained by printing two liquids, a first liquid containing salt and an ink composition.
[0005]
In addition, an ink jet recording method for printing two liquids has been proposed (for example, JP-A-3-240557 and JP-A-3-240558).
[0006]
SUMMARY OF THE INVENTION
In the reaction liquid containing a polyvalent metal salt, which has been used in the ink jet recording method for printing such two liquids, the present inventors have made a specific compound present so that the storage stability of the reaction liquid and The inventors have found that improvement in printing stability and further improvement in the quality of the printed image obtained can be obtained. The present invention is based on such knowledge.
[0007]
Accordingly, an object of the present invention is to provide a good reaction liquid used in an ink jet recording method for printing two liquids.
[0008]
Another object of the present invention is to provide an ink jet recording method that prints two liquids that are free from clogging and realize a good print image.
[0009]
The reaction liquid according to the present invention is used in an ink jet recording method in which a reaction liquid and an ink composition are attached to a recording medium to perform printing, and includes a polyvalent metal salt and a nitrogen-containing compound or sulfur-containing compound. , An amine, and a component selected from the group consisting of cationic surfactants.
[0010]
The ink jet recording method according to the present invention uses the reaction solution.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Inkjet recording method
The inkjet recording method according to the present invention includes a step of printing a reaction liquid and an ink composition on a recording medium.
[0012]
The reaction liquid and the ink composition may be applied to the recording medium in any order, that is, a method of attaching the reaction liquid to the recording medium and then attaching the ink composition to the recording medium, and the ink composition Both of the method of adhering the reaction liquid after printing and the method of mixing the reaction liquid and the ink composition immediately before or after the injection can be suitably performed.
[0013]
According to the ink jet recording method of the present invention, good printing can be realized. The following is a hypothetical theory, and it is not desired that the present invention be interpreted in a limited manner. However, the reason why good printing can be realized is considered as follows. When the reaction liquid and the ink composition come into contact with each other, the polyvalent metal salt in the reaction liquid destroys the dispersion state of the colorant and the like in the ink composition and causes the colorant component and the like to aggregate. It is considered that the aggregates adhere to the recording medium and realize printing with high color density, less bleeding and less unevenness. Furthermore, a color image has an advantage that non-uniform color mixing, that is, color bleeding, can be effectively prevented in a boundary area of different colors.
[0014]
Regarding the attachment of the reaction liquid to the recording medium, either a method of selectively attaching the reaction liquid only to a place where the ink composition is attached or a method of attaching the reaction liquid to the entire paper surface may be employed. . The former is economical because the consumption of the reaction liquid can be minimized, but a certain degree of accuracy is required at the position where both the reaction liquid and the ink composition are attached. On the other hand, in the latter case, the accuracy requirements for the attachment positions of the reaction liquid and the ink composition are eased compared to the former, but a large amount of the reaction liquid is attached to the entire paper surface, and the paper tends to curl during drying. Therefore, which method is adopted may be determined in consideration of the combination of the ink composition and the reaction liquid. When the former method is employed, the reaction liquid can be attached by an ink jet recording method.
[0015]
Reaction liquid
The reaction solution used in the present invention basically comprises at least a polyvalent metal salt and a component selected from the group consisting of a nitrogen-containing compound or sulfur-containing compound, an amine, and a cationic surfactant.
[0016]
Polyvalent metal salt
The polyvalent metal salt that can be used in the reaction solution is composed of divalent or higher polyvalent metal ions and anions that bind to these polyvalent metal ions, and is soluble in water. Specific examples of polyvalent metal ions include Ca²⁺, Cu²⁺, Ni²⁺, Mg²⁺, Zn²⁺, Ba²⁺Divalent metal ions such as Al³⁺, Fe³⁺, Cr³⁺And trivalent metal ions. Anions include Cl^-, NO_Three ^-, I^-, Br^-, ClO_Three ^-And CH_ThreeCOO^-Etc.
[0017]
In particular, Ca²⁺Or Mg²⁺The metal salt constituted from the above gives suitable results from the two viewpoints of the pH of the reaction solution and the quality of the obtained printed matter.
[0018]
The concentration of these polyvalent metal salts in the reaction solution may be determined as appropriate as long as the printing quality and the effect of preventing clogging are obtained, but is preferably about 0.1 to 40% by weight, more preferably 5 to 5%. It is about 25% by weight.
[0019]
In a preferred embodiment of the present invention, the polyvalent metal salt contained in the reaction solution is composed of a divalent or higher polyvalent metal ion and a nitrate ion or a carboxylate ion that binds to the polyvalent metal ion. It is soluble.
[0020]
Here, the carboxylate ion is preferably derived from a saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms or a carbocyclic monocarboxylic acid having 7 to 11 carbon atoms. Preferable examples of the saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hexanoic acid and the like. In particular, formic acid and acetic acid are preferred.
[0021]
The hydrogen atom on the saturated aliphatic hydrocarbon group of this monocarboxylic acid may be substituted with a hydroxyl group, and a preferred example of such a carboxylic acid is lactic acid.
[0022]
Furthermore, preferable examples of the carbocyclic monocarboxylic acid having 6 to 10 carbon atoms include benzoic acid and naphthoic acid, and benzoic acid is more preferable.
[0023]
Reaction liquid containing nitrogen-containing compound or sulfur-containing compound
According to the first aspect of the present invention, a reaction liquid containing a nitrogen-containing compound or a sulfur-containing compound is provided. In the present specification, the nitrogen-containing compound means a 5- or 6-membered saturated or unsaturated heterocyclic compound containing at least one nitrogen, and an amide derivative which may be alkyl-substituted.
[0024]
The reaction solution containing the nitrogen-containing compound according to the present invention generates little precipitates during storage. The presence of nitrogen-containing compounds or sulfur-containing compounds is considered to suppress the generation of precipitates. In the absence of a nitrogen-containing compound or sulfur-containing compound, precipitates having a size of about 10 μm to 50 μm are often generated in a reaction solution during storage, particularly a reaction solution once exposed to a high temperature (for example, a temperature exceeding 60 ° C.). Observed. Such precipitates are not preferable because they cause clogging of the nozzles of the ink jet recording head. The presence of nitrogen-containing compounds or sulfur-containing compounds in the reaction solution containing the polyvalent metal salt enables the generation of precipitates even in the reaction solution being stored, particularly in the reaction solution exposed to the high temperatures as described above. The advantage is that substantially no observation is made. This improves the reliability of the ink jet recording method.
[0025]
The reason why the generation of precipitates is suppressed by the presence of these nitrogen-containing compounds or sulfur-containing compounds in the reaction solution is not clear, but causes the precipitates by the action of unpaired electrons of nitrogen atoms or sulfur atoms. It is conceivable that ion species and the like are stabilized. However, these are only hypotheses, and the present invention is not limited to these hypotheses.
[0026]
As the 5- or 6-membered saturated or unsaturated heterocyclic compound comprising at least one nitrogen, pyrrolidine or piperidine as the 5- or 6-membered saturated compound, pyrrole, imidazole, pyrazole, as the 5- or 6-membered unsaturated compound, Pyridine, pyridazine, pyrimidine, pyrazine and (alkyl-substituted) amide derivatives include pyrrolidone, N-substituted pyrrolidone, imidazolidinone, N-substituted imidazolidinone and the like. More specific examples include 2-pyrrolidone, N-lower alkyl (preferably methyl) substituted pyrrolidone, 1,3-lower alkyl substituted (preferably methyl) -2-imidazolidinone and the like.
The sulfur-containing compound is preferably thiodiglycol.
[0027]
The concentration of the nitrogen-containing compound or sulfur-containing compound in the reaction solution may be appropriately determined within the range in which the effect of preventing printing quality and clogging can be obtained, but is preferably about 0.5 to 20% by weight, more preferably Is about 2 to 10% by weight.
[0028]
Reaction liquid containing amine
According to the second aspect of the present invention, a reaction liquid containing an amine is provided. By adding an amine, the print quality and the print stability can be improved at the same time. In this embodiment, the amine contained in the reaction solution means ammonia or one obtained by substituting 1 to 3 hydrogen atoms of ammonia with a hydrophobic hydrocarbon group, that is, primary, secondary and tertiary amines.
[0029]
According to a preferred embodiment of the present invention, the reaction solution according to the present invention comprises ammonia as an amine. Ammonia has a small increase in viscosity when added to a reaction solution compared to an amine having a normal hydrocarbon group, and also has a high solubility in water. Therefore, an amount sufficient to satisfy both the print quality and the print stability can be added. Addition of ammonia hardly affects the surface tension of the reaction solution, and does not unnecessarily reduce the wettability of the reaction solution. Therefore, the printed matter obtained has sharp edges and a high OD value. In addition, since ammonia has volatility, the drying speed of the ink is shortened, and after drying, the effect of having robust rubbing resistance is also obtained.
[0030]
The amount of ammonia added may be appropriately determined in consideration of the pH of the reaction solution, but is generally added in an amount of 0.5% by weight or less, preferably 0.1% by weight or less in the reaction solution.
[0031]
Further, the hydrocarbon group of primary, secondary, and tertiary amines may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be either a straight chain or a branched chain.
[0032]
According to a preferred embodiment of the present invention, an amino group (-NH₂) Is preferably a linear amine having a linear hydrocarbon group having about 6 to 18 carbon atoms, more preferably a linear carbon atom having about 12 to 18 carbon atoms. It is a hydrogen group. Specific examples thereof include laurylamine, cetylamine, and stearylamine. By these additions, both the print quality and the print stability can be achieved at a high level.
[0033]
The addition amount of these amines may be appropriately determined depending on the type of amine, and specifically can be determined for each amine individually in consideration of print quality, print stability, and amine solubility. Generally, it is added in an amount of about 0.01% to 1% by weight in the reaction solution. An amine having a small number of carbon atoms in the hydrocarbon group can be added to the reaction solution in a relatively large amount, but an amine having a large number of carbon atoms in the hydrocarbon group has low solubility and increases the viscosity of the reaction solution. Generally, the amount that can be added is limited.
[0034]
Secondary amines and tertiary amines can also be utilized in the present invention, as are the primary amines. Examples of secondary amines and tertiary amines include di-n-propylamine, di-n-butylamine, di-n-amylamine, di-n-octylamine, distearylamine (secondary amine). , Trimethylamine, propyldimethylamine, butyldimethylamine, octyldimethylamine, stearyldimethylamine (tertiary amine).
[0035]
It is also possible to use an amine in which the hydrocarbon group has a cyclic structure. Examples include cyclohexylamine, dicyclohexylamine, benzylamine, N-cyclohexyl-n-dodecylamine, N-benzyl-n-dodecylamine, N-o-tolyl-n-dodecylamine, Np-tolyl-n. -Dodecylamine and the like.
[0036]
Furthermore, in the present invention, an amine is used to mean a cyclic imine. Examples of the cyclic imine include pyrrolidine, piperidine, hexamethyleneimine, octamethyleneimine, and decamethyleneimine, and any of them can obtain stable printing characteristics. In particular, octamethyleneimine having a methylene chain of 8 to 10 gives a good effect, and the printing stability is dramatically improved as compared with octylamine or dibutylamine having the same total number of carbon atoms.
[0037]
In the present invention, the amine is preferably added in the form of an inorganic acid salt or amide. Examples of inorganic acids include various inorganic acids such as nitric acid, nitrous acid, hydrochloric acid, bromic acid, and chromic acid. By adding an amine to the reaction solution in the form of an inorganic acid salt, the solubility of the amine can be improved, and the storage stability and printing stability can be improved. Further, by appropriately selecting the kind of inorganic acid, it is possible to prevent the pH from being biased toward the alkali side.
[0038]
Examples of amides include those obtained by heat-treating a mixture of an amine and a fatty acid, and C_nH_{2n + 1}NH₂And C_n-1H_2n-1A mixture with COOH (n is an integer, the same shall apply hereinafter), (C_nH_{2n + 1})₂NH and C_n-1H_2n-1A mixture with COOH, (C_nH_{2n + 1})_ThreeN and C_n-1H_2n-1What heat-processed the mixture with COOH gives the same effect as the case where an amine is added to a reaction liquid.
[0039]
In addition, a part of amine whose hydrocarbon group has a cyclic structure, cyclic imine, and amide also have a function as a nitrogen-containing compound of the reaction liquid according to the first aspect.
[0040]
Moreover, according to the preferable aspect of this invention, it is preferable that an amine has moderate volatility. The ink composition containing a volatile amine is dried quickly after adhering to paper, and after drying, a printed matter having robust abrasion resistance is obtained.
[0041]
According to a preferred embodiment of the present invention, the vapor pressure of the amine is 0.01 Pa or higher at 25 ° C. Specifically, in addition to the above-mentioned ammonia, dicyclohexylamine nitrite and the like are applicable.
[0042]
Cationic surfactant
According to the third aspect of the present invention, a reaction solution comprising a cationic surfactant is provided. As described above, in the ink jet recording method according to the present invention, the polyvalent metal salt in the reaction liquid destroys the dispersion state of the colorant and the like in the ink composition, and aggregates the colorant component and the like. It is considered that printing that adheres to the medium and has high color density, less bleeding and less unevenness is realized. The addition of a cationic surfactant seems to further promote the generation of the aggregates. As a result, the colorant component can be quickly and surely fixed on the recording medium, and good printing can be performed. Here, since the cationic surfactant has high solubility in an aqueous solvent, it is advantageous in that the concentration of the cationic surfactant contained in the reaction solution can be increased. In addition, the cationic surfactant also acts as a penetrant. Therefore, there is also an advantage that improvement in drying property of the printed matter is realized at the same time. Furthermore, a color image has an advantage that non-uniform color mixing, that is, color bleeding, can be effectively prevented in a boundary area of different colors.
[0043]
Cationic surfactants used in the present invention include primary, secondary, tertiary, and quaternary ammonium salts and those derived therefrom, and sulfuric acid-based cationic surfactants. It is done. In particular, a cationic surfactant containing one quaternary nitrogen atom is preferable. Furthermore, it is preferable from the viewpoint of the high cohesive force that at least two of the substituents bonded to the quaternary nitrogen atom each contain six or more carbon atoms.
[0044]
Specific examples of the cationic surfactant include quaternary ammonium salts represented by the following formula (I).
[0045]
R¹R²R^ThreeR^FourN⁺X^-          (I)
(Wherein R¹And R²Is independently C₈~ C₂₀Represents an alkyl group, a benzyl group, or a phenyl group, R^ThreeAnd R^FourIs independently C₁~ C_FourRepresents an alkyl group, X^-Represents counter ion)
[0046]
Specific examples of the cationic surfactant represented by the formula (I) include lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, dioctyldimethylammonium chloride, distearyldimethylammonium chloride, octadecyldimethylbenzylammonium chloride, octadecylamine acetate Is mentioned.
[0047]
The amount of the cationic surfactant added to the reaction solution is not particularly limited, but is preferably about 0.1 to 20% by weight, more preferably about 5 to 10% by weight.
[0048]
Other components of the reaction solution
In addition, the reaction liquid according to the present invention may be colored by adding a color coloring agent described in the section of the ink composition described later, and may have a function of the ink composition. In this case, when the colorant is a dye, the reaction liquid preferably further contains glycerin. By making glycerin exist, generation | occurrence | production of the precipitate considered to originate in precipitation of dye can be suppressed more.
[0049]
The concentration of glycerin in the reaction solution may be appropriately determined within a range in which the effect of preventing clogging is obtained, but it is preferably about 0.5 to 40% by weight on the basis of the reaction solution (or dye basis), more preferably. It is about 2 to 20% by weight.
[0050]
According to a preferred embodiment of the present invention, the reaction solution may contain a wetting agent composed of a high boiling point organic solvent. The high boiling point organic solvent prevents clogging of the head by preventing the reaction solution from drying. Preferred examples of the high boiling point organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, triglyceride, Polyhydric alcohols such as methylolethane and trimethylolpropane; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether , Triethylene glycol monobutyl ether Alkyl ethers of all polyols, urea, triethanolamine and the like.
[0051]
The amount of the high-boiling organic solvent added is not particularly limited, but is preferably about 0.5 to 40% by weight, more preferably about 2 to 20% by weight.
[0052]
According to a preferred embodiment of the present invention, the reaction solution may contain a low boiling point organic solvent. Preferable examples of the low boiling point organic solvent include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, sec-butanol, tert-butanol, iso-butanol, n-pentanol and the like. A monohydric alcohol is particularly preferable. The low boiling point organic solvent has an effect of shortening the drying time of the ink. The amount of the low-boiling organic solvent added is preferably 0.5 to 10% by weight, more preferably 1.5 to 6% by weight.
[0053]
According to a preferred embodiment of the present invention, the reaction solution may contain a penetrant. Examples of penetrants include various surfactants such as anionic surfactants and amphoteric surfactants, alcohols such as methanol, ethanol and iso-propyl alcohol, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, And lower alkyl ethers of polyhydric alcohols such as ethylene glycol monobutyl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether.
[0054]
Furthermore, the penetrant that can be used in the present invention is more preferably a compound represented by the following formula (I) and / or a lower alcohol ether of a polyhydric alcohol.
[0055]
[Chemical 1]

(Where 0 ≦ m + n ≦ 50, R¹, R², R^ThreeAnd R^FourAre independently alkyl groups)
Specific examples of the compound represented by the above formula (I) include Orphine Y, Surfinol 82, Surfinol 440, Surfinol 465, Surfinol 485 (all manufactured by Air Products and Chemicals. Inc. ) Etc. These may be used alone or in combination of two or more.
[0056]
According to a preferred embodiment of the present invention, the reaction solution contains triethanolamine for pH adjustment. When triethanolamine is added, the addition amount is preferably about 0 to 2.0% by weight.
[0057]
Ink composition
In the present invention, the ink composition means a black ink composition when performing monochrome printing, and a color ink composition, specifically a yellow ink composition, a magenta ink composition when performing color printing. And a cyan ink composition, and optionally a black ink composition.
[0058]
The ink composition used in the present invention comprises at least a colorant and water.
[0059]
The colorant contained in the ink composition used in the present invention may be either a dye or a pigment, but it suppresses the penetration of the coloring component in the ink by the action of insolubilization or thickening of the ink composition. If so, a pigment dispersed is more advantageous than a dye dissolved in an aqueous medium.
[0060]
As dyes, use various dyes that are usually used for inkjet recording, such as direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, and reactive disperse dyes. Can do.
[0061]
As the pigment, inorganic pigments and organic pigments can be used without any particular limitation. As the inorganic pigment, in addition to titanium oxide and iron oxide, carbon black produced by a known method such as a contact method, a furnace method, or a thermal method can be used. Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (for example, basic dye chelate, acid dye chelate, etc.), nitro pigments, nitroso pigments, aniline black, and the like.
[0062]
According to a preferred embodiment of the present invention, these pigments are preferably added to the ink as a pigment dispersion obtained by dispersing the pigment in an aqueous medium with a dispersant or a surfactant. As a preferable dispersant, a dispersant conventionally used for preparing a pigment dispersion, for example, a polymer dispersant can be used.
[0063]
Preferred examples of the dispersant or surfactant include polyacrylic acid, polymethacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid alkyl ester copolymer, styrene. -Acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-acrylic acid-alkyl acrylate copolymer, styrene-methacrylic acid-alkyl acrylate copolymer, styrene-α-methylstyrene-acrylic acid Copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid alkyl ester copolymer, styrene-maleic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate- Fatty acid vinyl ethylene copolymer, vinyl acetate-male Examples of the acid ester copolymer include a vinyl acetate-crotonic acid copolymer and a vinyl acetate-acrylic acid copolymer.
[0064]
According to a preferred embodiment of the present invention, these copolymers preferably have a weight average molecular weight of about 3,000 to 50,000, more preferably about 5,000 to 30,000, and most preferably 7,000. 000 to 15,000.
[0065]
The addition amount of the dispersant may be appropriately added as long as the pigment is stably dispersed and the other effects of the present invention are not lost. According to a preferred embodiment of the present invention, the amount used is preferably in the range of about 1: 0.06 to 1: 3, more preferably in the range of about 1: 0.125 to 1: 3 as pigment: dispersant. .
[0066]
The amount of the pigment added to the ink is preferably about 0.5 to 25% by weight, more preferably about 2 to 15% by weight.
[0067]
According to a preferred embodiment of the present invention, the ink composition preferably comprises a resin emulsion. Here, the resin emulsion means an emulsion in which the continuous phase is water and the dispersed phase is the following resin component. As the resin component of the dispersed phase, acrylic resin, vinyl acetate resin, styrene-butadiene resin, vinyl chloride resin, acrylic-styrene resin, butadiene resin, styrene resin, crosslinked acrylic resin, crosslinked styrene resin, Examples thereof include benzoguanamine resin, phenol resin, silicone resin, and epoxy resin.
[0068]
According to a preferred embodiment of the present invention, the resin is preferably a polymer having both a hydrophilic part and a hydrophobic part. The particle size of these resin components is not particularly limited as long as an emulsion is formed, but is preferably about 150 nm or less, more preferably about 5 to 100 nm.
[0069]
These resin emulsions can be obtained by subjecting a resin monomer to dispersion polymerization in water, optionally with a surfactant. For example, an acrylic resin or a styrene-acrylic resin emulsion can be obtained by subjecting (meth) acrylic acid ester or (meth) acrylic acid ester and styrene to dispersion polymerization in water together with a surfactant. The mixing ratio of the resin component and the surfactant is usually preferably about 10: 1 to 5: 1. When the amount of the surfactant used is in the above range, better water resistance and penetrability of the ink can be obtained. The surfactant is not particularly limited, but preferable examples include anionic surfactants (for example, sodium dodecyl benzene sulfonate, sodium laurate, ammonium salt of polyoxyethylene alkyl ether sulfate), nonionic surfactants ( For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, etc.). A mixture of seeds or more can be used. Also, acetylene glycol (olefin Y and Surfinol 82, 104, 440, 465, and 485 (all manufactured by Air Products and Chemicals Inc.)) can be used.
[0070]
Further, the ratio of the resin and water as the dispersed phase component is 60 to 400 parts by weight, preferably 100 to 200 parts by weight with respect to 100 parts by weight of the resin.
[0071]
Commercially available resin emulsions can also be used. For example, Microgel E-1002, E-5002 (styrene-acrylic resin emulsion, manufactured by Nippon Paint Co., Ltd.), Boncoat 4001 (acrylic resin emulsion, Dainippon) Manufactured by Ink Chemical Co., Ltd.) Boncoat 5454 (styrene-acrylic resin emulsion, manufactured by Dainippon Ink & Chemicals, Inc.), SAE-1014 (styrene-acrylic resin emulsion, manufactured by Nippon Zeon Co., Ltd.), Cybinol SK-200 ( Acrylic resin emulsion, manufactured by Seiden Chemical Co., Ltd.).
[0072]
The ink used in the present invention preferably contains a resin emulsion such that the resin component is 0.1 to 40% by weight of the ink, more preferably 1 to 25% by weight.
[0073]
The resin emulsion has an effect of suppressing the penetration of the coloring component by the interaction with the polyvalent metal ion and further promoting the fixing to the recording medium. Further, depending on the type of the resin emulsion, a film is formed on the recording medium, and it has an effect of improving the abrasion resistance of the printed matter.
[0074]
According to a preferred embodiment of the present invention, the ink composition can include a thermoplastic resin in the form of a resin emulsion. Here, the thermoplastic resin has a softening temperature of 50 ° C to 250 ° C, preferably 60 ° C to 200 ° C. Here, the term softening temperature means that the glass transition point, melting point and viscosity of a thermoplastic resin are 10¹¹-10¹²When it is in the form of a poise, pour point, and resin emulsion, it means the lowest temperature among its minimum film-forming temperature (MFT). When an ink composition containing such a resin emulsion is used, it is preferable to carry out a heating step in which the recording medium after recording is heated at a temperature equal to or higher than the softening temperature of the thermoplastic resin.
[0075]
Further, as these resins, those which form a film having strong water resistance and abrasion resistance when heated to the softening or melting temperature or higher and cooled are preferably selected.
[0076]
Specific examples of water-insoluble thermoplastic resins include polyacrylic acid, polymethacrylic acid, polymethacrylic acid ester, polyethylacrylic acid, styrene-butadiene copolymer, polybutadiene, acrylonitrile-butadiene copolymer, and chloroprene copolymer. Polymer, fluororesin, vinylidene fluoride, polyolefin resin, cellulose, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, polystyrene, styrene-acrylamide copolymer, polyisobutyl acrylate, polyacrylonitrile, polyacetic acid Vinyl, polyvinyl acetal, polyamide, rosin resin, polyethylene, polycarbonate, vinylidene chloride resin, cellulose resin, vinyl acetate resin, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic copolymer, Vinyl resins, polyurethane, rosin ester and the like are not limited thereto.
[0077]
Specific examples of low molecular weight thermoplastic resins include polyethylene wax, montan wax, alcohol wax, synthetic oxide wax, α-olefin-maleic anhydride copolymer, carnauba wax and other animal and plant waxes, lanolin, paraffin wax, microcrystalline. A wax etc. are mentioned.
[0078]
As such a resin emulsion, a known resin emulsion may be used. For example, JP-B-62-1426, JP-A-3-56573, JP-A-3-79678, JP-A-3-160068, JP-A-3-160068 Resin emulsions described in No. 4-18462 can be used as they are.
[0079]
According to a preferred embodiment of the present invention, the ink composition can contain an alginic acid derivative. Preferable examples of the alginic acid derivative include alginic acid alkali metal salts (for example, sodium salts and potassium salts), alginic acid organic salts (for example, triethanolamine salts), and alginic acid ammonium salts.
[0080]
The amount of the alginic acid derivative added to the ink composition is preferably about 0.01 to 1% by weight, more preferably about 0.05 to 0.5% by weight.
[0081]
The reason why a good image can be obtained by the addition of an alginic acid derivative cannot be determined, but the polyvalent metal salt present in the reaction solution reacts with the alginic acid derivative in the ink composition, changes the dispersion state of the colorant, and the colorant This is thought to be due to the fact that the fixing to the recording medium is promoted.
[0082]
Further, the ink composition used in the present invention may contain an inorganic oxide colloid. Preferable examples of the inorganic oxide colloid include colloidal silica and alumina colloid. These are generally SiO₂, Al₂0_ThreeIt is a colloidal solution in which ultrafine particles such as are dispersed in water or an organic solvent. Commercially available inorganic oxide colloids include dispersion media such as water, methanol, 2-propanol, n-propanol, and xylene, and SiO 2₂, Al₂0_ThreeA particle having a particle size of 5 to 100 nm is generally used. In many cases, the pH of the inorganic oxide colloidal solution is adjusted to be acidic or alkaline rather than neutral. This is because the stable dispersion region of the inorganic oxide colloid exists on the acidic side or alkaline side. When added to the ink composition, the pH of the stable dispersion region of the inorganic oxide colloid and the pH of the ink are set. It is necessary to add in consideration.
[0083]
The addition amount of the inorganic oxide colloid in the ink composition is preferably 0.1 to 15% by weight, and two or more kinds can be added.
[0084]
According to a preferred embodiment of the present invention, the ink composition preferably comprises an organic solvent. This organic solvent is preferably a low boiling point organic solvent, and preferred examples thereof include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, sec-butanol, tert-butanol, iso-butanol, Examples thereof include n-pentanol. A monohydric alcohol is particularly preferable. The low boiling point organic solvent has an effect of shortening the drying time of the ink.
[0085]
According to a preferred aspect of the present invention, the ink composition used in the present invention preferably further comprises a wetting agent composed of a high-boiling organic solvent. Preferred examples of the high boiling point organic solvent agent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, Polyhydric alcohols such as trimethylolethane and trimethylolpropane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, triethylene glycol monobutyl ether Alkyl ethers of polyhydric alcohols such as urea, 2-pyrrolidone, N- methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, triethanolamine and the like.
[0086]
The amount of the wetting agent added is preferably 0.5 to 40% by weight of the ink, more preferably 2 to 20% by weight. The amount of the low-boiling organic solvent added is preferably 0.5 to 10% by weight of the ink, more preferably 1.5 to 6% by weight.
[0087]
According to a preferred embodiment of the present invention, the ink composition preferably contains a sugar. Examples of saccharides include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucosiyl. (Sorbit), maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like. Here, the polysaccharide means a saccharide in a broad sense, and is used to include a substance that exists widely in nature, such as alginic acid, α-cyclodextrin, and cellulose.
[0088]
In addition, derivatives of these saccharides include reducing sugars of the aforementioned saccharides (for example, sugar alcohol (general formula HOCH₂(CHOH) n CH₂Examples thereof include OH (represented by an integer of n = 2 to 5), oxidized sugar (for example, aldonic acid, uronic acid, etc.), amino acid, thiosugar and the like. Particularly preferred are sugar alcohols, and specific examples include maltitol and sorbit.
[0089]
The content of these saccharides is 0.1 to 40% by weight, preferably 0.5 to 30% by weight of the ink.
[0090]
In addition, you may add a pH adjuster, antiseptic | preservative, a fungicide, etc. as needed.
[0091]
Inkjet recording device
Hereinafter, an ink jet recording apparatus for carrying out an ink jet recording method according to the present invention will be described with reference to the drawings.
[0092]
The ink jet recording apparatus of FIG. 1 is an embodiment in which an ink composition and a reaction liquid are stored in a tank, and the ink composition and the reaction liquid are supplied to a recording head via an ink tube. That is, the recording head 1 and the ink tank 2 are communicated with each other through the ink tube 3. Here, the inside of the ink tank 2 is partitioned, and an ink composition, and in some cases, a plurality of color ink composition rooms and a reaction liquid room are provided.
[0093]
The recording head 1 moves along a carriage 4 by a timing belt 6 driven by a motor 5. On the other hand, the paper 7 as a recording medium is placed at a position facing the recording head 1 by a platen 8 and a guide 9. In this embodiment, a cap 10 is provided. A suction pump 11 is connected to the cap 10 to perform a so-called cleaning operation. The sucked ink composition is stored in the waste ink tank 13 through the tube 12.
[0094]
An enlarged view of the nozzle surface of the recording head 1 is shown in FIG. The portion indicated by 1b is the nozzle surface of the reaction liquid, and the nozzle 21 for discharging the reaction liquid is provided in the vertical direction. On the other hand, the portion denoted by 1c is the nozzle surface of the ink composition, and the yellow ink composition, magenta ink composition, cyan ink composition and black ink composition are respectively supplied from the nozzles 22, 23, 24 and 25. Discharged.
[0095]
Further, an ink jet recording method using the recording head shown in FIG. 2 will be described with reference to FIG. The recording head 1 moves in the direction of arrow A. During the movement, the reaction liquid is discharged from the nozzle surface 1 b to form a belt-like reaction liquid adhesion region 31 on the recording medium 7. Next, the recording medium 7 is transferred to the paper feed direction arrow B by a predetermined amount. Meanwhile, the recording head 1 moves in the direction opposite to the arrow A in the figure and returns to the left end position of the recording medium 7. Then, the ink composition is printed on the reaction liquid adhesion area where the reaction liquid has already adhered, and the printing area 32 is formed.
[0096]
Further, as shown in FIG. 4, in the recording head 1, all the nozzles can be arranged in the horizontal direction. In the figure, reference numerals 41a and 41b denote discharge nozzles for the reaction liquid, and the yellow ink composition, the magenta ink composition, the cyan ink composition, and the black ink composition are discharged from the nozzles 42, 43, 44, and 45, respectively. Is discharged. In the recording head of such a mode, printing can be performed in both the forward path and the backward path in which the recording head 1 reciprocates on the carriage, and at a higher speed than when the recording head shown in FIG. 2 is used. Printing can be expected.
[0097]
Further, by adjusting the surface tension of the reaction liquid and the ink composition, high quality printing can be obtained more consistently regardless of the order of attachment. In this case, it is possible to use a single discharge nozzle for the reaction liquid (for example, the nozzle 41b in the figure can be omitted), and further miniaturization of the head and high-speed printing can be achieved.
[0098]
Further, some ink jet recording apparatuses are replenished with an ink composition by replacing a cartridge which is an ink tank. The ink tank may be integrated with the recording head.
[0099]
A preferred example of an ink jet recording apparatus using such an ink tank is shown in FIG. In the figure, the same members as those in the apparatus of FIG. In the embodiment of FIG. 5, the recording heads 1a and 1b are integrated with the ink tanks 2a and 2b. The recording head 1a or 1b is assumed to discharge the ink composition and the reaction liquid, respectively. The printing method may be basically the same as that of the apparatus shown in FIG. In this embodiment, the recording head 1a, the ink tank 2a, the recording head 1a, and the ink tank 2b move together on the carriage 4.
[0100]
Further, FIG. 6 shows a preferred example of an ink jet recording apparatus provided with a heater for heating a recording medium on which printing has been performed. FIG. 6 is the same as that shown in FIG. 1 except that the heater 14 is provided. The heater 14 may be a heater that contacts and heats the recording medium, or a heater that does not contact the recording medium, such as irradiating infrared rays or blowing hot air.
[0101]
According to a preferred aspect of the present invention, the ink jet recording apparatus further stores the reaction liquid and the ink composition, and the amount of the ink composition and the reaction liquid is such that the ink composition is consumed first. Are preferred.
[0102]
Moreover, according to another preferable aspect, the ink tank used for an inkjet recording device is provided. The ink tank may preferably be a replaceable cartridge type, and more preferably may be integrated with the recording head. In any of the embodiments, it is preferable that the reaction liquid and the ink composition are accommodated, and the amount of the ink composition and the reaction liquid is such that the ink composition is consumed first.
[0103]
Contrary to this aspect, when the reaction liquid is consumed before the ink composition, the reaction liquid is generally transparent, and thus consumed. It becomes difficult to know the time. That is, the fact that the reaction solution has been consumed is observed only by observing the print and the print quality is deteriorated, and thus the user is always required to observe the print quality.
[0104]
On the other hand, in the ink jet recording apparatus according to this aspect, since the ink composition itself is colored, its exhaustion can be easily known. Furthermore, since the reaction liquid does not run out before the ink composition is consumed, an ink jet recording method that stably prints two liquids can be performed. On the other hand, it is conceivable to provide sensor means or the like in the tank portion for storing the ink composition and the reaction liquid and observe the consumption thereof. However, in this aspect, such a complicated mechanism can be replaced with a very simple mechanism. It can be said that it is also valuable in terms of points.
[0105]
In this embodiment, when a plurality of ink compositions are used, “the ink composition is consumed earlier than the reaction liquid” means that any one ink composition is consumed. As long as the reaction liquid remains at that time, it does not necessarily mean that the reaction liquid must remain even when all of the plurality of ink compositions are consumed. It is preferable that the reaction solution remains even when all of the product is consumed.
[0106]
【Example】
Hereinafter, the present invention will be described in detail with reference to the following examples, but the present invention is not limited thereto.
[0107]
Example A
Preparation of reaction solution
Reaction liquid A1-10 was prepared by mixing the following components.
[0108]
Reaction solution A1
Magnesium nitrate hexahydrate 5% by weight
Glycerin 20% by weight
Triethylene glycol
Monobutyl ether 10% by weight
2-pyrrolidone 5% by weight
Triethanolamine 0.2% by weight
Pure water remaining
[0109]
Reaction solution A2
Magnesium nitrate hexahydrate 5% by weight
Glycerin 20% by weight
Triethylene glycol
Monobutyl ether 10% by weight
2-pyrrolidone 10% by weight
Triethanolamine 0.2% by weight
Pure water remaining
[0110]
Reaction solution A3
Magnesium nitrate hexahydrate 5% by weight
Glycerin 20% by weight
Diethylene glycol
Monobutyl ether 10% by weight
1,3-dimethyl
2-Imidazolidinone 10% by weight
Triethanolamine 0.2% by weight
Pure water remaining
[0111]
Reaction solution A4
Magnesium nitrate hexahydrate 5% by weight
Glycerin 20% by weight
Surfynol 465 0.7% by weight
Thiodiglycol 5% by weight
Triethanolamine 0.2% by weight
Pure water remaining
[0112]
Reaction solution A5
Calcium nitrate tetrahydrate 5% by weight
Glycerin 20% by weight
Triethylene glycol
Monobutyl ether 10% by weight
2-pyrrolidone 5% by weight
Triethanolamine 0.2% by weight
Pure water remaining
[0113]
Reaction solution A6
Acid Yellow 23 3.2% by weight
Magnesium nitrate hexahydrate 5% by weight
Glycerin 12% by weight
Diethylene glycol
Monobutyl ether 3% by weight
Surfynol 465 0.7% by weight
Siethylene glycol 4% by weight
2-pyrrolidone 5% by weight
Triethanolamine 0.1% by weight
Pure water remaining
[0114]
Reaction solution A7
Reactive Red 180 4.2% by weight
Magnesium nitrate hexahydrate 5% by weight
Glycerin 17% by weight
Siethylene glycol
Monobutyl ether 3% by weight
Surfynol 465 0.7% by weight
Diethylene glycol 4% by weight
2-pyrrolidone 5% by weight
Triethanolamine 0.9% by weight
Pure water remaining
[0115]
Reaction solution A8
Acid Blue 9 1.5% by weight
Direct Blue 199 3.5% by weight
Magnesium nitrate hexahydrate 5% by weight
Glycerin 12% by weight
Siethylene glycol
Monobutyl ether 3% by weight
Surfynol 465 0.7% by weight
Diethylene glycol 4% by weight
2-pyrrolidone 5% by weight
Triethanolamine 0.1% by weight
Pure water remaining
[0116]
Reaction solution A9
Magnesium nitrate hexahydrate 5% by weight
Glycerin 20% by weight
Triethylene glycol
Monobutyl ether 10% by weight
Triethanolamine 0.2% by weight
Pure water remaining
[0117]
Reaction solution A10
Calcium nitrate tetrahydrate 5% by weight
Glycerin 20% by weight
Triethylene glycol
Monobutyl ether 10% by weight
Triethanolamine 0.2% by weight
Pure water remaining
[0118]
Preparation of ink composition
Black ink A1
Carbon black MA7 5% by weight
(Made by Mitsubishi Kasei)
Styrene-acrylic acid copolymer 1% by weight
(Dispersant)
Sucrose 0.7% by weight
Maltitol 6.3% by weight
Glycerin 10% by weight
2-pyrrolidone 2% by weight
4% by weight of ethanol
Pure water remaining
[0119]
Carpon black and a dispersant were mixed and dispersed in a sand mill (manufactured by Yaskawa Seisakusho) with glass peas (diameter 1.7 mm, 1.5 times the weight of the mixture (weight)) for 2 hours. Thereafter, the glass peas were removed, other components were added, and the mixture was stirred at room temperature for 20 minutes. The mixture was filtered through a 5 μm membrane filter to obtain a black ink for inkjet recording.
[0120]
Evaluation of reaction solution A
Evaluation A1: Foreign matter generation
The reaction mixture was sealed in Teflon bottle and allowed to stand at 70 ° C. for 1 week. After standing, 10 ml of the reaction solution was passed through a 10 μm mesh filter to collect foreign matters. The results were as shown in Table 1. In the table,
Less than 20 foreign matter collected by filtration -A
The number of collected foreign matter is 20 or more and less than 100 -B
More than 100 foreign substances collected by filtration -C
It was.
[0121]
Evaluation A2: Printing stability
The reaction liquid was filled into an ink cartridge of MJ-500C (manufactured by Seiko Epson Corporation) and mounted on a printer. 10000 patterns of mixed characters and graphics were printed on A4 paper, and “flight bends” and “missing” were observed during the process.
[0122]
Since reaction solutions 1 to 5 were transparent, 0.5% by weight of acid blue 9 (dye) was added and colored so that bending and removal could be easily confirmed.
[0123]
The results were as shown in Table 1. In the table,
Less than 20 occurrences of bending or omission -A
The number of occurrences of bending or omission is 20 times or more and less than 50 times -B
The number of occurrences of bending and omission is 50 times or more -C
It was.
[0124]
Evaluation A3: Print quality (smudge)
Printing was performed on each of the following papers using an inkjet printer MJ-500C. Printing was performed by printing the reaction liquid with 100% duty and then printing characters with black ink A1. After drying, the characters were checked for bleeding.
[0125]
(1) XeroxP paper (manufactured by Xerox Corporation)
(2) Rcopy 6200 paper (Ricoh Co., Ltd.)
(3) Xerox 4024 paper (manufactured by Xerox Corporation)
(4) Neenah Bond paper (made by Kimberly Clark)
(5) Xerox R paper (Xerox Co., Ltd., recycled paper)
(6) Yamayuri paper (Honshu Paper Co., Ltd., recycled paper)
[0126]
The results were as shown in Table 1. In the table,
For clear prints without blurring -A,
If whisker-like bleeding occurs -B,
When blurring occurs so that the outline of the character is not clear -C
It was.
[0127]

[0128]
Example B
Preparation of reaction solution
Reaction liquid B1-10 was prepared by mixing the following components.
Reaction solution B1
Magnesium nitrate hexahydrate 25% by weight
Triethylene glycol
Monobutyl ether 10% by weight
Glycerin 20% by weight
Ammonia water (29% aqueous solution) 0.05% by weight
Pure water remaining
The above components were mixed and stirred at room temperature for 1 hour, and then the composition was suction filtered with a 5 μm membrane filter to obtain a reaction solution.
[0129]
Reaction solution B2
Magnesium nitrate hexahydrate 25% by weight
Triethylene glycol
Monobutyl ether 10% by weight
Glycerin 20% by weight
Ammonia water (29% aqueous solution) 0.2% by weight
Pure water remaining
[0130]
Reaction solution B3
Magnesium nitrate hexahydrate 25% by weight
Triethylene glycol
Monobutyl ether 10% by weight
Glycerin 20% by weight
Cyclohexylamine 0.1% by weight
Pure water remaining
[0131]
Reaction solution B4
Magnesium nitrate hexahydrate 25% by weight
Triethylene glycol
Monobutyl ether 10% by weight
Glycerin 20% by weight
N-cyclohexyl-
N-dodecylamine 0.1% by weight
Pure water remaining
[0132]
Reaction solution B5
Magnesium nitrate hexahydrate 25% by weight
Triethylene glycol
Monobutyl ether 10% by weight
Glycerin 20% by weight
Decamethyleneimine 0.1% by weight
Pure water remaining
[0133]
Reaction solution B6
Magnesium nitrate hexahydrate 25% by weight
Triethylene glycol
Monobutyl ether 10% by weight
Glycerin 20% by weight
Dicyclohexylamine nitrite 0.1% by weight
Pure water remaining
[0134]
Reaction solution B7
Magnesium nitrate hexahydrate 25% by weight
Triethylene glycol
Monobutyl ether 10% by weight
Glycerin 20% by weight
Dioctylamine 0.1% by weight
Heptanoic acid 0.1% by weight
Pure water remaining
[0135]
Reaction solution B8
Calcium nitrate tetrahydrate 20% by weight
Triethylene glycol
Monobutyl ether 10% by weight
Glycerin 20% by weight
Ammonia water (29%) 0.2% by weight
Pure water remaining
[0136]
Reaction solution B9
Magnesium nitrate hexahydrate 25% by weight
Triethylene glycol
Monobutyl ether 10% by weight
Glycerin 20% by weight
Pure water remaining
[0137]
Reaction solution B10
Calcium nitrate tetrahydrate 20% by weight
Triethylene glycol
Monobutyl ether 10% by weight
Glycerin 20% by weight
Pure water remaining
[0138]
Preparation of ink composition
Black ink B1
Carbon black MA7 5% by weight
(Made by Mitsubishi Kasei)
Styrene acrylic acid copolymer 1% by weight
(Dispersant)
Boncoat 4001 3% by weight
(Acrylic resin emulsion, resin component 50%, MFT 5 ° C, manufactured by Dainippon Ink Co., Ltd.)
Sucrose 0.7% by weight
Maltitol 6.3% by weight
Glycerin 10% by weight
2-pyrrolidone 2% by weight
4% by weight of ethanol
Pure water remaining
[0139]
Carbon black and a dispersant were mixed and dispersed in a sand mill (manufactured by Yasukawa Seisakusho) with glass beads (diameter 1.7 mm, 1.5 times the weight (weight) of the mixture) for 2 hours. Thereafter, the glass beads were removed, other components were added, and the mixture was stirred for 20 minutes at room temperature. The mixture was filtered through a 5 μm membrane filter to obtain an inkjet recording ink.
[0140]
Evaluation of reaction solution
Evaluation B1: Print quality (smudge)
Using the inkjet printer MJ-500C (manufactured by Seiko Epson Corporation), printing was performed on each of the following papers. For printing, first, the reaction liquid was printed at 100% duty, and then characters were printed with the black ink B1. After drying, the characters were checked for bleeding.
[0141]
(1) Xerox P paper (Xerox Co., Ltd.)
(2) Rcopy 6200 paper (Ricoh Co., Ltd.)
(3) Xerox 4024 paper (manufactured by Xerox Corporation)
(4) Neenah Bond paper (made by Kimberly Clark)
(5) Xerox R paper (Xerox Co., Ltd., recycled paper)
(6) Yamayuri paper (Honshu Paper Co., Ltd., recycled paper)
[0142]
The results were as shown in Table 2. In the table,
For clear prints without blurring -A
When whisker-like blurring occurs -B
When blurring occurs so that the outline of the character is not clear-C.
[0143]
Evaluation B2: Clogging property
The reaction liquid was filled in the head of the inkjet printer MJ-500C, and alphanumeric characters were printed continuously for 10 minutes. Thereafter, the printer was stopped and left for 1 month in an environment of 40 ° C. and 25 Rh without a cap. Alphanumeric characters were printed again after being left, and the number of clogging recovery operations required until a print equivalent to that before being left was obtained was examined. The results were as shown in Table 2. In the table,
Possible to perform printing equivalent to the initial stage with 0 to 2 return operations -A
Printing equivalent to the initial stage is possible with 3 to 5 return operations -B
Even if the return operation is performed 6 times or more, it is impossible to perform printing equivalent to the initial state-C.
[0144]
Evaluation B3: Discharge stability
The head of an inkjet printer MJ-500C was filled with the reaction solution, and alphanumeric characters were continuously printed on A4 size paper. When a flight bend occurs during printing (which means that ink droplets do not fly straight), a return operation is performed. If the flight bend does not correct even after performing the return operation, the number of prints made so far was used as a parameter representing the discharge stability.
[0145]
The results are shown in Table 2.
[0146]
More than 10000 copies before flight bends return -A
The number of prints until the flight bend does not return is 10,000 sheets or less -B
The number of prints until the flight bend does not return is 5000 sheets or less -C
[0147]

[0148]
  Reference example
  Preparation of reaction solution
  Reaction liquids C1-5 were prepared by mixing the following components.
[0149]
Reaction liquid C1
Swanol CA-2150 10% by weight
(Lauryltrimethylammonium chloride, solid content 50%, manufactured by Nikko Chemicals Co., Ltd.)
Magnesium nitrate hexahydrate 5% by weight
Glycerin 10% by weight
Triethanolamine 0.2% by weight
Pure water remaining
[0150]
Reaction liquid C2
Swanol CA-2350 10% by weight
(Cetyltrimethylammonium chloride, solid content 50%, manufactured by Nikko Chemicals Co., Ltd.)
Calcium nitrate tetrahydrate 5% by weight
Glycerin 10% by weight
Triethanolamine 0.2% by weight
Pure water remaining
[0151]
Reaction liquid C3
Swanol CA-3080 3% by weight
(Dioctyldimethylammonium chloride, solid content 80%, manufactured by Nikko Chemicals Co., Ltd.)
Magnesium acetate tetrahydrate 5% by weight
Glycerin 10% by weight
Triethanolamine 0.2% by weight
Pure water remaining
[0152]
Reaction liquid C4
Cation M2-100 5% by weight
(Octadecyldimethylbenzylammonium chloride, manufactured by NOF Corporation)
Calcium acetate monohydrate 5% by weight
Glycerin 10% by weight
Triethanolamine 0.2% by weight
Pure water remaining
[0153]
Reaction liquid C5
Cation SA 5% by weight
(Octadecylamine acetate, manufactured by NOF Corporation)
Calcium formate (anhydrous) 5% by weight
Glycerin 10% by weight
Triethanolamine 0.2% by weight
Pure water remaining
[0154]
Preparation of ink composition
Black ink C1
Carbon black Raven 1080 5% by weight
(Colombian carbon)
Styrene-acrylic acid copolymer 1% by weight
(Dispersant)
Boncourt 4001 5% by weight
(Acrylic resin emulsion, resin component 50%, manufactured by Dainippon Ink & Chemicals, Inc.)
Sucrose 0.7% by weight
Maltitol 6.3% by weight
Glycerin 10% by weight
2-pyrrolidone 2% by weight
4% by weight of ethanol
Pure water remaining
[0155]
Carbon black and a dispersant were mixed and dispersed in a sand mill (manufactured by Yasukawa Seisakusho) with glass beads (diameter 1.7 mm, 1.5 times the weight of the mixture (weight)) for 2 hours. Thereafter, the glass beads were removed, other components were added, and the mixture was stirred at room temperature for 20 minutes. Filtration through a 5 μm membrane filter gave an ink composition for ink jet recording.
[0156]
The following black ink C2 and a color ink set C1 composed of yellow, cyan and magenta ink compositions were prepared according to the method of the black ink C1.
[0157]
Black ink C2
Carbon black MA7 5% by weight
(Mitsubishi Chemical Corporation)
Styrene-acrylic acid copolymer 1% by weight
(Dispersant)
Boncourt 5454 5% by weight
(Styrene-acrylic resin emulsion, resin component 45%, manufactured by Dainippon Ink & Chemicals, Inc.)
Sucrose 0.7% by weight
Maltitol 6.3% by weight
Glycerin 10% by weight
2-pyrrolidone 2% by weight
4% by weight of ethanol
Pure water remaining
[0158]
Color ink set C1
Yellow ink, magenta ink, and cyan ink were prepared from the following colorant (pigment) and liquid medium, respectively.
[0159]
<Pigment>
Yellow ink
Pigment KETYELLOW403 2% by weight
(Dainippon Ink Chemical Co., Ltd.)
Magenta ink
Pigment KETRED309 2% by weight
(Dainippon Ink Chemical Co., Ltd.)
Cyan ink
Pigment KETBLUEEX-1 2% by weight
(Dainippon Ink Chemical Co., Ltd.)
<Liquid medium>
Styrene-acrylic acid copolymer 0.4% by weight
(Dispersant)
Boncoat 4001 2% by weight
Sucrose 0.7% by weight
Maltitol 6.3% by weight
Glycerin 10% by weight
2-pyrrolidone 2% by weight
4% by weight of ethanol
Pure water (remaining amount)
[0160]
Print evaluation test
The ink composition and the reaction liquid shown above were combined as shown in Table 3 below, and printing was actually performed with an inkjet printer to evaluate the print quality and the like.
[0161]
Evaluation C1: Print quality (smudge)
It carried out according to evaluation A3. The results were as shown in Table 3 below.
[0162]
Evaluation C2: Print quality (OD value)
The reaction liquid was printed at 100% duty on the paper used in the evaluation C1 using an inkjet printer MJ-700V2C, and then letters were printed with black ink. After drying, the reflection OD value of the printed material was measured with Macbeth PCMII (manufactured by Macbeth).
[0163]
The results were as shown in Table 3 below.
[0164]
Evaluation C3: Printing unevenness
Printing was performed at 100% duty on each of the following papers using an inkjet printer MJ-700V2C.
[0165]
(1) Rcopy 6200 paper (manufactured by Ricoh Co., Ltd.)
(2) Canon PB PAPER paper (Canon Co., Ltd.)
The OD values at five arbitrary points of the obtained printed matter were measured using Machbeth PCMII, and the average value was obtained. This procedure was repeated 5 times, and the maximum and minimum values of the five average values were determined. If this difference is less than 0.5, there is no practical problem, and more preferably less than 0.4.
[0166]
The results were as shown in Table 3 below. In the table,
A: OD value difference is less than 0.2
B: Difference in OD value is 0.2 or more and less than 0.4
C: Difference in OD value is 0.4 or more.
[0167]
Evaluation C4: Color bleed
A 100% duty reaction liquid is printed on the paper used in the evaluation A3 using an inkjet printer MJ-700V2C, and then 100% duty is printed with each color ink composition of the color ink set C1, and the black ink C1 or Characters were printed by C2. The obtained printed matter was examined for the presence or absence of uneven color mixing at the boundary between characters. The print was observed visually.
[0168]
The results were as shown in Table 3 below. In the table,
A: There is no color mixing and the boundary is clear
B: A whisker-like color mixture occurred
C: Colors are mixed so that the characters and outlines are not clear.
[0169]
Table 3
Reaction liquid Black ink Evaluation C1 Evaluation C2 Evaluation C3 Evaluation C4
Reference Example 1 C1 1 A 1.41 A −
      2 C1 2 A 1.43 A −
      3 C2 2 A 1.43 A −
      4 C3 2 A 1.45 A −
      5 C4 1 A 1.45 A −
      6 C4 2 A 1.48 A A
7 C5 2 A 1.46 A A
8-2B 1.33 BC
[Brief description of the drawings]
FIG. 1 is a diagram showing an ink jet recording apparatus for carrying out a method according to the present invention. In this embodiment, a recording head and an ink tank are independent from each other. To be supplied.
FIG. 2 is an enlarged view of a nozzle surface of a recording head, where 1b is a nozzle surface of a first liquid and 1c is a nozzle surface of an ink composition.
FIG. 3 is a diagram illustrating ink jet recording using the recording head of FIG. In the figure, 31 is a first liquid adhesion area, and 32 is a printing area where an ink composition is printed on the first liquid adhered.
FIG. 4 is a diagram illustrating another aspect of the recording head, in which all the discharge nozzles are arranged in the horizontal direction.
FIG. 5 is a diagram showing an ink jet recording apparatus for performing the method according to the present invention, and in this embodiment, a recording head and an ink tank are integrated.
FIG. 6 is a view showing an ink jet recording apparatus for performing the method according to the present invention, and in this embodiment, heating means 14 for heating a recording medium after an image is recorded is provided.
[Explanation of symbols]
1 Recording head
2 Ink tank
3 Ink tube
21 First liquid discharge nozzle
22, 23, 24, 25 Ink composition discharge nozzle
31 First liquid adhesion area
32 Print area

Claims (5)

A reaction liquid used in an ink jet recording method for performing printing by attaching a reaction liquid and an ink composition to a recording medium,
A polyvalent metal salt,
At least one selected from 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, thiodiglycol, ammonia, cyclohexylamine, N-cyclohexyl-N-dodecylamine, decamethyleneimine, dicyclohexylamine, and dioctylamine A reaction solution comprising at least a component of   The reaction solution according to claim 1, wherein the polyvalent metal salt is a nitrate or a carboxylate.   An ink jet recording method for performing printing by adhering the reaction liquid of claim 1 or 2 and an ink composition to a recording medium.   The ink jet recording method according to claim 3, wherein the ink composition comprises a colorant and a resin emulsion.   The inkjet recording method according to claim 3 or 4, wherein the reaction liquid is attached to a recording medium, and then the ink composition is printed on the recording medium.

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