JP2004330695A - Recording medium, recording medium-treatment liquid, ink composition, method and apparatus for ink jet recording and ink head - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a recording image of a high image quality grade wherein feathering, color mixing and the like are not generated, outlines are distinct, and density and visibility of the image are high, by an ink jetting system. <P>SOLUTION: A silicone-containing vinyl pyrrolidone base copolymer is held on and/or inside a recording medium. When water base ink containing coloring material to be used by an ink jet system, is discharged to such recording medium, since the coloring material is immobilized by polyvinyl pyrrolidone containing a silicone, permeation and diffusion of not less than necessity of the coloring material and in its turn occurrence of bleeding are prevented, and a recording image having the high grade image quality can be formed. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００７６】
〔式中、ｄおよびｅはそれぞれ、０≦ｄ＋ｅ≦３０の関係を満たす０または０〜３０の範囲の正数を示す。〕
で表されるアセチレングリコール・エチレンオキシド付加物、一般式
【００７７】
【化２】

【００７８】
〔式中、ｆは１１〜１３の整数を示す。ｇは３〜３０の整数を示す。〕
で表される化合物、一般式
【００７９】
【化３】

【００８０】
〔式中、ｈおよびｉはそれぞれ０〜１１の整数を示す。ｊは３〜５０の整数を示す。〕
で表される化合物、一般式
【００８１】
【化４】

【００８２】
〔式中、ｑは５〜９の整数を示す。ｒは２．５〜５の正数を示す。ｋおよびｌはそれぞれ、９≦ｋ＋ｌ≦１１の関係を満たす０〜１１の整数を示す。〕
で表される化合物、一般式

〔式中、ｓは０〜１８の整数を示す。ｔは２〜１５の整数を示す。ｕは０〜１８の整数を示す。〕
で表される化合物などのエチレンオキシド含有非イオン性界面活性剤が好ましい。本発明では、市販の非イオン性界面活性剤を使用することもでき、たとえば、サーフィノール（商品名、エアープロダクツ社製）、ソフタノールＥＰ（商品名、（株）日本触媒製）などが挙げられる。なお、サーフィノールは日信化学（株）からも市販されている。界面活性剤は１種を単独で使用できまたは２種以上を併用できる。
【００８３】
界面活性剤の含有量は特に制限されないけれども、通常は記録媒体処理液全量の０．００１〜５重量％、好ましくは０．００１〜３重量％である。
【００８４】
防カビ剤としては公知のものを使用でき、たとえば、デヒドロ酢酸ナトリウム、安息香酸ナトリウム、ソルビタン酸ナトリウム、２−ピリジンチオール−１−オキシドナトリウム、ペンタクロロフェノールナトリウムなどが挙げられる。防カビ剤は１種を単独で使用できまたは２種以上を併用できる。防カビ剤の含有量は特に制限されないけれども、通常は記録媒体処理液全量の０．００１〜０．１重量％である。
【００８５】
さらに記録媒体処理液は、その好ましい特性を損なわない範囲で、ｐＨ調整剤、キレート化剤、防錆剤、紫外線吸収剤などの、インクジェット用インク組成物の一般的な添加剤を含んでいてもよい。ｐＨ調整剤としては、たとえば、ジエタノールアミン、トリエタノールアミンなどのアミン、水酸化リチウム、水酸化カリウム、水酸化ナトリウムなどのアルカリ金属水酸化物、水酸化アンモニウム、第４級アンモニウム水酸化物、第４級ホスホニウム水酸化物、炭酸リチウム、炭酸ナトリウム、炭酸カリウムなどのアルカリ金属炭酸塩、硝酸ナトリウム、硝酸カリウムなどのアルカリ金属硝酸塩などが挙げられる。キレート化剤としては、たとえば、エチレンジアミン四酢酸ナトリウム、ニトリロ三酢酸ナトリウム、ヒドロキシエチルエチレンジアミン三酢酸ナトリウム、ジエチレントリアミン五酢酸ナトリウム、ウラミル二酢酸ナトリウムなどが挙げられる。防錆剤としては、たとえば、酸性亜硫酸塩、チオ硫酸ナトリウム、チオジグリコール酸アンモン、ジイソプロピルアンモニウムニトライト、四硝酸ペンタエリスリトール、ジシクロヘキシルアンモニウムニトライトなどが挙げられる。紫外線吸収剤としては、たとえば、ベンゾトリアゾール化合物、ベンゾフェノン化合物、シアノアクリレート化合物などが挙げられる。添加剤は１種を単独で使用できまたは２種以上を併用できる。
【００８６】
さらに記録媒体処理液は、必要に応じて、溶解助剤、酸化防止剤、消泡剤、粘度調整剤などを含んでいてもよい。
【００８７】
記録媒体処理液は、シリコーン含有ビニルピロリドン系共重合体ならびに、必要に応じて、水溶性有機溶剤、界面活性剤、防カビ剤およびその他の添加剤のそれぞれ適量を用い、さらに水を用いて全量を１００重量％とし、これらを一般的な方法に従って混合または分散し、必要に応じて固液分離処理（ろ過、遠心分離など）を施すことによって調製できる。分散には、たとえば、ディスパ、サンドミル、ホモジナイザ、ボールミル、ビーズミル、ペイントシェーカ、超音波分散機などの分散装置が使用できる。混合には、攪拌用の羽根を備えている攪拌機、高速の分散機、乳化機などが使用できる。
【００８８】
このようにして得られる記録媒体処理液は、その表面張力が好ましくは５０ｍＮ／ｍ以下、より好ましくは４０ｍＮ／ｍ以下である。このような表面張力値を有する記録媒体処理液は、シリコーン含有ビニルピロリドン系共重合体の含有量の調整、水溶性有機溶剤、界面活性剤など他成分の添加などによって得ることができる。本明細書において、表面張力は、協和界面化学（株）製、表面張力計ＣＢＶＰ−Ａ３を用いて測定した。さらに記録媒体処理液は、その２５℃における粘度が、好ましくは１Ｐａ・ｓ以下、より好ましくは８０ｍＰａ・ｓ以下である。このような粘度値を有する記録媒体処理液は、シリコーン含有ビニルピロリドン系共重合体の含有量の調整、水溶性有機溶剤、界面活性剤などの他成分の添加などによって得ることができる。本明細書において、粘度は、記録媒体処理液を１分間攪拌したのち、ブルックフィールド（株）製粘度計ＬＶＤＶ−ＩＩＩ＋を用い、２５℃での６ｒｐｍ、１分値を記録した。粘度および／または表面張力を前述の範囲に調整することによって、処理液の記録媒体に対する塗工性が一層向上し、処理液の記録媒体への塗布が容易になるとともに、シリコーン含有ポリビニルピロリドンの記録媒体表面および記録媒体内部での分散性が著しく向上し、ひいては色材の余分な部分への浸透が防止され、フェザリング、混色、ベタ部分のむらなどの発生がさらに防止される。
【００８９】
記録媒体処理液を基材表面に塗布するに際しては、液状成分を固形物の表面に塗布する公知の方法を採用できる。該方法の具体例としては、たとえば、ハケ塗り、ロールコーター法、ブレードコーター法、エアナイフコーター法、バーコーター法、サイズプレス法、スプレーコート法、グラビアコーター法、カーテンコーター法などが挙げられる。基材表面に塗布された記録媒体処理液に含まれる成分は、基材表面に拡がって保持され、および／または、基材内部に浸透して保持される。記録媒体処理液の基材に対する塗布量は特に制限されず、有効成分であるシリコーン含有ビニルピロリドン系共重合体の含有量、基材の材質、表面物性およびインク吸収特性、得られる記録媒体に適用されるインク組成物の種類などの各種条件に応じて広い範囲から適宜選択できるけれども、通常は０．１〜３０ｇ／ｍ^２、好ましくは０．５〜２０ｇ／ｍ^２である。
【００９０】
または、基材を記録媒体処理液中に浸漬してもよい。浸漬量は、前記の塗布量と同様でよい。
【００９１】
記録媒体処理液を塗布または含浸された基材の乾燥は、５〜４０℃の温度下に行われる。
【００９２】
〔インク組成物〕
本発明のインク組成物は、色材および水を含む組成物であり、該色材は、シリコーン含有ビニルピロリドン系共重合体と反応して沈殿物を生成するものである。
【００９３】
シリコーン含有ビニルピロリドン系共重合体と反応して沈殿物を生成する色材には、染料および顔料が使用できる。
【００９４】
染料としては公知のものを使用でき、たとえば、酸性染料、直接染料、反応性染料などの水溶性染料が挙げられる。染料の具体例をカラーインデックスナンバー（ＣＩ）で示すと、アシッドブルー７、９、２９、４５、９２、２４９、ダイレクトブルー１、２、６、１５、２２、２５、７１、７６、７９、８６、９０、９８、１６３、１６５、１９９、２０２、リアクティブブルー１、２、７、１４、１５、２３、３２、３８、４１、６３、８０、９５などの青系染料、アシッドレッド１、８、１３、１４、１８、２６、２７、３５、３７、４２、５２、８２、８７、８９、９２、９７、１０６、１１１、１１４、１１５、１３４、１８６、２４９、２５４、２８９、ダレクトレッド１、４、９、１３、１７、２０、２８、３１、３９、８０、８１、８３、８９、２２５、２２７、ダイレクトオレンジ２６、２９、６２、１０２、リアクティブレッド１、１４、１７、２５、２６、３２、３７、４４、４６、５５、６０、６６、７４、７９、９６、９７、１４１、１４７、１８１などの赤系染料、アシッドイエロー１、７、１７、２３、４２、４４、７９、１４２、ダイレクトイエロー１、１２、２４、２６、３３、４４、５０、８６、１２０、１３２、１４２、１４４、リアクティブイエロー１、５、１１、１３、１４、２０、２１、２２、２５、４０、４７、５１、５５、６５、６７などの黄色系染料、フードブラック２、ダイレクトブラック１９、２２、３２、３８、５１、５６、７１、７４、７５、７７、１５４、１６８、１７１、リアクティブブラック３、４、７、１１、１２、１７などの黒系染料などが挙げられる。これらの中でも、耐水性、耐光性、人体に対する安全性などに優れるものが好ましい。染料は１種を単独で使用できまたは必要に応じて２種以上を併用できる。染料の含有量は特に制限されず、本発明記録媒体の基材の材質、表面特性、インク吸収特性、シリコーン含有ビニルピロリドン系共重合体の含有量などの各種条件に応じて広い範囲から適宜選択できるけれども、通常はインク組成物全量の０．１〜１０重量％、好ましくは０．１〜７重量％である。０．１重量％未満では、画像濃度が低くなり、色を表現することが困難になる可能性がある。１０重量％を大幅に超えると、染料のインク組成物中での溶解性が不安定になり、インク組成物の吐出安定性などに悪影響を及ぼすおそれがある。
【００９５】
顔料としては、公知の無機顔料および有機顔料を使用できる。無機顔料としては、たとえば、酸化チタン、酸化鉄、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るカーボンブラックなどが挙げられる。有機顔料の具体例をカラーインデックスナンバー（ＣＩ）で示すと、たとえば、ピグメントブルー１、２、１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、１７、２２、２１、２２、６０、６４などの青系顔料、ピグメントレッド１、２、３、５、１０、１６、２３、３０、３１、４８：１、４８：２、４９：１、５２、５３：１、５７：１、５８：４、６３、１２２、２０９、ピグメントバイオレッド１９などの赤系顔料、ピグメントイエロー３、１２、１３、１４、１５、２３、５５、７４、８３、９３、９５、９７、１２８、１３８、１５０、１５４、１６７、１８０、１９３などの黄色系顔料などが挙げられる。これらの中でも、人体に対する安全性の高いものが好ましい。
【００９６】
また本発明では、顔料の表面に親水基を導入することによって水中での自己分散性が付与された自己分散顔料を使用してもよい。親水基としては特に制限されず、たとえば、カルボニル基、カルボキシル基、ヒドロキシル基、スルホン基などが挙げられる。また親水基は顔料表面で塩を形成していてもよい。
【００９７】
自己分散顔料は、公知の方法に従って得ることができる。たとえば、顔料と有機溶剤との混合物にハイスピードミキサーなどで高速せん断を加える方法が挙げられる。また、スルホン基を有する自己分散顔料は、顔料をビーズミル、ジェットミルなどで衝撃を加えて水に分散させ、これに撹拌下、発煙硫酸、硫酸、クロロ硫酸、フルオロ硫酸などのスルホン化剤を添加し、さらに６０〜２００℃に加熱処理することによって得ることができる。この自己分散顔料は、水洗、限外ろ過、逆浸透、遠心分離、ろ過などの公知の手段に従って、反応系から容易に単離精製できる。さらに、真空プラズマ処理などの物理的処理、シラン化合物などのカップリング剤による処理、ポリマーグラフト化処理などの上記以外の化学処理によっても、自己分散顔料を得ることができる。
【００９８】
顔料の中でも、インク中での分散性およびインクの保存安定性を考慮すると、自己分散顔料が好ましい。
【００９９】
顔料は１種を単独で使用できまたは必要に応じて２種以上を併用できる。顔料の含有量は特に制限されず、本発明記録媒体の基材の材質、表面特性、インク吸収特性、シリコーン含有ビニルピロリドン系共重合体の含有量などに応じて広い範囲から適宜選択できるけれども、通常はインク組成物全量の０．１〜１０重量％、好ましくは０．１〜８重量％である。０．１重量％未満では、画像濃度が低くなり、記録媒体上で色を表現することが困難である可能性がある。一方１０重量％を大幅に超えると、インク組成物の粘度が高くなり、ノズルからの吐出不良、記録媒体への浸透不良などを起こすおそれがある。
【０１００】
インク組成物は、必要に応じて、水溶性有機溶剤、界面活性剤および合成樹脂から選ばれる１種または２種以上を含んでいてもよい。水溶性有機溶剤および界面活性剤は、記録媒体処理液の項で述べたものと同様のものを使用できる。含有量も、記録媒体処理液における含有量と同様でよい。
【０１０１】
合成樹脂は、たとえば、シリコーン含有ビニルピロリドン系共重合体による色材の固定化を一層強固にするための定着剤として用いられる。該成分としては、たとえば、水溶性樹脂、水分散性樹脂などの樹脂成分が挙げられる。水溶性樹脂としては、たとえば、水溶性天然高分子化合物、水溶性合成樹脂などが挙げられる。水溶性天然高分子化合物の具体例としては、たとえば、アラビアゴムなどの天然ゴム類、サボニンなどのグルコシド類、リグニンスルホン酸塩、セラックなどが挙げられる。水溶性合成樹脂としては、たとえば、アクリル酸樹脂およびその塩、メタクリル酸樹脂およびその塩、スチレン−アクリル酸共重合体およびその塩、ビニルナフタレン−アクリル酸共重合体およびその塩、スチレン−マレイン酸−アクリル酸アルキルエステル共重合体およびその塩、ビニルナフタレン−マレイン酸共重合体およびその塩、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およびその塩、β−ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩およびリン酸塩などの陰イオン性高分子化合物、ポリエステル樹脂、ポリビニルアルコール、ポリビニルピロリドンなどの非イオン性高分子化合物、アクリロニトリル、酢酸ビニル、アクリルアミド、塩化ビニル、塩化ビニリデン、エチレン、ヒドロキシエチルアクリレート、グリシジルメタクリレートなどのモノマーからなる共重合体などが挙げられる。水分散性樹脂としては、公知の水分散性合成樹脂を使用でき、たとえば、ポリエステル樹脂、アクリル樹脂、スチレン−アクリル共重合体、マレイン酸樹脂、ポリウレタン樹脂などが挙げられる。市販の水分散性樹脂を使用することもでき、たとえば、日本ペイント（株）製のマイクロジェル（商品名、水分散性スチレン−アクリル系樹脂）、大日本インキ化学工業（株）製のボンコート（商品名、水分散性スチレン−アクリル系樹脂）、東洋紡績（株）製のバイロナール（商品名、水分散性ポリエステル樹脂）、ジョンソンポリマー社製のジョンクリル（商品名、エマルジョンタイプ）などが挙げられる。これら樹脂成分の中でも、シリコーン含有ビニルピロリドン系共重合体との反応性などを考慮すると、水溶性アクリル−スチレン共重合体、水分散性ポリエステル樹脂、水分散性アクリル樹脂などが好ましい。樹脂成分は１種を単独で使用できまたは必要に応じて２種以上を併用できる。樹脂成分の含有量は特に制限されず、色材の種類および含有量、他成分の有無、他成分を含む場合にはその種類および含有量、記録媒体の種類および特性などの各種条件に応じて広い範囲から適宜選択できるけれども、樹脂成分の添加効果が充分に発揮され、かつインク組成物の吐出安定性、保存性（保存時に成分の凝集・沈殿などが起こらないこと）などを損なわないようにするには、通常はインク組成物全量の０．０１〜３０重量％、好ましくは０．１〜２０重量％である。
【０１０２】
さらにインク組成物は、必要に応じて、ｐＨ調整剤、キレート化剤、防錆剤、紫外線吸収剤、溶解助剤、酸化防止剤、消泡剤、粘度調整剤、目詰まり防止剤などを含んでいてもよい。
【０１０３】
本発明のインク組成物は、たとえば、顔料および必要に応じて、水溶性有機溶剤、非イオン性界面活性剤、合成樹脂、その他の添加剤のそれぞれ適量を用い、さらに水を用いて全量を１００重量％に調整し、各成分を水に分散または溶解させることによって製造できる。
【０１０４】
ここで使用される水としては特に制限されず、水道水、純水、イオン交換水、活性炭処理水などを使用できる。これらの中でも、インク組成物の吐出安定性、記録媒体に対する浸透性および乾燥性、保存安定性などを考慮すると、電気伝導率（２５℃）が２５０μＳ／ｃｍ以下の水が好ましく、１μＳ／ｃｍ以下のものが特に好ましい。電気伝導率は、水の純度を示す指標、換言すれば、水に含まれる不純物の量を示す指標である。不純物とは、水に一般的に含まれる微量成分であり、たとえば、無機塩その他のミネラル分などが挙げられる。
【０１０５】
分散は、一般的な分散機を用いて行われる。該分散機としては、たとえば、ディスパ、サンドミル、ホモジナイザ、ボールミル、ビーズミル、ペイントシェーカ、超音波分散機などが挙げられる。混合は、攪拌用の羽根を備えている攪拌機、高速の分散機、乳化機などによって行われる。
【０１０６】
分散および／または混合ののち、固液分離手段を施してもよい。固液分離手段としては、ろ過、遠心分離などが挙げられる。たとえば、ろ過は、各成分を水媒体に混合または分散させた後に、ろ過を行ってもよい。ろ過は、たとえば、孔径０．８μｍ以下のフィルター、孔径０．４５μｍ以下のフィルターなどを用い、常圧下または減圧下に行われる。
【０１０７】
このようにして得られる本発明インク組成物の好ましい形態としては、
（ａ）顔料が、ピグメントブルー１５：３およびピグメントブルー１５：４、ピグメントブルー１５：６から選ばれる１種または２種以上のシアン顔料を含むシアン色系インク組成物、
（ｂ）顔料が、ピグメントレッド１２２、ピグメントレッド２０９およびピグメントヴァイオレット１９から選ばれる１種または２種以上のマゼンタ顔料を含むマゼンタ色系インク組成物、
（ｃ）顔料が、ピグメントイエロー７４、ピグメントイエロー１２８、ピグメントイエロー１３８、ピグメントイエロー１５０およびピグメントイエロー１８０から選ばれる１種または２種以上のイエロー顔料を含むイエロー色系インク組成物、
（ｄ）顔料が、カーボンブラックであるブラック顔料を含むインク組成物、
（ｅ）前記（ａ）、（ｂ）、（ｃ）および（ｄ）のインク組成物から選ばれる２種以上からなるインクセット、
などを挙げることができる。これらの中でも、（ａ）、（ｂ）および（ｃ）のインク組成物からなるインクセットは、色のバランスなどから、特に好ましい。
【０１０８】
本発明のインク組成物は、インクジェット方式に用いる場合は、その表面および／または内部にシリコーン含有ポリビニルピロリドンが保持された記録媒体に適用されるけれども、インクジェット方式以外の水性インクとして使用することもできる。インクジェット方式以外の水性インクの用途としては、たとえば、グラビアインクなどの印刷インク、水性塗料、化粧品、筆記具用インク、トナー、液体現像剤、電子写真用材料などが挙げられる。
【０１０９】
〔インクジェット記録方法〕
本発明のインクジェット記録方法は、インクジェット方式によってインク組成物を記録媒体に吐出して記録画像を形成する方法であって、記録媒体が本発明の記録媒体であることを特徴にする。
【０１１０】
記録媒体としては、前述のように、本発明の記録媒体、すなわちその表面および／または内部にシリコーン含有ビニルピロリドン系共重合体が保持されている記録媒体を使用する。
【０１１１】
インク組成物は、一般的なインクジェット方式に従い、インク吐出ノズルから、記録媒体の画像記録面に供給され、画像記録面に付着する。インク組成物としては特に制限されないけれども、本発明インク組成物または本発明のインク組成物の２種以上からなるインクセットであることが好ましい。
【０１１２】
インクジェット方式としては特に制限されず、公知の方式を採用できる。たとえば、圧電素子を用いるインクジェット方式（ピエゾ方式）、インクに圧力をかけてインクの液滴を吐出するインクジェット方式、膜沸騰現象を利用して気泡を発生させ、インクを吐出するインクジェット方式（サーマル方式）などが挙げられる。これらの中でも、ピエゾ方式、サーマル方式などが好ましい。
【０１１３】
また、本発明インクジェット記録方法の別の形態では、色材を含有するインク組成物を記録媒体に付着させて記録を行うに際し、記録前、記録時または記録後に、記録媒体に、シリコーン含有ポリビニルピロリドンを含む記録媒体処理液を記録媒体に付着させることを特徴にする。
【０１１４】
インク組成物としては特に制限されないけれども、本発明インク組成物または本発明のインク組成物の２種以上からなるインクセットであることが好ましい。
【０１１５】
インクジェット方式は、前述のインクジェット記録方法と同様である。この方法においても、ピエゾ方式、サーマル方式などが好ましい。
【０１１６】
記録媒体処理液としては、本発明の記録媒体処理液を使用することができる。
記録媒体処理液は、インク組成物を画像記録面に付着させる前、インク組成物を画像記録面に付着させるのと同時、またはインク組成物を画像記録面に付着させた後に、画像記録面に付着させる。中でも、インク組成物を付着させる前に、記録媒体処理液を供給することによって、好ましくは記録媒体処理液を付着させた直後にインク組成物を付着させることによって、記録画像に要求される各種特性を極めて高水準で充足する記録画像を得ることができる。
【０１１７】
記録媒体処理液は、記録媒体の画像記録面の全面または一部に付着させる。一部に付着させる場合は、インク組成物を付着させるのと同じ部分に供給すればよい。
【０１１８】
記録媒体処理液の画像記録面への付着は、処理液を画像記録面に塗布することによって行われる。塗布には、液状物を固形基材に塗布する一般的な方法が採用でき、たとえば、ロールコーター、エアナイフコーター、ブレードコーター、刷毛などを用いて行われ、また、スプレーコート、ディッピングコート（浸漬）などを行うこともできる。
【０１１９】
また、後述するように、記録媒体処理液を記録媒体に塗布するための転写ロールを備えるインクジェット記録装置を用いることもできる。
【０１２０】
インク組成物と記録媒体処理液との使用割合は特に制限されず、それぞれの中に含まれる各成分の種類および含有量、これらを供給する記録媒体の種類、記録媒体の被印刷面積、インクジェット方式の種類、インク組成物の液滴量などの各種条件に応じて広い範囲から適宜選択できるけれども、一つの目安を挙げれば、たとえば、インク組成物の液滴量が１〜５０ｐｌ程度の場合には、インク組成物１００重量部に対して、通常は処理液を１〜１０^７重量部、好ましくは１０〜１０^７重量部使用すればよい。
【０１２１】
記録媒体としては、従来から使用されているものを用いることができ、たとえば、普通紙、葉書、カラーコピー用紙、インクジェット用紙、プラスチックシート、プラスチックフィルムなどが挙げられる。
【０１２２】
〔インクジェット記録装置〕
図１は、実施の第１形態であるインクジェット記録装置１の構成を簡略化して示す断面図である。インクジェット記録装置１は、記録媒体８を装置１内に供給するための記録媒体供給手段２と、記録媒体供給手段２によって装置１内部に供給される記録媒体８を搬送するための記録媒体搬送手段３と、記録媒体搬送手段３に含まれるように設けられ、記録媒体８にシリコーン含有ポリビニルピロリドンを含有する処理液を付着させるための処理液転写手段４と、記録媒体搬送手段３によって搬送されかつ処理液転写手段４によって処理液を付着させた記録媒体８に、色材を含むインク組成物を付着させて画像を記録するための印刷手段５と、印刷手段５によって記録画像が形成された記録画像８を装置１の外へ排出するための排出手段６とを含んで構成され、図１中矢符９で示す記録媒体８の搬送方向に上流側から下流側に向かってこの順序で配置される。
【０１２３】
記録媒体給紙手段２は、記録媒体８を収容する給紙トレイ７と、給紙トレイ７の下流側に配置される給紙ローラ１０とおよび分離板１１を含んで構成される。
【０１２４】
記録媒体搬送手段３は、２つのガイド板１２，１８と、ガイド板１８の下流に配置される一対の搬送ローラ１９とを含んで構成され、ガイド板１２とガイド板１８との間には、処理液転写手段４が設けられている。
【０１２５】
処理液転写手段４は、支持ローラ１３と、転写ローラ１４と、グラビアローラ１５と、インクパン１６とを含んで構成され、インクパン１６には、グラビアローラ１５のグラビア面が処理液１７に浸漬するように、処理液１７が充填される。支持ローラ１３と転写ローラ１４とは、それぞれの面が接触しているけれども、その間を記録媒体８が通過できるように配置される。また転写ローラ１４とグラビアローラ１５とは接触するように配置される。
【０１２６】
印刷手段５は、記録媒体８にインク組成物を吐出して付着させるインクヘッド２０と、インクヘッド２０と一体化されかつインクヘッド２０を記録媒体８の印字面８ａに対して移動させるためのインクキャリッジ２２と、インクキャリッジ２２を図面に対して垂直方向に摺動可能に支持するガイドシャフト２３と、記録媒体８を載置するためのプラテン２４とを含んで構成される。
【０１２７】
排出手段６は、排出ローラ２５と、排出トレイ２６とを含んで構成される。
以下、本実施の形態の、インクジェット記録装置１の動作について説明する。
【０１２８】
インクジェット記録装置１によれば、給紙トレイ７に収容される記録媒体８は、タイミング信号に応じて矢符１０ａの方向に回転する給紙ローラ１０と分離板１１とによって、一枚ずつ分離して記録媒体搬送手段３に供給され、ガイド板１２を介して処理液転写手段４に搬送される。
【０１２９】
処理液転写手段４においては、グラビアローラ１５が、図示しない駆動手段によって矢符１５ａの方向に回転すると、インクパン１６に充填されている処理液１７はグラビアローラ１５のグラビア面に浸透し、さらに転写ローラ１４の表面に付着する。転写ローラ１４の表面に付着した処理液１７は、転写ローラ１４がグラビアローラ１５の回転に従動して矢符１４ａの方向に回転することによって、支持ローラ１３と転写ローラ１４との間を通って搬送される記録媒体８に接触し、記録媒体８の印字面８ａの裏面に転写される。その際、記録媒体８は、支持ローラ１３と転写ローラ１４とによって押圧されるので、処理液１７は、確実に、記録媒体８の印字面８ａにまで浸透する。
【０１３０】
この様にして処理液を塗布された記録媒体８は、ガイド板１８を介して搬送ローラ１９に供給され、さらに搬送ローラ１９によって印刷部５に搬送され、印字面８ａを上にしてプラテン２４上に載置される。このとき、記録媒体８の印字面８ａには、インクヘッド２０からインク組成物が吐出されて付着し、記録画像が形成される。記録画像が形成された記録媒体８は、排出ローラ２６を介して矢符２７の方向に排出され、排出トレイ２６に収容される。
【０１３１】
本実施の形態では、処理液転写手段４は、記録媒体搬送手段３に含まれるように設けられているけれども、これに限定されることなく、搬送ローラ１９と印刷手段５との間に設けられてもよい。
【０１３２】
また本実施の形態では、処理液転写手段４と搬送ローラ１９との間、または搬送ローラ１９と印刷手段５との間に、記録媒体８を反転させ、処理液を塗布した面にインク組成物が吐出されるようにするための、記録媒体８の反転手段を設けてもよい。このような反転手段は、公知の方法に従えばよい。
【０１３３】
〔インクヘッド〕
図２は、本発明のインクジェット記録装置において使用される実施の第２形態であるインクヘッド３１の構成を模式的に示す分解斜視図であり、図３は、図２に示すインクヘッド３１を構成するヘッドプレート４０の構成の一部を拡大して示す図である。図３に示す駆動電極４３は、図２では記載を省略する。
【０１３４】
インクヘッド３１は、圧電材料からなる平板状の底壁部４１および底壁部４１から予め定める間隔をあけて垂直に立ち上がるように形成される複数の隔壁部４２とを有するヘッドプレート４０と、隔壁部４２の上面に接して設けられる天板５０と、複数の吐出口６１を備え底壁部４１の一方の端部に設けられるノズルプレート２１と、底壁部４１の他方の端部に設けられる図示しない背面板と、天板５０の上面に接して設けられる開口部８１を有するインクタンク８０とを含んで構成される。複数の隔壁部４２は、底壁部４１上で一端部から他端部に向かって垂直に延びて互いに平行に配置されており、複数の隔壁部４２と底壁部４１と天板５０とノズルプレート２１と図示しない背面板とによって複数のインク室７０が形成されている。天板５０には、各インク室７０に連通するインク供給路５１と、インク供給路５１とインクタンク８０の開口部８１とを連結するインク供給管５２とが形成される。インクタンク８０にはインク組成物９０が貯留され、このインク組成物９０はインク供給路５１内を流過して各インク室７０に供給される。
【０１３５】
また図３に示すように、ヘッドプレート４０の底壁部４１および複数の隔壁部４２のインク室７０に臨む表面には、複数の隔壁部４２に電圧を印加する駆動電極４３が設けられる。また複数の隔壁部４２をなす圧電材料は、矢符９５の方向に分極しており、複数の隔壁部４２は圧電素子として機能する。
【０１３６】
図４は、図２に示すインクヘッド３１をインク室４０の延長方向から見た断面図である。図４には３つのインク室７０ａ，７０ｂ，７０ｃが示されているけれども、ここでは、インク室７０ｂからインク組成物９０を吐出する動作について説明する。
【０１３７】
インク室７０ｂを構成する隔壁部４２ａおよび４２ｂに電圧が印加されていないとき、すなわちインク室７０ｂの駆動電極４３ｂとインク室７０ａの駆動電極４３ａとの間、およびインク室７０ｂの駆動電極４３ｂとインク室７０ｃの駆動電極４３ｃとの間に電位差が生じていないとき、インク室７０ｂには、毛管作用によってインクタンク８０から供給されるインク組成物９０で充填されている。同様に、インク室７０ａおよび７０ｃもインク組成物９０で充填されている。
【０１３８】
駆動電極４３ａおよび駆動電極４３ｃに電圧が印加されると、駆動電極４３ｂと駆動電極４３ａとの間、および駆動電極４３ｂと駆動電極４３ｃとの間に電位差が生じ、インク室７０ｂを構成する隔壁部４２ａおよび４２ｂに電圧が印加されると、隔壁部４２ａおよび４２ｂにそれぞれ矢符９６および９７の方向の電界が発生する。この電界の作用によって、インク室７０ｂを構成する隔壁部４２ａおよび４２ｂにひずみが生じ、インク室７０ｂ側に凸になるように変形する。これによって、圧力波が発生し、インク室７０ｂ内のインク組成物９０に大きな圧力がかかり、インク組成物９０の液滴が吐出口６１から吐出する。
【０１３９】
駆動電極４３ａおよび駆動電極４３ｃへの電圧の印加を止めると、隔壁部４２ａおよび４２ｂの形状が元に戻ってインク室７０ｂの体積が元に戻り、復元された体積分のインク組成物９０がインク供給路５１を介してインクタンク８０から供給され、インク室７０ｂは、インク組成物９０が充填された状態に戻る。
【０１４０】
本実施の形態では、インク室４０を構成する隔壁部４２を圧電材料で形成し、圧電素子として機能させるけれども、これに限定されることなく、インク室を構成する隔壁を圧電材料以外の材料で形成し、隔壁の内方または外方に圧電素子を設けてもよい。
【０１４１】
インクヘッド３１を備えるピエゾ方式のインクジェット記録装置において、本発明の方法に係るインク組成物を用いて記録を行うと、インクヘッド内のインク供給系への濡れ性が向上し、インクの供給がスムーズに行われるため、信頼性の高いピエゾ方式のインクジェット記録装置が実現できる。
【０１４２】
図５は、本発明のインクジェット記録装置において使用される、実施の第３形態であるインクヘッド１０１の構成を模式的に示す分解斜視図であり、図６は、図５に示すインクヘッド１０１の構成の一部を示す平面図である。図５に示す天板５０およびインクタンク８０は、図６では記載を省略する。インクヘッド１０１は、インクヘッド３１と類似し、対応する部分については同一の参照符号を付して説明を省略する。
【０１４３】
インクヘッド１０１は、ヘッドプレート１０２が、基板１０３と、基板１０３上で予め定める間隔をあけ、一端部から他端部へ向かって垂直に延びて互いに平行に配置される複数の隔壁１０４と、基板１０３のインク室７０に臨む表面上に設けられる発熱体であるヒータ１０５と、ヒータ１０５に電圧を印加する駆動電極１０６および１０７とを含んで構成されることを特徴とする。
【０１４４】
図７は、図５に示すインクヘッド１０１の切断面線Ｉ−Ｉにおける断面構成を示すであり、インク室７０からインク組成物９０の液滴９１が吐出される状態を示している。
【０１４５】
ヒータ１０５に電圧が印加されていないとき、前述のインクヘッド３１において隔壁部４２に電圧が印加されていないときと同様に、インク室７０はインク組成物９０が充填されている。
【０１４６】
駆動電極１０６および１０７によってヒータ１０５に電圧が印加されると、ヒータ１０５が発熱し、インク室７０内のインク組成物９０が加熱されて、気泡９２が発生する。これによって、圧力波が発生し、インク室７０内のインク組成物９０に大きな圧力がかかり、インク組成物９０の液滴９１が吐出口６１から吐出される。
【０１４７】
ヒータ１０５への電圧の印加を止めると、インク室７０内のインク組成物９０が冷却されて気泡９２が消滅し、消滅した気泡の体積分のインク組成物９０がインク供給路５１を介してインクタンク８０から供給され、インク室７０は、インク組成物９０が充填された状態に戻る。
【０１４８】
本実施の形態によるインクヘッド１０１を備えるサーマルインクジェット方式のインクジェット記録装置において、本発明方法に係るインク組成物を用いて記録を行うと、ヘッド内のインク供給系への濡れ性が向上し、インクの供給がスムーズに行われるため、信頼性の高いサーマル方式のインクジェット記録装置が実現できる。
【０１４９】
［実施例］
以下に実施例、比較例および試験例を挙げ、本発明を具体的に説明する。なお、以下において「％」とあるのは、特に断らないかぎり「重量％」を意味する。
【０１５０】
実施例１および比較例１（記録媒体の製造）
表１に示す割合（％、樹脂成分は固形分量で示した）で各成分を混合し、これに水を加えて全量を１００％とした。この混合物を２５℃で１時間攪拌し、記録媒体処理液を調製した。
【０１５１】
なお、表１における樹脂成分および界面活性剤は、具体的には、次のとおりである。
【０１５２】
〔樹脂成分〕
ＧＡＦＱＵＡＴ・ＨＳｉ：商品名、ＩＳＰ社製、ポリメチルシロキサンを内包する、ビニルピロリドンとメタクリルアミドプロピルトリメチルアンモニウムクロライドとの共重合体、２０％水溶液。
１０％ＰＶＡ：ポリビニルアルコールの１０％水溶液
【０１５３】
〔界面活性剤〕
エチレンオキシド化合物２Ａ：一般式（２）において、ｄ＋ｅ＝１０である化合物、商品名サーフィノール４６５、日信化学（株）製
エチレンオキシド化合物２Ｂ：一般式（２）において、ｄ＋ｅ＝３．５である化合物、商品名サーフィノール４４０、日信化学（株）製
エチレンオキシド化合物５Ａ：一般式（５）において、ｋ＋ｌ＝１１、ｑ＝９、ｒ＝５である化合物、商品名ソフタノール９０５０、（株）日本触媒製
【０１５４】
【表１】

【０１５５】
上記で得られた記録媒体処理液を、転写方式のゴムローラーによって、ステキヒトサイズ度が１０秒の紙に塗布量が８ｇ／ｍ^２となるように塗布し、実施例１の記録媒体（Ｎｏ．１〜５）および比較例１の記録媒体（Ｎｏ．６〜７）を製造した。
【０１５６】
実施例２（インク組成物の調製）
表２に示す割合（％）で各成分を混合し、これに水を加えて全量を１００％とした。この混合物を２５℃で１時間攪拌した後、１．２μｍのメンブランフィルタを用いて加圧濾過し、インク組成物（Ｎｏ．イ〜ホ）を調製した。
【０１５７】
なお、表２において、商品名で記載されている界面活性剤および定着剤は、具体的には次のとおりである。
【０１５８】
〔界面活性剤〕
サーフィノール２５０２、サーフィノール４６５：いずれもエチレンオキシド含有アセチレン系非イオン界面活性剤、エアープロダクツ社製
【０１５９】
〔定着剤〕
バイロナールＭＤ１４００、ポリエステルエマルジョン（水分散性樹脂）、東洋紡績（株）製
【０１６０】
【表２】

【０１６１】
試験例１
実施例１および比較例１で得られた記録媒体Ｎｏ．１〜７、ならびに実施例２で得られたインク組成物Ｎｏ．イ〜ホを用い、次の評価試験を行った。結果を表３に示す。
【０１６２】
［印字濃度（画像濃度）］
インクジェットプリンタ（商品名：ＡＪ２０００、シャープ（株）製）のインクヘッドを本発明のインクヘッドに交換できるように改造し、このプリンタを用いてベタ印字を行い、その印字濃度を測色計（商品名：Ｘ−Ｌｉｔｅ９３８、マクベス社製）によって測定した。記録媒体処理液を塗布していない紙における、ベタの印刷濃度に比べ、濃度が上昇しているものを「○」、変化しないものを「△」、下がったものを「×」と評価した。
【０１６３】
［フェザリング］
記録媒体に試験用パターンを印刷して、該パターンのライン幅を測定し、記録媒体処理液を塗布していない紙におけるライン幅を１００とし、それに対する相対値として評価した。１００未満のものを「○」、１００〜１２０のものを「△」および１２０以上ものを「×」と評価した。
【０１６４】
【表３】

【０１６５】
表３から、シリコーン含有ビニルピロリドン系共重合体を保持した記録媒体に記録を行うと、フェザリングの発生が防止され、印字濃度（画像濃度）の高い記録画像が形成されることが明らかである。一方、比較例１のＮｏ．６の記録媒体を用いると、印字濃度は大きく低下しないけれども、フェザリングの発生が著しいことが判る。また比較例１のＮｏ．７の記録媒体を用いると、印字濃度が著しく低下すると共に、フェザリングの発生が甚だしいことが判る。
【０１６６】
実施例３および比較例２
ステキヒトサイズ度１０秒の紙に代えて、ステキヒトサイズ２１秒の紙を使用する以外は、実施例１と同様にして、実施例３の記録媒体（Ｎｏ．８〜１２）および比較例２の記録媒体（Ｎｏ．１３〜１４）を製造した。
【０１６７】
試験例２
実施例３および比較例２で得られた記録媒体を用い、試験例１と同様にして、印字濃度およびフェザリングの有無について評価を行った。結果を表４に示す。
【０１６８】
【表４】

【０１６９】
表４から、ステキヒトサイズ度が２０秒を超える紙に、シリコーン含有ビニルピロリドン系共重合体を担持させても、フェザリングを防止する効果が不充分であることが判る。
【０１７０】
試験例３
実施例１および比較例１で得られた記録媒体処理液Ｎｏ．１〜７と、実施例２で得られたインク組成物Ｎｏ．イ〜ホとをそれぞれ混合し、凝集・沈殿が生じるか否かを目視により観察した。結果を表５に示す。表５においては、凝集・沈殿が生じる場合を「○」および凝集・沈殿が生じない場合を「×」で示した。
【０１７１】
【表５】

【０１７２】
表５から、シリコーン含有ポリビニルピロリドンを含む記録媒体処理液は、インク組成物との混合によって凝集・沈殿を生じることが明らかである。
【０１７３】
実施例４および比較例３（記録媒体の製造）
表６に示す割合（％、樹脂成分は固形分量で示した）で各成分を用いる以外は実施例１と同様にして記録媒体処理液を調製し、さらに実施例４の記録媒体（Ｎｏ．１５〜１９）および比較例３の記録媒体（Ｎｏ．２０〜２１）を製造した。
【０１７４】
【表６】

【０１７５】
実施例５（インク組成物の調製）
表７に示す割合（％）で各成分を用いる以外は実施例２と同様に操作し、インク組成物（Ｎｏ．へ〜ル）を調製した。
【０１７６】
なお、表７において商品名で示される界面活性剤は具体的には次の通りである。
【０１７７】
サーフィノール４４０：エチレンオキシド含有アセチレン系非イオン界面活性剤、エアープロダクツ社製
アクリル樹脂エマルジョン：商品名ジョンクリル７３４、ジョンソンポリマー社製
【０１７８】
【表７】

【０１７９】
試験例４
実施例４および比較例３で得られた記録媒体Ｎｏ．１５〜２１、ならびに実施例５で得られたインク組成物Ｎｏ．へ〜ルを用い、試験例１と同様にして印字濃度（画像濃度）およびフェザリングの有無を評価した。結果を表８に示す。
【０１８０】
【表８】

【０１８１】
表８から、シリコーン含有ビニルピロリドン系共重合体を保持した記録媒体に記録を行うと、フェザリングの発生が防止され、印字濃度（画像濃度）の高い記録画像が形成されることが明らかである。一方、比較例３のＮｏ．２０の記録媒体を用いると、印字濃度は大きく低下しないけれども、フェザリングの発生が著しいことが判る。また比較例３のＮｏ．２１の記録媒体を用いると、印字濃度が著しく低下すると共に、フェザリングの発生が甚だしいことが判る。
【０１８２】
実施例６および比較例４（記録媒体の製造）
ステキヒトサイズ度１０秒の紙に代えて、ステキヒトサイズ２１秒の紙を使用する以外は、実施例４と同様にして、実施例６の記録媒体（Ｎｏ．２２〜２６）および比較例４の記録媒体（Ｎｏ．２７〜２８）を製造した。
試験例５
実施例６および比較例４で得られた記録媒体Ｎｏ．２２〜２８を用い、試験例４と同様にして、印字濃度およびフェザリングの有無について評価を行った。結果を表９に示す。
【０１８３】
【表９】

【０１８４】
表９から、ステキヒトサイズ度が２０秒を超える紙であっても、シリコーン含有ビニルピロリドン系共重合体を担持させると、フェザリングを防止する効果がほぼ充分に発現されることが判る。
【０１８５】
試験例６
実施例４および比較例３で得られた記録媒体処理液Ｎｏ．１５〜２１と、実施例５で得られたインク組成物Ｎｏ．へ〜ルとをそれぞれ混合し、凝集・沈殿が生じるか否かを目視により観察した。結果を表５に示す。表５においては、凝集・沈殿が生じる場合を「○」および凝集・沈殿が生じない場合を「×」で示した。
【０１８６】
【表１０】

【０１８７】
表１０から、シリコーン含有ポリビニルピロリドンを含む処理液は、インクとの混合によって凝集・沈殿を生じることが明らかである。
【０１８８】
実施例７（記録媒体の製造）
表１１に示す割合（％）で各成分を用いる以外は実施例１と同様にして記録媒体処理液を調製した。なお、樹脂成分は固形分量で示した。この記録媒体処理液を、転写方式のゴムローラを用いて、ＰＰＣ用紙（商品名：ＳＦ４ＡＭ３、シャープ（株）製）に、８ｇ／ｍ^２の割合で塗布し、本発明の記録媒体Ｎｏ．２９〜３３を製造した。
【０１８９】
【表１１】

【０１９０】
実施例８〜１４（インク組成物の調製）
表１２に示す割合（％）で各成分を用いる以外は、実施例２と同様にして、本発明および比較例のインク組成物を調製した。なお、顔料分散体および樹脂成分は固形分量で示した。これらのインク組成物について、次の評価試験を行った。結果を表１２に併記する。
【０１９１】
［高速印刷性］
インクジェットプリンタ（商品名：ＡＪ２０００、シャープ（株）製）のインクヘッドを本発明のインクヘッドに交換したプリンタを用い、印刷濃度５％、１０ＰＰＭ（１０枚／分）で連続的に印刷を行い、良好な画質品位を有する記録画像を印字できる枚数を調べた。印刷枚数が２００枚を超えるものを「○」、１５０〜２００枚であるものを「△」、１５０枚未満のものを「×」と評価した。
【０１９２】
［乾燥性］
印刷終了直後、印刷面に印刷紙と同じ紙を１５秒間押し当て、印刷が転写しないものを「○」、転写するものを「×」と評価した。
【０１９３】
［にじみ性］
ＰＰＣ用紙（商品名：ＳＦ４ＡＭ３、シャープ（株）製）に特定のパターンを印刷して１日間放置後、該パターンのライン幅を測定し、にじみがない場合のライン幅を１００とし、それに対する相対値として評価を行った。１５０未満のものを「○」、１５０〜２５０のものを「△」および２５０を超えるものを「×」と評価した。
【０１９４】
［起泡性］
インク組成物を２０秒間振とうして５分間静置した後、泡高さを測定し、１０ｍｍ以下のものを「○」および１０ｍｍを超えるものを「×」と評価した。泡高さが大きいほど、起泡性が高い。起泡性の高いインク組成物は、吐出ノズル内で泡を発生し、該ノズルが泡をかみ込むので、吐出される液滴量が変化しやすい。起泡性の高いインク組成物は、吐出安定性が低く、高速印刷には使用できない。
【０１９５】
【表１２】

【０１９６】
表１２から、ピグメントブルー１５：３、ピグメントブルー１５：４、ピグメントレッド１２２、ピグメントイエロー７４、ピグメントイエロー１８０などの顔料およびダイレクトブルー１９９などの染料を用いる場合に、４種の評価を高い水準で満たすインク組成物が得られることが明らかである。
【０１９７】
試験例７
実施例７で得られた記録媒体、および実施例８〜１２で得られたインク組成物を用い、試験例１と同様にして、印字濃度およびフェザリングの有無について評価を行った。結果を表１３に示す。
【０１９８】
【表１３】

【０１９９】
表１３から、本発明の記録媒体に、特定の顔料を含み、さらに水溶性有機溶剤、非イオン性界面活性剤および定着剤を含むインク組成物を用いて記録画像を形成すると、フェザリングが著しく防止され、印字濃度の高い記録画像が得られることが明らかである。
【０２００】
試験例８
実施例８〜１２のインク組成物から、表１４に示す組み合わせでシアンインク、マゼンタインクおよびイエローインクを選択し、試験例１と同じインクジェットプリンタにて、実施例７の記録媒体Ｎｏ．２９に印字率１：１：１でスリーカラーブラックを印刷した。
【０２０１】
一方、実施例１３のインク組成物を用い、上記と同様にして、ブラック単色を記録媒体Ｎｏ．２９に印刷した。
【０２０２】
スリーカラーブラックおよびブラック単色の印字を測色計（Ｘ−Ｒｉｔｅ９３８）にかけ、ａ^＊およびｂ^＊を測定した。スリーカラーブラックのａ^＊をＡ２、ｂ^＊をＢ２、ブラック単色のａ^＊をＡ１、ｂ^＊をＢ１としたとき、下記式で表される値（Δａ^＊ｂ^＊）が２０以下のものを「○」および２０より大きいものを「×」と評価した。結果を表１４に示す。
Δａ^＊ｂ^＊＝｛（Ａ１−Ａ２）^２＋（Ｂ１−Ｂ２）^２｝^１／２
【０２０３】
【表１４】

【０２０４】
表１４から、実施例８〜１２から選ばれる３種のインク組成物を重ね合わせて得られる（１）〜（４）の黒色画像は、高い画像濃度を有する黒色画像であることが判る。すなわち、本発明の４種のインクセットは、黒色再現性が良好であり、カラーバランスに優れることが判る。
【０２０５】
以上のように、Ｃ．Ｉ．ピグメントブルー１５：３および１５：４のうちの少なくとも一方の顔料を含有するシアンのインク組成物と、Ｃ．Ｉ．ピグメントレッド１２２、２０９およびＣ．Ｉ．ピグメントヴァイオレット１９からなる群から選ばれる少なくとも１つの顔料を含有するマゼンタのインク組成物と、Ｃ．Ｉ．ピグメントイエロー７４、１３８、１５０および１８０からなる群から選ばれる少なくとも１つの顔料を含有するイエローのインク組成物とを組合せることによって、カラーバランスに優れるインクセットを得られることが判る。
【０２０６】
【発明の効果】
本発明によれば、記録媒体の表面および／または内部にシリコーン含有ビニルピロリドン系共重合体を存在させることによって、シリコーン含有ビニルピロリドン系共重合体が色材である染料または顔料を固定化するので、染料または顔料が記録媒体の内部または表面の余白部分にまで浸透、拡散するのを防止することができ、にじみの発生が著しく防止され、フェザリング、混色などが起こらず、その結果ベタ部分が均一で、輪郭部分が明瞭で、画像濃度および鮮明度か高く、高画質品位の記録画像をインクジェット方式により形成することができる。
【０２０７】
本発明によれば、シリコーン含有ビニルピロリドン系共重合体を存在させる基材として、ステキヒトサイズ度が２０秒以下のものを用いることによって、本発明の記録媒体に対してインク組成物が適度に浸透するので、フェザリングが防止されるとともに、画像濃度が一層高くなり、得られる記録画像の画質品位がさらに向上する。
【０２０８】
本発明によれば、シリコーン含有ビニルピロリドン系共重合体の中でも、コアがシリコーンからなりかつシェルがビニルピロリドン系共重合体系共重合体からなるコアシェル構造を有するものを用いることによって、にじみの発生が一層防止され、記録画像の画質品位は向上する。
【０２０９】
本発明によれば、シリコーンとしてポリアルキルシロキサンを含有するビニルピロリドン系共重合体を用いることによって、記録画像の画質品位のさらなる向上が達成される。
【０２１０】
本発明によれば、ビニルピロリドンと特定の４級アンモニウム化合物およびアミン化合物から選ばれる１種または２種以上のモノマー化合物とからなるビニルピロリドン系共重合体を用いることによって、記録媒体の表面および内部で色材を強固に固定化することができる。
【０２１１】
本発明によれば、ビニルピロリドン系共重合体を含み、必要に応じて、水溶性有機溶剤（好ましくは多価アルコール、グリコールエーテル）、界面活性剤（好ましくは非イオン性界面活性剤）、防カビ剤などを含んでもよい記録媒体処理液を用いて記録媒体を処理することによって、本発明の記録媒体を製造することができる。
【０２１２】
本発明によれば、シリコーン含有ビニルピロリドン系共重合体と反応して沈殿物を生成する染料または顔料を含み、さらに必要に応じて水溶性有機溶剤、非イオン性界面活性剤、合成樹脂（定着剤）などを含んでもよく、本発明の記録媒体に記録画像を形成するのに適したインク組成物が提供される。
【０２１３】
本発明によれば、本発明のインク組成物において、顔料として自己分散顔料を用いることによって、インク組成物の保存安定性が向上し、インク組成物の保存中に、吐出ノズルの目詰まりの原因になる、顔料の凝集・沈降の発生が防止される。
【０２１４】
本発明によれば、本発明のインク組成物の中でも、特定の顔料を含むシアン系、マゼンタ系、イエロー系および黒色系インク組成物、ならびにこれらの２種以上を含むインクセットが好ましい。これらのインク組成物またはインクセットを用いることによって、カラーバランスが極めて良好であり、かつ高画質品位を有する記録画像を形成することができる。
【０２１５】
本発明によれば、インクジェット記録方法により、前述の記録媒体に前述のインク組成物を付着させるか、または、前述のインク組成物を付着させる前、付着と同時もしくは付着させた後に、記録媒体に前述の記録媒体処理液を付着させることによって、高画質品位の記録画像を形成することができる。
【０２１６】
本発明によれば、本発明のインクジェット記録方法を実施するのに適し、高画質品位の記録画像を形成することができ、しかも高速印刷を容易に実施することができるインクジェット記録装置が提供される。
【０２１７】
本発明によれば、前述のインク組成物を連続してかつ安定的に吐出することができ、高速印刷を実施するのに適したピエゾ方式およびサーマル方式のインクヘッドが提供される。
【図面の簡単な説明】
【図１】本発明のインクジェット記録装置の構成を模式的に示す断面図である。
【図２】本発明のインクジェット装置に使用するインクヘッドの構成を模式的に示す分解斜視図である。
【図３】図２に示すインクヘッドに含まれるヘッドプレートの構成の一部を拡大して示す図である。
【図４】図２に示すインクヘッドをインク室の延長方向から見た断面図である。
【図５】本発明のインクジェット記録装置に使用するインクヘッドの構成を模式的に示す分解斜視図である。
【図６】図５に示すインクヘッドの構成の一部を示す平面図である。
【図７】図６に示すインクヘッドの切断面線Ｉ−Ｉにおける断面構成を示す図面である。
【符号の説明】
１ インクジェット記録装置
２ 記録媒体供給手段
３ 記録媒体搬送手段
４ 処理液転写手段
５ 印刷手段
６ 排出手段
７ 給紙トレイ
８ 記録媒体
８ａ 印字面
９，１０ａ，１３ａ，１４ａ，１５ａ，２７，９５，９６，９７ 矢符
１０ 給紙ローラ
１１ 分離板
１２，１８ ガイド板
１３ 支持ローラ
１４ 転写ローラ
１５ グラビアローラ
１６ インクパン
１７ 処理液
１９ 搬送ローラ
２０ インクヘッド
２１ ノズルプレート
２２ インクキャリッジ
２３ ガイドシャフト
２４ プラテン
２５ 排出ローラ
２６ 排出トレイ
３１，１０１ インクヘッド
４０，１０２ ヘッドプレート
４１ 底壁部
４２，４２ａ，４２ｂ 隔壁部
４３，４３ａ，４３ｂ，４３ｃ，１０６，１０７ 駆動電極
５０ 天板
５１ インク供給路
６０ ノズルプレート
６１ 吐出口
７０，７０ａ，７０ｂ，７０ｃ インク室
８０ インクタンク
８１ 開口部
９０ インク組成物
９１ 液滴
９２ 気泡
１０３ 基板
１０４ 隔壁
１０５ ヒータ[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a recording medium, a recording medium treatment liquid, an ink composition, an inkjet recording method, an ink head, and an inkjet recording apparatus.
[0002]
[Prior art]
The ink jet method employed in output devices such as personal computers, copiers, and facsimile machines is a printing method in which fine droplets of an ink composition are discharged from a discharge nozzle onto a recording medium, and an image is recorded on the recording medium. A very useful printing method with a number of desirable features such as excellent quietness, easy density and colorization, high-speed printing, and inexpensive printing of relatively high-quality recorded images. It is. Well-known methods for discharging microdroplets include a method using a piezoelectric element and a method using bubbles generated by a film boiling phenomenon.
[0003]
In the ink jet system, in order to obtain a recorded image without printing unevenness, it is necessary to continuously and stably eject a substantially constant amount of fine droplets of the ink composition. Therefore, a low-viscosity aqueous ink containing a dye or a pigment, using water as a main medium, and having excellent ejection stability is used. On the other hand, as the recording medium, papers that can easily record an image with water-based ink, particularly plain paper (PPC paper) are used. However, since the water-based ink has low drying properties despite its high permeability to papers, bleeding is likely to occur when it is attached to papers. In addition, there are various types of plain paper having different ink absorption characteristics depending on surface characteristics such as surface shape and surface roughness, and sizing agents contained therein. To prevent the occurrence of bleeding, it is necessary to select an appropriate ink for each plain paper, but such selection is practically impossible. Therefore, in the ink jet method, the dye or pigment contained in the aqueous ink is diffused together with the liquid component such as water in the ink to the inside of the plain paper or to the margin on the surface to cause bleeding, and the whiskers in the outline portion of the recorded image are generated. The blurring (feathering), color mixture in which inks of different colors are mixed, and the like are likely to occur. As a result, the solid portion becomes non-uniform, the outline portion of the recorded image becomes unclear, and the image density, sharpness, and image quality deteriorate. In view of such a problem, various studies have been made from both sides of the recording medium and the ink composition.
[0004]
First, regarding improvement of a recording medium, for example, a coated paper in which a coating layer made of inorganic particles such as diatomaceous earth is provided on the surface of plain paper has been proposed (for example, see Patent Document 1). However, even with such coated paper, feathering cannot be sufficiently prevented. Further, since the dye has an anionic group, a recording medium in which a compound having a cationic group on the surface and / or inside is present has been proposed. Examples of the compound having a cationic group include polycationic polymer electrolytes such as polyvinylpyridinium halide, polyethyleneimine and polyamine (for example, see Patent Document 2), and cationic groups such as vinylpyrrolidone and amine groups and quaternary ammonium groups. (For example, see Patent Document 3). Even if these recording media are used, the occurrence of feathering cannot be prevented, and the image density of the recorded image is not sufficient. Further, when the coloring material of the ink composition is a pigment, the effect is further reduced.
[0005]
On the other hand, in order to prevent bleeding from the surface of the ink composition and improve the image quality of a recorded image, a water-soluble organic solvent, a surfactant and the like are appropriately selected and added to the ink composition. . For example, an ink composition containing a water-soluble dye, a water-soluble organic solvent such as diethylene glycol, a nonionic surfactant such as an acetylene glycol-ethylene oxide adduct, and water has been proposed (for example, see Patent Document 4). However, this ink composition does not have sufficiently satisfactory performance, particularly in terms of ejection stability during high-speed printing, drying property for a recording medium, prevention of occurrence of feathering in a recorded image, definition of a recorded image, and the like. .
[0006]
Further, an ink composition containing a recording medium under heating containing a dye or pigment, a water-soluble organic solvent such as glycerin, thiodiglycol, and urea, a nonionic surfactant such as acetylene glycol / ethylene oxide adduct, and water. There has been proposed an ink jet recording method for discharging ink (see, for example, Patent Document 5). However, in the ink jet system, printing is sometimes performed on hundreds of sheets, and sometimes on thousands of sheets per day. In such a case, the power consumption for heating the recording medium becomes too large. Not a target. Furthermore, when high-speed printing is performed, unevenness in the way of heat transmission occurs, which in turn causes unevenness in the recorded image, deteriorating the image quality.
[0007]
Further, there has been proposed an ink composition containing a water-soluble dye, a polyhydric alcohol such as ethylene glycol, and a surfactant having a surface tension at a micelle concentration of 20 to 50 dyne / cm in water, with the balance being water. (For example, see Patent Document 6). According to Patent Document 6, by adding a surfactant having specific properties, the surface tension of the ink composition is reduced, and the permeability of the ink to a recording medium is increased. However, since this ink composition permeates too much into a recording medium, it is unavoidable that feathering occurs, image density and sharpness are reduced, and image quality of recorded images becomes insufficient.
[0008]
As described above, in order to obtain a high-quality printed image in the inkjet method, it is necessary to appropriately combine the ink absorption characteristics of the recording medium, the permeability of the ink composition on the recording medium, the drying property, and the like. Is a major issue.
[0009]
[Patent Document 1]
JP-A-1-216881
[Patent Document 2]
JP-A-56-89992
[Patent Document 3]
JP-A-4-288283
[Patent Document 4]
JP-A-56-5871
[Patent Document 5]
JP-A-11-129460
[Patent Document 6]
JP-A-55-29546
[0010]
[Problems to be solved by the invention]
An object of the present invention is to produce a recorded image of high image quality with high uniformity, clear contours, high image density and sharpness, no feathering, no color mixing of different inks, etc. It is an object of the present invention to provide a recording medium, an ink composition, and an ink jet recording method which can maintain a high quality image of a recorded image even after performing the method.
[0011]
Another object of the present invention is to provide an ink jet recording apparatus capable of forming a recorded image of high image quality and an ink head which can be used in the ink jet recording apparatus and which can continuously and stably discharge an ink composition at high speed. It is.
[0012]
[Means for Solving the Problems]
The present invention provides a recording medium comprising applying a recording medium treatment liquid containing a silicone-containing vinylpyrrolidone copolymer as an active ingredient to the surface of a substrate and / or impregnating the inside of the substrate. It is.
[0013]
According to the present invention, the presence of a silicone-containing vinylpyrrolidone-based copolymer (hereinafter referred to as “silicone-containing vinylpyrrolidone-based copolymer”) on the surface and / or inside of the recording medium allows the silicone-containing vinylpyrrolidone to be present. Since the system copolymer fixes the dye or pigment as a coloring material, it prevents the dye or pigment from penetrating and diffusing into the inside of the recording medium or into a margin on the surface together with a liquid component such as water in the ink. be able to. As a result, bleeding is significantly prevented, and feathering and color mixing do not occur. Can be formed.
[0014]
Further, the recording medium of the present invention is characterized in that the above-mentioned substrate has a Steckigt sizing degree of 20 seconds or less.
[0015]
According to the present invention, the substrate on which the silicone-containing vinylpyrrolidone-based copolymer is present preferably has a Stockigt size of 20 seconds or less. This allows the ink composition to appropriately penetrate into the recording medium of the present invention, thereby preventing feathering, further increasing the image density, and further improving the quality of the obtained recorded image.
[0016]
The recording medium of the present invention is characterized in that the silicone-containing vinylpyrrolidone-based copolymer has a core-shell structure in which silicone is used as a core and the vinylpyrrolidone-based copolymer is used as a shell.
[0017]
According to the present invention, among the silicone-containing vinylpyrrolidone-based copolymers, those having a core-shell structure in which the core is made of silicone and the shell is made of a vinylpyrrolidone-based copolymer are preferred. As a result, the occurrence of bleeding is further prevented, and the image quality of the recorded image is improved.
[0018]
The recording medium of the present invention is characterized in that the silicone is a polyalkylsiloxane.
[0019]
According to the present invention, the silicone contained in the silicone-containing vinylpyrrolidone-based copolymer is preferably a polyalkylsiloxane. As a result, the image quality of the recorded image is further improved.
[0020]
Further, in the recording medium of the present invention, the above-mentioned vinylpyrrolidone-based copolymer is a compound of the general formula
CH₂= CR¹-X- (CH₂)_a-Y (1)
[Wherein, R¹Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X represents a group -COO-, a group -CO-, a group -CONH- or a methylene group. Y represents a quaternary ammonium group or a dialkylamino group. a shows the integer of 1-10. ]
And a copolymer with one or more monomer compounds selected from quaternary ammonium compounds having a polymerizable double bond and amine compounds.
[0021]
According to the present invention, the vinylpyrrolidone-based copolymer is preferably a copolymer of vinylpyrrolidone and one or more selected from specific quaternary ammonium compounds and amine compounds. Such a copolymer has a high ability to firmly bond to the surface and inside of the recording medium and to fix the coloring material.
[0022]
The present invention is a recording medium treatment liquid containing the above-mentioned silicone-containing vinylpyrrolidone copolymer as an active ingredient.
[0023]
According to the present invention, there is provided a recording medium treatment liquid that can be suitably used for producing the above-described recording medium of the present invention.
[0024]
Further, the recording medium treatment liquid of the present invention is characterized by further containing one or more selected from a water-soluble organic solvent, a surfactant and a fungicide.
[0025]
The recording medium treatment liquid of the present invention is characterized in that the water-soluble organic solvent is one or more selected from polyhydric alcohols and glycol ethers.
[0026]
The recording medium treatment liquid of the present invention is characterized in that the surfactant is a nonionic surfactant.
[0027]
According to the present invention, recording is carried out by adding a water-soluble organic solvent (preferably polyhydric alcohol and glycol ether), a surfactant (preferably a nonionic surfactant), and the like to the above-mentioned recording medium treatment liquid. Since the permeability of the medium treatment liquid is further improved, and the silicone-containing vinylpyrrolidone-based copolymer, which is an active ingredient, is more uniformly dispersed in the recording medium, the quality of the recorded image can be further improved.
[0028]
The present invention is an aqueous ink containing a dye or a pigment as a coloring material, and the balance being water, wherein the coloring material reacts with a vinylpyrrolidone-based copolymer containing silicone to form a precipitate. An ink composition characterized in that:
[0029]
According to the present invention, an ink composition suitable for forming a recorded image on the recording medium of the present invention is provided.
[0030]
Further, the ink composition of the present invention is characterized by further comprising one or more selected from a water-soluble organic solvent and a nonionic surfactant.
[0031]
According to the present invention, by adding a water-soluble organic solvent, a nonionic surfactant and the like to the above-described ink composition, foaming and drying of the ink composition in the discharge nozzle are prevented, and the discharge stability is improved. And high-speed printing can be easily performed.
[0032]
Further, the ink composition of the present invention is characterized in that the pigment is a self-dispersed pigment obtained by introducing a hydrophilic group on the surface of the pigment.
[0033]
According to the present invention, in the above-described ink composition, by using a self-dispersed pigment as a pigment, storage stability of the ink composition is improved, and during storage of the ink composition, clogging of a discharge nozzle may be caused. , The occurrence of aggregation and sedimentation of the pigment is prevented.
[0034]
Further, the ink composition of the present invention is a cyan ink composition containing one or more cyan pigments selected from Pigment Blue 15: 3, Pigment Blue 15: 4, and Pigment Blue 15: 6. And
[0035]
Further, the ink composition of the present invention is a magenta ink composition containing one or more magenta pigments selected from Pigment Red 122, Pigment Red 209 and Pigment Violet 19.
[0036]
Further, the ink composition of the present invention is a yellow ink composition containing one or more yellow pigments selected from Pigment Yellow 74, Pigment Yellow 128, Pigment Yellow 138, Pigment Yellow 150 and Pigment Yellow 180. It is characterized by.
[0037]
The ink composition of the present invention is a black ink composition containing carbon black.
[0038]
The present invention is an ink set including two or more selected from the above-mentioned cyan-based ink composition, magenta-based ink composition, yellow-based ink composition, and black-based ink composition.
[0039]
According to the present invention, among the above-described ink compositions, a cyan-based, magenta-based, yellow-based, and black-based ink composition containing a specific pigment, and an ink set containing two or more of these are preferable. By using these ink compositions or ink sets, a recorded image having extremely good color balance and high image quality can be formed.
[0040]
According to the present invention, there is provided an ink jet recording method for performing recording by attaching an ink composition to a recording medium, wherein the recording medium is any one of the recording media described above.
[0041]
The present invention relates to an ink jet recording method for performing recording by adhering an ink composition to a recording medium, wherein any of the above-described recording medium treatment liquids is adhered to a recording medium before recording, simultaneously with recording, or after recording. An ink jet recording method characterized by the above-mentioned.
[0042]
According to the present invention, the ink composition is applied to the recording medium by an inkjet recording method, or the recording medium is applied to the recording medium before, simultaneously with or after the application of the ink composition. By attaching the processing liquid, a high quality image can be formed.
[0043]
The present invention provides a recording medium supply unit that supplies a recording medium, a recording medium conveyance unit that conveys a recording medium supplied by the recording medium supply unit, and an ink composition attached to the recording medium conveyed by the recording medium conveyance unit. In an ink jet recording apparatus including a printing unit that performs recording by discharging, and a discharging unit that discharges a recording medium on which a recording image is formed by the printing unit,
An ink jet recording apparatus comprising a processing liquid transfer unit for attaching any of the above-described recording medium processing liquids to a recording medium.
[0044]
Further, in the ink jet recording apparatus of the present invention, the processing liquid transfer unit may include:
To be included in the recording medium transport means, or
It is provided between the recording medium conveying means and the printing means.
[0045]
According to the present invention, there is provided an ink jet recording apparatus suitable for performing the above ink jet recording method. By using this apparatus, it is possible to form a high-quality recorded image and to easily perform high-speed printing.
[0046]
The present invention provides an ink tank for storing any one of the above ink compositions,
An ink chamber having an ejection port for ejecting the ink composition supplied from the ink tank as droplets,
A piezoelectric element that is provided in the ink chamber, generates strain in response to an applied voltage, and applies pressure to the ink composition;
An electrode for applying a voltage to the piezoelectric element.
[0047]
The present invention provides an ink tank for storing any one of the above ink compositions,
An ink chamber having an ejection port for ejecting the ink composition supplied from the ink tank as droplets,
A heating element that is provided in the ink chamber, generates heat in response to an applied voltage, and applies pressure to the ink composition by generating bubbles in the ink composition;
An electrode for applying a voltage to the heating element.
[0048]
According to the present invention, there is provided an ink jet recording ink head which can continuously and stably discharge the above-mentioned ink composition and is suitable for high-speed printing.
[0049]
BEST MODE FOR CARRYING OUT THE INVENTION
(Recording medium and recording medium treatment liquid)
The recording medium of the present invention comprises (1) a recording medium having a silicone-containing vinylpyrrolidone-based copolymer on the surface of a substrate, and (2) a silicone-containing vinylpyrrolidone-based copolymer having the inside of the substrate. A recording medium, and (3) a recording medium in which a silicone-containing vinylpyrrolidone-based copolymer is held on the surface and inside of a substrate.
[0050]
The recording medium of the present invention is produced, for example, by applying a recording medium treatment liquid containing a silicone-containing vinylpyrrolidone copolymer to the surface of a substrate and / or impregnating the inside of the substrate with the recording medium treatment liquid. Can be.
[0051]
Here, the substrate is not particularly limited, and a known recording medium can be used. Among them, for example, a general paper-based recording medium containing a pulp material such as plain paper, coated paper (for example, color copy paper, ink-jet paper, etc.), glossy paper, etc., is preferable. Certain common paper-based recording media are more preferred. These recording media include one or more of inorganic pigments such as bentonite, calcium carbonate, magnesium hydroxide, and magnesium silicate, polyvalent metal salts, and polymers having a dye fixing action on the surface and / or inside thereof. May be included. Examples of the polymer having a dye fixing action include cationic polymers such as polyallylamine and polymers having a dimethylaminoethyl methacrylate structure.
[0052]
The recording medium treatment liquid applied or impregnated on the base material is a composition containing a silicone-containing vinylpyrrolidone-based copolymer and the balance being water.
[0053]
The silicone-containing vinylpyrrolidone-based copolymer is a mixture of the vinylpyrrolidone-based copolymer and silicone, and more specifically, a mixture in which silicone is dispersed in a matrix composed of the vinylpyrrolidone-based copolymer. In this specification, such a state is referred to as that the vinylpyrrolidone-based copolymer contains silicone.
[0054]
In a preferred embodiment of the silicone-containing vinylpyrrolidone copolymer, a core-shell structure having a silicone core and a shell made of the vinylpyrrolidone copolymer is exhibited.
[0055]
Here, the silicone is not particularly limited, and a known organopolysiloxane can be used, and examples thereof include polyalkylsiloxane, polyarylsiloxane, and polyethersiloxane. Among these, polyalkylsiloxane is preferable, and polymethylsiloxane is particularly preferable. One type of silicone can be used alone, or two or more types can be used in combination.
[0056]
As the vinylpyrrolidone copolymer, for example, vinylpyrrolidone and a compound represented by the general formula
CH₂= CR¹-X- (CH₂)_a-Y (1)
[Wherein, R¹, X, Y and a are as defined above. ]
And a copolymer with one or more monomer compounds selected from quaternary ammonium compounds having a polymerizable double bond and amine compounds.
[0057]
In the general formula (1), the symbol R¹Examples of the alkyl group having 1 to 4 carbon atoms include a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. A chain alkyl group is exemplified.
[0058]
Examples of the quaternary ammonium group represented by the symbol Y include a straight-chain or branched-chain alkyl group having an alkyl portion having 1 to 4 carbon atoms, such as a trimethylammonium group and a triethylammonium group, and preferably having 1 to 4 carbon atoms. A quaternary ammonium group in which an anion is added to a trialkylammonium group which is a straight-chain alkyl group is exemplified. Here, the anion is not particularly limited, and may be a halogen ion such as a chloride ion or a bromine ion, a sulfate ion, an acetate ion, a formate ion, a sulfamate ion, a butyrate ion, a nitrate ion, a perchlorate ion, a bromate ion, or a fluoride ion. Hydrogen ions and the like. Of these, halogen ions are preferred.
[0059]
Examples of the dialkylamino group represented by the symbol Y include, for example, an alkyl moiety such as a dimethylamino group, a diethylamino group, a methylethylamino group, a dipropylamino group, a methylpropylamino group, an ethylpropylamino group, and a dibutylamino group. Examples thereof include a linear or branched alkyl group having 1 to 4 carbon atoms, preferably a dialkylamino group which is a linear alkyl group having 1 to 4 carbon atoms.
[0060]
More specifically, such a quaternary ammonium compound and an amine compound may be represented, for example, by the general formula
CH₂= CR¹-CONH- (CH₂)_a-Y¹              (1a)
[Wherein, R¹And a are the same as above. Y¹Represents a quaternary ammonium group. ]
A quaternary ammonium compound represented by the general formula
CH₂= CR¹-COO- (CH₂)_a-Y (1b)
[Wherein, R¹, Y and a are the same as above. ]
A quaternary ammonium compound or an amine compound represented by the formula:
CH₂= CR¹-CH₂− (CH₂)_a-Y²                (1c)
[Wherein, R¹Is the same as above. Y²Represents a dialkylamino group. ]
An amine compound represented by the general formula
CH₂= CR¹-CO- (CH₂)_a-Y²                    (1d)
[Wherein, R¹And Y²Is the same as above. ]
And the like. Among these, compound (1a) and compound (1b) are preferable, and compound (1a) is particularly preferable.
[0061]
Specific examples of such quaternary ammonium compounds and amine compounds include, for example, (meth) acrylamidopropyltrimethylammonium chloride, (meth) acrylamidopropyltriethylammonium chloride, (meth) acrylamidoethyltrimethylammonium chloride, (meth) acrylamidoethyl Triethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, dimethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, diethylaminoethyl ( (Meth) acrylate and the like.
[0062]
As the quaternary ammonium compound and the amine compound, one type can be used alone, or two or more types can be used in combination.
[0063]
The content ratio of vinylpyrrolidone and the monomer compound selected from quaternary ammonium compounds and amine compounds in the vinylpyrrolidone-based copolymer is not particularly limited, and the type of the recording medium to which the recording medium treatment liquid is to be applied and the type of the recording medium Although it can be appropriately selected from a wide range depending on conditions such as the composition of the ink composition to be attached to the ink, usually, 50 to 99 mol% of vinylpyrrolidone and 1 to 50 of a monomer compound selected from a quaternary ammonium compound and an amine compound are used. It may be contained by mol%.
[0064]
A silicone-containing vinylpyrrolidone-based copolymer can be prepared by the method described in, for example, U.S. Pat. No. 5,073,296 and U.S. Pat. It can be produced by copolymerizing one or more monomer compounds selected from the group consisting of: Specifically, first, silicone is added to water containing 0.01 to 10% by weight of a surfactant, preferably a nonionic surfactant (HLB value of about 11 to 14), and the mixture is mixed. Disperse in water as drops. One or more monomer compounds selected from vinylpyrrolidone, a quaternary ammonium compound and an amine compound, and a radical polymerization initiator are added thereto, and copolymerization is performed. Known radical polymerization initiators can be used, for example, azo compounds such as azobisisobutyronitrile, 2,2-azobisdimethylvaleronitrile and azobiscyanovaleric acid, benzoyl peroxide, di-t-butyl peroxide , T-butyl hydroperoxide, t-butyl peroxypivalate, organic peroxides such as cumene hydroperoxide, and inorganic peroxides such as ammonium persulfate, potassium persulfate, sodium persulfate, and hydrogen peroxide. . The polymerization reaction is usually performed at a temperature of about 50 to 90 ° C, preferably about 70 to 85 ° C, and is completed usually in about 1 to 20 hours, preferably in about 2 to 10 hours. As a result, an aqueous dispersion of the silicone-containing vinylpyrrolidone copolymer is obtained. This aqueous dispersion can be used as it is as the recording medium treatment liquid of the present invention. Further, if necessary, the silicone-containing vinylpyrrolidone-based copolymer may be isolated and purified from the aqueous dispersion and used according to general means such as filtration, centrifugation, washing with water, a solvent, and the like, and drying. .
[0065]
The silicone-containing vinylpyrrolidone-based copolymer can also be produced by mixing the vinylpyrrolidone-based copolymer with silicone. Incidentally, the vinylpyrrolidone-based copolymer is prepared from vinylpyrroliton and a quaternary ammonium compound and an amine compound in a suitable solvent in the same manner as described above in the presence of a polymerization initiator, preferably a radical polymerization initiator. It can be produced by copolymerizing one or more selected monomer compounds.
[0066]
In the silicone-containing vinylpyrrolidone-based copolymer, although the ratio of the silicone and the vinylpyrrolidone-based copolymer is not particularly limited, usually, 5 to 30 parts by weight of silicone with respect to 100 parts by weight of the vinylpyrrolidone-based copolymer, Preferably, 5 to 15 parts by weight may be used.
[0067]
In the present invention, a commercially available silicone-containing vinylpyrrolidone-based copolymer can also be used. Specific examples thereof include, for example, GAFQUAT.HSi (trade name, manufactured by ISP). GAFQUAT · HSi is a vinylpyrrolidone-based copolymer containing polymethylsiloxane, and the vinylpyrrolidone-based copolymer is a copolymer of vinylpyrrolidone and methacrylamidopropyltrimethylammonium chloride.
[0068]
As the silicone-containing vinylpyrrolidone copolymer, one type can be used alone, or two or more types can be used in combination.
[0069]
The content of the silicone-containing vinylpyrrolidone-based copolymer is not particularly limited, the material of the substrate to be coated or impregnated, the surface physical properties and ink absorption properties, the presence or absence of other components, the type and content when other components are included, Although it can be appropriately selected from a wide range according to various conditions such as characteristics of the ink composition applied to the obtained recording medium, it is usually 0.1 to 10% by weight, preferably 0.1 to 5% by weight of the total amount of the recording medium processing liquid. % By weight. If it is less than 0.1% by weight, the effect of preventing the penetration and diffusion of the coloring material may not be sufficiently exhibited. On the other hand, if it exceeds 10% by weight, the increase in viscosity may be large.
[0070]
The recording medium treatment liquid may contain one or more selected from a water-soluble organic solvent, a surfactant, and a fungicide.
[0071]
The water-soluble organic solvent improves, for example, workability (coating stability) when applying or impregnating the recording medium treatment liquid onto the base material, increases the permeability of the recording medium treatment liquid into the base material, and contains silicone. The vinylpyrrolidone copolymer is more uniformly dispersed on the surface of the substrate and inside the substrate. Known water-soluble organic solvents can be used, for example, amides such as dimethylformamide and dimethylacetamide, polyethylene glycol, polypropylene glycol, ethylene glycol, diethylene glycol, thiodiglycol, propylene glycol, triethylene glycol, 1,5 Glycols such as pentanediol, 1,4-butanediol, 1,2-hexanediol, and 1,3-propanediol; trihydric or higher polyhydric alcohols such as glycerin and 1,2,6-hexanetriol; Ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, professional Glycol ethers such as leneglycol monoethyl ether, tetraethylene glycol monomethyl ether and ethylene glycol monophenyl ether; sulfur-containing compounds such as sulfolane and dimethyl sulfoxide; and nitrogen-containing heteroatoms such as 2-pyrrolidone, N-methylpyrrolidone and ε-caprolactam. Ring compounds, oxygen-containing heterocyclic compounds such as γ-butyrolactone, and polyfunctional compounds such as dimethylaminoethanol, diethylaminoethanol, triethanolamine, and morpholine.
[0072]
Among these water-soluble organic solvents, glycol ethers, glycols, polyhydric alcohols, and the like are preferable in consideration of the degree of improving coating stability and permeability to a recording medium. Are more preferably 6.6665 Pa (0.05 mmHg) or less, for example, glycols such as 1,2-hexanediol and 1,5-pentanediol, and polyhydric alcohols such as glycerin.
[0073]
One type of water-soluble organic solvent can be used alone, or two or more types can be used in combination.
Although the content of the water-soluble organic solvent is not particularly limited, it is usually 10 to 70% by weight, preferably 10 to 50% by weight of the total amount of the processing solution for the recording medium in consideration of further improving the permeability to the base material. is there. However, when an attempt is made to obtain a recording medium treatment liquid containing more water than a water-soluble organic solvent, the content of the water-soluble organic solvent is determined in consideration of the drying property and the permeability to the base material. It is 10 to 40% by weight of the total amount, preferably 10 to 30% by weight.
[0074]
The surfactant can further improve the permeability of the recording medium treatment liquid to the base material. Among the surfactants, nonionic surfactants are preferred. Known nonionic surfactants can be used, and among them, for example, the general formula
[0075]
Embedded image

[0076]
[Wherein, d and e each represent 0 or a positive number in the range of 0 to 30 that satisfies the relationship of 0 ≦ d + e ≦ 30. ]
Acetylene glycol / ethylene oxide adduct represented by the general formula
[0077]
Embedded image

[0078]
[In formula, f shows the integer of 11-13. g shows the integer of 3-30. ]
A compound represented by the general formula
[0079]
Embedded image

[0080]
[Wherein, h and i each represent an integer of 0-11. j represents an integer of 3 to 50. ]
A compound represented by the general formula
[0081]
Embedded image

[0082]
[In the formula, q represents an integer of 5 to 9. r shows a positive number of 2.5-5. k and l each represent an integer of 0 to 11 that satisfies the relationship of 9 ≦ k + 1 ≦ 11. ]
A compound represented by the general formula

[In the formula, s represents an integer of 0 to 18. t shows the integer of 2-15. u shows the integer of 0-18. ]
Preferred are ethylene oxide-containing nonionic surfactants such as the compounds represented by In the present invention, commercially available nonionic surfactants can also be used, and examples thereof include Surfynol (trade name, manufactured by Air Products), Softanol EP (trade name, manufactured by Nippon Shokubai Co., Ltd.) and the like. . Surfynol is also commercially available from Nissin Chemical Co., Ltd. One surfactant may be used alone, or two or more surfactants may be used in combination.
[0083]
Although the content of the surfactant is not particularly limited, it is usually 0.001 to 5% by weight, preferably 0.001 to 3% by weight based on the total amount of the recording medium processing liquid.
[0084]
Known fungicides can be used, and examples thereof include sodium dehydroacetate, sodium benzoate, sodium sorbitanate, sodium 2-pyridinethiol-1-oxide, and sodium pentachlorophenol. One kind of fungicide can be used alone, or two or more kinds can be used in combination. Although the content of the fungicide is not particularly limited, it is usually 0.001 to 0.1% by weight based on the total amount of the processing solution for the recording medium.
[0085]
Further, the recording medium treatment liquid may contain a general additive of the ink composition for inkjet, such as a pH adjuster, a chelating agent, a rust inhibitor, and an ultraviolet absorber, as long as the preferable properties are not impaired. Good. Examples of the pH adjuster include amines such as diethanolamine and triethanolamine, alkali metal hydroxides such as lithium hydroxide, potassium hydroxide and sodium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, and quaternary ammonium hydroxide. Alkali metal carbonates such as graded phosphonium hydroxide, lithium carbonate, sodium carbonate and potassium carbonate; and alkali metal nitrates such as sodium nitrate and potassium nitrate. Examples of the chelating agent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uramildiacetate. Examples of the rust inhibitor include acid sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and the like. Examples of the ultraviolet absorber include a benzotriazole compound, a benzophenone compound, a cyanoacrylate compound, and the like. One type of additive may be used alone, or two or more types may be used in combination.
[0086]
Further, the recording medium treatment liquid may contain a solubilizing agent, an antioxidant, an antifoaming agent, a viscosity modifier, and the like, as necessary.
[0087]
The recording medium treatment liquid was prepared by using an appropriate amount of a silicone-containing vinylpyrrolidone copolymer and, if necessary, a water-soluble organic solvent, a surfactant, a fungicide, and other additives, and further using water. To 100% by weight, and these are mixed or dispersed according to a general method, and if necessary, subjected to a solid-liquid separation treatment (filtration, centrifugation, etc.). For dispersing, for example, a dispersing device such as a disperser, a sand mill, a homogenizer, a ball mill, a bead mill, a paint shaker, and an ultrasonic disperser can be used. For mixing, a stirrer having a stirring blade, a high-speed disperser, an emulsifier, or the like can be used.
[0088]
The recording medium treatment liquid thus obtained has a surface tension of preferably 50 mN / m or less, more preferably 40 mN / m or less. A recording medium treatment liquid having such a surface tension value can be obtained by adjusting the content of the silicone-containing vinylpyrrolidone copolymer, and adding other components such as a water-soluble organic solvent and a surfactant. In this specification, the surface tension was measured using a surface tension meter CBVP-A3 manufactured by Kyowa Interface Chemical Co., Ltd. Further, the recording medium treatment liquid has a viscosity at 25 ° C. of preferably 1 Pa · s or less, more preferably 80 mPa · s or less. A recording medium treatment liquid having such a viscosity value can be obtained by adjusting the content of the silicone-containing vinylpyrrolidone copolymer, and adding other components such as a water-soluble organic solvent and a surfactant. In the present specification, the viscosity was recorded at 25 rpm at 6 rpm for 1 minute using a viscometer LVDV-III + manufactured by Brookfield after stirring the recording medium treatment liquid for 1 minute. By adjusting the viscosity and / or the surface tension to the above-mentioned ranges, the coatability of the treatment liquid on the recording medium is further improved, the treatment liquid can be easily applied to the recording medium, and the recording of the silicone-containing polyvinylpyrrolidone can be performed. The dispersibility on the medium surface and inside the recording medium is remarkably improved, and furthermore, the permeation of the coloring material into an extra portion is prevented, and the occurrence of feathering, color mixing, and unevenness in a solid portion is further prevented.
[0089]
In applying the recording medium treatment liquid to the surface of the base material, a known method of applying a liquid component to the surface of a solid material can be employed. Specific examples of the method include a brush coating method, a roll coater method, a blade coater method, an air knife coater method, a bar coater method, a size press method, a spray coat method, a gravure coater method, and a curtain coater method. The components contained in the recording medium treatment liquid applied to the surface of the base material are spread and held on the surface of the base material and / or penetrated and held inside the base material. The amount of the recording medium treatment liquid applied to the substrate is not particularly limited, and the content of the silicone-containing vinylpyrrolidone-based copolymer as an active ingredient, the material of the substrate, the surface physical properties and the ink absorption properties, and the application to the obtained recording medium Although it can be appropriately selected from a wide range according to various conditions such as the type of the ink composition to be used, it is usually 0.1 to 30 g / m2.², Preferably 0.5 to 20 g / m²It is.
[0090]
Alternatively, the base material may be immersed in the recording medium treatment liquid. The immersion amount may be the same as the above-mentioned application amount.
[0091]
Drying of the substrate coated or impregnated with the recording medium treatment liquid is performed at a temperature of 5 to 40C.
[0092]
(Ink composition)
The ink composition of the present invention is a composition containing a coloring material and water, and the coloring material reacts with the silicone-containing vinylpyrrolidone-based copolymer to form a precipitate.
[0093]
Dyes and pigments can be used as the coloring material that reacts with the silicone-containing vinylpyrrolidone-based copolymer to form a precipitate.
[0094]
Known dyes can be used, and examples thereof include water-soluble dyes such as acid dyes, direct dyes, and reactive dyes. When a specific example of the dye is represented by a color index number (CI), Acid Blue 7, 9, 29, 45, 92, 249, Direct Blue 1, 2, 6, 15, 22, 25, 71, 76, 79, 86 , 90, 98, 163, 165, 199, 202, Reactive Blue 1, 2, 7, 14, 15, 23, 32, 38, 41, 63, 80, 95, etc., Acid Red 1, 8 , 13, 14, 18, 26, 27, 35, 37, 42, 52, 82, 87, 89, 92, 97, 106, 111, 114, 115, 134, 186, 249, 254, 289, Directred 1, 4, 9, 13, 17, 20, 28, 31, 39, 80, 81, 83, 89, 225, 227, Direct Orange 26, 29, 62, 102, Reactive Red 1, 1 , 17, 25, 26, 32, 37, 44, 46, 55, 60, 66, 74, 79, 96, 97, 141, 147, 181 and the like, acid yellow 1, 7, 17, 23, 42, 44, 79, 142, Direct Yellow 1, 12, 24, 26, 33, 44, 50, 86, 120, 132, 142, 144, Reactive Yellow 1, 5, 11, 13, 14, 20, 21 , 22, 25, 40, 47, 51, 55, 65, 67, etc., food black 2, direct black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171 and reactive blacks 3, 4, 7, 11, 12, 17 and the like. Among these, those excellent in water resistance, light resistance, safety to the human body, and the like are preferable. One type of dye can be used alone, or two or more types can be used in combination as needed. The content of the dye is not particularly limited, and is appropriately selected from a wide range according to various conditions such as the material of the base material of the recording medium of the present invention, surface properties, ink absorption properties, and the content of the silicone-containing vinylpyrrolidone-based copolymer. If possible, it is usually 0.1 to 10% by weight, preferably 0.1 to 7% by weight of the total amount of the ink composition. If it is less than 0.1% by weight, the image density may be low, and it may be difficult to express colors. If the amount exceeds 10% by weight, the solubility of the dye in the ink composition becomes unstable, which may adversely affect the ejection stability of the ink composition.
[0095]
As the pigment, known inorganic pigments and organic pigments can be used. Examples of the inorganic pigment include titanium oxide, iron oxide, carbon black produced by a known method such as a contact method, a furnace method, and a thermal method. When a specific example of the organic pigment is represented by a color index number (CI), for example, Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, Blue pigments such as 22, 21, 22, 60, 64, and Pigment Red 1, 2, 3, 5, 10, 16, 23, 30, 31, 48: 1, 48: 2, 49: 1, 52, 53 Pigment Yellow 3, 12, 13, 14, 15, 23, 55, 74, 83, 93, 95, such as red pigments such as 1, 57: 1, 58: 4, 63, 122, 209, and Pigment Bio Red 19. , 97, 128, 138, 150, 154, 167, 180, 193 and the like. Among them, those having high safety for the human body are preferable.
[0096]
Further, in the present invention, a self-dispersible pigment having self-dispersibility in water by introducing a hydrophilic group to the surface of the pigment may be used. The hydrophilic group is not particularly limited, and includes, for example, a carbonyl group, a carboxyl group, a hydroxyl group, and a sulfone group. Further, the hydrophilic group may form a salt on the pigment surface.
[0097]
The self-dispersion pigment can be obtained according to a known method. For example, a method of applying high-speed shearing to a mixture of a pigment and an organic solvent using a high-speed mixer or the like can be used. In addition, self-dispersed pigments having a sulfone group are dispersed in water by applying an impact with a bead mill, jet mill, etc., and a sulfonating agent such as fuming sulfuric acid, sulfuric acid, chlorosulfuric acid, fluorosulfuric acid is added to this under stirring Then, it can be obtained by further performing a heat treatment at 60 to 200 ° C. This self-dispersed pigment can be easily isolated and purified from the reaction system according to known means such as washing with water, ultrafiltration, reverse osmosis, centrifugation, and filtration. Further, the self-dispersed pigment can be obtained by a physical treatment such as a vacuum plasma treatment, a treatment with a coupling agent such as a silane compound, or a chemical treatment other than the above such as a polymer grafting treatment.
[0098]
Among the pigments, self-dispersion pigments are preferable in consideration of dispersibility in ink and storage stability of ink.
[0099]
One type of pigment can be used alone, or two or more types can be used in combination as needed. The content of the pigment is not particularly limited, although it can be appropriately selected from a wide range according to the material of the base material of the recording medium of the present invention, the surface properties, the ink absorption properties, the content of the silicone-containing vinylpyrrolidone copolymer, and the like. Usually, it is 0.1 to 10% by weight, preferably 0.1 to 8% by weight of the total amount of the ink composition. If the content is less than 0.1% by weight, the image density becomes low, and it may be difficult to express a color on a recording medium. On the other hand, when the content exceeds 10% by weight, the viscosity of the ink composition becomes high, and there is a possibility that ejection failure from a nozzle, penetration failure into a recording medium, and the like may occur.
[0100]
The ink composition may contain one or more selected from a water-soluble organic solvent, a surfactant, and a synthetic resin, if necessary. As the water-soluble organic solvent and the surfactant, those similar to those described in the section of the recording medium treatment liquid can be used. The content may be the same as the content in the recording medium processing liquid.
[0101]
The synthetic resin is used, for example, as a fixing agent for further fixing the coloring material with the silicone-containing vinylpyrrolidone-based copolymer. Examples of the component include resin components such as a water-soluble resin and a water-dispersible resin. Examples of the water-soluble resin include a water-soluble natural polymer compound and a water-soluble synthetic resin. Specific examples of the water-soluble natural polymer compound include, for example, natural gums such as gum arabic, glucosides such as savonin, lignin sulfonate, shellac and the like. Examples of the water-soluble synthetic resin include acrylic acid resin and its salt, methacrylic acid resin and its salt, styrene-acrylic acid copolymer and its salt, vinylnaphthalene-acrylic acid copolymer and its salt, styrene-maleic acid -Alkyl acrylate copolymer and salt thereof, vinyl naphthalene-maleic acid copolymer and salt thereof, styrene-methacrylic acid-alkyl acrylate copolymer and salt thereof, sodium of β-naphthalene sulfonic acid formalin condensate Anionic polymer compounds such as salts and phosphates, polyester resins, nonionic polymer compounds such as polyvinyl alcohol and polyvinylpyrrolidone, acrylonitrile, vinyl acetate, acrylamide, vinyl chloride, vinylidene chloride, ethylene, hydroxyethyl alcohol Relate, and a copolymer consisting of monomers such as glycidyl methacrylate. As the water-dispersible resin, a known water-dispersible synthetic resin can be used, and examples thereof include a polyester resin, an acrylic resin, a styrene-acryl copolymer, a maleic acid resin, and a polyurethane resin. Commercially available water-dispersible resins can also be used, for example, Microgel (trade name, water-dispersible styrene-acrylic resin) manufactured by Nippon Paint Co., Ltd., Bon Coat (manufactured by Dainippon Ink and Chemicals, Inc.) Trade name, water-dispersible styrene-acrylic resin), Vironal (trade name, water-dispersible polyester resin) manufactured by Toyobo Co., Ltd., and John Krill (trade name, emulsion type) manufactured by Johnson Polymer Co., Ltd. . Among these resin components, a water-soluble acryl-styrene copolymer, a water-dispersible polyester resin, a water-dispersible acrylic resin, and the like are preferable in consideration of the reactivity with the silicone-containing vinylpyrrolidone copolymer. As the resin component, one type can be used alone, or two or more types can be used in combination as needed. The content of the resin component is not particularly limited, and depends on various conditions such as the type and content of the coloring material, the presence / absence of other components, and the type and content of other components when including other components, and the type and characteristics of the recording medium. Although it can be appropriately selected from a wide range, the effect of the addition of the resin component is sufficiently exerted, and the ejection stability and the storage stability of the ink composition (the components do not aggregate or precipitate during storage) are not impaired. To achieve this, the amount is usually 0.01 to 30% by weight, preferably 0.1 to 20% by weight of the total amount of the ink composition.
[0102]
Further, the ink composition contains a pH adjuster, a chelating agent, a rust inhibitor, an ultraviolet absorber, a dissolution aid, an antioxidant, an antifoaming agent, a viscosity adjuster, an anti-clogging agent, etc., as necessary. You may go out.
[0103]
The ink composition of the present invention is, for example, using a pigment and, if necessary, an appropriate amount of a water-soluble organic solvent, a nonionic surfactant, a synthetic resin, and other additives, and further using water to adjust the total amount to 100%. It can be manufactured by adjusting the weight% and dispersing or dissolving each component in water.
[0104]
The water used here is not particularly limited, and tap water, pure water, ion-exchanged water, activated carbon treated water and the like can be used. Among these, water having an electric conductivity (25 ° C.) of 250 μS / cm or less is preferable in consideration of the ejection stability of the ink composition, permeability and drying property to a recording medium, storage stability, and the like, and 1 μS / cm or less. Are particularly preferred. The electric conductivity is an index indicating the purity of water, in other words, an index indicating the amount of impurities contained in water. The impurities are trace components generally contained in water, and include, for example, inorganic salts and other mineral components.
[0105]
Dispersion is performed using a general disperser. Examples of the disperser include a disperser, a sand mill, a homogenizer, a ball mill, a bead mill, a paint shaker, and an ultrasonic disperser. Mixing is performed by a stirrer having a stirring blade, a high-speed disperser, an emulsifier, or the like.
[0106]
After dispersion and / or mixing, a solid-liquid separation means may be provided. Examples of the solid-liquid separation means include filtration and centrifugation. For example, the filtration may be performed after each component is mixed or dispersed in an aqueous medium. The filtration is performed under normal pressure or reduced pressure using, for example, a filter having a pore size of 0.8 μm or less, a filter having a pore size of 0.45 μm or less, or the like.
[0107]
Preferred forms of the ink composition of the present invention thus obtained include:
(A) a cyan ink composition in which the pigment contains one or more cyan pigments selected from Pigment Blue 15: 3, Pigment Blue 15: 4, and Pigment Blue 15: 6;
(B) a magenta ink composition in which the pigment contains one or more magenta pigments selected from Pigment Red 122, Pigment Red 209 and Pigment Violet 19;
(C) a yellow ink composition in which the pigment contains one or more yellow pigments selected from Pigment Yellow 74, Pigment Yellow 128, Pigment Yellow 138, Pigment Yellow 150 and Pigment Yellow 180;
(D) an ink composition containing a black pigment, wherein the pigment is carbon black;
(E) an ink set comprising at least two ink compositions selected from the ink compositions of (a), (b), (c) and (d);
And the like. Among these, an ink set composed of the ink compositions (a), (b) and (c) is particularly preferable from the viewpoint of color balance and the like.
[0108]
When the ink composition of the present invention is used in an ink-jet method, it is applied to a recording medium having a silicone-containing polyvinylpyrrolidone held on its surface and / or inside, but can also be used as an aqueous ink other than the ink-jet method. . Examples of uses of aqueous inks other than the ink jet method include printing inks such as gravure inks, aqueous paints, cosmetics, inks for writing implements, toners, liquid developers, and materials for electrophotography.
[0109]
[Inkjet recording method]
The inkjet recording method of the present invention is a method of forming a recorded image by discharging an ink composition onto a recording medium by an inkjet method, wherein the recording medium is the recording medium of the present invention.
[0110]
As described above, a recording medium of the present invention, that is, a recording medium having a silicone-containing vinylpyrrolidone-based copolymer held on its surface and / or inside is used as a recording medium.
[0111]
The ink composition is supplied from an ink discharge nozzle to an image recording surface of a recording medium and adheres to the image recording surface according to a general inkjet method. The ink composition is not particularly limited, but is preferably an ink composition of the present invention or an ink set including two or more of the ink compositions of the present invention.
[0112]
The inkjet method is not particularly limited, and a known method can be employed. For example, an ink-jet method using a piezoelectric element (piezo method), an ink-jet method in which ink is ejected by applying pressure to ink, and an ink-jet method in which bubbles are generated using a film boiling phenomenon to discharge ink (thermal method) ). Among these, a piezo method, a thermal method, and the like are preferable.
[0113]
Further, in another embodiment of the inkjet recording method of the present invention, when recording is performed by attaching an ink composition containing a coloring material to a recording medium, before recording, at the time of recording, or after recording, the recording medium includes a silicone-containing polyvinylpyrrolidone. The method is characterized in that a recording medium treatment liquid containing is attached to a recording medium.
[0114]
The ink composition is not particularly limited, but is preferably an ink composition of the present invention or an ink set including two or more of the ink compositions of the present invention.
[0115]
The ink jet method is the same as the above-described ink jet recording method. Also in this method, a piezo method, a thermal method, or the like is preferable.
[0116]
The recording medium treatment liquid of the present invention can be used as the recording medium treatment liquid.
The recording medium processing liquid is applied to the image recording surface before the ink composition is applied to the image recording surface, at the same time as the ink composition is applied to the image recording surface, or after the ink composition is applied to the image recording surface. Attach. Among them, by supplying the recording medium treatment liquid before applying the ink composition, preferably by applying the ink composition immediately after applying the recording medium treatment liquid, various characteristics required for a recorded image Can be obtained at a very high level.
[0117]
The recording medium treatment liquid is attached to the entire or a part of the image recording surface of the recording medium. When the ink composition is to be adhered to a part, the ink composition may be supplied to the same part where the ink composition is adhered.
[0118]
The treatment liquid for the recording medium is attached to the image recording surface by applying the treatment liquid to the image recording surface. For the application, a general method of applying a liquid material to a solid substrate can be adopted, for example, using a roll coater, an air knife coater, a blade coater, a brush, and the like, and spray coating, dipping coating (dipping). And so on.
[0119]
Further, as described later, an ink jet recording apparatus having a transfer roll for applying a recording medium treatment liquid to a recording medium can be used.
[0120]
The proportions of the ink composition and the treatment liquid for the recording medium are not particularly limited, and the type and content of each component contained in each, the type of the recording medium supplying these, the printing area of the recording medium, the ink jet method Can be appropriately selected from a wide range according to various conditions such as the type of the ink composition and the amount of the ink composition, but as one guide, for example, when the amount of the ink composition is about 1 to 50 pl, The processing liquid is usually 1 to 10 parts by weight based on 100 parts by weight of the ink composition.⁷Parts by weight, preferably 10 to 10⁷It is sufficient to use parts by weight.
[0121]
As the recording medium, those conventionally used can be used, and examples thereof include plain paper, postcards, color copy paper, inkjet paper, plastic sheets, plastic films, and the like.
[0122]
[Inkjet recording device]
FIG. 1 is a cross-sectional view showing a simplified configuration of an inkjet recording apparatus 1 according to the first embodiment. The inkjet recording apparatus 1 includes a recording medium supply unit 2 for supplying a recording medium 8 into the apparatus 1 and a recording medium transport unit for transporting the recording medium 8 supplied into the apparatus 1 by the recording medium supply unit 2. 3, a treatment liquid transfer means 4 provided to be included in the recording medium conveying means 3 for attaching a treatment liquid containing silicone-containing polyvinylpyrrolidone to the recording medium 8, and conveyed by the recording medium conveying means 3; A printing unit 5 for applying an ink composition containing a color material to the recording medium 8 to which the processing liquid has been applied by the processing liquid transfer unit 4 to print an image; And a discharging unit 6 for discharging the image 8 to the outside of the apparatus 1. The discharging unit 6 is arranged in this order from the upstream side to the downstream side in the transport direction of the recording medium 8 indicated by an arrow 9 in FIG. In it is located.
[0123]
The recording medium feeding means 2 includes a sheet feeding tray 7 for storing a recording medium 8, a sheet feeding roller 10 disposed downstream of the sheet feeding tray 7, and a separation plate 11.
[0124]
The recording medium conveying means 3 is configured to include two guide plates 12 and 18 and a pair of conveying rollers 19 arranged downstream of the guide plate 18, and between the guide plate 12 and the guide plate 18, A processing liquid transfer unit 4 is provided.
[0125]
The processing liquid transfer unit 4 includes a support roller 13, a transfer roller 14, a gravure roller 15, and an ink pan 16. The gravure surface of the gravure roller 15 is immersed in the processing liquid 17 in the ink pan 16. The processing liquid 17 is filled as described above. Although the support roller 13 and the transfer roller 14 are in contact with each other, they are arranged so that the recording medium 8 can pass between them. The transfer roller 14 and the gravure roller 15 are arranged so as to be in contact with each other.
[0126]
The printing unit 5 includes an ink head 20 that ejects and adheres the ink composition to the recording medium 8, and an ink that is integrated with the ink head 20 and moves the ink head 20 with respect to the printing surface 8 a of the recording medium 8. It includes a carriage 22, a guide shaft 23 that supports the ink carriage 22 slidably in a direction perpendicular to the drawing, and a platen 24 on which the recording medium 8 is placed.
[0127]
The discharge unit 6 includes a discharge roller 25 and a discharge tray 26.
Hereinafter, the operation of the inkjet recording apparatus 1 according to the present embodiment will be described.
[0128]
According to the ink jet recording apparatus 1, the recording medium 8 accommodated in the paper supply tray 7 is separated one by one by the paper supply roller 10 and the separation plate 11 which rotate in the direction of the arrow 10a according to the timing signal. The recording medium is supplied to the recording medium transport unit 3 and is transported to the processing liquid transfer unit 4 via the guide plate 12.
[0129]
In the processing liquid transfer means 4, when the gravure roller 15 is rotated in the direction of arrow 15a by a driving means (not shown), the processing liquid 17 filled in the ink pan 16 permeates the gravure surface of the gravure roller 15, and It adheres to the surface of the transfer roller 14. The processing liquid 17 adhering to the surface of the transfer roller 14 passes between the support roller 13 and the transfer roller 14 by rotating the transfer roller 14 in the direction of the arrow 14 a following the rotation of the gravure roller 15. The recording medium 8 comes into contact with the conveyed recording medium 8 and is transferred to the back side of the printing surface 8 a of the recording medium 8. At this time, since the recording medium 8 is pressed by the support roller 13 and the transfer roller 14, the processing liquid 17 permeates the printing surface 8a of the recording medium 8 without fail.
[0130]
The recording medium 8 to which the processing liquid has been applied in this manner is supplied to the transport roller 19 via the guide plate 18, further transported to the printing unit 5 by the transport roller 19, and prints on the platen 24 with the print surface 8 a facing upward. Placed on At this time, the ink composition is ejected from the ink head 20 and adheres to the print surface 8a of the recording medium 8 to form a recorded image. The recording medium 8 on which the recording image is formed is discharged in the direction of the arrow 27 via the discharge roller 26 and stored in the discharge tray 26.
[0131]
In the present embodiment, the processing liquid transfer unit 4 is provided so as to be included in the recording medium transport unit 3, but is not limited to this, and is provided between the transport roller 19 and the printing unit 5. You may.
[0132]
In the present embodiment, the recording medium 8 is reversed between the processing liquid transfer unit 4 and the transport roller 19 or between the transport roller 19 and the printing unit 5, and the ink composition is applied to the surface to which the processing liquid is applied. May be provided for reversing the recording medium 8 so that the recording medium 8 is ejected. Such a reversing means may follow a known method.
[0133]
[Ink head]
FIG. 2 is an exploded perspective view schematically showing a configuration of an ink head 31 according to a second embodiment used in the ink jet recording apparatus of the present invention. FIG. 3 is a diagram showing the configuration of the ink head 31 shown in FIG. FIG. 3 is an enlarged view showing a part of the configuration of a head plate 40 to be used. The description of the drive electrode 43 shown in FIG. 3 is omitted in FIG.
[0134]
The ink head 31 includes a head plate 40 having a flat bottom wall 41 made of a piezoelectric material and a plurality of partition walls 42 formed so as to stand upright at predetermined intervals from the bottom wall 41. A top plate 50 provided in contact with the upper surface of the portion 42, a nozzle plate 21 provided with a plurality of discharge ports 61 and provided at one end of the bottom wall portion 41, and provided at the other end portion of the bottom wall portion 41 It is configured to include a back plate (not shown) and an ink tank 80 having an opening 81 provided in contact with the upper surface of the top plate 50. The plurality of partitions 42 extend vertically from one end to the other end on the bottom wall 41 and are arranged in parallel with each other. The plurality of partitions 42, the bottom wall 41, the top plate 50, and the nozzle A plurality of ink chambers 70 are formed by the plate 21 and a back plate (not shown). An ink supply path 51 communicating with each ink chamber 70 and an ink supply pipe 52 connecting the ink supply path 51 and the opening 81 of the ink tank 80 are formed in the top plate 50. An ink composition 90 is stored in the ink tank 80, and the ink composition 90 flows through the ink supply path 51 and is supplied to each ink chamber 70.
[0135]
Further, as shown in FIG. 3, a drive electrode 43 for applying a voltage to the plurality of partition portions 42 is provided on a surface of the bottom wall portion 41 of the head plate 40 and the plurality of partition portions 42 facing the ink chamber 70. Further, the piezoelectric material forming the plurality of partition portions 42 is polarized in the direction of arrow 95, and the plurality of partition portions 42 function as piezoelectric elements.
[0136]
FIG. 4 is a cross-sectional view of the ink head 31 shown in FIG. Although FIG. 4 shows three ink chambers 70a, 70b, and 70c, an operation of discharging the ink composition 90 from the ink chamber 70b will be described.
[0137]
When no voltage is applied to the partition portions 42a and 42b constituting the ink chamber 70b, that is, between the drive electrode 43b of the ink chamber 70b and the drive electrode 43a of the ink chamber 70a, and between the drive electrode 43b of the ink chamber 70b and the ink. When a potential difference is not generated between the driving electrode 43c of the chamber 70c and the driving electrode 43c, the ink chamber 70b is filled with the ink composition 90 supplied from the ink tank 80 by capillary action. Similarly, the ink chambers 70 a and 70 c are also filled with the ink composition 90.
[0138]
When a voltage is applied to the drive electrode 43a and the drive electrode 43c, a potential difference is generated between the drive electrode 43b and the drive electrode 43a, and between the drive electrode 43b and the drive electrode 43c. When a voltage is applied to 42a and 42b, an electric field in the directions of arrows 96 and 97 is generated in the partition portions 42a and 42b, respectively. Due to the action of the electric field, the partition walls 42a and 42b constituting the ink chamber 70b are distorted and deformed so as to protrude toward the ink chamber 70b. As a result, a pressure wave is generated, a large pressure is applied to the ink composition 90 in the ink chamber 70b, and the droplet of the ink composition 90 is ejected from the ejection port 61.
[0139]
When the application of the voltage to the drive electrode 43a and the drive electrode 43c is stopped, the shape of the partition walls 42a and 42b returns to the original shape, and the volume of the ink chamber 70b returns to the original volume. The ink is supplied from the ink tank 80 via the supply path 51, and the ink chamber 70b returns to a state where the ink composition 90 is filled.
[0140]
In the present embodiment, the partition 42 forming the ink chamber 40 is formed of a piezoelectric material and functions as a piezoelectric element. However, the present invention is not limited to this, and the partition forming the ink chamber is formed of a material other than the piezoelectric material. The piezoelectric element may be formed inside or outside the partition.
[0141]
When recording is performed using the ink composition according to the method of the present invention in a piezo-type inkjet recording apparatus including the ink head 31, the wettability to the ink supply system in the ink head is improved, and the ink supply is smooth. Therefore, a highly reliable piezo-type inkjet recording apparatus can be realized.
[0142]
FIG. 5 is an exploded perspective view schematically showing a configuration of an ink head 101 according to a third embodiment used in the ink jet recording apparatus of the present invention, and FIG. 6 is a perspective view of the ink head 101 shown in FIG. It is a top view which shows a part of structure. The description of the top plate 50 and the ink tank 80 shown in FIG. 5 is omitted in FIG. The ink head 101 is similar to the ink head 31, and the corresponding parts are denoted by the same reference numerals and description thereof will be omitted.
[0143]
The ink head 101 includes a head plate 102, a substrate 103, a plurality of partition walls 104 extending vertically from one end to the other end at predetermined intervals on the substrate 103, and arranged in parallel with each other; It is characterized by including a heater 105 as a heating element provided on a surface of the 103 facing the ink chamber 70, and drive electrodes 106 and 107 for applying a voltage to the heater 105.
[0144]
FIG. 7 is a cross-sectional configuration of the ink head 101 shown in FIG. 5 taken along a cutting plane line II, and shows a state in which droplets 91 of the ink composition 90 are ejected from the ink chamber 70.
[0145]
When no voltage is applied to the heater 105, the ink chamber 70 is filled with the ink composition 90, as in the case where no voltage is applied to the partition 42 in the ink head 31 described above.
[0146]
When a voltage is applied to the heater 105 by the drive electrodes 106 and 107, the heater 105 generates heat, and the ink composition 90 in the ink chamber 70 is heated, so that bubbles 92 are generated. As a result, a pressure wave is generated, a large pressure is applied to the ink composition 90 in the ink chamber 70, and the droplet 91 of the ink composition 90 is ejected from the ejection port 61.
[0147]
When the application of the voltage to the heater 105 is stopped, the ink composition 90 in the ink chamber 70 is cooled, the bubbles 92 disappear, and the ink composition 90 corresponding to the volume of the disappeared bubbles is supplied through the ink supply path 51. The ink is supplied from the tank 80, and the ink chamber 70 returns to a state where the ink composition 90 is filled.
[0148]
In the thermal inkjet type inkjet recording apparatus including the ink head 101 according to the present embodiment, when recording is performed using the ink composition according to the present invention, the wettability to the ink supply system in the head is improved, and Is supplied smoothly, so that a highly reliable thermal inkjet recording apparatus can be realized.
[0149]
[Example]
Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples, and Test Examples. In the following, “%” means “% by weight” unless otherwise specified.
[0150]
Example 1 and Comparative Example 1 (production of recording medium)
The components were mixed at the ratios shown in Table 1 (%, resin components are shown by solid content), and water was added thereto to make the total amount 100%. This mixture was stirred at 25 ° C. for 1 hour to prepare a recording medium treatment liquid.
[0151]
In addition, the resin component and surfactant in Table 1 are specifically as follows.
[0152]
(Resin component)
GAFQUAT HSi: trade name, manufactured by ISP, a copolymer of vinylpyrrolidone and methacrylamidopropyltrimethylammonium chloride containing polymethylsiloxane, 20% aqueous solution.
10% PVA: 10% aqueous solution of polyvinyl alcohol
[0153]
(Surfactant)
Ethylene oxide compound 2A: a compound of general formula (2) wherein d + e = 10, trade name Surfynol 465, manufactured by Nissin Chemical Co., Ltd.
Ethylene oxide compound 2B: a compound having d + e = 3.5 in the general formula (2), trade name Surfynol 440, manufactured by Nissin Chemical Co., Ltd.
Ethylene oxide compound 5A: a compound in which k + 1 = 11, q = 9, and r = 5 in the general formula (5), trade name SOFTANOL 9050, manufactured by Nippon Shokubai Co., Ltd.
[0154]
[Table 1]

[0155]
The recording medium treatment liquid obtained above was applied to a paper having a Stöckigt sizing degree of 10 seconds by a transfer type rubber roller at an application amount of 8 g / m2.²Then, the recording medium of Example 1 (No. 1 to 5) and the recording medium of Comparative Example 1 (No. 6 to 7) were manufactured.
[0156]
Example 2 (Preparation of ink composition)
Each component was mixed at the ratio (%) shown in Table 2, and water was added thereto to make the total amount 100%. After stirring this mixture at 25 ° C. for 1 hour, the mixture was filtered under pressure using a 1.2 μm membrane filter to prepare ink compositions (Nos. I to E).
[0157]
In Table 2, the surfactants and fixing agents described by trade names are specifically as follows.
[0158]
(Surfactant)
Surfynol 2502, Surfynol 465: both acetylene-based nonionic surfactants containing ethylene oxide, manufactured by Air Products
[0159]
(Fixing agent)
Vylonal MD1400, polyester emulsion (water-dispersible resin), manufactured by Toyobo Co., Ltd.
[0160]
[Table 2]

[0161]
Test example 1
The recording medium No. obtained in Example 1 and Comparative Example 1 was used. Nos. 1 to 7 and the ink compositions No. 1 obtained in Example 2. The following evaluation tests were performed using a to e. Table 3 shows the results.
[0162]
[Print density (image density)]
The ink head of an ink jet printer (trade name: AJ2000, manufactured by Sharp Corporation) was modified so that it could be replaced with the ink head of the present invention. (Name: X-Lite 938, manufactured by Macbeth). Compared to the solid print density of the paper to which the recording medium treatment liquid was not applied, those having an increased density were evaluated as “○”, those that did not change were evaluated as “Δ”, and those that decreased were evaluated as “x”.
[0163]
[Feathering]
A test pattern was printed on a recording medium, and the line width of the pattern was measured. The line width of paper on which the recording medium treatment liquid was not applied was set to 100, and the relative value was evaluated. Those with less than 100 were evaluated as “「 ”, those with 100 to 120 were evaluated as“ Δ ”, and those with 120 or more were evaluated as“ x ”.
[0164]
[Table 3]

[0165]
From Table 3, it is clear that when recording is performed on a recording medium holding a silicone-containing vinylpyrrolidone copolymer, the occurrence of feathering is prevented, and a recorded image having a high print density (image density) is formed. . On the other hand, in Comparative Example 1, When the recording medium No. 6 is used, the print density does not decrease significantly, but it is found that feathering occurs remarkably. Also, in Comparative Example 1, It can be seen that when the recording medium No. 7 was used, the print density was remarkably reduced and feathering was extremely generated.
[0166]
Example 3 and Comparative Example 2
The recording media of Example 3 (Nos. 8 to 12) and Comparative Example 2 were prepared in the same manner as in Example 1 except that paper having a Steckigt size of 21 seconds was used instead of paper having a Steckigt size of 10 seconds. No. 13 to 14 were manufactured.
[0167]
Test example 2
Using the recording media obtained in Example 3 and Comparative Example 2, the print density and the presence or absence of feathering were evaluated in the same manner as in Test Example 1. Table 4 shows the results.
[0168]
[Table 4]

[0169]
Table 4 shows that the effect of preventing feathering is insufficient even when a silicone-containing vinylpyrrolidone-based copolymer is supported on paper having a degree of Steckigt size of more than 20 seconds.
[0170]
Test example 3
The recording medium treating liquid No. 1 obtained in Example 1 and Comparative Example 1 was used. 1 to 7 and the ink compositions Nos. 1 to 3 obtained in Example 2. (A) to (e) were mixed, and whether or not aggregation and precipitation occurred was visually observed. Table 5 shows the results. In Table 5, the case where aggregation / precipitation occurs is indicated by “○”, and the case where aggregation / precipitation does not occur is indicated by “×”.
[0171]
[Table 5]

[0172]
From Table 5, it is clear that the recording medium treatment liquid containing silicone-containing polyvinylpyrrolidone causes aggregation and precipitation when mixed with the ink composition.
[0173]
Example 4 and Comparative Example 3 (production of recording medium)
A recording medium treatment liquid was prepared in the same manner as in Example 1 except that each component was used in the proportions (%, resin components indicated by solid content) shown in Table 6, and the recording medium of Example 4 (No. 15) To 19) and Comparative Example 3 (Nos. 20 to 21) were produced.
[0174]
[Table 6]

[0175]
Example 5 (Preparation of ink composition)
An ink composition (No. 1 to No. 2) was prepared in the same manner as in Example 2 except that each component was used at the ratio (%) shown in Table 7.
[0176]
In addition, the surfactant shown by a brand name in Table 7 is specifically as follows.
[0177]
Surfynol 440: acetylene-based nonionic surfactant containing ethylene oxide, manufactured by Air Products
Acrylic resin emulsion: trade name: John Krill 734, manufactured by Johnson Polymer
[0178]
[Table 7]

[0179]
Test example 4
The recording medium No. obtained in Example 4 and Comparative Example 3 was used. 15 to 21 and the ink composition Nos. The print densities (image densities) and the presence or absence of feathering were evaluated in the same manner as in Test Example 1 by using a gel. Table 8 shows the results.
[0180]
[Table 8]

[0181]
From Table 8, it is clear that when recording is performed on a recording medium holding a silicone-containing vinylpyrrolidone copolymer, the occurrence of feathering is prevented, and a recorded image having a high print density (image density) is formed. . On the other hand, in Comparative Example 3 When the recording media No. 20 were used, the print density was not significantly reduced, but it was found that feathering occurred remarkably. Also, in Comparative Example 3, It is found that when the recording medium No. 21 is used, the print density is remarkably lowered and feathering is extremely generated.
[0182]
Example 6 and Comparative Example 4 (production of recording medium)
The recording media of Example 6 (Nos. 22 to 26) and Comparative Example 4 were carried out in the same manner as in Example 4 except that paper having a Stighit size of 21 seconds was used instead of paper having a Stighit size of 10 seconds. (No. 27 to 28) were manufactured.
Test example 5
The recording medium No. obtained in Example 6 and Comparative Example 4 was used. 22 to 28, the print density and the presence or absence of feathering were evaluated in the same manner as in Test Example 4. Table 9 shows the results.
[0183]
[Table 9]

[0184]
From Table 9, it can be seen that the effect of preventing feathering is almost fully exhibited when a silicone-containing vinylpyrrolidone-based copolymer is supported, even on paper having a Steckigt sizing degree exceeding 20 seconds.
[0185]
Test Example 6
The recording medium treatment liquid No. obtained in Example 4 and Comparative Example 3 was used. 15 to 21 and the ink composition Nos. And each of them was mixed with each other, and whether or not aggregation and precipitation occurred was visually observed. Table 5 shows the results. In Table 5, the case where aggregation / precipitation occurs is indicated by “○”, and the case where aggregation / precipitation does not occur is indicated by “×”.
[0186]
[Table 10]

[0187]
From Table 10, it is clear that the treatment liquid containing the silicone-containing polyvinylpyrrolidone causes aggregation and precipitation when mixed with the ink.
[0188]
Example 7 (production of recording medium)
A recording medium treatment liquid was prepared in the same manner as in Example 1 except that each component was used at the ratio (%) shown in Table 11. In addition, the resin component was shown by the solid content. 8 g / m2 of this recording medium treatment liquid was applied to PPC paper (trade name: SF4AM3, manufactured by Sharp Corporation) using a transfer type rubber roller.²Of the recording medium of the present invention. 29-33 were produced.
[0189]
[Table 11]

[0190]
Examples 8 to 14 (Preparation of ink composition)
Ink compositions of the present invention and comparative examples were prepared in the same manner as in Example 2 except that each component was used at a ratio (%) shown in Table 12. In addition, the pigment dispersion and the resin component were shown by solid content. The following evaluation tests were performed on these ink compositions. The results are shown in Table 12.
[0191]
[High-speed printability]
Using a printer in which the ink head of an inkjet printer (trade name: AJ2000, manufactured by Sharp Corporation) is replaced with the ink head of the present invention, printing is continuously performed at a print density of 5% and 10 PPM (10 sheets / min). The number of sheets on which a recorded image having good image quality can be printed was examined. When the number of printed sheets exceeded 200, the result was evaluated as “○”, when the number of printed sheets was 150 to 200, the result was evaluated as “△”, and when the number was less than 150, the result was evaluated as “x”.
[0192]
[Dryability]
Immediately after printing was completed, the same paper as the printing paper was pressed against the printing surface for 15 seconds, and those that did not transfer the printing were evaluated as “O”, and those that transferred were evaluated as “X”.
[0193]
[Smearability]
After printing a specific pattern on PPC paper (trade name: SF4AM3, manufactured by Sharp Corporation) and leaving it for one day, measure the line width of the pattern. The evaluation was performed as a value. Those with less than 150 were evaluated as “「 ”, those with 150 to 250 as“ Δ ”, and those with more than 250 as“ x ”.
[0194]
[Foaming property]
After the ink composition was shaken for 20 seconds and allowed to stand for 5 minutes, the bubble height was measured, and those having a height of 10 mm or less were evaluated as "O" and those exceeding 10 mm were evaluated as "X". The higher the foam height, the higher the foamability. The ink composition having a high foaming property generates bubbles in the discharge nozzle, and the nozzle bites the bubbles, so that the amount of discharged droplets is likely to change. An ink composition having a high foaming property has low ejection stability and cannot be used for high-speed printing.
[0195]
[Table 12]

[0196]
From Table 12, when pigments such as Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Red 122, Pigment Yellow 74, and Pigment Yellow 180 and dyes such as Direct Blue 199 are used, four kinds of evaluations are performed at a high level. It is clear that a satisfying ink composition is obtained.
[0197]
Test example 7
Using the recording medium obtained in Example 7 and the ink compositions obtained in Examples 8 to 12, the print density and the presence or absence of feathering were evaluated in the same manner as in Test Example 1. Table 13 shows the results.
[0198]
[Table 13]

[0199]
From Table 13, it can be seen that when a recording image is formed on the recording medium of the present invention using an ink composition containing a specific pigment and further containing a water-soluble organic solvent, a nonionic surfactant and a fixing agent, feathering is remarkable. It is clear that a recorded image with high print density can be obtained.
[0200]
Test Example 8
From the ink compositions of Examples 8 to 12, cyan ink, magenta ink and yellow ink were selected in combinations shown in Table 14, and the same ink jet printer as in Test Example 1 was used. 29, three-color black was printed at a printing ratio of 1: 1: 1.
[0201]
On the other hand, using the ink composition of Example 13, the recording medium No. 29 printed.
[0202]
Three color black and black single color printing are applied to a colorimeter (X-Rite 938), and a^*And b^*Was measured. Three color black a^*To A2, b^*Is B2, black monochromatic a^*To A1, b^*Is B1, the value represented by the following equation (Δa^*b^*) Was 20 or less as “○”, and those larger than 20 were evaluated as “x”. Table 14 shows the results.
Δa^*b^*= ｛(A1-A2)²+ (B1-B2)²｝^1/2
[0203]
[Table 14]

[0204]
From Table 14, it can be seen that the black images (1) to (4) obtained by superimposing the three types of ink compositions selected from Examples 8 to 12 are black images having a high image density. That is, it can be seen that the four types of ink sets of the present invention have good black reproducibility and excellent color balance.
[0205]
As described above, C.I. I. A cyan ink composition containing at least one pigment selected from the group consisting of C.I. Pigment Blue 15: 3 and 15: 4; I. Pigment Red 122, 209 and C.I. I. Pigment Violet 19, a magenta ink composition containing at least one pigment selected from the group consisting of C.I. I. It can be seen that an ink set having an excellent color balance can be obtained by combining with a yellow ink composition containing at least one pigment selected from the group consisting of CI Pigment Yellow 74, 138, 150 and 180.
[0206]
【The invention's effect】
According to the present invention, the presence of the silicone-containing vinylpyrrolidone-based copolymer on the surface and / or inside of the recording medium allows the silicone-containing vinylpyrrolidone-based copolymer to immobilize a dye or pigment as a coloring material. , Dyes or pigments can be prevented from penetrating and diffusing into the inside of the recording medium or into the margins of the surface, and the occurrence of bleeding is significantly prevented, and feathering and color mixing do not occur. A uniform, clear outline portion, high image density and sharpness, and a high quality image can be formed by the ink jet method.
[0207]
According to the present invention, the ink composition can be appropriately adjusted with respect to the recording medium of the present invention by using, as a substrate on which the silicone-containing vinylpyrrolidone-based copolymer is present, a substrate having a Stigget sizing degree of 20 seconds or less. Because of the permeation, feathering is prevented, the image density is further increased, and the quality of the obtained recorded image is further improved.
[0208]
According to the present invention, among the silicone-containing vinylpyrrolidone-based copolymers, the occurrence of bleeding is caused by using those having a core-shell structure in which the core is made of silicone and the shell is made of a vinylpyrrolidone-based copolymer. This is further prevented, and the image quality of the recorded image is improved.
[0209]
According to the present invention, the use of a vinylpyrrolidone-based copolymer containing a polyalkylsiloxane as the silicone further improves the quality of recorded images.
[0210]
According to the present invention, by using a vinylpyrrolidone copolymer comprising vinylpyrrolidone and one or more monomer compounds selected from a specific quaternary ammonium compound and an amine compound, the surface and the inside of a recording medium can be obtained. With this, the coloring material can be firmly fixed.
[0211]
According to the present invention, a vinylpyrrolidone-based copolymer is contained, and if necessary, a water-soluble organic solvent (preferably polyhydric alcohol or glycol ether), a surfactant (preferably a nonionic surfactant), The recording medium of the present invention can be manufactured by treating the recording medium with a recording medium treatment liquid that may contain a mold agent or the like.
[0212]
According to the present invention, the composition contains a dye or pigment that reacts with the silicone-containing vinylpyrrolidone copolymer to form a precipitate, and further includes a water-soluble organic solvent, a nonionic surfactant, a synthetic resin (fixing And an ink composition suitable for forming a recorded image on the recording medium of the present invention.
[0213]
According to the present invention, in the ink composition of the present invention, by using a self-dispersed pigment as a pigment, the storage stability of the ink composition is improved, and during storage of the ink composition, the cause of clogging of the discharge nozzle is reduced. And the occurrence of aggregation and sedimentation of the pigment is prevented.
[0214]
According to the present invention, among the ink compositions of the present invention, a cyan-based, magenta-based, yellow-based, and black-based ink composition containing a specific pigment, and an ink set containing two or more of these are preferable. By using these ink compositions or ink sets, a recorded image having extremely good color balance and high image quality can be formed.
[0215]
According to the present invention, the ink composition is applied to the recording medium by an inkjet recording method, or before, simultaneously with or after the application of the ink composition, By adhering the above-described recording medium processing liquid, a high-quality image can be formed.
[0216]
According to the present invention, there is provided an ink jet recording apparatus suitable for carrying out the ink jet recording method of the present invention, capable of forming a recorded image of high quality, and capable of easily performing high-speed printing. .
[0217]
According to the present invention, there are provided piezo-type and thermal-type ink heads capable of continuously and stably discharging the above-described ink composition and suitable for performing high-speed printing.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view schematically illustrating a configuration of an inkjet recording apparatus of the present invention.
FIG. 2 is an exploded perspective view schematically showing a configuration of an ink head used in the ink jet device of the present invention.
3 is an enlarged view showing a part of a configuration of a head plate included in the ink head shown in FIG. 2;
FIG. 4 is a sectional view of the ink head shown in FIG. 2 as viewed from the direction in which the ink chamber extends.
FIG. 5 is an exploded perspective view schematically showing a configuration of an ink head used in the ink jet recording apparatus of the present invention.
FIG. 6 is a plan view showing a part of the configuration of the ink head shown in FIG. 5;
FIG. 7 is a drawing showing a cross-sectional configuration of the ink head shown in FIG. 6 along a cutting plane line II.
[Explanation of symbols]
1 inkjet recording device
2 Recording medium supply means
3 Recording medium transport means
4 Processing liquid transfer means
5 printing means
6 means of discharge
7 Paper tray
8 Recording media
8a Printing surface
9, 10a, 13a, 14a, 15a, 27, 95, 96, 97
10 Paper feed roller
11 Separation plate
12, 18 Guide plate
13 Support rollers
14 Transfer roller
15 Gravure roller
16 Ink pan
17 Treatment liquid
19 Transport roller
20 ink head
21 Nozzle plate
22 Ink carriage
23 Guide shaft
24 Platen
25 Discharge roller
26 Ejection tray
31, 101 ink head
40,102 head plate
41 Bottom wall
42, 42a, 42b Partition part
43, 43a, 43b, 43c, 106, 107 Drive electrode
50 Top plate
51 Ink supply path
60 Nozzle plate
61 Discharge port
70, 70a, 70b, 70c Ink chamber
80 Ink tank
81 Opening
90 ink composition
91 droplets
92 bubbles
103 substrate
104 partition
105 heater

Claims (23)

A recording medium characterized in that a recording medium treatment liquid containing a vinylpyrrolidone-based copolymer containing silicone as an active ingredient is applied to the surface of a substrate and / or impregnated inside the substrate. 2. The recording medium according to claim 1, wherein the substrate has a Steckigt sizing degree of 20 seconds or less. 3. The recording medium according to claim 1, wherein the vinylpyrrolidone-based copolymer containing silicone has a core-shell structure in which silicone is used as a core and the vinylpyrrolidone-based copolymer is used as a shell. The recording medium according to any one of claims 1 to 3, wherein the silicone is a polyalkylsiloxane. Vinylpyrrolidone-based copolymer, _-X- vinylpyrrolidone and general formula ^{_{CH 2 = CR 1 (CH 2}} ) a -Y (1)
[In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X represents a group -COO-, a group -CO-, a group -CONH- or a methylene group. Y represents a quaternary ammonium group or a dialkylamino group. a shows the integer of 1-10. ]
A copolymer with one or more monomer compounds selected from quaternary ammonium compounds having a polymerizable double bond group and amine compounds represented by the following formula: The recording medium according to any one of the above. A recording medium treatment liquid comprising a silicone-containing vinylpyrrolidone copolymer as an active ingredient, and the balance being water. The recording medium processing liquid according to claim 6, further comprising one or more selected from a water-soluble organic solvent, a surfactant, and a fungicide. The recording medium treatment liquid according to claim 7, wherein the water-soluble organic solvent is one or more kinds selected from polyhydric alcohols and glycol ethers. 9. The recording medium processing liquid according to claim 7, wherein the surfactant is a nonionic surfactant. A water-based ink containing a dye or pigment as a color material and the remainder being water, wherein the color material reacts with a silicone-containing vinylpyrrolidone-based copolymer to form a precipitate. An ink composition comprising: The ink composition according to claim 10, further comprising one or more selected from a water-soluble organic solvent, a nonionic surfactant, and a synthetic resin. 12. The ink composition according to claim 10, wherein the pigment is a self-dispersed pigment obtained by introducing a hydrophilic group to the surface of the pigment. 13. The pigment is one or more cyan pigments selected from Pigment Blue 15: 3, Pigment Blue 15: 4 and Pigment Blue 15: 6. Ink composition. 13. The ink composition according to claim 10, wherein the pigment is one or more magenta pigments selected from Pigment Red 122, Pigment Red 209, and Pigment Violet 19. The pigment is one or more yellow pigments selected from Pigment Yellow 74, Pigment Yellow 128, Pigment Yellow 138, Pigment Yellow 150, and Pigment Yellow 180. The pigment according to any one of claims 10 to 12, wherein: 3. The ink composition according to claim 1. The ink composition according to any one of claims 10 to 12, wherein the pigment is carbon black. An ink set comprising two or more kinds selected from the ink compositions according to claim 13. An ink jet recording method for performing recording by attaching an ink composition to a recording medium, wherein the recording medium is the recording medium according to any one of claims 1 to 4. In the ink jet recording method of performing recording by adhering an ink composition to a recording medium, adhering the recording medium treatment liquid according to any one of claims 6 to 9 to a recording medium before, simultaneously with, or after recording. An ink jet recording method characterized by the above-mentioned. Recording medium supply means for supplying a recording medium, recording medium conveyance means for conveying the recording medium supplied by the recording medium supply means, and recording by attaching the ink composition to the recording medium conveyed by the recording medium conveyance means. In the ink jet recording apparatus including a printing unit that performs, and a discharging unit that discharges a recording medium on which a recording image is formed by the printing unit,
10. An ink jet recording apparatus, comprising: a processing liquid transfer unit for applying the recording medium processing liquid according to claim 6 to a recording medium. The processing liquid transfer means,
21. The ink jet recording apparatus according to claim 20, wherein the recording apparatus is provided so as to be included in the recording medium conveying means or between the recording medium conveying means and the printing means. An ink tank for storing the ink composition according to any one of claims 10 to 16,
An ink chamber having an ejection port for ejecting the ink composition supplied from the ink tank as droplets,
A piezoelectric element that is provided in the ink chamber, generates strain in response to an applied voltage, and applies pressure to the ink composition;
An electrode for applying a voltage to the piezoelectric element. An ink tank for storing the ink composition according to any one of claims 10 to 16,
An ink chamber having an ejection port for ejecting the ink composition supplied from the ink tank as droplets,
A heating element that is provided in the ink chamber, generates heat in response to an applied voltage, and applies pressure to the ink composition by generating bubbles in the ink composition;
An electrode for applying a voltage to the heating element.

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