JP4196559B2 - Colored fine particles, inkjet recording ink containing the colored fine particles, method for producing the ink, and inkjet recording method - Google Patents

Description

【００６５】
【化１４】

【００６６】
【化１５】

【００６７】
【化１６】

【００６８】
【化１７】

【００６９】
【化１８】

【００７０】
【化１９】

【００７１】
【化２０】

【００７２】
【化２１】

【００７３】
【化２２】

【００７４】
【化２３】

【００７５】
【化２４】

【００７６】
《一般式（Ｈ）で表される金属錯体色素》
上記記載の、一般式（Ａ）〜一般式（Ｇ）で表される色素の金属錯体と同様に用いられる、前記一般式（Ｈ）で表される金属錯体色素について説明する。
【００７７】
一般式（Ｈ）において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄で、各々表される置換基としては、一般式（Ｅ）において、Ｒ₁、Ｒ₂で表される置換基、Ｒ₃で表される置換基と同義であるが、好ましくはハロゲン原子、炭素数１〜８のアルキル基（例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ｉｓｏ−ペンチル基、２−エチル−ヘキシル基、オクチル基等）、アリール基（例えば、フェニル基、ナフチル基等）、複素環基（例えば、イミダゾリル基、チアゾリル基、ベンゾオキサゾリル基、ピリジル基、ピロリル基、インドリル基、ピリミジニル基等）、アシル基（例えば、アセチル基、ベンゾイル基等）、アミノ基（例えばアミノ基、Ｎ，Ｎ−ジメチルアミノ基、Ｎ，Ｎ−ジエチルアミノ基等）、アルコキシル基（例えば、メトキシ基、エトキシ基、プロポキシ基等）である。
【００７８】
また、Ｒ₁〜Ｒ₄の少なくとも１つがハロゲン原子または前記の置換基であることがより好ましく、更に好ましくは、ｍおよびｎが互いに１であり、Ｒ₁、Ｒ₃及びＲ₄が水素原子であってＲ₂がハロゲン原子または前記の置換基の場合である。
【００７９】
一般式（Ｈ）において、Ｙ₁は、３縮合複素環、４縮合複素環または置換基を有する２縮合複素環を表すが、ここで、３縮合複素環とは、少なくとも１つが複素環である３つの環が縮合した構造を有し、４縮合複素環とは、少なくとも１つが複素環である４つの環が縮合した構造を有し、３縮合複素環、４縮合複素環は、各々、置換基を有していても、無置換でもよい。また、置換基を有する２縮合複素環とは、少なくとも１つが複素環である２個の環が縮合した構造を有し、且つ、環上に置換基を有するものである。前記２縮合複素環の置換基としては、一般式（Ａ）に記載の芳香族炭素環の置換基、複素環の置換基と同義である。
【００８０】
一般式（Ｈ）において、Ｍで表される金属イオンは、上記記載の色素の金属錯体における、Ｍ^l+で表される金属イオンと同義である。
【００８１】
一般式（Ｈ）において、Ｚで表される陰イオンとしては、ハライドイオン（フルオライド、クロライド、ブロマイド、アイオダイド等）、亜硫酸イオン、硫酸イオン、アルキル又はアリールスルホン酸イオン、硝酸イオン、亜硝酸イオン、過塩素酸イオン、カルボキシレート（アセテート、トリフルアセテート、ステアリレート等）、サリシネート、ベンゾエート、ヘキサフルオロホスフェート、テトラフルオロボレート等が挙げられる。
【００８２】
一般式（Ｈ）において、Ｘ₁としては、前記一般式（Ｈ−１）〜一般式（Ｈ−４）で表される２価の置換基が好ましく用いられる。
【００８３】
一般式（Ｈ−１）〜（Ｈ−４）で各々表される２価の置換基において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇で各々表される置換基としては、一般式（Ａ）に記載の芳香族炭素環の置換基、複素環の置換基と同義である。
【００８４】
一般式（Ｈ−１）において、Ｒ₁、Ｒ₂の少なくとも１つは一般式（Ｈ−１）の窒素原子とともに、金属イオンＭに対して少なくとも２座の配位結合を形成することが可能な置換基を表す。
【００８５】
一般式（Ｈ−２）において、Ｒ₃は一般式（Ｈ−２）の窒素原子とともに、金属イオンＭに対して少なくとも２座の配位結合を形成することが可能な置換基を表す。
【００８６】
一般式（Ｈ−３）において、Ｒ₃、Ｒ₄の少なくとも１つは一般式（Ｈ−３）の窒素原子とともに、金属イオンＭに対して少なくとも２座の配位結合を形成することが可能な置換基を表す。
【００８７】
一般式（Ｈ−４）において、Ｌ₁は窒素原子または−ＣＲ₈＝を表し、Ｌ₂は窒素原子または−ＣＲ₉＝を表し、Ｌ₃は窒素原子または−ＣＲ₁₀＝を表す。
【００８８】
ここで、Ｒ₈、Ｒ₉およびＲ₁₀で各々表される置換基としては、水素原子、ハロゲン原子（フッ素原子、塩素原子、臭素原子、沃素原子）または一般式（Ａ）に記載の芳香族炭素環の置換基、複素環の置換基等が挙げられる。
【００８９】
また、Ｒ₈、Ｒ₉およびＲ₁₀のうち少なくとも一つは、一般式（Ｈ−４）の窒素原子とともに、金属原子に対して少なくとも２座の配位結合を形成することが可能な原子の集まりを表す。
【００９０】
一般式（Ｈ）において、Ｙ₁で表される３縮合複素環、４縮合複素環または置換基を有する２縮合複素環を含む２価の置換基としては、上記の一般式（Ｙ−１）〜（Ｙ−１１）からなる置換基群が好ましく用いられる。
【００９１】
ここで、一般式（Ｙ−１）〜一般式（Ｙ−１１）からなる置換基群について説明する。
【００９２】
一般式（Ｙ−１）〜（Ｙ−１１）において、Ｒ₁、Ｒ₂で表されるハロゲン原子としては、フッ素原子、臭素原子、塩素原子、沃素原子が挙げられる。
【００９３】
一般式（Ｙ−１）〜（Ｙ−１１）において、Ｒ₁、Ｒ₂で表されるアルキル基としては、例えばメチル基、エチル基、ブチル基、ペンチル基、２−メトキシエチル基、トリフルオロメチル基、２−エチルヘキシル基などが挙げられる。これらの置換基は更に置換基を有していても良い。
【００９４】
一般式（Ｙ−１）〜（Ｙ−１１）において、Ｒ₁、Ｒ₂で表されるアリール基としては、フェニル基、ナフチル基等が挙げられる。これらの置換基は更に置換基を有していても良い。
【００９５】
一般式（Ｙ−１）〜（Ｙ−１１）において、Ｒ₁、Ｒ₂で表されるアルコキシル基としては、例えば、メトキシ基、エトキシ基、ブトキシ基等が挙げられる。これらの置換基は更に置換基を有していても良い。
【００９６】
一般式（Ｙ−１）〜（Ｙ−１１）において、Ｒ₁、Ｒ₂で表されるアルキルチオ基としては、例えば、メチルチオ基、エチルチオ基、オクチルチオ基等が挙げられる。これらの置換基は更に置換基を有していても良い。
【００９７】
一般式（Ｙ−１）〜（Ｙ−１１）において、Ｒ₁、Ｒ₂で表されるアリールチオ基としては、例えば、フェニルチオ基、ｐ−トリルチオ基等が挙げられる。これらの置換基は更に置換基を有していても良い。
【００９８】
一般式（Ｙ−１）〜（Ｙ−１１）において、Ｒ₁、Ｒ₂で表されるアミノ基としては、例えば、アミノ基、メチルアミノ基、ジエチルアミノ基、メトキシエチルアミノ基、フェニルアミノ基等が挙げられる。これらの置換基は更に置換基を有していても良い。
【００９９】
一般式（Ｙ−１）〜（Ｙ−１１）において、Ｙ₁₁、Ｙ₁₂は、各々、−（ＮＲ₅）−基を表すが、前記Ｒ₅で表される置換基としては、アルキル基（例えば、メチル基、エチル基、ブチル基、ペンチル基、２−メトキシエチル基、トリフルオロメチル基、２−エチルヘキシル基等）、アリール基（フェニル基、ナフチル基等）が挙げられる。これらの置換基は更に置換基を有していても良い。
【０１００】
本発明に記載の効果をより好ましく得る観点から、上記一般式（Ｙ−１）〜（Ｙ−１１）の中で、Ｙ₁₁、Ｙ₁₂の少なくとも一方、またはＹ₂₁、Ｙ₂₂、Ｙ₂₃のうちで少なくとも１つが−（ＮＲ₅）−基であることが好ましく、更に好ましくは、Ｙ₁₁とＹ₁₂がともに−（ＮＲ₅）−基である場合には、各々のＲ₅の炭素原子数の合計が３以上であるように調整することである。
【０１０１】
また、好ましい態様のひとつとしては、前記一般式（Ｙ−１）、（Ｙ−４）または（Ｙ−８）で表される縮合環化合物残基を用いることであり、また、別の好ましい態様のひとつとしては、前記一般式（Ｙ−１）、（Ｙ−４）または（Ｙ−８）においてｍ１またはｍ２のうち少なくともどちらかが０ではなく、且つ、前記一般式（Ｙ−１）、（Ｙ−４）または（Ｙ−８）で表される化合物残基が置換基を有する２縮合複素環化合物残基の場合である。
【０１０２】
また、上記記載の一般式（Ｈ−１）〜（Ｈ−４）の中でも、好ましく用いられるのは、下記一般式（Ｘ−１）〜（Ｘ−８）で表される部分構造パーツである。
【０１０３】
【化２５】

【０１０４】
式中、Ｒ₂₂、Ｒ₂₃、Ｒ₂₄は、各々、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子等）または置換基（例えば、アルキル基、アリール基、複素環基、アシル基、アミノ基、ニトロ基、シアノ基、アシルアミノ基、アルコキシル基、ヒドロキシル基、アルコキシカルボニル基等）を表す。
【０１０５】
一般式（Ｘ−１）〜（Ｘ−８）において、Ｑは含窒素原子群を形成するのに必要な非金属原子群を表すが、上記一般式（Ｅ）に記載のＱと同義である。また、Ｌは−ＣＨ＝基または−Ｎ＝基を表し、好ましくは−Ｎ＝基である。
【０１０６】
以下に、本発明に係る、前記一般式（Ｈ）で表される金属錯体色素の具体例を挙げるが、本発明はこれらに限定されない。
【０１０７】
【化２６】

【０１０８】
【化２７】

【０１０９】
【化２８】

【０１１０】
一般式（Ｈ）においてＭで表される金属イオンとしては、Ｎｉ²⁺、Ｃｏ²⁺、Ｃｕ²⁺、Ｚｎ²⁺、Ｃｒ²⁺、Ｐｔ²⁺、Ｐｄ²⁺、Ｆｅ²⁺、Ｆｅ³⁺等が好ましい。
【０１１１】
Ｚで表される陰イオンとしては、例えば、エノレート（アセチルアセトナート、ヘキサフルオロアセチルアセトナート等）、ハロゲンイオン（フルオライド、クロライド、ブロマイド、アイオダイド等）、水酸化物イオン、亜硫酸イオン、硫酸イオン、アルキルまたはアリールスルホン酸イオン、硝酸イオン、亜硝酸イオン、炭酸イオン、過塩素酸イオン、アルキルまたはアリールカルボン酸イオン、脂肪酸イオン、フェノールイオン、ジチオカルボン酸イオン、テトラアルキルボレート、サリシネート、ベンゾエート、ＰＦ^6-、ＢＦ^4-、ＳｂＦ^6-等が好ましいものとして挙げられる。
【０１１２】
前記一般式（Ｈ）においてｑは０、１、２または３を表し、ｑが２または３である場合には複数のＺで表される陰イオンが同じ化学種であっても異なっていてもよい。
【０１１３】
本発明に関わる前記一般式（Ａ）〜（Ｇ）で表される色素の金属錯体、前記一般式（Ｈ）で表される金属錯体色素は、例えば、特願２０００−１６０１３０号、同２０００−１６５９０７号、同２０００−２３９８８９号、同２００１−２０４５９４等にて開示されている、当業に従事する技術者には周知の合成法を参照して合成することが出来る。
【０１１４】
《ポリマー微粒子》
本発明の着色微粒子は、ポリマー微粒子が上記記載の色素の金属錯体または金属錯体色素を含有することが特徴である。ここで、本発明に係るポリマー微粒子について説明する。
【０１１５】
上記金属錯体色素または色素の金属錯体を含む、ポリマー微粒子の平均粒径は、５００ｎｍ以下であることが好ましく、更に好ましくは、１０ｎｍ〜３００ｎｍであり、特に好ましくは、２０ｎｍ〜２００ｎｍである。ポリマー微粒子の平均粒径の求め方は、上記記載の着色微粒子の平均粒径の求め方と同様である。
【０１１６】
本発明に係るポリマー微粒子の調製には、下記に示す（Ａ）〜（Ｄ）の群から選択されるポリマが好ましく用いられる。
【０１１７】
（Ａ）：ポリエチレン、ポリプロピレンなどの他、ポリスチレン、ポリ塩化ビニル、ポリ酢酸ビニル、ポリアクリル酸（メタクリル酸）エステル、ポリアクリルニトリル、ポリビニルブチラール、ポリビニルアルコールなどが挙げられる。
【０１１８】
（Ｂ）：ポリエチレンテレフタレート、アルキド樹脂、マレイン酸樹脂、ウレタンゴム、ポリカーボネートなどが挙げられる。
【０１１９】
（Ｃ）：ナイロンや、ポリウレタンが挙げられる。
（Ｄ）：ポリエチレンオキシド、ポリプロピレンオキシド、ポリホルムアルデヒド、エポキシ樹脂などが挙げられる。
【０１２０】
これらのポリマーは、置換基を有していてもよく、その置換基は直鎖状、分岐、或いは環状構造をとっていてもよい。
【０１２１】
本発明に係る、上記記載の（Ａ）−（Ｄ）から選ばれる繰り返し構造を有するポリマーについては、その種類、物性などが例えば、ＰＯＬＹＭＥＲ ＨＡＮＤＢＯＯＫ 第４版（ＪＯＨＮ ＷＩＬＥＹ＆ＳＯＮＳ，ＩＮＣ．）に記載され、容易に情報を得ることが出来る。
【０１２２】
本発明に係るポリマー微粒子の調製に用いられる前記ポリマーは、その数平均分子量が５００〜１０００００、特に１０００〜３００００であることが、着色微粒子の耐久性及びサスペンションの形成性の点から好ましい。
【０１２３】
該ポリマーのガラス転移点（Ｔｇ）は、各種用いることが可能であるが、用いるポリマーのうち、少なくとも１種はＴｇが１０℃以上であることが好ましい。
【０１２４】
上記の（Ａ）〜（Ｄ）に示されるポリマーは、各種のものが市販されているが、常法によって合成することもできる。又、これらの共重合体は、例えば１つのポリマー分子中にエポキシ基を導入しておき、後に他のポリマーと縮重合させたり、光や放射線を用いてグラフト重合を行っても得られる。
【０１２５】
本発明に係るポリマー微粒子の調製において、特に好ましく用いられるポリマーは、アセタール基を含有するポリマー、炭酸エステル基を含有するポリマー、水酸基を含有するポリマー及びエステル基を有するポリマーである。
【０１２６】
主な官能基としてアセタールを含有するポリマーとしては、ポリビニルブチラール樹脂などが挙げられる。例えば、電気化学工業株式会社製の＃２０００−Ｌ、＃３０００−１、＃３０００−２、＃３０００−４、＃３０００−Ｋ、＃４０００−１、＃４０００−２、＃５０００−Ａ、＃６０００−Ｃ、＃６０００−ＥＰ、或いは積水化学工業製のＢＬ−１、ＢＬ−１Ｈ、ＢＬ−２、ＢＬ−２Ｈ、ＢＬ−５、ＢＬ−１０、ＢＬ−Ｓ、ＢＬ−ＳＨ、ＢＸ−１０、ＢＸ−Ｌ、ＢＭ−１、ＢＭ−２、ＢＭ−５、ＢＭ−Ｓ、ＢＭ−ＳＨ、ＢＨ−３、ＢＨ−６、ＢＨ−Ｓ、ＢＸ−１、ＢＸ−３、ＢＸ−５、ＫＳ−１０、ＫＳ−１、ＫＳ−３、ＫＳ−５などがある。
【０１２７】
ポリビニルブチラール樹脂は、ＰＶＡ（ポリビニルアルコール）の誘導体として得られるが、もとのＰＶＡの水酸基のアセタール化は最大でも８０ｍｏｌ％程度であり、通常は５０ｍｏｌ％から、８０ｍｏｌ％程度である。尚、ここで言うアセタールは狭義の１，１−ジエトキシエタン基を指すのではなく、オルトアルデヒドとの化合物一般を指す。水酸基については、特に規定はないが、１０〜４０ｍｏｌ％含有されていることが好ましい。またアセチル基の含有率に特に規定はないが、１０ｍｏｌ％以下であることが好ましい。主な官能基としてアセタールを含有するポリマーとは、ポリマー中に含まれる酸素原子のうち、少なくとも３０ｍｏｌ％がアセタール基を形成していることをいう。
【０１２８】
他に主な官能基としてアセタールを含有するポリマーとして、三菱エンジニアリングプラスチックス株式会社製のユピタールシリーズなども使用可能である。
【０１２９】
主な官能基として炭酸エステルを含有するポリマーとしては、ポリカーボネート樹脂が挙げられる。たとえば、三菱エンジニアリングプラスチックス株式会社製のユーピロンシリーズ、ノバレックスシリーズがある。ユーピロンシリーズはビスフェノールＡを原料として作られており、測定法によってその値は異なるが各種の分子量のものを用いることができる。ノバレックスシリーズでは分子量が２０，０００〜３０，０００、ガラス点移転１５０℃付近のものを用いることができるが、これらに限定されない。
【０１３０】
主な官能基として炭酸エステル基を含有するポリマーとは、ポリマー中に含まれる酸素原子のうち、少なくとも３０ｍｏｌ％が炭酸エステル基の形成に寄与していることをいう。
【０１３１】
主な官能基として水酸基を含有するポリマーとしては、例えばＰＶＡが挙げられる。ＰＶＡの有機溶剤への溶解度は小さいものが多いが、けん化価の小さいＰＶＡであれば、有機溶剤への溶解度は上昇する。水溶性が高いＰＶＡは水相中に添加しておき有機溶剤除去後に、ポリマーのサスペンションに吸着させるようにして使用することもできる。
【０１３２】
ＰＶＡとしては市販のものを用いることができ、たとえば、クラレのポバールＰＶＡ−１０２、ＰＶＡ−１１７、ＰＶＡ−ＣＳＡ、ＰＶＡ−６１７、ＰＶＡ−５０５などのほか、特殊銘柄のサイズ剤用ＰＶＡ、熱溶融成形用ＰＶＡ、その他機能性ポリマーとして、ＫＬ−５０６、Ｃ−１１８、Ｒ−１１３０、Ｍ−２０５、ＭＰ−２０３、ＨＬ−１２Ｅ、ＳＫ−５１０２、などを用いることができる。けん化度は５０ｍｏｌ％以上のものが一般的であるが、ＬＭ−１０ＨＤのように４０ｍｏｌ％程度であっても、これを用いることも可能である。このようなＰＶＡ以外でも主な官能基として水酸基を有するものが使用可能であるが、ポリマー中に含まれる酸素原子のうち少なくとも２０ｍｏｌ％が水酸基を形成しているものが使用可能である。
【０１３３】
主な官能基としてエステル基を含有するポリマーとしては、たとえばメタクリル樹脂が挙げられる。旭化成製デルペットシリーズの５６０Ｆ、６０Ｎ、８０Ｎ、ＬＰ−１、ＳＲ８５００、ＳＲ６５００などを用いることができる。主な官能基としてエステル基を含有するポリマーとは、ポリマー中に含まれる酸素原子のうち、少なくとも３０ｍｏｌ％がエステル基を形成していることをいう。
【０１３４】
これらのポリマーはそれぞれ１種ないし２種以上を混合して用いてもよい。又、これらのポリマーが質量比で５０％以上含まれていれば、他のポリマーや無機物のフィラーが含有されていてもよい。
【０１３５】
これらのポリマーの共重合体を用いることも好ましいが、例えば水酸基を含有するポリマーと、各種のポリマーを共重合させる手法として、水酸基をグリシジルメタクリレートの様なエポキシ基を有するモノマーと反応させ、その後、懸濁重合でメタクリル酸エステルモノマーと共重合させて得ることもできる。
【０１３６】
《インクジェット記録用インク》
本発明のインクジェット記録用インクについて説明する。
【０１３７】
本発明のインクジェット記録用インクは、上記記載のポリマー微粒子中に金属錯体色素または色素の金属錯体が封入された（含むとも言う）ポリマーが水性媒体中で分散された状態、すなわち、サスペンションである。
【０１３８】
即ち、上記金属錯体色素は、少なくとも該ポリマーによって形成されるミセル中に封入され、そして、本発明のインクジェット記録用インクは、金属錯体色素を封入した該ポリマのミセルが水性媒体中にサスペンションとして存在してなるものが好ましい。
【０１３９】
本発明に係る金属錯体色素または色素の金属錯体は、後述する転相乳化によって上記ポリマーに効率的に封入される観点から、エステル系ないしケトン系溶剤に１０ｇ／Ｌ以上溶解することが好ましく、１００〜６００ｇ／Ｌ溶解することが更に好ましい。
【０１４０】
本発明のインクジェット記録用インクを用いるにあたり、インクジェットヘッドのノズル先端部でのインク蒸発に伴うインクの増粘やサスペンションの凝集を適切に抑制し、プリンタヘッドの目詰りを効果的に防止する観点から、本発明のインクジェット記録用インクにおいては、上記ポリマーは、該インク中に０．５質量％〜５０質量％配合されることが好ましく、０．５質量％〜３０質量％配合されることが更に好ましい。
【０１４１】
一方、サスペンション粒径の経時安定性を向上させ、且つ、粒径増大を抑制する観点から、該インク中の上記金属錯体色素の含有量は、１質量％〜３０質量％配合されることが好ましく、１．５質量％〜２５質量％配合されることが更に好ましい。
【０１４２】
本発明のインクジェット記録用インクにおいては、吐出安定性、プリントヘッドやインクカートリッジ適合性、保存安定性、画像保存性、その他の諸性能向上の目的に応じて、従来公知の各種添加剤、例えば多価アルコール類の様な湿潤剤、シリコーン系等の消泡剤、粘度調整剤、表面張力調整剤、比抵抗調整剤、皮膜形成剤、分散剤、界面活性剤、紫外線吸収剤、酸化防止剤、退色防止剤、クロロメチルフェノール系等の防黴剤及び／または、ＥＤＴＡ等のキレート剤、又、亜硫酸塩等の酸素吸収剤等、防錆剤等を添加することもできる。
【０１４３】
湿潤剤としては、例えばエチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、グリセリン、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノ−ｎ−ブチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、メチルカルビトール、エチルカルビトール、ブチルカルビトール、エチルカルビトールアセテート、ジエチルカルビトール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル等の多価アルコール及びそのエーテル、アセテート類、Ｎ−メチル−２−ピロリドン、１，３−ジメチルイミダゾリジノン、トリエタノールアミン、ホルムアミド、ジメチルホルムアミド等の含窒素化合物類、ジメチルサルフォキサイドの一種または、二種以上を使用することができる。これらの湿潤剤の配合量に特に制限はないが、上記インク中に好ましくは０．１〜５０質量％配合することができ、更に好ましくは０．１〜３０質量％配合することができる。
【０１４４】
分散剤としては、特に制限されるものではないが、そのＨＬＢ値が８〜１８であることが、分散剤としての効果が発現し、サスペンションの粒子径の増大抑制効果がある点から好ましい。分散剤として市販品も使用することができ、例えば花王（株）製の分散剤デモールＳＮＢ，ＭＳ，Ｎ，ＳＳＬ，ＳＴ，Ｐ（商品名）が挙げられる。
【０１４５】
分散剤の配合量に特に制限はないが、本発明のインクジェット記録用水系インク中に、０．０１〜１０質量％配合されることが好ましい。該化合物の配合量が０．０１質量％に満たないとサスペンションの小粒径化が困難であり、１０質量％を超えるとサスペンションの粒径が増大したりサスペンション安定性が低下し、ゲル化するおそれがあるので、上記範囲内とすることが好ましい。
【０１４６】
消泡剤としては、特に制限なく、市販品を使用することができ、例えば信越シリコーン社製のＫＦ９６、６６、６９、ＫＳ６８、６０４、６０７Ａ、６０２、６０３、ＫＭ７３、７３Ａ、７３Ｅ、７２、７２Ａ、７２Ｃ、７２Ｆ、８２Ｆ、７０、７１、７５、８０、８３Ａ、８５、８９、９０、６８−１Ｆ、６８−２Ｆ（商品名）等が挙げられる。これら化合物の配合量に特に制限はないが、本発明に係る水系インク中に、０．００１〜２質量％配合されることが好ましい。該化合物の配合量が０．００１質量％に満たないとインク調製時に泡が発生し易く、又、インク内での小泡の除去が難しく、２質量％を超えると泡の発生は抑えられるものの、印字の際、インク内でハジキが発生し印字品質の低下が起こる場合があるので、上記範囲内とすることが好ましい。
【０１４７】
また、本発明のインクジェット記録用インクは、インクジェット記録用のインクとして以外に、例えば、一般の万年筆、ボールペン、サインペン等の筆記具用のインクとしても使用可能である。本発明のサスペンジョンを乾燥し、微粒の粉体を得ることもできる。得られた粉体は、電子写真のトナーなどにも使用可能である。
【０１４８】
《本発明のインクジェット記録用インクの製造方法》
次に、本発明のインクジェット記録用インクの製造方法について説明する。本発明のインクジェット記録用インクは、従来公知の各種の乳化法で製造することができる。
【０１４９】
乳化法としては、各種の方法を用いることができる。それらの例は、例えば、「機能性乳化剤・乳化技術の進歩と応用展開 シー エム シー」の８６頁の記載にまとめられている。本発明においては、特に、超音波、高速回転せん断、高圧による乳化分散装置を使用することが好ましい。
【０１５０】
超音波による乳化分散では、いわゆるバッチ式と連続式の２通りが使用可能である。バッチ式は、比較的少量の作製に適し、連続式は大量の作製に適する。連続式では、たとえば、ＵＨ−６００ＳＲ（株式会社エスエムテー製）のような装置を用いることが可能である。このような連続式の場合、超音波の照射時間は、分散室容積／流速×循環回数で求めることができる。超音波照射装置が複数ある場合は、それぞれの照射時間の合計として、もとめられる。超音波の照射時間は実際上３秒以上必要であり、それ以内で乳化が完了するのであれば、超音波乳化分散装置を必要としない。また、１００００秒以上必要であると、工程の負荷が大きく、実際上は乳化剤の再選択などにより乳化分散時間を短くする必要がある。そのため１００００秒以上は必要でない。さらに好ましくは、１０秒以上、２０００秒以内である。
【０１５１】
高速回転せん断による乳化分散装置としては、「機能性乳化剤・乳化技術の進歩と応用展開 シー エム シー」の２５５〜２５６頁に記載されているような、ディスパーミキサーや、２５１頁に記載されているようなホモミキサー、２５６頁に記載されているようなウルトラミキサーなどが使用できる。これらの型式は、乳化分散時の液粘度によって使い分けることができる。これらの高速回転せん断による乳化分散機では、攪拌翼の回転数が重要である。ステーターとのクリアランスは通常０．５ｍｍ程度で、極端に狭くはできないので、せん断力は主として攪拌翼の周速に依存する。周速が５ｍ／ｓ〜１５０ｍ／ｓであれば本発明の乳化・分散に使用できる。周速が遅い場合、乳化時間を延ばしても小粒径化が達成できない場合が多く、１５０ｍ／ｓにするにはモーターの性能を極端に上げる必要があるからである。更に好ましくは、２０ｍ／ｓ〜１００ｍ／ｓである。
【０１５２】
高圧による乳化分散では、ＬＡＢ２０００（エスエムテー社製）などが使用できるが、その乳化・分散能力は、試料にかけられる圧力に依存する。
【０１５３】
圧力は、９．８ＭＰａ〜４９０ＭＰａ（１００ｋｇ／ｃｍ²〜５０００ｋｇ／ｃｍ²以下）が好ましい。また必要に応じて数回乳化・分散を行い、目的の粒径を得ることができる。更に好ましくは、４９ＭＰａ〜１９６ＭＰａ（５００ｋｇ／ｃｍ²〜２０００ｋｇ／ｃｍ²）である。
【０１５４】
これらの乳化・分散装置は単独で用いてもよいが、必要に応じて組み合わせて使用することが可能である。コロイドミルや、フロージェットミキサなども単独では本発明の目的を達成できないが、本発明の装置との組み合わせにより、単時間で乳化・分散を可能にするなど本発明の効果を高めることが可能である。
【０１５５】
また本発明のインクは、上記の装置を用いるほか、いわゆる転相乳化によって製造することができる。
【０１５６】
ここで転相乳化は、上記ポリマーを、上記金属錯体色素と共にエステル、ケトンなどの有機溶剤に溶解させ、必要に応じて中和剤を加えて該ポリマー中のカルボキシル基をイオン化し、次いで水相を加えた後、上記有機溶剤を留去して水系に転相することからなる。
【０１５７】
転相が完了した後、系を減圧下に加熱することにより、上記エステル、ケトン系溶剤を除去すると共に、所定量の水を除去して、所望の濃度を有する本発明のインクジェット記録用インクが得られる。
【０１５８】
《本発明の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について説明する。
【０１５９】
本発明のインクジェット記録方法においては、上記記載のインクジェット記録用インクを用いて、下記に示すような、シリカまたはアルミナの微粒子と少なくとも１種類の親水性バインダを含有する記録メディアに画像記録を行うことが特徴である。
【０１６０】
（シリカ微粒子、アルミナ微粒子）
本発明に係るシリカ微粒子、アルミナの微粒子について説明する。
【０１６１】
本発明においては、インクジェット記録用紙で高品位なプリントを得る観点から、シリカまたはアルミナの微粒子が用いられる。前記微粒子としては、アルミナ、コロイダルシリカもしくは気相法により合成された微粒子シリカが好ましく、気相法で合成された微粒子シリカが、特に好ましい。この気相法で合成されたシリカは、表面がＡｌで修飾されたものであっても良い。表面がＡｌで修飾された気相法シリカのＡｌ含有率は、シリカに対して質量比で０．０５〜５％のものが好ましい。
【０１６２】
画像記録後の光沢性、発色性向上の観点から、上記微粒子の粒径は、いかなる粒径のものも用いることができるが、平均粒径が１μｍ以下であることが好ましく、更に好ましくは、０．２μｍ以下であり、特に好ましくは、０．１μｍ以下である。粒径の下限は特に限定されないが、微粒子の製造上の観点から、概ね０．００３μｍ以上、特に０．００５μｍ以上が好ましい。
【０１６３】
上記微粒子の平均粒径は、記録メディアの断面や表面を電子顕微鏡で観察し、１００個の任意の粒子の粒径を求めて、その単純平均値（個数平均）として求められる。ここで、個々の粒径は、その投影面積に等しい円を仮定した時の直径で表したものである。
【０１６４】
また、微粒子の分散度は、光沢性や発色性の観点から０．５以下が好ましい。０．５を越えると光沢やプリント時の発色性が低下しやすい。特に、０．３以下が好ましい。ここで、微粒子の分散度とは、上記平均粒径を求めるのと同様に電子顕微鏡で多孔質層の微粒子を観察し、その粒径に標準偏差を平均粒径で割ったものを示す。
【０１６５】
上記微粒子は、１次粒子のままで、あるいは２次粒子もしくはそれ以上の高次凝集粒子で多孔質皮膜中に存在していても良いが、上記の平均粒径は、電子顕微鏡で観察したときに記録メディア中で独立の粒子を形成しているものの粒径を言う。
【０１６６】
上記微粒子の記録メディア中における含有量は、５質量％〜４０質量％が好ましく、更に好ましくは、７質量％〜３０質量％である。
【０１６７】
《親水性バインダ》
本発明に係る親水性バインダについて説明する。
【０１６８】
本発明でいう親水性であるとは、単に水で可溶である場合の他に、例えば、メタノール、イソプロピルアルコール、アセトン、酢酸エチルなどの水混和性の有機溶媒と水との混合溶媒に可溶なポリマーも含まれる。この場合、水混和性の有機溶媒の量は、溶媒全量に対して通常５０質量％以下のものをいう。
【０１６９】
また、親水性であるとは、上記溶媒に、バインダーが室温で通常１質量％以上溶解するものをいい、より好ましくは３質量％以上溶解するものである。
【０１７０】
本発明で用いる親水性バインダーとしては、例えば、ポリビニルアルコール、ゼラチン、ポリエチレンオキサイド、ポリビニルピロリドン、カゼイン、澱粉、寒天、カラギーナン、ポリアクリル酸、ポリメタクリル酸、ポリアクリルアミド、ポリメタクリルアミド、ポリスチレンスルホン酸、セルロース、ヒドロキシルエチルセルロース、カルボキシルメチルセルロース、ヒドロキシルエチルセルロース、デキストラン、デキストリン、プルラン、水溶性ポリビニルブチラール等の親水性ポリマーが挙げられる。これらの親水性ポリマーは、２種以上併用することも可能である。
【０１７１】
（インクジェットヘッド）
本発明のインクジェット記録方法で使用できるインクジェットヘッドは、オンデマンド方式でもコンティニュアス方式でも構わない。また、吐出方式としては、電気−機械変換方式（例えば、シングルキャビティー型、ダブルキャビティー型、ベンダー型、ピストン型、シェアーモード型、シェアードウォール型等）、電気−熱変換方式（例えば、サーマルインクジェット型、バブルジェット（Ｒ）型等）、静電吸引方式（例えば、電界制御型、スリットジェット型等）及び放電方式（例えば、スパークジェット型等）などを具体的な例として挙げることができるが、いずれの吐出方式を用いても構わない。
【０１７２】
上記のような構成により、画像記録することにより、印字部と非印字部との光沢差の低減による違和感を改良し、耐擦性、印字濃度及びプリンタ搬送性に優れたインクジェット記録方法を提供することが出来る。
【０１７３】
【実施例】
以下、実施例により本発明を説明するが、本発明はこれらに限定されない。
【０１７４】
実施例１
《着色微粒子Ａの調製》
ポリマー微粒子として、ポリビニルブチラール（積水化学製ＢＬ−Ｓ、平均重合度３５０）１５ｇを用い、色素（Ａ−１）のニッケルアセチルアセトナト錯体である金属錯体色素１０ｇ、及び酢酸エチル１５０ｇをセパラブルフラスコに入れ、フラスコ内を窒素置換後、攪拌して上記ポリマー及び金属錯体色素を完全溶解させた。引き続き、更に、分散剤として、ラウリル硫酸ナトリウム６ｇ、水溶性ポリマーＭＰ−２０３（クラレ製）２ｇを含む水溶液１５０ｇを滴下して撹拌した後、超音波分散機（ＵＨ−１５０型、株式会社エスエムテー製）を用いて３００秒間乳化した。その後、減圧下で酢酸エチルを除去し、色素（Ａ−１）の金属錯体色素が粒子内部に分散、含浸されたポリマー微粒子の水分散体として、本発明の着色微粒子Ａを得た。
【０１７５】
《着色微粒子Ｂ〜Ｐの調製》
着色微粒子Ａの調製において、色素（Ａ−１）の金属錯体色素に代えて、表１に示す金属錯体色素を用いた以外は同様にして、本発明の着色微粒子Ｂ〜Ｐを、各々得た。
【０１７６】
《比較の着色微粒子Ｑの調製》
着色微粒子Ａの調製において、色素（Ａ−１）に代えて、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ８を用いた以外は同様にして、比較の着色微粒子Ｑを得た。
【０１７７】
《インクジェット記録用インク１〜１６の調製》
表１に示す着色微粒子 ８０ｇ
ジエチレングリコール １０ｇ
グリセリン ９．８ｇ
アセチレノールＥＬ（川研ファインケミカル製） ０．２０ｇ
上記の材料を混合、攪拌、分散し、得られた分散液を５μｍのフィルターによって濾過し、ゴミ及び粗大粒子を除去して、本発明のインクジェット記録用インク１〜１６を各々調製した。
【０１７８】
《比較のインクジェット記録用インク１７の調製》
本発明のインクジェット記録用インク１の調製において、金属錯体色素として、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ８のニッケルアセチルアセトナト錯体を用いた以外は同様にして、比較のインクジェット記録用インク１７を調製した。
【０１７９】
《比較のインクジェット記録用インク１８の調製》
Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ５２ ４ｇ
ジエチレングリコール ７．５ｇ
グリセリン ７．５ｇ
水 ８０．６０ｇ
アセチレノールＥＬ（川研ファインケミカル製） ０．４０ｇ
上記の材料をボールミルを用いて１２時間混合し、得られた分散液を５μｍのフィルターによって濾過し、ゴミ及び粗大粒子を除去して、比較のインクジェット記録用インク１８を得た。
【０１８０】
得られたインクジェット記録用インク１〜１８の各々を下記に記載のように評価した。
【０１８１】
《画像作製及びその評価方法》
上記記載のインクジェット記録用インク１〜１８の各々のインクを用いて、市販のエプソン製インクジェットプリンター（型番ＰＭ−８００）でコニカフォトジェットペーパー Ｐｈｏｔｏｌｉｋｅ、ＱＰ光沢紙（コニカ株式会社製）に印字して、表１に記載の本発明の試料１〜１６、比較の試料１７、１８を得た。
【０１８２】
得られた試料について、下記に記載のように、耐光性と色調の評価を行った。
（耐光性評価）
耐光性はキセノンフェードメーターにて２４時間曝射した後のサンプルの、未曝射サンプルからの可視領域極大吸収波長における反射スペクトル濃度の低下率を算出して、以下の４段階評価とした。
【０１８３】
◎：低下率が１０％未満
○：低下率が１０％以上３０％未満
△：低下率が３０％以上５０％未満
×：低下率が５０％以上
（色調評価）
色調の評価は無作為に選んだ成人男性５名と成人女性５名の計１０名のモニターによる目視判定を実施し、許容レベルと判定したモニターの人数によりランク評価した。
【０１８４】
○：許容レベルが７人以上（実用可）
×：許容レベルが７人未満（実用不可）
得られた評価結果を表１に示す。
【０１８５】
【表１】

【０１８６】
表１から、比較に比べて、本発明の試料は耐光性、色調ともに優れていることが明らかである。
【０１８７】
【発明の効果】
本発明により、色素の堅牢性が向上し、褪色の少ない着色微粒子、前記着色微粒子を用いて色再現性、画像堅牢性に優れるインクジェット記録用インク、インクジェット記録用インクの製造方法及びインクジェット記録方法を提供することが出来た。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to colored fine particles in which polymer fine particles contain a metal complex of a dye, an ink for inkjet recording containing the colored fine particles, a method for producing the ink, and an inkjet recording method.
[0002]
[Prior art]
Inkjet recording, which is a recording method that ejects fine ink droplets from fine nozzles and attaches them to the recording medium, uses low noise and good operability, and not only specially prepared recording paper but also plain paper In recent years, it has become widespread due to the advantage that it can be used in the field.
[0003]
There are various recording methods for ink for ink jet recording methods (1: a method in which droplets are pressure-discharged by electro-mechanical conversion of a piezo element, 2: a bubble is generated by electro-thermal conversion, and the droplets are pressure-discharged. System 3: a system in which droplets are sucked and discharged by electrostatic force), a high recording density and good color tone, and excellent image fastness such as light resistance, heat resistance and water resistance, Fast fixing on a recording medium is required to prevent bleeding after recording, excellent storability as an ink, no toxicity and flammability, and low cost from the viewpoint of safety.
[0004]
Various ink jet recording inks have been proposed and studied from the above viewpoints, but ink jet recording inks that satisfy many of the requirements at the same time have not yet been developed.
[0005]
In many of the conventionally known inks for inkjet recording, aqueous solutions of water-soluble dyes, glycols as humectants, alkanolamines, surfactants for adjusting surface tension, alcohols, resin components as binder components, etc. Is used. Inks using these water-soluble dyes have high reliability against clogging in the recording system, but on the other hand, they are easy to bleed on recording paper because they are aqueous dye solutions, and they use water-soluble dyes. Therefore, there is a problem that the water resistance is not sufficient.
[0006]
Furthermore, water-soluble dyes that have only penetrated into the recording paper and have been dry-fixed cannot be said to be “dyed” and have a problem that the light fastness is very low.
[0007]
Therefore, in recent years, as described in JP-A No. 2000-281947, in a two-component system with a cationic polymer, blurring is prevented by improving the dyeing property by utilizing the interaction between the dye and the polymer. Several methods such as a method for enhancing fastness have been attempted, but the effect of improving the fastness of image while maintaining the color reproducibility of the water-soluble dye is not sufficient, and Japanese Patent Application Laid-Open No. 55-18418. No. 5 proposes an ink jet recording material to which latex is added, and JP-A-54-146109 proposes a recording material using a water-soluble dye to which vinyl polymer fine particles colored with an oily dye are added. However, all have problems such as low recording quality and fastness of recorded images, poor ink storage stability, and nozzle clogging. In the present circumstances that there is no shall.
[0008]
On the other hand, in order to improve the drawbacks of recording materials using water-soluble dyes, proposals have been made to use carbon black or organic pigments as recording materials. In such a recording material using pigment dispersion, the water resistance of the ink is greatly improved. However, these pigments generally have a high specific gravity of 1.5 to 2.0, and the dispersed particles tend to settle. Therefore, in order to stably disperse a pigment having a high specific gravity, it is necessary to finely disperse the average particle diameter to 0.1 μm or less, resulting in high dispersion cost and very expensive ink. End up.
[0009]
Furthermore, polymer fine particles colored with oil-soluble or hydrophobic dyes described in JP-A-54-58504, JP-A-55-139471, JP-A-3-250069, JP-A-4-185672 and the like are used as recording agents. Although proposals have been made, these proposals are still not sufficient in terms of ink storage stability, ink jet recording system reliability, and the like. In particular, in ink-jet recording media that have been widely used in recent years and formed a void layer with silica or alumina fine particles to increase the water absorption of the ink, the fastness of oil-soluble dyes is not sufficient for market needs. I can't say that.
[0010]
In addition, there is a technical proposal to meet market demands by improving the chemical structure of a dye, such as an ink jet recording liquid using a metal complex dye described in JP-A-8-156399 and JP-A-10-204351. Has been made. Furthermore, as described in JP-A Nos. 2001-011347 and 2001-019880, an ink jet recording liquid using polymer fine particles containing a coordination body of a metal compound and a dye has been proposed.
[0011]
However, even with the dyes disclosed in these proposals, various ink-jet recording inks such as good color reproducibility and fastness of recorded images, ink storage stability, and reliability of ink-jet recording systems can be used. The present condition is that the thing which satisfies all the requirements is not obtained.
[0012]
[Problems to be solved by the invention]
An object of the present invention is to provide colored fine particles that improve the fastness of a dye and suppress discoloration, to provide an ink for ink jet recording excellent in color reproducibility and image fastness using the same, It is providing the manufacturing method of the ink which has, and providing the recording method using the said ink.
[0013]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following configurations 1 to 14.
[0014]
1. Colored fine particles, wherein the polymer fine particles contain a metal complex of the dye represented by the general formula (A).
[0015]
2. 2. The colored fine particles as described in 1 above, wherein the dye represented by the general formula (A) is a dye represented by the general formula (B).
[0016]
3. Colored fine particles, wherein the polymer fine particles contain a metal complex of a dye represented by the general formula (C).
[0017]
4). Colored fine particles, wherein the polymer fine particles contain a metal complex of the dye represented by the general formula (D).
[0018]
5. Colored fine particles, wherein the polymer fine particles contain a metal complex of a dye represented by the general formula (E).
[0019]
6). Colored fine particles, wherein the polymer fine particles contain a metal complex of a dye represented by the general formula (F).
[0020]
7). Colored fine particles, wherein the polymer fine particles contain a metal complex of a dye represented by the general formula (G).
[0021]
8). Colored fine particles, wherein the polymer fine particles contain a metal complex dye represented by the general formula (H).
[0022]
9. In the general formula (H), Y ₁ 9. The colored fine particles as described in 8 above, wherein is a divalent substituent selected from the group consisting of the general formulas (Y-1) to (Y-11).
[0023]
10. The metal complex of the dye according to any one of 1 to 7, the metal complex dye of 8, and the metal complex dye of 9 are contained in a molecular dispersion with respect to the polymer. 10. The colored fine particles according to any one of 1 to 9 above, wherein
[0024]
11. 11. An ink for ink jet recording, wherein the colored fine particles according to any one of 1 to 10 are dispersed in an aqueous medium.
[0025]
12 In producing the inkjet recording ink according to 11 above, at least one polymer and a metal complex of a dye represented by the general formulas (A) to (G) or the general formula (H) are used. And a step of emulsifying and dispersing the obtained oil phase mixture in an aqueous medium, and then removing the organic solvent. Method.
[0026]
13. 12. An ink jet recording method, wherein the ink for ink jet recording according to 11 is ejected imagewise.
[0027]
14 14. The ink jet recording method according to item 13, wherein the ink for ink jet recording described in item 11 is ejected onto a recording medium containing fine particles of silica or alumina and at least one hydrophilic binder.
[0028]
Hereinafter, the present invention will be described in detail.
As a result of intensive studies to solve the above-described problems, the present inventors have used the colored fine particles of the present invention containing a metal complex of a dye according to any one of claims 1 to 10 to obtain a color. It has been found that an ink for ink jet recording excellent in reproducibility and image fastness can be obtained. In addition, the present inventors have succeeded in providing an ink jet recording ink production method having the above-described excellent characteristics and an ink jet recording method.
[0029]
The colored fine particles of the present invention will be described.
In the colored fine particles of the present invention, the polymer fine particles are metal complexes of at least one dye selected from the group of dyes represented by the general formulas (A) to (G), or the general formula (H). It is characterized by containing a metal complex dye represented by
[0030]
In the colored fine particles of the present invention, the metal complex dye or the metal complex of the dye is dispersed in the polymer fine particles and dispersed in a medium (for example, water), specifically, a suspension is formed. Is preferred.
[0031]
Here, the average particle diameter of the colored fine particles of the present invention is preferably 10 nm to 300 nm, and more preferably 20 nm to 200 nm. The average particle size can be measured using a commercially available particle size measuring device such as Coulter Counter N4 (manufactured by Coulter).
[0032]
《Metallic complex of dye》
The metal complex of the pigment | dye which concerns on this invention points out the compound formed by the pigment | dye interacting with a metal ion as a ligand. It seems to be a complex (hybrid) of metal ions and dyes in which the ratio of the number of metal atoms to the number of dye molecules is not an integer ratio, as well as the complex in which the ratio of the number of metal atoms to the number of dye molecules is a simple integer ratio. Also included.
[0033]
The metal ion used for forming a complex with at least one dye selected from the dye group represented by the above general formulas (A) to (G) according to the present invention is M. ^{l +} The metal ion represented by these is preferably used. Here, l represents a natural number of 1 to 5.
[0034]
M above ^{l +} Examples of the metal that forms the metal ion represented by the formula: silver (I), aluminum (III), gold (III), cerium (III, IV), cobalt (II, III), chromium (III), copper (I, II), europium (III), iron (II, III), gallium (III), germanium (IV), indium (III), lanthanum (III), manganese (II), nickel (II), palladium ( II), platinum (II, IV), rhodium (II, III), ruthenium (II, III, IV), scandium (III), silicon (IV), samarium (III), titanium (IV), zinc (II) Zirconium (IV) and the like. Among these, in the case of a bidentate metal complex dye, a transition metal ion that can coordinate in a tetradentate or hexadentate form is preferable, and a tridentate metal complex. In the case of a dye, a transition metal ion capable of coordination at a hexadentate is preferable. Particularly preferred transition metal ions include zinc (II), nickel (II), cobalt (II, III), copper (II), chromium (III), iron (II, III), palladium (II), platinum (II, IV) and the like.
[0035]
When the above-described dye is coordinated with the metal ion, the metal ion is usually mixed with the dye in the form of a salt. Examples of anions that form salts with metal ions in advance are enolates (acetylacetonate, hexafluoroacetylacetonate, etc.), halide ions (fluoride, chloride, bromide, iodide, etc.), hydroxide ions , Sulfite ion, sulfate ion, alkyl or aryl sulfonate ion, nitrate ion, nitrite ion, carbonate ion, perchlorate ion, alkyl or aryl carboxylate ion, fatty acid ion, phenol ion, dithiocarboxylate ion, tetraalkylborate , Salicinate, benzoate, PF ^6- , BF ^Four- , SbF ^6- And the like are preferable.
[0036]
In addition, a plurality of metal salts may be used in combination to form a metal complex of a dye. In that case, different types of metal elements may be used in combination, or the same metal element may be used. Those formed with different anions may be used in combination, or a plurality of types of metal salts having different metal elements and anions may be used in combination.
[0037]
<Dye>
The dye represented by the general formula (A) to the general formula (G) constituting the metal complex of the dye according to the present invention will be described.
[0038]
<< Dye Represented by Formula (A) >>
In general formula (A), Z ₁ , Z ₂ Represents an atomic group forming an aromatic carbocycle or a heterocycle, and specific examples include a carbon atom, a nitrogen atom, a sulfur atom, and a selenium atom. The ring may further have a substituent, and a condensed ring can also be formed. Z ₁ , Z ₂ May be the same or different from each other.
[0039]
Examples of the aromatic carbocycle include a phenyl ring and a naphthalene ring. Examples of the heterocyclic ring include 5-pyrazolone, pyrazolopyrrole, pyrazolopyrazole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, and thiohydantoin. Oxazolone, isoxazolone, indanedione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, pyrazolopyridone, and the like.
[0040]
Examples of the substituent for the aromatic carbocycle and heterocyclic ring include an alkyl group (for example, a methyl group, an ethyl group, a butyl group, a pentyl group, a 2-methoxyethyl group, a trifluoromethyl group, a 2-ethylhexyl group). Etc.), aryl group (for example, phenyl group, naphthyl group, etc.), alkoxyl group (for example, methoxy group, ethoxy group, butoxy group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group, i-propoxycarbonyl group, etc.) , Acyloxy groups (eg acetyloxy group, ethylcarbonyloxy group etc.), carbamoyl groups (eg methylcarbamoyl group, ethylcarbamoyl group, butylcarbamoyl group, phenylcarbamoyl group etc.), sulfamoyl groups (eg sulfamoyl group, methylsulfamoyl group) Famoyl group, dimethyl Sulfamoyl group, phenylsulfamoyl group, etc.), alkylthio group (eg, methylthio group, ethylthio group, octylthio group, etc.), arylthio group (eg, phenylthio group, p-tolylthio group, etc.), amino group (eg, amino group, Methylamino group, diethylamino group, methoxyethylamino group, etc.), acylamino group (eg, acetylamino group, chloroacetylamino group, propionylamino group, benzoylamino group, trifluoroacetylamino group, etc.), alkylureido group (eg, Methylureido group, ethylureido group, methoxyethylureido group, dimethylureido group, etc.), arylureido group (eg, phenylureido group etc.), alkylsulfonamide group (eg, methanesulfonamide group, ethanesulfonamide group, Sulfoneamide group, trifluoromethylsulfonamide group, 2,2,2-trifluoroethylsulfonamide group, etc.), arylsulfonamide groups (eg, phenylsulfonamide group, tolylsulfonamide group, etc.), alkylaminosulfonylamino Groups (eg, methylaminosulfonylamino group, ethylaminosulfonylamino group, etc.), arylaminosulfonylamino groups (eg, phenylaminosulfonylamino group, etc.), hydroxyl groups, cyano groups, nitro groups, heterocyclic groups (eg, pyridyl) Group, pyrimidyl group, pyrazyl group, pyrrolyl group, indolyl group, pyrazolyl group, imidazolyl group, furyl group, oxazolyl group, thiazolyl group, quinolyl group, thienyl group, etc.). The heterocyclic group may further have a substituent or may have a condensed ring, which may further have a substituent, and are further bonded to each other to form a 5-membered or 6-membered group. A member ring may be formed.
[0041]
In the general formula (A), the alkyl group represented by R ′ has the same meaning as the alkyl group described as the substituent for the 5-membered or 6-membered aromatic carbocycle and heterocyclic ring.
[0042]
<< Dye Represented by Formula (B) >>
In general formula (B), Z ₁ , Z ₂ , Z _Three And Z _Four A group of atoms forming a 5-membered or 6-membered aromatic carbocycle or heterocycle represented by the formula: ₁ , Z ₂ The types of aromatic carbocycles and heterocycles formed are also synonymous. Moreover, the substituent on an aromatic carbocyclic ring or a heterocyclic ring is synonymous with the substituent of the aromatic carbocyclic ring or heterocyclic ring described in the general formula (A).
[0043]
In the present invention, among the metal complexes of the dye represented by the general formula (A), a metal complex of the dye represented by the general formula (B) is preferably used.
[0044]
<< Dye Represented by Formula (C) >>
In general formula (C), A ₁ , A ₂ , A _Three , A _Four , B ₁ , B ₂ , B _Three , B _Four Represents a carbon atom or a nitrogen atom, and A ₁ , A ₂ , A _Three , A _Four Each ring containing B ₁ , B ₂ , B _Three , B _Four The ring containing each of them may be unsubstituted or may have a substituent, and may further form a condensed ring. The substituent may be an aromatic carbocycle or a heterocycle described in the general formula (A). Synonymous with ring substituent.
[0045]
In general formula (C), R ₁ , R ₂ , R _Three And R _Four Examples of the substituent represented by formula (A) include those having the same meanings as the substituents of the aromatic carbocycle and heterocyclic ring described in the general formula (A). Among them, aryl groups and alkyl groups are preferably used. It is a group.
[0046]
<< Dye Represented by Formula (D) >>
In general formula (D), X ₁ Represents a heterocyclic group having a nitrogen atom adjacent to the substitution position. Examples of the heterocyclic group include 2-pyridyl group, 2-pyrazyl group, 2-thiazolyl group, 2-thiazolidyl group, 2- A pyrrolyl group, a 2-imidazolyl group, a 2-oxazolyl group, and the like can be given.
Etc.
[0047]
In general formula (D), Y ₁ Is a synonym with the substituent of the aromatic carbocyclic ring or heterocyclic ring described in the general formula (A).
[0048]
In general formula (D), Z ₁ Examples of the aromatic carbocyclic group represented by the formula include a phenyl group and a naphthyl group. In the general formula (D), Z ₁ The heterocyclic group represented by ₁ It is synonymous with the heterocyclic group as described in.
[0049]
<< Dye Represented by Formula (E) >>
In the general formula (E), L represents a -CH = group or a -N = group, preferably -N = group.
[0050]
In general formula (E), R ₁ , R ₂ A substituent represented by R _Three Is specifically a linear or branched alkyl group (for example, methyl group, ethyl group, iso-propyl group, tert-butyl group, n-dodecyl group, 1-hexylnonyl group, etc.) ), A cycloalkyl group (for example, cyclopropyl group, cyclohexyl group, bicyclo [2.2.1] heptyl group, adamantyl group, etc.), alkenyl group (for example, 2-propenyl group, 3-butenyl group, 1-methyl- 3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group, etc.), aryl group (for example, phenyl group, naphthyl group, o-tolyl group, m-tolyl group, p- Tolyl group, 9-anthranyl group, etc.), aralkyl group (for example, benzyl group, o-anisyl group, m-anisyl group, p-anisyl group, phenethyl group, etc.), complex Groups (for example, 2-tetrahydrofuryl group, 2-thiophenyl group, 4-imidazolyl group, 2-pyridyl group, etc.), halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, etc.), cyano group, nitro group, hydroxyl group An acyl group (for example, acetyl group, trifluoroacetyl group, pivaloyl group, benzoyl group, pentafluorobenzoyl group, 3,5-di-t-butyl-4-hydroxybenzoyl group), alkoxycarbonyl group (for example, methoxycarbonyl group) , Cyclohexyloxycarbonyl groups, alkoxycarbonyl groups such as n-dodecyloxycarbonyl groups, phenoxycarbonyl groups, 2,4-di-t-amylphenoxycarbonyl groups, aryloxycarbonyl groups such as 1-naphthyloxycarbonyl groups, and 2 -Pyridyloxycarbo Group, heterocyclic oxycarbonyl group such as 1-phenylpyrazolyl-5-oxycarbonyl group, etc.), carbamoyl group (for example, dimethylcarbamoyl group, 4- (2,4-di-t-amylphenoxy) butylaminocarbonyl group, etc.) Alkylcarbamoyl group, phenylcarbamoyl group, arylcarbamoyl group such as 1-naphthylcarbamoyl group), alkoxy group (for example, methoxy group, 2-ethoxyethoxy group, etc.), aryloxy group (for example, phenoxy group, 2,4-di-) t-amylphenoxy group, 4- (4-hydroxyphenylsulfonyl) phenoxy group, etc.), heterocyclic oxy group (eg 4-pyridyloxy group, 2-hexahydropyranyloxy group etc.), carbonyloxy group (eg acetyloxy) Group, trifluoroacetyloxy group, pivaloyl Alkylcarbonyloxy groups such as xy groups, aryloxy groups such as benzoyloxy groups and pentafluorobenzoyloxy groups), urethane groups (eg alkyl urethane groups such as N, N-dimethylurethane groups, N-phenylurethane groups, N Aryl urethane groups such as-(p-cyanophenyl) urethane group), sulfonyloxy groups (for example, methanesulfonyloxy group, trifluoromethanesulfonyloxy group, alkylsulfonyloxy group such as n-dodecanesulfonyloxy group, benzenesulfonyloxy group, arylsulfonyloxy groups such as p-toluenesulfonyloxy group), amino groups (for example, alkylamino groups such as dimethylamino group, cyclohexylamino group, n-dodecylamino group, anilino group, pt-octylanilino group, etc. Arylua Group), sulfonylamino groups (eg, methanesulfonylamino groups, heptafluoropropanesulfonylamino groups, alkylsulfonylamino groups such as n-hexadecylsulfonylamino groups, p-toluenesulfonylamino groups, pentafluorobenzenesulfonylamino groups, etc.) Arylsulfonylamino group), sulfamoylamino group (for example, alkylsulfamoylamino group such as N, N-dimethylsulfamoylamino group, arylsulfamoylamino group such as N-phenylsulfamoylamino group), Acylamino groups (eg alkylcarbonylamino groups such as acetylamino group and myristoylamino group, arylcarbonylamino groups such as benzoylamino group), ureido groups (eg alkylureido groups such as N, N-dimethylaminoureido group) Arylureido groups such as N-phenylureido group, N- (p-cyanophenyl) ureido group), sulfonyl groups (eg alkylsulfonyl groups such as methanesulfonyl group, trifluoromethanesulfonyl group, and aryl such as p-toluenesulfonyl group) Sulfonyl groups), sulfamoyl groups (for example, dimethylsulfamoyl groups, alkylsulfamoyl groups such as 4- (2,4-di-t-amylphenoxy) butylaminosulfonyl group, arylsulfamo groups such as phenylsulfamoyl groups) Moyl group), alkylthio group (eg, methylthio group, t-octylthio group, etc.), arylthio group (eg, phenylthio group, etc.), and heterocyclic thio group (eg, 1-phenyltetrazole-5-thio group, 5-methyl-1, 3,4-oxadiazole-2-thio group, etc.) R ₁ And R ₂ At least one of the groups is a group represented by the general formula (E-1).
[0051]
In general formula (E), Q is not particularly limited as long as it is a nonmetallic atom group necessary for forming a dye having absorption in the visible and infrared, but is preferably an aromatic carbocyclic group or heterocyclic group. Examples of such aromatic carbocycles and heterocycles include benzene rings, naphthalene rings, pyridine rings, pyrimidine rings, furan rings, thiophene rings, thiazole rings, imidazole rings, 3-H pyrrole rings, oxazoles. Ring, 3H-pyrrolidine ring, oxazolidine ring, oxazolinedione ring, hydroxypyridone ring, imidazolidine ring, thiazolidine ring, 3-Hindole ring, quinoline ring, isoquinoline ring, indolenine ring, barbitur ring, thiobarbitur ring, Rhodanine ring, hydantoin ring, thiohydantoin ring, pyrazolidinedione ring, pyridinedione ring, triazine ring, Razole ring, thiadiazole ring, 5-pyrazolone ring, pyrazolopyrrole ring, pyrazolopyrazole ring, pyrazoloimidazole ring, pyrazolotriazole ring, pyrazolotetrazole ring, pyrazolopyridone ring, oxazolone ring, isoxazolone ring, indandione ring, etc. Is mentioned.
[0052]
Among these, a benzene ring, a pyridine ring, a pyrimidine ring, a naphthalene ring, and the like are preferable, and these rings are further substituted with an alkyl group, a cycloalkyl group, or an aryl group at the para position with respect to the bonding position with L. It preferably has an amino group.
[0053]
In addition, the aromatic carbocycle and heterocycle represented by the above Q may further have a substituent, and the substituent is a substituent of the aromatic carbocycle described in formula (A), a heterocycle Synonymous with ring substituent.
[0054]
However, in the general formula (E), R ₁ , R ₂ Is a group represented by the general formula (E-1), and examples of the nitrogen-containing heterocycle represented by the general formula (E-1) include a pyridine ring, a pyrimidine ring, a thiazole ring, and an imidazole ring. , 3-H pyrrole ring, oxazole group, 3H-pyrrolidine ring, oxazolidine ring, oxazolinedione ring, hydroxypyridone ring, imidazolidine ring, thiazolidine ring, 3-H indole ring, quinoline ring, isoquinoline ring, indolenine ring, rhodanine Ring, hydantoin ring thiohydantoin ring, pyrazolidinedione ring, pyridinedione ring, triazine ring, pyrazole ring, thiadiazole ring, 5-pyrazolone ring, pyrazolopyrrole ring, pyrazolopyrazole ring, pyrazoloimidazole ring, pyrazolotriazole Ring, pyrazolotetrazole ring, pyrazolopyridone ring, oxazo Ring, isoxazolone ring, indandione ring, pyrazine ring, pyridazine ring, indolizine ring, indole ring, indazole ring, purine ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, pteridine ring , Isoxazole ring, pyrroline ring and the like. These heterocyclic rings may further have a substituent, and the substituent is synonymous with the aromatic carbocyclic substituent and the heterocyclic substituent described in Formula (A).
[0055]
<< Dye Represented by Formula (F) >>
In the general formula (F), L represents a -CH = group or a -N = group, preferably -N = group.
[0056]
In the general formula (F), the substituent represented by R has the same meaning as the aromatic carbocyclic and heterocyclic substituents described in the general formula (A).
[0057]
In the general formula (F), the nonmetallic atom group necessary for forming a dye having visible or infrared absorption represented by Q has the same meaning as Q described in the general formula (E).
[0058]
In the general formula (F), examples of the nitrogen-containing heterocyclic ring containing Z include a pyrrole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, and a piperidine ring.
[0059]
<< Dye Represented by General Formula (G) >>
In general formula (G), R ₁ , R ₂ The substituent represented by is synonymous with the substituent of the aromatic carbocyclic ring and heterocyclic ring described in the general formula (A). However, in general formula (G), R ₁ , R ₂ Is a nitrogen-containing heterocyclic group represented by the general formula (G-1).
[0060]
Examples of the nitrogen-containing heterocyclic group represented by the general formula (G-1) include the same substituents as those given as examples of the general formula (E-1). These heterocyclic rings may further have a substituent, and examples of the substituent are the same as the aromatic carbocyclic substituent and the heterocyclic substituent described in the general formula (A). .
[0061]
In the general formula (G), X is —NR. _Three -In the case of a group, R _Three Is the same as the substituent of the aromatic carbocycle and the substituent of the heterocyclic ring described in the general formula (A).
[0062]
In the general formula (G), the nonmetallic atom group necessary for forming a dye having visible or infrared absorption represented by Q is synonymous with Q described in the general formula (E).
[0063]
Although the specific example of the pigment | dye represented by the said general formula (A)-general formula (G) which comprises the metal complex of the pigment | dye which concerns on this invention below is shown, this invention is not limited to these.
[0064]
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[0065]
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[0066]
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[0067]
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[0068]
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[0069]
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[0070]
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[0071]
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[0072]
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[0073]
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[0074]
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[0075]
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[0076]
<< Metal Complex Dye Represented by Formula (H) >>
The metal complex dye represented by the general formula (H) used in the same manner as the metal complex of the dye represented by the general formula (A) to the general formula (G) described above will be described.
[0077]
In general formula (H), R ₁ , R ₂ , R _Three , R _Four In the general formula (E), each of the substituents represented by R ₁ , R ₂ A substituent represented by R _Three Are preferably the same as the substituents represented by formula (1), preferably a halogen atom, an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, iso-pentyl group, 2- Ethyl-hexyl group, octyl group, etc.), aryl group (for example, phenyl group, naphthyl group, etc.), heterocyclic group (for example, imidazolyl group, thiazolyl group, benzoxazolyl group, pyridyl group, pyrrolyl group, indolyl group, Pyrimidinyl group etc.), acyl group (eg acetyl group, benzoyl group etc.), amino group (eg amino group, N, N-dimethylamino group, N, N-diethylamino group etc.), alkoxyl group (eg methoxy group, Ethoxy group, propoxy group, etc.).
[0078]
R ₁ ~ R _Four It is more preferable that at least one of the above is a halogen atom or the above-described substituent, and it is more preferable that m and n are 1 each other, and R ₁ , R _Three And R _Four Is a hydrogen atom and R ₂ Is a halogen atom or the aforementioned substituent.
[0079]
In general formula (H), Y ₁ Represents a 3-fused heterocycle, a 4-fused heterocycle or a 2-fused heterocycle having a substituent. Here, the 3-fused heterocycle has a structure in which at least one of the 3 rings is a heterocycle. The 4-fused heterocycle has a structure in which four rings, at least one of which is a heterocycle, are condensed, and the 3-fused heterocycle and the 4-fused heterocycle each have a substituent. Substitution is also possible. Moreover, the bicondensed heterocyclic ring having a substituent has a structure in which two rings, at least one of which is a heterocyclic ring, are condensed, and has a substituent on the ring. As a substituent of the said 2 condensed heterocyclic ring, it is synonymous with the substituent of the aromatic carbocyclic ring described in General formula (A), and the substituent of a heterocyclic ring.
[0080]
In the general formula (H), the metal ion represented by M is M in the metal complex of the dye described above. ^{l +} It is synonymous with the metal ion represented by these.
[0081]
In the general formula (H), examples of the anion represented by Z include halide ions (fluoride, chloride, bromide, iodide, etc.), sulfite ions, sulfate ions, alkyl or aryl sulfonate ions, nitrate ions, nitrite ions, Examples include perchlorate ion, carboxylate (acetate, trifluacetate, stearylate, etc.), salicinate, benzoate, hexafluorophosphate, tetrafluoroborate and the like.
[0082]
In general formula (H), X ₁ As for, the bivalent substituent represented by the said general formula (H-1)-general formula (H-4) is used preferably.
[0083]
In the divalent substituents represented by the general formulas (H-1) to (H-4), R ₁ , R ₂ , R _Three , R _Four , R _Five , R ₆ , R ₇ Are each synonymous with the aromatic carbocyclic substituent and heterocyclic substituent described in Formula (A).
[0084]
In the general formula (H-1), R ₁ , R ₂ At least one represents a substituent capable of forming at least a bidentate coordination bond with the metal ion M together with the nitrogen atom of the general formula (H-1).
[0085]
In general formula (H-2), R _Three Represents a substituent capable of forming at least a bidentate coordination bond with the metal ion M together with the nitrogen atom of the general formula (H-2).
[0086]
In general formula (H-3), R _Three , R _Four At least one represents a substituent capable of forming at least a bidentate coordination bond with the metal ion M together with the nitrogen atom of the general formula (H-3).
[0087]
In general formula (H-4), L ₁ Is a nitrogen atom or -CR ₈ = And L ₂ Is a nitrogen atom or -CR ₉ = And L _Three Is a nitrogen atom or -CR _Ten =.
[0088]
Where R ₈ , R ₉ And R _Ten And each of the substituents represented by formula (A) includes a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or an aromatic carbocyclic substituent or a heterocyclic substituent described in Formula (A) Etc.
[0089]
R ₈ , R ₉ And R _Ten At least one of these represents a group of atoms capable of forming at least a bidentate coordination bond with a metal atom together with the nitrogen atom of the general formula (H-4).
[0090]
In general formula (H), Y ₁ As the divalent substituent containing a 3-fused heterocycle, a 4-fused heterocycle or a 2-fused heterocycle having a substituent, a substituent composed of the above general formulas (Y-1) to (Y-11) A base group is preferably used.
[0091]
Here, the substituent group which consists of general formula (Y-1)-general formula (Y-11) is demonstrated.
[0092]
In the general formulas (Y-1) to (Y-11), R ₁ , R ₂ Examples of the halogen atom represented by the formula include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom.
[0093]
In the general formulas (Y-1) to (Y-11), R ₁ , R ₂ Examples of the alkyl group represented by the formula include a methyl group, an ethyl group, a butyl group, a pentyl group, a 2-methoxyethyl group, a trifluoromethyl group, and a 2-ethylhexyl group. These substituents may further have a substituent.
[0094]
In the general formulas (Y-1) to (Y-11), R ₁ , R ₂ Examples of the aryl group represented by the formula include a phenyl group and a naphthyl group. These substituents may further have a substituent.
[0095]
In the general formulas (Y-1) to (Y-11), R ₁ , R ₂ Examples of the alkoxyl group represented by the formula include a methoxy group, an ethoxy group, and a butoxy group. These substituents may further have a substituent.
[0096]
In the general formulas (Y-1) to (Y-11), R ₁ , R ₂ Examples of the alkylthio group represented by the formula include a methylthio group, an ethylthio group, and an octylthio group. These substituents may further have a substituent.
[0097]
In the general formulas (Y-1) to (Y-11), R ₁ , R ₂ Examples of the arylthio group represented by the formula include a phenylthio group and a p-tolylthio group. These substituents may further have a substituent.
[0098]
In the general formulas (Y-1) to (Y-11), R ₁ , R ₂ Examples of the amino group represented by the formula include amino group, methylamino group, diethylamino group, methoxyethylamino group, and phenylamino group. These substituents may further have a substituent.
[0099]
In general formulas (Y-1) to (Y-11), Y ₁₁ , Y ₁₂ Are respectively-(NR _Five )-Group represents R _Five As the substituent represented by formula (1), an alkyl group (for example, methyl group, ethyl group, butyl group, pentyl group, 2-methoxyethyl group, trifluoromethyl group, 2-ethylhexyl group, etc.), aryl group (phenyl group, Naphthyl group, etc.). These substituents may further have a substituent.
[0100]
From the viewpoint of obtaining the effects described in the present invention more preferably, among the above general formulas (Y-1) to (Y-11), Y ₁₁ , Y ₁₂ At least one of or Y _{twenty one} , Y _{twenty two} , Y _{twenty three} At least one of which is-(NR _Five )-Group, more preferably Y ₁₁ And Y ₁₂ Are both-(NR _Five )-Group, each R _Five The total number of carbon atoms is adjusted to be 3 or more.
[0101]
Moreover, as one of the preferable aspects, it is using the condensed ring compound residue represented by the said general formula (Y-1), (Y-4), or (Y-8), and another preferable aspect. As one of the general formulas (Y-1), (Y-4), or (Y-8), at least one of m1 and m2 is not 0, and the general formula (Y-1), This is a case where the compound residue represented by (Y-4) or (Y-8) is a bi-fused heterocyclic compound residue having a substituent.
[0102]
Of the general formulas (H-1) to (H-4) described above, partial structural parts represented by the following general formulas (X-1) to (X-8) are preferably used. .
[0103]
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[0104]
Where R _{twenty two} , R _{twenty three} , R _{twenty four} Are each a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.) or a substituent (eg, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, a nitro group, a cyano group, An acylamino group, an alkoxyl group, a hydroxyl group, an alkoxycarbonyl group, etc.).
[0105]
In the general formulas (X-1) to (X-8), Q represents a nonmetallic atomic group necessary for forming a nitrogen-containing atomic group, and is synonymous with Q described in the general formula (E). . L represents a -CH = group or -N = group, and preferably -N = group.
[0106]
Although the specific example of the metal complex dye represented by the said general formula (H) based on this invention is given to the following, this invention is not limited to these.
[0107]
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[0108]
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[0109]
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[0110]
In the general formula (H), the metal ion represented by M is Ni. ²⁺ , Co ²⁺ , Cu ²⁺ , Zn ²⁺ , Cr ²⁺ , Pt ²⁺ , Pd ²⁺ , Fe ²⁺ , Fe ³⁺ Etc. are preferred.
[0111]
Examples of the anion represented by Z include enolate (acetylacetonate, hexafluoroacetylacetonate, etc.), halogen ion (fluoride, chloride, bromide, iodide, etc.), hydroxide ion, sulfite ion, sulfate ion, Alkyl or aryl sulfonate ion, nitrate ion, nitrite ion, carbonate ion, perchlorate ion, alkyl or aryl carboxylate ion, fatty acid ion, phenol ion, dithiocarboxylate ion, tetraalkylborate, salicinate, benzoate, PF ^6- , BF ^Four- , SbF ^6- And the like are preferable.
[0112]
In the general formula (H), q represents 0, 1, 2 or 3, and when q is 2 or 3, a plurality of anions represented by Z may be the same or different chemical species. Good.
[0113]
Examples of the metal complex of the dye represented by the general formulas (A) to (G) and the metal complex dye represented by the general formula (H) according to the present invention include, for example, Japanese Patent Application Nos. 2000-160130 and 2000-. 165907, 2000-239889, 2001-204594, etc., and can be synthesized by referring to synthesis methods well known to those skilled in the art.
[0114]
<Polymer fine particles>
The colored fine particles of the present invention are characterized in that the polymer fine particles contain a metal complex or a metal complex dye of the dye described above. Here, the polymer fine particles according to the present invention will be described.
[0115]
The average particle diameter of the polymer fine particles containing the metal complex dye or the metal complex of the dye is preferably 500 nm or less, more preferably 10 nm to 300 nm, and particularly preferably 20 nm to 200 nm. The method for obtaining the average particle size of the polymer fine particles is the same as the method for obtaining the average particle size of the colored fine particles described above.
[0116]
For the preparation of the polymer fine particles according to the present invention, a polymer selected from the following groups (A) to (D) is preferably used.
[0117]
(A): Polyethylene, polypropylene, etc., polystyrene, polyvinyl chloride, polyvinyl acetate, polyacrylic acid (methacrylic acid) ester, polyacrylonitrile, polyvinyl butyral, polyvinyl alcohol, and the like.
[0118]
(B): Polyethylene terephthalate, alkyd resin, maleic acid resin, urethane rubber, polycarbonate and the like can be mentioned.
[0119]
(C): Nylon and polyurethane are mentioned.
(D): Examples include polyethylene oxide, polypropylene oxide, polyformaldehyde, and epoxy resin.
[0120]
These polymers may have a substituent, and the substituent may have a linear, branched, or cyclic structure.
[0121]
About the polymer which has a repeating structure chosen from the above-mentioned description (A)-(D) concerning the present invention, the kind, physical properties, etc. are described in POLYMER HANDBOOK 4th edition (JOHN WILEY & SONS, INC.), Information can be obtained easily.
[0122]
The polymer used for the preparation of polymer fine particles according to the present invention preferably has a number average molecular weight of 500 to 100,000, particularly 1,000 to 30,000 from the viewpoint of durability of colored fine particles and suspension formability.
[0123]
The glass transition point (Tg) of the polymer can be variously used, but at least one of the polymers used preferably has a Tg of 10 ° C. or higher.
[0124]
Various polymers shown in the above (A) to (D) are commercially available, but can be synthesized by a conventional method. These copolymers can also be obtained, for example, by introducing an epoxy group into one polymer molecule and then performing polycondensation with another polymer or graft polymerization using light or radiation.
[0125]
In the preparation of the polymer fine particles according to the present invention, polymers particularly preferably used are a polymer containing an acetal group, a polymer containing a carbonate group, a polymer containing a hydroxyl group, and a polymer having an ester group.
[0126]
Examples of the polymer containing acetal as a main functional group include polyvinyl butyral resin. For example, # 2000-L, # 3000-1, # 3000-2, # 3000-4, # 3000-K, # 4000-1, # 4000-2, # 5000-A, # 5000 manufactured by Denki Kagaku Kogyo Co., Ltd. 6000-C, # 6000-EP, or BL-1, BL-1H, BL-2, BL-2H, BL-5, BL-10, BL-S, BL-SH, BX-10 manufactured by Sekisui Chemical Co., Ltd. , BX-L, BM-1, BM-2, BM-5, BM-S, BM-SH, BH-3, BH-6, BH-S, BX-1, BX-3, BX-5, KS -10, KS-1, KS-3, KS-5, and the like.
[0127]
The polyvinyl butyral resin is obtained as a derivative of PVA (polyvinyl alcohol), and the acetalization of the hydroxyl group of the original PVA is about 80 mol% at the maximum, and usually about 50 mol% to about 80 mol%. In addition, the acetal said here does not indicate a 1,1-diethoxyethane group in a narrow sense but indicates a compound in general with orthoaldehyde. The hydroxyl group is not particularly defined but is preferably contained in an amount of 10 to 40 mol%. Moreover, although there is no restriction | limiting in particular in the content rate of an acetyl group, it is preferable that it is 10 mol% or less. The polymer containing acetal as the main functional group means that at least 30 mol% of the oxygen atoms contained in the polymer forms an acetal group.
[0128]
In addition, Iupital series manufactured by Mitsubishi Engineering Plastics Co., Ltd. can be used as a polymer containing acetal as a main functional group.
[0129]
Polycarbonate resin is mentioned as a polymer which contains carbonate ester as a main functional group. For example, there are Iupilon series and Novalex series manufactured by Mitsubishi Engineering Plastics. The Iupilon series is made with bisphenol A as a raw material, and various molecular weights can be used although the values differ depending on the measurement method. In the NOVAREX series, those having a molecular weight of 20,000 to 30,000 and a glass point transfer of around 150 ° C. can be used, but are not limited thereto.
[0130]
The polymer containing a carbonate group as a main functional group means that at least 30 mol% of oxygen atoms contained in the polymer contribute to the formation of the carbonate group.
[0131]
Examples of the polymer containing a hydroxyl group as a main functional group include PVA. Although the solubility of PVA in organic solvents is often small, the solubility in organic solvents increases with PVA having a low saponification value. PVA having high water solubility can be used by adding it to the aqueous phase and adsorbing it to the polymer suspension after removing the organic solvent.
[0132]
Commercially available PVA can be used, for example, Kuraray's Poval PVA-102, PVA-117, PVA-CSA, PVA-617, PVA-505, and other special brands of sizing agents, PVA As the PVA for molding and other functional polymers, KL-506, C-118, R-1130, M-205, MP-203, HL-12E, SK-5102, and the like can be used. The saponification degree is generally 50 mol% or more, but even when it is about 40 mol% as in LM-10HD, it can be used. Other than such PVA, those having a hydroxyl group as the main functional group can be used, but those having at least 20 mol% of the oxygen atoms contained in the polymer forming a hydroxyl group can be used.
[0133]
Examples of the polymer containing an ester group as a main functional group include a methacrylic resin. Asahi Kasei Delpet series 560F, 60N, 80N, LP-1, SR8500, SR6500, etc. can be used. The polymer containing an ester group as a main functional group means that at least 30 mol% of the oxygen atoms contained in the polymer form an ester group.
[0134]
These polymers may be used alone or in combination of two or more. Further, if these polymers are contained in a mass ratio of 50% or more, other polymers and inorganic fillers may be contained.
[0135]
It is also preferable to use a copolymer of these polymers. For example, as a method of copolymerizing a polymer containing a hydroxyl group and various polymers, the hydroxyl group is reacted with a monomer having an epoxy group such as glycidyl methacrylate, and then, It can also be obtained by copolymerizing with a methacrylic acid ester monomer by suspension polymerization.
[0136]
Ink for inkjet recording
The ink for inkjet recording of the present invention will be described.
[0137]
The ink for inkjet recording of the present invention is a suspension in which a polymer in which a metal complex dye or a metal complex of a dye is encapsulated (also referred to as containing) is dispersed in an aqueous medium in the polymer fine particles described above.
[0138]
That is, the metal complex dye is encapsulated in at least a micelle formed by the polymer, and the inkjet recording ink of the present invention has the polymer micelle encapsulating the metal complex dye present as a suspension in an aqueous medium. What is formed is preferable.
[0139]
The metal complex dye or the metal complex of the dye according to the present invention is preferably dissolved in an ester solvent or a ketone solvent in an amount of 10 g / L or more from the viewpoint of being efficiently encapsulated in the polymer by phase inversion emulsification described later. It is more preferable to dissolve ~ 600 g / L.
[0140]
In using the inkjet recording ink of the present invention, from the viewpoint of effectively preventing clogging of the printer head by appropriately suppressing ink thickening and suspension aggregation due to ink evaporation at the nozzle tip of the inkjet head. In the ink for ink jet recording of the present invention, the polymer is preferably blended in the ink in an amount of 0.5% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass. preferable.
[0141]
On the other hand, from the viewpoint of improving the temporal stability of the suspension particle diameter and suppressing the increase in the particle diameter, the content of the metal complex dye in the ink is preferably blended in an amount of 1% by mass to 30% by mass. More preferably, the blended amount is 1.5 to 25% by mass.
[0142]
In the ink for inkjet recording of the present invention, various conventionally known additives such as various additives are used depending on the purpose of improving ejection stability, compatibility with a print head or ink cartridge, storage stability, image storage stability, and other various performances. Wetting agents such as monohydric alcohols, silicone-based antifoaming agents, viscosity modifiers, surface tension modifiers, specific resistance modifiers, film forming agents, dispersants, surfactants, ultraviolet absorbers, antioxidants, An anti-fading agent, an antifungal agent such as chloromethylphenol and / or a chelating agent such as EDTA, an oxygen absorber such as sulfite, and a rust inhibitor may be added.
[0143]
Examples of the wetting agent include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Polyhydric alcohols such as glycol monobutyl ether, methyl carbitol, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, diethyl carbitol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether and ethers thereof , Acetates, N-methyl- - pyrrolidone, 1,3-dimethylimidazolidinone, triethanolamine, formamide, nitrogen-containing compounds such as dimethyl formamide, one dimethyl monkey sulfoxide or may be used two or more kinds. Although there is no restriction | limiting in particular in the compounding quantity of these wetting agents, Preferably 0.1-50 mass% can be mix | blended in the said ink, More preferably, 0.1-30 mass% can be mix | blended.
[0144]
Although it does not restrict | limit especially as a dispersing agent, The HLB value is 8-18 from the point which the effect as a dispersing agent expresses and there exists an increase suppression effect of the particle diameter of a suspension. A commercial item can also be used as a dispersing agent, for example, the dispersing agent demol SNB, MS, N, SSL, ST, P (brand name) by Kao Co., Ltd. is mentioned.
[0145]
Although there is no restriction | limiting in particular in the compounding quantity of a dispersing agent, It is preferable to mix | blend 0.01-10 mass% in the aqueous ink for inkjet recording of this invention. When the compounding amount of the compound is less than 0.01% by mass, it is difficult to reduce the particle size of the suspension. When the compounding amount exceeds 10% by mass, the particle size of the suspension increases or the suspension stability decreases, resulting in gelation. Since there exists a possibility, it is preferable to set it as the said range.
[0146]
The antifoaming agent is not particularly limited, and a commercially available product can be used. For example, KF96, 66, 69, KS68, 604, 607A, 602, 603, KM73, 73A, 73E, 72, 72A manufactured by Shin-Etsu Silicone Co., Ltd. 72C, 72F, 82F, 70, 71, 75, 80, 83A, 85, 89, 90, 68-1F, 68-2F (trade name) and the like. Although there is no restriction | limiting in particular in the compounding quantity of these compounds, It is preferable to mix | blend 0.001-2 mass% in the water-system ink which concerns on this invention. If the compounding amount of the compound is less than 0.001% by mass, bubbles are likely to be generated at the time of preparing the ink, and it is difficult to remove small bubbles in the ink. During printing, repellency may occur in the ink and the print quality may be deteriorated.
[0147]
In addition, the ink for ink jet recording of the present invention can be used as ink for writing instruments such as general fountain pens, ballpoint pens, sign pens, etc. in addition to ink for ink jet recording. The suspension of the present invention can be dried to obtain a fine powder. The obtained powder can be used for toner for electrophotography.
[0148]
<< Method for Producing Ink for Inkjet Recording of the Present Invention >>
Next, the manufacturing method of the ink for inkjet recording of this invention is demonstrated. The ink for inkjet recording of the present invention can be produced by various conventionally known emulsification methods.
[0149]
Various methods can be used as the emulsification method. Examples thereof are summarized in, for example, the description on page 86 of “Advances in Functional Emulsifier / Emulsification Technology and Application Development CMC”. In the present invention, it is particularly preferable to use an emulsifying and dispersing apparatus using ultrasonic waves, high-speed rotational shearing, and high pressure.
[0150]
In the emulsification dispersion using ultrasonic waves, two types of so-called batch type and continuous type can be used. The batch method is suitable for producing a relatively small amount, and the continuous method is suitable for producing a large amount. In the continuous type, for example, a device such as UH-600SR (manufactured by SMT Co., Ltd.) can be used. In the case of such a continuous type, the irradiation time of ultrasonic waves can be obtained by the dispersion chamber volume / flow velocity × the number of circulations. When there are a plurality of ultrasonic irradiation apparatuses, the total irradiation time is obtained. The ultrasonic irradiation time is actually required for 3 seconds or more, and if the emulsification is completed within that time, an ultrasonic emulsification dispersion apparatus is not required. Further, if it is necessary for 10000 seconds or more, the load on the process is large, and in practice, it is necessary to shorten the emulsification dispersion time by reselecting the emulsifier. Therefore, more than 10,000 seconds are not necessary. More preferably, it is 10 seconds or more and 2000 seconds or less.
[0151]
Examples of the emulsifying and dispersing apparatus using high-speed rotational shearing include a disper mixer as described in pages 255 to 256 of "Functional emulsifier / emulsification technology and application development CMC", and page 251. Such a homomixer can be used, and an ultramixer as described on page 256 can be used. These types can be properly used depending on the liquid viscosity at the time of emulsification dispersion. In the emulsification disperser using these high-speed rotary shears, the rotational speed of the stirring blade is important. Since the clearance with the stator is usually about 0.5 mm and cannot be made extremely narrow, the shearing force mainly depends on the peripheral speed of the stirring blade. If the peripheral speed is 5 m / s to 150 m / s, it can be used for emulsification and dispersion of the present invention. This is because when the peripheral speed is low, it is often impossible to reduce the particle size even if the emulsification time is extended, and in order to achieve 150 m / s, it is necessary to extremely increase the performance of the motor. More preferably, it is 20 m / s-100 m / s.
[0152]
For emulsification and dispersion by high pressure, LAB2000 (manufactured by SMT) can be used, but the emulsification and dispersion ability depends on the pressure applied to the sample.
[0153]
The pressure is 9.8 MPa to 490 MPa (100 kg / cm ² ~ 5000kg / cm ² The following is preferable. Further, the desired particle size can be obtained by emulsifying and dispersing several times as necessary. More preferably, 49 MPa to 196 MPa (500 kg / cm ² ~ 2000kg / cm ² ).
[0154]
These emulsifying / dispersing devices may be used alone or in combination as necessary. Colloid mills and flow jet mixers alone cannot achieve the object of the present invention, but by combining with the apparatus of the present invention, it is possible to enhance the effects of the present invention, such as enabling emulsification and dispersion in a single hour. is there.
[0155]
The ink of the present invention can be produced by so-called phase inversion emulsification in addition to using the above-described apparatus.
[0156]
In the phase inversion emulsification, the polymer is dissolved in an organic solvent such as ester or ketone together with the metal complex dye, and a neutralizing agent is added as necessary to ionize the carboxyl group in the polymer, and then the aqueous phase. Is added, and then the organic solvent is distilled off and the phase is changed to an aqueous system.
[0157]
After the phase inversion is completed, the above-mentioned ester and ketone solvents are removed by heating the system under reduced pressure, and a predetermined amount of water is removed, whereby the inkjet recording ink of the present invention having a desired concentration is obtained. can get.
[0158]
<< Inkjet recording method of the present invention >>
The ink jet recording method of the present invention will be described.
[0159]
In the ink jet recording method of the present invention, image recording is performed on a recording medium containing fine particles of silica or alumina and at least one hydrophilic binder as described below, using the ink for ink jet recording described above. Is a feature.
[0160]
(Silica fine particles, alumina fine particles)
The silica fine particles and alumina fine particles according to the present invention will be described.
[0161]
In the present invention, fine particles of silica or alumina are used from the viewpoint of obtaining high-quality prints on inkjet recording paper. As the fine particles, alumina, colloidal silica, or fine particle silica synthesized by a gas phase method is preferable, and fine particle silica synthesized by a gas phase method is particularly preferable. The silica synthesized by this vapor phase method may have a surface modified with Al. The Al content of vapor-phase process silica whose surface is modified with Al is preferably 0.05 to 5% by mass with respect to silica.
[0162]
From the viewpoint of improving glossiness and color developability after image recording, the fine particles may have any particle size, but the average particle size is preferably 1 μm or less, more preferably 0. .2 μm or less, particularly preferably 0.1 μm or less. The lower limit of the particle size is not particularly limited, but is preferably about 0.003 μm or more, particularly preferably about 0.005 μm or more from the viewpoint of production of fine particles.
[0163]
The average particle size of the fine particles is obtained as a simple average value (number average) by observing the cross section or surface of the recording medium with an electron microscope and determining the particle size of 100 arbitrary particles. Here, each particle size is expressed by a diameter assuming a circle equal to the projected area.
[0164]
Further, the degree of dispersion of the fine particles is preferably 0.5 or less from the viewpoint of glossiness and color developability. If it exceeds 0.5, gloss and color developability at the time of printing tend to decrease. In particular, 0.3 or less is preferable. Here, the degree of dispersion of the fine particles refers to a value obtained by observing the fine particles of the porous layer with an electron microscope in the same manner as obtaining the average particle size and dividing the standard deviation by the average particle size.
[0165]
The fine particles may remain as primary particles, or may be present in the porous film as secondary particles or higher-order aggregated particles, but the average particle size is determined by observation with an electron microscope. Refers to the particle size of the particles forming independent particles in the recording medium.
[0166]
The content of the fine particles in the recording medium is preferably 5% by mass to 40% by mass, and more preferably 7% by mass to 30% by mass.
[0167]
《Hydrophilic binder》
The hydrophilic binder according to the present invention will be described.
[0168]
The term “hydrophilic” as used in the present invention is applicable to a mixed solvent of water and a water-miscible organic solvent such as methanol, isopropyl alcohol, acetone, ethyl acetate, etc. Soluble polymers are also included. In this case, the amount of the water-miscible organic solvent is usually 50% by mass or less based on the total amount of the solvent.
[0169]
The term “hydrophilic” refers to a solvent in which the binder is usually dissolved in an amount of 1% by mass or more at room temperature, and more preferably 3% by mass or more.
[0170]
Examples of the hydrophilic binder used in the present invention include polyvinyl alcohol, gelatin, polyethylene oxide, polyvinyl pyrrolidone, casein, starch, agar, carrageenan, polyacrylic acid, polymethacrylic acid, polyacrylamide, polymethacrylamide, polystyrene sulfonic acid, Examples thereof include hydrophilic polymers such as cellulose, hydroxylethylcellulose, carboxymethylcellulose, hydroxylethylcellulose, dextran, dextrin, pullulan, and water-soluble polyvinyl butyral. Two or more of these hydrophilic polymers can be used in combination.
[0171]
(Inkjet head)
The inkjet head that can be used in the inkjet recording method of the present invention may be an on-demand system or a continuous system. In addition, as a discharge method, an electro-mechanical conversion method (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.), an electro-thermal conversion method (for example, a thermal type) Specific examples include an ink jet type, a bubble jet (R) type, an electrostatic attraction method (for example, an electric field control type, a slit jet type, etc.) and a discharge method (for example, a spark jet type). However, any discharge method may be used.
[0172]
By providing an image with the above-described configuration, an uncomfortable feeling due to a reduction in gloss difference between the printed portion and the non-printed portion is improved, and an inkjet recording method having excellent abrasion resistance, print density, and printer transportability is provided. I can do it.
[0173]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.
[0174]
Example 1
<< Preparation of colored fine particles A >>
As polymer fine particles, 15 g of polyvinyl butyral (BL-S manufactured by Sekisui Chemical Co., Ltd., average polymerization degree 350) is used, 10 g of a metal complex dye which is a nickel acetylacetonate complex of dye (A-1), and 150 g of ethyl acetate are separable flasks. The flask was purged with nitrogen and stirred to completely dissolve the polymer and the metal complex dye. Subsequently, as a dispersant, 150 g of an aqueous solution containing 6 g of sodium lauryl sulfate and 2 g of a water-soluble polymer MP-203 (manufactured by Kuraray) was added dropwise and stirred. ) For 300 seconds. Thereafter, ethyl acetate was removed under reduced pressure, and the colored fine particles A of the present invention were obtained as an aqueous dispersion of polymer fine particles in which the metal complex dye of the dye (A-1) was dispersed and impregnated inside the particles.
[0175]
<< Preparation of colored fine particles BP >>
In the preparation of the colored fine particles A, the colored fine particles B to P of the present invention were obtained in the same manner except that the metal complex dyes shown in Table 1 were used instead of the metal complex dyes of the dye (A-1). .
[0176]
<< Preparation of Comparative Colored Fine Particles Q >>
In the preparation of the colored fine particles A, instead of the dye (A-1), C.I. I. Comparative colored fine particles Q were obtained in the same manner except that Solvent Red8 was used.
[0177]
<< Preparation of inkjet recording inks 1-16 >>
80 g of colored fine particles shown in Table 1
Diethylene glycol 10g
Glycerin 9.8g
Acetylenol EL (manufactured by Kawaken Fine Chemicals) 0.20g
The above materials were mixed, stirred and dispersed, and the resulting dispersion was filtered through a 5 μm filter to remove dust and coarse particles, thereby preparing ink jet recording inks 1 to 16 of the present invention.
[0178]
<< Preparation of Comparative Inkjet Recording Ink 17 >>
In the preparation of the inkjet recording ink 1 of the present invention, C.I. I. A comparative inkjet recording ink 17 was prepared in the same manner except that the Solvent Red 8 nickel acetylacetonate complex was used.
[0179]
<< Preparation of Comparative Inkjet Recording Ink 18 >>
C. I. Acid Red52 4g
Diethylene glycol 7.5g
Glycerin 7.5g
80.60g of water
Acetylenol EL (Kawaken Fine Chemical) 0.40g
The above materials were mixed for 12 hours using a ball mill, and the resulting dispersion was filtered through a 5 μm filter to remove dust and coarse particles, whereby a comparative ink jet recording ink 18 was obtained.
[0180]
Each of the obtained ink jet recording inks 1 to 18 was evaluated as described below.
[0181]
<< Image preparation and evaluation method >>
Using each of the inks for ink jet recording 1 to 18 described above, printing is performed on Konica photo jet paper Photolike, QP glossy paper (manufactured by Konica Corporation) with a commercially available Epson ink jet printer (model number PM-800). Samples 1 to 16 of the present invention shown in Table 1 and comparative samples 17 and 18 were obtained.
[0182]
The obtained samples were evaluated for light resistance and color tone as described below.
(Light resistance evaluation)
The light fastness was evaluated by the following four-step evaluation by calculating the reduction rate of the reflection spectrum concentration at the maximum absorption wavelength in the visible region from the unexposed sample after being exposed for 24 hours with a xenon fade meter.
[0183]
A: Decrease rate is less than 10%
○: Decrease rate of 10% or more and less than 30%
Δ: Decrease rate of 30% or more and less than 50%
X: Reduction rate is 50% or more
(Color evaluation)
The evaluation of the color tone was performed by visual judgment using a total of 10 monitors of 5 adult men and 5 adult women selected at random, and the rank was evaluated based on the number of monitors determined to be an acceptable level.
[0184]
○: Allowable level is 7 or more (practical)
×: Acceptable level is less than 7 (unusable)
The obtained evaluation results are shown in Table 1.
[0185]
[Table 1]

[0186]
From Table 1, it is clear that the sample of the present invention is superior in both light resistance and color tone as compared with the comparison.
[0187]
【The invention's effect】
According to the present invention, there are provided colored fine particles having improved color fastness and less discoloration, an ink for ink jet recording excellent in color reproducibility and image fastness using the color fine particles, a method for producing an ink for ink jet recording, and an ink jet recording method. I was able to provide it.

Claims (14)

Colored fine particles, wherein the polymer fine particles contain a metal complex of a dye represented by the following general formula (A).

[In the formula, Z ₁ and Z ₂ represent an aromatic carbon ring or a group of atoms forming a heterocyclic ring, and the ring may further have a substituent or may form a condensed ring. Good. Z ₁ and Z ₂ may be the same or different. X is an oxygen atom, —N (R ′) — group (R ′ represents a hydrogen atom or an alkyl group), or a sulfur atom, and X is bonded to Z ₁ or Z ₂ to form a ring. Also good. L _1, L _2, L ₃ represents a methine group. n represents 0, 1, 2; ] The colored fine particles according to claim 1, wherein the dye represented by the general formula (A) is a dye represented by the following general formula (B).

[In the formula, Z ₁ , Z ₂ , Z ₃ and Z ₄ represent an aromatic carbocyclic ring or a group of atoms forming a heterocyclic ring, and the ring may further have a substituent, and a condensed ring May be formed. Z ₁ , Z ₂ , Z ₃ and Z ₄ may be the same or different. L _1, L _2, L ₃ represents a methine group. n represents 0, 1, 2; ] Colored fine particles, wherein the polymer fine particles contain a metal complex of a dye represented by the following general formula (C).

[Wherein, A ₁ , A ₂ , A ₃ , A ₄ , B ₁ , B ₂ , B ₃ , B ₄ represent a carbon atom or a nitrogen atom, and the ring may have a substituent. Further, a condensed ring may be formed. R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent. ] Colored fine particles, wherein the polymer fine particles contain a metal complex of a dye represented by the following general formula (D).

[Wherein, X ₁ represents a heterocyclic group having a nitrogen atom adjacent to the substitution position, Y ₁ represents a substituent, and Z ₁ represents an aromatic carbocyclic group or a heterocyclic group. ] Colored fine particles, wherein the polymer fine particles contain a metal complex of a dye represented by the following general formula (E).

[Wherein, R ₁ and R ₂ represent a hydrogen atom or a substituent, and R ₃ represents a substituent. L represents a -CH = group or a -N = group. Q represents an aromatic carbocyclic group or heterocyclic group necessary for forming a dye having absorption in the visible or infrared. However, either R ₁ or R ₂ is a nitrogen-containing heterocyclic group represented by the following general formula (E-1). ]

[In formula, Za represents a nonmetallic atom group required in order to form a nitrogen-containing heterocyclic ring. ] Colored fine particles, wherein the polymer fine particles contain a metal complex of a dye represented by the following general formula (F).

[Wherein, R represents a hydrogen atom or a substituent. L represents a -CH = group or a -N = group. Q represents an aromatic carbocyclic group or heterocyclic group necessary for forming a dye having absorption in the visible or infrared. Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle. ] Colored fine particles, wherein the polymer fine particles contain a metal complex of a dye represented by the following general formula (G).

[In formula, R < ₁ >, R < ₂ > represents a hydrogen atom or a substituent. X represents O, S, NR ₃ (R ₃ represents a hydrogen atom or a substituent). L represents a -CH = group or a -N = group. Q represents an aromatic carbocyclic group or heterocyclic group necessary for forming a dye having absorption in the visible or infrared. At least one of R ₁ and R ₂ is a nitrogen-containing heterocyclic group represented by the following general formula (G-1). ]

[Wherein, Zb represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring. ] Colored fine particles, wherein the polymer fine particles contain a metal complex dye represented by the following general formula (H).

Wherein, X ₁ is the following formula (H-1), (H -2), represents a divalent substituent represented by (H-3) or (H-4), Y ₁ is 3 Condensation A divalent substituent including a heterocycle, a 4-fused heterocycle, or a 2-fused heterocycle having a substituent is represented. R ₁ , R ₂ , R ₃ and R ₄ each represents a hydrogen atom or a substituent. M represents a metal ion forming at least a bidentate coordination bond. m and n each represents an integer of 0, 1 or 2, and p represents an integer of 1, 2 or 3. Z represents an anion, and q represents 0, 1, 2, or 3. However, when q is 2 or 3, Z may be the same or different. ]

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ represent a hydrogen atom, a halogen atom or a substituent. At least one of R ₁ and R ₂ represents a substituent capable of forming at least a bidentate coordination bond with the metal ion together with the nitrogen atom of the general formula (H-1). R ₃ represents a substituent capable of forming at least a bidentate coordination bond with the metal atom together with the nitrogen atom of the general formula (H-2). At least one of R ₄ and R ₅ represents a substituent capable of forming at least a bidentate coordination bond with a metal atom together with the nitrogen atom of the general formula (H-3). L ₁ represents a nitrogen atom or —CR ₈ ═, L ₂ represents a nitrogen atom or —CR ₉ ═, L ₃ represents a nitrogen atom or —CR ₁₀ ═, and R ₈ , R ₉ and R ₁₀ each represents Represents a hydrogen atom or a substituent, and at least one of R ₈ , R ₉ and R ₁₀ , together with the nitrogen atom of the general formula (H-4), has at least a bidentate coordination bond to the metal ion. This represents a group of atoms that can be formed. ] The general formula (H), wherein Y ₁ is a divalent substituent selected from the group consisting of the following general formulas (Y-1) to (Y-11). Colored fine particles.

[Wherein R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxyl group, a mercapto group, an alkylthio group, an arylthio group, or an amino group; m1, m2, m3 Each represents an integer from 0 to 2. When m1, m2, and m3 are 2 or more, R ₁ and R ₂ may be the same or different from each other, and may further form a ring. At least one of Y ₁₁ and Y ₁₂ represents an oxygen atom, a sulfur atom, or a — (NR ₅ ) — group, and R ₅ represents a hydrogen atom or a substituent. When one of Y ₁₁ or Y ₁₂ represents a — (NR ₅ ) — group, m1 represents an integer of 1 or more. Further, when both Y ₁₁ and Y ₁₂ represent a — (NR ₅ ) — group, each substituent R ₅ of Y ₁₁ and Y ₁₂ may be the same or different. The total is 3 or more. At least one of Y ₂₁ , Y ₂₂ and Y ₂₃ represents an oxygen, nitrogen or sulfur atom. ] The metal complex of the dye according to any one of claims 1 to 7, the metal complex dye of claim 8, and at least one of the metal complex dye of claim 9 is molecularly dispersed with respect to the polymer. The colored fine particles according to any one of claims 1 to 9, which are contained. An ink for inkjet recording, wherein the colored fine particles according to any one of claims 1 to 10 are dispersed in an aqueous medium. In producing the ink for inkjet recording according to claim 11, the ink is selected from the group of at least one polymer and a dye represented by formulas (A) to (G) described in claims 1 to 7. The metal complex of at least one kind of dye or the metal complex dye represented by the general formula (H) described in claim 8 is dissolved in an organic solvent, and the resulting oil phase mixture is dissolved in an aqueous medium. A method for producing an ink for ink-jet recording, comprising a step of emulsifying and dispersing therein, and then a step of removing the organic solvent. An ink jet recording method comprising ejecting the ink for ink jet recording according to claim 11 imagewise. 14. The ink jet recording method according to claim 13, wherein the ink for ink jet recording according to claim 11 is ejected onto a recording medium containing fine particles of silica or alumina and at least one hydrophilic binder.