JP2004338361A - Ink set, and image formation method, image forming apparatus, cartridge and record using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set, which does not cause feathering and color bleeding on an absorptive recording medium or a nonabsorptive recording medium (including a nonabsorptive medium having surface irregularities) and can realize high density and high chroma saturation and can impart high glossiness to prints, and to provide an image recording method, an image recording apparatus and a record using the same. <P>SOLUTION: A fine particle-containing treatment liquid, which has been regulated so that the dispersed state is kept or broken by an external factor (for example, contact of a material or ultraviolet irradiation), and a colorant-containing recording liquid, which has been regulated so that the dispersed state or dissolved state is kept or broken by the external factor, are separately ejected by ink jet recording on a recording medium, and droplets thereof are brought into contact with each other to cause a change of state (for example, a pH change or a solubility change), whereby agglomeration is allowed to occur so that the fine particles in the treatment liquid are not substantially mixed with the colorant in the recording liquid to form an image. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００８１】
（式中、Ｒは分岐していてもよい炭素数６〜１４の炭化水素鎖、ｋ：５〜２０を表す。）
【００８２】
【化２】

【００８３】
（式中、ｍ、ｎは、ｍ、ｎ≦２０であり、ｍ＋ｎは、０＜ｍ＋ｎ≦４０の範囲である。）
【００８４】
【化３】

【００８５】
（式中、Ｒは分岐してもよい炭素数６〜１４の炭化水素鎖を表し、ｎは５〜２０の範囲である。）
【００８６】
【化４】

【００８７】
（式中、Ｒは炭素数６〜１４の炭化水素鎖を表し、ｍ、ｎはそれぞれ２０以下の数である。）
【００８８】
前記式（Ｉ）〜（ＩＶ）の化合物以外では、例えばジエチレングリコールモノフェニルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノアリルエーテル、ジエチレングリコールモノフェニルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテル、テトラエチレングリコールクロロフェニルエーテル等の多価アルコールのアルキル及びアリールエーテル類、ポリオキシエチレンポリオキシプロピレンブロック共重合体等のノニオン系界面活性剤、フッ素系界面活性剤、エタノール、２−プロパノール等の低級アルコール類を用いることができるが、特にジエチレングリコールモノブチルエーテルが好ましい。
【００８９】
微粒子の平均粒子径は、１０００ｎｍ以下であることが好ましく、５００ｎｍ以下が吐出安定性の観点から更に好ましい。すなわち、平均粒子径が１０００ｎｍよりも大きいと吐出ヘッドの目詰まりが生じやすくなり、吐出不良が生じやすくなる。なお、平均粒子径は光学式粒度分布計で測定することができ、粒子数５０％の粒子径をもって表す。
【００９０】
微粒子は、水を主成分とするビヒクルに分散処理されて処理液となる。分散する際には、分散を安定化させるために解膠剤を用いることが好ましい。解膠剤とは、帯電性粒子表面に電気二重層を形成し、電気二重層が静電的に反発して粒子の接近を防止し、分散を安定化させるものである。微粒子は中性から酸性にかけては正に帯電するため、陰イオン源である酢酸、硝酸、塩酸、蟻酸、乳酸、及びこれらのアルカリ金属塩、オキシ塩化ジルコニウム水和物等のジルコニウム化合物、ピロリン酸ナトリウム、ヘキサメタリン酸ナトリウム、タウリン等が解膠剤として用いられるが、本発明はこれらに限定されるものではない。
【００９１】
本発明の処理液は、次の方法によって製造することができる。基本的には、微粒子と水と解膠剤とを混合して分散液を調合する。必要に応じて水溶性溶剤を添加し、解膠機によって解膠する。この際、使用される解膠機としては、高速回転高せん断型攪拌解膠機、デゾルバー、コロイドミル、ホモジナイザー、超音波式解膠機などが挙げられ、より具体的には、Ｔ．Ｋ．オートホモミキサー、Ｔ．Ｋ．ホモミックラインフロー、ウルトラホモミキサー、ＮＮＫコロイドミルなどが挙げられる。解膠時の回転数は、解膠機の種類、構造によって異なるが、５００〜１００００ｒｐｍであることが好ましく、２０００〜８０００ｒｐｍであることがより好ましい。解膠時の温度は、５〜１００℃であることが好ましい。解膠時間は解膠機の種類、構造によって異なるが、０．０１〜４８時間であることが好ましい。
【００９２】
本発明の処理液は、第４級アンモニウム塩、ピリジニウム塩、イミダゾリン型化合物等のカチオン性界面活性剤を含有することができる。具体的には、ラウリルトリメチルアンモニウムクロライド、ラウリルジメチルベンジルアンモニウムクロライド、ベンジルトリブチルアンモニウムクロライド、塩化ベンザルコニウム、セチルピリジニウムクロライド、２−ヘプタデセニルヒドロキシエチルイミダゾリン等が挙げられる。
例えば、カチオン性界面活性剤は、表面張力を下げて被記録媒体との濡れ性を高めて微粒子層を速やかに形成すると共に、アニオン性色材を凝集する作用があり、画質改善に効果がある。
【００９３】
本発明の処理液の表面張力は、２０〜６０ｍＮ／ｍであることが好ましく、被記録媒体との濡れ性と液滴の粒子化の両立の観点からは、３０〜５０ｍＮ／ｍであることが更に好ましい。
本発明の処理液の粘度は、１．０〜２０．０ｃＰであることが好ましく、吐出安定性の観点からは３．０〜１０．０ｃＰであることが更に好ましい。
また、本発明の処理液のｐＨは３〜１１であることが好ましく、微粒子の分散安定性の観点からは３〜６、及び８〜１１であることが更に好ましい。
【００９４】
＜記録液＞
次に、本発明のインクセットに用いる記録液について説明する。
本発明の記録液に用いる色材としては、染料、顔料、あるいは染料と顔料とを混合して用いることができる。そして、前記インクセットの一方の処理液に含有される微粒子がカチオン性である場合には、微粒子と逆極性のアニオン性である色材を含む記録液を用いる方が電気的に中和されて凝集するので、画質向上の点から好ましい。なお、微粒子がアニオン性である場合には、当然に、色材はカチオン性であることが好ましい。
また、色材としては、染料よりも顔料を用いる方が好適である。すなわち、溶解状態とされる染料よりも、分散状態にある顔料の方が電荷が中和された際に、より効率的な凝集が生じるため、画質を向上する効果が高い。
【００９５】
本発明に用いられる記録液に用いる顔料としては特に限定はないが、例えば以下に挙げる顔料が好適に用いられる。
ブラック顔料インク（記録液）に使用されるカーボンブラックとしては、ファーネス法、チャネル法で製造されたカーボンブラックがある。これらは、一次粒径が１５〜４０ミリミクロン、ＢＥＴ法による比表面積が５０〜３００平方メートル／ｇ、ＤＢＰ吸油量が４０〜１５０ｍｌ／１００ｇ、揮発分が０．５〜１０％、ｐＨ値が２〜９を有するものが好ましい。
【００９６】
このような具体例としては、例えば、Ｎｏ．２３００、Ｎｏ．９００、ＭＣＦ８８、Ｎｏ．４０、Ｎｏ．５２、ＭＡ７、ＭＡ８、Ｎｏ．２２００Ｂ（以上、三菱化成製）、ＲＡＶＥＮ１２５５（コロンビア製）、ＲＥＧＡＬ４００Ｒ、ＲＥＧＡＬ６６０Ｒ、ＭＯＧＵＬ Ｌ（以上、キヤボット製）、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１８、Ｃｏｌｏｒ Ｂｌａｃｋ Ｓ１７０、Ｃｏｌｏｒ Ｂｌａｃｋ Ｓ１５０、Ｐｒｉｎｔｅｘ ３５、Ｐｒｉｎｔｅｘ Ｕ（以上、デグッサ製）等の市販品を使用することができる。また、本発明のために新たに試作されたような樹脂被覆型の顔料でもよい。
また、本発明の記録液に含有される色材として用いられるカラー顔料としては、有機顔料及び無機顔料の何れでも構わない。以下に具体例を挙げる。
【００９７】
有機顔料としては、アゾ系、フタロシアニン系、アントラキノン系、キナクリドン系、ジオキサジン系、インジゴ系、チオインジゴ系、ペリレン系、イソインドレノン系、アニリンブラツク、アゾメチン系、ローダミンＢレーキ顔料、カーボンブラック等が挙げられる。また、無機顔料としては、酸化鉄、酸化チタン、炭酸カルシウム、硫酸バリウム、水酸化アルミニウム、バリウムイエロー、紺青、カドミウムレッド、クロムイエロー、金属粉等が挙げられる。
本発明における顔料は、顔料分散剤と共に用いてもよく、顔料分散剤を用いることによって分散安定性を向上させる効果がある。
【００９８】
アニオン性の顔料分散剤としては、顔料を水、若しくは水性媒体に安定に分散させる機能を有する（アニオン性基を有する）水溶性樹脂であればどのようなものでも使用可能である。特に、重量平均分子量が１，０００〜３０，０００の範囲のものが好ましい。更に、好ましくは３，０００〜１５，０００の範囲である。
具体的には、例えばスチレン、スチレン誘導体、ビニルナフタレン、ビニルナフタレン誘導体、α，β−エチレン性不飽和カルボン酸の脂肪族アルコールエステル等の疎水性単量体、またはアクリル酸、アクリル酸誘導体、マレイン酸、マレイン酸誘導体、イタコン酸、イタコン酸誘導体、フマル酸、フマル酸誘導体から選ばれる二つ以上の単量体からなるブロック共重合体、グラフト共重合体あるいはランダム共重合体、若しくはこれらの塩等が挙げられる。
【００９９】
これらの樹脂は、塩基を溶解させた水溶液に可溶なアルカリ可溶型の樹脂である。更に、親水性単量体からなるホモポリマーまたはそれらの塩でもよい。また、ポリビニルアルコール、カルボキシメチルセルロース、ナフタレンスルホン酸ホルムアルデヒド縮合物等の水溶性樹脂も使用することが可能である。しかし、アルカリ可溶型の樹脂を用いた場合の方が、分散液の低粘度化が可能であり、分散も容易であるという利点がある。前記、水溶性樹脂は、インク（記録液）全量に対して、０．１〜５重量％の範囲で使用されることが好ましい。
【０１００】
カチオン性の顔料分散剤としては、以下に説明するカチオン性モノマーを重合したポリマーが好適に使用できる。なお、これらポリマーの分子量としては、２０００以上であるのが望ましい。本発明で用いられるカチオン性モノマーとしては、下記に例示するモノマーの４級化された化合物である。下記モノマーを４級化するには、塩化メチル、ジメチル硫酸、ベンジルクロライド、エピクロルヒドリンなどを用いて常法により処理を行えばよい。
モノマーとしては、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート：［ＣＨ_２＝Ｃ（ＣＨ_３）−ＣＯＮＨ−ＣＨ_２ＣＨ_２Ｎ（ＣＨ_３）_２］、Ｎ，Ｎ−ジメチルアミノエチルアクリレート：［ＣＨ_２＝ＣＨ−ＣＯＮＨ−ＣＨ_２ＣＨ_２Ｎ（ＣＨ_３）_２］、Ｎ，Ｎ−ジメチルアミノアクリルアミド：［ＣＨ_２＝ＣＨ−ＣＯＮ（ＣＨ_３）_２］、Ｎ，Ｎ−ジメチルアミノメタアクリルアミド：［ＣＨ_２＝Ｃ（ＣＨ_３）−ＣＯＮ（ＣＨ_３）_２］、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド：［ＣＨ_２＝ＣＨ−ＣＯＮＨ−Ｃ_３Ｈ_６Ｎ（ＣＨ_３）_２］、Ｎ，Ｎ−ジメチルアミノプロピルメタクリルアミド：［ＣＨ_２＝Ｃ（ＣＨ_３）−ＣＯＮＨ−Ｃ_３Ｈ_６Ｎ（ＣＨ_３）_２］などが挙げられる。
【０１０１】
本発明の顔料分散剤としての水溶性樹脂は、顔料の性質に応じた親和性を向上するため、樹脂中の成分として疎水性モノマーを用いてもよく、この場合の疎水性モノマーとしては、例えばスチレン、α−メチルスチレン、ビニルトルエンなどのスチレン類、及び（メタ）アクリル酸アルキルエステル類が挙げられる。
（メタ）アクリル酸アルキルエステルとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｓｅｃ−メチルブチル（メタ）アクリレート、ｔｅｒｔ−ブメチル（メタ）アクリレート、２−メチルブチル（メタ）アクリレート、２−エチルブチル（メタ）アクリレート、３−メチルブチル（メタ）アクリレート、１，３−ジメチルブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、３−ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オチクル（メタ）アクリレート、ノニル（メタ）アクリレート、２−エトキシエチルアクリレート、３−エトキシプロピルアクリレート、２−エトキシブチルアクリレート、３−エトキシブチルアクリレート、３−エトキシブチルアクリレート、ジメチルアミノエチルアクリレート、ハーフエステル化に用いられるアルコール成分としては、メタノール、エタノール、プロパノール、任意に用いられるモノマーとしては、（メタ）アクリルアミド、１−メチロール（メタ）アクリルアミド、ジアセトンアクリルアミド等が挙げられる。なお、顔料分散剤を用いなくとも安定して分散できる自己分散型顔料を用いてもよい。
【０１０２】
アニオン性自己分散型の顔料は、顔料表面に少なくとも１種のアニオン性親水性基が直接若しくは他の原子団を介して結合されているものである。アニオン性の親水性基としては、例えば、下記に挙げた親水性基の中から選択される少なくとも１種であるもの、更に他の原子団が、炭素原子数１〜１２のアルキル基、置換基を有してもよいフェニル基または置換基を有してもよいナフチル基であるものが挙げられる。
−ＣＯＯＭ、−ＳＯ_３Ｍ、−ＳＯ_２ＮＨ_２、−ＰＯ_３ＨＭ、−ＰＯ_３Ｍ_２
但し、上記親水性基中のＭは、水素原子、アルカリ金属、アンモニウムの何れかを示す。
【０１０３】
上記のような親水性基をカーボンブラック表面に導入してアニオン性に帯電させたカーボンブラックは、イオン（アニオン）の反発に基づく優れた水分散性を有するため、水性インク中に含有させた場合にも分散剤等を添加しなくても安定した分散状態を維持することができる。
【０１０４】
また、カチオン性自己分散型の顔料は、顔料表面に少なくとも１種のカチオン性親水性基が直接若しくは他の原子団を介して結合されているものである。
カチオン性に帯電したカーボンブラックの場合、直接若しくは他の原子団を介して結合した親水性基として、例えば下記に示す第４級アンモニウム基から選ばれる少なくとも１つを結合したものが挙げられる。しかし、本発明は、これらに限定されるものではない。
【０１０５】
【化５】

【０１０６】
（式中、Ｒは炭素原子数１〜１２の直鎖状または分岐鎖状のアルキル基、置換若しくは未置換のフェニル基、または置換若しくは未置換のナフチル基を表す。）
【０１０７】
なお、上記のカチオン性基のカウンターイオンとして、例えばＮＯ_３ ⁻やＣＨ_３ＣＯＯ⁻が存在する。
上記したような親水性基が結合されてカチオン性に帯電している自己分散型カーボンブラックを得るには、例えば下記式に示す構造のＮ−エチルピリジル基を結合させる場合を例にとると、カーボンブラックを３−アミノ−Ｎ−エチルピリジニウムブロマイドで処理する方法により製造することができる。
【０１０８】
【化６】

【０１０９】
このようにカーボンブラック表面への親水性基の導入によってカチオン性に帯電させたカーボンブラックは、イオンの反発によって優れた水分散性を示すため、水性インク中に含有させた場合にも分散剤等を添加することなく安定した分散状態を維持する。
【０１１０】
次に、本発明で用いられる水溶性染料としては、カラーインデックスにおいて酸性染料（アニオン性染料）、直接性染料、塩基性染料（カチオン性染料）、反応性染料、食用染料に分類される染料で耐水、耐光性が優れたものが用いられる。
これら染料は、複数種類を混合して用いてもよいし、あるいは必要に応じて顔料等の他の色材と混合して用いてもよい。これら着色剤としての色材は、本発明の効果が阻害されない範囲で添加される。下記に各種染料を例示する。
【０１１１】
（ａ）酸性染料としては、
Ｃ．Ｉ．アシッド・イエロー １７，２３，４２，４４，７９，１４２、
Ｃ．Ｉ．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、
Ｃ．Ｉ．アシッド・ブルー ９，２９，４５，９２，２４９、
Ｃ．Ｉ．アシッド・ブラック １，２，７，２４，２６，９４等が使用できる。
（ｂ）食用染料としては、
Ｃ．Ｉ．フード・イエロー ３，４、
Ｃ．Ｉ．フード・レッド ７，９，１４、
Ｃ．Ｉ．フード・ブラック １，２等が使用できる。
（ｃ）直接染料としては、
Ｃ．Ｉ．ダイレクト・イエロー １，１２，２４，２６，３３，４４，５０，８６，１２０，１３２，１４２，１４４、
Ｃ．Ｉ．ダイレクト・レッド １，４，９，１３，１７，２０，２８，３１，３９，８０，８１，８３，８９，２２５，２２７、
Ｃ．Ｉ．ダイレクト・オレンジ ２６，２９，６２，１０２、
Ｃ．Ｉ．ダイレクト・ブルー １，２，６，１５，２２，２５，７１，７６，７９，８６，８７，９０，９８，１６３，１６５，１９９，２０２、
Ｃ．Ｉ．ダイレクト・ブラック １９，２２，３２，３８，５１，５６，７１，７４，７５，７７，１５４，１６８，１７１等が使用できる。
（ｄ）塩基性染料としては、
Ｃ．Ｉ．ベーシック・イエロー １，２，１１，１３，１４，１５，１９，２１，２３，２４，２５，２８，２９，３２，３６，４０，４１，４５，４９，５１，５３，６３，６４，６５，６７，７０，７３，７７，８７，９１、
Ｃ．Ｉ．ベーシック・レッド ２，１２，１３，１４，１５，１８，２２，２３，２４，２７，２９，３５，３６，３８，３９，４６，４９，５１，５２，５４，５９，６８，６９，７０，７３，７８，８２，１０２，１０４，１０９，１１２、
Ｃ．Ｉ．ベーシック・ブルー １，３，５，７，９，２１，２２，２６，３５，４１，４５，４７，５４，６２，６５，６６，６７，６９，７５，７７，７８，８９，９２，９３，１０５，１１７，１２０，１２２，１２４，１２９，１３７，１４１，１４７，１５５、
Ｃ．Ｉ．ベーシック・ブラック ２，８等が使用できる。
（ｅ）反応性染料としては、
Ｃ．Ｉ．リアクティブ・ブラック ３，４，７，１１，１２，１７、
Ｃ．Ｉ．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、
Ｃ．Ｉ．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、
Ｃ．Ｉ．リアクティブ・ブルー １，２，７，１４，１５，２３，３２，３５，３８，４１，６３，８０，９５等が使用できる。
【０１１２】
本発明の記録液を所望の物性にするため、あるいは乾燥による記録ヘッドのノズルの詰まりを防止するためなどの目的から、前記色材の他に水溶性有機溶媒を使用することが好ましい。水溶性有機溶媒には、湿潤剤、浸透剤が含まれる。
湿潤剤は、乾燥による記録ヘッドのノズルの詰まりを防止することを目的に添加される。湿潤剤の具体例としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、プロピレングリコール、１，３−ブタンジオール、１，３−プロパンジオール、２−メチル−１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−へキサンジオール、グリセリン、１，２，６−へキサントリオール、２−エチル−１，３−ヘキサンジオール、１，２，４−ブタントリオール、１，２，３−ブタントリオール、ペトリオール等の多価アルコール類、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノブチルエーテル、テトラエチレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等の多価アルコールアルキルエーテル類、エチレングリコールモノフェニルエーテル、エチレングリコールモノベンジルエーテル等の多価アルコールアリールエ−テル額；Ｎ−メチル−２−ピロリドン、Ｎ−ヒドロキシエチル−２−ピロリドン、２−ピロリドン、１，３−ジメチルイミダゾリジノン、ε−カプロラクタム等の含窒素複素環化合物；ホルムアミド、Ｎ−メチルホルムアミド、ホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド等のアミド類；モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン等のアミン類、ジメチルスルホキシド、スルホラン、チオジエタノ−ル等の含硫黄化合物類、プロピレンカーボネート、炭酸エチレン、γ−ブチロラクトン等が挙げられる。これらの溶媒は、水とともに単独もしくは複数混合して用いられる。
【０１１３】
また、浸透剤は、記録液と被記録材の濡れ性を向上させ、浸透速度を調整する目的で添加される。浸透剤としては、前記（Ｉ）〜（ＩＶ）で表わされるものが好ましい。すなわち、前記（Ｉ）のポリオキシエチレンアルキルフェニルエーテル系界面活性剤、式（ＩＩ）のアセチレングリコール系界面活性剤、式（ＩＩＩ）のポリオキシエチレンアルキルエーテル系界面活性剤ならびに式（ＩＶ）のポリオキシエチレンポリオキシプロピレンアルキルエーテル系界面活性剤は、液の表面張力を低下させることができるので、濡れ性を向上させ、浸透速度を高めることができる。
【０１１４】
前記式（Ｉ）〜（ＩＶ）の化合物以外では、例えばジエチレングリコールモノフェニルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノアリルエーテル、ジエチレングリコールモノフェニルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテル、テトラエチレングリコールクロロフェニルエーテル等の多価アルコールのアルキル及びアリールエーテル類、ポリオキシエチレンポリオキシプロピレンブロック共重合体等のノニオン系界面活性剤、フッ素系界面活性剤、エタノール、２−プロパノール等の低級アルコール類を用いることができるが、特にジエチレングリコールモノブチルエーテルが好ましい。
【０１１５】
本発明の記録液の表面張力は、２０〜６０ｍＮ／ｍであることが好ましく、被記録材との濡れ性と液滴の粒子化の両立の観点からは３０〜５０ｍＮ／ｍであることがさらに好ましい。
本発明の記録液の粘度は、１．０〜２０．０ｃＰであることが好ましく、吐出安定性の観点からは３．０〜１０．０ｃＰであることが更に好ましい。
本発明の記録液のｐＨは３〜１１であることが好ましく、接液する金属部材の腐食防止の観点からは６〜１０であることが更に好ましい。
【０１１６】
前記本発明の処理液及び記録液は、防腐・防黴剤を含有することができる。防腐・防黴剤を含有することによって、菌の繁殖を押さえることができ、保存安定性、画質安定性を高めることができる。
防腐・防黴剤としては、ベンゾトリアゾール、デヒドロ酢酸ナトリウム、ソルビン酸ナトリウム、２−ピリジンチオール−１−オキサイドナトリウム、イソチアゾリン系化合物、安息香酸ナトリウム、ペンタクロロフェノールナトリウム等が使用できる。
【０１１７】
また、本発明の処理液及び記録液は、防錆剤を含有することができる。防錆剤を含有することによって、ヘッド等の接液する金属面に被膜を形成し、腐食を防ぐことができる。防錆剤としては、例えば酸性亜硫酸塩、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等が使用できる。
【０１１８】
更に、本発明者の処理液、および記録液は酸化防止を含有することができる。酸化防止剤には生成したラジカルのペルオキシドにプロトンを与えて安定化させるラジカル受容体型のものと、ヒドロペルオキシドを安定なアルコールに変質させる過酸化物分離型の２種類がある。
【０１１９】
前者としては、フェノール系化合物類、アミン系化合物類が代表的であるがフェノール系化合物類としては、ハイドロキノン、ガレート等の化合物、２，６−ジーｔｅｒｔ−ブチル−ｐ−クレゾール、ステアリル−β−（３，５−ジーｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、２，２’−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレンビス（４−エチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−チオビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ブタン、１，３，５−トリメチル−２，４，６−トリス（３，５−ジーｔｅｒｔ−４−ヒドキシベンジル）ベンゼン、トリス（３，５−ジーｔｅｒｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、テトラキス［メチレン−３（３’，５’−ジーｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン等のヒンダードフェノール系化合物が例示され、アミン系化合物類としては、Ｎ，Ｎ’−ジフェニル−ｐ−フェニレンジアミン、フェニル−β−ナフチルアミン、フェニル−α−ナフチルアミン、Ｎ，Ｎ’−β−ナフチル−ｐ−フェニレンジアミン、Ｎ，Ｎ’−ジフェニルエチレンジアミン、フェノチアジン、Ｎ，Ｎ’−ジーｓｅｃ−ブチル−ｐ−フェニレンジアミン、４，４’−テトラメチル−ジアミノジフェニルメタン等が例示される。
また、後者としては、硫黄系化合物類、リン系化合物類が代表的であるが、硫黄系化合物としては、ジラウリルチオジプロピオネート、ジステアリルチオジプロピオネート、ラウリルステアリルチオジプロピオネート、ジミリスチルチオジプロピオネート、ジステリアルβ，β’−チオジブチレート、２−メルカプトベンゾイミダゾール、ジラウリルサルファイド等が例示され、リン系化合物類としては、トリフェニルフォスファイト、トリオクタデシルフォスファイト、トリデシルフォスファイト、トリラウリルトリチオフォスファイト、ジフェニルイソデシルフォスファイト、トリノニルフェニルフォスファイト、ジステアリルペンタエリスリトールフォスファイト等が例示される。
【０１２０】
前述のように本発明の処理液及び記録液は、ｐＨ調整剤を含有することができる。ｐＨ調整剤としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム等のアルカリ金属元素の水酸化物、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、炭酸カリウム等のアルカリ金属の炭酸塩、ジエタノールアミン、トリエタノ−ルアミン等のアミン類、硼酸、塩酸、硝酸、硫酸、酢酸等を用いることができる。
また、前述のように紫外線照射により、酸（あるいは塩基）を発生する光酸発生剤（あるいは光塩基派生剤）などの潜在性の酸（あるいは塩基）を用いることができる。
【０１２１】
次に、本発明のインクセットと画像形成方法により画像記録を実施する画像形成装置について、図面を用いて説明する。
図６は、本発明における一例である画像形成装置の概略構成を示す斜視図である。図６において、処理液及び記録液がそれぞれ個別に収容された各カートリッジ２０は、キャリッジ１８に収納される。すなわち、処理液用あるいは色毎の記録液用として別々に準備されたカートリッジ２０は、それぞれの液が分離された状態で取り付けられている。このような状態で処理液及び記録液がカートリッジ２０からキャリッジ１８に搭載された記録ヘッド１８ａに供給される。なお、図６において、記録ヘッド１８ａ面は下方方向を向いた状態であるため、ヘッド面は見えない状態である。
キャリッジ１８に搭載された記録ヘッド１８ａは、主走査モータ２４で駆動されるタイミングベルト２３によってガイドシャフト２１、２２にガイドされて移動する。一方、被記録材料はプラテン１９によって記録ヘッド１８ａと対面する位置に置かれる。なお、図中、１６はギア機構、１７は副走査モーター、２６は主走査モーターを示す。
【０１２２】
また図７は、本発明における別の例である紫外線照射手段（高圧水銀灯）を備えた画像形成装置の概略構成を示す斜視図である。
基本的な構成は上記図６で説明した内容と同じであるが、紫外線照射手段として高圧水銀灯２７が備えられている。
すなわち、上記図６と同様にキャリッジ１８に搭載された記録ヘッド１８ａは、主走査モータ２４で駆動されるタイミングベルト２３によってガイドシャフト２１、２２にガイドされて移動する。このとき、キャリッジ上部に設置される高圧水銀灯２７によって印字面に紫外線が照射される。記録液が記録媒体に着弾するとすぐに紫外線が照射されて光反応が生じる。いわゆる非接触で作用する外的要因によって、状態変化が生じる。一方、被記録材料はプラテン１９によって記録ヘッド１８ａと対面する位置に置かれる。なお、図７中、１６はギア機構、１７は副走査モーター、２６は主走査モーターを示す。
【０１２３】
図６および図７における記録ヘッド１８ａのノズル面を拡大した概略図を図８に示す
例えば、処理液が吐出されるノズル３１が縦方向に設けられ、ノズル３２、３３、３４、３５からは、適宜収納されたカートリッジに応じて、例えばイエロー記録液、マゼンタ記録液、シアン記録液、そしてブラック記録液がそれぞれ吐出される。
【０１２４】
また、図９に記載のような別の形態の記録ヘッドのように、ノズルを全て横方向に並べて構成することも可能である。例えば、図９中でノズル３６及びノズル４１は処理液の吐出ノズルであり、ノズル３７、３８、３９、４０からは、適宜収納されたカートリッジに応じて、例えばイエロー記録液、マゼンタ記録液、シアン記録液、そしてブラック記録液がそれぞれ吐出される。このような態様の記録ヘッド１８ａにおいては、処理液の吐出ノズルが左右の端に設けられているため、キャリッジ１８に搭載された記録ヘッドがガイドシャフト２１、２２にガイドされて往復する往路、復路いずれにおいても印字が可能である。すなわち、往路、復路のいずれにおいても、被記録媒体上に対して処理液を先に付着させ、その上からカラー記録液を付着させること、あるいはその逆が可能であり、記録ヘッド１８ａの移動方向の違いによって画像濃度差を生じないようにすることが可能である。
【０１２５】
本発明の画像形成装置は、処理液及び記録液の補充をカートリッジ単位で取り替えることが可能であるが、このカートリッジは記録ヘッド１８ａと一体化されたものであってもよい。本発明の処理液あるいは記録液をそれぞれ収容可能なカートリッジの概略構成を示す外観斜視図を図１０に、またカートリッジの概略内部構成を示す正断面図を図１１に示す。図１０、図１１に示す構成のカートリッジは、処理液及び記録液の何れも共通して収容することができる。
カートリッジ２０は、図１０、１１に示すように、カートリッジ筐体４９内に所要の記録液若しくは処理液を吸収させた液吸収体４２を収容している。液吸収体４２は、多孔質体からなり、記録液若しくは処理液を吸収している。カートリッジ筐体４９には、上部に広い開口を有するケース４３の上部開口に上蓋部材４４が形成されている。Ａは空間を示す。更に上蓋部材４４には、大気解放口４７、カートリッジ着脱用突起部８１が設けられている。５５は、大気解放口４７のシール部材である。また、カートリッジ筐体４９のケース４３底部には、記録ヘッド１８ａへ各液を供給するための液供給口４５が形成されており、この液供給口４５内周辺にはシーリング４６が嵌着されている。カートリッジ筐体４９には、画像形成装置に装填する前の状態において液の漏洩を防止するため、液供給口４５を塞ぎためのキャップ部材５３が装着されている。
【０１２６】
前述のように本発明においては、各記録ヘッド１８ａによって記録液および処理液が、いわゆるインクジェット記録方式によってそれぞれの液滴が同一箇所に重ねられるように噴射され（吐出され）ることが最も好ましい。しかし、本発明の適用は、このそれぞれの液滴が同一箇所に重ねられる範囲に限定されない。例えば、処理液を間引いて付与し、滲み等によって拡大した処理液の上に記録液を重ねたり、画像の輪郭部だけに処理液を付与し、記録液の一部を重ねる場合も本発明の範囲に含まれる。
【０１２７】
前記本発明のインクセットと画像形成方法、並びに画像形成装置を用いて形成された本発明の記録物の断面形態は、記録物をミクロトームなどの鋭利な切断手段で薄片に切断し、透過型電子顕微鏡（Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ：ＴＥＭ）による分析で観察し（ＴＥＭ写真）、確認することができる。また、透過型電子顕微鏡（ＴＥＭ）の代りに、走査型電子顕微鏡（Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ：ＳＥＭ）を用いても観察することができる。
本発明になる記録物を透過型電子顕微鏡（ＴＥＭ）で計測すると、記録物の断面形態に濃淡の縞模様が観察される。この濃淡部分を更に、エネルギー分散型蛍光Ｘ線分析装置（Ｅｎｅｒｇｙ Ｄｉｓｐｅｒｓｉｖｅ Ｘ−ｒａｙ Ｆｌｕｏｒｅｓｃｅｎｃｅ Ｓｐｅｃｔｒｏｍｅｔｅｒ：ＥＤＸ）、あるいは電子線マイクロアナライザー（Ｅｌｅｃｔｒｏｎ Ｐｒｏｂｅ Ｍｉｃｒｏａｎａｌｙｚｅｒ：ＥＰＭＡ）などの元素分析装置を用いて定量することにより、主に微粒子で構成されている層（実質的に微粒子で形成される層）と、主に色材で構成されている層（実質的に色材で形成される層）であることが特定できる。
【０１２８】
すなわち、実質的に微粒子で形成される層の中の微粒子、あるいは実質的に色材で形成される層の中の色材は上記の分析装置を使うことで定量的に知ることができる。例えば、エネルギー分散型蛍光Ｘ線分析装置（ＥＤＸ）を用いた場合、記録物のスペクトルには構成元素毎にピークが観測される。このピーク高さは元素の存在量に比例しており、検量線を作成することで各元素の存在量を正確に知ることができる。ここで言う“実質的に”とは、前記のように処理液中の微粒子と記録液中の色材の多くが互いに混合しない状態（液境界等において多少の混合をした状態は含む）であるが、微粒子、あるいは色材の上記それぞれ形成される層の中に占める割合が７０％以上であることが好ましく、微粒子あるいは色材の割合が８０％以上であれば更に本発明の画質改善効果が高くなり好ましい。
【０１２９】
【実施例】
以下、実施例により本発明を更に詳細に説明する。ただし、本発明はなんら実施例に限定されるものではない。
まず、本発明に係るインクセットを構成する処理液と記録液、及び比較例に用いる場合の処理液と記録液などを以下に示す処方により配合して調製した。なお、処方における配合量に記載の「部」は重量部を表し、各液の合計配合量は１００重量部である。
【０１３０】
＜処理液１＞
カチオン性コロイダルシリカ
（日産化学（株）製：スノーテックスＡＫ） １５．０部
２−ピロリドン １２．５部
ジエチレングリコール １２．５部
オクタンジオール １．０部
カチオン性界面活性剤
（三洋化成（株）製：カチオンＧ５０） ２．０部
ベンゾトリアゾール １．０部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．２部
水 残量
なお、上記配合液を更に酢酸でｐＨ４．３に調整して用いた。
【０１３１】
＜処理液２＞
二酸化チタン
（出光興産（株）製：出光チタニアＩＴ−Ｓ） １５．０部
２−ピロリドン １２．５部
ジエチレングリコール １２．５部
オクタンジオール １．０部
カチオン性界面活性剤
（三洋化成（株）製：カチオンＧ５０） ２．０部
ベンゾトリアゾール １．０部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．２部
水 残量
なお、上記配合液を更に酢酸でｐＨ３．８に調整して用いた。
【０１３２】
＜処理液３＞
アルミナ
（日産化学（株）製：アルミナゾル５２０） １５．０部
２−ピロリドン １２．５部
ジエチレングリコール １２．５部
オクタンジオール １．０部
カチオン性界面活性剤
（三洋化成（株）製：カチオンＧ５０） ２．０部
ベンゾトリアゾール １．０部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．２部
水 残量
なお、上記配合液を更に酢酸でｐＨ３．９に調整して用いた。
【０１３３】
＜処理液４＞
アニオン性コロイダルシリカ
（日産化学（株）製：スノーテックス２０） １５．０部
２−ピロリドン １２．５部
ジエチレングリコール １２．５部
オクタンジオール １．０部
カチオン性界面活性剤
（三洋化成（株）製：カチオンＧ５０） ２．０部
ベンゾトリアゾール １．０部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．２部
水 残量
なお、上記配合液を更に酢酸でｐＨ３．９に調整して用いた。
【０１３４】
特許第２７１１０９８号公報の実施例（１）に従って処理液５を調製した。
＜処理液５＞
４級アンモニウム塩 ３．０部
グリセリン １０．０部
ジエチレングリコール ２０．０部
水 残量
【０１３５】
特許第２６６７４０１号公報の実施例Ｐ−１に従って処理液６を調製した。
＜処理液６＞
ポリアリルアミン ５．０部
グリセリン １０．０部
エチレングリコール １１．０部
ジエチレングリコール ２０．０部
ジエチレングリコールモノブチルエーテル １２．０部
デヒドロ酢酸ソーダ ０．１部
水 残量
【０１３６】
特開２００１−１９９１４９号公報の実施例、液体組成物Ａの製造例に従って処理液７を調製した。
＜処理液７＞
アルミナ水和物 １０．０部
グリセリン ７．５部
ジエチレングリコール ７．５部
硝酸 ０．２部
水 残量
【０１３７】
特開２００２−２０１３８５号公報の実施例、液体組成物１の製造例に従って処理液８を調製した。
＜処理液８＞
アルミナ水和物 １０．０部
グリセリン ７．５部
ジエチレングリコール ７．５部
オキシ硝酸ジルコニウム２水和物 ０．４部
水 残量
【０１３８】
＜処理液９＞
特開２００１−３０６１６号公報の実施例、反応液Ａの製造例に従って処理液９を調製した。
硝酸マグネシウム／６水和物 ２５．０部
トリエチレングリコールモノブチルエーテル １０．０部
グリセリン １０．０部
水 残量
【０１３９】
＜処理液１０＞
カチオン性コロイダルシリカ
（日産化学（株）製：スノーテックスＡＫ） １５．０部
ＮａＣｌ １０．０部
２−ピロリドン １２．５部
ジエチレングリコール １２．５部
オクタンジオール １．０部
カチオン性界面活性剤
（三洋化成（株）製：カチオンＧ５０） ２．０部
ベンゾトリアゾール １．０部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．２部
水 残量
【０１４０】
＜黒色記録液１（アニオン性顔料含有記録液）＞
カーボンブラック（キャボット社製、キャボジェット３００）１０部
１，３−ブタンジオール ２２．５部
グリセリン ７．５部
界面活性剤（Ｉ）、Ｒ＝Ｃ_９Ｈ_１９、ｋ＝１２ １部
２−ピロリドン ２部
デヒドロ酢酸ナトリウム ０．２部
チオ硫酸ナトリウム ０．２部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．４部
イオン交換水 残量
なお、上記配合液を更にＬｉＯＨ水溶液でｐＨ１０．５に調整して用いた。
【０１４１】
＜イエロー記録液１（アニオン性顔料含有記録液）＞
樹脂被覆型イエロー分散体 ５０部（イエロー顔料固形分１０部）
１，３−ブタンジオール ２２．５部
グリセリン ７．５部
界面活性剤（Ｉ）、Ｒ＝Ｃ_９Ｈ_１９、ｋ＝１２ １部
２−ピロリドン ２部
デヒドロ酢酸ナトリウム ０．２部
チオ硫酸ナトリウム ０．２部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．４部
イオン交換水 残量
なお、上記配合液を更にＬｉＯＨ水溶液でｐＨ１０．５に調整して用いた。
【０１４２】
上記イエロー記録液１（アニオン性顔料含有記録液）の処方において用いた「記樹脂被覆型イエロー分散体」は、以下のようにして製造した。
樹脂被覆型イエロー分散体の製造例：
（１） ポリマー溶液の調製
機械式攪拌機、温度計、窒素ガス導入管、還流管及び滴下漏斗を備えたフラスコ（容積１Ｌ）内を窒素ガスで十分置換した後、スチレン１１．２ｇ、アクリル酸２．８ｇ、ラウリルメタクリレート１２．０ｇ、ポリエチレングリコールメタクリレート４．０ｇ、スチレンマクロマー（東亜合成（株）製、商品名：ＡＳ−６）４．０ｇ及びメルカプトエタノール０．４ｇを仕込み、６５℃に昇温した。
次に、スチレン１００．８ｇ、アクリル酸２５．２ｇ、ラウリルメタクリレート１０８．０ｇ、ポリエチレングリコールメタクリレート３６．０ｇ、ヒドロキシエチルメタクリレート６０．０ｇ、スチレンマクロマー（東亜合成（株）製、商品名：ＡＳ−６）３６．０ｇ、メルカプトエタノール３．６ｇ、アゾビスジメチルバレロニトリル２．４ｇ及びメチルエチルケトン１８ｇの混合溶液を２．５時間かけてフラスコ内に滴下した。
滴下終了後、アゾビスジメチルバレロニトリル０．８ｇ及びメチルエチルケトン１８ｇの混合溶液を０．５時間かけてフラスコ内に滴下した。６５℃で１時間熟成した後、アゾビスジメチルバレロニトリル０．８ｇを添加し、更に１時間熟成した。反応終了後、フラスコ内に、メチルエチルケトン３６４ｇを添加し、濃度が５０％のポリマー溶液８００ｇを得た。
ポリマー溶液の一部を乾燥し、ゲルパーミエイションクロマトグラフィー（標準：ポリスチレン、溶媒：テトラヒドロフラン）で測定したところ、ポリマーの重量平均分子量は１５０００であった。
【０１４３】
（２）樹脂被覆型イエロー分散体の調製
上記（１）で得られたポリマー溶液２２．２ｇ、イエロー顔料（大日本インキ化学工業（株）製、商品名：Ｓｙｍｕｌｅｒ Ｆａｓｔ Ｙｅｌｌｏｗ ４１８１）２６．０ｇ、１ｍｏｌ／Ｌの水酸化リチウム水溶液１３．６ｇ、メチルエチルケトン２０ｇ及びイオン交換水３０ｇを十分に攪拌した後、３本ロールミル〔（株）ノリタケカンパニー製、商品名：ＮＲ−８４Ａ〕を用いて２０回混練した。得られたペーストをイオン交換水２００ｇに投入し、十分に攪拌した後、エパポレーターを用いてメチルエチルケトン及び水を留去し、固形分量が２０．０重量％の樹脂被覆型イエロー顔料分散体１６０ｇを得た。
この製造例によって得られたイエロー顔料分散体をベースに上記の組成でイエロー記録液１を調製した。
【０１４４】
＜黒色記録液２（アニオン性染料含有記録液）＞
Ｃ．Ｉ．ダイレクトブラック１６８ ４部
エチレングリコール １５部
グリセリン ５部
界面活性剤（Ｉ）、Ｒ＝Ｃ_９Ｈ_１９、ｋ＝１２ １部
デヒドロ酢酸ナトリウム ０．２部
チオ硫酸ナトリウム ０．２部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．４部
イオン交換水 残量
なお、上記配合液を更にＬｉＯＨ水溶液でｐＨ１０．５に調整して用いた。
【０１４５】
＜イエロー記録液２（アニオン性染料含有記録液）＞
Ｃ．Ｉ．アシッドイエロー２３ ４部
エチレングリコール １５部
グリセリン ５部
界面活性剤（Ｉ）、Ｒ＝Ｃ_９Ｈ_１９、ｋ＝１２ １部
デヒドロ酢酸ナトリウム ０．２部
チオ硫酸ナトリウム ０．２部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．４部
イオン交換水 残量
なお、更にＬｉＯＨ水溶液でｐＨ１０．５に調整して用いた。
【０１４６】
＜黒色記録液３（顔料＋カチオン性分散剤含有記録液）＞
カーボンブラック（三菱化学社製、ＭＡ７） １０部
カチオン性分散剤
（Ｎ，Ｎ−ジメチルアミノエチルメタクリレート） ２部
１，３−ブタンジオール ２２．５部
グリセリン ７．５部
界面活性剤（Ｉ）、Ｒ＝Ｃ_９Ｈ_１９、ｋ＝１２ １部
２−ピロリドン ２部
デヒドロ酢酸ナトリウム ０．２部
チオ硫酸ナトリウム ０．２部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．４部
イオン交換水 残量
なお、上記配合液を更にＬｉＯＨ水溶液でｐＨ１０．５に調整して用いた。
【０１４７】
＜イエロー記録液３（顔料＋カチオン性分散剤含有記録液）＞
Ｃ．Ｉ．ピグメントイエロー１ １０部
カチオン性分散剤
（Ｎ，Ｎ−ジメチルアミノエチルメタクリレート） ２部
１，３−ブタンジオール ２２．５部
グリセリン ７．５部
界面活性剤（Ｉ）、Ｒ＝Ｃ_９Ｈ_１９、ｋ＝１２ １部
２−ピロリドン ２部
デヒドロ酢酸ナトリウム ０．２部
チオ硫酸ナトリウム ０．２部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．４部
イオン交換水 残量
なお、上記配合液を更にＬｉＯＨ水溶液でｐＨ１０．５に調整して用いた。
【０１４８】
＜黒色記録液４（カチオン性染料含有記録液）＞
Ｃ．Ｉ．ベーシックブラック２ １０部
１，３−ブタンジオール ２２．５部
グリセリン ７．５部
界面活性剤（Ｉ）、Ｒ＝Ｃ_９Ｈ_１９、ｋ＝１２ １部
２−ピロリドン ２部
デヒドロ酢酸ナトリウム ０．２部
チオ硫酸ナトリウム ０．２部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．４部
イオン交換水 残量
なお、上記配合液を更にＬｉＯＨ水溶液でｐＨ１０．５に調整して用いた。
【０１４９】
＜イエロー記録液４（カチオン性染料含有記録液）＞
Ｃ．Ｉ．ベーシックイエロー３３ １０部
１，３−ブタンジオール ２２．５部
グリセリン ７．５部
界面活性剤（Ｉ）、Ｒ＝Ｃ_９Ｈ_１９、ｋ＝１２ １部
２−ピロリドン ２部
デヒドロ酢酸ナトリウム ０．２部
チオ硫酸ナトリウム ０．２部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．４部
イオン交換水 残量
なお、上記配合液を更にＬｉＯＨ水溶液でｐＨ１０．５に調整して用いた。
【０１５０】
特開２００１−１９９１４９号公報の実施例（ブラックインクＢｋ２に記載）に従って黒色記録液５を調製した。
＜黒色記録液５（アニオン性顔料含有記録液）＞
カーボンブラック ３．０部
トリメチロールプロパン ６．０部
グリセリン ６．０部
エチレングリコール ６．０部
水 残量
【０１５１】
特開２００１−１９９１４９号公報の実施例（イエロー顔料インクＹ３に記載）に従ってイエロー記録液５を調製した。
＜イエロー記録液５（アニオン性顔料含有記録液）＞
Ｃ．Ｉ．ピグメントイエロー７４ ３．０部
グリセリン １０．０部
エチレングリコール ５．０部
Ｎ−メチルピロリドン ５．０部
エチルアルコール ２．０部
水 残量
【０１５２】
特開２００２−２０１３８５９号公報の実施例（ブラックインクＢｋ２に記載）に従って黒色記録液６を調製した。
＜黒色記録液６（アニオン性顔料含有記録液）＞
カーボンブラック ３．０部
グリセリン １０．０部
エチレングリコール ５．０部
Ｎ−メチルピロリドン ５．０部
エチルアルコール ２．０部
水 残量
【０１５３】
特開２００２−２０１３８５９号公報の実施例（イエローインクＹ２に記載）に従ってイエロー記録液６を調製した。
＜イエロー記録液６（アニオン性顔料含有記録液）＞
Ｃ．Ｉ．ピグメントイエロー７４ ３．０部
グリセリン １０．０部
エチレングリコール ５．０部
Ｎ−メチルピロリドン ５．０部
エチルアルコール ２．０部
水 残量
【０１５４】
特開２００１−３０６１６号公報の実施例（ブラックインクＡ１に記載）に従って黒色記録液７を調製した。
＜黒色記録液７（アニオン性顔料含有記録液）＞
カーボンブラックＭＡ７ ５．０部
スチレン−アクリル酸共重合体 １．０部
アクリル系樹脂エマルジョン １０．０部
グリセリン １０．０部
水 残量
【０１５５】
特開２００１−３０６１６号公報の実施例（イエローインクＡ１に記載）に従ってイエロー記録液７を調製した。
＜イエロー記録液７（アニオン性顔料含有記録液）＞
Ｃ．Ｉ．ピグメントイエロー７４ ３．５部
スチレン−アクリル酸共重合体 １．０部
アクリル系樹脂エマルジョン １５．０部
グリセリン ８．０部
水 残量
【０１５６】
＜黒色記録液８（紫外線反応型黒色顔料記録液）＞
カーボンブラック
（キャボット社製、キャボジェット３００） １０部
光酸発生剤（三和ケミカル社製、ＷＳ−トリアジン） ２．０部
１，３−ブタンジオール ２２．５部
グリセリン ７．５部
界面活性剤（Ｉ）、Ｒ＝Ｃ_９Ｈ_１９、ｋ＝１２ １部
２−ピロリドン ２部
デヒドロ酢酸ナトリウム ０．２部
チオ硫酸ナトリウム ０．２部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．４部
イオン交換水 残量
なお、上記配合液を更にＬｉＯＨ水溶液でｐＨ１０．５に調整して用いた。
【０１５７】
＜イエロー記録液８（紫外線反応型イエロー顔料記録液）＞
樹脂被覆型イエロー分散体 ５０部（イエロー顔料固形分１０部）
光酸発生剤（三和ケミカル社製、ＷＳ−トリアジン） ２．０部
１，３−ブタンジオール ２２．５部
グリセリン ７．５部
界面活性剤（Ｉ）、Ｒ＝Ｃ_９Ｈ_１９、ｋ＝１２ １部
２−ピロリドン ２部
デヒドロ酢酸ナトリウム ０．２部
チオ硫酸ナトリウム ０．２部
防腐防黴剤（アビシア社製、ＰＲＯＸＥＬ ＬＶ（ｓ）） ０．４部
イオン交換水 残量
なお、上記配合液を更にＬｉＯＨ水溶液でｐＨ１０．５に調整して用いた。
【０１５８】
実施例１
上記で調製した処理液１を処理液用カートリッジに、イエロー記録液１をイエロー記録液用カートリッジに、黒色記録液１を黒色記録液用カートリッジにそれぞれ収容（充填）して、前記図６に示す構成の画像形成装置（インクジェット記録装置）に装着し、印字評価実験を行なった。実施例１の処理液と記録液の主成分をまとめて表１に示す。なお、カートリッジはいずれも共通の構成、形態のものである。
印字評価実験の被記録媒体（被記録材）としてマイペーパー（普通紙、ＮＢＳリコー製）を用いて試験を行なった。ただし、細線再現性の実験には、油絵用のキャンバス地（世界堂製、細目）を用いて印字試験を行なった。インクジェットによる印字は、先に処理液が紙に付着し、その上から各色の記録液が付着する順番で行なった。印刷時の記録液付着量、処理液付着量はおおよそ下記の量となるように調整して実施した。
記録液付着量：１１．０ｇ／ｍ２
処理液付着量：１３．０ｇ／ｍ２
【０１５９】
印字された印刷物（記録物）の、フェザリング、カラーブリード、画像濃度、彩度、乾燥性、光沢度、細線再現性、定着性について評価を行なった。各項目の評価は、以下に示す評価方法、基準に基づいて行った。結果を表２に示す。
また、記録物の黒ベタ部分を切断し、その断面を透過型電子顕微鏡（ＴＥＭ）で観察した。断面ＴＥＭ写真を図１２に示す。図から分かるように縞状の濃淡が現れている。更に、元素分析（ＥＤＸ）の結果から、濃い部分が微粒子凝集層、淡い部分が色材凝集層であることが特定できた。
【０１６０】
＜画質評価方法＞
（１）フェザリング：
黒文字部分を観察し、ランク見本と比較することで画質評価を行なった。
ランク５…滲み出しが全くない
ランク４…滲み出しがわずかにある
ランク３…滲み出しがあるが、実用上問題なし
ランク２…滲み出しがやや多い
ランク１…滲み出しが多い
（２）カラーブリード：
黒ベタの中にイエローで“Ａ”文字を印字した印刷物の色境界部分を観察し、ランク見本と比較することで画質評価を行なった。
ランク５…混色が全くない
ランク４…混色がわずかにある
ランク３…混色があるが、実用上問題なし
ランク２…混色がやや多い
ランク１…混色が多い
（３）画像濃度：
黒ベタ部分の表面からの光学濃度を測定し、画像濃度を求めた。
（４）彩度：
イエローベタ部分の表面からＬａｂを測定し、イエローの彩度を求めた。
（５）乾燥性：
印刷直後に印刷物に普通紙（マイペーパー、ＮＢＳリコー製）を押し当てて、普通紙への黒ベタ部分のインク転移を観察した。
○…インク転移無し
×…インク転移有り
（６）光沢度：
印刷物の６０度光沢度を光沢度計（ＢＹＫ Ｇａｒｄｅｎｅｒ社製、４５０１）を用いて求めた。
（７）細線再現性：
幅０．５ｍｍのラインとスペースが繰り返されるパターンを印字し、細線再現性を観察した。
○…隣接するラインが独立している
×…隣接するラインがつながっている
（８）定着性：
印刷物の表面を手で擦り、画像部の定着性を評価した。
○…色移り無し
×…色移り有り
（９）断面ＴＥＭ観察：
印刷物の黒ベタ部分を切断し、透過型電子顕微鏡（ＴＥＭ）で観察した。元素分布の偏りがある場合には濃淡が目視で観察でき、色材と微粒子がそれぞれ層を形成していることが分かる。また、元素を色分けしてマッピングすることで、よりはっきりと色材と微粒子の分布を確認することができる。
【０１６１】
実施例２〜６
実施例１において、処理液１、黒色記録液１、イエロー記録液１をそれぞれ用いたのに代えて、表１に示した組み合わせでそれぞれの実施例における記録液及び処理液を用いた以外は実施例１と同様にして実施例２〜６の印字試験を行なった。結果を表２に示す。
【０１６２】
実施例７
実施例１において、処理液１、黒色記録液１、イエロー記録液１をそれぞれ用いた代りに、表１に示した記録液及び処理液を用いた以外は実施例１と同様に実施例７の印字試験を行なった。結果を表２に示す。
【０１６３】
実施例８
実施例１において、処理液１、黒色記録液１、イエロー記録液１をそれぞれ用いた代りに、表１に示した記録液及び処理液を用い、図６に示すインクジェット記録装置の代りに図７に示す紫外線照射装置付きインクジェット記録装置を用いた以外は実施例１と同様に実施例８の印字試験を行なった。結果を表２に示す。
【０１６４】
比較例１〜７
実施例１において、処理液１、黒色記録液１、イエロー記録液１をそれぞれ用いたのに代えて、表１に示した組み合わせでそれぞれの比較例における記録液及び処理液を用いた以外は実施例１と同様にして比較例１〜７の印字試験を行なった。結果を表２に示す。
【０１６５】
【表１】

【０１６６】
【表２】

【０１６７】
上記評価の結果、本発明における構成の処理液と記録液とから構成されるインクセットを用いた実施例１〜８の場合には、いずれもフェザリング及びカラーブリードにおいて滲み出しが防止されており、しかも画像濃度、彩度共に良好である。また、インク転写も無く乾燥性においても良好で、光沢度は非常に優れている。更に、印字された細線も隣接ラインが独立しておりギザギザ状態が発生せず、細線再現性も良好である。また、印刷物の表面における手による擦りにおいても色移りも無く定着性も優れている。
また、各記録物の透過型電子顕微鏡（ＴＥＭ）による断面観察の結果、本発明の実施例１〜８ではいずれも実施例１で示したと同じような縞状の濃淡が現れている。
一方、比較例１〜７の場合には、いずれの特性も本発明に較べて劣っており、また、透過型電子顕微鏡（ＴＥＭ）による断面観察でも縞状の濃淡は認められなかった。
【０１６８】
【発明の効果】
本発明の外的要因（例えば、物質の接触や紫外線照射などによりｐＨの変化や溶解度の変化等を生じさせる要因）によって分散状態を維持するか若しくは破壊するように調整された微粒子を含む処理液と、前記外的要因によって分散状態あるいは溶解状態を維持するか若しくは破壊するように調整された色材を含む記録液とから構成されたインクセットを用い、この処理液と記録液とを個別にインクジェット方式によって液滴として被記録媒体（吸収性記録媒体あるいは非吸収性記録媒体）上に噴射し、それぞれの液滴を接触させて、処理液と記録液とに状態変化（例えば、ｐＨの変化や溶解度の変化等）を生じさせて、処理液中の微粒子と記録液中の色材とが実質的に混合することなく凝集するようにして画像を形成する方法により、フェザリング及びカラーブリードを防止し、高濃度、かつ高彩度であり、しかも光沢感のある印刷物（記録物）が得られる。
また、本発明における処理液及び記録液をそれぞれ個別に収容したカートリッジを搭載したインクジェット方式の画像形成装置により、上記画像形成方法が達成され、インクセットの優れた特性と相俟ってフェザリング及びカラーブリードの効果的な抑制、高濃度化と高彩度化、光沢感の付与などを実現し、原稿に忠実で鮮明な印刷物が提供される。
更に、本発明における処理液と記録液とを個別に収容したカートリッジを画像形成装置に搭載するようにすることで、画像装置をコンパクトに構成することができる他、簡単でしかも着実なメンテナンス作業を行うことが可能となる。また、部品の交換を容易とし、総合的なコストダウンが図れて、しかも画像品質の安定化を実現する。
【図面の簡単な説明】
【００５２】
【図１】本発明のインクセットと画像形成方法を適用し物質接触により処理液と記録液のｐＨが変化する場合の画像形成過程を示す模式図である。
【図２】本発明のインクセットと画像形成方法を適用し物質接触によるイオン移動や塩析等でｐＨ変化、溶解度変化を生じさせ画像形成する過程を示す模式図である。
【図３】本発明のインクセットと画像形成方法を適用し紫外線を照射して、光酸発生剤から酸を発生させてｐＨ変化を生じさせ画像形成する過程を示す模式図である。
【図４】平滑な非吸収性記録媒体に細線を印字する場合の従来法と本発明による画像形成の違い（線幅）を概念的に示す模式図である。
【図５】凹凸を有する非吸収性記録媒体に細線を印字する場合の従来法と本発明による画像形成の違い（ギザギザ状態）を概念的に示す模式図である。
【図６】実施の形態における本発明の一例である画像形成装置を説明するための概略構成を示す斜視図である。
【図７】実施の形態における本発明の別の例である紫外線照射手段（高圧水銀灯）を備えた画像形成装置を説明するための概略構成を示す斜視図である。
【図８】図４の画像形成装置のキャリッジに搭載される記録ヘッドの吐出ノズルの構成例を説明するための概略断面図である。
【図９】図４の画像形成装置のキャリッジに搭載される記録ヘッドの吐出ノズルの別の構成例を説明するための概略断面図である。
【図１０】実施の形態における本発明の画像形成装置に搭載される処理液あるいは記録液を収容可能なカートリッジを説明するための概略構成例を示す外観斜視図である。
【図１１】図７に示すカートリッジの内部概略構成を示す正断面図である。
【図１２】実施例１の記録物の黒ベタ部分を切断した断面を透過型電子顕微鏡（ＴＥＭ）で観察した断面ＴＥＭ写真である。
【符号の説明】
１ 画像形成装置
２ 本体筐体
１６ ギア機構
１７ 副走査モーター
１８ キャリッジ
１８ａ 記録ヘッド
１９ プラテン
２０ カートリッジ
２１ ガイドシャフト
２２ ガイドシャフト
２３ タイミングベルト
２４ 主走査モーター
２６ 主走査モーター
２７ 高圧水銀灯
３１ ノズル（処理液が吐出される）
３２ ノズル（記録液が吐出される）
３３ ノズル（記録液が吐出される）
３４ ノズル（記録液が吐出される）
３５ ノズル（記録液が吐出される）
３６ ノズル（処理液が吐出される）
３７ ノズル（記録液が吐出される）
３８ ノズル（記録液が吐出される）
３９ ノズル（記録液が吐出される）
４０ ノズル（記録液が吐出される）
４１ ノズル（処理液が吐出される）
４２ 液吸収体
４３ ケース
４４ 上蓋部材
４５ 液供給口
４６ シールリング
４７ 大気解放口
４９ カートリッジ筐体
５０ キャップ部材
５５ シール部材
８１ カートリッジ着脱用突状部
Ａ 空間[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an image recording system using an ink jet recording method, and particularly to an absorbent recording medium and a non-absorbent recording medium (feathering and color bleed are suppressed, and high-density, high-chroma, glossy images can be formed. 2.) An ink set composed of two liquids, an image recording method using the ink set, an image forming apparatus, and a recorded matter.
[0002]
[Prior art]
An ink jet recording method for recording an image using ink (recording liquid) containing a color material as droplets is excellent in that the printing mechanism is simple and no noise is generated. However, on the other hand, in the image recording by the ink jet recording method, when combined with a fibrous recording medium having a property of absorbing a recording liquid, that is, a so-called absorptive recording medium, the color material in the recording liquid becomes a fiber of the recording medium. When the color ink is irregularly penetrated along the surface, the outline of the recorded character is distorted like a whisker (feathering), or when different color inks are struck adjacently on the recording medium, And the color boundary becomes unclear (color bleed).
[0003]
In order to cope with this problem, a method has been proposed in which a treatment liquid that reacts with the ink is used together with the ink.
For example, a recording method has been disclosed in which a treatment liquid containing a quaternary ammonium salt or an amine salt is reacted with an ink containing a water-soluble dye (for example, see Patent Document 1). Alternatively, there is disclosed a recording method in which a treatment liquid containing a compound having two or more cationic groups in one molecule is reacted with an ink containing an anionic dye (for example, see Patent Document 2). Also disclosed is an image forming method in which an ink and a liquid composition are combined and mixed to react a coloring material in the ink with fine particles in the liquid composition, thereby adsorbing the coloring material on the fine particle surface, and then causing aggregation. (For example, see Patent Document 3). Further, there is disclosed an image forming method in which a cationic fine particle and a treatment liquid containing a different cationic substance from the ink are reacted with an ink to adsorb or bond a coloring material to the surface of the fine particle (for example, see Patent Document 4). ).
According to the proposal of the above disclosure, the coloring material can be agglomerated as compared with the conventional ink-jet method using only ink, so that a certain effect can be obtained with respect to reduction of feathering and reduction of color bleed. However, each has the following disadvantages.
[0004]
For example, when a quaternary ammonium salt as used in Patent Literature 1 is used as a reactant, a large aggregate is not formed, so that the colorant is diffused. Further, when polyallylamine as used in Patent Document 2 is used as a reactant, the amount of polyallylamine added must be reduced in order to suppress the increase in the viscosity of the processing solution, and thus the formation of aggregates is slow. As a result, there is a problem that the coloring material is also diffused. Accordingly, the speed of coagulating the coloring material is not rapid in any case, and thus the effect of improving the image quality is limited.
Further, in the mechanism described in Patent Document 3, “the coloring agent is adsorbed on the fine particles in a monomolecular state, and the adsorbent forms aggregates”. Need to be sufficiently mixed, and it takes a long time to be sufficiently mixed, and actually, the flow of the coloring material starts before all the coloring materials are aggregated. Alternatively, ink that does not substantially participate in the reaction flows out, and as a result, feathering and color bleeding tend to occur. In addition, unreacted ink, so-called undried ink, remains on the surface of the printed matter for a while due to the non-rapid aggregation of the coloring material, and when touching the printed matter, the hands become dirty and image defects occur. easy. Furthermore, it is necessary for the coloring material or the fine particles having a large particle size to move while avoiding the agglomerates one by one, and to react while mixing each other. In this case, the movement is hindered due to the steric hindrance of the coloring material or the fine particles. And the reaction speed is slow. Furthermore, in the method of Patent Document 3, since an image is formed by a form in which the coloring material and the fine particles are uniformly mixed, the coloring material does not completely ride on the surface of the recording medium, and a large amount of the coloring material remains inside the recording medium. , Thereby suppressing an improvement in image density and saturation. The case of Patent Document 4 is similar to the above.
[0005]
Further, the method of using a treatment liquid that reacts with the ink together with the ink has a problem in imparting gloss to a printed matter and a problem in printing on a non-absorbent medium, as described below.
First, a description will be given of the above-described problem in imparting glossiness to a printed matter.
Insufficient glossiness of ink-jet prints is one of the reasons that users who are accustomed to offset prints, gravure prints, and electrophotographic prints usually feel uncomfortable with ink-jet prints and feel inferior in quality. In particular, when viewing an image that appeals to sensitivity, such as a photographic image, the glossiness gives a sense of quality and gives the user a high-quality impression. However, the ink jet recording method basically fixes the color material by penetrating the ink containing the color material into the recording medium. For this reason, a layer in which the coloring material is localized is not formed on the surface layer of the recording medium, and the paper fibers are exposed on the surface of the recording medium. .
[0006]
With respect to this problem, proposals have been made to provide a glossy feeling even when an ink jet recording method is applied. For example, an ink containing a microcapsule pigment is disclosed (for example, see Patent Document 5). However, in this proposal, the microcapsule pigment is small in size and sinks into and penetrates the recording medium, so that the paper fibers are exposed to the surface and irregular reflection of incident light is likely to occur. The effect of imparting gloss by this method cannot be said to be sufficient, resulting in a printed matter having poor glossiness.
Further, a recording method of overcoating a liquid containing a resin emulsion on a printed material is disclosed (for example, see Patent Document 6). However, in this proposal, there is a concern that the printing apparatus is complicated due to the necessity of performing a special surface treatment, and the cost is increased due to the large consumption of the coating liquid.
[0007]
Next, a problem in printing on the second non-absorbable medium will be described.
In the printing field, in addition to paper, there is also a great demand for printing on recording media such as plastics, resin films, metals, glass, and oil-painting materials, that is, non-absorbent media showing little ink absorbency. These fields are important fields for obtaining higher value-added printed matter. However, when printing is performed on a non-absorbent recording medium using a conventional ink jet recording method, ink does not absorb, causing character bleeding and color mixing, and image quality is greatly reduced.
[0008]
To cope with this problem, a recording method of applying ultraviolet light to ink containing photoreactive polymer fine particles (for example, see Patent Document 7) or a recording method of applying heat to ink containing a thermosetting agent (for example, Patent Document 8) is disclosed.
However, in these proposals, an idle time is generated between the time when the ink is jetted onto the recording medium and the time when the ultraviolet rays or heat is applied, and it is difficult to obtain an effect on the improvement of the image quality. It becomes necessary to mount the device, and it is inevitable that the device becomes complicated and large.
[0009]
Other methods have been proposed to cope with high quality printing on non-absorbent recording media. For example, an ink jet recording method in which an ink containing a resin emulsion having a minimum film forming temperature of 20 ° C. or more is reacted with a reaction liquid (for example, see Patent Document 9), or an ink containing resin emulsion particles, a reactant and a cation A recording method in which a reaction solution containing reactive polymer fine particles is reacted (for example, see Patent Document 10) is disclosed.
However, in Patent Document 9, it takes time until the coloring material and the fine particles are completely mixed, and the unreacted coloring material flows. Therefore, in a non-absorbent recording medium having irregularities, the coloring material that remains fluid flows into the concave portions, and the fine lines are likely to be jagged. Further, even in Patent Document 10, the reactivity is not always sufficient, and it is difficult to obtain a satisfactory image quality in a non-absorbing recording medium.
[0010]
[Patent Document 1]
Patent No. 2711098
[Patent Document 2]
Japanese Patent No. 2667401
[Patent Document 3]
JP 2001-199149 A
[Patent Document 4]
JP-A-2002-201385
[Patent Document 5]
JP-A-2002-256166
[Patent Document 6]
JP 2001-039006 A
[Patent Document 7]
JP 2001-115067 A
[Patent Document 8]
JP 2001-262022 A
[Patent Document 9]
JP 2001-030616 A
[Patent Document 10]
JP-A-2002-225414
[0011]
[Problems to be solved by the invention]
The present invention has been made in view of the above-described problems, and has as its object the purpose of using a recording medium which is either an absorbing recording medium or a non-absorbing recording medium (including a non-absorbing medium having irregularities). Also, an ink set and a high-density, high-saturation ink set that can effectively suppress feathering and color bleed, obtain a high-density and high-saturation print that is faithful to the original, and can impart glossiness to the print An object of the present invention is to provide an image recording method, an image recording apparatus, and a printed matter (recorded matter) used.
[0012]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and have found that a treatment liquid containing fine particles adjusted to maintain or destroy a dispersed state due to external factors, and a dispersion state or a dissolved state due to external factors. Using an ink set composed of a recording liquid containing a coloring material adjusted to maintain or destroy the ink, a state change occurs between the processing liquid and the recording liquid on the recording medium, and the A method of forming an image by agglomerating the fine particles of the particles and the colorant in the recording liquid without substantially mixing them, thereby preventing feathering and color bleeding, achieving high density, high chroma, and glossiness. It has been found that a printed matter (recorded matter) having a certainty can be obtained, and the present invention has been completed. When a state change is caused between the processing liquid and the recording liquid on the recording medium, for example, the processing liquid and the recording liquid are individually formed as droplets by an inkjet method as droplets on the recording medium (absorbent recording medium or non-absorbent recording medium). (Recording medium), and the respective droplets are brought into contact with each other. Alternatively, it can be performed by causing a state change by a non-contact action such as an electromagnetic wave or heat.
Hereinafter, the present invention will be described specifically.
[0013]
According to the first aspect of the present invention, there is provided a treatment liquid containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and to maintain or destroy a dispersed state or a dissolved state by an external factor. And a recording liquid containing the adjusted coloring material, wherein the processing liquid and the recording liquid are dispersed or dissolved on a recording medium, whereby the fine particles in the processing liquid and the recording liquid are destroyed. An ink set characterized in that the coloring material in the liquid aggregates without substantially mixing to form an image.
[0014]
The invention according to claim 2 is the ink set according to claim 1, wherein the recording liquid and the processing liquid constituting the ink set are aqueous liquids.
[0015]
By using the ink set according to claim 1 or 2, a layer of fine particles and a coloring material can be formed on any of an absorbing recording medium and a non-absorbing recording medium (including a non-absorbing medium having irregularities). It can be formed instantly. For this reason, feathering and color bleeding can be satisfactorily suppressed, high-density, high-saturation, excellent glossiness, and good image formation with good drying and fixing properties can be achieved. Recorded matter) can be obtained.
[0016]
According to a third aspect of the present invention, the coloring material contained in the recording liquid has an anionic group or a cationic group, or the surface of the coloring material is directly or indirectly formed by a compound having an anionic group or a cationic group. The ink set according to claim 1, wherein the ink set is coated.
[0017]
The invention according to claim 4 is characterized in that the fine particles contained in the treatment liquid have a cationic group or an anionic group, or the fine particles have a surface having a cationic group or an anionic group directly or indirectly by a compound having the cationic group or the anionic group. The ink set according to claim 1, wherein the ink set is coated.
[0018]
The ink according to any one of claims 1 to 4, wherein when the colorant and the fine particles are anionic or cationic, the respective polarities are opposite to each other. It is a set.
[0019]
According to the configuration of the third to fifth aspects, a clear aggregation layer is formed at the interface between the recording liquid and the processing liquid by using the anionic or cationic recording liquid and using the processing liquid having the opposite polarity. Accordingly, a thick layer of the coloring material (substantially mainly of the coloring material) can be instantaneously formed on the recording medium. For this reason, feathering and color bleeding are more favorably suppressed, and high density, high chroma, excellent gloss, good drying and fixing properties can be formed, and a high quality recorded matter can be obtained.
[0020]
According to a sixth aspect of the present invention, there is provided a treatment liquid containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and to maintain or destroy a dispersed or dissolved state by an external factor. By using an ink set composed of a recording liquid containing the adjusted coloring material, the processing liquid and the recording liquid are destroyed in a dispersed state or a dissolved state on a recording medium, whereby the processing liquid An image forming method for forming an image by aggregating fine particles and a coloring material in the recording liquid without substantially mixing them,
Contacting the processing liquid and the recording liquid in the image forming step;
A step of causing a state change between the treatment liquid and the recording liquid by the contact;
Causing the state change to cause aggregation of the fine particles in the processing solution,
A step of causing the color materials in the recording liquid to aggregate with each other by the state change;
Is an image forming method.
[0021]
According to the configuration of claim 6, the fine particles and the color material aggregate due to a state change (for example, a pH change or a solubility change) caused by an external factor, so that the color material aggregated portion is substantially equal to the fine particle aggregated portion. It is formed by agglomeration on one side (for example, on the fine particle aggregation portion) without mixing. For this reason, the coloring material can efficiently remain on one side of the recording medium (for example, on the agglomerated portion of the fine particles), and a high-density, high-chroma image can be formed, and a high-quality recorded matter can be obtained. it can.
[0022]
According to a seventh aspect of the present invention, there is provided a treatment liquid containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and to maintain or destroy a dispersed or dissolved state by an external factor. By using an ink set composed of a recording liquid containing the adjusted coloring material, the processing liquid and the recording liquid are destroyed in a dispersed state or a dissolved state on a recording medium, whereby the processing liquid An image forming method for forming an image by aggregating fine particles and a coloring material in the recording liquid without substantially mixing them,
Contacting the processing liquid and the recording liquid in the image forming step;
A step of causing a state change between the treatment liquid and the recording liquid by the contact;
A process of causing the surface potential of the fine particles in the treatment liquid to change to cause aggregation of the fine particles,
A process of causing the surface potential of the color material in the recording liquid to change by the state change to cause aggregation of the color materials;
Is an image forming method.
[0023]
According to the configuration of the seventh aspect, the surface potential of the fine particles and the surface potential of the coloring material change, whereby the respective aggregations occur instantaneously. For this reason, an image with higher density and higher saturation can be formed, and an image can be formed in which feathering and color bleeding are suppressed, and a high-quality recorded matter can be obtained.
[0024]
The invention of claim 8 provides a processing solution containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and to maintain or destroy a dispersed state or a dissolved state by an external factor. By using an ink set composed of a recording liquid containing the adjusted coloring material, the processing liquid and the recording liquid are destroyed in a dispersed state or a dissolved state on a recording medium, whereby the processing liquid An image forming method for forming an image by aggregating fine particles and a coloring material in the recording liquid without substantially mixing them,
Contacting the processing liquid and the recording liquid in the image forming step;
A step of causing a state change between the treatment liquid and the recording liquid by the contact;
A step of causing the fine particles in the processing liquid to aggregate by the state change to form a layer of the fine particles,
Forming a layer of the color material by causing the color materials in the recording liquid to aggregate by the state change;
Is an image forming method.
[0025]
According to the configuration of claim 8, since the layer of fine particles and the layer of color material are formed respectively, the color material aggregated portion is not substantially mixed with the fine particle aggregate portion on one side (for example, on the fine particle aggregate portion). ) Is clearly formed. For this reason, the coloring material can remain more efficiently on one side of the recording medium (for example, on the agglomerated portion of the fine particles), and a high-density, high-saturation image can be formed. Obtainable.
[0026]
According to a ninth aspect of the present invention, there is provided a treatment liquid containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and to maintain or destroy a dispersed or dissolved state by an external factor. By using an ink set composed of a recording liquid containing the adjusted coloring material, the processing liquid and the recording liquid are destroyed in a dispersed state or a dissolved state on a recording medium, whereby the processing liquid An image forming method for forming an image by aggregating fine particles and a coloring material in the recording liquid without substantially mixing them,
Contacting the processing liquid and the recording liquid in the image forming step;
A step of causing a state change between the treatment liquid and the recording liquid by the contact;
The state change, the surface potential of the fine particles in the treatment liquid is changed to cause aggregation of the fine particles, a process of forming a layer of fine particles,
A process of changing the surface potential of the coloring material in the recording liquid to cause agglomeration of the coloring materials, thereby forming a coloring material layer;
Is an image forming method.
[0027]
According to the configuration of claim 9, since the surface potential of the fine particles and the surface potential of the coloring material change, and in addition, the fine particle layer and the coloring material layer are formed, respectively, Are instantaneously formed. For this reason, an image with higher density and higher saturation can be formed, and an image can be formed in which feathering and color bleeding are suppressed, and a high-quality recorded matter can be obtained.
[0028]
According to a tenth aspect of the present invention, there is provided a treatment liquid containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and to maintain or destroy a dispersed or dissolved state by an external factor. By using an ink set composed of a recording liquid containing the adjusted coloring material, the processing liquid and the recording liquid are destroyed in a dispersed state or a dissolved state on a recording medium, whereby the processing liquid An image forming method for forming an image by aggregating fine particles and a coloring material in the recording liquid without substantially mixing them,
Contacting the processing liquid and the recording liquid in the image forming step;
A step of causing the ions to move from the recording liquid to the processing liquid to cause a state change by the contact, thereby causing aggregation of the fine particles in the processing liquid;
A step of causing the ions to move from the processing liquid to the recording liquid to cause a state change by the contact, thereby causing aggregation of the color materials in the recording liquid;
Is an image forming method.
[0029]
According to the configuration of the tenth aspect, the movement of the ions further increases the aggregation speed, so that a thick color material layer and a fine particle layer can be instantaneously formed. For this reason, in addition to the above-mentioned effects, it is possible to form an image with high dryness and glossiness, and it is possible to obtain a high quality recorded matter.
[0030]
According to the eleventh aspect of the present invention, there is provided a treatment liquid containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and to maintain or destroy a dispersed state or a dissolved state by an external factor. By using an ink set composed of a recording liquid containing the adjusted coloring material, the processing liquid and the recording liquid are destroyed in a dispersed state or a dissolved state on a recording medium, whereby the processing liquid An image forming method for forming an image by aggregating fine particles and a coloring material in the recording liquid without substantially mixing them,
Contacting the processing liquid and the recording liquid in the image forming step;
The contact causes ions to move from the recording liquid to the processing liquid to cause a state change, and change the surface potential of the fine particles in the processing liquid to cause aggregation of the fine particles;
By the contact, ions move from the processing liquid to the recording liquid to cause a change in state, and the surface potential of the coloring material in the recording liquid changes to cause aggregation of the coloring materials;
Is an image forming method.
[0031]
According to the configuration of the eleventh aspect, in addition to further increasing the aggregation speed due to the movement of the ions, the aggregation speed is further increased by changing the surface potential of the fine particles and the coloring material. For this reason, in addition to the above-mentioned effects, it is possible to obtain a recorded matter having high fine line reproducibility on a non-absorbent recording medium.
[0032]
According to a twelfth aspect of the present invention, there is provided a treatment liquid containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and to maintain or destroy a dispersed state or a dissolved state by an external factor. By using an ink set composed of a recording liquid containing the adjusted coloring material, the processing liquid and the recording liquid are destroyed in a dispersed state or a dissolved state on a recording medium, whereby the processing liquid An image forming method for forming an image by aggregating fine particles and a coloring material in the recording liquid without substantially mixing them,
Contacting the processing liquid and the recording liquid in the image forming step;
A process in which the contact changes the state of the processing liquid to fix an aggregate formed by aggregation of the fine particles in the processing liquid on the surface of the recording medium;
A process in which the contact causes a change in the state of the recording liquid to fix an aggregate formed by agglomeration of the color materials in the recording liquid on the surface of the recording medium or the surface of the aggregate of the fine particles;
Is an image forming method.
[0033]
According to the twelfth aspect of the invention, the aggregate of the coloring material and the aggregate of the fine particles are fixed on the recording medium, so that a recorded matter having a high fixing property can be obtained without the recording layer falling even when rubbed.
[0034]
According to a thirteenth aspect of the present invention, there is provided a treatment liquid containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and to maintain or destroy a dispersed or dissolved state by an external factor. An image forming apparatus comprising: a storage unit that independently stores a recording liquid containing a color material that has been adjusted, and a discharge unit that individually discharges the recording liquid and the processing liquid,
By breaking each of the processing liquid and the recording liquid into a dispersed state or a dissolved state on a recording medium, the fine particles in the processing liquid and the coloring material in the recording liquid are aggregated without being substantially mixed. An image forming apparatus is characterized in that an image is formed by the image forming apparatus.
[0035]
According to a fourteenth aspect of the present invention, the image formation on the recording medium is performed by applying any one of the image forming methods according to the sixth to twelfth aspects. Image forming apparatus.
[0036]
According to the configuration of the thirteenth or fourteenth aspect, the image formation of obtaining the high quality image according to the sixth to twelfth aspects is realized.
[0037]
The invention according to claim 15 is the image forming apparatus according to claim 13, wherein the ejection unit is an ink jet recording head.
[0038]
According to the configuration of the fifteenth aspect, by using the inkjet recording head as the ejection unit, a recorded matter of a fine image can be obtained.
[0039]
The invention according to claim 16 is the image forming apparatus according to claim 15, wherein the inkjet recording head is an ejection head using thermal energy.
[0040]
According to the configuration of the sixteenth aspect, it is possible to obtain a recorded matter of a higher resolution image by using the ejection head by the thermal energy.
[0041]
The invention according to claim 17, wherein the storage unit of the image forming apparatus includes a storage unit that stores the processing liquid and the recording liquid independently, and a discharge unit that discharges the recording liquid and the processing liquid individually. Cartridge stored in the
A processing liquid containing fine particles adjusted to maintain or destroy the liquid storage portion of the cartridge individually by an external factor, or maintain or destroy the dispersed or dissolved state by an external factor And a recording liquid containing a coloring material adjusted to perform the recording.
[0042]
According to the configuration of claim 17, in addition to being able to configure the image apparatus compactly, it is possible to perform simple and steady maintenance work, further facilitate replacement of parts, and achieve a total cost reduction. Moreover, the image quality is stabilized.
[0043]
The invention according to claim 18 is a recorded matter on which an image is formed using an ink set composed of a processing liquid containing fine particles and a recording liquid containing a coloring material,
The agglomerated fine particles and the coloring material are formed separately in a layer substantially formed of the fine particles and a layer substantially formed of the coloring material in a cross section of the recorded matter. It is a recorded matter to be performed.
[0044]
According to a nineteenth aspect of the present invention, the recorded matter maintains a dispersed state due to an external factor or a processing liquid containing fine particles adjusted to be destroyed, and maintains a dispersed state or a dissolved state due to an external factor. Or, by using an ink set composed of a recording liquid containing a coloring material adjusted to be destroyed, by disintegrating the treatment liquid and the recording liquid in their dispersed state or dissolved state on a recording medium, 19. The recorded matter according to claim 18, wherein the recorded matter is an image formed by agglomeration of the fine particles in the processing liquid and the coloring material in the recording liquid without being substantially mixed to form an image.
[0045]
The invention according to claim 20, wherein the layer substantially formed of the fine particles causes the state of the processing liquid to change due to the contact between the processing liquid and the recording liquid, thereby causing aggregation of the fine particles in the processing liquid. The layer formed in the process of causing the layer to be substantially formed of the colorant, the contact between the processing liquid and the recording liquid causes a change in the state of the recording liquid, and 19. The recorded matter according to claim 18, wherein the layer is formed in a process of causing aggregation of the color materials.
[0046]
According to the constitutions of claims 18 to 20, fine particles and color materials aggregate due to a state change (pH change, solubility change, etc.) caused by an external factor, so that the color material aggregated portion substantially corresponds to the fine particle aggregated portion. Formed on one side (for example, on the aggregated portion of fine particles) without mixing. For this reason, the coloring material can efficiently remain on one side of the recording medium (for example, on the fine particle aggregation portion), and a high-density, high-chroma recording material can be obtained.
[0047]
The invention according to claim 21, wherein the layer substantially formed of the fine particles changes the state of the processing liquid due to the contact between the processing liquid and the recording liquid, and the surface potential of the fine particles in the processing liquid is reduced. A layer formed in the process of causing the fine particles to change and causing agglomeration of the fine particles. The layer substantially formed of the coloring material is in a state of the recording liquid due to the contact between the processing liquid and the recording liquid. 19. The recorded matter according to claim 18, wherein the layer is formed in a process in which a change occurs to change a surface potential of the coloring material in the recording liquid to cause aggregation of the coloring material. .
[0048]
According to the configuration of the twenty-first aspect, the surface potential of the fine particles and the surface potential of the coloring material change, so that aggregation occurs instantaneously. For this reason, it is possible to obtain a recorded matter in which feathering and color bleed are suppressed in addition to higher density and higher saturation.
[0049]
The invention according to claim 22, wherein in the layer substantially formed of the fine particles, the contact between the processing liquid and the recording liquid causes ions to move from the recording liquid to the processing liquid, causing a state change to occur. A layer formed in the process of causing agglomeration of the fine particles in the liquid, wherein the layer substantially formed of the colorant is formed from the processing liquid by contact between the processing liquid and the recording liquid. 19. The recorded matter according to claim 18, wherein the layer is formed in a process in which ions move to the liquid to cause a state change to cause aggregation of the coloring materials in the recording liquid.
[0050]
According to the configuration of the twenty-second aspect, the movement of the ions further increases the aggregation speed, so that a thick color material layer and a fine particle layer can be formed instantaneously. For this reason, in addition to the above-mentioned effects, it is possible to obtain a recorded matter having high dryness and glossiness.
[0051]
The invention according to claim 23, wherein in the layer substantially formed of fine particles, the contact between the processing liquid and the recording liquid causes ions to move from the recording liquid to the processing liquid to cause a state change to occur. A layer formed in the process of causing the surface potential of the fine particles in the liquid to change and causing the aggregation of the fine particles, and the layer substantially formed of the coloring material is a layer formed of the processing liquid and the recording liquid. Due to the contact, ions are transferred from the processing liquid to the recording liquid to cause a state change, and the surface potential of the coloring material in the recording liquid changes to cause agglomeration of the coloring materials. The recorded matter according to claim 18, wherein:
[0052]
According to the configuration of claim 23, the aggregation speed is further increased by moving the ions, and the aggregation potential is further increased by changing the surface potential of the fine particles and the coloring material. For this reason, in addition to the above effects, it is possible to obtain a recorded matter having high fine line reproducibility on a non-absorbent recording medium.
[0053]
BEST MODE FOR CARRYING OUT THE INVENTION
First, an outline of an image forming method using the ink set of the present invention will be described.
As described above, in the present invention, a treatment liquid containing fine particles adjusted to maintain or destroy a dispersed state due to external factors, and to maintain or destroy a dispersed or dissolved state due to external factors An ink set composed of a recording liquid containing a coloring material adjusted to a predetermined temperature is brought into contact with a recording medium, causing a state change between the processing liquid and the recording liquid, thereby causing fine particles in the processing liquid and the recording liquid to change. An image is formed such that the colorants in the medium aggregate without substantially mixing.
In the present invention, the “external factor” refers to the fact that a substance is in contact with a processing liquid or a recording liquid and acts, or that an electromagnetic wave such as ultraviolet rays or heat acts in a non-contact manner and acts. This is a factor that causes physical, chemical, and other changes such as pH, temperature, and pressure. The “state change” refers to a change in the state of the processing liquid or the recording liquid that results when an external factor acts on the processing liquid or the recording liquid. Examples of the state change include a pH change, a solubility change, a temperature change, a pressure change, and the like. Further, "without substantial mixing" refers to a state in which many of the fine particles in the processing liquid and the coloring material in the recording liquid do not mix with each other (including a state where some mixing is performed at a liquid boundary or the like). Such a state in which the fine particles in the processing liquid and many of the coloring materials in the recording liquid are not mixed with each other, for example, when observing the cross section of the printed matter, the fine particles in the processing liquid and the coloring material in the recording liquid form separate layers. Observed as if you were.
[0054]
In the image formation according to the present invention, for example, the processing liquid and the recording liquid are separately jetted as droplets onto a recording medium by an ink jet method, and the respective droplets are brought into contact (external factor: action due to contact of a substance). Then, a state change (a change in pH and a change in solubility) is caused by ion migration, salting out, and the like, so that the fine particles in the processing liquid and the coloring material in the recording liquid are aggregated without being substantially mixed. be able to. Alternatively, ultraviolet rays are radiated to droplets (for example, a recording liquid) ejected on a recording medium to generate an acid from a photoacid generator to cause a state change (pH change), thereby causing a change in the processing liquid. This can be performed so that the fine particles and the coloring material in the recording liquid aggregate without substantially mixing.
[0055]
Hereinafter, first, as an external factor, a case where a substance comes into contact with a treatment liquid and a recording liquid to act and a pH changes as a state change will be described with reference to a schematic diagram 1. The order of landing of the liquid droplets (the processing liquid and the recording liquid) ejected on the recording medium may be any order. Hereinafter, the case where the processing liquid lands first will be described.
Further, as described later, it is preferable to add an acid or a base as a pH adjuster in order to stabilize the dispersion of the fine particles contained in the treatment liquid. Here, the case where an acid is added will be described. Similarly, in the case of a recording liquid, it is preferable to add a base or an acid as a pH adjuster in order to stabilize the dispersion of the coloring material contained therein. However, the case where a base is added will be described here.
[0056]
Under the above conditions, the processing liquid first lands on the recording medium, and then the recording liquid lands on the processing liquid, so that the two liquids come into contact with each other. Next, near the interface where the processing liquid and the recording liquid are in contact with each other, the acid and the fine particles as the pH adjuster diffuse from the processing liquid into the recording liquid by a concentration gradient, and the base as the pH adjuster is diffused from the recording liquid. And the coloring material are diffused into the processing liquid by a concentration gradient.
In this way, first, in the vicinity of the interface, a pH change is caused by the acid and the base, and the system of the processing liquid and the recording liquid is neutralized, so that both the fine particles in the processing liquid and the coloring material in the recording liquid are removed. The dispersed or dissolved state is destroyed. When the dispersed or dissolved state is destroyed, a single aggregate of fine particles or a color material or a mixed aggregate of fine particles and a color material is formed near the interface.
[0057]
Looking at the above phenomenon more microscopically, in the processing liquid near the interface, the base penetrating from the recording liquid neutralizes the cation species (for example, protons) on the surface of the fine particles, lowers the surface charge, and causes Steal repulsion and destroy dispersion. As a result, the fine particles are aggregated with each other, and a layer substantially formed of the fine particles is generated. In addition, the cationic species on the surface of the fine particles means that the surface of the fine particles is directly covered with an ionic species such as proton, the fine particles themselves have a cationic group, or the surface of the fine particles is directly covered with a compound having a cationic group. Or indirectly (with a dispersant, a surfactant or the like). In addition, the substantially fine particle layer referred to herein means a layer formed mostly of fine particles, and includes a case in which a trace amount of a coloring material or another component is mixed.
[0058]
On the other hand, when the acid entering from the processing solution is adsorbed on the coloring material, it neutralizes the anionic groups of the coloring material, lowers the surface charge, deprives the coloring materials of repulsion, and destroys the dispersion. As a result, the color materials are aggregated with each other, and a layer substantially formed of the color material is generated. Note that the anionic group of the coloring material refers to a case where the coloring material surface is directly covered with a compound having an anionic group or indirectly (with a dispersant, a surfactant, or the like). In addition, the substantial color material layer referred to herein means a layer which is mostly formed of the color material as described above, and includes a case where a minute amount of fine particles or other constituent components are mixed. The concept of these image forming processes is as shown in the schematic diagram of FIG.
The image forming step includes a step of bringing the processing liquid into contact with the recording liquid, a step of causing a pH change between the processing liquid and the recording liquid by the contact, and a step of causing the pH of the processing liquid to change by the pH change. And a process of causing the color materials in the recording liquid to aggregate due to the pH change.
[0059]
Next, as an external factor, a case will be described with reference to FIG. 2 in which a substance contacts and acts (a treatment liquid and a recording liquid come into contact with each other) to cause a change in pH and a change in solubility due to salting out as a state change. Note that a case will be described in which the processing liquid contains a salt (NaCl) in addition to the fine particles, and the recording liquid contains a base as a pH adjuster for stabilizing the dispersion of the contained coloring material. Either of the droplets (the processing liquid and the recording liquid) ejected on the recording medium may land in any order. Hereinafter, the case where the processing liquid lands first will be described.
[0060]
Under the above conditions, the processing liquid first lands on the recording medium, and then the recording liquid lands on the processing liquid, so that the two liquids come into contact with each other. Next, near the interface where the processing liquid and the recording liquid contact each other, salts (NaCl) and fine particles are diffused from the processing liquid into the recording liquid by a concentration gradient. The material diffuses into the processing solution due to the concentration gradient. In this way, an aggregate layer is first formed near the interface.
Ions and salts (NaCl) further move through the aggregation layer, and a sudden dispersion destruction occurs on the recording liquid side due to a change in ion concentration, and aggregation is promoted due to a decrease in solubility due to salting out. On the other hand, on the processing liquid side, the flocculation proceeds due to rapid dispersion destruction due to the pH change. As a result, the fine particles in the processing liquid and the coloring material in the recording liquid aggregate without being substantially mixed. The concept of the image forming process is as shown in the schematic diagram of FIG.
[0061]
Further, a case where a state change is caused by a non-contact external factor due to ultraviolet irradiation will be described with reference to FIG.
Note that the recording liquid contains a photoacid generator that generates an acid upon irradiation with ultraviolet light. Although the treatment liquid may contain either an acid or a base, FIG. 3 shows a case where an acid is contained.
First, when the recording liquid lands and is irradiated with ultraviolet rays, the irradiation of the ultraviolet rays generates an acid. As a result, the pH of the recording liquid changes, causing rapid dispersion and destruction, and the coloring material aggregates. Next, when the treatment liquid lands, the fine particles (eg, silica) start to be aggregated near the interface, and subsequently the concentration changes due to the penetration of moisture, causing rapid dispersion and destruction, and the fine particles are aggregated. When the processing liquid contains a base, dispersion destruction occurs due to a pH change due to ion movement of both the recording liquid and the processing liquid, and the aggregation of fine particles is promoted. The concept of the image forming process is as shown in the schematic diagram of FIG.
[0062]
As described above, in the initial stage in which the treatment liquid and the recording liquid constituting the ink set of the present invention come into contact with each other, an aggregate layer is formed in the vicinity of the interface between the two. When this layer is formed, most of the coloring material and fine particles in each droplet cannot move through the formed layer, and the coloring material and the recording liquid substantially aggregate without being mixed. Thus, an aggregated layer formed of a color material and an aggregated layer substantially formed of fine particles are formed.
For example, the acid in the treatment liquid and the base in the recording liquid can easily pass through the gap between the layers of the aggregates due to their small size, and quickly diffuse through the aggregate layer. The diffusion of these ions also neutralizes the remaining fine particles and the coloring material and lowers the surface potential, so that the dispersed state or the dissolved state is destroyed, and all the fine particles and the coloring material aggregate. Since these aggregation processes are instantaneously completed by the diffusion of ions, in the image forming method of the present invention, the aggregation of the entire system is completed before the coloring material flows.
[0063]
According to such an image forming method of the present invention, feathering and color bleeding can be prevented. Further, since the coloring material does not sink into the recording medium, the density is high, and since the paper fibers are not exposed on the surface, a high-colored printed matter can be obtained.
Further, according to the image forming method of the present invention, since the color material can be formed on the initial aggregation layer, the color material can be completely put on the surface of the recording medium. Therefore, the image density is high and the saturation can be high. In addition, not only the initial aggregate layer but also the color material on it can be surely aggregated without flowing laterally, so that a thick color material layer can be obtained. For this reason, the paper fiber is completely covered, and a smooth color material layer is obtained on the printed matter surface, so that a high glossiness can be obtained.
[0064]
Furthermore, according to the image forming method of the present invention, even when printing is performed on a non-absorbing recording medium in which the vehicle is not absorbed, the color material is formed on one side (for example, the upper side) of the initially formed aggregation layer. Is instantaneously formed on the other side (for example, on the lower side), and a strong film is formed, resulting in a clear image.
In the image forming method of the present invention, a state change due to an external factor (pH change due to movement of ions, solubility decrease due to movement of salt (salting out), ion generation / pH change due to ultraviolet irradiation (non-contact), etc.) As a result, the fine particles of the entire system and the coloring material are instantaneously aggregated, so that a clear image without feathering or color bleed can be obtained even on a non-absorbing recording medium. In particular, in the case of a non-absorbent recording medium having unevenness, in the related art, the landed ink flows into the concave portion, so that when trying to draw a fine line, the landing position is out of order and the line tends to be jagged, but the image of the present invention According to the forming method, since the speed until all the coloring materials and the fine particles are aggregated is high, even in the case of a fine line, it does not have a jagged line and has excellent drawing properties. FIGS. 4 and 5 show the conventional method for printing fine lines on a smooth non-absorbent recording medium or the method for printing fine lines on a non-absorbing recording medium having irregularities, respectively. The difference (line width) or (jagged state) is conceptually shown.
[0065]
Next, the processing liquid and the recording liquid constituting the ink set of the present invention will be described in detail. However, the present invention is not limited by the following description.
First, the definition of an anionic or cationic recording liquid and a cationic or anionic processing liquid in the present invention will be described.
When the ionic characteristics of the recording liquid or the processing liquid are viewed as a whole, each of the recording liquid and the processing liquid itself has a neutral charge.
For example, the anionic or cationic recording liquid referred to in the present invention refers to a component in the recording liquid, that is, one in which the colorant itself has an anionic group or a cationic group, or the surface of the colorant has an anionic or cationic group. Directly coated with a compound having a cationic group, or indirectly coated with a compound having a cationic group (for example, with a dispersant or a surfactant), and in a recording liquid, It refers to a recording liquid in which these groups are adjusted to behave as an anionic group or a cationic group. Similarly, the meaning of the anionic or cationic treatment liquid of the treatment liquid is the same as described above.
Hereinafter, the processing liquid and the recording liquid of the present invention will be described.
[0066]
<Treatment liquid>
When the fine particles included in the processing liquid and the coloring material contained in the recording liquid that can be used in the present invention are anionic or cationic, the polarities thereof are preferably opposite to each other. Therefore, fine particles used according to the polarity of the coloring material include cationic fine particles and anionic fine particles.
Here, the cationic fine particles refer to particles having a positive zeta potential. The surface property of the fine particle dispersion system is discussed by an electric double layer generated at the interface between the dispersoid and the dispersion medium, and is actually replaced by zeta potential obtained from electrophoretic mobility or the like. The value of the zeta potential is determined by the value of H existing at the interface.⁺It is largely governed by the concentration of ions, and thus the surface properties of the fine particles are greatly affected by the pH of the processing solution. On the other hand, the anionic fine particles have a negative zeta potential. The value of the zeta potential depends on the OH present at the interface.⁻It is largely governed by the concentration of ions, and thus the surface properties of the fine particles are greatly affected by the pH of the processing solution.
[0067]
The zeta potential of the fine particles that can be used in the image forming method of the present invention is preferably from +5 to +90 mV when cationic. Within this range, there is no feathering and no color bleed, and an image with rich gloss and excellent reproducibility of fine lines can be obtained. In the case of an anionic property, it is preferably from -5 to -90 mV. In this range, an image excellent in glossiness and excellent in reproducibility of fine lines can be obtained without feathering and color bleed similarly to the above.
The pH of the treatment liquid is determined so as to ensure the dispersion stability of the fine particles. It should also be noted that the components that the processing liquid contacts do not corrode.
The fine particles that can be suitably used in the image forming method of the present invention are not particularly limited in material type, and may be organic fine particles, inorganic fine particles, or organic / inorganic composite fine particles. You may. The shape of the particles is not particularly limited, and may be spherical, beaded, or amorphous.
[0068]
Examples of the organic fine particles include polystyrene, styrene-acryl copolymer, polymethyl methacrylate, melamine resin, epoxy resin, silicone resin, benzoguanamine resin, polyamide resin, fluorine-based resin, and α, β-unsaturated ethylenic monomer. Examples include polymers obtained by emulsion polymerization and the like.
[0069]
Examples of the inorganic fine particles include inorganic salts such as calcium carbonate and silica (SiO 2).₂) And the like.
Specific examples of the inorganic salt include, but are not limited to, calcium carbonate, calcium nitrate, calcium chloride, calcium sulfate, aluminum nitrate, aluminum chloride, aluminum sulfate, and iron sulfate.
As the inorganic fine particles for use in the aqueous treatment liquid, it is preferable to use those having low solubility in water, such as calcium carbonate, calcium nitrate, and iron sulfate, because a dispersion can be easily obtained. Further, these can be further preferably subjected to a cationization treatment, because the adsorption ability and the aggregation ability of the fine particles can be further increased. Such a method of modifying with a cationic agent can be carried out by a conventionally known technique (for example, JP-A-10-129113, JP-A-11-20301, etc.).
[0070]
Specific examples of the inorganic fine particles include cationized silica (SiO 2).₂), Alumina (Al₂O₃), Alumina hydrate, titania, zirconia, boria, silica boria, ceria, magnesia, silica magnesia, calcium carbonate, magnesium carbonate, zinc oxide, hydrotalcite and the like.
Examples of the organic fine particles include styrene acrylic and acrylate copolymers, methacrylate ester copolymers, conjugated diene copolymers such as SBR latex, and vinyl copolymers such as ethylene vinyl acetate copolymer. Examples include, but are not limited to, cationic emulsions and latexes, and cation modified products such as melamine beads and plastic pigments.
[0071]
Among the inorganic fine particles, cationic silica is particularly preferable in terms of reactivity (rapid cohesion based on a change in pH of the treatment liquid). As the cationic silica, any silica can be used as long as the surface of the silica has been subjected to a cationization treatment.
In order to cationize the surface of silica, a cationic compound may be chemically or physically introduced into the silica surface in a direct or indirect form. For example, a chemical surface treatment can be performed by a method of coupling an amino compound to a silanol group of silica or a method of reacting an aluminum compound. Alternatively, silica and a cationic compound may be mixed in a solvent, and the cationic compound may be physically adsorbed, and then the solvent may be removed to physically perform surface treatment (coating).
[0072]
When the cationic compound is physically adsorbed on the silica surface, specific examples of the anionic silica used as a core material thereof include ST-ZL, ST-20, ST-30, ST-40, ST-C, ST-N, ST-O, ST-S, ST-50, ST-20L, ST-OL, ST-XS, ST-YL, ST-XL, ST-UP, ST-OUP (Nissan Chemical) , Cataloid SI-350, SI-500 (manufactured by DuPont), Nipgel AY-220, AY-420, AY-460 (manufactured by Nippon Silica) and the like.
The above is an example, and the present invention is not limited to these methods, and any method can be suitably used as long as the silica surface is treated to be cationic.
[0073]
The inorganic fine particles can also be obtained as a product. Examples of the cationized product of silica include ST-AK (manufactured by Nissan Chemical Industries, Ltd.). Examples of the alumina include alumina sols 100, 200, and 520 (all manufactured by Nissan Chemical Industries, Ltd.). Examples of the titanium dioxide include a titania series (made by Idemitsu Kosan). Some of these fine particles are already available in an adjusted form as an aqueous dispersion.
[0074]
As described above, the fine particles of the present invention may be cationic inorganic / organic composite fine particles, and any particulate cationic inorganic / organic composite fine particles can be used.
The cationic inorganic / organic composite fine particles can be obtained by adsorbing a cationic organic compound on the surface of the inorganic fine particles, or conversely, adsorbing a cationic inorganic compound on the surface of the organic compound.
For example, inorganic / organic composite fine particles coated with a cationic polymer, inorganic fine particles were dispersed in a solvent such as water, and the cationic polymer was dissolved in water or a water-soluble organic solvent in this dispersion. It can be obtained by gradually adding the solution.
[0075]
Specific examples of the cationic polymer include polyallylamine, polyvinylamine, polyimine, polyvinylpyrrolidone, polyethyleneimine, polyvinylpyridine, aminoacetalized polyvinyl alcohol, ionene polymer, polyvinylimidazole, polyvinylbenzylphosphonium, polyalkylallylammonium, Examples include polymers such as polyamidine, polyamine sulfone, and cationic starch.
In addition, a single particle having low dispersion stability and a compound exhibiting cationic or anionic properties can be used alone.
[0076]
Further, specific examples of the cationic compound include polyallylamine, polyamine sulfone, polyvinylamine, chitosan and a neutralized product or a partially neutralized product thereof with an acid such as hydrochloric acid or acetic acid, and a part of a polymer nonionic compound. Cationized compounds, such as copolymers of vinylpyrrolidone and quaternary salts of aminoalkyl alkylates, copolymers of acrylamide and quaternary salts of aminomethylacrylamide, and other primary, secondary and tertiary amines One or two or more selected from salt-type compounds and amino acid-type amphoteric compounds can be used.
Specific examples of the anionic compound include polyvinyl alcohol and polyvinyl carbazole.
[0077]
Further, a resin component may be added to the treatment liquid in order to improve the abrasion resistance of the printed matter. The resin can be used in combination within a range that does not impair the storage stability and the ejection stability of the treatment liquid. For example, the resin can be freely selected from water-soluble polymers, emulsions, latex, and the like.
The addition amount of the fine particles in the treatment liquid of the present invention is preferably at least 10 wt% based on the total amount of the treatment liquid, and more preferably at least 15 wt% from the viewpoint of improving the glossiness. If the content is less than 10 wt%, the effect of improving image quality cannot be sufficiently obtained. As the fine particles to be added, plural kinds of fine particles may be used in combination.
[0078]
The treatment liquid of the present invention preferably contains a water-soluble organic solvent for the purpose of preventing nozzles of the recording head from being clogged by drying. Such water-soluble organic solvents include wetting agents and penetrants.
Specific examples of the wetting agent include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,3-butanediol, 1,3-propanediol, and 2-methyl-1,3-propane. Diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, 1,2 Polyhydric alcohols such as 1,4-butanetriol, 1,2,3-butanetriol, petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl Polyhydric alcohol alkyl ethers such as glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether Forehead; nitrogen-containing heterocyclic compounds such as N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam; formamide, N-methylformamide; Amides such as formamide and N, N-dimethylformamide; monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethyl Examples thereof include amines such as ruamine, sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, and thiodiethanol, propylene carbonate, ethylene carbonate, and γ-butyrolactone. These solvents can be used alone or in combination of two or more with water.
[0079]
The penetrant is added for the purpose of improving the wettability between the treatment liquid and the recording medium and adjusting the penetration speed. As the penetrant, those represented by the following formulas (I) to (IV) are preferable. That is, a polyoxyethylene alkyl phenyl ether surfactant of the following formula (I), an acetylene glycol surfactant of the following formula (II), a polyoxyethylene alkyl ether surfactant of the following formula (III) and the following formula The polyoxyethylene polyoxypropylene alkyl ether-based surfactant (IV) can reduce the surface tension of the liquid, so that the wettability can be improved and the penetration rate can be increased.
[0080]
Embedded image

[0081]
(In the formula, R represents an optionally branched hydrocarbon chain having 6 to 14 carbon atoms, k: 5 to 20.)
[0082]
Embedded image

[0083]
(In the formula, m and n are m and n ≦ 20, and m + n is in the range of 0 <m + n ≦ 40.)
[0084]
Embedded image

[0085]
(In the formula, R represents a hydrocarbon chain having 6 to 14 carbon atoms which may be branched, and n is in a range of 5 to 20.)
[0086]
Embedded image

[0087]
(In the formula, R represents a hydrocarbon chain having 6 to 14 carbon atoms, and m and n are each a number of 20 or less.)
[0088]
Other than the compounds of the formulas (I) to (IV), for example, diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetraethylene glycol chlorophenyl Use of alkyl and aryl ethers of polyhydric alcohols such as ethers, nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymers, fluorine surfactants, and lower alcohols such as ethanol and 2-propanol. However, diethylene glycol monobutyl ether is particularly preferred.
[0089]
The average particle diameter of the fine particles is preferably 1000 nm or less, and more preferably 500 nm or less from the viewpoint of ejection stability. That is, if the average particle diameter is larger than 1000 nm, clogging of the discharge head is likely to occur, and discharge failure is likely to occur. The average particle size can be measured with an optical particle size distribution meter, and is represented by a particle size of 50% of the number of particles.
[0090]
The fine particles are dispersed in a vehicle containing water as a main component to form a treatment liquid. When dispersing, it is preferable to use a deflocculant in order to stabilize the dispersion. The deflocculant forms an electric double layer on the surface of the chargeable particles, and the electric double layer electrostatically repels to prevent the particles from approaching and to stabilize the dispersion. Since the fine particles are positively charged from neutral to acidic, anionic sources of acetic acid, nitric acid, hydrochloric acid, formic acid, lactic acid, and alkali metal salts thereof, zirconium compounds such as zirconium oxychloride hydrate, sodium pyrophosphate , Sodium hexametaphosphate, taurine and the like are used as peptizers, but the present invention is not limited to these.
[0091]
The treatment liquid of the present invention can be produced by the following method. Basically, a dispersion is prepared by mixing fine particles, water and a deflocculant. If necessary, a water-soluble solvent is added, and the mixture is peptized by a peptizer. In this case, examples of the peptizer used include a high-speed rotating high-shear stirring peptizer, a dissolver, a colloid mill, a homogenizer, an ultrasonic peptizer and the like. K. Auto homomixer, T.I. K. Homomic line flow, ultra homomixer, NNK colloid mill and the like can be mentioned. The number of revolutions during peptization varies depending on the type and structure of the peptizer, but is preferably 500 to 10000 rpm, and more preferably 2000 to 8000 rpm. The temperature at the time of peptization is preferably 5 to 100 ° C. The peptizing time varies depending on the type and structure of the peptizer, but is preferably 0.01 to 48 hours.
[0092]
The treatment liquid of the present invention can contain a cationic surfactant such as a quaternary ammonium salt, a pyridinium salt, and an imidazoline compound. Specific examples include lauryltrimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltributylammonium chloride, benzalkonium chloride, cetylpyridinium chloride, 2-heptadecenylhydroxyethylimidazoline and the like.
For example, the cationic surfactant has a function of lowering the surface tension and increasing the wettability with the recording medium to quickly form the fine particle layer, and has an action of aggregating the anionic colorant, which is effective in improving the image quality. .
[0093]
The surface tension of the treatment liquid of the present invention is preferably 20 to 60 mN / m, and from the viewpoint of achieving both wettability with the recording medium and dropletization of droplets, it is preferably 30 to 50 mN / m. More preferred.
The viscosity of the treatment liquid of the present invention is preferably from 1.0 to 20.0 cP, and more preferably from 3.0 to 10.0 cP from the viewpoint of ejection stability.
Further, the pH of the treatment liquid of the present invention is preferably 3 to 11, and more preferably 3 to 6, and 8 to 11 from the viewpoint of dispersion stability of the fine particles.
[0094]
<Recording liquid>
Next, the recording liquid used in the ink set of the present invention will be described.
As the coloring material used in the recording liquid of the present invention, a dye, a pigment, or a mixture of a dye and a pigment can be used. When the fine particles contained in one of the treatment liquids of the ink set are cationic, the use of a recording liquid containing an anionic coloring material having a polarity opposite to that of the fine particles is electrically neutralized. Aggregation is preferred from the viewpoint of improving image quality. When the fine particles are anionic, it is naturally preferable that the coloring material is cationic.
As a coloring material, it is more preferable to use a pigment than a dye. That is, the pigment in the dispersion state is more efficiently aggregated when the charge is neutralized than the dye in the dissolved state, so that the effect of improving the image quality is higher.
[0095]
The pigment used in the recording liquid used in the present invention is not particularly limited. For example, the following pigments are preferably used.
Examples of the carbon black used in the black pigment ink (recording liquid) include a carbon black manufactured by a furnace method and a channel method. These have a primary particle size of 15 to 40 millimicrons, a BET specific surface area of 50 to 300 square meters / g, a DBP oil absorption of 40 to 150 ml / 100 g, a volatile content of 0.5 to 10%, and a pH of 2 Those having from 9 to 9 are preferred.
[0096]
As such a specific example, for example, 2300, no. 900, MCF88, No. 40, no. 52, MA7, MA8, No. 2200B (manufactured by Mitsubishi Kasei), RAVEN1255 (manufactured by Columbia), REGAL400R, REGAL660R, MOGUL L (manufactured by Cabot), Color Black FW1, Color Black FW18, Color Black S170, Color Black ex S, P As described above, commercially available products such as Degussa) can be used. Further, a resin-coated pigment newly produced for the present invention may be used.
Further, as the color pigment used as the coloring material contained in the recording liquid of the present invention, either an organic pigment or an inorganic pigment may be used. Specific examples are described below.
[0097]
Examples of the organic pigment include azo, phthalocyanine, anthraquinone, quinacridone, dioxazine, indigo, thioindigo, perylene, isoindolenone, aniline black, azomethine, rhodamine B lake pigment, carbon black, and the like. Can be Examples of the inorganic pigment include iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, dark blue, cadmium red, chrome yellow, and metal powder.
The pigment in the present invention may be used together with a pigment dispersant, and the use of the pigment dispersant has an effect of improving dispersion stability.
[0098]
As the anionic pigment dispersant, any water-soluble resin (having an anionic group) having a function of stably dispersing the pigment in water or an aqueous medium can be used. In particular, those having a weight average molecular weight in the range of 1,000 to 30,000 are preferred. Further, it is preferably in the range of 3,000 to 15,000.
Specifically, for example, hydrophobic monomers such as styrene, styrene derivatives, vinyl naphthalene, vinyl naphthalene derivatives, aliphatic alcohol esters of α, β-ethylenically unsaturated carboxylic acids, or acrylic acid, acrylic acid derivatives, maleic acid Acid, maleic acid derivative, itaconic acid, itaconic acid derivative, fumaric acid, block copolymer, graft copolymer or random copolymer composed of two or more monomers selected from fumaric acid derivatives, or salts thereof And the like.
[0099]
These resins are alkali-soluble resins that are soluble in an aqueous solution in which a base is dissolved. Further, a homopolymer composed of a hydrophilic monomer or a salt thereof may be used. It is also possible to use water-soluble resins such as polyvinyl alcohol, carboxymethylcellulose, and naphthalenesulfonic acid formaldehyde condensate. However, when an alkali-soluble resin is used, there is an advantage that the viscosity of the dispersion can be reduced and the dispersion is easy. The water-soluble resin is preferably used in the range of 0.1 to 5% by weight based on the total amount of the ink (recording liquid).
[0100]
As the cationic pigment dispersant, a polymer obtained by polymerizing a cationic monomer described below can be suitably used. The molecular weight of these polymers is preferably 2000 or more. The cationic monomer used in the present invention is a quaternized compound of the monomers exemplified below. The following monomers can be quaternized by a conventional method using methyl chloride, dimethyl sulfate, benzyl chloride, epichlorohydrin, or the like.
As the monomer, N, N-dimethylaminoethyl methacrylate: [CH₂= C (CH₃) -CONH-CH₂CH₂N (CH₃)₂], N, N-dimethylaminoethyl acrylate: [CH₂= CH-CONH-CH₂CH₂N (CH₃)₂], N, N-dimethylaminoacrylamide: [CH₂= CH-CON (CH₃)₂], N, N-dimethylaminomethacrylamide: [CH₂= C (CH₃) -CON (CH₃)₂], N, N-dimethylaminopropylacrylamide: [CH₂= CH-CONH-C₃H₆N (CH₃)₂], N, N-dimethylaminopropyl methacrylamide: [CH₂= C (CH₃) -CONH-C₃H₆N (CH₃)₂And the like.
[0101]
The water-soluble resin as a pigment dispersant of the present invention may use a hydrophobic monomer as a component in the resin in order to improve the affinity according to the properties of the pigment, and in this case, as the hydrophobic monomer, for example, Examples include styrenes such as styrene, α-methylstyrene, and vinyl toluene, and alkyl (meth) acrylates.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-methylbutyl (meth) acrylate, tert-butylmethyl (meth) acrylate, 2-methylbutyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, 3-methylbutyl (meth) acrylate, 1,3-dimethylbutyl (meth) acrylate, pentyl (meth) acrylate, 3 -Pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, 2-eth Ciethyl acrylate, 3-ethoxypropyl acrylate, 2-ethoxybutyl acrylate, 3-ethoxybutyl acrylate, 3-ethoxybutyl acrylate, dimethylaminoethyl acrylate, alcohol components used for half-esterification include methanol, ethanol, propanol, Examples of the optionally used monomer include (meth) acrylamide, 1-methylol (meth) acrylamide, and diacetone acrylamide. Note that a self-dispersible pigment that can be stably dispersed without using a pigment dispersant may be used.
[0102]
The anionic self-dispersion pigment is a pigment in which at least one kind of anionic hydrophilic group is bonded to the pigment surface directly or via another atomic group. Examples of the anionic hydrophilic group include, for example, at least one selected from the following hydrophilic groups, and further another atomic group is an alkyl group having 1 to 12 carbon atoms, a substituent. And a naphthyl group optionally having a substituent.
-COOM, -SO₃M, -SO₂NH₂, -PO₃HM, -PO₃M₂
Here, M in the hydrophilic group represents any one of a hydrogen atom, an alkali metal, and ammonium.
[0103]
The carbon black charged anionically by introducing a hydrophilic group as described above into the surface of the carbon black has excellent water dispersibility based on the repulsion of ions (anions). A stable dispersion state can be maintained without adding a dispersant or the like.
[0104]
Further, the cationic self-dispersion type pigment has at least one cationic hydrophilic group bonded directly or via another atomic group to the pigment surface.
In the case of cationically charged carbon black, examples of the hydrophilic group bonded directly or via another atomic group include those bonded with at least one selected from the following quaternary ammonium groups. However, the present invention is not limited to these.
[0105]
Embedded image

[0106]
(In the formula, R represents a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group.)
[0107]
As the counter ion of the cationic group, for example, NO₃ ⁻And CH₃COO⁻Exists.
In order to obtain a cationically charged self-dispersible carbon black in which a hydrophilic group is bonded as described above, for example, when an N-ethylpyridyl group having a structure represented by the following formula is bonded, It can be produced by a method of treating carbon black with 3-amino-N-ethylpyridinium bromide.
[0108]
Embedded image

[0109]
Since carbon black charged cationically by the introduction of a hydrophilic group to the surface of carbon black exhibits excellent water dispersibility due to repulsion of ions, even when it is contained in an aqueous ink, a dispersant or the like is used. And maintain a stable dispersion state.
[0110]
Next, the water-soluble dyes used in the present invention include dyes classified into acid dyes (anionic dyes), direct dyes, basic dyes (cationic dyes), reactive dyes and food dyes in the color index. Those having excellent water resistance and light resistance are used.
These dyes may be used by mixing a plurality of types, or may be used by mixing with other coloring materials such as pigments as necessary. These coloring materials as coloring agents are added within a range that does not impair the effects of the present invention. Various dyes are exemplified below.
[0111]
(A) As the acid dye,
C. I. Acid Yellow 17, 23, 42, 44, 79, 142,
C. I. 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,
C. I. Acid Blue 9, 29, 45, 92, 249,
C. I. Acid Black 1, 2, 7, 24, 26, 94, etc. can be used.
(B) As food dyes,
C. I. Food Yellow 3,4,
C. I. Food Red 7, 9, 14,
C. I. Food Black 1, 2 etc. can be used.
(C) As the direct dye,
C. I. Direct yellow 1,12,24,26,33,44,50,86,120,132,142,144,
C. I. Direct Red 1,4,9,13,17,20,28,31,39,80,81,83,89,225,227,
C. I. Direct orange 26,29,62,102,
C. I. Direct Blue 1,2,6,15,22,25,71,76,79,86,87,90,98,163,165,199,202,
C. I. Direct Black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171 and the like can be used.
(D) As the basic dye,
C. I. Basic Yellow 1,2,11,13,14,15,19,21,23,24,25,28,29,32,36,40,41,45,49,51,53,63,64,65 , 67, 70, 73, 77, 87, 91,
C. I. Basic Red 2,12,13,14,15,18,22,23,24,27,29,35,36,38,39,46,49,51,52,54,59,68,69,70 , 73, 78, 82, 102, 104, 109, 112,
C. I. Basic Blue 1,3,5,7,9,21,22,26,35,41,45,47,54,62,65,66,67,69,75,77,78,89,92,93 , 105, 117, 120, 122, 124, 129, 137, 141, 147, 155,
C. I. Basic Black 2,8 etc. can be used.
(E) As the reactive dye,
C. I. Reactive Black 3,4,7,11,12,17,
C. I. Reactive Yellow 1,5,11,13,14,20,21,22,25,40,47,51,55,65,67,
C. I. Reactive Red 1,14,17,25,26,32,37,44,46,55,60,66,74,79,96,97,
C. I. Reactive Blue 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80, 95, etc. can be used.
[0112]
It is preferable to use a water-soluble organic solvent in addition to the coloring material for the purpose of providing the recording liquid of the present invention with desired physical properties or preventing clogging of nozzles of the recording head due to drying. The water-soluble organic solvent includes a wetting agent and a penetrating agent.
The wetting agent is added for the purpose of preventing clogging of the nozzles of the recording head due to drying. Specific examples of the wetting agent include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,3-butanediol, 1,3-propanediol, and 2-methyl-1,3-propane. Diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, 1,2 Polyhydric alcohols such as 1,4-butanetriol, 1,2,3-butanetriol, petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl Polyhydric alcohol alkyl ethers such as glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether Forehead; nitrogen-containing heterocyclic compounds such as N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam; formamide, N-methylformamide; Amides such as formamide and N, N-dimethylformamide; monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethyl Examples thereof include amines such as ruamine, sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, and thiodiethanol, propylene carbonate, ethylene carbonate, and γ-butyrolactone. These solvents are used alone or in combination with water.
[0113]
The penetrant is added for the purpose of improving the wettability between the recording liquid and the recording material and adjusting the penetration speed. As the penetrant, those represented by the above (I) to (IV) are preferable. That is, the polyoxyethylene alkyl phenyl ether-based surfactant (I), the acetylene glycol-based surfactant of the formula (II), the polyoxyethylene alkyl ether-based surfactant of the formula (III), and the formula (IV) The polyoxyethylene polyoxypropylene alkyl ether-based surfactant can lower the surface tension of the liquid, so that the wettability can be improved and the penetration rate can be increased.
[0114]
Other than the compounds of the formulas (I) to (IV), for example, diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetraethylene glycol chlorophenyl Use of alkyl and aryl ethers of polyhydric alcohols such as ethers, nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymers, fluorine surfactants, and lower alcohols such as ethanol and 2-propanol. However, diethylene glycol monobutyl ether is particularly preferred.
[0115]
The surface tension of the recording liquid of the present invention is preferably 20 to 60 mN / m, and more preferably 30 to 50 mN / m from the viewpoint of achieving both wettability with the recording material and dropletization. preferable.
The viscosity of the recording liquid of the invention is preferably from 1.0 to 20.0 cP, and more preferably from 3.0 to 10.0 cP from the viewpoint of ejection stability.
The pH of the recording liquid of the present invention is preferably from 3 to 11, and more preferably from 6 to 10 from the viewpoint of preventing corrosion of the metal member in contact with the liquid.
[0116]
The treatment liquid and the recording liquid of the present invention may contain an antiseptic / antifungal agent. By containing an antiseptic / antifungal agent, the growth of bacteria can be suppressed, and storage stability and image quality stability can be enhanced.
As antiseptic / antifungal agents, benzotriazole, sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, isothiazoline compounds, sodium benzoate, sodium pentachlorophenol and the like can be used.
[0117]
Further, the treatment liquid and the recording liquid of the present invention can contain a rust preventive. By containing a rust inhibitor, a film can be formed on a metal surface that comes into contact with the liquid, such as a head, to prevent corrosion. As the rust preventive, for example, acid sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like can be used.
[0118]
Further, the processing liquid and the recording liquid of the present inventor can contain antioxidation. There are two types of antioxidants: a radical acceptor type which stabilizes the generated peroxide by giving a proton to the peroxide, and a peroxide separated type which converts hydroperoxide into a stable alcohol.
[0119]
Typical examples of the former include phenolic compounds and amine compounds. Examples of the phenolic compounds include compounds such as hydroquinone and gallate, 2,6-ditert-butyl-p-cresol, and stearyl-β-. (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert- Butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 5-trimethyl-2,4,6-tris (3,5-ditert-4-hydroxybenzyl) benzene, tris ( Hindered phenolic compounds such as 1,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and tetrakis [methylene-3 (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane. And amine compounds such as N, N′-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine, phenyl-α-naphthylamine, N, N′-β-naphthyl-p-phenylenediamine, N, N '-Diphenylethylenediamine, phenothiazine, N, N'-disec-butyl-p-phenylenediamine, 4,4'-tetramethyl-diaminodiphenylmethane and the like are exemplified.
As the latter, sulfur-based compounds and phosphorus-based compounds are typical, and as the sulfur-based compound, dilaurylthiodipropionate, distearylthiodipropionate, laurylstearylthiodipropionate, Examples include myristyl thiodipropionate, disterial β, β′-thiodibutyrate, 2-mercaptobenzimidazole, dilauryl sulfide, and the like. Phosphorus compounds include triphenyl phosphite, trioctadecyl phosphite, and tridecyl phosphite. Phyto, trilauryl trithiophosphite, diphenylisodecyl phosphite, trinonylphenyl phosphite, distearyl pentaerythritol phosphite and the like are exemplified.
[0120]
As described above, the processing liquid and the recording liquid of the present invention can contain a pH adjuster. Examples of the pH adjuster include hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, lithium carbonate, Alkali metal carbonates such as sodium carbonate and potassium carbonate, amines such as diethanolamine and triethanolamine, boric acid, hydrochloric acid, nitric acid, sulfuric acid, acetic acid and the like can be used.
As described above, a latent acid (or a base) such as a photoacid generator (or a photobase derivative) that generates an acid (or a base) by ultraviolet irradiation can be used.
[0121]
Next, an image forming apparatus that performs image recording by the ink set and the image forming method of the present invention will be described with reference to the drawings.
FIG. 6 is a perspective view showing a schematic configuration of an image forming apparatus as an example of the present invention. In FIG. 6, each cartridge 20 in which the processing liquid and the recording liquid are individually stored is stored in a carriage 18. That is, the cartridges 20 separately prepared for the processing liquid or the recording liquid for each color are mounted in a state where the respective liquids are separated. In such a state, the processing liquid and the recording liquid are supplied from the cartridge 20 to the recording head 18a mounted on the carriage 18. In FIG. 6, the surface of the recording head 18a faces downward, and the head surface cannot be seen.
The recording head 18a mounted on the carriage 18 moves while being guided by guide shafts 21 and 22 by a timing belt 23 driven by a main scanning motor 24. On the other hand, the recording material is placed at a position facing the recording head 18a by the platen 19. In the drawing, 16 indicates a gear mechanism, 17 indicates a sub-scanning motor, and 26 indicates a main scanning motor.
[0122]
FIG. 7 is a perspective view illustrating a schematic configuration of an image forming apparatus provided with an ultraviolet irradiation unit (high-pressure mercury lamp) as another example of the present invention.
The basic configuration is the same as that described with reference to FIG. 6, but a high-pressure mercury lamp 27 is provided as an ultraviolet irradiation unit.
That is, the recording head 18a mounted on the carriage 18 moves while being guided by the guide shafts 21 and 22 by the timing belt 23 driven by the main scanning motor 24 as in FIG. At this time, the printing surface is irradiated with ultraviolet rays by the high-pressure mercury lamp 27 installed above the carriage. Immediately after the recording liquid lands on the recording medium, the recording liquid is irradiated with ultraviolet rays to cause a photoreaction. A state change is caused by an external factor acting in a non-contact manner. On the other hand, the recording material is placed at a position facing the recording head 18a by the platen 19. In FIG. 7, 16 indicates a gear mechanism, 17 indicates a sub-scanning motor, and 26 indicates a main scanning motor.
[0123]
FIG. 8 is a schematic diagram in which the nozzle surface of the recording head 18a in FIGS. 6 and 7 is enlarged.
For example, a nozzle 31 from which the processing liquid is discharged is provided in a vertical direction, and from the nozzles 32, 33, 34, and 35, for example, a yellow recording liquid, a magenta recording liquid, a cyan recording liquid, Then, the black recording liquid is respectively discharged.
[0124]
Further, like a recording head of another form as shown in FIG. 9, all the nozzles can be arranged in the horizontal direction. For example, in FIG. 9, the nozzles 36 and 41 are discharge nozzles of the processing liquid, and the nozzles 37, 38, 39, and 40 output, for example, yellow recording liquid, magenta recording liquid, cyan The recording liquid and the black recording liquid are respectively discharged. In the recording head 18a of such an embodiment, the discharge nozzles of the processing liquid are provided at the left and right ends, so that the recording head mounted on the carriage 18 reciprocates while being guided by the guide shafts 21 and 22, and returns. In any case, printing is possible. In other words, in both the forward path and the return path, the processing liquid can be first applied to the recording medium and the color recording liquid can be applied from above, or vice versa. It is possible to prevent an image density difference from occurring due to the difference.
[0125]
In the image forming apparatus of the present invention, the replenishment of the processing liquid and the recording liquid can be replaced for each cartridge, but this cartridge may be integrated with the recording head 18a. FIG. 10 is an external perspective view showing a schematic configuration of a cartridge capable of storing the processing liquid or the recording liquid of the present invention, and FIG. 11 is a front sectional view showing a schematic internal configuration of the cartridge. The cartridge having the configuration shown in FIGS. 10 and 11 can commonly store both the processing liquid and the recording liquid.
As shown in FIGS. 10 and 11, the cartridge 20 houses a liquid absorber 42 in which a required recording liquid or processing liquid is absorbed in a cartridge housing 49. The liquid absorber 42 is made of a porous material and absorbs a recording liquid or a processing liquid. In the cartridge housing 49, an upper lid member 44 is formed at an upper opening of a case 43 having a wide opening at an upper portion. A indicates a space. Further, the upper cover member 44 is provided with an atmosphere opening port 47 and a cartridge attaching / detaching projection 81. Reference numeral 55 denotes a seal member for the air release port 47. A liquid supply port 45 for supplying each liquid to the recording head 18a is formed at the bottom of the case 43 of the cartridge housing 49, and a sealing 46 is fitted around the inside of the liquid supply port 45. I have. The cartridge housing 49 is provided with a cap member 53 for closing the liquid supply port 45 in order to prevent leakage of the liquid before the cartridge is loaded into the image forming apparatus.
[0126]
As described above, in the present invention, it is most preferable that the recording liquid and the processing liquid are ejected (discharged) by the respective recording heads 18a by the so-called ink jet recording method so that the respective droplets are superimposed on the same location. However, the application of the present invention is not limited to the range in which the respective droplets are overlapped on the same location. For example, the present invention is also applicable to a case where the processing liquid is applied by thinning out, and the recording liquid is superimposed on the processing liquid enlarged by bleeding or the like, or the processing liquid is applied only to the outline of the image and a part of the recording liquid is superimposed. Included in the range.
[0127]
The ink set and image forming method of the present invention, and the cross-sectional morphology of the recorded matter of the present invention formed using the image forming apparatus, the recorded matter is cut into thin pieces by a sharp cutting means such as a microtome, and transmission electron It can be confirmed by observation (TEM photograph) by analysis with a microscope (Transmission Electron Microscope: TEM). In addition, observation can be performed by using a scanning electron microscope (SEM) instead of a transmission electron microscope (TEM).
When the recorded matter according to the present invention is measured with a transmission electron microscope (TEM), a light and shade stripe pattern is observed in the cross-sectional form of the recorded matter. The light and shade portions are further quantified using an elemental analyzer such as an energy dispersive X-ray Fluorescence Spectrometer (EDX) or an electron probe microanalyzer (Electron Probe Microanalyzer: EPMA). It is specified that the layer mainly includes fine particles (a layer substantially formed of fine particles) and the layer mainly includes a color material (a layer substantially formed of a color material). it can.
[0128]
That is, the fine particles in the layer substantially formed of fine particles or the color material in the layer substantially formed of color material can be quantitatively known by using the above-described analyzer. For example, when an energy dispersive X-ray fluorescence spectrometer (EDX) is used, a peak of each constituent element is observed in the spectrum of the recorded matter. This peak height is proportional to the abundance of the element, and the abundance of each element can be accurately known by preparing a calibration curve. The term “substantially” as used herein refers to a state in which the fine particles in the processing liquid and many of the coloring materials in the recording liquid do not mix with each other (including a state in which some mixing occurs at the liquid boundary or the like). Is preferably 70% or more of the fine particles or the coloring material in the above-described layers, and if the fine particles or the coloring material is 80% or more, the image quality improving effect of the present invention is further improved. Higher is preferable.
[0129]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the embodiments.
First, a treatment liquid and a recording liquid constituting the ink set according to the present invention, and a treatment liquid and a recording liquid used in a comparative example were blended and prepared according to the following formulation. "Parts" described in the compounding amount in the prescription represent parts by weight, and the total compounding amount of each liquid is 100 parts by weight.
[0130]
<Treatment liquid 1>
Cationic colloidal silica
(Nissan Chemical Co., Ltd .: Snowtex AK) 15.0 copies
12.5 parts of 2-pyrrolidone
Diethylene glycol 12.5 parts
Octanediol 1.0 part
Cationic surfactant
(Manufactured by Sanyo Chemical Co., Ltd .: Cation G50) 2.0 parts
Benzotriazole 1.0 part
0.2 parts of antiseptic / antifungal agent (PROXEL LV (s), manufactured by Avicia)
Water remaining
The above mixture was further adjusted to pH 4.3 with acetic acid before use.
[0131]
<Treatment liquid 2>
titanium dioxide
(Idemitsu Kosan Co., Ltd .: Idemitsu Titania IT-S) 15.0 copies
12.5 parts of 2-pyrrolidone
Diethylene glycol 12.5 parts
Octanediol 1.0 part
Cationic surfactant
(Manufactured by Sanyo Chemical Co., Ltd .: Cation G50) 2.0 parts
Benzotriazole 1.0 part
0.2 parts of antiseptic / antifungal agent (PROXEL LV (s), manufactured by Avicia)
Water remaining
The above mixture was further adjusted to pH 3.8 with acetic acid before use.
[0132]
<Treatment liquid 3>
alumina
(Nissan Chemical Co., Ltd .: Alumina Sol 520) 15.0 parts
12.5 parts of 2-pyrrolidone
Diethylene glycol 12.5 parts
Octanediol 1.0 part
Cationic surfactant
(Manufactured by Sanyo Chemical Co., Ltd .: Cation G50) 2.0 parts
Benzotriazole 1.0 part
0.2 parts of antiseptic / antifungal agent (PROXEL LV (s), manufactured by Avicia)
Water remaining
The above mixture was further adjusted to pH 3.9 with acetic acid before use.
[0133]
<Treatment liquid 4>
Anionic colloidal silica
(Nissan Chemical Co., Ltd .: Snowtex 20) 15.0 copies
12.5 parts of 2-pyrrolidone
Diethylene glycol 12.5 parts
Octanediol 1.0 part
Cationic surfactant
(Manufactured by Sanyo Chemical Co., Ltd .: Cation G50) 2.0 parts
Benzotriazole 1.0 part
0.2 parts of antiseptic / antifungal agent (PROXEL LV (s), manufactured by Abisia)
Water remaining
The above mixture was further adjusted to pH 3.9 with acetic acid before use.
[0134]
Treatment liquid 5 was prepared according to Example (1) of Japanese Patent No. 2711098.
<Treatment liquid 5>
3.0 parts of quaternary ammonium salts
Glycerin 10.0 parts
Diethylene glycol 20.0 parts
Water remaining
[0135]
A processing solution 6 was prepared according to Example P-1 of Japanese Patent No. 2667401.
<Treatment liquid 6>
5.0 parts of polyallylamine
Glycerin 10.0 parts
Ethylene glycol 11.0 parts
Diethylene glycol 20.0 parts
Diethylene glycol monobutyl ether 12.0 parts
Sodium dehydroacetate 0.1 part
Water remaining
[0136]
Treatment liquid 7 was prepared according to the examples of JP-A-2001-149149 and the production example of liquid composition A.
<Treatment liquid 7>
Alumina hydrate 10.0 parts
Glycerin 7.5 parts
7.5 parts of diethylene glycol
Nitric acid 0.2 parts
Water remaining
[0137]
A treatment liquid 8 was prepared according to the examples of JP-A-2002-201385 and the production example of the liquid composition 1.
<Treatment liquid 8>
Alumina hydrate 10.0 parts
Glycerin 7.5 parts
7.5 parts of diethylene glycol
0.4 parts of zirconium oxynitrate dihydrate
Water remaining
[0138]
<Treatment liquid 9>
Treatment liquid 9 was prepared in accordance with the examples of JP 2001-30616 A and the production example of reaction liquid A.
Magnesium nitrate / 6 hydrate 25.0 parts
Triethylene glycol monobutyl ether 10.0 parts
Glycerin 10.0 parts
Water remaining
[0139]
<Treatment liquid 10>
Cationic colloidal silica
(Nissan Chemical Co., Ltd .: Snowtex AK) 15.0 copies
NaCl 10.0 parts
12.5 parts of 2-pyrrolidone
Diethylene glycol 12.5 parts
Octanediol 1.0 part
Cationic surfactant
(Manufactured by Sanyo Chemical Co., Ltd .: Cation G50) 2.0 parts
Benzotriazole 1.0 part
0.2 parts of antiseptic / antifungal agent (PROXEL LV (s), manufactured by Abisia)
Water remaining
[0140]
<Black recording liquid 1 (anionic pigment-containing recording liquid)>
10 parts of carbon black (Cabot Jet 300, manufactured by Cabot Corporation)
1,3-butanediol 22.5 parts
Glycerin 7.5 parts
Surfactant (I), R = C₉H₁₉, K = 12 1 copy
2-pyrrolidone 2 parts
0.2 parts of sodium dehydroacetate
0.2 parts of sodium thiosulfate
Antiseptic / antifungal agent (PROXEL LV (s), manufactured by Abisia) 0.4 part
Deionized water remaining
The above mixture was further adjusted to pH 10.5 with an aqueous LiOH solution before use.
[0141]
<Yellow recording liquid 1 (anionic pigment-containing recording liquid)>
50 parts of resin-coated yellow dispersion (10 parts of yellow pigment solid content)
1,3-butanediol 22.5 parts
Glycerin 7.5 parts
Surfactant (I), R = C₉H₁₉, K = 12 1 copy
2-pyrrolidone 2 parts
0.2 parts of sodium dehydroacetate
0.2 parts of sodium thiosulfate
Antiseptic / antifungal agent (PROXEL LV (s), manufactured by Abisia) 0.4 part
Deionized water remaining
The above mixture was further adjusted to pH 10.5 with an aqueous LiOH solution before use.
[0142]
The “resin-coated yellow dispersion” used in the formulation of the above-mentioned yellow recording liquid 1 (anionic pigment-containing recording liquid) was produced as follows.
Production example of resin-coated yellow dispersion:
(1) Preparation of polymer solution
After sufficiently replacing the inside of a flask (volume: 1 L) equipped with a mechanical stirrer, a thermometer, a nitrogen gas inlet tube, a reflux tube, and a dropping funnel with nitrogen gas, 11.2 g of styrene, 2.8 g of acrylic acid, and lauryl methacrylate12. 0 g, polyethylene glycol methacrylate 4.0 g, styrene macromer (manufactured by Toagosei Co., Ltd., trade name: AS-6) 4.0 g and mercaptoethanol 0.4 g were charged, and the temperature was raised to 65 ° C.
Next, 100.8 g of styrene, 25.2 g of acrylic acid, 108.0 g of lauryl methacrylate, 36.0 g of polyethylene glycol methacrylate, 60.0 g of hydroxyethyl methacrylate, styrene macromer (manufactured by Toagosei Co., Ltd., trade name: AS-6) ) A mixed solution of 36.0 g, 3.6 g of mercaptoethanol, 2.4 g of azobisdimethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 2.5 hours.
After completion of the dropping, a mixed solution of 0.8 g of azobisdimethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 0.5 hours. After aging at 65 ° C. for 1 hour, 0.8 g of azobisdimethylvaleronitrile was added, and the mixture was further aged for 1 hour. After the completion of the reaction, 364 g of methyl ethyl ketone was added to the flask to obtain 800 g of a 50% concentration polymer solution.
A part of the polymer solution was dried and measured by gel permeation chromatography (standard: polystyrene, solvent: tetrahydrofuran) to find that the weight average molecular weight of the polymer was 15,000.
[0143]
(2) Preparation of resin-coated yellow dispersion
22.2 g of the polymer solution obtained in the above (1), 26.0 g of a yellow pigment (trade name: Symler Fast Yellow 4181, manufactured by Dainippon Ink and Chemicals, Inc.) and 13.6 g of a 1 mol / L aqueous lithium hydroxide solution After thoroughly stirring 20 g of methyl ethyl ketone and 30 g of ion-exchanged water, the mixture was kneaded 20 times using a three-roll mill (trade name: NR-84A, manufactured by Noritake Co., Ltd.). The obtained paste was poured into 200 g of ion-exchanged water, and after sufficiently stirring, methyl ethyl ketone and water were distilled off using an evaporator to obtain 160 g of a resin-coated yellow pigment dispersion having a solid content of 20.0% by weight. Was.
A yellow recording liquid 1 having the above composition was prepared based on the yellow pigment dispersion obtained in this production example.
[0144]
<Black recording liquid 2 (anionic dye-containing recording liquid)>
C. I. Direct Black 168 4 copies
15 parts of ethylene glycol
Glycerin 5 parts
Surfactant (I), R = C₉H₁₉, K = 12 1 copy
0.2 parts of sodium dehydroacetate
0.2 parts of sodium thiosulfate
Antiseptic / antifungal agent (PROXEL LV (s), manufactured by Abisia) 0.4 part
Deionized water remaining
The above mixture was further adjusted to pH 10.5 with an aqueous LiOH solution before use.
[0145]
<Yellow recording liquid 2 (anionic dye-containing recording liquid)>
C. I. Acid Yellow 23 4 parts
15 parts of ethylene glycol
Glycerin 5 parts
Surfactant (I), R = C₉H₁₉, K = 12 1 copy
0.2 parts of sodium dehydroacetate
0.2 parts of sodium thiosulfate
Antiseptic / antifungal agent (PROXEL LV (s), manufactured by Abisia) 0.4 part
Deionized water remaining
The pH was further adjusted to 10.5 with a LiOH aqueous solution.
[0146]
<Black recording liquid 3 (pigment + cationic dispersant-containing recording liquid)>
Carbon black (MA7, manufactured by Mitsubishi Chemical Corporation) 10 parts
Cationic dispersant
(N, N-dimethylaminoethyl methacrylate) 2 parts
1,3-butanediol 22.5 parts
Glycerin 7.5 parts
Surfactant (I), R = C₉H₁₉, K = 12 1 copy
2-pyrrolidone 2 parts
0.2 parts of sodium dehydroacetate
0.2 parts of sodium thiosulfate
Antiseptic / antifungal agent (PROXEL LV (s), manufactured by Abisia) 0.4 part
Deionized water remaining
The above mixture was further adjusted to pH 10.5 with an aqueous LiOH solution before use.
[0147]
<Yellow recording liquid 3 (pigment + cationic dispersant-containing recording liquid)>
C. I. Pigment Yellow 1 10 parts
Cationic dispersant
(N, N-dimethylaminoethyl methacrylate) 2 parts
1,3-butanediol 22.5 parts
Glycerin 7.5 parts
Surfactant (I), R = C₉H₁₉, K = 12 1 copy
2-pyrrolidone 2 parts
0.2 parts of sodium dehydroacetate
0.2 parts of sodium thiosulfate
Antiseptic / antifungal agent (PROXEL LV (s), manufactured by Abisia) 0.4 part
Deionized water remaining
The above mixture was further adjusted to pH 10.5 with an aqueous LiOH solution before use.
[0148]
<Black recording liquid 4 (cationic dye-containing recording liquid)>
C. I. Basic Black 2 10 copies
1,3-butanediol 22.5 parts
Glycerin 7.5 parts
Surfactant (I), R = C₉H₁₉, K = 12 1 copy
2-pyrrolidone 2 parts
0.2 parts of sodium dehydroacetate
0.2 parts of sodium thiosulfate
Antiseptic / antifungal agent (PROXEL LV (s), manufactured by Abisia) 0.4 part
Deionized water remaining
The above mixture was further adjusted to pH 10.5 with an aqueous LiOH solution before use.
[0149]
<Yellow recording solution 4 (cationic dye-containing recording solution)>
C. I. Basic Yellow 33 10 copies
1,3-butanediol 22.5 parts
Glycerin 7.5 parts
Surfactant (I), R = C₉H₁₉, K = 12 1 copy
2-pyrrolidone 2 parts
0.2 parts of sodium dehydroacetate
0.2 parts of sodium thiosulfate
Antiseptic / antifungal agent (PROXEL LV (s), manufactured by Abisia) 0.4 part
Deionized water remaining
The above mixture was further adjusted to pH 10.5 with an aqueous LiOH solution before use.
[0150]
A black recording liquid 5 was prepared according to the example of JP-A-2001-149149 (described in Black Ink Bk2).
<Black recording liquid 5 (anionic pigment-containing recording liquid)>
3.0 parts of carbon black
Trimethylolpropane 6.0 parts
Glycerin 6.0 parts
Ethylene glycol 6.0 parts
Water remaining
[0151]
A yellow recording liquid 5 was prepared according to the example of JP-A-2001-149149 (described in the yellow pigment ink Y3).
<Yellow recording liquid 5 (anionic pigment-containing recording liquid)>
C. I. Pigment Yellow 74 3.0 parts
Glycerin 10.0 parts
Ethylene glycol 5.0 parts
N-methylpyrrolidone 5.0 parts
2.0 parts of ethyl alcohol
Water remaining
[0152]
A black recording liquid 6 was prepared according to the example of JP-A-2002-201359 (described in Black Ink Bk2).
<Black recording liquid 6 (anionic pigment-containing recording liquid)>
3.0 parts of carbon black
Glycerin 10.0 parts
Ethylene glycol 5.0 parts
N-methylpyrrolidone 5.0 parts
2.0 parts of ethyl alcohol
Water remaining
[0153]
A yellow recording liquid 6 was prepared according to the example of JP-A-2002-201359 (described in the yellow ink Y2).
<Yellow recording liquid 6 (anionic pigment-containing recording liquid)>
C. I. Pigment Yellow 74 3.0 parts
Glycerin 10.0 parts
Ethylene glycol 5.0 parts
N-methylpyrrolidone 5.0 parts
2.0 parts of ethyl alcohol
Water remaining
[0154]
A black recording liquid 7 was prepared according to the example of JP-A-2001-30616 (described in Black Ink A1).
<Black recording liquid 7 (anionic pigment-containing recording liquid)>
Carbon black MA7 5.0 parts
Styrene-acrylic acid copolymer 1.0 part
Acrylic resin emulsion 10.0 parts
Glycerin 10.0 parts
Water remaining
[0155]
A yellow recording liquid 7 was prepared according to the example of JP-A-2001-30616 (described in Yellow Ink A1).
<Yellow recording liquid 7 (anionic pigment-containing recording liquid)>
C. I. Pigment Yellow 74 3.5 parts
Styrene-acrylic acid copolymer 1.0 part
Acrylic resin emulsion 15.0 parts
Glycerin 8.0 parts
Water remaining
[0156]
<Black recording liquid 8 (ultraviolet reactive black pigment recording liquid)>
Carbon black
(Cabot Jet 300 manufactured by Cabot Corporation) 10 parts
2.0 parts of photoacid generator (manufactured by Sanwa Chemical Company, WS-Triazine)
1,3-butanediol 22.5 parts
Glycerin 7.5 parts
Surfactant (I), R = C₉H₁₉, K = 12 1 copy
2-pyrrolidone 2 parts
0.2 parts of sodium dehydroacetate
0.2 parts of sodium thiosulfate
Antiseptic / antifungal agent (PROXEL LV (s), manufactured by Abisia) 0.4 part
Deionized water remaining
The above mixture was further adjusted to pH 10.5 with an aqueous LiOH solution before use.
[0157]
<Yellow recording liquid 8 (ultraviolet reactive yellow pigment recording liquid)>
50 parts of resin-coated yellow dispersion (10 parts of yellow pigment solid content)
2.0 parts of photoacid generator (manufactured by Sanwa Chemical Company, WS-Triazine)
1,3-butanediol 22.5 parts
Glycerin 7.5 parts
Surfactant (I), R = C₉H₁₉, K = 12 1 copy
2-pyrrolidone 2 parts
0.2 parts of sodium dehydroacetate
0.2 parts of sodium thiosulfate
Antiseptic / antifungal agent (PROXEL LV (s), manufactured by Abisia) 0.4 part
Deionized water remaining
The above mixture was further adjusted to pH 10.5 with an aqueous LiOH solution before use.
[0158]
Example 1
The processing liquid 1 prepared above was accommodated (filled) in the cartridge for the processing liquid, the yellow recording liquid 1 in the cartridge for the yellow recording liquid, and the black recording liquid 1 in the cartridge for the black recording liquid, respectively, as shown in FIG. It was mounted on an image forming apparatus (inkjet recording apparatus) having the above configuration, and a printing evaluation experiment was performed. Table 1 summarizes the main components of the processing liquid and the recording liquid of Example 1. The cartridges have a common configuration and form.
A test was performed using my paper (plain paper, manufactured by NBS Ricoh) as a recording medium (recording material) for the print evaluation experiment. However, in the experiment of reproducibility of fine lines, a printing test was performed using a canvas for oil painting (manufactured by Sekaido Co., Ltd.). Inkjet printing was performed in the order in which the treatment liquid first adhered to the paper, and the recording liquid of each color adhered thereon. The printing liquid adhesion amount and the processing liquid adhesion amount at the time of printing were adjusted so as to be approximately the following amounts.
Recording liquid adhesion amount: 11.0 g / m2
Treatment liquid adhesion amount: 13.0 g / m2
[0159]
The printed matter (recorded matter) printed was evaluated for feathering, color bleed, image density, saturation, drying properties, glossiness, fine line reproducibility, and fixability. Each item was evaluated based on the following evaluation methods and criteria. Table 2 shows the results.
Further, a black solid portion of the recorded matter was cut, and a cross section thereof was observed with a transmission electron microscope (TEM). FIG. 12 shows a cross-sectional TEM photograph. As can be seen from the figure, stripe-like shading appears. Further, from the result of the elemental analysis (EDX), it was possible to specify that the dark portion was the fine particle aggregation layer and the light portion was the color material aggregation layer.
[0160]
<Image quality evaluation method>
(1) Feathering:
The image quality was evaluated by observing the black characters and comparing with the rank sample.
Rank 5: No bleeding
Rank 4: Slight bleeding
Rank 3: There is seepage, but there is no problem in practical use
Rank 2: Slightly exuding
Rank 1: Lots of seepage
(2) Color bleed:
The image quality was evaluated by observing the color boundary portion of a printed matter in which the letter "A" was printed in yellow on a black solid, and comparing it with a rank sample.
Rank 5: No color mixing
Rank 4: Slight color mixing
Rank 3: There is color mixing, but there is no practical problem
Rank 2: Some color mixing
Rank 1: Many colors
(3) Image density:
The optical density from the surface of the solid black portion was measured to determine the image density.
(4) Saturation:
Lab was measured from the surface of the yellow solid portion, and the saturation of yellow was obtained.
(5) Dryness:
Immediately after printing, plain paper (My Paper, manufactured by NBS Ricoh) was pressed against the printed matter, and the ink transfer of the solid black portion to the plain paper was observed.
○… No ink transfer
×: with ink transfer
(6) Glossiness:
The 60-degree glossiness of the printed matter was determined using a glossmeter (4501 manufactured by BYK Gardener).
(7) Fine line reproducibility:
A pattern in which lines and spaces having a width of 0.5 mm were repeated was printed, and the reproducibility of fine lines was observed.
○… Adjacent lines are independent
×: Adjacent lines are connected
(8) Fixing property:
The surface of the printed material was rubbed by hand, and the fixability of the image area was evaluated.
○… No color transfer
×: with color transfer
(9) Cross-sectional TEM observation:
The black solid portion of the printed matter was cut and observed with a transmission electron microscope (TEM). When there is a bias in the element distribution, the density can be visually observed, and it can be seen that the coloring material and the fine particles each form a layer. In addition, by mapping the elements in different colors, the distribution of the coloring material and the fine particles can be confirmed more clearly.
[0161]
Examples 2 to 6
Example 1 was repeated except that the processing liquid 1, the black recording liquid 1, and the yellow recording liquid 1 were used in place of the recording liquid and the processing liquid in each example in the combinations shown in Table 1. The printing tests of Examples 2 to 6 were performed in the same manner as in Example 1. Table 2 shows the results.
[0162]
Example 7
Example 7 was repeated in the same manner as in Example 1 except that the recording liquid and the processing liquid shown in Table 1 were used instead of the processing liquid 1, the black recording liquid 1, and the yellow recording liquid 1, respectively. A printing test was performed. Table 2 shows the results.
[0163]
Example 8
In Example 1, instead of using the processing liquid 1, the black recording liquid 1, and the yellow recording liquid 1, respectively, the recording liquid and the processing liquid shown in Table 1 were used, and instead of the ink jet recording apparatus shown in FIG. The printing test of Example 8 was conducted in the same manner as in Example 1 except that the ink jet recording apparatus equipped with an ultraviolet irradiation device shown in FIG. Table 2 shows the results.
[0164]
Comparative Examples 1 to 7
Example 1 was repeated except that the processing liquid 1, the black recording liquid 1 and the yellow recording liquid 1 were used in place of the recording liquid and the processing liquid in each of the comparative examples in the combinations shown in Table 1. Printing tests of Comparative Examples 1 to 7 were performed in the same manner as in Example 1. Table 2 shows the results.
[0165]
[Table 1]

[0166]
[Table 2]

[0167]
As a result of the above evaluation, in Examples 1 to 8 using the ink set composed of the processing liquid and the recording liquid having the configuration according to the present invention, bleeding was prevented in feathering and color bleed. Moreover, both the image density and the saturation are good. In addition, there is no ink transfer and the drying property is good, and the glossiness is very excellent. Further, the printed fine line also has an independent adjacent line, no jagged state occurs, and the fine line reproducibility is good. Further, even when the surface of the printed matter is rubbed by hand, there is no color transfer and the fixing property is excellent.
Further, as a result of cross-sectional observation of each recorded material by a transmission electron microscope (TEM), striped shading similar to that shown in Embodiment 1 appears in Examples 1 to 8 of the present invention.
On the other hand, in the case of Comparative Examples 1 to 7, all of the properties were inferior to those of the present invention, and no stripe-like shading was observed by cross-sectional observation with a transmission electron microscope (TEM).
[0168]
【The invention's effect】
Treatment liquid containing fine particles adjusted to maintain or destroy a dispersed state by an external factor of the present invention (for example, a factor that causes a change in pH, a change in solubility, or the like due to contact with a substance, ultraviolet irradiation, or the like). And a recording liquid containing a coloring material adjusted to maintain or destroy a dispersed state or a dissolved state by the external factor, and separately treat the processing liquid and the recording liquid separately. A droplet is ejected as a droplet onto a recording medium (absorptive recording medium or non-absorbent recording medium) by an ink jet method, and the droplets are brought into contact with each other to change the state of the processing liquid and the recording liquid (for example, a change in pH) And changes in solubility) to form an image by causing the fine particles in the processing liquid and the coloring material in the recording liquid to aggregate without substantially mixing. Preventing ring and color bleeding, a high density, and high saturation, yet there prints (recorded matter) glossy feeling is obtained.
Further, the image forming method described above is achieved by an ink jet type image forming apparatus equipped with cartridges that individually accommodate the processing liquid and the recording liquid according to the present invention, and the feathering and the ink setting are performed in combination with the excellent characteristics of the ink set. Effective suppression of color bleed, high density and high saturation, glossiness, and the like are realized, and a clear printed matter faithful to a document is provided.
Furthermore, by mounting the cartridge containing the processing liquid and the recording liquid separately in the image forming apparatus in the present invention, the image apparatus can be made compact, and simple and steady maintenance work can be performed. It is possible to do. Further, replacement of parts is facilitated, overall cost is reduced, and image quality is stabilized.
[Brief description of the drawings]
[0052]
FIG. 1 is a schematic diagram showing an image forming process when the pH of a processing liquid and a recording liquid changes due to substance contact by applying an ink set and an image forming method of the present invention.
FIG. 2 is a schematic diagram showing a process of forming an image by applying a change in pH and a change in solubility by ion transfer or salting out due to substance contact by applying the ink set and the image forming method of the present invention.
FIG. 3 is a schematic diagram showing a process of applying an ink set and an image forming method of the present invention to irradiate ultraviolet rays to generate an acid from a photoacid generator to cause a pH change to form an image.
FIG. 4 is a schematic view conceptually showing a difference (line width) between image forming according to the present invention and a conventional method when printing fine lines on a smooth non-absorbent recording medium.
FIG. 5 is a schematic view conceptually showing a difference (jagged state) between image formation according to the present invention and a conventional method when printing a fine line on a non-absorbent recording medium having irregularities.
FIG. 6 is a perspective view showing a schematic configuration for explaining an image forming apparatus as an example of the present invention in the embodiment;
FIG. 7 is a perspective view showing a schematic configuration for explaining an image forming apparatus provided with an ultraviolet irradiation unit (high-pressure mercury lamp) which is another example of the present invention in the embodiment.
8 is a schematic cross-sectional view for explaining a configuration example of a discharge nozzle of a recording head mounted on a carriage of the image forming apparatus of FIG.
FIG. 9 is a schematic cross-sectional view illustrating another configuration example of a discharge nozzle of a print head mounted on a carriage of the image forming apparatus of FIG.
FIG. 10 is an external perspective view showing a schematic configuration example for describing a cartridge capable of storing a processing liquid or a recording liquid mounted on the image forming apparatus of the present invention in the embodiment.
11 is a front sectional view showing the schematic internal configuration of the cartridge shown in FIG. 7;
FIG. 12 is a cross-sectional TEM photograph of a cross-section obtained by cutting a solid black portion of the recorded matter of Example 1 observed with a transmission electron microscope (TEM).
[Explanation of symbols]
1 Image forming apparatus
2 Body case
16 Gear mechanism
17 Sub-scanning motor
18 Carriage
18a recording head
19 Platen
20 cartridges
21 Guide shaft
22 Guide shaft
23 Timing belt
24 Main scanning motor
26 Main scanning motor
27 High-pressure mercury lamp
31 nozzles (the processing liquid is discharged)
32 nozzles (the recording liquid is ejected)
33 nozzles (recording liquid is ejected)
34 nozzles (recording liquid is ejected)
35 nozzles (recording liquid is ejected)
36 nozzles (the processing liquid is discharged)
37 nozzles (recording liquid is ejected)
38 nozzles (recording liquid is ejected)
39 nozzles (recording liquid is ejected)
40 nozzles (recording liquid is ejected)
41 nozzle (the processing liquid is discharged)
42 liquid absorber
43 cases
44 Upper lid member
45 liquid supply port
46 Seal ring
47 Open to the atmosphere
49 Cartridge housing
50 Cap member
55 Sealing member
81 Cartridge mounting / removing projection
A space

Claims (23)

Including a treatment liquid containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and a coloring material adjusted to maintain or destroy a dispersed or dissolved state by an external factor The processing liquid and the recording liquid are destroyed in a dispersed state or a dissolved state on the recording medium, so that the fine particles in the processing liquid and the coloring material in the recording liquid are substantially reduced. An ink set characterized by forming an image by aggregating without mixing. The ink set according to claim 1, wherein the recording liquid and the processing liquid constituting the ink set are aqueous liquids. The coloring material contained in the recording liquid has an anionic group or a cationic group, or that the surface of the coloring material is directly or indirectly coated with a compound having an anionic group or a cationic group. The ink set according to claim 1 or 2, wherein The fine particles contained in the treatment liquid have a cationic group or an anionic group, or the surface of the fine particles is directly or indirectly coated with a compound having a cationic group or an anionic group. The ink set according to claim 1, wherein: The ink set according to any one of claims 1 to 4, wherein when the coloring material and the fine particles are anionic or cationic, the respective polarities are opposite polarities. Including a processing solution containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and a coloring material adjusted to maintain or destroy a dispersed or dissolved state by an external factor By using an ink set composed of a recording liquid and destroying each of the processing liquid and the recording liquid in a dispersed state or a dissolved state on a recording medium, the fine particles in the processing liquid and the particles in the recording liquid are destroyed. An image forming method for forming an image by aggregating without substantially mixing the coloring material,
Contacting the processing liquid and the recording liquid in the image forming step;
A step of causing a state change between the treatment liquid and the recording liquid by the contact;
Causing the state change to cause aggregation of the fine particles in the processing solution,
A step of causing the color materials in the recording liquid to aggregate with each other by the state change;
An image forming method comprising: Including a processing solution containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and a coloring material adjusted to maintain or destroy a dispersed or dissolved state by an external factor By using an ink set composed of a recording liquid and destroying each of the processing liquid and the recording liquid in a dispersed state or a dissolved state on a recording medium, the fine particles in the processing liquid and the particles in the recording liquid are destroyed. An image forming method for forming an image by aggregating without substantially mixing the coloring material,
Contacting the processing liquid and the recording liquid in the image forming step;
A step of causing a state change between the treatment liquid and the recording liquid by the contact;
A process of causing the surface potential of the fine particles in the treatment liquid to change to cause aggregation of the fine particles,
A process of causing the surface potential of the color material in the recording liquid to change by the state change to cause aggregation of the color materials;
An image forming method comprising: Including a processing solution containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and a coloring material adjusted to maintain or destroy a dispersed or dissolved state by an external factor By using an ink set composed of a recording liquid and destroying each of the processing liquid and the recording liquid in a dispersed state or a dissolved state on a recording medium, the fine particles in the processing liquid and the particles in the recording liquid are destroyed. An image forming method for forming an image by aggregating without substantially mixing the coloring material,
Contacting the processing liquid and the recording liquid in the image forming step;
A step of causing a state change between the treatment liquid and the recording liquid by the contact;
A step of causing the fine particles in the processing liquid to aggregate by the state change to form a layer of the fine particles,
Forming a layer of the color material by causing the color materials in the recording liquid to aggregate by the state change;
An image forming method comprising: Including a processing solution containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and a coloring material adjusted to maintain or destroy a dispersed or dissolved state by an external factor By using an ink set composed of a recording liquid and destroying each of the processing liquid and the recording liquid in a dispersed state or a dissolved state on a recording medium, the fine particles in the processing liquid and the particles in the recording liquid are destroyed. An image forming method for forming an image by aggregating without substantially mixing the coloring material,
Contacting the processing liquid and the recording liquid in the image forming step;
A step of causing a state change between the treatment liquid and the recording liquid by the contact;
The state change, the surface potential of the fine particles in the treatment liquid is changed to cause aggregation of the fine particles, a process of forming a layer of fine particles,
A process of changing the surface potential of the coloring material in the recording liquid to cause agglomeration of the coloring materials, thereby forming a coloring material layer;
An image forming method comprising: Including a processing solution containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and a coloring material adjusted to maintain or destroy a dispersed or dissolved state by an external factor By using an ink set composed of a recording liquid and destroying each of the processing liquid and the recording liquid in a dispersed state or a dissolved state on a recording medium, the fine particles in the processing liquid and the particles in the recording liquid are destroyed. An image forming method for forming an image by aggregating without substantially mixing the coloring material,
Contacting the processing liquid and the recording liquid in the image forming step;
A step of causing the ions to move from the recording liquid to the processing liquid to cause a state change by the contact, thereby causing aggregation of the fine particles in the processing liquid;
A step of causing the ions to move from the processing liquid to the recording liquid to cause a state change by the contact, thereby causing aggregation of the color materials in the recording liquid;
An image forming method comprising: Including a processing solution containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and a coloring material adjusted to maintain or destroy a dispersed or dissolved state by an external factor By using an ink set composed of a recording liquid and destroying each of the processing liquid and the recording liquid in a dispersed state or a dissolved state on a recording medium, the fine particles in the processing liquid and the particles in the recording liquid are destroyed. An image forming method for forming an image by aggregating without substantially mixing the coloring material,
Contacting the processing liquid and the recording liquid in the image forming step;
The contact causes ions to move from the recording liquid to the processing liquid to cause a state change, and change the surface potential of the fine particles in the processing liquid to cause aggregation of the fine particles;
By the contact, ions move from the processing liquid to the recording liquid to cause a change in state, and the surface potential of the coloring material in the recording liquid changes to cause aggregation of the coloring materials;
An image forming method comprising: Including a processing solution containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and a coloring material adjusted to maintain or destroy a dispersed or dissolved state by an external factor By using an ink set composed of a recording liquid and destroying each of the processing liquid and the recording liquid in a dispersed state or a dissolved state on a recording medium, the fine particles in the processing liquid and the particles in the recording liquid are destroyed. An image forming method for forming an image by aggregating without substantially mixing the coloring material,
Contacting the processing liquid and the recording liquid in the image forming step;
A process in which the contact changes the state of the processing liquid to fix an aggregate formed by aggregation of the fine particles in the processing liquid on the surface of the recording medium;
A process in which the contact causes a change in the state of the recording liquid to fix an aggregate formed by agglomeration of the color materials in the recording liquid on the surface of the recording medium or the surface of the aggregate of the fine particles;
An image forming method comprising: Including a processing solution containing fine particles adjusted to maintain or destroy a dispersed state by an external factor, and a coloring material adjusted to maintain or destroy a dispersed or dissolved state by an external factor An image forming apparatus comprising: a storage unit that stores recording liquids independently, and a discharge unit that discharges the recording liquid and the processing liquid individually.
By breaking each of the processing liquid and the recording liquid into a dispersed state or a dissolved state on the recording medium, the fine particles in the processing liquid and the coloring material in the recording liquid are aggregated without being substantially mixed. An image forming apparatus characterized in that an image is formed by using the image forming apparatus. 14. The image forming apparatus according to claim 13, wherein the image forming on the recording medium is performed by applying any one of the image forming methods according to any one of claims 6 to 12. The image forming apparatus according to claim 13, wherein the ejection unit is an inkjet recording head. 16. The image forming apparatus according to claim 15, wherein the inkjet recording head is an ejection head using thermal energy. A cartridge accommodated in the accommodation section of the image forming apparatus, comprising: a storage section for independently storing the processing liquid and the recording liquid; and a discharge unit for discharging the recording liquid and the processing liquid individually. hand,
A treatment liquid containing fine particles adjusted to maintain or destroy the dispersion state of each of the liquid storage portions of the cartridge individually by an external factor, or maintain or destroy the dispersion state or the dissolved state by an external factor A recording liquid containing a coloring material adjusted to perform the recording. A recording material on which an image is formed using an ink set composed of a processing liquid containing fine particles and a recording liquid containing a coloring material,
The agglomerated fine particles and the coloring material are each formed separately in a layer substantially formed of the fine particles and a layer substantially formed of the coloring material in a cross section of the recorded matter. Recorded material. The recorded matter is a processing liquid containing fine particles adjusted to maintain or destroy the dispersed state by an external factor, and adjusted to maintain or destroy the dispersed or dissolved state by an external factor. By using an ink set composed of a recording liquid containing a coloring material, the processing liquid and the recording liquid are destroyed in a dispersed state or a dissolved state on a recording medium by the fine particles and the fine particles in the processing liquid. 19. The recorded matter according to claim 18, wherein the recorded matter is a recorded matter in which the color material in the recording liquid is aggregated without being substantially mixed to form an image. The layer substantially formed of fine particles is formed in a process in which the state of the processing liquid changes due to the contact between the processing liquid and the recording liquid to cause aggregation of the fine particles in the processing liquid. A layer substantially formed of a colorant, the contact between the treatment liquid and the recording liquid causes a change in the state of the recording liquid and causes aggregation of the colorants in the recording liquid. 19. The recorded matter according to claim 18, wherein the recorded matter is a layer formed in a process of causing the recorded matter. The layer substantially formed of the fine particles, due to the contact between the processing liquid and the recording liquid, a change in the state of the processing liquid occurs, the surface potential of the fine particles in the processing liquid changes, and The layer formed in the process of causing agglomeration, and the layer substantially formed of the colorant, the state of the recording liquid changes due to the contact between the processing liquid and the recording liquid, and the recording liquid 19. The recorded matter according to claim 18, wherein the recording material is a layer formed in a process in which the surface potential of the coloring material inside changes to cause aggregation of the coloring materials. The layer substantially formed of the fine particles forms a state change due to the transfer of ions from the recording liquid to the processing liquid due to the contact between the processing liquid and the recording liquid, and aggregation of the fine particles in the processing liquid occurs. Is a layer formed in the process of causing, the layer substantially formed of the coloring material, by the contact between the processing liquid and the recording liquid, ions move from the processing liquid to the recording liquid 19. The recorded matter according to claim 18, wherein the layer is formed in a process in which a state change occurs to cause agglomeration of the coloring materials in the recording liquid. The layer substantially formed of the fine particles, the contact between the processing liquid and the recording liquid, ions are transferred from the recording liquid to the processing liquid, a state change occurs, the surface potential of the fine particles in the processing liquid Is a layer formed in the process of causing the aggregation of the fine particles to change, the layer substantially formed of the colorant, by contact of the processing liquid and the recording liquid, from the processing liquid The layer is formed in a process in which ions move to the recording liquid to cause a state change, and a surface potential of the coloring material in the recording liquid changes to cause aggregation of the coloring materials. Item 19. A recorded matter according to Item 18.

Images