JP3541976B2 - Colored water dispersion - Google Patents

Description

を仕込み１５０〜２２０℃で１８０分間加熱してエステル交換反応を行った。次いで、２４０℃に昇温した後、系の圧力を徐々に減じて３０分後に１０ｍｍＨｇとし、９０分間反応を続けた。共重合ポリエステル樹脂（Ａ１）を得た。得られた共重合ポリエステル樹脂は平均分子量は３１００、酸価５eq./ton 、ガラス転移温度は５８℃、スルホン酸ナトリウム基当量９８eq.ton、であった。
【００４３】
温度計、撹拌機を備えたオ−トクレ−ブ中に、
シクロヘキサンジカルボン酸ジメチルエステル １９６重量部、
エチレングリコ−ル １０２重量部、
トリシクロデカンジメタノール ９９重量部、
テトラブトキシチタネ−ト ０．１重量部、
を仕込み１５０〜２２０℃で１８０分間加熱してエステル交換反応を行った。次いで、２４０℃に昇温した後、系の圧力を徐々に減じて３０分後に１０ｍｍＨｇとし、１２０分間反応を続けた。その後オ−トクレ−ブ中を窒素ガスで置換し、大気圧とした。温度を２００℃に保ち、
無水トリメリット酸 ４重量部を加え、
６０分間反応を行い、共重合ポリエステル樹脂（Ａ２）を得た。得られた共重合ポリエステル樹脂は平均分子量は３５００、酸価２１４eq./ton 、ガラス転移温度は７０℃であった。
【００４４】
［着色水分散体の製造］
温度計、コンデンサ−、撹拌羽根を備えた四つ口の１０リットルセパラブルフラスコにポリエステル樹脂（Ａ１）２００重量部、メチルエチルケトン１００重量部、テトラハイドロフラン５０重量部、染料としてサ−マルトランスファーＳＥ０７８０（油性染料ケーキ）［ＢＡＳＦ社製］２０重量部を仕込み７０℃にて溶解した。次いで７０℃のイオン交換水５００重量部を加え、水分散化した後、蒸留用フラスコにて留分温度が１０３℃に達するまで蒸留し、着色ポリエステル水分散体（Ｂ１）とした。得られたポリエステル水分散体に存在する微分散粒子の平均粒子径は０．１２μｍ、ゼ−タ電位は−４６ｍＶであった。
温度計、コンデンサ−、撹拌羽根を備えた四つ口の１０リットルセパラブルフラスコにポリエステル樹脂（Ａ２）２００重量部、メチルエチルケトン２００重量部、テトラハイドロフラン１００重量部、染料としてＣ．Ｉ．ＤｉｓｐｅｒｓｅＲｅｄ６０（AmesNega）［三井東圧染料製］コンクケーキ１０重量部、マクロレックスイエロー３Ｇ［ＢＡＹＥＲ社製］１０重量部を仕込み７０℃にて溶解した。
【００４５】
次いで塩基として２，２',２''−ニトリルトリエタノール６重量部を加えた後、７０℃のイオン交換水５００重量部を加え、水分散化した後、蒸留用フラスコにて留分温度が１０３℃に達するまで蒸留し、冷却後に水を加え固形分濃度を２５％の着色ポリエステル水分散体（Ｂ２）とした。得られたポリエステル水分散体に存在する微分散粒子の平均粒子径は０．２２μｍ、ゼ−タ電位は−５５ｍＶであった。
【００４６】
【実施例１】
下記構成となるように試料を混合調製し、１．０μｍのメンブレンフィルタ−にて濾過し記録剤（１）を得た。
着色ポリエステル微粒子（Ｂ１） （不揮発分換算）１５．０wt％
エチレングリコール ４．０wt％
エチルアルコール １．０wt％
エチレン−プロピレン共重合体微粒子 （不揮発分換算）５．０wt％
水 残
ここにエチレン−プロピレン共重合体微粒子はエチレン９０wt％、プロピレン１０wt％からなるソープフリー乳化重合により得られた共重合体樹脂粒子水分散体であり、
平均粒子径 ０．３８μｍ
樹脂比重 ０．９２
最低造膜温度 ９５℃
ビカット軟化点 ７６℃
である。
【００４７】
本樹脂はメタノール、エタノール、イソプロピルアルコール、エチレングリコール、ニトリルトリエタノールに対して溶解せず、膨潤している様子も観察されなかった。さらに不揮発分濃度を２０wt％に調製した水分散体１００wt部にイソプロピルアルコール１０wt部を添加した場合においても最低造膜には変化がなく、粒子径にも変化がないため低級アルコールによる膨潤性は事実上ないと判断された。
記録剤の粘度は３．２センチポイズ、表面張力は５２ｄｙｎ／ｃｍに調整された。また以下に示す実施例、比較例においても一定条件下にて比較するべき観点より記録剤粘度は２．５〜４．０センチポイズの範囲内に、表面張力は４８〜５４ｄｙｎ／ｃｍの範囲に入るように調整された。
なお平均粒子径は光散乱式粒度分布計、樹脂比重は浮沈法、最低造膜温度は常法、ビカット軟化点はＡＳＴＭＤ１５２５−７０準拠の方法で測定した。
【００４８】
得られた試作記録剤（１）を用いて烏口にて、再生紙に幅０．３ｍｍの線を罫がき、記録品位を目視評価した。また書道用半紙にも同様に０．３ｍｍの線を罫がき、本来の線幅と実際に罫かれた線幅より線の太りを求め、ニジミ幅とした。罫書を行なった紙をイオン交換水に５分間浸し、色材のニジミだしの有無をもって耐水性を評価した。絵筆により記録紙上に乾燥平均膜厚（重量換算）１．０μｍとなるようにベタ画像を形成しマクベス光学濃度計にて記録濃度を計測した。さらに試作記録剤を深さ１０ｃｍの試験管に満たし、密封して３ヶ月間静置し、三ヶ月後に試験管の最下部における沈殿物の有無、液面下５ｍｍからサンプリングした記録剤と、底から１ｃｍ上の部分からサンプリングした記録剤との固形分濃度比をもって保存安定性の評価を行なった。結果を表１．に示す。
【００４９】
【表１】

なお表１．中
ＭＦＴ：最低造膜温度
ＳＰ ：ビカット軟化点
記録品位（目視）：１線長１ｃｍあたりのヒゲ状ノイズ（フェザリング）
１本未満 ◎
１〜２本 ○
２〜４本 △
４本以上 ×
である。
【００５０】
【実施例２】
下記組成の記録剤（２）を実施例１と同様の手順にて調製し、同様の評価を行なった。結果を表１．に示す。

ここにパラメチルスチレン−メタクリル酸ブチル共重合体微粒子はパラメチルスチレン７５wt％、メタクリル酸ブチル２０wt％、ジビニルベンゼン５wt％からなるソープフリー乳化重合により得られた共重合体樹脂粒子水分散体であり、
平均粒子径 ０．４５μｍ
樹脂比重 １．０２
最低造膜温度 １０２℃
ビカット軟化点 ９５℃
である。本樹脂は、メタノール、エタノール、イソプロパノール、エチレングリコール、ニトリルトリエタノールに対して溶解しなかった、ただしメタノールに対し若干膨潤が観察された。不揮発分濃度を２０wt％に調製した水分散体１００wt部にイソプロピルアルコール１０wt部を添加した場合においては最低造膜が約４℃低下したが、粒子径には検出できる程の変化がないため低級アルコールによる膨潤性は低いと判断された。
【００５１】
【実施例３】
下記組成の記録剤（３）を実施例１と同様の手順にて調製し、同様の評価を行なった。結果を表１．に示す。
着色ポリエステル微粒子（Ｂ１） （不揮発分換算）１５．０wt％
エチレングリコール ５．０wt％
イソプロピルアルコール １．０wt％
アイオノマー樹脂微粒子Ｓ−２００ （不揮発分換算）５．０wt％
水 残
ここにアイオノマー樹脂微粒子はアルカリ金属イオンにより部分的イオン架橋されたエチレン−メタクリル酸共重合体（エチレン８０〜９０wt％、メタクリル酸１０〜２０wt％）からなりソープフリー乳化手法により得られた水分散体であり、ケミパールＳ−２００として三井石油化学社より上市されているものであり、
平均粒子径 ０．４３μｍ
樹脂比重 ０．９５
最低造膜温度 ８５℃
ビカット軟化点 ５７℃
である。本樹脂はメタノール、エタノール、イソプロピルアルコール、エチレングリコール、ニトリルトリエタノールに対して溶解せず、膨潤している様子も観察されなかった。さらに不揮発分濃度を２０wt％に調製した水分散体１００wt部にイソプロピルアルコール１０wt部を添加した場合においても最低造膜には変化がなく、粒子径にも変化がないため低級アルコールによる膨潤性は事実上ないと判断された。
【００５２】
【実施例４】
下記組成の記録剤（４）を実施例１と同様の手順にて調製し、同様の評価を行なった。結果を表１．に示す。
着色ポリエステル微粒子（Ｂ１） （不揮発分換算）１５．０wt％
プロピレングリコール ５．０wt％
ブタノール ０．８wt％
ニトリルトリエタノール ０．２wt％
クエン酸 ０．１wt％
アイオノマー樹脂微粒子Ｓ−３００ （不揮発分換算）２．０wt％
水 残
ここにアイオノマー樹脂微粒子はアルカリ金属イオンにより部分的イオン架橋されたエチレン−メタクリル酸共重合体（エチレン８０〜９０wt％、メタクリル酸１０〜２０wt％）からなりソープフリー乳化手法により得られた水分散体であり、ケミパールＳ−３００として三井石油化学社より上市されているものであり、
平均粒子径 ０．５３μｍ
樹脂比重 ０．９５
最低造膜温度 ９４℃
ビカット軟化点 ６７℃
である。本樹脂は実施例３に用いられたアイオノマー樹脂と同様、低級アルコールによる膨潤性は事実上ないと判断された。
【００５３】
【実施例５】
下記組成の記録剤（５）を実施例１と同様の手順にて調製し、同様の評価を行なった。結果を表１．に示す。
着色ポリエステル微粒子（Ｂ１） （不揮発分換算）１５．０wt％
エチレングリコール ５．０wt％
変性アイオノマー樹脂微粒子ＳＡ−１００（不揮発分換算）２．０wt％
水 残
ここに変性アイオノマー樹脂微粒子はアルカリ金属イオンにより部分的イオン架橋されたエチレン−メタクリル酸共重合体（エチレン８０〜９０wt％、メタクリル酸１０〜２０wt％）にさらにスチレンをグラフトしたグラフト共重合体からなるソープフリー乳化手法により得られた水分散体であり、ケミパールＳＡ−１００として三井石油化学社より上市されているものであり、
平均粒子径 ０．７５μｍ
樹脂比重 １．００
最低造膜温度 ７０℃
ビカット軟化点 ５５℃
である。本樹脂は、メタノール、エタノール、イソプロパノール、エチレングリコール、ニトリルトリエタノールに対して溶解しなかった、ただしメタノールに対し若干膨潤が観察された。不揮発分濃度を２０wt％に調製した水分散体１００wt部にイソプロピルアルコール１０wt部を添加した場合においては最低造膜が約２℃低下したが、粒子径には検出できる程の変化がないため低級アルコールによる膨潤性は低いと判断された。
【００５４】
【実施例６】
下記組成の記録剤（６）を実施例１と同様の手順にて調製し、同様の評価を行なった。結果を表１．に示す。
着色ポリエステル微粒子（Ｂ１） （不揮発分換算）３０．０wt％
スチレン−ブタジエン共重合体ラテックス（不揮発分換算）２．０wt％
水 残
ここにスチレン−ブタジエン共重合体ラテックスはスチレン２５wt％を含む共重合体の乳化重合により得られたラテックスである。
平均粒子径 ０．３８μｍ
樹脂比重 ０．９７
最低造膜温度 ２４℃
ビカット軟化点 １０℃
である。本樹脂は、メタノール、エタノール、イソプロパノールに溶解した。エチレングリコール、ニトリルトリエタノールに対して溶解しなかった。不揮発分濃度を２０wt％に調製した水分散体１００wt部にイソプロピルアルコール１０wt部を添加した場合においては最低造膜は２４℃以上低下、すなわち氷点以下にならない場合には自然乾燥により造膜した。
【００５５】
【実施例７】
下記組成の記録剤（７）を実施例１と同様の手順にて調製し、同様の評価を行なった。結果を表１．に示す。
着色ポリエステル微粒子（Ｂ１） （不揮発分換算）２５．０wt％
エタノール ５．０wt％
ポリメチルメタクリレートラテックス （不揮発分換算）１．０wt％
水 残
ここにポリメチルメタクリレートラテックスはマイクロジェルＰ−５００２［日本ペイント］として市販されているものである。
平均粒子径 ０．５２μｍ
樹脂比重 １．１９
最低造膜温度 １２０℃
ビカット軟化点 １１０℃
である。本樹脂は、メタノール、エタノール、イソプロパノール、エチレングリコール、ニトリルトリエタノールに対して溶解はしなかったが、メタノール、イソプロパノールに対して若干表面が軟化膨潤のきざしを示した。不揮発分濃度を２０wt％に調製した水分散体１００wt部にイソプロピルアルコール１０wt部を添加した場合においては最低造膜は１２℃低下した。膨潤性はそれほど高くないが若干は認められるものとされた。
【００５６】
【実施例８】
下記組成の記録剤（８）を実施例１と同様の手順にて調製し、同様の評価を行なった。結果を表１．に示す。
着色ポリエステル微粒子（Ｂ１） （不揮発分換算）２５．０wt％
ジエチレングリコール １．０wt％
エチレングリコール ３．０wt％
ネオペンチルグリコール １．０wt％
イソプロピルアルコール ０．８wt％
ニトリルトリエタノール ０．２wt％
アクリル系共重合体ラテックス （不揮発分換算）５．０wt％
水 残
ここにアクリル系共重合体ラテックスはメチルメタクリレート、エチルメタクリレート、ブチルメタクリレートからなる乳化重合により得られた共重合体ラテックス粒子である。
平均粒子径 ０．４５μｍ
樹脂比重 １．０４
最低造膜温度 ８４℃
ビカット軟化点 ８０℃
である。本樹脂は、エタノール、エチレングリコール、ニトリルトリエタノールに対して溶解はしなかったが、メタノール、イソプロパノールに対して若干溶解性が観察された。不揮発分濃度を２０wt％に調製した水分散体１００wt部にイソプロピルアルコール１０wt部を添加した場合においては最低造膜は３０℃近く低下した。
【００５７】
【実施例９】
下記組成の記録剤（９）を実施例１と同様の手順にて調製し、同様の評価を行なった。ただし１．０μｍメンブレンフィルターによる濾過工程は省略した。結果を表１．に示す。
着色ポリエステル微粒子（Ｂ１） （不揮発分換算）２５．０wt％
ジエチレングリコール １．０wt％
エチレングリコール ３．０wt％
ニトリルトリエタノール ０．５wt％
クエン酸 ０．２wt％
ポリオレフィン微粒子Ｗ−５００ （不揮発分換算）５．０wt％
水 残
ここにポリオレフィン微粒子は低分子量ポリオレフィン（主にポリエチレン）からなりソープフリー乳化手法により得られた水分散体であり、ケミパールＷ−５００として三井石油化学社より上市されているものであり、
平均粒子径 ２．５０μｍ
樹脂比重 ０．９２
最低造膜温度 ９０℃
ビカット軟化点 ３８℃
である。本樹脂はメタノール、エタノール、イソプロピルアルコール、エチレングリコール、ニトリルトリエタノールに対して溶解せず、膨潤している様子も観察されなかった。さらに不揮発分濃度を２０wt％に調製した水分散体１００wt部にイソプロピルアルコール１０wt部を添加した場合においても最低造膜には変化がなく、粒子径にも変化がないため低級アルコールによる膨潤性は事実上ないと判断された。
【００５８】
【実施例１０】
実施例３において着色ポリエステル微粒子（Ｂ１）を（Ｂ２）に代え、記録剤（１０）とした。
【００５９】
【実施例１１】
実施例４において着色ポリエステル微粒子（Ｂ１）を（Ｂ２）に代え、記録剤（１１）とした。
【００６０】
【実施例１２】
実施例５において着色ポリエステル微粒子（Ｂ１）を（Ｂ２）に代え、記録剤（１２）とした。以下同様に評価した。結果を表１．に示す。
【００６２】
【比較例１】
下記組成の記録剤（１４）を実施例１と同様の手順にて調製し、同様の評価を行なった。結果を表１．に示す。

染料の精製操作は主に無機不純物である硫酸ナトリウムの除去を意味する。本試作インクは樹脂粒子を含まない所謂典型的な水溶性染料型インクである。
【００６３】
【比較例２】
下記組成の記録剤（１５）を実施例１と同様の手順にて調製し、同様の評価を行なった。
着色ポリエステル微粒子（Ｂ１） （不揮発分換算）１５．０wt％
エチレングリコール ５．０wt％
水 残
【００６４】
【比較例３】
マゼンタ顔料Ｃ．Ｉ．ＰｉｇｍｅｎｔＲｅｄ１２２ ２５重量部、スチレン−マレイン酸共重合体部分エステル樹脂（水溶液）不揮発分換算５重量部、水７０重量部をボールミルポットに仕込み、２４時間分散処理し、１μｍメンブレンフィルターにて濾過し記録剤１６とした。
【００６５】
【発明の効果】
以上述べてきたように、本発明の着色水分散体は高記録品位を有する記録剤として優れた特性を有する物であり、筆記具から印刷機等に広く用いることができるものである。[0001]
[Industrial applications]
The present invention relates to an aqueous dispersion of a resin widely used from paints, water-based paints, paper coating agents, coating materials for films, etc. to recording materials, and particularly to writing instruments, markers, and marking pens. The present invention relates to an aqueous dispersion of a colored resin that can be suitably used as an ink recording material for various printing machines, ferroelectric printers, and the like.
[0002]
[Prior art]
2. Description of the Related Art In recent years, measures against environmental problems have been demanded in all fields, and recording materials and inking materials used for printers, printing machines, markers, writing instruments, and the like have also been required to be desolvated and made water-soluble. As the aqueous recording material, those mainly comprising an aqueous solution of a water-soluble dye and those mainly comprising a fine dispersion of a pigment are widely used.
[0003]
As recording materials using water-soluble dyes, there are mainly water-soluble dyes classified as acid dyes, direct dyes and some food dyes, and humectants such as glycols, alkanolamines, and surface tension. To which a surfactant, an alcohol, a resin component as a binder component and the like are added.
Recording materials using these water-soluble dyes are most commonly used because of their high reliability against clogging at the brush tip or recording system. However, a recording material using such a water-soluble dye tends to bleed on recording paper because it is an aqueous solution of the dye. In addition, since it is necessary to increase the apparent drying speed, the ink is prepared so as to quickly penetrate the recording paper, so that the recording quality is inevitably degraded due to ink bleeding. It is obvious that the dye is inferior in water resistance because it is a water-soluble dye. Furthermore, water-soluble dyes which merely permeate into recording paper and are fixed by drying are not said to be "dyed" and have very low light fastness.
[0004]
As a measure for solving the problems of the recording material using a water-soluble dye as described above, the addition of resin fine particles such as an emulsion and a latex has been studied for a long time.
Japanese Patent Application Laid-Open No. 55-18418 discloses a latex which is a kind of a colloid solution in which components such as rubber and resin are dispersed in water in the form of fine particles (particle diameter: about 0.01 to several μm) by an emulsifier. There is a proposal regarding a recording agent for ink jet recording. As the latex preferably used,
Styrene-butadiene copolymer latex,
Acrylonitrile-butadiene copolymer latex,
Polychloroprene latex,
Vinylpyridine-styrene-butadiene latex,
Butyl rubber latex,
Polybutadiene latex,
Polyisoprene latex,
Polysulfide rubber latex,
Such as synthetic rubber-based latex, or
Acrylic ester latex,
Styrene-butadiene resin latex,
Vinyl acetate latex,
PVC latex,
Vinylidene chloride-based latex,
And the like.
[0005]
According to the proposal, the particle diameter of latex particles that can be added is in the range of about 0.01 to several μm. However, if the particle diameter is less than 0.2 μm, the effect of preventing ink bleeding on recording paper is insufficient, and high recording quality cannot be obtained. When the particle diameter is 1.0 μm or more, clogging of the nozzle frequently occurs, and it becomes difficult to use the nozzle from the viewpoint of reliability. Therefore, it is considered that a practically usable range is approximately 0.2 to 1.0 μm.
When such resin fine particles are added to the ink, attention must be paid to the sedimentation or floating due to the difference between the specific gravity of the particles and the specific gravity of the medium. In the case of the water-based ink, it is difficult for the specific gravity of the medium to largely deviate from 1.0. Since the effect of gravity is greater in the fine particles having a size of about 0.2 μm or more than the diffusion force of the particles due to the Brownian motion, the difference between the specific gravity of the particles and the specific gravity of the medium in such a region is 0.1 or less, preferably 0.1 to 0.1. 07 or less.
[0006]
The specific gravity of the synthetic rubber-based latex exemplified in the patent proposal is approximately in the range of 0.9 to 1.0, and although these conditions are satisfied to some extent, many of the synthetic rubbers have an unsaturated double bond in the molecule. There is a problem in light resistance and weather resistance. If the unsaturated bonds are reduced by vulcanization, fixation of the particles on the recording paper is hindered, which causes a problem in recording quality. Furthermore, if the vulcanization is excessive, the specific gravity becomes 1.1 or more, and a problem of sedimentation occurs. Furthermore, such a synthetic rubber-based latex has a low glass transition temperature, so that it is easy to form a film at room temperature, and when dried at the tip of an inkjet nozzle, the nozzle is easily clogged, and the dried product is soft and slightly tacky. It is very difficult to remove it.
The specific gravity of the synthetic resin latex exemplified in this patent reaches 1.1 or more, and particularly, in the case of a synthetic resin containing a halogen element, the specific gravity approaches 1.3 to 1.5. Sedimentation occurs in all areas.
Further, as can be said for these latexes in general, many emulsifiers used in the production of the latex tend to promote the bubbling of the ink and lower the surface tension more than necessary, which is problematic.
[0007]
JP-A-54-146109 proposes a recording material using a water-soluble dye to which vinyl polymer fine particles which are swollen with a solvent and colored with an oil dye are added. As the polymer preferably used, (meth) acrylate-based copolymer fine particles are mainly exemplified, and it is further described that a glass transition temperature of 30 ° C. or lower is a preferable condition. There is no description about the particle size in the proposal. It is obvious that the fine particles swollen with a solvent at such a low glass transition temperature have a film forming property when dried at room temperature, and when such an ink is used, nozzle clogging will frequently occur. It is easily analogized.
[0008]
(Recording material using pigment dispersion)
In order to improve the drawbacks of recording materials using water-soluble dyes, it has been proposed to use carbon black or an organic pigment as a recording material. In a recording material using such a pigment dispersion, the water resistance of the ink is greatly improved. However, these pigments have a high specific gravity of 1.5 to 2.0, so that attention must be paid to sedimentation of dispersed particles. In order to stably disperse such a pigment having a high specific gravity, it is necessary to finely disperse the pigment to an average particle diameter of about 0.1 μm or less, which results in a high dispersion cost and an extremely expensive ink. Further, when the particle diameter is 0.1 μm or less, the effect of preventing bleeding is insufficient, and high-quality recorded characters and images cannot be obtained. Further, there is a problem that the physical properties of the ink, such as surface tension and foaming properties, are restricted by the dispersant used for dispersion.
[0009]
(Recording material using colored resin particles)
A proposal for coloring a water-dispersible resin with an oil-soluble dye or a hydrophobic dye has been made as an ink for inkjet recording. These are proposals regarding “ink using colored polymer fine particles as a recording agent”. For example, JP-A-54-58504 proposes an ink in which a mixture of a hydrophobic dye solution and vinyl polymer fine particles is oil-in-water dispersed. It is disclosed in the text that the vinyl polymer fine particles swell in the solvent of the dye solution by being mixed with the hydrophobic dye solution, and are further colored by the dye. Since a hydrophobic dye is used as a recording agent, the resulting image may have water resistance. In this proposal, water is used as a continuous phase, and colored vinyl polymer particles swollen with a solvent are used as a dispersed phase, so that water has control of ink viscosity, and has a somewhat high viscosity (low volatility) as a solvent. It is allowed to use something.
[0010]
JP-A-55-139471 and JP-A-3-2500069 propose inks using emulsion-polymerized or dispersed-polymer particles dyed with a dye. The gist of the proposal is to prevent bleeding by using colored particles as a dispersoid and water (transparent) as a medium, as in JP-A-54-58504. It needs to be fixed on recording paper by forming a film. From the viewpoint of necessity of film formation and securing of dispersion stability, it has been suggested that a desirable particle size is in a submicron region.
In each proposal, the water-dispersible resin is a vinyl polymer. In these vinyl polymers, it is difficult to perform high-concentration coloring because the solubility of the dye in the resin is low. In Japanese Patent Application Laid-Open No. 54-58504, it is accepted that dyeing properties can be obtained by swelling polymer fine particles with a solvent, but in this case, there is a problem of nozzle clogging due to dry film formation at the nozzle tip. Occurs.
Japanese Patent Application Laid-Open No. 4-185672 discloses a method of dissolving a water-soluble compound in an aqueous medium in an ink composed of colored resin particles and an aqueous medium to reduce the specific gravity difference between the colored resin particles and the aqueous medium to 0.04 or less, and to settle the particles. It has been proposed to prevent Here, inorganic salts are preferably used as the water-soluble compound. However, when such inorganic salts are dissolved in an aqueous medium, the ionic strength in the system increases, and the stability of the dispersion system decreases, so that the colored resin particles aggregate and the fluid properties as an inkjet ink cannot be maintained.
[0011]
JP-A-4-185673 and JP-A-4-185674 disclose that an effective specific gravity is lowered by swelling a colored resin particle with a solvent in an ink composed of a colored resin particle and an aqueous medium. It has been proposed that the specific gravity difference be 0.04 or less. In such a case, it is difficult to avoid nozzle clogging as described above.
As mentioned above, the recording material mainly used for ink jet recording has been mainly reviewed, but the sedimentation of the particles, and the clogging due to dry film formation, are caused by writing instruments, markers, marking pens, other types of printers, and such aqueous printers. This also occurs when a recording material is used.
[0012]
The present inventors have conducted intensive studies in view of such a situation, and found that an aqueous dispersion of a polyester resin can be colored at an extremely high concentration with an oily or hydrophobic dye. It was proposed to use it as ink or as a recording agent for various printers. A recording material using such colored polyester fine particles has characteristics such as good recording quality on recording paper and excellent water resistance of a dry film-formed product, but non-woven fabric, waste, cloth, knit, etc. The recording quality when recording on textiles was not sufficient. This is because the fiber density of such a fiber structure is coarser than that of the recording paper. Further, there were cases where the recording quality was unsatisfactory even for cardboard with low paper quality, recycled paper, and the like. It is easily presumed that the recording quality will be improved by increasing the particle diameter. However, in this case, similarly to the pigment-dispersed recording agent, it is easily analogized that a problem due to sedimentation of particles occurs.
[0013]
[Problems to be solved by the invention]
As described above, the fine particle-dispersed recording material using pigments, colored resin particles, etc. overcomes the problems of the water-soluble dye-type recording material and has no possibility of realizing high recording quality. However, many of them have problems in terms of reliability such as sedimentation of particles and clogging due to dry film formation, and have not been able to replace all of the water-soluble dye-type recording agents.
[0014]
[Means for Solving the Problems]
In view of such a situation, the present inventors have continued intensive research and, as a result, have arrived at the next invention. That is, the present invention
a) 0.1 to 40% by weight of fine particles mainly composed of a polyester resin colored with a dye that is insoluble or hardly soluble in water and soluble in an organic solvent.
b) 0.5 to 15% by weight of synthetic resin fine particles having a specific gravity of 0.9 to 1.1 and an average particle diameter of 0.1 to 3.0 μm
Is a colored water dispersion containing an essential component,
A colored water dispersion, wherein the specific gravity of the synthetic resin fine particles is in a range of 0.93 to 1.00, and the average particle size is in a range of 0.3 to 0.8 μm.
A colored water dispersion, wherein the synthetic resin fine particles are non-swellable with respect to lower alcohols and / or alkylene glycols and / or alkanolamines,
A colored water dispersion, wherein the synthetic resin fine particles are composed of a (co) polymer containing 50% by weight or more of ethylene and / or propylene,
A colored water dispersion, wherein the synthetic resin fine particles are composed of a (co) polymer comprising 50% by weight or more of methylstyrene,
A colored aqueous dispersion, wherein the synthetic resin particles are made of an ethylene / (meth) acrylic acid copolymer,
A colored water dispersion, wherein the synthetic resin fine particles are composed of an ionomer resin composed of an ethylene / (meth) acrylic acid copolymer, and have a Vicat softening point in a range of 40 to 100 ° C;
A colored water dispersion, characterized in that the synthetic resin particles are obtained by an emulsifying means without using an emulsifier,
The polyester resin has an ionic group of 20 to 2000 eq. / Ton is a colored water dispersion characterized by containing in the range of
A colored water dispersion, wherein the ionic group contained in the polyester resin is an organic amine salt of a carboxylic acid group,
A colored water dispersion, wherein the average particle diameter of the polyester resin fine particles is in the range of 0.01 to 0.2 μm.
[0015]
First,
a) With a dye that is insoluble or hardly soluble in water and soluble in an organic solvent
Fine particles mainly composed of colored polyester resin
To explain
The polyester resin in the present invention is obtained by condensation of a polyvalent carboxylic acid and a polyvalent alcohol.
Examples of the polycarboxylic acids used in the polyester resin include dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and aromatic compounds such as diphenic acid. Aromatic dicarboxylic acids, aromatic carboxylic acids such as p-oxybenzoic acid, p- (hydroxyethoxy) benzoic acid, aromatic unsaturated polycarboxylic acids such as phenylenediacrylic acid, succinic acid, adipic acid, azelaic acid, Sebacic acid, aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, hexahydrophthalic acid, tetrahydrophthalic acid, aliphatic unsaturated polycarboxylic acid, and cyclohexanedicarboxylic acid An alicyclic dicarboxylic acid such as an acid; Other trimellitic acid, trimesic acid, can be exemplified such as trivalent or higher polyvalent carboxylic acids such as pyromellitic acid.
[0016]
Examples of the polyvalent alcohols used for the polyester resin include aliphatic polyvalent alcohols, alicyclic polyvalent alcohols, and aromatic polyvalent alcohols.
Examples of the aliphatic polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, and 1,5-butanediol. Pentanediol, 1,6-hexanediol, neopentylglycol, dimethylolheptane, diethyleneglycol, dipropyleneglycol, 2,2,4-trimethyl-1,3-pentaneddiol, polyethyleneglycol Diols, such as aliphatic diols such as phenol, polypropylene glycol and polytetramethylene glycol, and triols and tetraols such as trimethylolethane, trimethylolpropane, glycerin and pentaerthritol. Can be illustrated.
Examples of the alicyclic polyhydric alcohols include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, spiroglycol, hydrogenated bisphenol A, and hydrogenated bisphenol A ethylene oxide. Examples thereof include adducts and propylene oxide adducts, tricyclodecanediol, and tricyclodecanedimethanol.
[0017]
Examples of aromatic polyvalent alcohols include para-xylene glycol, meta-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol, and ethylene oxide adduct of 1,4-phenylene glycol. , Bisphenol A, an ethylene oxide adduct of bisphenol A and a propylene oxide adduct. Further, examples of the polyester polyol include lactone-based polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone.
In addition, a monofunctional monomer may be introduced into the polyester for the purpose of blocking a part of the polar group at the terminal of the polyester polymer.
Monofunctional monomers include benzoic acid, chlorobenzoic acid, bromobenzoic acid, parahydroxybenzoic acid, monoammonium sulfobenzoate, monosodium sulfobenzoate, cyclohexylaminocarbonylbenzoic acid, n-dodecylaminocarbonylbenzoic acid Acid, tert-butylbenzoic acid, naphthalenecarboxylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, salicylic acid, thiosalicylic acid, phenylacetic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, octanecarboxylic acid, lauric acid, stearyl acid And monocarboxylic acids such as lower alkyl esters thereof, and monoalcohols such as aliphatic alcohols, aromatic alcohols and alicyclic alcohols.
[0018]
The polyester resin preferably used in the present invention is an aromatic dicarboxylic acid and / or an alicyclic dicarboxylic acid as a polyvalent carboxylic acid component, and an aliphatic diol and / or an alicyclic diol as a polyvalent alcohol component. Is used. In the present invention, it is preferable to use a polyester resin obtained from an aromatic dicarboxylic acid and an aliphatic diol, or a polyester resin obtained from an alicyclic dicarboxylic acid and an aliphatic diol and an alicyclic diol.
[0019]
The polyester resin can be obtained by a conventional method such as a vacuum polymerization method or a reduced pressure polymerization method. The former is a method used for polymerizing polyethylene terephthalate and the like, which is used for fibers, films, poly bottles and the like, and can obtain a relatively high molecular weight polyester. The latter is a method used when polymerizing an unsaturated polyester resin such as an alkyd resin, and a polyester having a relatively low molecular weight can be obtained. In addition to these conventional methods, a polyester resin can be obtained by an acid chloride method or the like.
The number average molecular weight of the polyester resin in the invention is preferably from 1,000 to 20,000, more preferably from 1500 to 10,000, and even more preferably from 2,000 to 5,000. If the molecular weight is low, the physical properties of the obtained coating film may be insufficient. On the other hand, if the molecular weight is too high, dry film formation may be inhibited.
The glass transition temperature of the polyester resin in the present invention is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, still more preferably 50 ° C. or higher, and even more preferably 60 to 80 ° C. If the glass transition temperature is too low, the dried coating film becomes tacky, which may be inconvenient depending on the use. If the glass transition temperature is too high, dry film formation may be hindered.
[0020]
Examples of the “dye that is insoluble or hardly soluble in water and soluble in an organic solvent” in the present invention include oil-soluble dyes, disperse dyes, and some building bath dyes. These are classified into “Solvent Dye”, “Disperse Dye”, and “Vat Dye” in the color index.
Chemical structure, anthraquinone dye, azo dye, disazo dye, triazo dye, phthalocyanine dye, indigo dye, methine dye, nitro dye, quinophthalone dye, quinoline dye, cyanomethine dye, Triphenylmethane dyes, xanthene dyes and the like can be used.
[0021]
More specifically, as an oil-soluble dye
・ C. I. Solvent Yellow 96
・ C. I. Solvent Yellow 162
・ C. I. Solvent Red 49
・ C. I. Solvent Blue 25
・ C. I. Solvent Blue 35
・ C. I. Solvent Blue 38
・ C. I. Solvent Blue 64
・ C. I. Solvent Blue 70
・ C. I. Solvent Black 3
Etc. can be exemplified. Also as a disperse dye
・ C. I. Disperse Yellow 33
・ C. I. Disperse Yellow 42
・ C. I. Disperse Yellow 54
・ C. I. Disperse Yellow 64
・ C. I. Disperse Yellow 198
・ C. I. Disperse Red 60
・ C. I. Disperse Red 92
・ C. I. Disperse Violet 26
・ C. I. Disperse Violet 35
・ C. I. Disperse Violet 38
・ C. I. Disperse Blue 56
・ C. I. Disperse Blue 60
・ C. I. Disperse Blue 87
At least one dye selected from the following is preferably used. These are particularly excellent in light fastness, sublimation fastness, hue and saturation, and are preferable as three primary colors for process colors. In addition, known dyes and pigments may be used in combination for fine adjustment of hue. Such a dye is blended in a range of 0.2 to 30% by weight with respect to the polyester resin, more preferably 2 to 25% by weight, still more preferably 5 to 20% by weight, and still more preferably 10 to 20% by weight. It is blended in the range of weight%. If the amount is too small, a sufficient coloring density cannot be obtained. Conversely, if the amount is too large, the stability of the aqueous dispersion is impaired.
[0022]
Such a polyester resin preferably contains an ionic group in the range of 20 to 2000 eq./ton.
Examples of the ionic group which may be introduced into the polyester include an alkali metal sulfonate or ammonium sulfonate, an alkali metal carboxylate or ammonium carboxylate, a sulfate group, a phosphate group, a phosphonate group, a phosphinate group or Anionic groups such as ammonium salts and alkali metal salts thereof, and cationic groups such as primary to tertiary amine groups can be used. The ionic group can be introduced by using an ionic group-containing monomer.
In order to introduce a cationic group, 2-aminopropane 1,3-diol, nitrile monoalkanol, nitrile dialkanol, and nitrile trialkanol can be preferably used.
In order to introduce an alkali metal sulfonic acid base or an ammonium sulfonate base into a polyester, sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5 [4- Sulfophenoxy] An alkali metal salt or an ammonium salt of a mono- or polyvalent carboxylic acid having a sulfonic acid group such as isophthalic acid and metasulfobenzoic acid may be copolymerized with the polyester. Examples thereof include salts with alkali metal ions such as Li, Na, and K, alkaline earth metal ions, ammonium ions, primary to quaternary alkyl ammonium ions, and alkanolamines.
[0023]
The content of these ionic groups is required to be 20 to 2000 meq / 1000 g, preferably 20 to 1000 meq / 1000 g, more preferably 50 to 500 meq / 1000 g, and still more preferably 50 to 500 meq / 1000 g of the polyester resin. ２００200 meq / 1000 g.
The ionic group has a function of imparting dispersion stability to the polyester resin fine particles, and if the content of the ionic group is less than a predetermined amount, sufficient water dispersibility may not be obtained. If the content of the group is too large, the polyester resin may be solubilized and the desired aqueous dispersion may not be obtained.
[0024]
The ionic group contained in the polyester resin used in the present invention is particularly preferably an organic amine salt of a carboxylic acid group. Such an ionic group can be obtained by introducing a carboxyl group into the polyester resin and then neutralizing with a base. As the base, an alkali metal, ammonia, or other organic amines can be used. In the present invention, it is particularly preferable to use organic amines. As a method of introducing a carboxyl group into a polyester resin, in a vacuum polymerization method, a method of introducing a polycarboxylic anhydride such as trimellitic anhydride, phthalic anhydride, or pyromellitic anhydride into the system at the final stage of polyester polymerization. Can be exemplified. In the vacuum polymerization method, a carboxyl group remaining at the polyester terminal can be used as it is.
As the organic amine, an alkylamine, an alkanolamine, an alkylalkanolamine, an aromatic amine, a cyclic amine, an alkylenediamine and the like can be used, and the use of an alkanolamine is particularly preferable. Examples of the alkanolamine include a monoalkanolamine, a dialkylmonoalkanolamine, a dialkanolamine, a monoalkyldialkanolamine, and a trialkanolamine, preferably a trialkanolamine, and more preferably 2,2 ′. , 2 ″ -nitrile triethanol, tripropanolamine, tributanolamine and trihexanolamine can be used.
[0025]
The average particle diameter of the polyester resin fine particles in the present invention is preferably in the range of 0.01 to 0.2 μm, more preferably in the range of 0.03 to 0.2 μm, and more preferably in the range of 0.05 to 0.16. Still more preferably, the range of 0.05 to 0.1 μm is still more preferable.
The method for producing the polyester resin fine particles in the present invention is not particularly limited, and can be obtained by using a known mechanical or surface chemistry dispersion method. That is, a method of mechanically emulsifying the solution of the polyester resin in the presence of an emulsifying aid such as a surfactant with a high-speed stirrer such as a homogenizer and removing the solvent can be used. Alternatively, a method in which the resin is directly pulverized and finely dispersed by a jet mill, a freezer mill, a ball mill, an attritor, a sand mill, or the like can be used.
In the present invention, when the polyester resin is an ionic group-containing polyester resin, fine particles can be produced by a transfer self-emulsification method since the polyester resin has self-emulsifying properties.
[0026]
A method of adding water after previously mixing the ionic group-containing polyester resin and the water-soluble organic compound with the fine particle dispersion of the polyester resin, and mixing and heating the ionic group-containing polyester resin, the water-soluble organic compound, and water all at once It can be obtained by a method or the like. At that time, a surfactant or the like may be used in combination.
Examples of water-soluble organic compounds include ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, tert-butyl cellosolve, acetone, methyl ethyl ketone, tetrahydrofuran, and dioxane. Etc. can be used. The water-soluble organic compound is preferably one which can be removed by azeotropic distillation after dispersing the ionic group-containing polyester resin in water.
As a preferred method for obtaining a preferred aqueous dispersion of the colored polyester resin in the present invention, a polyester resin having a predetermined amount of a carboxyl group is first polymerized, and the polyester resin, dye, water-soluble organic compound, and base are sufficiently mixed and dissolved. Thereafter, a method of adding water, dispersing in water, and optionally removing the water-soluble organic compound by azeotropic distillation or the like can be exemplified. Alternatively, a colored water dispersion can be similarly obtained by adding a dye into the system after obtaining the water dispersion of the polyester resin and treating at a high temperature.
[0027]
The aqueous dispersion means a state generally called an emulsion or a colloidal dispersion. The ionic group dissociates in the aqueous medium to form an electric double layer at the interface between the polyester resin and water. When the polyester resin is present in the aqueous system as fine microparticles, the action of the electric double layer causes electrostatic repulsion between the microparticles, and the microparticles are stably dispersed in the aqueous medium. The particle size of the polyester resin fine particles can be controlled by the emulsification conditions such as the ionic group content, the ratio of the polyester resin to the water-soluble organic compound at the time of emulsification, the number of rotations, and the temperature.
The zeta potential of the colored polyester fine particles of the present invention is not particularly limited, but is in the range of 20 to 70 mV, preferably 30 to 60 mV.
In the present invention, after the unsaturated monomer is introduced into the polyester and dispersed in water, the dispersed fine particles can be swollen with styrene, divinylbenzene, acrylic acid or methacrylic acid, or an ester thereof, and then post-crosslinked.
[0028]
next
b) having a specific gravity of 0.9 to 1.1 and an average particle diameter of 0.1 to 3.0 μm
0.5-15% by weight of synthetic resin fine particles
Will be described.
It is essential that the synthetic resin fine particles, which are the second essential component in the present invention, have a specific gravity in the range of 0.9 to 1.1 and an average particle diameter in the range of 0.1 to 3.0 μm.
The specific gravity of the synthetic resin fine particles is preferably in the range of 0.93 to 1.00, and more preferably in the range of 0.94 to 0.98. The average particle size is preferably in the range of 0.1 to 1.0 μm, more preferably in the range of 0.2 to 0.8 μm, and still more preferably in the range of 0.3 to 0.8 μm. If the specific gravity is below this range, there is a possibility that phase separation will occur due to floating of particles when the colored aqueous dispersion is stored for a long period of time. If the specific gravity greatly exceeds this range, sedimentation may occur. If the average particle diameter is below this range, the recording quality is not sufficiently improved, and bleeding is likely to occur particularly on poor-quality paper such as recycled paper.
[0029]
If the average particle size exceeds this range, the risk of phase separation due to sedimentation or floating increases, and the risk of clogging of the pen tip increases. More interestingly, when particles having a particle size exceeding this range are added, the bleeding preventing effect gradually decreases. This is considered to be because the effect of the particles closing the fiber gap of the recording paper is rather weakened because the diameter of the particles is too large. In the present invention, the lower limit of the particle size distribution is not limited as long as a problem such as an increase in the viscosity of the colored aqueous dispersion does not occur, and a range up to about 0.01 μm is allowable. However, the upper limit of the particle size distribution needs to be controlled to about 5.0 μm, preferably 3.0 μm, more preferably 2.0 μm or less. That is, the preferred particle size distribution in the present invention is not necessarily a normal distribution, and a shape with a slight tail on the small-diameter particle side is preferable. Highly monodisperse particles are not always preferred.
[0030]
Further, such synthetic resin fine particles are required to be non-swellable with respect to a lower alcohol and / or an alkylene glycol and / or an alkanolamine which is a water-soluble organic compound which is a colored water dispersion additive. Here, the term "non-swellable" means that the resin does not dissolve in the organic compound as a physical property as a bulk of the resin, but means that the resin does not absorb the organic compound in an amount of 10 wt%, preferably 5 wt% or more. From another viewpoint, it means that such a water dispersion of resin particles does not cause a decrease in film forming temperature of 10 ° C. or more, preferably 5 ° C. or more. When these water-soluble organic compounds added to the colored water dispersion are swelled, dry film formation of resin particles occurs at the tip of the pen, causing clogging of the pen.
[0031]
In the resin fine particles used in the present invention, the minimum film-forming temperature is preferably 40 ° C or higher, more preferably 60 ° C or higher, still more preferably in the range of 70 to 100 ° C, and furthermore The temperature is preferably in the range of 80 to 100 ° C. In order to realize such a minimum film forming temperature, the Vicat softening point defined by ASTM D1525-70 is preferably from 40 to 100, more preferably from 45 to 80 ° C, and still more preferably from 50 to 70 ° C. It is preferable that
[0032]
The material of the synthetic resin fine particles in the present invention is not particularly limited, and a known vinyl polymer, condensation polymer, or the like having the above-mentioned characteristics can be used.
As resin fine particles having such properties, a (co) polymer containing 50% by weight or more of ethylene and / or propylene, a (co) polymer composed of 50% by weight or more of methylstyrene, and an ethylene / (meth) acrylic acid copolymer Can be exemplified. As methylstyrene, any of isomers at the α, ortho, meta and para positions may be used, but those having a methyl group at the meta and para positions are particularly preferred. Such resin fine particles can be obtained by any method such as a so-called emulsion polymerization method, and in the present invention, when resin fine particles obtained by an emulsion polymerization method are particularly used, those obtained by a method using no emulsifier such as soap-free emulsion polymerization. It is preferred to use
[0033]
The so-called resin particles particularly preferably used in the present invention are mainly composed of an ethylene / (meth) acrylic acid copolymer and partially ion-crosslinked by an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. It is preferable to use an aqueous dispersion composed of an ionomer resin. Further, such an ionomer resin preferably has a Vicat softening point in the range of 40 to 100 ° C. An aqueous dispersion of such a resin can be obtained by a method other than emulsion polymerization, such as forced mechanical emulsification using both heating and mechanical stirring, and the degree of freedom of a method for obtaining a fine dispersion of resin particles without using an emulsifier. Is high. Examples of aqueous dispersions of such resins include Chemipearl S-100, S-200, S-300, and SA-100 types (trade names, manufactured by Mitsui Petrochemical Co., Ltd.).
[0034]
The synthetic resin fine particles used in the present invention preferably have a non-spherical shape. The non-spherical shape preferably has an average degree of non-sphericity of 1.2 or more, more preferably 1.5 or more, still more preferably 2.0 or more, and even more preferably 2.5 or more.
Where the non-sphericity is
(1) In the projected figure which projected the particle on the plane
The ratio of the circumference of the projected figure to the circumference of the area-converted circle
(2) Ratio of major axis to minor axis in planar projection figure
(3) For specific surface area calculated from volume-converted particle diameter
Ratio of measured specific surface area
(4) The ratio of the diameter of the circumscribed circle to the equivalent circle diameter in a planar projection figure
Preferably, the smallest value among the numerical values obtained by these methods is defined as the non-sphericity. The non-sphericity is preferably measured using an image processing device or the like. Since it is expected that a considerable measurement error will occur in actual measurement, it is necessary to calibrate in advance using particles having a high sphericity, for example, latex particles for microscope calibration.
[0035]
The weight-converted particle diameter has the same meaning as the volume-converted particle diameter, and indicates the particle diameter of a solid sphere having the same weight or volume as the non-spherical particles. The weight-converted particle diameter can be preferably determined by the Coulter counter method. In a centrifugal sedimentation type particle size distribution meter, accurate measurement is difficult because the particle shape affects the sedimentation velocity. Also in a light scattering type particle size distribution meter, accurate evaluation is difficult because the particle shape affects the scattered light intensity distribution. As an alternative, a sphere-converted diameter obtained by using an image processing device can be used.
[0036]
In the present invention, both the colored polyester fine particles and the synthetic resin fine particles are essential components, but the content is 0.1 to 40% by weight of the colored polyester fine particles and 0.5 to 15% by weight of the synthetic resin fine particles. Yes, colored polyester fine particles 2 to 40 wt%, synthetic resin fine particles 1 to 10 wt% of synthetic resin fine particles are preferable, colored polyester fine particles 5 to 40 wt%, synthetic resin fine particles 2 to 8 wt% of synthetic resin fine particles are more preferable, and colored polyester fine particles More preferably, the content is 10 to 30% by weight and the fine synthetic resin particles are 2 to 8% by weight. The remainder is preferably an aqueous medium. In the present invention, it is preferable that the relationship of the particle diameter of the colored polyester resin particles ≦ the particle diameter of the synthetic resin particles be satisfied. Here, the particle size is an average particle size or a maximum particle size.
[0037]
A fluorine-based or silicone-based antifoaming agent can be added to the colored water dispersion of the present invention. Further, various fungicides and fungicides, and if necessary, inorganic and organic pigments can be added to such an extent that transparency is not impaired.
Addition of a trace amount of an alkali metal ion or an alkaline earth metal ion of about 5 to 50 ppm may be preferable in order to lower the viscosity of the aqueous dispersion.
The pH of the colored water dispersion of the invention is preferably 4 or more, more preferably 6 or more, still more preferably 7.5 or more, and still more preferably the range of 7.5 to 9.5.
The viscosity of the colored aqueous dispersion of the present invention is preferably in the range of 1.5 to 30 centipoise, more preferably 1.8 to 15 centipoise, still more preferably 2.0 to 10 centipoise. A range of 0 centipoise is additionally preferred. The surface tension of the colored aqueous dispersion of the present invention is not particularly limited, but is preferably 10 to 72, more preferably 20 to 70, and still more preferably 30 to 60 dyn / cm at 25 ° C.
[0038]
Although the viscosity of the colored aqueous dispersion of the present invention is not particularly limited, it is 0.9 to 100 at 25C, preferably 1.0 to 20, more preferably 1.2 to 5.0, and still more preferably. Ranges from 1.3 to 2.8 centipoise.
The aqueous medium can contain various water-soluble additives. Examples of the additive include a water-soluble organic compound. Examples of the water-soluble organic compound include methanol, ethyl alcohol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butyl cellosolve, tert-butyl cellosolve, and diethylene glycol. , Triethylene glycol, polyethylene glycol, thiodiglycol, glycerin, 2,2 ′, 2 ″ -nitrile triethanol, ethylenediamine, alkylene glycol monoether and the like. Such a water-soluble organic compound can be appropriately added in a range not exceeding 50% of the aqueous medium.
A fluorine-based or silicone-based antifoaming agent can be added to the aqueous medium of the present invention. Further, various fungicides and fungicides, and if necessary, inorganic and organic pigments can be added to such an extent that transparency is not impaired.
[0039]
Also, addition of a small amount of an alkali metal ion or an alkaline earth metal ion of about 5 to 50 ppm is preferable for decreasing the viscosity of the aqueous dispersion.
The pH of the aqueous dispersion of the present invention is preferably 4 or more, more preferably 6 or more, still more preferably 7.5 or more, and still more preferably the range of 7.5 to 9.5.
In the present invention, an ultraviolet absorber, an antioxidant and the like can be added for the purpose of improving light resistance and heat resistance.
Salicylate compounds, benzophenone compounds, benzotriazole compounds and the like can be used as the ultraviolet absorber and light stabilizer.
Examples of the metal deactivator include N-salicyloyl-N'-aldehyde hydrazine, N-salicyloyl-N'-acetylhydrazine, N, N'-diphenyl-oxamide, N, N'-di (2-hydroxyphenyl) oxamide and the like. Can be used.
As the ozone deterioration inhibitor, 6-ethoxy-2,2,4-trimethyl-1,2 dihydroquinoline, N-phenyl-N'-isopropyl-p-phenylenediamine and the like can be used.
As the radical chain inhibitor (primary antioxidant), a phenolic compound, an amine compound, an ascorbic acid compound or the like can be used.
As a peroxide decomposing agent (secondary antioxidant), a sulfur compound can be used, and as a synergist, citric acid, phosphoric acid, or the like can be used.
In the present invention, it is preferable to use at least one ultraviolet absorber selected from benzotriazole, benzophenone, and benzosalicylate. The compounding amount of these antioxidants is about 0.01 to 5.0% by weight, preferably about 0.02 to 1.0% by weight, and more preferably about 0.05 to 0.5% by weight, based on the polyester resin.
[0040]
The fine particles of the colored polyester resin, which is the first component in the colored aqueous dispersion of the present invention, have a high concentration, high transparency, and a function relating to good coloring properties. Such a property is because the polyester resin of the present invention has a very large tolerance for dissolving the dye, and cannot be obtained with an aqueous dispersion obtained by vinyl-based emulsion polymerization of styrene, acrylic, vinyl chloride and the like.
On the other hand, the synthetic resin fine particles as the second component in the colored aqueous dispersion of the present invention have a recording quality, and in particular, have a function of preventing bleeding in a recording medium in which bleeding easily occurs. As described above, it is widely known that the recording quality is improved when resin fine particles are added to a recording agent, and many patent proposals have been made. However, they are concerned only with the recording quality, and do not give any consideration to the storage stability of the recording agent itself and the reliability against pen tip clogging. An object of the present invention is to provide an ink that achieves high recording quality while satisfying storage stability and reliability against clogging, and among specific synthetic resin fine particles, only a specific substance is used for this purpose. Was found to be satisfied. In the present invention, the specific gravity of the resin and the particle size of the resin are simultaneously defined, but it is only when these are compatible that the storage stability and the recording quality are compatible. Furthermore, by satisfying this condition and having a specific softening temperature and realizing characteristics in which the physical properties are not greatly affected by other added components, reliability against pen tip clogging is ensured.
[0041]
Further, in the present invention, it is more preferable to blend the synthetic resin fine particles having such properties together with the colored polyester fine particles to achieve a more preferable result. It should be noted that the recording density is improved in such a configuration. This fact is based on the fact that the colored polyester fine particle component, which permeates and diffuses along with the medium (water) along the recording paper fibers, is blocked by the added synthetic resin fine particles, thereby suppressing bleeding and the surface of the recording paper. It can be understood that this is because a relatively large amount remains in the vicinity. This effect is particularly noticeable in synthetic resin fine particles satisfying the limiting conditions of the present invention, and conversely, the degree of the bleeding prevention effect can be evaluated. Although the colored polyester resin fine particles themselves also have a bleeding prevention function, the present invention exhibits a higher bleeding prevention function.
[0042]
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the Examples shown here. .
【Example】
[Polymerization of polyester resin]
In an autoclave equipped with a thermometer and a stirrer,

Was heated at 150 to 220 ° C. for 180 minutes to perform a transesterification reaction. Next, after the temperature was raised to 240 ° C., the pressure of the system was gradually reduced to 10 mmHg 30 minutes later, and the reaction was continued for 90 minutes. A copolymerized polyester resin (A1) was obtained. The resulting copolymerized polyester resin had an average molecular weight of 3,100, an acid value of 5 eq./ton, a glass transition temperature of 58 ° C., and a sodium sulfonate group equivalent of 98 eq. Ton.
[0043]
In an autoclave equipped with a thermometer and a stirrer,
196 parts by weight of cyclohexanedicarboxylic acid dimethyl ester,
102 parts by weight of ethylene glycol,
99 parts by weight of tricyclodecane dimethanol,
0.1 parts by weight of tetrabutoxy titanate,
Was heated at 150 to 220 ° C. for 180 minutes to perform a transesterification reaction. Next, after the temperature was raised to 240 ° C., the pressure of the system was gradually reduced to 10 mmHg after 30 minutes, and the reaction was continued for 120 minutes. Thereafter, the autoclave was replaced with nitrogen gas, and the pressure was adjusted to atmospheric pressure. Keep the temperature at 200 ° C,
Add 4 parts by weight of trimellitic anhydride,
The reaction was carried out for 60 minutes to obtain a copolymerized polyester resin (A2). The resulting copolymerized polyester resin had an average molecular weight of 3,500, an acid value of 214 eq./ton, and a glass transition temperature of 70 ° C.
[0044]
[Production of colored aqueous dispersion]
200 parts by weight of a polyester resin (A1), 100 parts by weight of methyl ethyl ketone, 50 parts by weight of tetrahydrofuran, thermal transfer SE0780 as a dye were placed in a four-necked 10-liter separable flask equipped with a thermometer, a condenser, and a stirring blade. 20 parts by weight of an oil-based dye cake (manufactured by BASF) were charged and dissolved at 70 ° C. Next, 500 parts by weight of ion-exchanged water at 70 ° C. was added and the mixture was dispersed in water, and then distilled in a distillation flask until the fraction temperature reached 103 ° C. to obtain a colored polyester aqueous dispersion (B1). The finely dispersed particles present in the obtained aqueous polyester dispersion had an average particle size of 0.12 μm and a zeta potential of −46 mV.
200 parts by weight of a polyester resin (A2), 200 parts by weight of methyl ethyl ketone, 100 parts by weight of tetrahydrofuran, and C.I. as a dye were placed in a four-necked 10-liter separable flask equipped with a thermometer, a condenser, and a stirring blade. I. Disperse Red 60 (AmesNega) [manufactured by Mitsui Toatsu Dye] 10 parts by weight of a conc cake and Macrolex Yellow 3G [manufactured by BAYER] 10 parts by weight were charged and dissolved at 70 ° C.
[0045]
Next, after adding 6 parts by weight of 2,2 ′, 2 ″ -nitrile triethanol as a base, 500 parts by weight of ion-exchanged water at 70 ° C. was added and dispersed in water. Distillation was performed until the temperature reached 103 ° C, and after cooling, water was added to obtain a colored polyester aqueous dispersion (B2) having a solid content concentration of 25%. The average particle size of the finely dispersed particles present in the obtained aqueous polyester dispersion was 0.22 μm, and the zeta potential was −55 mV.
[0046]
Embodiment 1
Samples were mixed and prepared so as to have the following composition, and filtered with a 1.0 μm membrane filter to obtain a recording agent (1).
Colored polyester fine particles (B1) (in terms of nonvolatile content) 15.0 wt%
Ethylene glycol 4.0wt%
Ethyl alcohol 1.0wt%
Ethylene-propylene copolymer fine particles (non-volatile content) 5.0 wt%
Remaining water
Here, the ethylene-propylene copolymer fine particles are an aqueous dispersion of copolymer resin particles obtained by soap-free emulsion polymerization composed of 90 wt% of ethylene and 10 wt% of propylene,
Average particle size 0.38μm
Resin specific gravity 0.92
Minimum film formation temperature 95 ℃
Vicat softening point 76 ℃
It is.
[0047]
The resin did not dissolve in methanol, ethanol, isopropyl alcohol, ethylene glycol, or nitrile triethanol, and no swelling was observed. Furthermore, even when 10 wt parts of isopropyl alcohol are added to 100 wt parts of the aqueous dispersion prepared to have a nonvolatile concentration of 20 wt%, the minimum film formation does not change and the particle diameter does not change, so that the swelling property by the lower alcohol is not changed. It was determined not to go up.
The viscosity of the recording agent was adjusted to 3.2 centipoise, and the surface tension was adjusted to 52 dyn / cm. Further, in the following Examples and Comparative Examples, from the viewpoint of comparison under certain conditions, the viscosity of the recording agent falls within the range of 2.5 to 4.0 centipoise, and the surface tension falls within the range of 48 to 54 dyn / cm. Was adjusted as follows.
The average particle diameter was measured by a light scattering particle size distribution meter, the resin specific gravity was measured by a floating / sedimentation method, the minimum film forming temperature was measured by a conventional method, and the Vicat softening point was measured by a method according to ASTM D1525-70.
[0048]
Using the obtained prototype recording agent (1), a line having a width of 0.3 mm was scored on recycled paper in Karasuguchi, and the recording quality was visually evaluated. Similarly, a line of 0.3 mm was also ruled on the calligraphy half-paper, and the thickness of the line was determined from the original line width and the actually ruled line width, and the width was determined as the bleed width. The scribed paper was immersed in ion-exchanged water for 5 minutes, and the water resistance was evaluated based on the presence or absence of bleeding of the coloring material. A solid image was formed on a recording paper with a paint brush so as to have a dry average film thickness (in terms of weight) of 1.0 μm, and the recording density was measured with a Macbeth optical densitometer. Further, the test recording agent was filled in a test tube having a depth of 10 cm, sealed, and allowed to stand for 3 months. The storage stability was evaluated based on the solid content ratio of the recording agent sampled from a portion 1 cm above the recording material. Table 1 shows the results. Shown in
[0049]
[Table 1]

Table 1. During ~
MFT: Minimum film formation temperature
SP: Vicat softening point
Recording quality (visual): Whisker noise per 1 cm line length (feathering)
Less than one ◎
1 or 2 ○
2 to 4 △
4 or more ×
It is.
[0050]
Embodiment 2
A recording agent (2) having the following composition was prepared in the same procedure as in Example 1, and the same evaluation was performed. Table 1 shows the results. Shown in

Here, the paramethylstyrene-butyl methacrylate copolymer fine particles are an aqueous dispersion of copolymer resin particles obtained by soap-free emulsion polymerization comprising 75% by weight of paramethylstyrene, 20% by weight of butyl methacrylate, and 5% by weight of divinylbenzene. ,
Average particle size 0.45μm
Resin specific gravity 1.02
Minimum film formation temperature 102 ℃
Vicat softening point 95 ℃
It is. This resin did not dissolve in methanol, ethanol, isopropanol, ethylene glycol, and nitrile triethanol, but slightly swelled in methanol. When 10 wt parts of isopropyl alcohol were added to 100 wt parts of the aqueous dispersion prepared to have a nonvolatile concentration of 20 wt%, the minimum film formation decreased by about 4 ° C. Was determined to be low.
[0051]
Embodiment 3
A recording agent (3) having the following composition was prepared in the same procedure as in Example 1, and the same evaluation was performed. Table 1 shows the results. Shown in
Colored polyester fine particles (B1) (in terms of nonvolatile content) 15.0 wt%
Ethylene glycol 5.0 wt%
Isopropyl alcohol 1.0wt%
Ionomer resin fine particles S-200 (non-volatile content conversion) 5.0 wt%
Remaining water
Here, the ionomer resin fine particles are composed of an ethylene-methacrylic acid copolymer (80 to 90% by weight of ethylene, 10 to 20% by weight of methacrylic acid) partially ion-crosslinked with an alkali metal ion, and an aqueous dispersion obtained by a soap-free emulsification method. And is marketed by Mitsui Petrochemical Company as Chemipearl S-200,
Average particle size 0.43μm
Resin specific gravity 0.95
Minimum film formation temperature 85 ℃
Vicat softening point 57 ℃
It is. The resin did not dissolve in methanol, ethanol, isopropyl alcohol, ethylene glycol, or nitrile triethanol, and no swelling was observed. Furthermore, even when 10 wt parts of isopropyl alcohol are added to 100 wt parts of the aqueous dispersion prepared to have a nonvolatile concentration of 20 wt%, the minimum film formation does not change and the particle diameter does not change, so that the swelling property by the lower alcohol is not changed. It was determined not to go up.
[0052]
Embodiment 4
A recording agent (4) having the following composition was prepared in the same procedure as in Example 1, and the same evaluation was performed. Table 1 shows the results. Shown in
Colored polyester fine particles (B1) (in terms of nonvolatile content) 15.0 wt%
Propylene glycol 5.0 wt%
Butanol 0.8wt%
Nitrile triethanol 0.2wt%
Citric acid 0.1wt%
Ionomer resin fine particles S-300 (nonvolatile content conversion) 2.0 wt%
Remaining water
Here, the ionomer resin fine particles are composed of an ethylene-methacrylic acid copolymer (80 to 90% by weight of ethylene, 10 to 20% by weight of methacrylic acid) partially ion-crosslinked with an alkali metal ion, and an aqueous dispersion obtained by a soap-free emulsification method. Which is marketed by Mitsui Petrochemical Company as Chemipearl S-300,
Average particle size 0.53μm
Resin specific gravity 0.95
Minimum film formation temperature 94 ℃
Vicat softening point 67 ℃
It is. This resin was judged to have practically no swellability with a lower alcohol, similarly to the ionomer resin used in Example 3.
[0053]
Embodiment 5
A recording agent (5) having the following composition was prepared in the same procedure as in Example 1, and the same evaluation was performed. Table 1 shows the results. Shown in
Colored polyester fine particles (B1) (in terms of nonvolatile content) 15.0 wt%
Ethylene glycol 5.0 wt%
Modified ionomer resin fine particles SA-100 (non-volatile content conversion) 2.0 wt%
Remaining water
Here, the modified ionomer resin fine particles comprise a graft copolymer obtained by further grafting styrene to an ethylene-methacrylic acid copolymer (ethylene: 80 to 90 wt%, methacrylic acid: 10 to 20 wt%) partially ion-crosslinked with an alkali metal ion. An aqueous dispersion obtained by a soap-free emulsification method, which is marketed by Mitsui Petrochemical Company as Chemipearl SA-100,
Average particle size 0.75μm
Resin specific gravity 1.00
Minimum film formation temperature 70 ℃
Vicat softening point 55 ℃
It is. This resin did not dissolve in methanol, ethanol, isopropanol, ethylene glycol, and nitrile triethanol, but slightly swelled in methanol. When 10 wt. Parts of isopropyl alcohol were added to 100 wt. Parts of the aqueous dispersion prepared to have a nonvolatile concentration of 20 wt.%, The minimum film formation decreased by about 2 ° C. Was determined to be low.
[0054]
Embodiment 6
A recording agent (6) having the following composition was prepared in the same procedure as in Example 1, and the same evaluation was performed. Table 1 shows the results. Shown in
Colored polyester fine particles (B1) (in terms of nonvolatile content) 30.0wt%
Styrene-butadiene copolymer latex (non-volatile content conversion) 2.0 wt%
Remaining water
Here, the styrene-butadiene copolymer latex is a latex obtained by emulsion polymerization of a copolymer containing 25% by weight of styrene.
Average particle size 0.38μm
Resin specific gravity 0.97
Minimum film formation temperature 24 ℃
Vicat softening point 10 ℃
It is. This resin was dissolved in methanol, ethanol, and isopropanol. It did not dissolve in ethylene glycol and nitrile triethanol. When 10 wt parts of isopropyl alcohol were added to 100 wt parts of the aqueous dispersion having a nonvolatile concentration adjusted to 20 wt%, the minimum film formation was lowered by 24 ° C. or more.
[0055]
Embodiment 7
A recording agent (7) having the following composition was prepared in the same procedure as in Example 1, and the same evaluation was performed. Table 1 shows the results. Shown in
Colored polyester fine particles (B1) (in terms of nonvolatile content) 25.0 wt%
Ethanol 5.0wt%
Polymethyl methacrylate latex (non-volatile content) 1.0wt%
Remaining water
Here, the polymethyl methacrylate latex is commercially available as Microgel P-5002 [Nippon Paint].
Average particle size 0.52μm
Resin specific gravity 1.19
Minimum film formation temperature 120 ° C
Vicat softening point 110 ℃
It is. This resin did not dissolve in methanol, ethanol, isopropanol, ethylene glycol, and nitrile triethanol, but showed a slight softening and swelling surface on methanol and isopropanol. When 10 wt parts of isopropyl alcohol were added to 100 wt parts of the aqueous dispersion prepared to have a nonvolatile content of 20 wt%, the minimum film formation decreased by 12 ° C. The swellability was not very high, but was slightly recognized.
[0056]
Embodiment 8
A recording agent (8) having the following composition was prepared in the same procedure as in Example 1, and the same evaluation was performed. Table 1 shows the results. Shown in
Colored polyester fine particles (B1) (in terms of nonvolatile content) 25.0 wt%
Diethylene glycol 1.0wt%
Ethylene glycol 3.0wt%
Neopentyl glycol 1.0wt%
Isopropyl alcohol 0.8wt%
Nitrile triethanol 0.2wt%
Acrylic copolymer latex (non-volatile content) 5.0 wt%
Remaining water
Here, the acrylic copolymer latex is a copolymer latex particle obtained by emulsion polymerization comprising methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
Average particle size 0.45μm
Resin specific gravity 1.04
Minimum film formation temperature 84 ℃
Vicat softening point 80 ℃
It is. This resin did not dissolve in ethanol, ethylene glycol and nitrile triethanol, but slightly soluble in methanol and isopropanol. When 10 wt parts of isopropyl alcohol was added to 100 wt parts of the aqueous dispersion prepared to have a nonvolatile content of 20 wt%, the minimum film formation decreased by about 30 ° C.
[0057]
Embodiment 9
A recording agent (9) having the following composition was prepared in the same procedure as in Example 1, and the same evaluation was performed. However, a filtration step using a 1.0 μm membrane filter was omitted. Table 1 shows the results. Shown in
Colored polyester fine particles (B1) (in terms of nonvolatile content) 25.0 wt%
Diethylene glycol 1.0wt%
Ethylene glycol 3.0wt%
Nitrile triethanol 0.5wt%
Citric acid 0.2wt%
Polyolefin fine particles W-500 (non-volatile content conversion) 5.0 wt%
Remaining water
Here, the polyolefin fine particles are a low molecular weight polyolefin (mainly polyethylene), an aqueous dispersion obtained by a soap-free emulsification method, which is marketed by Mitsui Petrochemical Company as Chemipearl W-500,
Average particle size 2.50 μm
Resin specific gravity 0.92
Minimum film formation temperature 90 ℃
Vicat softening point 38 ℃
It is. The resin did not dissolve in methanol, ethanol, isopropyl alcohol, ethylene glycol, or nitrile triethanol, and no swelling was observed. Furthermore, even when 10 wt parts of isopropyl alcohol are added to 100 wt parts of the aqueous dispersion prepared to have a nonvolatile concentration of 20 wt%, the minimum film formation does not change and the particle diameter does not change, so that the swelling property by the lower alcohol is not changed. It was determined not to go up.
[0058]
Embodiment 10
In Example 3, the coloring agent fine particles (B1) were replaced with (B2), and a recording agent (10) was used.
[0059]
Embodiment 11
In Example 4, the recording agent (11) was used in place of the colored polyester fine particles (B1) in place of (B2).
[0060]
Embodiment 12
In Example 5, a coloring agent (12) was used instead of the colored polyester fine particles (B1) in place of (B2). Hereinafter, the same evaluation was performed. Table 1 shows the results. Shown in
[0062]
[Comparative Example 1]
A recording agent (14) having the following composition was prepared in the same procedure as in Example 1, and the same evaluation was performed. Table 1 shows the results. Shown in

The operation of purifying the dye mainly means removal of sodium sulfate which is an inorganic impurity. This prototype ink is a so-called typical water-soluble dye ink containing no resin particles.
[0063]
[Comparative Example 2]
A recording agent (15) having the following composition was prepared in the same procedure as in Example 1, and the same evaluation was performed.
Colored polyester fine particles (B1) (in terms of nonvolatile content) 15.0 wt%
Ethylene glycol 5.0 wt%
Remaining water
[0064]
[Comparative Example 3]
Magenta pigment C.I. I. Pigment Red 122, 25 parts by weight of styrene-maleic acid copolymer partial ester resin (aqueous solution), 5 parts by weight in terms of non-volatile content, and 70 parts by weight of water are charged in a ball mill pot, dispersed for 24 hours, filtered through a 1 μm membrane filter, and filtered. 16 was set.
[0065]
【The invention's effect】
As described above, the colored aqueous dispersion of the present invention has excellent properties as a recording agent having high recording quality, and can be widely used for writing instruments to printing machines and the like.

Claims (11)

a) 0.1 to 40% by weight of fine particles mainly composed of a polyester resin colored with a dye that is insoluble or hardly soluble in water and soluble in an organic solvent.
b) 0.5 to 15% by weight of synthetic resin fine particles having a specific gravity of 0.9 to 1.1 and an average particle diameter of 0.1 to 3.0 μm
A colored aqueous dispersion containing, as an essential component. A colored water dispersion, wherein the specific gravity of the synthetic resin fine particles is in the range of 0.93 to 1.00 and the average particle size is in the range of 0.3 to 0.8 μm. A colored aqueous dispersion, wherein the synthetic resin fine particles are non-swellable with respect to a lower alcohol and / or an alkylene glycol and / or an alkanolamine. A colored aqueous dispersion, wherein the synthetic resin fine particles comprise a (co) polymer (copolymer or homopolymer) containing 50% by weight or more of ethylene and / or propylene. A colored aqueous dispersion, wherein the synthetic resin fine particles comprise a (co) polymer comprising 50% by weight or more of methylstyrene. A colored aqueous dispersion, wherein the synthetic resin fine particles comprise an ethylene / (meth) acrylic acid copolymer. A colored aqueous dispersion, wherein the synthetic resin fine particles are made of an ionomer resin made of an ethylene / (meth) acrylic acid copolymer, and have a Vicat softening point in the range of 40 to 100 ° C. A colored aqueous dispersion, wherein the synthetic resin fine particles are obtained by an emulsifying means without using an emulsifier. The polyester resin has an ionic group of 20 to 2000 eq. / Colored water dispersion characterized by containing in the range of / ton. A colored aqueous dispersion, wherein the ionic group contained in the polyester resin is an organic amine salt of a carboxylic acid group. A colored aqueous dispersion, wherein the average particle diameter of the polyester resin fine particles is in the range of 0.01 to 0.2 µm.