JP4534437B2 - Treated pigments and inks - Google Patents

Description

【００１８】
Ｘ：−ＳＯ₂−、−ＣＯ−、−ＣＨ₂ＮＨＣＯＣＨ₂−、−ＣＨ₂−または直接結合を表す。
ｎ：１〜１０の整数を表す。
Ｒ₁、Ｒ₂：それぞれ独立に、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいフェニル基、またはＲ₁ とＲ₂ とで一体となって更なる窒素、酸素または硫黄原子を含む置換されていてもよい複素環を表す。アルキル基およびアルケニル基の炭素数は１〜１０が好ましい。
式（２）
【００１９】
【化２】

【００２０】
Ｒ₁、Ｒ₂：それぞれ独立に、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいフェニル基、またはＲ₁ とＲ₂ とで一体となって更なる窒素、酸素または硫黄原子を含む置換されていてもよい複素環を表す。アルキル基およびアルケニル基の炭素数は１〜１０が好ましい。
式（３）
【００２１】
【化３】

【００２２】
Ｘ：−ＳＯ₂−、−ＣＯ−、−ＣＨ₂ＮＨＣＯＣＨ₂−、−ＣＨ₂−または直接結合を表す。
Ｒ₃：置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいフェニル基を表す。アルキル基およびアルケニル基の炭素数は１〜１０が好ましい。
Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇：それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいフェニル基を表す。アルキル基およびアルケニル基の炭素数は１〜５が好ましい。
式（４）
【００２３】
【化４】

【００２４】
Ｘ：−ＳＯ₂−、−ＣＯ−、−ＣＨ₂ＮＨＣＯＣＨ₂−、−ＣＨ₂−または直接結合を表す。
Ｙ：−ＮＲ₈−Ｚ−ＮＲ₉−または直接結合を表す。
Ｒ₈、Ｒ₉：それぞれ独立に水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいフェニル基を表す。アルキル基およびアルケニル基の炭素数は１〜５が好ましい。
Ｚ：置換されていてもよいアルキレン基、置換されていてもよいアルケニレン基、または置換されていてもよいフェニレン基を表す。アルキル基およびアルケニル基の炭素数は１〜８が好ましい。
Ｐ：式（５）で示される置換基または式（６）で示される置換基を表す。
Ｑ：水酸基、アルコキシル基、式（５）で示される置換基または式（６）で示される置換基を表す。
式（５）
【００２５】
【化５】

【００２６】
ｎ：１〜１０の整数を表す。
Ｒ₁、Ｒ₂：それぞれ独立に、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいフェニル基、またはＲ₁ とＲ₂ とで一体となって更なる窒素、酸素または硫黄原子を含む置換されていてもよい複素環を表す。アルキル基およびアルケニル基の炭素数は１〜１０が好ましい。
式（６）
【００２７】
【化６】

【００２８】
Ｒ₃：置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいフェニル基を表す。アルキル基およびアルケニル基の炭素数は１〜１０が好ましい。
Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇：それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいフェニル基を表す。アルキル基およびアルケニル基の炭素数は１〜５が好ましい。
Ｐで表される色素残基としては、例えばジケトピロロピロール系色素、アゾ、ジスアゾ、ポリアゾ等のアゾ系色素、フタロシアニン系色素、ジアミノジアントラキノン、アントラピリミジン、フラバントロン、アントアントロン、インダントロン、ピラントロン、ビオラントロン等のアントラキノン系色素、キナクリドン系色素、ジオキサジン系色素、ペリノン系色素、ペリレン系色素、チオインジゴ系色素、イソインドリン系色素、イソインドリノン系色素、キノフタロン系色素、スレン系色素、金属錯体系色素、アントラキノン残基、トリアジン残基などがある。
また、トリアジン残基としては、メチル基、エチル基等のアルキル基またはアミノ基またはジメチルアミノ基、ジエチルアミノ基、ジブチルアミノ基等のアルキルアミノ基またはニトロ基または水酸基またはメトキシ基、エトキシ基、ブトキシ基等のアルコキシ基または塩素等のハロゲンまたはメチル基、メトキシ基、アミノ基、ジメチルアミノ基、水酸基等で置換されていてもよいフェニル基またはメチル基、エチル基、メトキシ基、エトキシ基、アミノ基、ジメチルアミノ基、ジエチルアミノ基、ニトロ基、水酸基等で置換されていてもよいフェニルアミノ基等の置換基を有していてもよい１，３，５−トリアジンである。
本発明を構成する顔料は、ジケトピロロピロール系顔料、アゾ、ジスアゾ、ポリアゾ等のアゾ系顔料、銅フタロシアニン、ハロゲン化銅フタロシアニン、無金属フタロシアニン等のフタロシアニン系顔料、アミノアントラキノン、ジアミノジアントラキノン、アントラピリミジン、フラバントロン、アントアントロン、インダントロン、ピラントロン、ビオラントロン等のアントラキノン系顔料、キナクリドン系顔料、ジオキサジン系顔料、ペリノン系顔料、ペリレン系顔料、チオインジゴ系顔料、イソインドリン系顔料、イソインドリノン系顔料、キノフタロン系顔料、スレン系顔料、金属錯体系顔料等の有機顔料、または、酸化チタン、亜鉛華、硫化亜鉛、鉛白、炭酸カルシウム、沈降性硫酸バリウム、ホワイトカーボン、アルミナホワイト、カオリンクレー、タルク、ベントナイト、黒色酸化鉄、カドミウムレッド、べんがら、モリブデンレッド、モリブデートオレンジ、クロムバーミリオン、黄鉛、カドミウムイエロー、黄色酸化鉄、チタンイエロー、酸化クロム、ビリジアン、チタンコバルトグリーン、コバルトグリーン、コバルトクロムグリーン、ビクトリアグリーン、群青、紺青、コバルトブルー、セルリアンブルー、コバルトシリカブルー、コバルト亜鉛シリカブルー、マンガンバイオレット、コバルトバイオレット等の無機顔料、または、アセチレンブラック、チャンネルブラック、ファーネスブラック等のカーボンブラックである。
本発明の一般式〔１〕の色素誘導体と顔料の組み合わせは類似の色相あるいは構造の化合物を用いた方が色相の変化が少なく好ましい。
本発明の被覆処理顔料は反応性乳化剤による被覆層を形成することができればどのような組成や手段でもよいが、顔料１００重量部に対して色素誘導体１〜３０重量部および反応性乳化剤が４〜６０重量部であることが好ましい。色素誘導体が１重量部以下あるいは３０重量部以上では被覆することが困難となる。反応性乳化剤が４重量部以下では被覆の効果が低く、６０重量部以上は被覆効果を十分得ることが困難であり、顔料の実質的な濃度低下となる。
反応性乳化剤としては、分子中、好ましくは末端に重合性基（ビニル基、アリル基など）を有するものであって、例えば下記の一般式（１）〜（９）で表される化合物が挙げられる。
【００２９】
【化７】

【００３０】
【化８】

【００３１】
（ＲおよびＲ^１は水素原子または炭素数１−８のアルキル基、Ｘはアルカリ金属またはＮＨ_４、ｎおよびｍは１−２００の整数を表す）
【００３２】
【化９】

【００３３】
【化１０】

【００３４】
（式中、Ｍは金属原子、好ましくはＮａ、Ｋなどのアルカリ金属原子を示す。ｍは５〜１０、ｐは７〜１２、ｒは７〜１２、ｓは６〜１１、ｔは７〜１２、ｕは８〜１３、ｗは８〜１３の整数を示す。Ｘはアニオン、好ましくは塩素、臭素などのハロゲン原子を示す。）
処理顔料は、前記顔料を水中に分散させて、反応性乳化剤および水溶性重合開始剤を加え、攪拌しながら重合を行わせて得られる。重合反応は、通常４０〜１００℃の温度で５〜１０時間、より好ましくは６０〜８０℃の温度で５〜８時間行われる。
顔料の添加量は特に限定されないが、水に対して２〜３０重量％、より好ましくは５〜２０重量％の濃度である。反応性乳化剤の添加量は、顔料の重量に対して０．１〜１０倍量、より好ましくは０．２５〜４倍量である。
【００３５】
水溶性重合開始剤としては、例えば２，２’−アゾビス（２−アミジノプロパン）二塩酸塩、２，２’−アゾビス（２−Ｎ−ベンジルアミジノプロパン）二塩酸塩、２，２’−アゾビス〔２−Ｎ−（２−ヒドロキシエチル）アミジノプロパン〕二塩酸塩などが挙げられる。水溶性重合開始剤の添加量は特に限定されないが、反応性乳化剤に対して５〜３０重量％、より好ましくは５〜２０重量％である。
【００３６】
本発明の被覆処理顔料の被覆層の厚さは顔料に被覆している樹脂量を仕込み顔料の比表面積から算出した値である。被覆層の厚さに制限はないが、０．５〜５ｎｍであることが好ましい。０．５ｎｍ以下では被覆処理の効果が低く、５ｎｍ以上は被覆重合処理することが困難となる。
【００３７】
本発明の被覆処理顔料は顔料、色素誘導体、反応性乳化剤からなる組成物を混合、溶解、分散、重合反応等をして製造する。組成物の配合比は顔料１００重量部に対して、色素誘導体１〜３０重量部、反応性乳化剤４〜６０重量部、必要に応じて水または、溶剤４〜２００重量部の範囲が好ましい。
顔料、色素誘導体が均一になるように予め混合してから分散機による分散を行う。その後、反応性乳化剤を加えて分散する。水または溶剤は上記組成物を機械の特性に応じて数量を調節することが望ましい。
【００３８】
溶剤としては芳香族炭化水素系、脂肪族炭化水素系、エステル系、ケトン系、アルコール系等から選ばれる１種または２種以上の溶剤であり、例えば、トルエン、キシレン、ヘキサン、シクロヘキサン、シクロヘキサノン、酢酸エチル、アセトン、メタノール、エタノール、プロパノール、イソプロパノール、ジアセトンアルコール、テトラヒドロフラン（ＴＨＦ）、ジオキサン、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、エチルセロソルブアセテート、メトキシプロピルアセテート等がある。
分散機としては、サンドミル、アトライター、ダイノミル、GPミル、ホモジナイザー、超音波分散機、高圧メディアレス分散機、ニーダー、ロールミル、ボールミル、バンバリーミキサー、ローラーミル、石臼式ミル等の分散機を単独あるいは組み合わせて使用できる。
第１工程として顔料への色素誘導体の濡れと吸着を進行させる。
第２工程は色素誘導体の吸着物に反応性乳化剤を造塩させる工程である。
第3工程は反応性乳化剤を重合反応させ顔料表面に被覆処理を施す。
【００３９】
この反応は重合開始剤の存在下または、不存在下、熱ないしエネルギー放射線（紫外線、電子線等）で反応させる。
本発明の被覆処理顔料を効果的に製造するためには、使用する反応性乳化剤は、塩基性色素誘導体の塩基性基と造塩する官能性基を含有していることが必須である。造塩するための酸性基としては、特にカルボキシル基、スルホン酸基であることが好ましい。
【００４０】
被覆量は処理顔料を溶媒抽出することにより、測定される。被覆物が十分に溶解する溶剤を選択し、処理顔料の１０〜１００倍の溶剤を添加し、超音波分散等によって被覆物を溶出させる。遠心分離等により分離した溶液を採取し、その重量測定等を行うことで全体の溶出量を算出することから被覆量を測定することがもっとも簡単で精度が高く好ましい。
【００４１】
顔料の被覆に使われなかった分は使用されるインキや塗料の溶剤等により洗浄し、ろ過等により除去することが望ましいが、余剰ないし残留の反応性乳化剤が物性に影響を及ぼさない場合は洗浄する必要がない。また、処理顔料を洗浄後、乾燥することは凝集がない場合に可能であるが、使用されるインキ等と同じ溶剤であればあえて乾燥する必要がない。
【００４２】
被覆処理した顔料は通常の顔料と同様に使用できる。顔料をビヒクル等に分散する際使用する分散機は、サンドミル、ダイノミル、ホモジナイザー、アトライター、ボールミル、ペイントシェーカー、フルイダイザー、高速ミキサー、超音波分散機等であり、ミル媒体として、ガラスビーズ、ジルコニアビーズ、ステンレスビーズなどを使用してもよいし、しなくてもよい。分散時間は５分〜２４時間、好ましくは３０分〜８時間である。
本発明の被覆処理顔料を使用した分散体は、低粘度で分散安定性に優れるので、この分散体を着色剤として含むインキや塗料に使用できる。
【００４３】
【実施例】
以下、実施例に基づいて本発明を説明する。例中、部および％は、重量部および重量％を示す。実施例および比較例で用いた顔料および樹脂は下記に示す。具体的な被覆処理顔料およびその製造方法を下記に示す。
［素材］
顔料：青色顔料（銅フタロシアニンブルー東洋インキ製造 リオノールブルーＦＧ７３５１）
赤色顔料（キナクリドン顔料 クラリアント製 ポスターピンクE）
黄色顔料（クラリアント社製“ホスタパームエローＨ３Ｇ）
色素誘導体(a)：
【００４４】
【化１１】

【００４５】
色素誘導体（ｂ）
【００４６】
【化１２】

【００４７】
色素誘導体(c)
【００４８】
【化１３】

【００４９】
色素誘導体(d)
【００５０】
【化１４】

【００５１】
色素誘導体（e）
【００５２】
【化１５】

【００５３】
反応性乳化剤
【００５４】
【化１６】

【００５５】
（１）
【００５６】
【化１７】

【００５７】
（２）
【００５８】
【化１８】

【００５９】
（３）
（ＲおよびＲ^１は水素原子、ＸはＮＨ_４、ｎおよびｍは１０である。）
【００６０】
【実施例１】
銅フタロシアニンブルー顔料９０部と色素誘導体（１０）８部 酢酸1.2部 精製水 ３９０部とをサンドミルにて均一に分散し、顔料表面に色素誘導体を十分吸着させた混合物を得た。
【００６１】
水洗後、中和し、水分量を５０％以下にしたウェットケーキに、酸性基を有する反応性乳化剤を加えて分散し、顔料周辺に反応性乳化剤のついた水性の分散体を製造した。
【００６２】
さらに、撹拌機, 温度計, 滴下ロート, 還流器を備えた反応容器に反応釜量を仕込み、窒素ガスで飽和させる。内温を55℃に昇温した後、重合開始剤を添加し、5 分後に滴下を開始した。滴下量を1 時間で滴下し、60〜65℃の間で重合を行い、さらに1 時間熟成した後に冷却を行い、アンモニアでpH8 〜9 に調製した。得られた分散液の粒子径の測定はレーザー散乱式微粒子径測定装置( UPA)日機装社製 で測定した。この分散液をインキ化し、充分に乾燥した後、記録面に水を垂らしてインキのにじみを調べたが、インキのにじみ,流れ出しはなく充分な耐水性を有していた。
【００６３】
被覆量を測定したところ９ｇ／１００ｇ（顔料）、被覆厚さ１．３ｎｍであった。
【００６４】
【表１】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a coated pigment and an ink obtained by dispersing the treated pigment in a liquid medium. More specifically, a pigment derivative is bonded to the surface of pigment particles, a reactive emulsifier (polymerizable emulsifier) having a basic group and an acidic group is formed, and further polymerized to form a coating layer. The present invention relates to a coating-treated pigment characterized by the above and an ink obtained by dispersing the treated pigment.
[0002]
[Prior art]
Conventionally, when a pigment is surface-treated with a resin, it is performed by adsorption, precipitation, reaction, or the like. Compared to untreated pigments, surface-treated pigments have superior viscosity and dispersion stability of dispersions, inks and paints, so that inks for applications that require fine dispersion and have high required physical properties as products It has become indispensable for paints. Among these, since the surface-crosslinked pigment has high solvent resistance, a surface-treated pigment having easy dispersibility that can be developed for various uses has been desired. However, as the pigment becomes finer, the quality of the surface-treated pigment becomes unstable, or the coating resin used for the surface treatment gradually dissolves and loses the balance of adsorption equilibrium. There were also problems such as agglomeration and deterioration of product characteristics. This is due to the fact that the surface free energy increases as the primary particles of the pigment become finer, making it difficult to break up the aggregation to the primary particles. Usually, even when a resin dispersant is used, it is not easy to disperse even primary particles. Furthermore, it is extremely difficult to simultaneously coat the surface of the pigment with a resin, because if it is performed in an insufficiently dispersed state, aggregates are formed.
[0003]
In the re-published patent WO96 / 23032 (Patent Document 1), a pigment and a basic dye derivative are used in combination to form an aqueous dispersion, and the dispersion stability is good and is used in the ink-jet ink. This is because the pigment is not coated with a resin, and the versatility is difficult.
[0004]
JP-A-8-183920 (Patent Document 2) discloses a method in which a pigment and a solvent solution of a self-dispersing resin are phase-inverted and emulsified, and then the solvent is stripped to form an aqueous dispersion. . In this method, there are various restrictions on the adsorption of the resin to the pigment, and selection thereof is necessary.
[0005]
Japanese Patent Application Laid-Open No. 2002-285028 (Patent Document 3) discloses that a pigment, a basic derivative, and a thermoplastic resin are mixed and the resin is coated around the pigment with a mechanical force. ing. In this method, a point that a large amount of mechanical energy is consumed becomes a bottleneck.
[0006]
[Patent Document 1]
Republished Patent WO 96/23032 Publication
[Patent Document 2]
JP-A-8-183920
[Patent Document 3]
Japanese Patent Laid-Open No. 2002-285028
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a coating-treated pigment that is easy to disperse and excellent in viscosity of the pigment dispersion and its dispersion stability, and an ink obtained by dispersing the treated pigment.
[0010]
[Means for Solving the Problems]
The inventors of the present invention have been developed through extensive research to solve the above problems, and after binding a reactive emulsifier having an acidic group to a pigment having a pigment derivative having a basic group on the surface, The present invention relates to a treated pigment obtained by polymerizing the reactive emulsifier.
[0011]
The present invention also relates to a treated pigment comprising 1 to 30 parts by weight of a pigment derivative having a basic group and 4 to 50 parts by weight of a reactive emulsifier having an acidic group with respect to 100 parts by weight of the pigment.
[0012]
Furthermore, the present invention relates to an ink obtained by dispersing the above-described treated pigment in a liquid medium.
[0013]
The present invention utilizes the action that the pigment particle surface adsorbs the dye skeleton of the dye derivative very well in water or a dispersion machine that can be strongly kneaded in water or a solvent dispersion. The dye skeleton of the derivative is adsorbed on the pigment surface, and the other basic functional group of the dye derivative is bonded by a salt-forming action with a reactive emulsifier having an acidic group. As a result, the pigment derivative is neutralized on the pigment surface, and an adsorption layer of the reactive emulsifier is formed on the pigment surface.
[0014]
As a result, the reactive emulsifier can be reacted while being dispersed up to the primary particle level and maintained in that state, and a pigment having a coating layer on the fine pigment surface can be provided. Another object of the present invention is to provide an ink obtained by dispersing the coated pigment in a liquid medium.
[0015]
The coated pigment thus obtained is intended to be used as a colorant in offset ink, inkjet ink, plastic, paint, and the like.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in further detail below.
The dye derivative in the present invention is represented by the general formula [1].
General formula [1] P-Fn
(In the formula, P is a pigment residue, F is a substituent shown below, and n is an integer of 1 to 4.)
The basic substituent F has at least one substituent consisting of the group represented by the following formula (1), formula (2), formula (3) and formula (4).
Formula (1)
[0017]
[Chemical 1]

[0018]
X: represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
n represents an integer of 1 to 10.
R ₁ and R ₂ : each independently an alkyl group which may be substituted, an alkenyl group which may be substituted, a phenyl group which may be substituted, or a combination of R ₁ and R ₂ Represents an optionally substituted heterocycle containing a nitrogen, oxygen or sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
Formula (2)
[0019]
[Chemical 2]

[0020]
R ₁ and R ₂ : each independently an alkyl group which may be substituted, an alkenyl group which may be substituted, a phenyl group which may be substituted, or a combination of R ₁ and R ₂ Represents an optionally substituted heterocycle containing a nitrogen, oxygen or sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
Formula (3)
[0021]
[Chemical 3]

[0022]
X: represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
R _{3 represents} an alkyl group which may be substituted, an alkenyl group which may be substituted or a phenyl group which may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ₄ , R ₅ , R ₆ , R ₇ : each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.
Formula (4)
[0023]
[Formula 4]

[0024]
X: represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
Y: represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.
Z: represents an optionally substituted alkylene group, an optionally substituted alkenylene group, or an optionally substituted phenylene group. As for carbon number of an alkyl group and an alkenyl group, 1-8 are preferable.
P: The substituent shown by Formula (5) or the substituent shown by Formula (6) is represented.
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the formula (5) or a substituent represented by the formula (6).
Formula (5)
[0025]
[Chemical formula 5]

[0026]
n represents an integer of 1 to 10.
R ₁ and R ₂ : each independently an alkyl group which may be substituted, an alkenyl group which may be substituted, a phenyl group which may be substituted, or a combination of R ₁ and R ₂ Represents an optionally substituted heterocycle containing a nitrogen, oxygen or sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
Formula (6)
[0027]
[Chemical 6]

[0028]
R _{3 represents} an alkyl group which may be substituted, an alkenyl group which may be substituted or a phenyl group which may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ₄ , R ₅ , R ₆ , R ₇ : each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.
Examples of the dye residue represented by P include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, Anthraquinone dyes such as pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, metal complexes There are systemic dyes, anthraquinone residues, triazine residues and the like.
Triazine residues include alkyl groups such as methyl and ethyl groups, amino groups or dimethylamino groups, alkylamino groups such as diethylamino groups and dibutylamino groups, nitro groups or hydroxyl groups, methoxy groups, ethoxy groups, and butoxy groups. Such as an alkoxy group such as chlorine or halogen such as chlorine or a methyl group, a methoxy group, an amino group, a dimethylamino group, a hydroxyl group or the like, a phenyl group or a methyl group, an ethyl group, a methoxy group, an ethoxy group, an amino group, 1,3,5-triazine which may have a substituent such as a phenylamino group which may be substituted with a dimethylamino group, a diethylamino group, a nitro group, a hydroxyl group or the like.
The pigment constituting the present invention includes diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine, aminoanthraquinone, diaminodianthraquinone, Anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone and other anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments Organic pigments such as pigments, quinophthalone pigments, selenium pigments, metal complex pigments, or titanium oxide, zinc white, zinc sulfide, white lead, calcium carbonate, precipitated barium sulfate, white carbon, alumina , Kaolin clay, talc, bentonite, black iron oxide, cadmium red, red pepper, molybdenum red, molybdate orange, chrome vermilion, chrome lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green , Cobalt green, cobalt chrome green, Victoria green, ultramarine, bitumen, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet and other inorganic pigments, or acetylene black, channel black, furnace black Carbon black.
In the combination of the dye derivative of the general formula [1] and the pigment of the present invention, it is preferable to use a compound having a similar hue or structure because the change in hue is small.
The coating-treated pigment of the present invention may have any composition and means as long as it can form a coating layer with a reactive emulsifier, but 1 to 30 parts by weight of a dye derivative and 4 to 4 parts of a reactive emulsifier with respect to 100 parts by weight of the pigment. The amount is preferably 60 parts by weight. When the pigment derivative is 1 part by weight or less or 30 parts by weight or more, it becomes difficult to coat. If the reactive emulsifier is 4 parts by weight or less, the coating effect is low, and if it is 60 parts by weight or more, it is difficult to obtain a sufficient coating effect, resulting in a substantial decrease in the pigment concentration.
The reactive emulsifier has a polymerizable group (vinyl group, allyl group, etc.) in the molecule, preferably at the terminal, and examples thereof include compounds represented by the following general formulas (1) to (9). It is done.
[0029]
[Chemical 7]

[0030]
[Chemical 8]

[0031]
(R and R ¹ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X represents an alkali metal or NH ₄ , and n and m represent an integer of 1 to 200)
[0032]
[Chemical 9]

[0033]
[Chemical Formula 10]

[0034]
(In the formula, M represents a metal atom, preferably an alkali metal atom such as Na or K. m is 5 to 10, p is 7 to 12, r is 7 to 12, s is 6 to 11, and t is 7 to 7. 12, u represents an integer of 8 to 13, and w represents an integer of 8 to 13. X represents an anion, preferably a halogen atom such as chlorine or bromine.
The treated pigment is obtained by dispersing the pigment in water, adding a reactive emulsifier and a water-soluble polymerization initiator, and performing polymerization while stirring. The polymerization reaction is usually performed at a temperature of 40 to 100 ° C for 5 to 10 hours, more preferably at a temperature of 60 to 80 ° C for 5 to 8 hours.
The addition amount of the pigment is not particularly limited, but is 2 to 30% by weight, more preferably 5 to 20% by weight with respect to water. The addition amount of the reactive emulsifier is 0.1 to 10 times, more preferably 0.25 to 4 times the weight of the pigment.
[0035]
Examples of the water-soluble polymerization initiator include 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-N-benzylamidinopropane) dihydrochloride, and 2,2′-azobis. [2-N- (2-hydroxyethyl) amidinopropane] dihydrochloride and the like. Although the addition amount of a water-soluble polymerization initiator is not specifically limited, It is 5-30 weight% with respect to a reactive emulsifier, More preferably, it is 5-20 weight%.
[0036]
The thickness of the coating layer of the coated pigment of the present invention is a value obtained by calculating the amount of resin coated on the pigment from the specific surface area of the prepared pigment. Although there is no restriction | limiting in the thickness of a coating layer, it is preferable that it is 0.5-5 nm. If it is 0.5 nm or less, the effect of the coating treatment is low, and if it is 5 nm or more, it is difficult to perform the coating polymerization treatment.
[0037]
The coated pigment of the present invention is produced by mixing, dissolving, dispersing, polymerizing, etc. a composition comprising a pigment, a dye derivative and a reactive emulsifier. The blending ratio of the composition is preferably in the range of 1 to 30 parts by weight of a pigment derivative, 4 to 60 parts by weight of a reactive emulsifier, and 4 to 200 parts by weight of a solvent or solvent if necessary.
The pigment and the pigment derivative are mixed in advance so as to be uniform, and then dispersed by a disperser. Thereafter, a reactive emulsifier is added and dispersed. The amount of water or solvent is preferably adjusted according to the characteristics of the machine.
[0038]
The solvent is one or more solvents selected from aromatic hydrocarbons, aliphatic hydrocarbons, esters, ketones, alcohols, and the like, such as toluene, xylene, hexane, cyclohexane, cyclohexanone, Examples include ethyl acetate, acetone, methanol, ethanol, propanol, isopropanol, diacetone alcohol, tetrahydrofuran (THF), dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethyl cellosolve acetate, and methoxypropyl acetate.
Dispersers include sand mills, attritors, dyno mills, GP mills, homogenizers, ultrasonic dispersers, high pressure medialess dispersers, kneaders, roll mills, ball mills, Banbury mixers, roller mills, stone mill mills, etc. Can be used in combination.
As the first step, wetting and adsorption of the pigment derivative to the pigment are advanced.
The second step is a step of salting a reactive emulsifier on the adsorbent of the pigment derivative.
In the third step, a reactive emulsifier is subjected to a polymerization reaction to coat the pigment surface.
[0039]
This reaction is carried out with heat or energy radiation (ultraviolet rays, electron beams, etc.) in the presence or absence of a polymerization initiator.
In order to effectively produce the coated pigment of the present invention, it is essential that the reactive emulsifier to be used contains a functional group that forms a salt with the basic group of the basic dye derivative. The acidic group for salt formation is particularly preferably a carboxyl group or a sulfonic acid group.
[0040]
The coating amount is measured by solvent extraction of the treated pigment. A solvent in which the coating is sufficiently dissolved is selected, 10 to 100 times the solvent of the treated pigment is added, and the coating is eluted by ultrasonic dispersion or the like. The solution separated by centrifugation or the like is collected, and the total elution amount is calculated by measuring the weight of the solution, so that it is most simple and highly accurate to measure the coating amount.
[0041]
It is desirable to wash away the amount not used for coating the pigment with the solvent of the ink or paint used, and remove it by filtration, etc., but if excess or residual reactive emulsifier does not affect the physical properties, wash it. There is no need to do. Further, it is possible to dry the treated pigment after washing, when there is no aggregation, but it is not necessary to dry it if it is the same solvent as the ink used.
[0042]
The coated pigment can be used in the same manner as a normal pigment. Dispersers used to disperse pigments in vehicles and the like are sand mills, dyno mills, homogenizers, attritors, ball mills, paint shakers, fluidizers, high speed mixers, ultrasonic dispersers, etc., and glass beads, zirconia as mill media Beads, stainless beads, etc. may or may not be used. The dispersion time is 5 minutes to 24 hours, preferably 30 minutes to 8 hours.
Since the dispersion using the coated pigment of the present invention has low viscosity and excellent dispersion stability, it can be used for inks and paints containing this dispersion as a colorant.
[0043]
【Example】
Hereinafter, the present invention will be described based on examples. In the examples, parts and% indicate parts by weight and% by weight. The pigments and resins used in the examples and comparative examples are shown below. Specific coating treatment pigments and production methods thereof are shown below.
[Material]
Pigment: Blue pigment (Copper phthalocyanine blue Toyo Ink Rionol Blue FG7351)
Red pigment (Quinacridone pigment Clariant Poster Pink E)
Yellow pigment ("Hosta Palm Yellow H3G" manufactured by Clariant)
Dye derivative (a):
[0044]
Embedded image

[0045]
Dye derivative (b)
[0046]
Embedded image

[0047]
Dye derivative (c)
[0048]
Embedded image

[0049]
Dye derivative (d)
[0050]
Embedded image

[0051]
Dye derivative (e)
[0052]
Embedded image

[0053]
Reactive emulsifier [0054]
Embedded image

[0055]
(1)
[0056]
Embedded image

[0057]
(2)
[0058]
Embedded image

[0059]
(3)
(R and R ¹ are hydrogen atoms, X is NH ₄ , and n and m are 10.)
[0060]
[Example 1]
90 parts of a copper phthalocyanine blue pigment and 8 parts of a dye derivative (10) 1.2 parts of acetic acid 390 parts of purified water were uniformly dispersed in a sand mill to obtain a mixture in which the dye derivative was sufficiently adsorbed on the pigment surface.
[0061]
After washing with water and neutralizing, a reactive emulsifier having an acidic group was added to and dispersed in a wet cake having a water content of 50% or less to produce an aqueous dispersion having a reactive emulsifier around the pigment.
[0062]
Further, charge the reaction kettle into a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and reflux, and saturate with nitrogen gas. After raising the internal temperature to 55 ° C., a polymerization initiator was added, and dropping was started after 5 minutes. The dropping amount was dropped in 1 hour, polymerization was carried out at 60 to 65 ° C., the mixture was further aged for 1 hour, cooled, and adjusted to pH 8 to 9 with ammonia. The particle size of the obtained dispersion was measured with a laser scattering fine particle size measuring device (UPA) manufactured by Nikkiso Co., Ltd. The dispersion was converted to ink and dried sufficiently, and then water was dripped onto the recording surface to examine ink bleed. However, the ink did not bleed or flow out and had sufficient water resistance.
[0063]
When the coating amount was measured, it was 9 g / 100 g (pigment) and the coating thickness was 1.3 nm.
[0064]
[Table 1]

Claims (3)

After the basic group of the dye derivative adsorbed on the surface of the pigment and the reactive emulsifier are salted on the pigment having the dye skeleton of the dye derivative having a basic group adsorbed on the pigment surface, the reactive emulsifier Treated pigment obtained by polymerizing   The treated pigment according to claim 1, comprising 1 to 30 parts by weight of a pigment derivative having a basic group and 4 to 50 parts by weight of a reactive emulsifier having an acidic group with respect to 100 parts by weight of the pigment.   An ink comprising the treated pigment according to claim 1 or 2 dispersed in a liquid medium.