JP3561847B2 - Pigment dispersant and pigment composition - Google Patents

Description

〔式中、Ａはエチレン基又はフェニレン基もしくはナフチレン基であって前述のように置換基を含むものであってもよい。Ｂは水酸基又は−ＮＨ−Ａ−ＳＯ_３Ｈで示される基を示す。Ｘは水素原子又は下記式（ＩＩ）〔化２〕で示される基を示す。〕
【化２】

【０００８】
Ａがエチレン基又はフェニレン基もしくはナフチレン基であって、スルホン基１個を有する代表的な脂肪族又は芳香族アミンとしては、タウリン、スルファニル酸、メタニル酸、オルタニル酸、ナフチオン酸、トビアス酸、２−アミノフェノ−ル−４−スルホン酸、２−メトキシアニリン−５−スルホン酸、４−クロロアニリン−３−スルホン酸、２−ニトロアニリン−４−スルホン酸、４Ｂ酸（ｐ−トルイジン−ｍ−スルホン酸）、２Ｂ酸（ｏ−クロロ−ｐ−トルイジン−ｍ−スルホン酸）、Ｃ酸（３−アミノ−６−クロロトルエン−４−スルホン酸）、３−アミノ−６−クロロ安息香酸−４−スルホン酸、ガンマ−酸（２−アミノ−８−ナフト−ル−６−スルホン酸）などがあげられる。次に上記化合物の構造式及び置換基の有無についての一覧表を記載する。表より明らかなように、フェニレン基は水酸基、メトキシ基、塩素、ニトロ基で置換されていてもよく、ナフチレン基は水酸基で置換されていてもよい。

【０００９】
一般式（Ｉ）で示される化合物の金属塩の金属としては、Ｍｎ、Ｓｒ、Ｂａ、Ｃａ、Ａｌ等があげられる。又アミン塩のアミンとしてはデヒドロアビエチルアミン、ステアリルアミン等があげられる。
【００１０】
本発明の顔料分散剤を調製するには、下記の１）、２）で示される２つの方法が代表的である。顔料分散剤（ａ）〔化３〕を例として調製法の概略を示す。
【化３】

【００１１】
１） まず、 Ｃ．Ｉ．ピグメントレッド１７７の１個のアミノ基と塩化シアヌルを反応させると〔化４〕で示される化合物（ＩＩＩ）が得られる。
【化４】

【００１２】
次に、化合物（ＩＩＩ）とスルファニル酸を反応させた後、加水分解させると顔料分散剤（ａ）が得られる。
【００１３】
２）先に、塩化シアヌルとスルファニル酸を反応させると〔化５〕で示される化合物（ＩＶ）が得られる。
【化５】

【００１４】
次に、Ｃ．Ｉ．ピグメントレッド１７７の１個のアミノ基と反応させた後、加水分解させると顔料分散剤（ａ）が得られる。
【００１５】
又、本発明の顔料組成物を調製する方法としては、該分散剤とＣ．Ｉ．ピグメントレッド１７７を粉体配合によつて、又、予め顔料分散剤の調製時に配合する、或は又、顔料の一部を反応させる方法などがあげられる。
【００１６】
【作用】
本発明の顔料分散剤及び顔料組成物を非水系ビヒクル中で使用する際は、Ｃ．Ｉ．ピグメントレッド１７７ １００部に対し、顔料分散剤を０．５〜３０重量部とするのが好ましい。０．５部より少ないと目的とする効果が得られず、また３０重量部より多くてもそれだけの効果は得られない。
【００１７】
本発明の顔料分散剤及び顔料組成物は、塗料、インキなどの非水系ビヒクルにおいて、Ｃ．Ｉ．ピグメントレッド１７７の凝集に対し顕著な改善効果を発揮する。色分かれを防ぎ流動性を改良し鮮明で優れた光沢を有する被膜を得ることができる。そして又、塗料、インキなどの非水系ビヒクルだけに限定されず、プラスチックの着色にも利用できる。
【００１８】
以下、本発明の顔料分散剤及び顔料組成物の調製法の概略を製造例として述べる。例中の「部」と百分率（％）は重量基準で示す。
【００１９】
製造例１
ジオキサン１００部にＣ．Ｉ．ピグメントレッド１７７ １０部と塩化シアヌル４．６部を加え、１００℃で７時間撹拌した。３０℃に冷却してから、ろ過、水洗した。得られたケーキを水１００部に再分散した後、スルファニル酸４．３部を炭酸ナトリウム１．５部で溶解した水溶液１００部を加えた。１０％炭酸ナトリウム水溶液でｐＨを６．０〜７．０に保ち、６０℃で４時間、８０℃で２時間撹拌した。ろ過、水洗、乾燥して式（ａ）〔化６〕の構造を有する顔料分散剤（ａ）１４．４部を得た。
【化６】

【００２０】
製造例２
水１００部にナフチオン酸ナトリウム１３．４部とポリオキシエチレンノニルフェニルエーテル（ＨＬＢ １４）０．５部を加え、更に塩化シアヌル１０部を添加して１５℃で２時間撹拌した。次いで、Ｃ．Ｉ．ピグメントレッド１７７ １０部と１０％炭酸ナトリウム水溶液を加え、ｐＨ６．５〜７．５に保ち４０℃で２時間、６０℃で２時間、そしてｐＨ８．０〜８．５に保ち８０℃で１０時間撹拌した後、ろ過、水洗した。
【００２１】
得られたケーキを水２００部に再分散し、３０％水酸化ナトリウム水溶液を加えてｐＨ１０．０とした後、２０％塩化カルシウム水溶液１５部を加え、７０℃で２時間撹拌した。ろ過、水洗、乾燥して式（ｂ）〔化７〕の構造を有する顔料分散剤（ｂ）２３．２部を得た。
【化７】

【００２２】
製造例３
キシレン１００部にＣ．Ｉ．ピグメントレッド１７７ １０部と塩化シアヌル４．６部を加え、１３５℃で５時間撹拌した。３０℃に冷却しろ過した。メタノール次いで水により洗浄した。得られたケーキを水１００部に再分散した後、２−アミノフェノール−４−スルホン酸１０部を炭酸ナトリウム４部で溶解した水溶液１００部を加えた。１０％炭酸ナトリウム水溶液でｐＨを５．５〜７．０に保ち６０℃で４時間、８０℃で２時間撹拌した後、ろ過、水洗した。得られたケーキを水２００部に再分散し、Ｃ．Ｉ．ピグメントレッド１７７ ２０部と３０％水酸化ナトリウム水溶液を加えてｐＨ１０とした。
【００２３】
次いで、１０％硫酸アルミニウム水溶液を加えｐＨ４．０に調整した後、７０℃で２時間撹拌した。ろ過、水洗して式〔ｅ）〔化８〕の構造を有する顔料分散剤（ｃ）約５０％を含むＣ．Ｉ ピグメントレッド１７７との顔料組成物（Ｄ）３８．２部を得た。
【化８】

【００２４】
製造例４
ジオキサン１００部にＣ．Ｉ．ピグメントレッド１７７ １０部と塩化シアヌル４．６部を加え、１００℃で７時間撹拌した。３０℃に冷却してからタウリン３．４部を含む水溶液１００部を加えた。１０％炭酸ナトリウム水溶液でｐＨ６．０〜７．０に保ち４０℃で１時間、６０℃で２時間、更に８０℃で２時間撹拌した後、ろ過、水洗した。得られたケーキを水２００部に再分散し、デヒドロアビエチルアミン６．６部を含む酢酸水溶液を添加してｐＨ４．０で、８０℃で２時間撹拌した。次いで２５％水酸化アンモニウム水溶液でｐＨ８．０に調整した後、ろ過、水洗、乾燥して式（Ｅ）〔化９〕の構造を有する顔料分散剤（Ｅ）１９．８部を得た。
【化９】

【００２５】
製造例５
水１００部にメタニル酸４．７部と炭酸ナトリウム２部及びポリオキシエチレンラウリルエーテル（ＨＬＢ １６）１．０部を加え、更に塩化シアヌル５部を添加して１５℃で２時間撹拌した。次いで、水２０００部とＣ．Ｉ．ピグメントレッド１７７ １９０部と炭酸ナトリウムを加え、ｐＨ５．６〜６．７に保ち４０℃で２時間、６０℃で２時間、更にｐＨ８．０〜８．５に保ち８０℃で２時間撹拌した後、ろ過、水洗した。得られたケーキを水２０００部に再分散し、ステアリルアミン５．８部を含む酢酸水溶液を添加してｐＨ４．５で、８０℃で２時間撹拌した。
【００２６】
次いで、２５％水酸化アンモニウム水溶液でｐＨ８．０に調整した後、ろ過、水洗、乾燥して式（Ｆ）〔化１０〕の構造を有する顔料分散剤（Ｆ）約１０％を含むＣ．Ｉ。ピグメントレッド１７７との顔料組成物（Ｇ）１９２部を得た。
【化１０】

【００２７】
製造例中の顔料分散剤及び顔料組成物が目的とする組成になつていることの確認は、元素分析法により行なつた。元素分析はＣ、Ｈ、Ｎ、Ｓ、Ａｌ、Ｃａについて行ない、Ｃ、Ｈ、Ｎは自動分析法、Ｓはフラスコ燃焼法のカラムクロマト法、Ａｌ、Ｃａは発光分析法により行なつた。
【００２８】
次に、顔料分散剤（ａ）、組成式 （Ｃ_３７Ｈ_２２Ｎ_６Ｏ_８Ｓ_１）についての元素分析結果を示す。

【００２９】
この分析結果からＣ、Ｈ、Ｎ、Ｓのいずれについても、ほぼ理論値に近い値が得られ、目的とする組成の化合物が得られていることが確認された。また（ａ）以外の顔料分散剤（ｂ）、（Ｅ）及び顔料組成物（Ｄ）、（Ｇ）についても元素分析によつて、それぞれほぼ目的とする組成の化合物が得られていることを確認した。
【００３０】
次に実施例、比較例をあげその効果を述べるが、例中の「部」および百分率（％）は重量基準で示す。なおアルファベットで示す各顔料分散剤及び顔料組成物の組成は、製造例に表示したものと対応する。
【００３１】
【実施例、比較例】
実施例１
容量１５０ｍｌのガラス容器に
Ｃ．Ｉ．ピグメントレッド１７７ ９．０部
顔料分散剤（ａ） １．０部
アクリル樹脂系ワニス（不揮発分６０％） ２６．４部
メラミン樹脂系ワニス（不揮発分５０％） １３．６部
シンナー（キシレン／ｎ−ブタノール＝８／２） ２０ 部
アルミナビーズ（直径３ｍｍ） １００ 部
を入れ、ペイントコンディショナーにて６０分間分散させた。次いで、
アクリル樹脂系ワニス（不揮発分６０％） ３１．９部
メラミン樹脂系ワニス（不揮発分５０％） １６．４部
〔アクリル樹脂／メラミン樹脂＝７／３（固型分）〕
を加え１０分間分散した。得られた塗料をアルミナビーズから分離し、粘度及び塗装後の光沢を測定した。その結果を表１に示す。
【００３２】
実施例２〜５
実施例１においてＣ．Ｉ．ピグメントレッド９．０部、顔料分散剤（ａ）１．０部のかわりに、顔料分散剤又は顔料組成物（ｂ）、（Ｄ）、（Ｅ）、（Ｇ）をそれぞれ１．５部、２．０部、１．０部、１０．０部用いてＣ．Ｉ．ピグメントレッド１７７の使用量との合計が１０．０部となる様に調整してＣ．Ｉ．ピグメントレッド１７７を加えた以外は、実施例１をそのまま行なつてそれぞれの塗料を調製した。その結果を表１に示す。
【００３３】
比較例１
実施例１において顔料分散剤（ａ）の添加を行なわず、Ｃ．Ｉ．ピグメントレッド１７７を１０．０部とした塗料を調製した。その結果は表１に示すように実施例１〜５よりも劣つていた。
【００３４】
【表１】

表１における粘度は、ブルックフィルド型粘度計にて測定した。
光沢は、光沢計にて６０°／６０°反射率を測定した。
耐色分かれ性については、メラミンアルキッドワニスで、予め調製した酸化チタンのベース塗料で、顔料と酸化チタンの比率が１／１０となるようにカットし淡色塗料を調製し、試験管にとつて凝集状態を観察した。
判定は、次の◎、○、△、×で行なつた。
◎：全く均一
○：僅かに白いスジが認められる
△：白い縞模様状態
×：白が完全に分離
【００３５】
表１に示したように本発明による顔料分散剤（ａ）、（ｂ）、（Ｅ）及び顔料組成物（Ｄ）、（Ｇ）を用いた実施例の総ての場合の流動性、光沢、耐色分かれ性において、優れた効果が認められた。またこれらの塗料を１週間放置後に同じ粘度計で測定したが、粘度の増加はほとんど認められなかつた。
【００３６】
実施例６
容量１５０ｍｌのガラス容器に
Ｃ．Ｉ．ピグメントレッド１７７ ９．０部
顔料分散剤（ａ） １．０部
グラビア用ウレタンワニス ４５．０部
シンナー（トルエン／ＩＰＡ／ＭＥＫ＝４０／２０／４０） ４５．０部
アルミナビーズ（直径３ｍｍ） １００部
〔ＩＰＡ：イソプロピルアルコール、ＭＥＫ：メチルエチルケトン〕
を入れ、ペイントコンディショナーにて６０分間分散させた。得られたインキをアルミナビーズから分離し 粘度及び展色後の光沢を測定した。その結果を表２に示す。
【００３７】
実施例７〜１０
実施例６においてＣ．Ｉ．ピグメントレッド１７７ ９．０部、顔料分散剤（ａ） １．０部のかわりに、顔料分散剤又は顔料組成物（ｂ）、（Ｄ）、（Ｅ）、（Ｇ）をそれぞれ１．５部、２．０部、１．０部、１０．０部用いて、Ｃ．Ｉ．ピグメントレッド１７７の使用量との合計が１０．０部となる様に調整してＣ．Ｉ．ピグメントレッド１７７を加えた以外は、実施例６をそのまま行なつてそれぞれのインキを調製した。その結果を表２に示す。
【００３８】
比較例２
実施例６において顔料分散剤（ａ）の添加を行なわずに、Ｃ．Ｉ．ピグメントレッド１７７を１０．０部としたインキを調製した。その結果は表２に示すように、実施例６〜１０よりも劣つていた。
【００３９】
【表２】

表２における粘度は、ブルックフィルド型粘度計にて測定した。
光沢は光沢計にて、６０°／６０°反射率を測定した。
【００４０】
表２に示したように、本発明による顔料分散剤（ａ）、（ｂ）、（Ｅ）及び顔料組成物（Ｄ）、（Ｇ）を用いた実施例の総ての場合の流動性、光沢において、優れた効果が認められた。また、これらの塗料を一週間放置後に同じ粘度計で測定したが、粘度の増加はほとんど認められなかつた。
【００４１】
本発明による顔料分散剤及び顔料組成物を用いた場合には、ニトロセルロースラッカー、焼付メラミンアルキッド樹脂塗料、アクリル系カラーフィルター用樹脂ワニス、ポリアミド／硝化綿インキ、ロジン変性樹脂等のオフセットインキ、ライムロジンインキ、塩化ビニル樹脂インキ等でも、Ｃ．Ｉ．ピグメントレット１７７の凝集を防ぎ良好な分散性を示した。
【００４２】
【発明の効果】
本発明の顔料分散剤及び顔料組成物は塗料、インキなどの非水系ビヒクルにおいて、Ｃ．Ｉ．ピグメントレッド１７７の凝集に対し顕著な改善効果を発揮する。即ち色分かれを防ぎ流動性を改良し鮮明で優れた光沢を有する被膜を得ることができる。さらにこれら本発明の顔料分散剤及び顔料組成物は、その調製の容易さから実用的にも極めて有用である。[0001]
[Industrial applications]
The present invention relates to a pigment dispersant and a pigment composition which provide a pigment dispersion having excellent non-aggregation properties.
[0002]
[Prior art]
Generally, pigments have various undesired effects such as deterioration of fluidity, color separation upon mixing with other pigments, or reduction in gloss of a coated surface due to aggregation caused by dispersion in a paint or ink vehicle. The phenomenon often occurs.
[0003]
As methods for improving such pigment defects, surface treatment of the pigment with a surfactant, metal soap, various resins, or the like, use of various derivatives of an organic pigment, and the like have been proposed.
[0004]
For example, in USP 3,296,001, a method of treating phthalocyanine blue with a rosin calcium salt, in US Pat. JP-A-3-9957 discloses a derivative of a diarylide / disazopyrazolone pigment, or JP-A-63-172772 discloses C.I. I. The use of novel compositions based on Pigment Red 177 has been reported.
[0005]
However, in reality, it has not been possible to obtain a coating composition or ink which has a sufficient effect of imparting non-cohesiveness.
[0006]
[Problems to be solved by the invention]
The present invention relates to C.I. I. An object of the present invention is to provide a pigment dispersant and a pigment composition having a remarkable improvement effect on the aggregation of Pigment Red 177 in a non-aqueous vehicle.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies and, as a result, have succeeded in developing a pigment dispersant and a pigment composition which are extremely useful in practical use to solve the above problems, and the present invention relates to an aliphatic or dispersant having one sulfone group. The following general formula (I) obtained by condensation of an aromatic amine, cyanuric chloride and 4,4'-diamino-1,1'-dianthraquinonyl pigment (CI Pigment Red 177) And a pigment dispersant which is a metal salt or an ammonium or amine salt thereof, and the dispersant and C.I. I. Pigment Red 177.
Embedded image

[In the formula, A may include a location substituent as described above an ethylene group or a phenylene group or a naphthylene group. B represents a group represented by a hydroxyl group or a -NH-A-SO ₃ H. X represents a hydrogen atom or a group represented by the following formula (II) [Formula 2]. ]
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[0008]
A is an ethylene group, a phenylene group, or a naphthylene group, and typical aliphatic or aromatic amines having one sulfone group include taurine, sulfanilic acid, metanilic acid, orthonilic acid, naphthonic acid, tobiasic acid, -Aminophenol-4-sulfonic acid, 2-methoxyaniline-5-sulfonic acid, 4-chloroaniline-3-sulfonic acid, 2-nitroaniline-4-sulfonic acid, 4B acid (p-toluidine-m-sulfone Acid), 2B acid (o-chloro-p-toluidine-m-sulfonic acid), C acid (3-amino-6-chlorotoluene-4-sulfonic acid) , 3 -amino-6-chlorobenzoic acid-4- Sulfonic acid, gamma-acid (2-amino-8-naphthol-6-sulfonic acid) and the like can be mentioned . Next, a list of the structural formulas of the above compounds and the presence or absence of a substituent is described. As is clear from the table, the phenylene group may be substituted with a hydroxyl group, a methoxy group, chlorine, or a nitro group, and the naphthylene group may be substituted with a hydroxyl group.

[0009]
Examples of the metal of the metal salt of the compound represented by the general formula (I) include Mn, Sr, Ba, Ca, Al and the like. Examples of the amine of the amine salt include dehydroabiethylamine and stearylamine.
[0010]
In order to prepare the pigment dispersant of the present invention, the following two methods 1) and 2) are representative. The outline of the preparation method is described below using the pigment dispersant (a) [formula 3] as an example.
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[0011]
1) First, C.I. I. When one amino group of CI Pigment Red 177 is reacted with cyanuric chloride, compound (III) represented by the following chemical formula (4) is obtained.
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[0012]
Next, the compound (III) is reacted with sulfanilic acid and then hydrolyzed to obtain a pigment dispersant (a).
[0013]
2) When cyanuric chloride is first reacted with sulfanilic acid, compound (IV) represented by the following formula (5) is obtained.
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[0014]
Next, C.I. I. Pigment Red 177 is reacted with one amino group and then hydrolyzed to obtain a pigment dispersant (a).
[0015]
The method for preparing the pigment composition of the present invention includes the dispersant and C.I. I. Pigment Red 177 may be prepared by mixing the powder with the powder or at the time of preparing the pigment dispersant, or a method of partially reacting the pigment.
[0016]
[Action]
When the pigment dispersant and the pigment composition of the present invention are used in a non-aqueous vehicle, C.I. I. The pigment dispersant is preferably used in an amount of 0.5 to 30 parts by weight based on 100 parts of Pigment Red 177. If the amount is less than 0.5 part, the desired effect cannot be obtained, and if the amount is more than 30 parts by weight, the effect cannot be obtained.
[0017]
The pigment dispersant and the pigment composition of the present invention can be used in non-aqueous vehicles such as paints and inks. I. Pigment Red 177 has a remarkable improvement effect on aggregation. Color separation is prevented, fluidity is improved, and a film having a clear and excellent gloss can be obtained. Further, the present invention is not limited to non-aqueous vehicles such as paints and inks, and can be used for coloring plastics.
[0018]
Hereinafter, an outline of a method for preparing the pigment dispersant and the pigment composition of the present invention will be described as a production example. "Parts" and percentages (%) in the examples are shown on a weight basis.
[0019]
Production Example 1
In 100 parts of dioxane, C.I. I. Pigment Red 177 (10 parts) and cyanuric chloride (4.6 parts) were added, and the mixture was stirred at 100 ° C. for 7 hours. After cooling to 30 ° C., the mixture was filtered and washed with water. After re-dispersing the obtained cake in 100 parts of water, 100 parts of an aqueous solution obtained by dissolving 4.3 parts of sulfanilic acid in 1.5 parts of sodium carbonate was added. The pH was maintained at 6.0 to 7.0 with a 10% aqueous sodium carbonate solution, and the mixture was stirred at 60 ° C for 4 hours and at 80 ° C for 2 hours. After filtration, washing and drying, 14.4 parts of a pigment dispersant (a) having the structure of the formula (a) [formula 6] was obtained.
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[0020]
Production Example 2
To 100 parts of water, 13.4 parts of sodium naphthionate and 0.5 part of polyoxyethylene nonylphenyl ether (HLB14) were added, and 10 parts of cyanuric chloride were further added, followed by stirring at 15 ° C for 2 hours. Then, C.I. I. Pigment Red 177 (10 parts) and a 10% aqueous sodium carbonate solution are added, and the mixture is maintained at pH 6.5 to 7.5 at 40 ° C for 2 hours, at 60 ° C for 2 hours, and at pH 8.0 to 8.5 and maintained at 80 ° C for 10 hours. After stirring, the mixture was filtered and washed with water.
[0021]
The obtained cake was redispersed in 200 parts of water, and a 30% aqueous sodium hydroxide solution was added to adjust the pH to 10.0. Then, 15 parts of a 20% aqueous calcium chloride solution was added, and the mixture was stirred at 70 ° C for 2 hours. After filtration, washing and drying, 23.2 parts of a pigment dispersant (b) having the structure of the formula (b) was obtained.
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[0022]
Production Example 3
In 100 parts of xylene, C.I. I. Pigment Red 177 (10 parts) and cyanuric chloride (4.6 parts) were added, and the mixture was stirred at 135 ° C. for 5 hours. It was cooled to 30 ° C. and filtered. Washed with methanol followed by water. After re-dispersing the obtained cake in 100 parts of water, 100 parts of an aqueous solution in which 10 parts of 2-aminophenol-4-sulfonic acid were dissolved in 4 parts of sodium carbonate was added. After maintaining the pH at 5.5 to 7.0 with a 10% aqueous sodium carbonate solution and stirring at 60 ° C for 4 hours and at 80 ° C for 2 hours, the mixture was filtered and washed with water. The obtained cake was redispersed in 200 parts of water, and C.I. I. Pigment Red 177 (20 parts) and a 30% aqueous sodium hydroxide solution were added to adjust the pH to 10.
[0023]
Subsequently, the pH was adjusted to 4.0 by adding a 10% aqueous solution of aluminum sulfate, and the mixture was stirred at 70 ° C for 2 hours. After filtration and washing with water, C.I. containing about 50% of a pigment dispersant (c) having the structure of formula (e) [Chem. 8]. Pigment Red 177 and 38.2 parts of a pigment composition (D) were obtained.
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[0024]
Production Example 4
In 100 parts of dioxane, C.I. I. Pigment Red 177 (10 parts) and cyanuric chloride (4.6 parts) were added, and the mixture was stirred at 100 ° C. for 7 hours. After cooling to 30 ° C., 100 parts of an aqueous solution containing 3.4 parts of taurine were added. After maintaining the pH at 6.0 to 7.0 with a 10% aqueous sodium carbonate solution, the mixture was stirred at 40 ° C for 1 hour, 60 ° C for 2 hours, and further at 80 ° C for 2 hours, and then filtered and washed with water. The obtained cake was re-dispersed in 200 parts of water, an aqueous acetic acid solution containing 6.6 parts of dehydroabiethylamine was added, and the mixture was stirred at 80 ° C for 2 hours at pH 4.0. Subsequently, the pH was adjusted to 8.0 with a 25% aqueous ammonium hydroxide solution, followed by filtration, washing with water and drying to obtain 19.8 parts of a pigment dispersant (E) having the structure of the formula (E).
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[0025]
Production Example 5
To 100 parts of water, 4.7 parts of metanilic acid, 2 parts of sodium carbonate and 1.0 part of polyoxyethylene lauryl ether (HLB 16) were added, and 5 parts of cyanuric chloride were further added, followed by stirring at 15 ° C. for 2 hours. Then, 2000 parts of water and C.I. I. After adding 190 parts of CI Pigment Red 177 and sodium carbonate, stirring at 40 ° C for 2 hours at 60 ° C for 2 hours while maintaining the pH at 5.6 to 6.7, and stirring at 80 ° C for 2 hours at pH 8.0 to 8.5. , Filtered and washed with water. The obtained cake was redispersed in 2,000 parts of water, and an aqueous acetic acid solution containing 5.8 parts of stearylamine was added, and the mixture was stirred at 80 ° C for 2 hours at pH 4.5.
[0026]
Then, the pH is adjusted to 8.0 with a 25% ammonium hydroxide aqueous solution, followed by filtration, washing with water, and drying, and C.I. containing about 10% of a pigment dispersant (F) having a structure of the formula (F) [Formula 10]. I. Pigment Red 177 and 192 parts of a pigment composition (G) were obtained.
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[0027]
It was confirmed by elemental analysis that the pigment dispersant and the pigment composition in the production examples had the desired compositions. Elemental analysis was performed for C, H, N, S, Al, and Ca. C, H, and N were performed by an automatic analysis method, S was performed by a column chromatography method of a flask combustion method, and Al and Ca were performed by an emission analysis method.
[0028]
Next, the results of elemental analysis of the pigment dispersant (a) and the composition formula (C ₃₇ H ₂₂ N ₆ O ₈ S ₁ ) are shown.

[0029]
From this analysis result, values close to theoretical values were obtained for all of C, H, N, and S, and it was confirmed that a compound having a desired composition was obtained. Elemental analysis of the pigment dispersants (b) and (E) and the pigment compositions (D) and (G) other than (a) showed that compounds having almost the desired compositions were obtained. confirmed.
[0030]
Next, the effects will be described with reference to Examples and Comparative Examples. "Parts" and percentages (%) in Examples are shown on a weight basis. The composition of each pigment dispersant and pigment composition indicated by an alphabet corresponds to that shown in the production example.
[0031]
[Examples and Comparative Examples]
Example 1
C. in a 150 ml glass container. I. Pigment Red 177 9.0 parts Pigment dispersant (a) 1.0 part Acrylic resin varnish (nonvolatile content 60%) 26.4 parts Melamine resin varnish (nonvolatile content 50%) 13.6 parts Thinner (xylene / n) -Butanol = 8/2) 20 parts Alumina beads (diameter: 3 mm) 100 parts were added and dispersed by a paint conditioner for 60 minutes. Then
Acrylic resin varnish (nonvolatile content 60%) 31.9 parts Melamine resin varnish (nonvolatile content 50%) 16.4 parts [acrylic resin / melamine resin = 7/3 (solid content)]
Was added and dispersed for 10 minutes. The obtained paint was separated from the alumina beads, and the viscosity and gloss after coating were measured. Table 1 shows the results.
[0032]
Examples 2 to 5
In Example 1, C.I. I. Instead of 9.0 parts of Pigment Red and 1.0 part of the pigment dispersant (a), 1.5 parts each of the pigment dispersant or the pigment compositions (b), (D), (E), and (G) are used. 2.0 parts, 1.0 parts, 10.0 parts and C.I. I. Pigment Red 177 so that the total amount thereof becomes 10.0 parts. I. Except that Pigment Red 177 was added, the same procedures as in Example 1 were carried out to prepare respective paints. Table 1 shows the results.
[0033]
Comparative Example 1
In Example 1, the pigment dispersant (a) was not added, and C.I. I. Pigment Red 177 was used as a coating material in 10.0 parts. The results were inferior to Examples 1 to 5 as shown in Table 1.
[0034]
[Table 1]

The viscosities in Table 1 were measured with a Brookfield viscometer.
The gloss was measured with a gloss meter at 60 ° / 60 ° reflectance.
Regarding the color separation resistance, a light-colored paint was prepared by cutting with a melamine alkyd varnish using a base paint of titanium oxide prepared in advance so that the ratio of pigment to titanium oxide was 1/10, and aggregating it in a test tube. The condition was observed.
The judgment was made with the following ◎, △, Δ, and ×.
：: Completely uniform ：: Slightly white streaks are observed △: White stripe pattern state X: White is completely separated [0035]
As shown in Table 1, the fluidity and gloss in all the examples using the pigment dispersants (a), (b) and (E) and the pigment compositions (D) and (G) according to the present invention. Excellent effect on color separation resistance was observed. When these paints were left for one week, they were measured with the same viscometer, and almost no increase in viscosity was observed.
[0036]
Example 6
C. in a 150 ml glass container. I. Pigment Red 177 9.0 parts Pigment dispersant (a) 1.0 part Urethane varnish for gravure 45.0 parts Thinner (toluene / IPA / MEK = 40/20/40) 45.0 parts Alumina beads (diameter 3 mm) 100 Part [IPA: isopropyl alcohol, MEK: methyl ethyl ketone]
And dispersed for 60 minutes with a paint conditioner. The obtained ink was separated from the alumina beads, and the viscosity and gloss after spreading were measured. Table 2 shows the results.
[0037]
Examples 7 to 10
In Example 6, C.I. I. Pigment Red 177 (9.0 parts), pigment dispersant (a) 1.0 part, instead of pigment dispersant or pigment composition (b), (D), (E), (G) 1.5 parts each , 2.0 parts, 1.0 part and 10.0 parts, and C.I. I. Pigment Red 177 so that the total amount thereof becomes 10.0 parts. I. Example 6 was repeated except that Pigment Red 177 was added to prepare each ink. Table 2 shows the results.
[0038]
Comparative Example 2
In Example 6, without adding the pigment dispersant (a), C.I. I. Pigment Red 177 at 10.0 parts was prepared. As shown in Table 2, the results were inferior to Examples 6 to 10.
[0039]
[Table 2]

The viscosities in Table 2 were measured with a Brookfield viscometer.
The gloss was measured with a gloss meter at 60 ° / 60 ° reflectance.
[0040]
As shown in Table 2, the fluidity in all cases of the examples using the pigment dispersants (a), (b), (E) and the pigment compositions (D), (G) according to the invention, Excellent effect on gloss was observed. When these paints were left for one week, they were measured with the same viscometer, and almost no increase in viscosity was observed.
[0041]
When the pigment dispersant and the pigment composition according to the present invention are used, nitrocellulose lacquer, baked melamine alkyd resin paint, resin varnish for acrylic color filter, polyamide / nitrified cotton ink, offset ink such as rosin-modified resin, lime Even with rosin ink, vinyl chloride resin ink, etc., C.I. I. Pigmentlet 177 was prevented from agglomerating and showed good dispersibility.
[0042]
【The invention's effect】
The pigment dispersant and the pigment composition of the present invention can be used in non-aqueous vehicles such as paints and inks. I. Pigment Red 177 has a remarkable improvement effect on aggregation. That is, it is possible to prevent color separation and improve the fluidity to obtain a film having a clear and excellent gloss. Further, these pigment dispersants and pigment compositions of the present invention are extremely useful practically because of their ease of preparation.

Claims (2)

The following compounds obtained by condensation of an aliphatic or aromatic amine having one sulfone group, cyanuric chloride and a 4,4'-diamino-1,1'-dianthraquinonyl pigment (CI Pigment Red 177) A pigment dispersant which is a compound represented by the general formula (I) [Formula 1] or a metal salt or an ammonium or amine salt thereof.

Wherein A is an ethylene group, a phenylene group or a naphthylene group, and when A is a phenylene group, A is 2-aminophenol-4-sulfonic acid, 2-methoxyaniline-5-sulfonic acid, 4-chloro Aniline-3-sulfonic acid, 2-nitroaniline-4-sulfonic acid, 4B acid (p-toluidine-m-sulfonic acid), 2B acid (o-chloro-p-toluidine-m-sulfonic acid), C acid ( 3-amino-6-chlorotoluene-4-sulfonic acid) or 3-amino-6-chlorobenzoic acid-4-sulfonic acid, and when A is a naphthylene group, gamma-acid (2 - amino-8-naphthol - le 6-sulfonic acid) may be I der. B represents a group represented by a hydroxyl group or a -NH-A-SO ₃ H. X represents a hydrogen atom or a group represented by the following formula (II). ]

A pigment composition comprising the dispersant according to claim 1 and 4,4'-diamino-1,1'-dianthraquinonyl pigment (CI Pigment Red 177).