JPWO2009136576A1 - Trisazo compound, ink composition, recording method and colored body - Google Patents

Abstract

Highly soluble in a medium containing water as a main component, stable even when a high-concentration aqueous solution and ink are stored for a long period of time, the density of the printed image is very high, and even when a high-concentration solution is printed The present invention provides a black ink coloring matter and an ink composition thereof, which do not cause bronzing and give a black recorded image having excellent fastness of printed image, particularly light resistance and ozone gas resistance. As the pigment for black ink, a trisazo compound represented by the following formula (1) or a tautomer thereof, or a salt thereof is used. [In the formula (1), the group A is substituted benzothiazolyl, etc., R1 is substituted C1-C4 alkyl, etc., R2 is cyano, R3 and R4 are each independently sulfo, etc., R5 to R7 are each independently hydrogen atom, substituted C1 -C4 alkyl, substituted C1-C4 alkoxy and the like, R8 to R10 each independently represent a hydrogen atom, C1-C4 alkyl, substituted C1-C4 alkoxy, substituted C1-C4 alkylthio or the like. ]

Description

  The present invention relates to a novel trisazo compound or a salt thereof, an ink composition containing the compound or the salt, and a colored product obtained from the compound or the salt.

A recording method using an ink jet printer, which is one of the representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.) for recording. Is. Since this method has a feature that the recording head and the recording material are not in direct contact with each other, the generation of sound is low and quiet, and the downsizing and the high-speed operation are easy. Large growth is expected in the future.
Conventionally, as inks for fountain pens, felt-tip pens and the like and inks for ink jet printing, aqueous inks in which water-soluble pigments are dissolved in an aqueous medium have been used. In these water-based inks, a water-soluble organic solvent is generally added to prevent clogging of the ink at the pen tip or the ink discharge nozzle. With these inks, it is possible to provide a recording image with sufficient density, no clogging of the pen tip and nozzles, good drying on the recording material, less bleeding, and storage stability. It is required to be excellent. Further, the water-soluble dye used is required to have particularly high solubility in water and high solubility in the water-soluble organic solvent added to the ink. Furthermore, the formed image is required to have fastness such as water resistance, light resistance, gas resistance and moisture resistance.

  Among these, the gas resistance is resistance to a phenomenon in which ozone gas having an oxidizing action that exists in the air acts on the dye in the recording material and discolors the printed image. In addition to ozone gas, examples of the oxidizing gas having this kind of action include NOx and SOx. However, among these oxidizing gases, ozone gas is considered to be a main causative substance that further promotes the discoloration and fading phenomenon of inkjet images. Therefore, ozone gas resistance tends to be regarded as the most important among gas resistances. Many ink-receiving layers provided on the surface of photographic image-dedicated inkjet paper use a material such as a porous white inorganic material in order to expedite ink drying and to reduce bleeding at high image quality. Discoloration due to ozone gas is noticeable on such recording paper. Since this discoloration phenomenon due to the oxidizing gas is characteristic of ink jet images, the improvement of ozone gas resistance is one of the most important issues in the ink jet printing method.

  In the future, in order to expand the field of use of printing methods using ink, the ink composition used for inkjet printing and the colored bodies colored thereby will be further improved in light resistance, ozone gas resistance, moisture resistance and water resistance. Is strongly demanded.

  Various hues of ink are prepared from various dyes, of which black ink is an important ink used for both monocolor and full color images. Many pigments for these black inks have been proposed to date, but have not yet been able to provide products that sufficiently satisfy market demands. Many of the proposed dyes are azo dyes, of which C.I. I. Disazo dyes such as Food Black 2 have problems such as poor color rendering, poor water resistance and moisture resistance, and insufficient light resistance and gas resistance. In general, polyazo dyes having a conjugated system have problems such as low water solubility and a tendency to cause a bronzing phenomenon in which a recorded image has a partial metallic luster, and insufficient light resistance and gas resistance. Similarly, many of the azo metal-containing dyes that have been proposed have good light resistance, but they contain metal ions, which are undesirable for biological safety and environmental problems, and are extremely resistant to ozone gas. There are problems such as weakness.

  Examples of the black pigment for ink jet improved with respect to ozone gas resistance, which has become the most important issue in recent years, include compounds described in Patent Documents 1 to 3. These compounds are not sufficient in terms of light resistance because ozone gas resistance does not sufficiently satisfy market requirements. Moreover, as an azo compound having a benzimidazolopyridone skeleton, which is one of the characteristics of the trisazo compound of the present invention, Patent Documents 4 to 7 and the like are described. Patent Documents 5 and 6 also disclose trisazo compounds, but these trisazo compounds are symmetrical in which two benzimidazolopyridone skeletons are further bonded to each end of a linking group containing an azo structure by an azo structure. Nothing similar to the asymmetric trisazo compound of the present invention is disclosed. Moreover, there are few water-soluble compounds and there is no usage example as a black pigment | dye for inkjet inks. Examples of the trisazo compound for inkjet ink having excellent ozone gas resistance include the compounds described in Patent Document 8, and it is disclosed that it can be used as a black pigment for water-soluble inkjet ink.

JP 2003-183545 A JP 2003-201412 A Special table 2007-517082 gazette International Publication No. 2004/050768 Pamphlet Specification of West German Patent No. 2004488 West German Patent No. 2023295 specification JP 05-134435 A International Publication No. 2007/077931 Pamphlet

  An object of the present invention is to provide a trisazo compound or a salt thereof used as a pigment in a black ink particularly suitable for ink jet printing, an ink composition containing the compound or salt as a pigment, and a colored body using the compound or salt. And

  As a result of intensive studies to solve the above-described problems, the present inventors have found that a specific trisazo compound can solve the above-described problems, and have completed the present invention.

［式（１）中、
Ｒ^１はカルボキシ基；非置換、若しくはカルボキシ基で置換されたＣ１−Ｃ４アルキル基；又は、非置換、若しくはスルホ基で置換されたフェニル基；であり、
Ｒ^２はシアノ基；カルバモイル基；又はカルボキシ基；であり、
Ｒ^３及びＲ^４はそれぞれ独立に水素原子；塩素原子；スルホ基；非置換Ｃ１−Ｃ４アルキル基；又は非置換Ｃ１−Ｃ４アルコキシ基；であり、
Ｒ^５からＲ^７が置換している環は、破線で表される環が存在しない場合にはベンゼン環；破線で表される環が存在する場合にはナフタレン環；であり、
Ｒ^５からＲ^７はそれぞれ独立に水素原子；塩素原子；ヒドロキシ基；スルホ基；カルボキシ基；スルファモイル基；カルバモイル基；非置換Ｃ１−Ｃ４アルキル基；非置換、若しくはヒドロキシ基、非置換Ｃ１−Ｃ４アルコキシ基、ヒドロキシＣ１−Ｃ４アルコキシ基、スルホ基、若しくはカルボキシ基で置換されたＣ１−Ｃ４アルコキシ基；非置換、若しくはヒドロキシ基、スルホ基、若しくはカルボキシ基で置換されたモノ若しくはジＣ１−Ｃ４アルキルアミノ基；非置換、若しくはヒドロキシ基若しくはカルボキシ基で置換されたＣ１−Ｃ４アルキルカルボニルアミノ基；非置換、若しくはヒドロキシ基、スルホ基、若しくはカルボキシ基で置換されたＮ’−Ｃ１−Ｃ４アルキルウレイド基；非置換、若しくはベンゼン環が塩素原子、非置換Ｃ１−Ｃ４アルキル基、ニトロ基、スルホ基、若しくはカルボキシ基で置換されたフェニルアミノ基；非置換、若しくはベンゼン環が塩素原子、非置換Ｃ１−Ｃ４アルキル基、ニトロ基、スルホ基、若しくはカルボキシ基で置換されたベンゾイルアミノ基；又は、非置換、若しくはベンゼン環が塩素原子、非置換Ｃ１−Ｃ４アルキル基、ニトロ基、スルホ基、若しくはカルボキシ基で置換されたフェニルスルホニルアミノ基；を表し、
Ｒ^８からＲ^１０が置換している環は、破線で表される環が存在しない場合にはベンゼン環；破線で表される環が存在する場合にはナフタレン環；であり、
Ｒ^８からＲ^１０はそれぞれ独立に水素原子；塩素原子；ヒドロキシ基；スルホ基；カルボキシ基；スルファモイル基；カルバモイル基；非置換Ｃ１−Ｃ４アルキル基；非置換、若しくはヒドロキシ基、非置換Ｃ１−Ｃ４アルコキシ基、ヒドロキシＣ１−Ｃ４アルコキシ基、スルホ基、若しくはカルボキシ基で置換されたＣ１−Ｃ４アルコキシ基；非置換、若しくはヒドロキシ基、スルホ基、若しくはカルボキシ基で置換されたＣ１−Ｃ４アルキルチオ基；非置換、若しくはヒドロキシ基、スルホ基、若しくはカルボキシ基で置換されたモノ若しくはジＣ１−Ｃ４アルキルアミノ基；非置換、若しくはヒドロキシ基若しくはカルボキシ基で置換されたＣ１−Ｃ４アルキルカルボニルアミノ基；非置換、若しくはヒドロキシ基、スルホ基、若しくはカルボキシ基で置換されたＮ’−Ｃ１−Ｃ４アルキルウレイド基；非置換、若しくはベンゼン環が塩素原子、非置換Ｃ１−Ｃ４アルキル基、ニトロ基、スルホ基、若しくはカルボキシ基で置換されたフェニルアミノ基；非置換、若しくはベンゼン環が塩素原子、非置換Ｃ１−Ｃ４アルキル基、ニトロ基、スルホ基、若しくはカルボキシ基で置換されたベンゾイルアミノ基；又は、非置換、若しくはベンゼン環が塩素原子、非置換Ｃ１−Ｃ４アルキル基、ニトロ基、スルホ基、若しくはカルボキシ基で置換されたフェニルスルホニルアミノ基；を表し、
基Ａは非置換又は置換基を有するベンゾチアゾリル基；チアジアゾリル基；又はチアゾリル基；であり、
該ベンゾチアゾリル基が置換基を有する場合には、塩素原子；スルホ基；ニトロ基；ヒドロキシ基；スルファモイル基；非置換Ｃ１−Ｃ４アルキル基；非置換、又はヒドロキシ基、Ｃ１−Ｃ４アルコキシ基、スルホ基、若しくはカルボキシ基で置換されたＣ１−Ｃ４アルコキシ基；非置換、又はヒドロキシ基、スルホ基、若しくはカルボキシ基で置換されたＣ１−Ｃ４アルキルスルホニル基；及び、非置換、又はベンゼン環が塩素原子、非置換Ｃ１−Ｃ４アルキル基、ニトロ基、スルホ基、若しくはカルボキシ基で置換されたフェニルスルホニル基；よりなる群から選択される置換基を有し、
該チアジアゾリル基又はチアゾリル基が置換基を有する場合には、塩素原子；スルホ基；ニトロ基；ヒドロキシ基；スルファモイル基；メルカプト基；及び、非置換、又はヒドロキシ基、Ｃ１−Ｃ４アルコキシ基、ヒドロキシＣ１−Ｃ４アルコキシ基、スルホ基、若しくはカルボキシ基で置換されたＣ１−Ｃ４アルキルチオ基；よりなる群から選択される置換基を有する。］
２）
上記式（１）で表されるトリスアゾ化合物が下記式（２）で表される上記１）に記載のトリスアゾ化合物若しくはその互変異性体、又はそれらの塩、

［式（２）中、基Ａ、Ｒ^１からＲ^１０、及びＲ^８からＲ^１０が置換している環は、破線で表される環を含めて式（１）におけるのと同じ意味を有する。］
３）
上記式（１）で表されるトリスアゾ化合物が下記式（３）で表される上記１）又は２）に記載のトリスアゾ化合物若しくはその互変異性体、又はそれらの塩、

［式（３）中、基Ａ、Ｒ^１からＲ^１０は、式（１）におけるのと同じ意味を有する。］
４）
上記式（１）で表されるトリスアゾ化合物が下記式（４）で表される上記１）乃至３）のいずれか一項に記載のトリスアゾ化合物若しくはその互変異性体、又はそれらの塩、

［式（４）中、
基Ａ、Ｒ^１からＲ^４、及びＲ^８からＲ^１０は式（１）におけるのと同じ意味を有し、
Ｒ^５及びＲ^７はそれぞれ独立に水素原子；非置換Ｃ１−Ｃ４アルキル基；又は、非置換、若しくはスルホ基若しくはヒドロキシ基で置換されたＣ１−Ｃ４アルコキシ基；を表し、Ｒ^６は水素原子を表す。］
５）
上記式（１）で表されるトリスアゾ化合物が下記式（５）で表される上記１）乃至４）のいずれか一項に記載のトリスアゾ化合物若しくはその互変異性体、又はそれらの塩、

［式（５）中、
基Ａ、Ｒ^１からＲ^４は式（１）におけるのと同じ意味を有し、
Ｒ^５からＲ^７は式（４）におけるのと同じ意味を有し、
Ｒ^８及びＲ^１０はそれぞれ独立に水素原子；スルホＣ１−Ｃ４アルコキシ基；非置換Ｃ１−Ｃ４アルキル基；非置換、若しくはスルホ基で置換されたＣ１−Ｃ４アルコキシ基；又はスルホ基若しくはカルボキシ基で置換されたＣ１−Ｃ４アルキルチオ基；を表し、Ｒ^９は水素原子を表す。］
６）
基Ａが下記式（６）で表される基である上記１）乃至５）のいずれか一項に記載のトリスアゾ化合物若しくはその互変異性体、又はそれらの塩、

［式（６）中、
Ｒ^１１からＲ^１３はそれぞれ独立に水素原子；塩素原子；スルホ基；ニトロ基；ヒドロキシ基；スルファモイル基；Ｃ１−Ｃ４アルキル基；非置換、若しくはヒドロキシ基、非置換Ｃ１−Ｃ４アルコキシ基、スルホ基、若しくはカルボキシ基で置換されたＣ１−Ｃ４アルコキシ基；又は、非置換、若しくはヒドロキシ基、スルホ基、若しくはカルボキシ基で置換されたＣ１−Ｃ４アルキルスルホニル基；を表す。］
７）
Ｒ^１がメチル基、Ｒ^２がシアノ基又はカルバモイル基、Ｒ^３が水素原子、Ｒ^４がスルホ基である上記１）乃至６）のいずれか一項に記載のトリスアゾ化合物若しくはその互変異性体、又はそれらの塩、
８）
Ｒ^５がスルホプロポキシ基又はスルホブトキシ基、Ｒ^６が水素原子、Ｒ^７が水素原子、メチル基、又はエチル基である上記１）乃至７）のいずれか一項に記載のトリスアゾ化合物若しくはその互変異性体、又はそれらの塩、
９）
Ｒ^８からＲ^１０がそれぞれ独立に水素原子；塩素原子；スルホ基；ニトロ基；メトキシ基；スルホプロポキシ基；及び、スルホ基又はカルボキシ基で置換されたＣ１−Ｃ４アルキルチオ基よりなる群から選択される基である上記１）乃至８）のいずれか一項に記載のトリスアゾ化合物若しくはその互変異性体、又はそれらの塩、
１０）
Ｒ^１がメチル基、Ｒ^２がシアノ基、Ｒ^３が水素原子、Ｒ^４がスルホ基、Ｒ^５がスルホプロポキシ基、Ｒ^６が水素原子、Ｒ^７がメチル基、Ｒ^８がスルホプロピルチオ基、Ｒ^９が水素原子、Ｒ^１０がメチル基、Ｒ^１１からＲ^１３のうち２つがスルホ基、１つが水素原子である上記６）に記載のトリスアゾ化合物又はその塩、
１１）
上記１）乃至１０）のいずれか一項に記載のトリスアゾ化合物若しくはその互変異性体、又はそれらの塩を、色素として少なくとも１種含有するインク組成物、
１２）
上記１１）に記載のインク組成物をインクとして用い、該インクのインク滴を記録信号に応じて吐出させて、被記録材に付着させることによりプリントするインクジェットプリント方法、
１３）
インクジェットプリント方法における上記被記録材が情報伝達用シートである上記１２）に記載のインクジェットプリント方法、
１４）
上記情報伝達用シートが多孔性白色無機物を含有するインク受容層を有するシートである上記１３）に記載のインクジェットプリント方法、
１５）
上記１４）に記載のインク組成物を含む容器が装填されたインクジェットプリンタ、
１６）
上記１）乃至１０）のいずれか一項に記載のトリスアゾ化合物若しくはその互変異性体、又はそれらの塩によって着色された着色体、
に関する。That is, the present invention
1)
A trisazo compound represented by the following formula (1) or a tautomer thereof, or a salt thereof;

[In Formula (1),
R ¹ is a carboxy group; a C1-C4 alkyl group that is unsubstituted or substituted with a carboxy group; or a phenyl group that is unsubstituted or substituted with a sulfo group;
R ² is a cyano group; a carbamoyl group; or a carboxy group;
R ³ and R ⁴ are each independently a hydrogen atom; a chlorine atom; a sulfo group; an unsubstituted C1-C4 alkyl group; or an unsubstituted C1-C4 alkoxy group;
The ring in which R ⁵ to R ⁷ are substituted is a benzene ring when a ring represented by a broken line is not present; a naphthalene ring when a ring represented by a broken line is present;
R ⁵ to R ⁷ are each independently a hydrogen atom; chlorine atom; hydroxy group; sulfo group; carboxy group; sulfamoyl group; carbamoyl group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 C1-C4 alkoxy group substituted with an alkoxy group, hydroxy C1-C4 alkoxy group, sulfo group, or carboxy group; mono- or di-C1-C4 alkyl unsubstituted or substituted with a hydroxy group, sulfo group, or carboxy group C1-C4 alkylcarbonylamino group unsubstituted or substituted with a hydroxy group or a carboxy group; N'-C1-C4 alkylureido group unsubstituted or substituted with a hydroxy group, a sulfo group, or a carboxy group ; Unsubstituted, or benzene ring is a chlorine atom, A phenylamino group substituted by a substituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group; unsubstituted or a benzene ring is a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group A benzoylamino group substituted with a group; or a phenylsulfonylamino group unsubstituted or substituted on the benzene ring with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group;
The ring in which R ⁸ to R ¹⁰ are substituted is a benzene ring when a ring represented by a broken line is not present; a naphthalene ring when a ring represented by a broken line is present;
R ⁸ to R ¹⁰ are each independently a hydrogen atom; chlorine atom; hydroxy group; sulfo group; carboxy group; sulfamoyl group; carbamoyl group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 C1-C4 alkoxy group substituted with an alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, or a carboxy group; unsubstituted, or a C1-C4 alkylthio group substituted with a hydroxy group, a sulfo group, or a carboxy group; A substituted or mono- or di-C1-C4 alkylamino group substituted with a hydroxy group, a sulfo group, or a carboxy group; an unsubstituted or C1-C4 alkylcarbonylamino group substituted with a hydroxy group or a carboxy group; Or hydroxy group, sulfo group, Is a N'-C1-C4 alkylureido group substituted with a carboxy group; phenylamino substituted with an unsubstituted or benzene ring with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group A benzoylamino group substituted by an unsubstituted or benzene ring with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group; or an unsubstituted or benzene ring with a chlorine atom, non-substituted A substituted C1-C4 alkyl group, a nitro group, a sulfo group, or a phenylsulfonylamino group substituted with a carboxy group;
The group A is an unsubstituted or substituted benzothiazolyl group; a thiadiazolyl group; or a thiazolyl group;
When the benzothiazolyl group has a substituent, chlorine atom; sulfo group; nitro group; hydroxy group; sulfamoyl group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, C1-C4 alkoxy group, sulfo group Or a C1-C4 alkoxy group substituted with a carboxy group; an unsubstituted or C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group, or a carboxy group; and an unsubstituted or benzene ring is a chlorine atom, A phenylsulfonyl group substituted with an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group; having a substituent selected from the group consisting of:
When the thiadiazolyl group or thiazolyl group has a substituent, chlorine atom; sulfo group; nitro group; hydroxy group; sulfamoyl group; mercapto group; and unsubstituted or hydroxy group, C1-C4 alkoxy group, hydroxy C1 A C1-C4 alkylthio group substituted with a C4 alkoxy group, a sulfo group, or a carboxy group; and a substituent selected from the group consisting of: ]
2)
The trisazo compound represented by the above formula (1), the trisazo compound according to the above 1) represented by the following formula (2) or a tautomer thereof, or a salt thereof:

[In the formula (2), the ring in which the groups A, R ¹ to R ¹⁰ , and R ⁸ to R ¹⁰ are substituted has the same meaning as in the formula (1) including the ring represented by a broken line. . ]
3)
The trisazo compound represented by the above formula (1), the trisazo compound according to the above 1) or 2) represented by the following formula (3) or a tautomer thereof, or a salt thereof:

[In formula (3), the groups A, R ¹ to R ¹⁰ have the same meaning as in formula (1). ]
4)
The trisazo compound represented by the above formula (1) or the tautomer thereof according to any one of 1) to 3) represented by the following formula (4), or a salt thereof:

[In Formula (4),
The groups A, R ¹ to R ⁴ , and R ⁸ to R ¹⁰ have the same meaning as in formula (1),
R ⁵ and R ⁷ each independently represent a hydrogen atom; an unsubstituted C1-C4 alkyl group; or a C1-C4 alkoxy group that is unsubstituted or substituted with a sulfo group or a hydroxy group; and R ⁶ represents a hydrogen atom. To express. ]
5)
The trisazo compound represented by the above formula (1) or the tautomer thereof according to any one of 1) to 4) represented by the following formula (5), or a salt thereof:

[In Formula (5),
The groups A, R ¹ to R ⁴ have the same meaning as in formula (1)
R ⁵ to R ⁷ have the same meaning as in formula (4),
R ⁸ and R ¹⁰ are each independently a hydrogen atom; a sulfo C1-C4 alkoxy group; an unsubstituted C1-C4 alkyl group; an unsubstituted or substituted C1-C4 alkoxy group with a sulfo group; or a sulfo group or a carboxy group Represents a substituted C1-C4 alkylthio group; and R ⁹ represents a hydrogen atom. ]
6)
The trisazo compound or a tautomer thereof according to any one of 1) to 5), wherein the group A is a group represented by the following formula (6), or a salt thereof:

[In Formula (6),
R ¹¹ to R ¹³ are each independently hydrogen atom; chlorine atom; sulfo group; nitro group; hydroxy group; sulfamoyl group; C1-C4 alkyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 alkoxy group, sulfo group Or a C1-C4 alkoxy group substituted with a carboxy group; or a C1-C4 alkylsulfonyl group unsubstituted or substituted with a hydroxy group, a sulfo group, or a carboxy group. ]
7)
The trisazo compound or the tautomer thereof according to any one of 1) to 6) above, wherein R ¹ is a methyl group, R ² is a cyano group or carbamoyl group, R ³ is a hydrogen atom, and R ⁴ is a sulfo group. Or a salt thereof,
8)
The trisazo compound according to any one of 1) to 7) above, wherein R ⁵ is a sulfopropoxy group or sulfobutoxy group, R ⁶ is a hydrogen atom, R ⁷ is a hydrogen atom, a methyl group, or an ethyl group, or a combination thereof. Mutants, or salts thereof,
9)
R ⁸ to R ¹⁰ are each independently selected from the group consisting of a hydrogen atom; a chlorine atom; a sulfo group; a nitro group; a methoxy group; a sulfopropoxy group; and a C1-C4 alkylthio group substituted with a sulfo group or a carboxy group The trisazo compound or a tautomer thereof according to any one of 1) to 8), or a salt thereof,
10)
R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfopropoxy group, R ⁶ is a hydrogen atom, R ⁷ is a methyl group, and R ⁸ is a sulfopropylthio group , R ⁹ is a hydrogen atom, R ¹⁰ is a methyl group, two of R ¹¹ to R ¹³ are sulfo groups, and one is a hydrogen atom, the trisazo compound or a salt thereof according to 6) above,
11)
An ink composition containing at least one trisazo compound or a tautomer thereof according to any one of 1) to 10), or a salt thereof as a coloring matter;
12)
An ink jet printing method for printing by using the ink composition described in 11) above as an ink, ejecting ink droplets of the ink in accordance with a recording signal, and attaching the ink droplet to a recording material;
13)
The inkjet printing method according to 12), wherein the recording material in the inkjet printing method is an information transmission sheet,
14)
The inkjet printing method according to 13), wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance,
15)
An inkjet printer loaded with a container containing the ink composition described in 14) above,
16)
A trisazo compound according to any one of 1) to 10) or a tautomer thereof, or a colored product colored by a salt thereof;
About.

The trisazo compound of the present invention or a tautomer thereof, or a salt thereof has high solubility in a medium containing water as a main component, and is stable even when a high concentration aqueous solution or ink of the compound is stored for a long period of time. The printed image has a very high density, is easy to synthesize, and is inexpensive.
Since the trisazo compound of the present invention or a tautomer thereof, or a salt thereof is excellent in water solubility, the filterability by a membrane filter in the process of producing the ink composition is good, and the ink composition containing the compound In addition, the storage stability and ejection stability of an ink prepared from the product or the ink composition are also excellent. That is, the ink composition of the present invention containing this trisazo compound or a tautomer thereof, or a salt thereof is free from solid precipitation, physical property change, color change, etc. after long-term storage, and has good storage stability. is there. In addition, the ink composition containing the trisazo compound of the present invention or a tautomer thereof, or a salt thereof is suitably used for inkjet printing and writing instruments, and when recorded on plain paper and inkjet dedicated paper, The print density of the recorded image is very high, and even when a high-concentration solution is printed, the image does not cause bronzing and is excellent in various fastness properties, particularly light resistance and ozone gas resistance. When used in combination with other ink compositions containing magenta, cyan, and yellow dyes, full-color inkjet printing with excellent fastness and storage stability is possible. Thus, the ink composition of the present invention is extremely useful as a black ink for inkjet printing.

Hereinafter, the present invention will be described in detail.
The trisazo compound of the present invention or a tautomer thereof, or a salt thereof is a black pigment. Hereinafter, for convenience, the “trisazo compound of the present invention or a tautomer thereof, or a salt thereof” including the “trisazo compound of the present invention or a salt thereof” will be simply described as “the trisazo compound of the present invention”.
The trisazo compound represented by the above formula (1) has a tautomer, and examples of the tautomer include the following formulas (7) and (8) in addition to the compound represented by the formula (1). Conceivable. These tautomers are also included in the present invention. In the following formulas (7) and (8), the ring substituted by the groups A and R ¹ to R ¹⁰ has the same meaning as in the above formula (1) including the ring represented by the broken line. .

In the above formula (1), R ¹ represents a carboxy group; a C1-C4 alkyl group that is unsubstituted or substituted with a carboxy group; or a phenyl group that is unsubstituted or substituted with a sulfo group.

When R ¹ in Formula (1) is an unsubstituted C1-C4 alkyl group, the alkyl group may be either a straight chain or a branched chain, but is preferably a straight chain. Specific examples of the unsubstituted C1-C4 alkyl group include linear chains such as methyl, ethyl, n-propyl and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl and tert-butyl.
When the C1-C4 alkyl group has a carboxy group, the alkyl group moiety may be the same as described above including preferable ones.
When R ¹ is a C1-C4 alkyl group substituted with a carboxy group, preferred specific examples include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl and the like.

Specific examples of the case where R ¹ in formula (1) is a phenyl group that is unsubstituted or substituted with a sulfo group include, for example, unsubstituted phenyl, 2-sulfophenyl, 4-sulfophenyl, 2,4- And sulfo-substituted phenyl in which the sulfo group is usually 1 to 4, preferably 1 to 3, more preferably 1 to 2, such as disulfophenyl and 3,5-disulfophenyl.

R ¹ in the above formula (1) is preferably an unsubstituted C1-C4 alkyl group among the above; or an unsubstituted phenyl group, and particularly preferably an unsubstituted C1-C4 alkyl.
Specific examples of preferable R ¹ in the formula (1) include methyl, ethyl, n-propyl, tert-butyl, and phenyl, more preferably methyl, n-propyl, and phenyl, and still more preferably methyl.

In the above formula (1), R ² represents a cyano group; a carbamoyl group; or a carboxy group. Any of R ² is preferable, but cyano or carbamoyl is more preferable, and cyano is more preferable.

A preferred combination of R ¹ and R ² in formula (1) is R ¹ is methyl and R ² is cyano, or R ¹ is methyl and R ² is carbamoyl. The former combination is more preferable.

In the above formula (1), R ³ and R ⁴ each independently represent a hydrogen atom; a chlorine atom; a sulfo group; an unsubstituted C1-C4 alkyl group; or an unsubstituted C1-C4 alkoxy group.

When R ³ and R ⁴ in Formula (1) are unsubstituted C1-C4 alkyl groups, the alkyl group is the same as the case where R ¹ is an unsubstituted C1-C4 alkyl group, including preferred ones. Good.

When R ³ and R ⁴ in Formula (1) are an unsubstituted C1-C4 alkoxy group, the alkoxy group is preferably either a straight chain or a branched chain. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and the like.

In the above formula (1), R ³ and R ⁴ are more preferably a hydrogen atom; a sulfo group; or an unsubstituted C1-C4 alkyl group.
Specific examples of preferable R ³ and R ⁴ in the formula (1) include a hydrogen atom, sulfo, methyl, ethyl, n-propyl, isopropyl, and tert-butyl, and more preferably a hydrogen atom, sulfo, methyl, and isopropyl. More preferably a hydrogen atom or sulfo.

Particularly preferred R ³ and R ⁴ in the formula (1) are a hydrogen atom, methyl, or sulfo. A preferred combination of R ³ and R ⁴ is that R ³ is a hydrogen atom and R ⁴ is sulfo, or R ³ is sulfo and R ⁴ is a hydrogen atom. The former combination is more preferable.

In the above formula (1), the ring in which R ⁵ to R ⁷ are substituted is a benzene ring when a ring represented by a broken line is not present; a naphthalene ring when a ring represented by a broken line is present; Respectively. It is preferable that there is no ring represented by a broken line, that is, the ring in which R ⁵ to R ⁷ are substituted is a benzene ring.
R ⁵ to R ⁷ are each independently a hydrogen atom; chlorine atom; hydroxy group; sulfo group; carboxy group; sulfamoyl group; carbamoyl group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 A C1-C4 alkoxy group substituted with an alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, or a carboxy group; a mono- or di-C1-C4 alkyl unsubstituted or substituted with a hydroxy group, a sulfo group, or a carboxy group C1-C4 alkylcarbonylamino group unsubstituted or substituted with a hydroxy group or a carboxy group; N'-C1-C4 alkylureido group unsubstituted or substituted with a hydroxy group, a sulfo group, or a carboxy group ; Unsubstituted, or benzene ring is a chlorine atom, unsubstituted C1-C4 al Phenylamino group substituted with a benzene, nitro, sulfo, or carboxy group; unsubstituted or substituted on the benzene ring with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group A benzoylamino group; and a phenylsulfonylamino group in which the benzene ring is unsubstituted or substituted with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group; Represents a group.

When R ^{5 to} R ⁷ are an unsubstituted C1-C4 alkyl group, the alkyl group may be either a straight chain or a branched chain, but is preferably a straight chain. Specific examples of the unsubstituted C1-C4 alkyl group include linear chains such as methyl, ethyl, n-propyl and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl and tert-butyl. A preferred embodiment is methyl or ethyl, more preferably methyl.
When R ^{5 to} R ⁷ in Formula (1) are an unsubstituted C1-C4 alkoxy group, the alkoxy group includes a preferable one, and R ³ and R ⁴ are an unsubstituted C1-C4 alkoxy group. It can be the same.
When the alkoxy group is substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, or a carboxy group, specific examples thereof include, for example, 2-hydroxyethoxy, 2-hydroxy Hydroxy C1-C4 alkoxy groups such as propoxy, 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, unsubstituted C1-C4 alkoxy C1-C4 alkoxy groups such as n-propoxybutoxy; hydroxy C1-C4 alkoxy C1-C4 alkoxy groups such as 2-hydroxyethoxyethoxy; 3-sulfopropoxy, 4- Sulfo C1-C4 alkoxy group such as Ruhobutokishi; carboxymethoxy, 2-carboxyethoxy, carboxy C1-C4 alkoxy group such as a 3-carboxypropoxy; and the like.

When R ^{5 to} R ⁷ in Formula (1) are an unsubstituted mono- or di-C1-C4 alkylamino group, the C1-C4 alkyl moiety is preferably both a straight chain and a branched chain. Specific examples thereof include linear chains such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino; sec- Branched chain such as butylamino, tert-butylamino, diisopropylamino, and the like.
When the mono- or di-C1-C4 alkylamino group is substituted with a hydroxy group, a sulfo group, or a carboxy group, specific examples thereof include, for example, 2-hydroxyethylamino, 2-hydroxypropylamino, 2,2 Hydroxy-substituted mono- or di-C1-C4 alkylamino groups such as'-dihydroxydiethylamino; sulfo-substitutions such as 2-sulfoethylamino, 3-sulfopropylamino, 4-sulfobutylamino, 3,3'-disulfodipropylamino Mono- or di-C1-C4 alkylamino group; carboxy-substituted mono- or di-C1-C4 alkylamino group such as carboxymethylamino, 2-carboxyethylamino, 3-carboxypropylamino, 2,2′-dicarboxydiethylamino, etc. Can be mentioned.

When R ^{5 to} R ⁷ in Formula (1) are an unsubstituted C1-C4 alkylcarbonylamino group, the C1-C4 alkyl moiety may be either a straight chain or a branched chain, preferable. Specific examples include acetylamino, propanoylamino, butanoylamino and the like.
When the C1-C4 alkylcarbonylamino group is substituted with a hydroxy group or a carboxy group, specific examples of the C1-C4 alkylcarbonylamino group include, for example, hydroxyethanoylamino, 2-hydroxypropanoylamino, 4 -Hydroxy C1-C4 alkylcarbonylamino group such as hydroxybutanoylamino; Carboxy C1-C4 alkylcarbonylamino group such as 3-carboxypropanoylamino; and the like.

When R < ⁵ > -R < ⁷ > in Formula (1) is a N'-C1-C4 alkylureido group, what has a substituent is preferable rather than unsubstituted.
When the N′-C1-C4 alkylureido group is substituted with a hydroxy group, a sulfo group, or a carboxy group, specific examples thereof include, for example, N′-2-hydroxyethylureido, N′-3-hydroxy N′-hydroxy C1-C4 alkylureido group such as ethylureido; N′-sulfoC1-C4 alkylureido group such as N′-2-sulfoethylureido, N′-3-sulfopropylureido; N′-carboxymethyl And N′-carboxy C1-C4 alkylureido groups such as ureido, N′-2-carboxyethylureido, N′-3-carboxypropylureido, N′-4-carboxybutylureido; and the like.

R ^{5 to} R ⁷ in formula (1) are each a phenylamino group, a benzoylamino group, or a phenylsulfonylamino group each having a substituent, which are sequentially described below, and the substituent of the benzene ring contained in each group When is a C1-C4 alkyl group, the alkyl group may be linear, branched or cyclic, but is preferably linear or branched. Specific examples include, for example, linear chains such as methyl, ethyl, n-propyl, and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl, and tert-butyl.

When R ^{5 to} R ⁷ in Formula (1) are unsubstituted or a phenylamino group in which the benzene ring is substituted with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group, Specific examples thereof include unsubstituted phenylamino, or chlorine atom-substituted phenylamino groups such as 2-chlorophenylamino, 4-chlorophenylamino, and 2,4-dichlorophenylamino; 2-methylphenylamino, 4-methylphenylamino, Unsubstituted C1-C4 alkyl-substituted phenylamino groups such as 4-tert-butylphenylamino; Nitro-substituted phenylamino groups such as 2-nitrophenylamino and 4-nitrophenylamino; 3-sulfophenylamino, 4-sulfophenylamino 2,4-disulfophenylamino, 3,5-disulfopheny Sulfo-substituted phenylamino groups such as amino; carboxy-substituted phenylamino groups such as 2-carboxyphenylamino, 4-carboxyphenylamino, 2,5-dicarboxyphenylamino, and 3,5-dicarboxyphenylamino; .

When R ^{5 to} R ⁷ in formula (1) are unsubstituted or a benzoylamino group in which the benzene ring is substituted with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group, Specific examples thereof include unsubstituted benzoylamino, or chlorine atom-substituted benzoylamino groups such as 2-chlorobenzoylamino, 4-chlorobenzoylamino, 2,4-dichlorophenylamino; 2-methylbenzoylamino, 3-methylbenzoyl C1-C4 alkyl-substituted benzoylamino groups such as amino and 4-methylbenzoylamino; Nitro-substituted benzoylamino groups such as 2-nitrobenzoylamino, 4-nitrobenzoylamino and 3,5-dinitrobenzoylamino; 2-sulfobenzoylamino , 4-sulfobenzoylamino and other sulfo Conversion benzoylamino group; 2-carboxy benzoylamino, 4-carboxyphenyl benzoylamino, 3,5-carboxymethyl benzoyl carboxy-substituted benzoylamino group of the amino or the like; and the like.

When R ^{5 to} R ⁷ in Formula (1) are unsubstituted or a phenylsulfonylamino group in which the benzene ring is substituted with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group Specific examples thereof include unsubstituted phenylsulfonylamino, or chlorine atom-substituted phenylsulfonylamino groups such as 2-chlorophenylsulfonylamino and 4-chlorophenylsulfonylamino; 2-methylphenylsulfonylamino, 4-methylphenylsulfonylamino, C1-C4 alkyl-substituted phenylsulfonylamino groups such as 4-tert-butylphenylsulfonylamino; nitro-substituted phenylsulfonyl groups such as 2-nitrophenylsulfonylamino, 3-nitrophenylsulfonylamino and 4-nitrophenylsulfonylamino Amino groups; sulfo-substituted phenylsulfonylamino groups such as 3-sulfophenylsulfonylamino and 4-sulfophenylsulfonylamino; carboxy-substituted phenylsulfonylamino groups such as 3-carboxyphenylsulfonylamino and 4-carboxyphenylsulfonylamino; It is done.

Specific examples of preferable R ⁵ to R ⁷ in formula (1) are a hydrogen atom, carboxy, sulfo, methyl, ethyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy. Carboxymethoxy, 2-carboxyethoxy, methylamino, ethylamino, 2-hydroxyethylamino, 2-sulfoethylamino, 3-sulfopropylamino, 2-carboxyethylamino, dimethylamino, diethylamino, 2,2′-dihydroxy Diethylamino, 2,2′-dicarboxydiethylamino, 3,3′-disulfodipropylamino, acetylamino, 3-carboxypropanoylamino, 4-hydroxybutanoylamino, N′-carboxymethylureido, N′-2 -Sulfoethylureido, 4- Sulfophenylamino, 2,4-disulfophenylamino, 2,5-dicarboxyphenylamino, benzoylamino, 3-sulfobenzoylamino, 2-carboxybenzoylamino, phenylsulfonylamino, 4-methylphenylsulfonylamino, 4- Nitrophenylsulfonylamino, 3-sulfophenylsulfonylamino, 4-carboxyphenylsulfonylamino and the like, more preferably hydrogen atom, sulfo, methyl, methoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, dimethylamino, 3,3′-disulfodipropylamino, acetylamino, 3-carboxypropanoylamino, N′-2-sulfoethylureido, 2,4-disulfophenylamino, benzoylamino , 4-methyl-phenylsulfonylamino, more preferably a hydrogen atom, sulfo, methyl, methoxy, 3-sulfopropoxy.

A preferable combination of R ⁵ to R ⁷ in the formula (1) is different depending on whether the ring substituted by these is a benzene ring or a naphthalene ring.
When the ring substituted by R ⁵ to R ⁷ is a naphthalene ring, a combination in which any two of R ⁵ to R ⁷ are hydrogen atoms and the remaining one is sulfo is preferable. The substitution position of the sulfo is not particularly limited, but the substitution position of the azo group bonded to the benzimidazolopyridone ring is the first position, and the substitution position of the azo group bonded to the ring substituted by R ⁸ to R ¹⁰ is the fourth position. In some cases, the sulfo is preferably substituted at the 7-position.
When the ring substituted by R ⁵ to R ⁷ is a benzene ring, R ⁵ is sulfopropoxy or sulfobutoxy, preferably 3-sulfopropoxy or 4-sulfobutoxy, more preferably 3-sulfopropoxy, R ⁶ is A hydrogen atom, R ⁷ is a hydrogen atom, methyl or ethyl, preferably methyl.

In the above formula (1), the ring in which R ⁸ to R ¹⁰ are substituted is a benzene ring when a ring represented by a broken line is not present; a naphthalene ring when a ring represented by a broken line is present; Respectively. It is preferable that there is no ring represented by a broken line, that is, the ring in which R ⁸ to R ¹⁰ are substituted is a benzene ring.
R ⁸ to R ¹⁰ are each independently a hydrogen atom; chlorine atom; hydroxy group; sulfo group; carboxy group; sulfamoyl group; carbamoyl group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, C1-C4 alkoxy group A C1-C4 alkoxy group substituted with a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group; a C1-C4 alkylthio group substituted with a hydroxy group, a sulfo group or a carboxy group; an unsubstituted or hydroxy group; Mono- or di-C1-C4 alkylamino group substituted with a sulfo group or a carboxy group; C1-C4 alkylcarbonylamino group substituted with an unsubstituted or hydroxy group or carboxy group; unsubstituted, or a hydroxy group, a sulfo group Or N′-C1-C4 substituted with a carboxy group Rilureido group; unsubstituted or phenylamino group in which the benzene ring is substituted with a chlorine atom, unsubstituted C1-C4 alkyl group, nitro group, sulfo group, or carboxy group; unsubstituted, or the benzene ring is a chlorine atom, unsubstituted A benzoylamino group substituted with a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group; and an unsubstituted or benzene ring is a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or A phenylsulfonylamino group substituted by a carboxy group; a group selected from the group consisting of:

When R ^{8 to} R ¹⁰ are an unsubstituted C1-C4 alkyl group, the alkyl group may be either a straight chain or a branched chain, but is preferably a straight chain. Specific examples of the unsubstituted C1-C4 alkyl group include linear chains such as methyl, ethyl, n-propyl and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl and tert-butyl. A preferred embodiment is methyl or ethyl, more preferably methyl.

When R ^{8 to} R ¹⁰ in Formula (1) are an unsubstituted C1-C4 alkoxy group, the alkoxy group includes a preferable one, and R ³ and R ⁴ are an unsubstituted C1-C4 alkoxy group. It can be the same.
When the alkoxy group is substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, or a carboxy group, specific examples thereof include, for example, 2-hydroxyethoxy, 2-hydroxy Hydroxy C1-C4 alkoxy groups such as propoxy, 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, unsubstituted C1-C4 alkoxy C1-C4 alkoxy groups such as n-propoxybutoxy; hydroxy C1-C4 alkoxy C1-C4 alkoxy groups such as 2-hydroxyethoxyethoxy; 3-sulfopropoxy, 4- Sulfo C1-C4 alkoxy group such as Ruhobutokishi; carboxymethoxy, 2-carboxyethoxy, carboxy C1-C4 alkoxy group such as a 3-carboxypropoxy; and the like.

When R ^{8 to} R ¹⁰ in Formula (1) are an unsubstituted C1-C4 alkylthio group, the C1-C4 alkyl moiety is preferably either a straight chain or a branched chain. Specific examples thereof include straight chain such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, dimethylthio, diethylthio, di-n-propylthio, di-n-butylthio; sec-butylthio, tert-butylthio, diisopropyl Branched chain such as thio;
When the alkylthio group is substituted with a hydroxy group, a sulfo group, or a carboxy group, specific examples thereof include 2-hydroxyethylthio, 2-hydroxypropylthio, 2,2′-dihydroxydiethylthio, and the like. Hydroxy-substituted C1-C4 alkylthio groups; sulfo-substituted C1-C4 alkylthio groups such as 2-sulfoethylthio, 3-sulfopropylthio, 4-sulfobutylthio, 3,3′-disulfodipropylthio; carboxymethylthio, 2 -Carboxy-substituted C1-C4 alkylthio groups such as carboxyethylthio, 3-carboxypropylthio, 2,2'-dicarboxydiethylthio; and the like. The number of these substituents is not particularly limited, but is usually 1 to 3, preferably 1 to 2, and more preferably 1.

When R ^{8 to} R ¹⁰ in Formula (1) are an unsubstituted mono- or di-C1-C4 alkylamino group, the C1-C4 alkyl moiety is preferably either a straight chain or a branched chain. Specific examples thereof include linear chains such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino; sec- Branched chain such as butylamino, tert-butylamino, diisopropylamino, and the like.
When the mono- or di-C1-C4 alkylamino group is substituted with a hydroxy group, a sulfo group, or a carboxy group, specific examples thereof include, for example, 2-hydroxyethylamino, 2-hydroxypropylamino, 2,2 Hydroxy-substituted mono- or di-C1-C4 alkylamino groups such as'-dihydroxydiethylamino; sulfo-substitutions such as 2-sulfoethylamino, 3-sulfopropylamino, 4-sulfobutylamino, 3,3'-disulfodipropylamino Mono- or di-C1-C4 alkylamino group; carboxy-substituted mono- or di-C1-C4 alkylamino group such as carboxymethylamino, 2-carboxyethylamino, 3-carboxypropylamino, 2,2′-dicarboxydiethylamino, etc. Can be mentioned.

When R ^{8 to} R ¹⁰ in Formula (1) are an unsubstituted C1-C4 alkylcarbonylamino group, the C1-C4 alkyl moiety may be either a straight chain or a branched chain, preferable. Specific examples include acetylamino, propanoylamino, butanoylamino and the like.
When the C1-C4 alkylcarbonylamino group is substituted with a hydroxy group or a carboxy group, specific examples of the C1-C4 alkylcarbonylamino group include, for example, hydroxyethanoylamino, 2-hydroxypropanoylamino, 4 -Hydroxy C1-C4 alkylcarbonylamino group such as hydroxybutanoylamino; Carboxy C1-C4 alkylcarbonylamino group such as 3-carboxypropanoylamino; and the like.

When R < ⁸ > -R < ¹⁰ > in Formula (1) is a N'-C1-C4 alkylureido group, what has a substituent is preferable rather than unsubstituted.
When the N′-C1-C4 alkylureido group is substituted with a hydroxy group, a sulfo group, or a carboxy group, specific examples thereof include, for example, N′-2-hydroxyethylureido, N′-3-hydroxy N′-hydroxy C1-C4 alkylureido group such as ethylureido; N′-sulfoC1-C4 alkylureido group such as N′-2-sulfoethylureido, N′-3-sulfopropylureido; N′-carboxymethyl And N′-carboxy C1-C4 alkylureido groups such as ureido, N′-2-carboxyethylureido, N′-3-carboxypropylureido, N′-4-carboxybutylureido; and the like.

R ^{8 to} R ¹⁰ in Formula (1) are each a phenylamino group, a benzoylamino group, or a phenylsulfonylamino group each having a substituent, which are sequentially described below, and the substituent of the benzene ring contained in each group When is a C1-C4 alkyl group, the alkyl group may be linear, branched or cyclic, but is preferably linear or branched. Specific examples include, for example, linear chains such as methyl, ethyl, n-propyl, and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl, and tert-butyl.

When R ^{8 to} R ¹⁰ in Formula (1) are unsubstituted or a phenylamino group in which the benzene ring is substituted with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group, Specific examples thereof include unsubstituted phenylamino, or chlorine atom-substituted phenylamino groups such as 2-chlorophenylamino, 4-chlorophenylamino, and 2,4-dichlorophenylamino; 2-methylphenylamino, 4-methylphenylamino, Unsubstituted C1-C4 alkyl-substituted phenylamino groups such as 4-tert-butylphenylamino; Nitro-substituted phenylamino groups such as 2-nitrophenylamino and 4-nitrophenylamino; 3-sulfophenylamino, 4-sulfophenylamino 2,4-disulfophenylamino, 3,5-disulfofe Sulfo-substituted phenylamino groups such as ruamino; carboxy-substituted phenylamino groups such as 2-carboxyphenylamino, 4-carboxyphenylamino, 2,5-dicarboxyphenylamino, 3,5-dicarboxyphenylamino; .

When R ^{8 to} R ¹⁰ in Formula (1) are unsubstituted or a benzoylamino group in which the benzene ring is substituted with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group, Specific examples thereof include unsubstituted benzoylamino, or chlorine atom-substituted benzoylamino groups such as 2-chlorobenzoylamino, 4-chlorobenzoylamino, 2,4-dichlorophenylamino; 2-methylbenzoylamino, 3-methylbenzoyl C1-C4 alkyl-substituted benzoylamino groups such as amino and 4-methylbenzoylamino; Nitro-substituted benzoylamino groups such as 2-nitrobenzoylamino, 4-nitrobenzoylamino and 3,5-dinitrobenzoylamino; 2-sulfobenzoylamino , 4-sulfobenzoylamino, etc. Substituted benzoylamino group; 2-carboxy benzoylamino, 4-carboxyphenyl benzoylamino, 3,5-carboxymethyl benzoyl carboxy-substituted benzoylamino group of the amino or the like; and the like.

When R ^{8 to} R ¹⁰ in Formula (1) are unsubstituted or a phenylsulfonylamino group in which the benzene ring is substituted with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group Specific examples thereof include unsubstituted phenylsulfonylamino, or chlorine atom-substituted phenylsulfonylamino groups such as 2-chlorophenylsulfonylamino and 4-chlorophenylsulfonylamino; 2-methylphenylsulfonylamino, 4-methylphenylsulfonylamino, C1-C4 alkyl-substituted phenylsulfonylamino group such as 4-tert-butylphenylsulfonylamino; nitro-substituted phenylsulfo such as 2-nitrophenylsulfonylamino, 3-nitrophenylsulfonylamino and 4-nitrophenylsulfonylamino A sulfo-substituted phenylsulfonylamino group such as 3-sulfophenylsulfonylamino and 4-sulfophenylsulfonylamino; a carboxy-substituted phenylsulfonylamino group such as 3-carboxyphenylsulfonylamino and 4-carboxyphenylsulfonylamino; It is done.

Specific examples of preferable R ⁸ to R ¹⁰ in the formula (1) are a hydrogen atom, carboxy, sulfo, methyl, ethyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy. 3-sulfopropylthio or 4-sulfobutylthio, carboxymethoxy, 2-carboxyethoxy, methylamino, ethylamino, 2-hydroxyethylamino, 2-sulfoethylamino, 3-sulfopropylamino, 2-carboxyethylamino , Dimethylamino, diethylamino, 2,2′-dihydroxydiethylamino, 2,2′-dicarboxydiethylamino, 3,3′-disulfodipropylamino, acetylamino, 3-carboxypropanoylamino, 4-hydroxybutanoylamino N'-carboxy Tilureido, N′-2-sulfoethylureido, 4-sulfophenylamino, 2,4-disulfophenylamino, 2,5-dicarboxyphenylamino, benzoylamino, 3-sulfobenzoylamino, 2-carboxybenzoylamino, Phenylsulfonylamino, 4-methylphenylsulfonylamino, 4-nitrophenylsulfonylamino, 3-sulfophenylsulfonylamino, 4-carboxyphenylsulfonylamino, and the like, more preferably a hydrogen atom, sulfo, methyl, methoxy, 2- Hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, dimethylamino, 3,3′-disulfodipropylamino, acetylamino, 3-carboxypropanoylamino, N′-2-sulfoethylurei , 2,4-sulfophenyl, benzoylamino, 4-methyl-phenylsulfonylamino, more preferably a hydrogen atom, sulfo, methyl, methoxy, 3-sulfopropoxy.

A preferable combination of R ⁸ to R ¹⁰ in the formula (1) differs depending on whether the ring they are substituted is a benzene ring or a naphthalene ring.
When the ring substituted by R ⁸ to R ¹⁰ is a naphthalene ring, R ⁸ is a hydrogen atom, R ⁹ is sulfopropoxy, R ¹⁰ is sulfo; or any two of R ⁸ to R ¹⁰ are hydrogen atoms, Combinations wherein the remaining one is sulfo; are preferred. The position of each substituent is not particularly limited, but when the substitution position of the azo group bonded to the group A is 4-position, and the substitution position of the azo group bonded to the ring substituted by R ⁵ to R ⁷ is 1-position, In the former, R ⁹ is in the 5-position and R ¹⁰ is in the 7-position; the latter sulfo is preferably substituted in the 7-position.
When the ring in which R ⁸ to R ¹⁰ are substituted is a benzene ring, R ⁸ is sulfopropoxy, sulfobutoxy, sulfopropylthio, or sulfobutylthio, preferably 3-sulfopropoxy or 3-sulfopropylthio, R ⁹ is a hydrogen atom, and R ¹⁰ is methyl or ethyl, preferably methyl. The position of each substituent is not particularly limited, but when the substitution position of the azo group bonded to the group A is 4-position, and the substitution position of the azo group bonded to the ring substituted by R ⁵ to R ⁷ is 1-position, It is preferable that R ⁸ is substituted at the 2-position and R ¹⁰ is substituted at the 5-position.

The group A in the formula (1) is an unsubstituted or substituted benzothiazolyl group; a thiadiazolyl group; or a thiazolyl group.
When the benzothiazolyl group has a substituent, chlorine atom; sulfo group; nitro group; hydroxy group; sulfamoyl group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, C1-C4 alkoxy group, sulfo group Or a C1-C4 alkoxy group substituted with a carboxy group; an unsubstituted or C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group, or a carboxy group; and an unsubstituted or benzene ring is a chlorine atom, A phenylsulfonyl group substituted with an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group; and a substituent selected from the group consisting of: Each of these substituents may be the same including the corresponding ones and preferred ones from R ⁵ to R ⁸ in the above formula (1). The number of substituents is not particularly limited, but is usually 1 to 4, preferably 1 to 3, and more preferably 2. Of the above, sulfo is preferred.
When the thiadiazolyl group or thiazolyl group has a substituent, chlorine atom; sulfo group; nitro group; hydroxy group; sulfamoyl group; mercapto group; and unsubstituted or hydroxy group, C1-C4 alkoxy group, hydroxy C1 A C1-C4 alkylthio group substituted with a C4 alkoxy group, a sulfo group, or a carboxy group; may have a substituent selected from the group consisting of; The number of substituents is not particularly limited, but 1 is preferable. Among the above, sulfo; or a C1-C4 alkylthio group substituted with a sulfo group or a carboxy group is preferable. More preferred are sulfo, sulfopropylthio, and carboxymethylthio.

A preferable compound represented by the above formula (1) is a compound represented by the above formula (2). In the formula (2), the groups A, R ¹ to R ¹⁰ , and R ⁸ to R ¹⁰ are preferably substituted in the formula (1) including the ring represented by a broken line, etc. The same may be included.

A preferable compound represented by the above formula (2) is a compound represented by the above formula (3). In the formula (3), the groups A and R ¹ to R ¹⁰ may be the same including those preferred in the above formula (1).

A preferable compound represented by the above formula (3) is a compound represented by the above formula (4). In the above formula (4), the groups A, R ¹ to R ⁴ , and R ⁸ to R ¹⁰ may be the same including those preferred in the above formula (1).
R ⁵ and ^{R 7} are independently a hydrogen atom; sulfo C1-C4 alkoxy groups; unsubstituted C1-C4 alkyl group; hydroxy group; or unsubstituted or hydroxy-substituted C1-C4 alkoxy group; a, ^{R 6} is Represents a hydrogen atom.
R ⁵ and R ⁷ in formula (4) may be the same as those corresponding to R ⁵ and R ⁷ in formula (1), including preferable ones.

A preferable compound represented by the above formula (4) is a compound represented by the above formula (5). In the above formula (5), the groups A, R ¹ to R ⁴ , and R ⁵ to R ⁷ may be the same as in the above formula (1), including those preferred.
R ⁸ and R ¹⁰ are each independently a hydrogen atom; a sulfo C1-C4 alkoxy group; an unsubstituted C1-C4 alkyl group; a hydroxy group; an unsubstituted or hydroxy-substituted C1-C4 alkoxy group; or a sulfo group or a carboxy group. And R ⁶ represents a hydrogen atom.
R ⁸ and R ¹⁰ in formula (5) may be the same as those corresponding to R ⁸ and R ¹⁰ in formula (1), including preferable ones.

In the above formulas (1) to (5), preferred as the group A is a group represented by the above formula (6).
In the above formula (6), R ¹¹ to R ¹³ are each independently a hydrogen atom; chlorine atom; sulfo group; nitro group; hydroxy group; sulfamoyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 alkoxy group, sulfo A C1-C4 alkoxy group substituted with a group or a carboxy group; or a C1-C4 alkylsulfonyl group unsubstituted or substituted with a hydroxy group, a sulfo group, or a carboxy group.

When R ¹¹ to R ¹³ in Formula (6) are unsubstituted or a C1-C4 alkoxy group substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group, or a carboxy group, the alkoxy group is Including the preferred ones, R ⁵ to R ⁷ in the above formula (1) may be the same as the corresponding C1-C4 alkoxy group.

When R ¹¹ to R ¹³ in formula (6) are unsubstituted or a C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group, or a carboxy group, specific examples thereof include, for example, methylsulfonyl, ethylsulfonyl , Propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl and the like linear or branched unsubstituted C1-C4 alkylsulfonyl groups; 2-hydroxyethylsulfonyl, 3-hydroxypropylsulfonyl and the like A hydroxy C1-C4 alkylsulfonyl group; a sulfo C1-C4 alkylsulfonyl group such as 2-sulfopropylsulfonyl, 3-sulfopropylsulfonyl, 4-sulfobutylsulfonyl; carboxymethylsulfonyl, 2-carboxyethyl Sulfonyl, carboxy C1-C4 alkylsulfonyl group such as 3-carboxypropyl sulfonyl; and the like.

Specific examples of preferable R ¹¹ to R ¹³ in the formula (6) include a hydrogen atom, a chlorine atom, sulfo, nitro, methoxy, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, Carboxymethoxy, 2-carboxyethoxy, methylsulfonyl, ethylsulfonyl, tert-butylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, 2-carboxyethylsulfonyl, phenylsulfonyl, 4-chlorophenylsulfonyl, 4-methylphenylsulfonyl 2,4-dimethylphenylsulfonyl, 4-nitrophenylsulfonyl, 4-sulfophenylsulfonyl, 2-carboxyphenylsulfonyl, 4-carboxyphenylsulfonyl, and the like, more preferably Atom, chlorine atom, sulfo, nitro, methoxy, methylsulfonyl, more preferably a hydrogen atom, sulfo, methoxy, 3-sulfopropoxy. Among R ¹¹ to R ¹³ , at least one is preferably a hydrogen atom, and at least one is preferably a substituent other than a hydrogen atom.

A preferable combination of R ¹¹ to R ¹³ in the formula (6) is one in which one is sulfo and the other two are hydrogen atoms, or two are sulfo and the other one is a hydrogen atom, and more preferably the latter combination. The position of sulfo substitution on the benzothiazole ring is not particularly limited, but the 6-position is preferable in the former case, and the 4-position and 6-position are preferable in the latter case.

The compound which combined the preferable thing described about the substituent of the said Formula (1) to Formula (6) is more preferable, and the compound which combined more preferable things is further more preferable. The same applies to preferable ones. As described above, in the formulas (7) to (8), the ring in which the groups A and R ¹ to R ¹⁰ are substituted is the same as that in the formula (1) including the ring represented by the broken line. Has meaning. Moreover, the same may be sufficient also in a preferable thing, the combination of preferable things, etc.

  The salt of the trisazo compound represented by the above formula (1) is an inorganic or organic cation salt. Among them, specific examples of inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts, and preferred inorganic salts are lithium, sodium, potassium salts, and ammonium salts. Examples of the organic cation salt include, but are not limited to, quaternary ammonium ions represented by the following formula (9). Moreover, the mixture of a free acid, its tautomer, and those various salts may be sufficient. For example, any combination such as a mixture of sodium salt and ammonium salt, a mixture of free acid and sodium salt, a mixture of lithium salt, sodium salt, and ammonium salt may be used. Depending on the type of salt, the physical properties such as solubility may differ, and if necessary, select the type of salt as appropriate, or change the ratio when containing multiple salts, etc. Mixtures having suitable physical properties can also be obtained.

In Formula (9), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyalkyl group, and a hydroxyalkoxyalkyl group.
Specific examples of the alkyl group of Z ¹ , Z ² , Z ³ , Z ^{4 in} the formula (9) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Can be mentioned. Specific examples of the hydroxyalkyl group include hydroxy C1-C4 alkyl groups such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like. . Examples of hydroxyalkoxyalkyl groups include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl, etc. A hydroxy C1-C4 alkoxy C1-C4 alkyl group is mentioned, Of these, hydroxyethoxy C1-C4 alkyl is preferred. Particularly preferred are hydrogen atoms; hydroxy C1-C4 alkyl groups such as methyl, hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, And hydroxyethoxy C1-C4 alkyl groups such as hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl and the like. It is done.

Specific examples of combinations of Z ¹ , Z ² , Z ³ , and Z ^{4 which} are preferable compounds as the formula (9) are shown in Table 1 below.

The trisazo compound represented by the above formula (1) can be synthesized, for example, by the following method. In addition, the acidic functional group of the compound in each process shall be represented in the form of a free acid for convenience. In the following formulas (10) to (15), each of the rings substituted by n, group A, R ¹ to R ¹⁰ , and R ⁵ to R ¹⁰ includes the ring represented by the broken line. Has the same meaning as in formula (1).
A compound represented by the following formula (10) is diazotized by a conventional method, and this and a compound represented by the following formula (11) are coupled by a conventional method to obtain a compound represented by the following formula (12). obtain. In addition, the compound represented by Formula (11) and (13) is compoundable by a conventional method. The same applies to the compound represented by the formula (10).

  The compound represented by the formula (12) thus obtained was diazotized by a conventional method, and this was then coupled with a compound represented by the following formula (13) by a conventional method to obtain a compound represented by the following formula (14). To obtain the compound.

  The compound represented by the formula (14) thus obtained is diazotized by a conventional method, and then this and a compound represented by the following formula (15) are subjected to a coupling reaction by a conventional method, whereby the above formula (1) The trisazo compound of this invention represented by these can be obtained.

  In addition, the compound represented by the said Formula (15) is compoundable according to the method of patent document 5.

Although it does not specifically limit as a suitable specific example of the compound of this invention shown to the said Formula (1), The compound represented by the structural formula given to the following Table 2 thru | or 5 etc. is mentioned.
In each table, functional groups such as sulfo group and carboxy group are described in the form of free acid for convenience.

  The diazotization of the compound represented by the above formula (10) is carried out by a method known per se. For example, using nitrosylsulfuric acid in sulfuric acid, acetic acid or phosphoric acid, for example at a temperature of -5 to 20 ° C, preferably 5 to 10 ° C. Coupling of the diazotized compound of the compound represented by the formula (10) and the compound represented by the formula (11) is also carried out under conditions known per se. For example, it is carried out at a temperature of, for example, -5 to 30 ° C, preferably 10 to 30 ° C in water or an aqueous organic medium (such as a mixture of water and a water-soluble organic solvent). The compound represented by formula (10) and the compound represented by formula (11) are used in approximately stoichiometric amounts.

  The diazotization of the compound represented by the formula (12) is also carried out by a method known per se. For example, an alkali metal nitrite such as a nitrite, for example sodium nitrite, in the presence of an inorganic acid such as hydrochloric acid, sulfuric acid in water or an aqueous organic medium, for example at a temperature of -5 to 40 ° C., preferably 5 to 30 ° C. Performed using salt. Coupling of the diazotized compound of the compound represented by formula (12) and the compound represented by formula (13) is also carried out under conditions known per se. For example, it is advantageous to carry out the reaction in water or an aqueous organic medium, for example at a temperature of -5 to 50 ° C, preferably 10 to 30 ° C, and a weakly acidic to alkaline pH value. It is preferably carried out at a weakly acidic to weakly alkaline pH value, for example, pH 6-10. Since the diazotization reaction solution is acidic and the reaction system is further acidified by the progress of the coupling reaction, it is preferable to adjust the pH value by adding a base. Examples of the base that can be used include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, acetates such as sodium acetate, ammonia, and organic amines. . The compound represented by formula (12) and the compound represented by formula (13) are used in approximately stoichiometric amounts.

  The diazotization of the compound represented by the formula (14) is also carried out by a method known per se. For example, nitrite in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid in water or an aqueous organic medium (such as a mixture of water and a water-soluble organic solvent), for example, at a temperature of -5 to 40 ° C, preferably 10 to 30 ° C. For example, using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of the compound represented by the formula (14) with the compound represented by the formula (15) is also carried out under conditions known per se. For example, it is advantageous to carry out the reaction in water or an aqueous organic medium, for example at a temperature of -5 to 50 ° C, preferably 10 to 30 ° C, and a weakly acidic to alkaline pH value. It is preferably carried out at a weakly acidic to weakly alkaline pH value, for example, pH 6 to 10, and the pH value is adjusted by adding a base. As the base, the same ones as described above can be used. The compound represented by formula (14) and the compound represented by formula (15) are used in approximately stoichiometric amounts.

  In order to make the trisazo compound represented by the formula (1) of the present invention into a desired salt, salting out is performed by adding a desired inorganic salt or organic cation salt to the reaction solution after the coupling reaction. Or isolated in the form of a free acid by the addition of a mineral acid such as hydrochloric acid, and this is washed with water, acidic water or an aqueous organic medium as necessary to remove inorganic salts, and then in an aqueous medium. The solution of the corresponding salt can be obtained by neutralizing with a desired inorganic or organic base. Here, acidic water refers to water obtained by dissolving a mineral acid such as sulfuric acid or hydrochloric acid or an organic acid such as acetic acid in water. The aqueous organic medium refers to water-containing organic materials miscible with water, so-called organic solvents miscible with water, and specific examples include water-soluble organic solvents described later. Examples of inorganic salts include alkali metal salts such as lithium chloride, sodium chloride, and potassium chloride, and ammonium salts such as ammonium chloride and ammonium bromide. Examples of organic cation salts include the above formula ( Examples thereof include halogen salts of organic amines represented by 9). Examples of inorganic bases include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate. Examples of the organic base include organic amines such as quaternary ammoniums represented by the above formula (9) such as diethanolamine and triethanolamine, but are not limited thereto. Absent.

  The ink composition of the present invention will be described. The aqueous ink composition containing the trisazo compound represented by the above formula (1) according to the present invention can dye a material made of cellulose. In addition, other materials having a carbonamide bond can be dyed, and can be widely used for dyeing leather, fabric and paper. On the other hand, a typical use of the compound of the present invention is an ink composition dissolved in a liquid medium, and is particularly suitable as an ink composition for inkjet printing.

  The reaction liquid containing the trisazo compound of the present invention represented by the above formula (1), for example, the reaction liquid before salting out with sodium chloride in (Step 5) of Example 1 described later, is used for the production of the ink composition. Can be used directly. It is first isolated by drying, eg spray drying; salting out by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate; minerals such as hydrochloric acid, sulfuric acid, nitric acid The trisazo compound of the present invention is isolated by, for example, acid precipitation by adding an acid; or by acid precipitation by combining the salting-out and acid precipitation described above, and an ink composition is prepared using the compound. You can also.

  The ink composition of the present invention usually contains 0.1 to 20% by mass, preferably 1 to 10% by mass, more preferably 2 to 8% by mass of the trisazo compound represented by the formula (1) of the present invention. The balance is a composition with water as the main medium. The ink composition of the present invention may further contain a water-soluble organic solvent, for example, 0 to 30% by mass, and an ink preparation agent, for example, 0 to 10% by mass. Moreover, you may contain another pigment | dye for the purpose of toning etc. if desired. Even in this case, the total mass of the pigment contained in the total mass of the ink composition including the pigment for toning may be in the above range. The pH of the ink composition is preferably 5 to 11 and more preferably 7 to 10 in terms of improving storage stability. Further, the surface tension of the ink composition is preferably 25 to 70 mN / m, and more preferably 25 to 60 mN / m. Furthermore, the viscosity of the ink composition is preferably 30 mPa · s or less, and more preferably 20 mPa · s or less. The pH and surface tension of the ink composition of the present invention can be appropriately adjusted with a pH adjusting agent and a surfactant as described later.

  In the ink composition of the present invention, the trisazo compound represented by the above formula (1) is dissolved in water or a water-soluble organic solvent (an organic solvent miscible with water), and an ink preparation agent is added as necessary. Is. For the purpose of adjusting a neutral black ink composition having no color, other toning dyes and the like may be appropriately added to the trisazo compound of the present invention. When this ink composition is used as an ink for an ink jet printer, it is preferable to use a trisazo compound of the present invention having a low content of inorganic impurities such as metal cation chlorides and sulfates. The standard of the inorganic impurity content is approximately 1% by mass or less with respect to the total mass of the pigment. In order to produce the azo compound of the present invention with less inorganic impurities, for example, a usual method using a reverse osmosis membrane, or a dried product or wet cake of the azo compound of the present invention is stirred in a mixed solvent of alcohol such as methanol and water. The desalting treatment may be performed by a method such as filtration separation and drying.

  Specific examples of water-soluble organic solvents that can be used in the preparation of the ink composition include C1-C4 alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, and tert-butanol; N, Carboxylic acid amides such as N-dimethylformamide and N, N-dimethylacetamide; Lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone and N-methylpyrrolidin-2-one; 1,3-dimethylimidazolidine-2 -Cyclic ureas such as 1,3-dimethylhexahydropyrimido-2-one; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; tetrahydrofuran, dioxane, etc. Cyclic ethers of ethylene glycol, 1 2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol , Mono-, oligo- or polyalkylene glycols or thioglycols having C2-C6 alkylene units such as polypropylene glycol, thiodiglycol, dithiodiglycol; polyols (triols) such as glycerin, hexane-1,2,6-triol; ethylene Glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Recall monobutyl ether (butyl carbitol) Triethylene glycol monomethyl ether, C1-C4 alkyl ethers of polyhydric alcohols such as triethylene glycol monoethyl ether; .gamma.-butyrolactone, dimethyl sulfoxide and the like. These organic solvents may be used alone or in combination of two or more.

  Examples of the ink preparation agent that is appropriately used in the preparation of the ink composition include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventive agents, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye dissolving agents, and antioxidants. Agents, surfactants and the like. These drugs are described below.

  Specific examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one, and salts thereof. . These are preferably used in the ink composition in an amount of 0.02 to 1.00% by mass.

  Specific examples of the preservative include, for example, organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, and 8-oxyquinoline. , Benzothiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated Indanone-based compounds, benzyl bromacetate-based compounds, inorganic salt-based compounds and the like can be mentioned. Specific examples of the organic halogen compound include sodium pentachlorophenol, and specific examples of the pyridine oxide compound include sodium 2-pyridinethiol-1-oxide, and specific examples of the isothiazoline compound. For example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2 -Methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride and the like. Specific examples of other antiseptic / antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate and the like.

  As the pH adjuster, any substance can be used as long as it can control the pH of the ink within a range of, for example, 5 to 11 without adversely affecting the prepared ink. Specific examples thereof include, for example, alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (ammonia water) Alkaline metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate and potassium carbonate; alkali metal salts of organic acids such as sodium silicate and potassium acetate; inorganic bases such as disodium phosphate;

  Specific examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate and the like.

  Specific examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.

  Specific examples of the water-soluble ultraviolet absorber include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

  Specific examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines, polyimines and the like.

Specific examples of the dye solubilizer include ε-caprolactam, ethylene carbonate, urea and the like.
As specific examples of the antioxidant, for example, various organic and metal complex antifading agents can be used. Specific examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocyclic rings. It is done.

Specific examples of the surfactant include known surfactants such as anionic, cationic, and nonionic surfactants.
Specific examples of the anionic surfactant include alkyl sulfonate, alkyl carboxylate, α-olefin sulfonate, polyoxyethylene alkyl ether acetate, N-acyl amino acid and its salt, N-acylmethyl taurate, Alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfone Acid salts, diethylsulfosuccinate, diethylhexylsylsulfosuccinate, dioctylsulfosuccinate and the like.
Specific examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
Specific examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, Examples include imidazoline derivatives.
Specific examples of nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether and the like. Ether type: polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, etc. Ester series; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3, -Acetylene glycol (alcohol) type such as dimethyl-1-hexyn-3-ol; other specific examples include, for example, trade name Surfinol 104, 105, 82, 465, Olphine STG, etc., manufactured by Nissin Chemical. .
These ink preparation agents are used alone or in combination.

  The ink composition of the present invention can be obtained by mixing and stirring the above components in an arbitrary order. The obtained ink composition may be filtered with a membrane filter or the like, if desired, in order to remove impurities. Moreover, in order to adjust the black color as an ink composition, in addition to the trisazo compound represented by the formula (1) of the present invention, other dyes having various hues may be mixed. In that case, black having a different hue or yellow (for example, CI Direct Yellow 34, CI Direct Yellow 58, CI Direct Yellow 86, CI Direct Yellow 132, CI Direct Yellow 161, etc.), orange (for example, CI Direct Orange 17, CI Direct Orange 26, CI Direct Orange 29, CI Direct Orange 39, CI Direct Orange 49, etc. ), Brown, scarlet (for example, CI Direct Red 89), red (for example, CI Direct Red 62, CI Direct Red 75, CI Direct Red 79, CI Direct Red) 80, CI Direct Red 84, CI Direct Red 225, CI Direct Red 226, etc.), magenta (for example C.I. Direct Red 227, etc.), can be violet, blue, navy, cyan, green, be used as a mixture of other colors of dye.

  The ink composition of the present invention can be used in various fields, but is suitable for a writing water-based ink, a water-based printing ink, an information recording ink, and the like, and is particularly preferably used as an ink-jet ink. It is suitably used in the inkjet printing method.

Next, the ink jet printing method of the present invention will be described. The inkjet printing method of the present invention is characterized in that inkjet recording is performed using the ink composition of the present invention. In the ink jet printing method of the present invention, recording is performed on a recording material using an ink jet ink containing the above ink composition, but there are no particular restrictions on the ink nozzles and the like used at that time, depending on the purpose. It can be selected appropriately.
A known method, for example, a charge control method that ejects ink using electrostatic attraction; a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element; an electric signal is converted into an acoustic beam and the ink is irradiated And adopting an acoustic ink jet method that discharges ink using the radiation pressure; a thermal ink jet that heats the ink to form bubbles and uses the generated pressure, that is, a bubble jet (registered trademark) method; Can do.
In the inkjet printing method, a method called a photo ink, in which a large number of inks having a low pigment concentration (pigment content) are ejected in a small volume; the pigment concentrations in the ink differ with substantially the same hue. A system that improves image quality using a plurality of inks; a system that uses colorless and transparent ink, and the like are also included.

The colored body of the present invention is colored by the compound of the present invention represented by the above formula (1) or an ink composition containing the compound, and more preferably by an inkjet printing method using an inkjet printer. The recording material is colored with the ink composition.
The recording material that can be colored is not particularly limited, and examples thereof include information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, and base materials for color filters. A transmission sheet is preferred.
The information transmission sheet is preferably a surface-treated sheet, specifically, a sheet such as paper, synthetic paper, or film provided with an ink receiving layer. The ink receiving layer is formed by, for example, impregnating or coating the base material with a cationic polymer; inorganic fine particles capable of absorbing pigments in inks such as porous silica, alumina sol, and special ceramics are hydrophilic such as polyvinyl alcohol and polyvinyl pyrrolidone. A method of coating the surface of the base material together with the conductive polymer; Those provided with such an ink receiving layer are usually called ink jet exclusive paper, ink jet exclusive film, glossy paper, gloss film and the like.

Among the above-mentioned information transmission sheets, a sheet coated with a porous white inorganic substance on the surface is particularly suitable for printing photographic images because of its high surface gloss and excellent water resistance. On the other hand, it is known that the images recorded in these images are greatly discolored by ozone gas. However, since the ink composition of the present invention is excellent in ozone gas resistance, it exhibits a particularly great effect when inkjet printing is performed on such a recording material.
An example of a typical commercial product as a sheet coated on the surface with the porous white inorganic material as described above is manufactured by Canon Inc. Trade name: Professional Photo Paper, Super Photo Paper, Glossy Gold, and Matt Photo Paper; Product name: Photographic paper Krispia (high gloss), Photographic paper (glossy), Photomat paper; Nihon Hewlett-Packard Co., Ltd. Product name: Advanced photo paper (glossy); Fuji Film Co., Ltd. Product Name: Painting Photo Finishing Pro;

In order to record on a recording material such as an information transmission sheet by the ink jet printing method of the present invention, for example, a container containing the above ink composition is loaded at a predetermined position of an ink jet printer, and the recording material is processed by a normal method. Can be recorded.
The inkjet printing method of the present invention includes the black ink composition of the present invention and, for example, known magenta, cyan, yellow, and, if necessary, each color ink such as green, blue (or violet), and red (or orange). A composition can also be used in combination.
The ink composition of each color is poured into each container, and each container is loaded into a predetermined position of the ink jet printer in the same manner as the container containing the black ink composition of the present invention, and used for ink jet printing.

The trisazo compound of the present invention is excellent in water solubility, and the ink composition of the present invention containing this compound as a pigment does not cause solid precipitation, change in physical properties, change in hue, etc. even when stored for a long period of time. Storage stability is good.
The ink composition containing the trisazo compound of the present invention can be used for inkjet printing and writing instruments.
Furthermore, when printed on information transmission sheets, especially inkjet paper, the print density of the printed image is high. In addition, various durability of the printed image, that is, water resistance, gas resistance, moisture resistance, etc., particularly ozone gas resistance. And excellent light resistance.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by the following example.
In the text, “parts” and “%” are based on mass unless otherwise specified. In the following formulas, functional groups such as sulfo and carboxy are expressed in the form of free acid.
Moreover, both the pH value and reaction temperature described below show measured values in the reaction system.
Further, the maximum absorption wavelength (λmax) of the synthesized compound was measured in an aqueous solution having an equal pH of 7 to 8, and the measured value was described in the examples for the measured compound.
In addition, all the synthesized trisazo compounds of the present invention showed a solubility of 100 g / L or more in water.

[Example 1]
(Process 1)
After 20 parts of 2-aminobenzothiazole was slowly added to 180 parts of 30% fuming sulfuric acid at 20 to 25 ° C., the temperature was raised to 120 ° C. and stirred at the same temperature for 3 hours. The reaction solution was dropped into 158 parts of ice water in about 15 minutes, and then the precipitated solid was separated by filtration to obtain 14.4 parts of a compound represented by the following formula (16).

(Process 2)
12.4 parts of the compound represented by the above formula (16) is dissolved in 100 parts of 97% sulfuric acid, and 75 parts of water is added and suspended with stirring. Then, 4.3 parts of 60% nitric acid is added and 5 to 10 ° C. Then, 20 parts of 40% nitrosylsulfuric acid was added dropwise over about 10 minutes and reacted for 1 hour to obtain a diazo reaction liquid.
Meanwhile, an aqueous solution was obtained by adding 10.8 parts of a compound represented by the following formula (17), 8.0 parts of sulfamic acid, and then sodium hydroxide to 130 parts of water to adjust the pH to 5.0 to 5.5. .
The above diazo reaction liquid was dropped into the obtained aqueous solution at a reaction temperature of 20 to 30 ° C. for about 20 minutes.
After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour, and after adding 400 parts of acetone, the precipitated solid was separated by filtration to obtain a wet cake containing a compound represented by the following formula (18).
In addition, the compound represented by following formula (17) was obtained by the method as described in Unexamined-Japanese-Patent No. 2004-083492.

(Process 3)
An aqueous solution was obtained by adding 5.4 parts of the compound represented by the above formula (17) to 35 parts of water and then adding sodium hydroxide to adjust the pH to 5.0 to 5.5.
On the other hand, by adding 110 parts of water and then sodium hydroxide to the wet cake containing the compound represented by the formula (18) obtained in the above (Step 2) under stirring, the pH is adjusted to 7.0 to 7.5. An aqueous solution was obtained.
To the obtained aqueous solution, 4.6 parts of 35% hydrochloric acid, and then 5.0 parts of 40% aqueous sodium nitrite solution at a reaction temperature of 15 to 20 ° C. were added dropwise over about 5 minutes, and reacted for 1 hour to obtain a diazo reaction liquid. Obtained.
The obtained diazo reaction liquid was dripped at reaction temperature 20-30 degreeC and 20 minutes to the aqueous solution containing the compound represented by Formula (17) obtained similarly to the previous method. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 5.0 to 5.4. After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, salted out by addition of sodium chloride, and the precipitated solid was separated by filtration to obtain a wet cake containing a compound represented by the following formula (19).

(Process 4)
The wet cake containing the compound represented by the formula (19) obtained in the above (Step 3) is dissolved in 150 parts of water, 4.1 parts of 35% hydrochloric acid, and then 40% nitrous acid at a reaction temperature of 20 to 25 ° C. A diazo reaction liquid was obtained by dropping 1.8 parts of an aqueous sodium solution over about 5 minutes and reacting for 1 hour.
On the other hand, an aqueous solution was obtained by adding 2.4 parts of the compound of the formula (20) obtained by the method described in Patent Document 8 to 55 parts of water and then adding sodium hydroxide to pH 7.5 to 8.0. The diazo reaction liquid obtained as described above was dropped into this aqueous solution at a reaction temperature of 20 to 30 ° C. for 30 minutes. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 7.0 to 8.0.
After completion of dropping, the mixture was stirred at the same temperature for 2 hours, sodium chloride was added for salting out, and the precipitated solid was separated by filtration to obtain a wet cake. The obtained wet cake was dissolved in 160 parts of water, 350 parts of acetone was added, and the precipitated solid was separated by filtration to obtain a wet cake. The obtained wet cake was dissolved again in 110 parts of water and 280 parts of acetone was added. Then, the precipitated solid was separated by filtration and dried, whereby the compound represented by the following formula (21) of the present invention (Table) No. 3 compound in No. 2) 6.5 parts as a sodium salt.
λmax: 575 nm.

[Example 2]
(Process 1)
A mixture of 17.1 parts of 4-chloro-3-nitrotoluene, 22.0 parts of sodium 3-mercaptopropanesulfonate and 60 parts of dimethyl sulfoxide was heated to 60 ° C. with stirring, and 11.2 parts of sodium carbonate was added thereto. Added. After the addition, the mixture was heated to 120 to 130 ° C. and stirred at the same temperature for 6 hours. The reaction solution was cooled to room temperature and added to 330 parts of 2-propanol with stirring. The precipitated solid was separated by filtration and washed with 100 parts of 2-propanol. After adding the obtained solid to 300 parts of water, the pH value is adjusted to 7.0 to 7.5 with 35% hydrochloric acid, salting out is performed by adding sodium chloride, and the precipitate is filtered and separated by the formula (22). A wet cake containing the represented compound was obtained.

(Process 2)
16.6 parts of iron powder, 120 parts of water, and 3.1 parts of 35% hydrochloric acid were heated to 90 ° C. with stirring. After stirring for 40 minutes, a solution obtained by suspending a wet cake containing the compound represented by the above formula (22) obtained in the above (Step 1) in 60 parts of water was dropped into this solution over about 15 minutes. After dripping, it stirred at 85-90 degreeC for 2 hours, and cooled to room temperature. The insoluble material was filtered off, 35% hydrochloric acid was added and acidified to precipitate out the solid, which was separated by filtration and dried to obtain 16.7 parts of a compound represented by the following formula (23).

(Process 3)
11.5 parts of the compound represented by the formula (23) obtained in (Step 2) of Example 2 instead of 10.8 parts of the compound represented by Formula (17) in (Step 2) of Example 1 In the same manner as in Example 1 except that was used, 7.0 parts of a compound (No. 2 compound in Table 2) represented by the following formula (24) of the present invention was obtained as a sodium salt.
λmax: 585 nm.

[Example 3]
[(A) Preparation of ink]
After mixing each component described in Table 6 below, a black ink composition of the present invention was obtained, and then impurities were filtered off with a 0.45 μm membrane filter to obtain an ink. This ink preparation is referred to as Example 3.
Moreover, ion-exchange water was used for water. At the time of ink preparation, the pH of the ink was adjusted to pH 7-9 with sodium hydroxide, and ion exchange water was added to make the total amount 100 parts. The aqueous black ink of the present invention did not cause precipitation separation during storage, and did not change its physical properties even after long-term storage.

[Comparative Example 1]
As a comparative black pigment, the same procedure as in Example 3 was conducted except that the pigment represented by the following formula (25) disclosed in Example 2-6 of Patent Document 8 was used instead of the compound of Example 2. A comparative ink was prepared. This is referred to as Comparative Example 1.

[(B) Inkjet print]
Glossy paper 1 (manufactured by Canon Inc., trade name Canon Photographic Paper Glossy Gold GK-101A450), glossy paper 2 (manufactured by Seiko Epson Corporation) using the ink obtained above, by Canon inkjet printer, trade name PIXUS iP4100 Inkjet printing was carried out on three types of information recording sheets (inkjet paper) of trade name photographic paper Crispier (high gloss) KA420SCK) and glossy paper 3 (manufactured by Seiko Epson Corporation, trade name photographic paper (gloss) KA420PSK). At the time of printing, an image pattern was created so that the reflection density was obtained with several gradations, and a black print was obtained.

[(C) Evaluation of recorded image]
For each print image obtained using the ink prepared in Example 3 and Comparative Example 1, the density change of the image before and after the test was evaluated with respect to each of light resistance and ozone gas resistance. Each printed image was dried at room temperature for 24 hours or more after printing.
For the density change of the print image, the gradation part where the black reflection density Dk value of the print image before the test is in the range of 1.2 to 1.4 is measured by using a colorimeter manufactured by GRETAG-MACBETH and the product name SpectroEye. It was measured by measuring the color. When measuring the reflection density Dk value of black, DIN was used as a density reference.
The test was performed for each of glossy papers 1 to 3, and the test results are shown in Table 7.
The specific test method is as follows.

1) Ozone gas resistance test Suga Test Instruments Co., Ltd., product name Each print image was allowed to stand for 8 hours under the conditions of ozone concentration 40 ppm, humidity 60% RH, temperature 24 ° C. using an ozone weatherometer. After the test, the colorimetry was performed using the above colorimeter, and the residual ratio of the dye in each print image was calculated as follows: (black reflection density Dk value after test / black reflection density Dk value before test) × 100 (%) It was calculated by the following formula. The test results were evaluated according to the following criteria.
◎: Residual rate is 90% or more ○: Residual rate is 80% or more and less than 90% △: Residual rate is 70% or more and less than 80% ×: Residual rate is less than 70%

2) Light resistance test Using a low-temperature xenon weatherometer XL75 manufactured by Suga Test Instruments Co., Ltd., 168 for each of the above print images under the conditions of 100,000 Lux illuminance, humidity 60% RH, temperature 24 ° C. After the time irradiation, the colorimetry was performed using the above-described colorimeter, and the residual ratio of the dye in each image (black reflection density Dk value after test / black reflection density Dk value before test) × 100 (% ). The test results were evaluated according to the following criteria.
◎: Residual rate is 80% or more ○: Residual rate is 70% or more and less than 80% △: Residual rate is 50% or more and less than 70% ×: Residual rate is less than 50%

As is clear from the results in Table 7, when the results of the ozone gas resistance test are compared for each glossy paper, the print image of Example 3 and the image of Comparative Example 1 are all compared with each other. The result is better than the example.
That is, in Comparative Example 1, when any glossy paper is used, the dye residual ratio is 80% or more and less than 90%, whereas Example 3 of the present invention uses any glossy paper in any case. The residual rate was 90% or more. Accordingly, it was found that each example was extremely excellent in ozone gas resistance as compared with Comparative Example 1.
Although no difference from Comparative Example 1 was shown in the light resistance test, Example 3 shows a very high light resistance of 80% in any glossy paper, and is extremely excellent in light resistance. There was found.
From the above results, the fastness of the printed image obtained with the ink containing the trisazo compound of the present invention is extremely excellent compared with the image of the conventional trisazo compound used in the comparative example, and particularly required for the inkjet printed image. It can be seen that the dye is extremely excellent in ozone gas resistance and light resistance.

  The ink composition containing the trisazo compound of the present invention is suitably used as a black ink liquid for ink jet printing and writing instruments.

Claims (16)

A trisazo compound represented by the following formula (1), a tautomer thereof, or a salt thereof.

[In Formula (1),
R ¹ is a carboxy group; a C1-C4 alkyl group that is unsubstituted or substituted with a carboxy group; or a phenyl group that is unsubstituted or substituted with a sulfo group;
R ² is a cyano group; a carbamoyl group; or a carboxy group;
R ³ and R ⁴ are each independently a hydrogen atom; a chlorine atom; a sulfo group; an unsubstituted C1-C4 alkyl group; or an unsubstituted C1-C4 alkoxy group;
The ring in which R ⁵ to R ⁷ are substituted is a benzene ring when a ring represented by a broken line is not present; a naphthalene ring when a ring represented by a broken line is present;
R ⁵ to R ⁷ are each independently a hydrogen atom; chlorine atom; hydroxy group; sulfo group; carboxy group; sulfamoyl group; carbamoyl group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 C1-C4 alkoxy group substituted with an alkoxy group, hydroxy C1-C4 alkoxy group, sulfo group, or carboxy group; mono- or di-C1-C4 alkyl unsubstituted or substituted with a hydroxy group, sulfo group, or carboxy group C1-C4 alkylcarbonylamino group unsubstituted or substituted with a hydroxy group or a carboxy group; N'-C1-C4 alkylureido group unsubstituted or substituted with a hydroxy group, a sulfo group, or a carboxy group ; Unsubstituted, or benzene ring is a chlorine atom, A phenylamino group substituted by a substituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group; unsubstituted or a benzene ring is a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group A benzoylamino group substituted with a group; or a phenylsulfonylamino group unsubstituted or substituted on the benzene ring with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group;
The ring in which R ⁸ to R ¹⁰ are substituted is a benzene ring when a ring represented by a broken line is not present; a naphthalene ring when a ring represented by a broken line is present;
R ⁸ to R ¹⁰ are each independently a hydrogen atom; chlorine atom; hydroxy group; sulfo group; carboxy group; sulfamoyl group; carbamoyl group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 C1-C4 alkoxy group substituted with an alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, or a carboxy group; unsubstituted, or a C1-C4 alkylthio group substituted with a hydroxy group, a sulfo group, or a carboxy group; A substituted or mono- or di-C1-C4 alkylamino group substituted with a hydroxy group, a sulfo group, or a carboxy group; an unsubstituted or C1-C4 alkylcarbonylamino group substituted with a hydroxy group or a carboxy group; Or hydroxy group, sulfo group, Is a N'-C1-C4 alkylureido group substituted with a carboxy group; phenylamino substituted with an unsubstituted or benzene ring with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group A benzoylamino group substituted by an unsubstituted or benzene ring with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group; or an unsubstituted or benzene ring with a chlorine atom, non-substituted A substituted C1-C4 alkyl group, a nitro group, a sulfo group, or a phenylsulfonylamino group substituted with a carboxy group;
The group A is an unsubstituted or substituted benzothiazolyl group; a thiadiazolyl group; or a thiazolyl group;
When the benzothiazolyl group has a substituent, chlorine atom; sulfo group; nitro group; hydroxy group; sulfamoyl group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, C1-C4 alkoxy group, sulfo group Or a C1-C4 alkoxy group substituted with a carboxy group; an unsubstituted or C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group, or a carboxy group; and an unsubstituted or benzene ring is a chlorine atom, A phenylsulfonyl group substituted with an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group; having a substituent selected from the group consisting of:
When the thiadiazolyl group or thiazolyl group has a substituent, chlorine atom; sulfo group; nitro group; hydroxy group; sulfamoyl group; mercapto group; and unsubstituted or hydroxy group, C1-C4 alkoxy group, hydroxy C1 A C1-C4 alkylthio group substituted with a C4 alkoxy group, a sulfo group, or a carboxy group; and a substituent selected from the group consisting of: ] The trisazo compound or a tautomer thereof, or a salt thereof according to claim 1, wherein the trisazo compound represented by the formula (1) is represented by the following formula (2).

[In the formula (2), the ring in which the groups A, R ¹ to R ¹⁰ , and R ⁸ to R ¹⁰ are substituted has the same meaning as in the formula (1) including the ring represented by a broken line. . ] The trisazo compound or a tautomer thereof according to claim 1 or 2, or a salt thereof, wherein the trisazo compound represented by the formula (1) is represented by the following formula (3).

[In formula (3), the groups A, R ¹ to R ¹⁰ have the same meaning as in formula (1). ] The trisazo compound represented by the above formula (1) or a tautomer thereof, or a salt thereof according to any one of claims 1 to 3, wherein the trisazo compound represented by the following formula (4):

[In Formula (4),
The groups A, R ¹ to R ⁴ , and R ⁸ to R ¹⁰ have the same meaning as in formula (1),
R ⁵ and R ⁷ each independently represent a hydrogen atom; an unsubstituted C1-C4 alkyl group; or a C1-C4 alkoxy group that is unsubstituted or substituted with a sulfo group or a hydroxy group; and R ⁶ represents a hydrogen atom. To express. ] The trisazo compound represented by the above formula (1) or a tautomer thereof, or a salt thereof according to any one of claims 1 to 4, wherein the trisazo compound represented by the following formula (5):

[In Formula (5),
The groups A, R ¹ to R ⁴ have the same meaning as in formula (1)
R ⁵ to R ⁷ have the same meaning as in formula (4),
R ⁸ and R ¹⁰ are each independently a hydrogen atom; a sulfo C1-C4 alkoxy group; an unsubstituted C1-C4 alkyl group; an unsubstituted or substituted C1-C4 alkoxy group with a sulfo group; or a sulfo group or a carboxy group Represents a substituted C1-C4 alkylthio group; and R ⁹ represents a hydrogen atom. ] The trisazo compound or a tautomer thereof, or a salt thereof according to any one of claims 1 to 5, wherein the group A is a group represented by the following formula (6).

[In Formula (6),
R ¹¹ to R ¹³ are each independently hydrogen atom; chlorine atom; sulfo group; nitro group; hydroxy group; sulfamoyl group; C1-C4 alkyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 alkoxy group, sulfo group Or a C1-C4 alkoxy group substituted with a carboxy group; or a C1-C4 alkylsulfonyl group unsubstituted or substituted with a hydroxy group, a sulfo group, or a carboxy group. ] The trisazo compound or a tautomer thereof according to any one of claims 1 to 6, wherein R ¹ is a methyl group, R ² is a cyano group or a carbamoyl group, R ³ is a hydrogen atom, and R ⁴ is a sulfo group. Or a salt thereof. The trisazo compound or a tautomer thereof according to any one of claims 1 to ⁷ , wherein R ⁵ is a sulfopropoxy group or a sulfobutoxy group, R ⁶ is a hydrogen atom, R ⁷ is a hydrogen atom, a methyl group, or an ethyl group. Sex or salt thereof. R ⁸ to R ¹⁰ are each independently selected from the group consisting of a hydrogen atom; a chlorine atom; a sulfo group; a nitro group; a methoxy group; a sulfopropoxy group; and a C1-C4 alkylthio group substituted with a sulfo group or a carboxy group The trisazo compound according to any one of claims 1 to 8, a tautomer thereof, or a salt thereof. R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfopropoxy group, R ⁶ is a hydrogen atom, R ⁷ is a methyl group, and R ⁸ is a sulfopropylthio group Wherein R ⁹ is a hydrogen atom, R ¹⁰ is a methyl group, two of R ¹¹ to R ¹³ are sulfo groups, and one is a hydrogen atom, or a trisazo compound or a tautomer thereof, or a salt thereof .   An ink composition containing at least one trisazo compound according to any one of claims 1 to 10 as a dye.   An ink jet printing method for printing by using the ink composition according to claim 11 as ink, ejecting ink droplets of the ink in accordance with a recording signal, and attaching the ink droplet to a recording material.   The ink jet printing method according to claim 12, wherein the recording material in the ink jet printing method is an information transmission sheet.   The inkjet printing method according to claim 13, wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance.   An ink jet printer loaded with a container containing the ink composition according to claim 14.   A colored product colored by the trisazo compound according to any one of claims 1 to 10, a tautomer thereof, or a salt thereof.