JP5238155B2 - Ink composition, ink set, and recording method - Google Patents

Description

  The present invention relates to an ink composition, an ink set, and a recording method, and particularly relates to an ink composition capable of forming a highly robust and high-density image.

In recent years, with the spread of computers, inkjet printers are widely used for printing on paper, film, cloth and the like not only in offices but also at home.
Ink jet recording methods include a method of ejecting droplets by applying pressure with a piezo element, a method of ejecting droplets by generating bubbles in ink by heat, a method of using ultrasonic waves, or a droplet by electrostatic force. There is a method of sucking and discharging. As these ink compositions for inkjet recording, water-based inks, oil-based inks, or solid (melted type) inks are used. Among these inks, water-based inks are mainly used from the viewpoints of production, handleability, odor, safety, and the like.

The colorant used in these inks for ink jet recording has high solubility in solvents, high density recording, good hue, light, heat, air, water and chemicals. Excellent fastness, good fixability to image-receiving materials, low bleeding, excellent storage stability as ink, no toxicity, high purity, and availability at low cost It is requested. However, it is extremely difficult to search for colorants that meet these requirements at a high level.
Various dyes and pigments have already been proposed and actually used for inkjet, but no colorant that satisfies all the requirements has yet been discovered. Conventionally well-known dyes and pigments having a color index (CI) number are difficult to achieve both hue and fastness required for ink jet recording inks.

  In recent years, trisazo dyes and tetrakisazo dyes have been studied as dyes for black ink, and Patent Documents 1 to 4 have been proposed, but they sufficiently satisfy market demands, particularly regarding fastness to gas and light. It has not yet reached.

  The inventors have so far studied about a fast dye having a good hue and developed an excellent ink-jet dye. Among these, as described in Patent Document 5, we have found that it is effective to use a highly associative dye in order to improve the fastness of the image.

  However, it has been found that when an associative dye is used, there are problems such that bronze (abnormal gloss) tends to occur at a high density portion and that the image density is lower than that of a non-associative dye.

JP-A-2005-222111 JP 2004-285351 A Japanese Patent Laid-Open No. 2005-2271 International Application Publication WO 03/106572 Pamphlet JP 2005-162823 A

  The problem to be solved by the present invention is that it is possible to print with excellent black tone and high density, has excellent image fastness, suppresses bronze gloss, has no bleeding, and has excellent fading balance. An ink composition, an ink set containing the ink composition, and an ink jet recording method using them.

一般式（Ｌ−１）中、Ａ、Ｂは、各々独立に、置換されていてもよい芳香族基または置換されていてもよいヘテロ環基を表す（Ａは一価の基であり、Ｂは二価の基である）。
Ｔ ₁ およびＴ ₂ は、各々＝ＣＲ _４３ −および−ＣＲ _４４ ＝を表すか、あるいはいずれか一方が窒素原子、他方が＝ＣＲ _４３ −または−ＣＲ _４４ ＝を表す。
Ｖ ₁ 、Ｒ _４３ およびＲ _４４ は、各々独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アラルキル基、アリール基、ヘテロ環基、シアノ基、カルボキシル基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、ヘテロ環オキシカルボニル基、アシル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、ヘテロ環オキシ基、シリルオキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基、アシルアミノ基、ウレイド基、スルファモイルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、ヘテロ環スルホニルアミノ基、ニトロ基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、アルキルスルホニル基、アリールスルホニル基、ヘテロ環スルホニル基、アルキルスルフィニル基、アリールスルフィニル基、ヘテロ環スルフィニル基、スルファモイル基、またはスルホ基を表し、各基は更に置換されていても良い。Ｒ _４１ およびＲ _４２ は各々独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アラルキル基、アリール基、ヘテロ環基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、アリールスルホニル基、スルファモイル基を表し、各基は更に置換基を有していても良い。但し、Ｒ _４１ 、Ｒ _４２ が同時に水素原子であることはない。また、Ｒ _４３ とＲ _４１ 、あるいはＲ _４１ とＲ _４２ が結合して５乃至６員環を形成しても良い。ただし、一般式（Ｌ−１）は少なくともひとつのイオン性親水性基を含む。

一般式（Ｌ−２）中、Ｘは、Ｎ原子または＝ＣＷ _１ −を表す。Ｗ ₁ は、ハメットの置換基定数σｐ値が０．２０以上の電子吸引性基を表す。Ａ、Ｖ _１ 、Ｔ _１ ，Ｔ _２ 、Ｒ _４１ 及びＲ _４２ は、前記一般式（Ｌ−１）中のＡ、Ｖ _１ 、Ｔ _１ ，Ｔ _２ 、Ｒ _４１ 及びＲ _４２ と同義である。
Ｗは、前記一般式（Ｌ−１）中のＶ ₁ と同義である。ただし、一般式（Ｌ−２）は少なくともひとつのイオン性親水性基を含む。

一般式（Ｌ−３）中、Ｖ _１ 、Ｗ、Ｘ、Ｔ _１ ，Ｔ _２ 、Ｒ _４１ 及びＲ _４２ は、前記一般式（Ｌ−２）中のＶ _１ 、Ｗ、Ｘ、Ｔ _１ ，Ｔ _２ 、Ｒ _４１ 及びＲ _４２ と同義である。Ｘ _１ 、Ｘ _２ 、Ｘ _３ 、Ｘ _４ 、Ｘ _５ 、Ｘ _６ 及びＸ _７ は、一価の基を表す。ただし、一般式（Ｌ−３）は少なくともひとつのイオン性親水性基を含む。

一般式（Ｌ−４）中、Ｒ _４３ は前記一般式（Ｌ−１）中のＲ _４３ と同義である。Ｒ _４４ は、前記一般式（Ｌ−１）中のＲ _４４ と同義である。Ｒ _４５ 、Ｒ _４６ は、前記一般式（Ｌ−１）中のＲ _４１ 及びＲ _４２ と同義である。Ｒ _４１ 及びＲ _４２ は、前記一般式（Ｌ−１）中のＲ _４１ 及びＲ _４２ と同義である。
Ｗは、前記一般式（Ｌ−１）中のＶ ₁ と同義である。Ｘ _１ 、Ｘ _２ 、Ｘ _３ 、Ｘ _４ 、Ｘ _５ 、Ｘ _６ 及びＸ _７ は一価の基を表す。
ただし、一般式（Ｌ−４）は少なくともひとつのイオン性親水性基を含む。

一般式（Ｌ−５）中、Ｒ _４３ は前記一般式（Ｌ−１）中のＲ _４３ と同義である。Ｒ _４４ は、前記一般式（Ｌ−１）中のＲ _４４ と同義である。Ｒ _４５ 、Ｒ _４６ は、前記一般式（Ｌ−１）中のＲ _４１ 及びＲ _４２ と同義である。Ｒ _４１ 及びＲ _４２ は、前記一般式（Ｌ−１）中のＲ _４１ 及びＲ _４２ と同義である。
Ｗは、前記一般式（Ｌ−１）中のＶ ₁ と同義である。Ｗ _１１ は、ハメットの置換基定数σｐ値が０．２０以上の電子吸引性基を表す。Ｘ _１ 、Ｘ _２ 、Ｘ _３ 、Ｘ _４ 、Ｘ _５ 、Ｘ _６ 及びＸ _７ は一価の基を表す。
ただし、一般式（Ｌ−５）は少なくともひとつのイオン性親水性基を含む。
一般式（Ｌ−６ａ）：

一般式（Ｌ−６ａ）中、Ａは下記式（Ｌ−６ａ−１）を表し、Ａの置換位置はアゾ基に対してｍ−位又はｐ−位であり、Ｒ ^１ 及びＲ ^２ は、それぞれ独立して水素原子；ハロゲン原子；シアノ基；カルボキシル基；スルホ基；スルファモイル基；Ｎ−アルキルアミノスルホニル基；Ｎ−フェニルアミノスルホニル基；ホスホ基；ニトロ基；アシル基；ウレイド基；ヒドロキシル基若しくは炭素数１〜４のアルコキシ基で置換されても良い炭素数１〜４のアルキル基；ヒドロキシル基、炭素数１〜４のアルコキシ基、スルホ基若しくはカルボキシル基で置換されても良い炭素数１〜４のアルコキシ基；炭素数１〜４のアルコキシ基、スルホ基若しくはカルボキシル基で置換されても良いアシルアミノ基を表し、Ｒ ^３ 及びＲ ^４ は、それぞれ独立して水素原子；ハロゲン原子；シアノ基；カルボキシル基；スルホ基；ニトロ基；炭素数１〜４のアルキル基；ヒドロキシル基；炭素数１〜４のアルコキシ基若しくはスルホ基で置換されても良い炭素数１〜４のアルコキシ基を表し、ｎは０又は１である。
一般式（Ｌ−６ａ−１）

式（Ｌ−６ａ−１）中、Ｒ ^５ はシアノ基；カルボキシル基；炭素数１〜４のアルキル基；炭素数１〜４のアルコキシカルボニル基またはフェニル基を表し、Ｒ ^６ 、Ｒ ^７ 及びＲ ^８ は、それぞれ独立して水素原子；ハロゲン原子；シアノ基；カルボキシル基；スルホ基；ニトロ基、炭素数１〜４のアルキル基；ヒドロキシル基；炭素数１〜４のアルコキシ基若しくはスルホ基で置換されても良い炭素数１〜４のアルコキシ基；ヒドロキシル基、炭素数１〜４のアルコキシ基若しくはスルホ基で置換されても良いアシルアミノ基を表す。
〔２〕水溶媒における吸収スペクトルの極大波長が４００ｎｍ〜５２０ｎｍである水溶性染料を少なくとも１種含有することを特徴とする前記〔１〕に記載のインク組成物。
〔３〕水溶媒における吸収スペクトルの極大波長が４００ｎｍ〜５２０ｎｍである前記水溶性染料を０．１〜４質量％含有することを特徴とする前記〔２〕に記載のインク組成物。
〔４〕前記〔１〕〜〔３〕のいずれか一項に記載のインク組成物を少なくとも１種含むことを特徴とするインクセット。
〔５〕前記〔１〕〜〔３〕のいずれか一項に記載のインク組成物を記録媒体上に付与して記録することを特徴とする記録方法。
〔６〕前記〔４〕に記載のインクセットを記録装置に装填し、記録装置から記録媒体上にインクを付与して記録することを特徴とする記録方法。
〔７〕インクジェットノズルよりインク組成物を記録媒体上に吐出させて記録することを特徴とする、前記〔５〕または〔６〕に記載の記録方法。
本発明は、上記〔１〕〜〔７〕項に関するものであるが、その他の事項についても参考のために記載した。
（１）水溶媒における吸収スペクトルの極大波長が５５０〜７００nmである水溶性染料を少なくとも２種含有するインク組成物であって、該水溶性染料の少なくとも１種が一般式（Ｌ−１）で表される化合物及びその塩、または少なくとも１つのヒドロキシル基で置換されたナフタレン環と３つ以上のアゾ基を有する化合物からなる群から選ばれることを特徴とするインク組成物。 [1] An ink composition containing at least two water-soluble dyes having a maximum absorption spectrum wavelength of 550 to 700 nm in an aqueous solvent, wherein the water-soluble dyes are represented by the following general formulas (L-1) and (L- 2) at least one compound represented by (L-3), (L-4), or (L-5), and at least one compound represented by the following general formula (L-6a) An ink composition comprising:

In general formula (L-1), A and B each independently represent an optionally substituted aromatic group or an optionally substituted heterocyclic group (A is a monovalent group, B Is a divalent group).
T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one represents a nitrogen atom and the other represents = CR ₄₃ -or -CR ₄₄ =.
V ₁ , R ₄₃ and R ₄₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl Group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group Represents a nitro group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfo group, The group may be further substituted. R ₄₁ and R ₄₂ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group Represents an arylsulfonyl group or a sulfamoyl group, and each group may further have a substituent. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring. However, general formula (L-1) contains at least one ionic hydrophilic group.

In General Formula (L-2), X represents an N atom or = CW _1- . W ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. _{A, V 1, T 1,} T 2, R 41 and _{R 42, A} in the formula (L-1), the same meaning as _{V 1, T 1, T 2} , R 41 and _{R 42.}
W is synonymous with V ₁ in the general formula (L-1) . However, general formula (L-2) contains at least one ionic hydrophilic group.

In the general formula (L-3), V ₁ , W, X, T ₁ , T ₂ , R ₄₁ and R ₄₂ represent V ₁ , W, X, T ₁ , T in the general formula (L-2). ₂ , Synonymous with R ₄₁ and R ₄₂ . X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ represent a monovalent group. However, general formula (L-3) contains at least one ionic hydrophilic group.

In the general formula _{(L-4), R 43} has the same meaning as _{R 43} in formula (L-1). R ₄₄ has the same meaning as _{R 44} in formula (L-1). R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in} formula (L-1) . R ₄₁ and _{R 42} has the same meaning as _{R 41} and _{R 42} in formula (L-1).
W is synonymous with V ₁ in the general formula (L-1) . X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ represent a monovalent group.
However, general formula (L-4) contains at least one ionic hydrophilic group.

In the general formula _{(L-5), R 43} has the same meaning as _{R 43} in formula (L-1). R ₄₄ has the same meaning as _{R 44} in formula (L-1). R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in} formula (L-1) . R ₄₁ and _{R 42} has the same meaning as _{R 41} and _{R 42} in formula (L-1).
W is synonymous with V ₁ in the general formula (L-1) . W ₁₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ represent a monovalent group.
However, general formula (L-5) contains at least one ionic hydrophilic group.
General formula (L-6a):

In general formula (L-6a), A represents the following formula (L-6a-1), the substitution position of A is the m-position or p-position with respect to the azo group, and R ¹ and R ² are Each independently hydrogen atom; halogen atom; cyano group; carboxyl group; sulfo group; sulfamoyl group; N-alkylaminosulfonyl group; N-phenylaminosulfonyl group; phospho group; nitro group; acyl group; ureido group; Or an alkyl group having 1 to 4 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbon atoms; 1 carbon atom which may be substituted with a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a sulfo group or a carboxyl group Represents an alkoxy group having 1 to 4 carbon atoms; an acylamino group which may be substituted with an alkoxy group having 1 to 4 carbon atoms, a sulfo group or a carboxyl group; R ³ and R ⁴ are each independently A hydrogen atom; a halogen atom; a cyano group; a carboxyl group; a sulfo group; a nitro group; an alkyl group having 1 to 4 carbon atoms; a hydroxyl group; a carbon number that may be substituted with an alkoxy group having 1 to 4 carbon atoms or a sulfo group. 1 to 4 alkoxy groups are represented, and n is 0 or 1.
General formula (L-6a-1)

In formula (L-6a-1), R ⁵ represents a cyano group; a carboxyl group; an alkyl group having 1 to 4 carbon atoms; an alkoxycarbonyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁶ , R ⁷ and R ⁸ are each independently substituted with a hydrogen atom; a halogen atom; a cyano group; a carboxyl group; a sulfo group; a nitro group, an alkyl group having 1 to 4 carbon atoms; a hydroxyl group; an alkoxy group having 1 to 4 carbon atoms or a sulfo group. Represents an alkoxy group having 1 to 4 carbon atoms which may be substituted; an acylamino group which may be substituted with a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms or a sulfo group.
[2] The ink composition as described in [1] above, which contains at least one water-soluble dye having an absorption spectrum maximum wavelength in a water solvent of 400 nm to 520 nm.
[3] The ink composition as described in [2] above, which contains 0.1 to 4% by mass of the water-soluble dye having a maximum absorption spectrum wavelength in a water solvent of 400 nm to 520 nm.
[4] An ink set comprising at least one ink composition according to any one of [1] to [3].
[5] A recording method comprising recording by applying the ink composition according to any one of [1] to [3] onto a recording medium.
[6] A recording method, wherein the ink set according to [4] is loaded in a recording apparatus, and ink is applied from the recording apparatus onto a recording medium for recording.
[7] The recording method according to [5] or [6], wherein recording is performed by discharging an ink composition onto a recording medium from an inkjet nozzle.
The present invention relates to the above items [1] to [7], but other matters are also described for reference.
(1) An ink composition containing at least two water-soluble dyes having a maximum wavelength of an absorption spectrum of 550 to 700 nm in an aqueous solvent, wherein at least one of the water-soluble dyes is represented by the general formula (L-1) An ink composition characterized in that it is selected from the group consisting of a compound represented by formula (I) and a salt thereof, or a compound having a naphthalene ring substituted with at least one hydroxyl group and three or more azo groups.

In general formula (L-1), A and B each independently represent an optionally substituted aromatic group or an optionally substituted heterocyclic group (A is a monovalent group, B Is a divalent group).
T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one represents a nitrogen atom and the other represents = CR ₄₃ -or -CR ₄₄ =.
V ₁ , R ₄₃ and R ₄₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl Group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group Represents a nitro group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfo group, The group may be further substituted. R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, It represents a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and each group may further have a substituent. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring. However, general formula (L-1) contains at least one ionic hydrophilic group.
(2) The ink composition as described in (1) above, wherein the compound represented by the general formula (L-1) is a compound represented by the following general formula (L-2).

In General Formula (L-2), X represents an N atom or = CW _1- . W ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. _{A, V 1, T 1,} T 2, R 41 and _{R 42, A} in the formula (L-1), the same meaning as _{V 1, T 1, T 2} , R 41 and _{R 42.} W is synonymous with V ₁ in the general formula (L-1).
(3) The ink according to (1) or (2), wherein the compound represented by the general formula (L-2) is a compound represented by the following general formula (L-3): Composition.

In the general formula (L-3), V ₁ , W, X, T ₁ , T ₂ , R ₄₁ and R ₄₂ represent V ₁ , W, X, T ₁ , T in the general formula (L-2). ₂ , Synonymous with R ₄₁ and R ₄₂ . X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ represent a monovalent group.
(4) The compound represented by the general formula (L-1) and the compound represented by the following general formula (L-4) each containing at least one of different structures. The ink composition according to any one of 1) to (3).

In the general formula _{(L-4), R 43} has the same meaning as _{R 43} in formula (L-1). R ₄₄ has the same meaning as _{R 44} in formula (L-1). R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in} formula (L-1). R ₄₁ and _{R 42} has the same meaning as _{R 41} and _{R 42} in formula (L-1).
W is synonymous with V ₁ in the general formula (L-1). X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ represent a monovalent group.
(5) The compound represented by the general formula (L-1) and the compound represented by the following general formula (L-5), each containing at least one of different structures. The ink composition according to any one of 1) to (3).

In the general formula _{(L-5), R 43} has the same meaning as _{R 43} in formula (L-1). R ₄₄ has the same meaning as _{R 44} in formula (L-1). R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in} formula (L-1). R ₄₁ and _{R 42} has the same meaning as _{R 41} and _{R 42} in formula (L-1). W is synonymous with V ₁ in the general formula (L-1). W ₁₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ represent a monovalent group.
(6) The number of azo groups in the compound having a naphthalene ring substituted with at least one hydroxyl group and three or more azo groups is 5 or less, wherein (1) to (5) The ink composition according to any one of (7), wherein the compound having a naphthalene ring substituted with at least one hydroxyl group and three or more azo groups is one or more sulfo groups, one or more carboxyl groups, or sulfo group One or more groups and one or more carboxyl groups are contained, The ink composition in any one of said (1)-(6) characterized by the above-mentioned.
(8) Compounds having a naphthalene ring substituted with at least one hydroxyl group and three or more azo groups are represented by the general formulas (L-6), (L-6a), (L-7) and (L-8). The ink composition according to any one of (1) to (7), wherein the ink composition is a compound selected from the group consisting of a compound represented by the formula:

In general formula (L-6), R ₁₁ and R ₁₂ are each independently a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a sulfo group, an alkyl group, or a sulfamoyl group that may be substituted with a phenyl group, phosphorus An acid group, a nitro group, an acyl group, a ureido group, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, An alkoxy group having 1 to 4 carbon atoms or an acylamino group which may be substituted with a sulfo group or a carboxyl group; E represents a phenyl group or a naphthyl group; a halogen atom, a cyano group, a carboxyl group, a sulfo group, an alkyl group or Sulfamoyl group, phosphate group, nitro group, acyl group, ureido group, hydroxyl group which may be substituted with phenyl group Or an optionally substituted alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a sulfo group, or a carboxyl group that may be substituted with a carboxyl group. It may be substituted with 1 to 4 alkoxy groups or acylamino groups. n ₁ is 0 or 1.

General formula (L-6a):

In general formula (L-6a), A represents the following formula (L-6a-1), the substitution position of A is the m-position or p-position with respect to the azo group, and R ¹ and R ² are Each independently hydrogen atom; halogen atom; cyano group; carboxyl group; sulfo group; sulfamoyl group; N-alkylaminosulfonyl group; N-phenylaminosulfonyl group; phospho group; nitro group; acyl group; ureido group; Or an alkyl group having 1 to 4 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbon atoms; 1 carbon atom which may be substituted with a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a sulfo group or a carboxyl group Represents an alkoxy group having 1 to 4 carbon atoms; an acylamino group which may be substituted with an alkoxy group having 1 to 4 carbon atoms, a sulfo group or a carboxyl group; R ³ and R ⁴ are each independently A hydrogen atom; a halogen atom; a cyano group; a carboxyl group; a sulfo group; a nitro group; an alkyl group having 1 to 4 carbon atoms; a hydroxyl group; a carbon number that may be substituted with an alkoxy group having 1 to 4 carbon atoms or a sulfo group. 1 to 4 alkoxy groups are represented, and n is 0 or 1.

General formula (L-6a-1)

In formula (L-6a-1), R ⁵ represents a cyano group; a carboxyl group; an alkyl group having 1 to 4 carbon atoms; an alkoxycarbonyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁶ , R ⁷ and R ⁸ are each independently substituted with a hydrogen atom; a halogen atom; a cyano group; a carboxyl group; a sulfo group; a nitro group, an alkyl group having 1 to 4 carbon atoms; a hydroxyl group; an alkoxy group having 1 to 4 carbon atoms or a sulfo group. Represents an alkoxy group having 1 to 4 carbon atoms which may be substituted; an acylamino group which may be substituted with a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms or a sulfo group.

In General Formula (L-7), G and J each independently represent a phenyl group, a naphthyl group, or an azo group, which is a 5-membered or 6-membered aromatic heterocyclic group bonded to a carbon atom. Each component contains at least one carboxyl group or sulfo group. One of X and Y is a hydroxyl group, and the other is an amino group, and l ₂ , m ₂ and n ₂ represent 1 or 2.

In the general formula (L-8), R ₂₁ represents a phenyl group having a substituent or a naphthyl group having a substituent, R ₂₂ represents a phenylene group having a substituent or a naphthylene group having a substituent, R ₂₃ Represents a 5- to 7-membered heterocyclic group having at least one double bond and a substituent. Further, the substituents are independently selected from the group consisting of the R ₂₁ to R _23, with _{OH, SO 3 H, PO 3} H 2, CO 2 H, NO 2, NH 2, alkyl group having 1 to 4 carbon atoms, a substituent It consists of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms having a substituent, an amino group, an amino group having a substituent, and a phenyl group having a substituent. Selected from the group.
(9) An ink composition containing at least two water-soluble dyes having a maximum wavelength of an absorption spectrum of 550 to 700 nm in an aqueous solvent, wherein the water-soluble dye is represented by the general formula (L-1 ), The general formula (L-2) described in (2), the general formula (L-3) described in (3), the general formula (L-4) described in (4), or the above (5) And at least one compound represented by the general formula (L-5), and the general formula (L-6), (L-6a), (L-7) or (L-8) described in (8) above An ink composition comprising at least one compound represented by the formula:
(10) The ink composition as described in (8) or (9) above, wherein the compound represented by the general formula (L-8) is a compound represented by the general formula (L-9) .

In General Formula (L-9), R _{31 to} R ₃₉ independently represent a group selected from the group consisting of H, OH, SO ₃ H, PO ₃ H ₂ , CO ₂ H, NO ₂ , and NH _2. Represent.
(11) The ink composition as described in any one of (1) to (10) above, which contains at least one water-soluble dye having an absorption spectrum maximum wavelength in a water solvent of 400 nm to 520 nm.
(12) The ink composition as described in (11) above, which contains 0.1 to 4% by mass of the water-soluble dye having a maximum absorption spectrum wavelength in a water solvent of 400 nm to 520 nm.
(13) An ink set comprising at least one ink composition according to any one of (1) to (12).
(14) A recording method comprising applying and recording the ink composition according to any one of (1) to (12) on a recording medium.
(15) A recording method comprising: loading the ink set according to (12) in a recording apparatus, and applying ink from the recording apparatus onto a recording medium for recording.
(16) The recording method according to (14) or (15), wherein the recording is performed by discharging an ink composition onto a recording medium from an inkjet nozzle.

Since the ink of the present invention is robust against light, ozone gas, and the like, the image has excellent storage stability with time and can provide a high-density image.
Moreover, the ink of the present invention can provide a high-density image having excellent weather resistance and excellent hue stability.
Furthermore, the ink of the present invention can provide a high-density image that suppresses bronze gloss and has no bleeding and excellent in fading balance.

Hereinafter, the present invention will be described in more detail.
The ink composition of the present invention contains at least two water-soluble dyes (hereinafter referred to as water-soluble long-wave dye L) having a maximum wavelength of an absorption spectrum in an aqueous solvent of 550 to 700 nm. At least one selected from the group consisting of a compound represented by formula (L-1) and a salt thereof, or a compound having a naphthalene ring substituted with at least one hydroxyl group and three or more azo groups Features. The ink composition of the present invention is preferably used as a black ink.

(Water-soluble long wave dye L)
In the present invention, the water-soluble long wave dye L is characterized in that the maximum (absorption maximum) of the absorption spectrum in an aqueous solvent is 550 to 700 nm. The maximum (absorption maximum) of the absorption spectrum of the water-soluble long wave dye L in the aqueous solvent is preferably 560 to 680 nm, and more preferably 570 to 650 nm. Moreover, it is preferable that those absorption spectra have wide absorption in a visible range, and the hue is preferably black rather than a vivid hue such as magenta or cyan. The full width at half maximum of the absorption spectrum is preferably 100 nm or more (preferably 120 to 500 nm, more preferably 120 to 350 nm). Here, the water solvent means a medium in which water is a main solvent and a dye that may appropriately contain a water-miscible organic solvent is dissolved or dispersed. Further, the absorption spectrum means that measured with a spectrophotometer using a 1 cm cell which is usually used. The same applies to the water-soluble long wave dye S described later.
The absorption spectrum of the water-soluble long wave dye L is measured using a single compound. That is, when measuring the absorption spectrum in an aqueous solvent, the water-soluble long wave dye L of the present invention does not exhibit physical properties such as a desired absorption maximum and a half-value width by combining a plurality of compounds, but the physical properties required by one compound. Is meant to indicate In the present invention, as long as the water-soluble long wave dye L (hereinafter also referred to as “long wave dye L”) satisfies the absorption spectrum, it is obvious that compounds having different structures may be used in combination. It is. Further, in the present invention, a dye other than the long wave dye L exhibiting the absorption spectrum characteristic may be used in combination.

Further, the long wave dye L is more preferably one having an associative property and a property capable of physically suppressing the reaction.
To determine whether the dye is in an associated state, measure the visible absorption spectrum while changing the dye concentration, and determine whether the dye has an association property by examining the absorption maximum wavelength, molar extinction coefficient, and waveform change. It can be easily judged from a comparison between the physical properties of the solution and the absorption spectrum of the dye on the image receiving material.
Specifically, as defined in JP-A No. 2004-307831, a molar extinction coefficient (ε1) at the maximum wavelength of absorption in the visible region measured with a 0.1 mmol / l aqueous dye solution using a cell having an optical path length of 1 cm, A dye that satisfies the relationship of ε1 / ε2> 1.2 between the molar extinction coefficients (ε2) when a 0.2 mol / l aqueous solution is measured using a liquid crystal cell having an optical path length of 5 μm is preferable.

In the present invention, the long wave dye L comprises a compound represented by the following general formula (L-1) and a salt thereof, or a compound having a naphthalene ring substituted with at least one hydroxyl group and three or more azo groups. It contains at least one compound selected from the group.
In the following general formula, the dye is represented by the structure of a free acid, but it goes without saying that it may be used in the form of a salt in actual use.

In general formula (L-1), A and B each independently represent an optionally substituted aromatic group or an optionally substituted heterocyclic group (A is a monovalent group, B Is a divalent group).
T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one represents a nitrogen atom and the other represents = CR ₄₃ -or -CR ₄₄ =.
V ₁ , R ₄₃ and R ₄₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl Group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group Represents a nitro group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfo group, The group may be further substituted. In the present specification, the amino group means an amino group in which a hydrogen atom is not substituted, an alkylamino group, an arylamino group, and a heterocyclic amino group. R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, It represents a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and each group may further have a substituent. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

  The general formula (L-1) of the present invention will be described in detail.

  In the general formula (L-1), preferable A includes a monovalent aromatic group which may be substituted or a monovalent heterocyclic group which may be substituted, and more specifically, a substituted phenyl group. A substituted naphthyl group and a substituted or unsubstituted heterocyclic group, and among them, a phenyl group substituted with an ionic hydrophilic group, a naphthyl group, and a 5- to 6-membered nitrogen-containing heterocycle having a substituent. In particular, a sulfo group (including salts thereof), a phenyl group substituted with a carboxyl group (including salts thereof), and a naphthyl group are preferable, and two or more sulfo groups (including salts thereof), carboxyl A phenyl group and a naphthyl group substituted with a group (including salts thereof) are preferred, and a naphthyl group substituted with 2 or 3 sulfo groups (including salts thereof) is most preferred.

  In the general formula (L-1), B includes a divalent aromatic group which may be substituted or a divalent heterocyclic group which may be substituted. A 6-membered heterocyclic group is preferable, and among them, a 5-membered heterocyclic group having a substituent is preferable. A 5-6 membered heterocycle means a 5-6 membered ring containing a hetero atom. Examples of the hetero atom of the hetero ring include N, S and O atoms.

  The heterocyclic ring represented by B may be condensed with an aliphatic group, an aromatic ring or another heterocyclic ring, and may further have a substituent on the condensed ring. The heterocycle represented by B means both a saturated heterocycle and an unsaturated heterocycle, and preferably an unsaturated heterocycle. In the case of a nitrogen-containing heterocycle, the N atom may be quaternized. In addition, as for the heterocycle that can be tautomeric, even when only one tautomer is described, other tautomers are also included.

  Particularly preferred examples of the heterocyclic ring represented by B include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a thiophene ring, a thiazole ring, an imidazole ring, a benzothiazole ring, and a thienothiazole ring.

In general formula (L-1), T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one is a nitrogen atom and the other is = CR ₄₃ -or -CR ₄₄ =. However, it is preferable that T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ = from the standpoint that more excellent performance can be exhibited.

In the general formula (L-1), R ₄₁ and R ₄₂ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, or aryl. Represents an oxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, a sulfamoyl group, and each group may further have a substituent, among which a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group , An alkyl or arylsulfonyl group is preferable, a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group is more preferable, and a hydrogen atom, an aryl group having a substituent or a heterocyclic group having a substituent is particularly preferable, a hydrogen atom or a substituent Most preferred is an aryl group having a group. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

In general formula (L-1), preferable V ₁ is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy group, hetero Ring oxy group, silyloxy group, acyloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylthio group, heterocyclic thio group, each group May be further substituted.

More preferable V ₁ represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a silyloxy group, an acyloxy group, an amino group, or an acylamino group, and among them, a hydrogen atom, an amino group Group, an acylamino group are preferable, an amino group having a substituent is particularly preferable, and an amino group substituted with an aryl group having an ionic hydrophilic group as a substituent (such as a substituted anilino group) is most preferable.

  Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable. Among them, a carboxyl group and a sulfo group are preferable, and a sulfo group is most preferable from the viewpoint of increasing the solubility in an aqueous solvent. The carboxyl group, phosphono group, and sulfo group may be in a salt state, and examples of the counter salt include ammonium, alkali metals (eg, lithium, sodium, potassium) and organic cations (eg, tetramethylammonium, Tetramethylguanidinium, tetramethylphosphonium) and the like. As the counter salt, ammonium, lithium, sodium, and potassium are preferable. Among them, sodium and lithium are more preferable, and lithium is most preferable.

  A particularly preferable combination as the compound represented by the general formula (L-1) of the present invention includes the following (A) to (E).

(A) A is preferably a substituted phenyl group, a substituted naphthyl group, or a substituted or unsubstituted heterocyclic group, and among them, has a phenyl group, a naphthyl group, or a substituent substituted with an ionic hydrophilic group. A 5- to 6-membered nitrogen-containing heterocycle is preferable, and a phenyl group and a naphthyl group substituted with a sulfo group (including salts thereof), a carboxyl group (including salts thereof) are particularly preferable, and two or more Preferred is a phenyl group or a naphthyl group substituted with a sulfo group (including salts thereof), a carboxyl group (including salts thereof), or a naphthyl substituted with 2 or 3 sulfo groups (including salts thereof) The group is most preferred.

(B) B is preferably a 5- to 6-membered heterocyclic group having a substituent, and among them, a 5-membered heterocyclic group having a substituent is preferable. Particularly preferred hetero rings include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a thiophene ring, a thiazole ring, an imidazole ring, a benzothiazole ring, and a thienothiazole ring.

(C) T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one represents a nitrogen atom and the other represents = CR ₄₃ -or -CR ₄₄ =, T ₁ and T ₂ are each preferably = CR ₄₃ -and -CR ₄₄ =, respectively, from the viewpoint that more excellent performance can be exhibited.

(D) R ₄₁ and R ₄₂ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group, and more preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, In particular, a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

(E) V ₁ represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a silyloxy group, an acyloxy group, an amino group, or an acylamino group, among which a hydrogen atom, An amino group and an acylamino group are preferred, an amino group having a substituent is particularly preferred, and an amino group substituted with an aryl group having an ionic hydrophilic group as a substituent (such as a substituted anilino group) is most preferred.

  As for the preferred combination of substituents of the dye represented by the general formula (L-1) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  In this invention, the compound represented by the following general formula (L-2) is preferable among the compounds represented by general formula (L-1).

In the general formula (L-2), X represents an N atom or ═CW ₁ —. W ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. _{A, V 1, T 1,} T 2, R 41 and _{R 42, A} in the formula (L-1), the same meaning as _{V 1, T 1, T 2} , R 41 and _{R 42.} W is synonymous with V ₁ in the general formula (L-1).

  General formula (L-2) is demonstrated in detail.

  In the general formula (L-2) of the present invention, preferable W is a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, a pyrrole ring, a thiophene ring, an imidazole ring, a thiazole ring). , A benzothiazole ring, a pyridine ring or a pyridazine ring, particularly preferably a substituted phenyl group (particularly a phenyl group substituted at the para position), a substituted or unsubstituted β-naphthyl group, a pyridine ring or a thiazole ring.

In the general formula (L-2), X represents an N atom or ═CW ₁ —, and W ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Among them, an electron-withdrawing group having a σp value of 0.30 or more is preferable, an electron-withdrawing group of 0.45 or more is more preferable, and an electron-withdrawing group of 0.60 or more is particularly preferable. It is desirable not to exceed zero. More specifically, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, A carbamoyl group having 1 to 20 carbon atoms and a halogenated alkyl group having 1 to 20 carbon atoms are preferred. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group.

  In general formula (L-2), A is synonymous with A in the said general formula (L-1), and its preferable example is also the same.

In formula (L-2), T ₁ and T ₂ has the same meaning as T ₁ and T ₂ in the formula (L-1), and preferred examples thereof are also the same.

In formula _{(L-2), R 41} , R 42 has the same meaning as _{R 41, R 42} in the formula (L-1), and preferred examples thereof are also the same.

In General Formula (L-2), V ₁ has the same meaning as V _{1 in} General Formula (L-1), and preferred examples are also the same.

  A particularly preferable combination as the compound represented by the general formula (L-2) of the present invention includes the following (a) to (f).

(A) Preferred W is a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, pyrrole ring, thiophene ring, imidazole ring, thiazole ring, benzothiazole ring, pyridine ring or pyridazine ring) And particularly preferably a substituted phenyl group (particularly a para-substituted phenyl group), a substituted or unsubstituted β-naphthyl group, a pyridine ring or a thiazole ring.

(B) X represents an N atom or ═CW ₁ —, and W ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. More specifically, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, A carbamoyl group having 1 to 20 carbon atoms and a halogenated alkyl group having 1 to 20 carbon atoms are preferred. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group.

(C) A is preferably a substituted phenyl group, a substituted naphthyl group, or a substituted or unsubstituted heterocyclic group, and among them, has a phenyl group substituted with an ionic hydrophilic group, a naphthyl group, and a substituent. A 5- to 6-membered nitrogen-containing heterocycle is preferable, and a phenyl group and a naphthyl group substituted with a sulfo group (including salts thereof), a carboxyl group (including salts thereof) are particularly preferable, and two or more Preferred is a phenyl group or a naphthyl group substituted with a sulfo group (including salts thereof), a carboxyl group (including salts thereof), or a naphthyl substituted with 2 or 3 sulfo groups (including salts thereof) The group is most preferred.

(D) T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one represents a nitrogen atom and the other represents = CR ₄₃ -or -CR ₄₄ =, T ₁ and T ₂ are each preferably = CR ₄₃ -and -CR ₄₄ =, respectively, from the viewpoint that more excellent performance can be exhibited.

(E) R ₄₁ and R ₄₂ are preferably a hydrogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkyl or arylsulfonyl group, more preferably a hydrogen atom, alkyl group, aryl group or heterocyclic group, In particular, a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

(F) V ₁ represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a silyloxy group, an acyloxy group, an amino group, or an acylamino group, among which a hydrogen atom, An amino group and an acylamino group are preferred, an amino group having a substituent is particularly preferred, and an amino group substituted with an aryl group having an ionic hydrophilic group as a substituent (such as a substituted anilino group) is most preferred.

  Regarding the preferred combination of substituents of the dye represented by the general formula (L-2) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  In this invention, the compound represented by the following general formula (L-3) is preferable among the compounds represented by general formula (L-2).

In the general formula (L-3), V ₁ , W, X, T ₁ , T ₂ , R ₄₁ and R ₄₂ are the same as V ₁ , W, X, T ₁ , T in the general formula (L-2). ₂ , Synonymous with R ₄₁ and R ₄₂ . X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ have the same meaning as V ₁ in the general formula (L-1).

  General formula (L-3) will be described in detail.

In the general formula (L-3) of the present invention, the monovalent group represented by X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ is a hydrogen atom or monovalent substitution Represents a group. The monovalent substituent will be described in more detail. Examples of the monovalent substituent include a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an alkoxy group, and an aryl group. Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, allylamino group), acylamino group (amide group), aminocarbonylamino Group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl A group, an azo group, or an imide group, each of which may further have a substituent.

Preferred X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an amido group, a ureido group Alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkoxycarbonyl group, sulfo group (including salts thereof), carboxyl group (including salts thereof), hydroxyl group (May be a salt), phosphono group (may be a salt) or quaternary ammonium, and among them, a hydrogen atom, a halogen atom, an alkyl group, a sulfo group (including salts thereof), a carboxyl group (including salts thereof) , A hydroxyl group (may be a salt) (including a salt thereof) is preferable, and further a hydrogen atom, a sulfo group (including a salt thereof), a carboxyl Preferably (including salts thereof), in particular _{X 1, X 2, X 3} ,
It is preferable that at least one of X ₄ , X ₅ , X ₆ and X ₇ is a sulfo group (including a salt thereof) or a carboxyl group (including a salt thereof).

  In General Formula (L-3), W has the same meaning as W in General Formula (L-2), and preferred examples are also the same.

  In general formula (L-3), X has the same meaning as X in general formula (L-2), and preferred examples thereof are also the same.

In formula (L-3), T ₁ and T ₂ has the same meaning as T ₁ and T ₂ in the formula (L-2), and preferred examples thereof are also the same.

In formula _{(L-3), R 41} , R 42 has the same meaning as _{R 41, R 42} in the formula (L-2), and preferred examples thereof are also the same.

In formula (L-3), _{V 1} has the same meaning as _{V 1} of the in the formula (L-2), and preferred examples thereof are also the same.

  A particularly preferable combination as the compound represented by the general formula (L-3) of the present invention includes the following (a) to (f).

(A) X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an amide group, Ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkoxycarbonyl group, sulfo group (including salts thereof), carboxyl group (including salts thereof) A hydroxyl group (which may be a salt), a phosphono group (which may be a salt) or a quaternary ammonium, and among them, a hydrogen atom, a halogen atom, an alkyl group, a sulfo group (including salts thereof), a carboxyl group (a salt thereof) Including), hydroxyl group (may be a salt) (including salts thereof), hydrogen atom, sulfo group (including salts thereof), carboxyl group (including salts thereof) Including those salts) are preferred, _{X 1, X 2, X 3} , X 4
, X ₅ , X ₆ and X ₇ are preferably sulfo groups (including salts thereof) or carboxyl groups (including salts thereof).

(B) Preferred W is a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, a pyrrole ring, thiophene ring, imidazole ring, thiazole ring, benzothiazole ring, pyridine ring or pyridazine ring) And particularly preferably a substituted phenyl group (particularly a para-substituted phenyl group), a substituted or unsubstituted β-naphthyl group, a pyridine ring or a thiazole ring.

(C) X represents an N atom or ═CW ₁ —, and W ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. More specifically, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, A carbamoyl group having 1 to 20 carbon atoms and a halogenated alkyl group having 1 to 20 carbon atoms are preferred. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group.

(D) T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one represents a nitrogen atom and the other represents = CR ₄₃ -or -CR ₄₄ =, T ₁ and T ₂ are each preferably = CR ₄₃ -and -CR ₄₄ =, respectively, from the viewpoint that more excellent performance can be exhibited.

(E) R ₄₁ and R ₄₂ are preferably a hydrogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkyl or arylsulfonyl group, more preferably a hydrogen atom, alkyl group, aryl group or heterocyclic group, In particular, a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

(F) V ₁ is hydrogen atom, halogen atom, alkyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, amino group (alkylamino group, arylamino group, hetero A cyclic amino group), and an acylamino group. Among them, a hydrogen atom, an amino group (including an alkylamino group, an arylamino group, and a heterocyclic amino group) and an acylamino group are preferable, and an amino group having a substituent is particularly preferable. An amino group substituted with an aryl group having an ionic hydrophilic group as a substituent (such as a substituted anilino group) is most preferable.

  As for the preferred combination of substituents of the dye represented by the general formula (L-3) of the present invention, a compound in which at least one of various substituents is the above-described preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  In this invention, the compound represented by the following general formula (L-4) and / or (L-5) among the compounds represented by general formula (L-3) is preferable.

In the general formula _{(L-4), R 43} has the same meaning as _{R 43} in formula (L-1). R ₄₄ has the same meaning as _{R 44} in formula (L-1). R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in} formula (L-3). R ₄₁ and _{R 42} has the same meaning as _{R 41} and _{R 42} in formula (L-3).
W is synonymous with W in the general formula (L-3). _{X 1, X 2, X 3} , X 4, X 5, X 6 and _{X 7,} wherein _X 1 in the general formula _{(L-3), X 2} , X 3, X 4, X 5, X 6 and X ₇ synonymous.

In the general formula _{(L-5), R 43} has the same meaning as _{R 43} in formula (L-1). R ₄₄ has the same meaning as _{R 44} in formula (L-1). R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in} formula (L-3). R ₄₁ and _{R 42} has the same meaning as _{R 41} and _{R 42} in formula (L-3). W is synonymous with W in the general formula (L-3). W ₁₁ has the same meaning as W _{1 in} formula (L-2). _{X 1, X 2, X 3} , X 4, X 5, X 6 and _{X 7,} wherein _X 1 in the general formula _{(L-3), X 2} , X 3, X 4, X 5, X 6 and X ₇ synonymous.

  The general formula (L-4) will be described in detail.

In the general formula (L-4), X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are X ₁ , X ₂ , X ₃ , _{X 4,} X 5, have the same meanings as _{X 6} and _{X 7,} and preferred examples thereof are also the same.

  In General Formula (L-4), W has the same meaning as W in General Formula (L-3), and preferred examples are also the same.

In formula _{(L-4), R 41} , R 42 is in the general formula _(L-3), has the same meaning as _{R 41,} R _42, and preferred examples thereof are also the same.

_{R 43, R 44} in the general formula (L-4) has the same meaning as _{R 43, R 44} in the formula (L-1), and preferred examples thereof are also the same.

In the general formula (L-4), R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in the} general formula (L-3), and preferred examples are also the same.

  A particularly preferred combination as the compound represented by formula (L-4) of the present invention includes the following (A) to (E).

(A) X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an amide group, Ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkoxycarbonyl group, sulfo group (including salts thereof), carboxyl group (including salts thereof) A hydroxyl group (which may be a salt), a phosphono group (which may be a salt) or a quaternary ammonium, and among them, a hydrogen atom, a halogen atom, an alkyl group, a sulfo group (including salts thereof), a carboxyl group (a salt thereof) Including), hydroxyl group (may be a salt) (including salts thereof), hydrogen atom, sulfo group (including salts thereof), carboxyl group (including salts thereof) Including those salts) are preferred, _{X 1, X 2, X 3} , X 4
, X ₅ , X ₆ and X ₇ are preferably sulfo groups (including salts thereof) or carboxyl groups (including salts thereof).

(B) Preferred W is a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, a pyrrole ring, thiophene ring, imidazole ring, thiazole ring, benzothiazole ring, pyridine ring or pyridazine ring) And particularly preferably a substituted phenyl group (particularly a para-substituted phenyl group), a substituted or unsubstituted β-naphthyl group, a pyridine ring or a thiazole ring.

(C) R ₄₁ and R ₄₂ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group, more preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, In particular, a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or RR ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

(D) Preferred examples of R ₄₃ and R ₄₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group , Alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, hydroxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group Represents an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl or arylsulfonylamino group, or a heterocyclic sulfonylamino group, and each group may be further substituted.

More preferred R ₄₃ represents a hydrogen atom, a halogen atom, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a heterocyclic oxycarbonyl group, among which a cyano group, A carboxyl group, a carbamoyl group, and an alkoxycarbonyl group are preferable, and a cyano group is particularly preferable.

R ₄₄ is more preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a hydroxy group, an amino group (an alkylamino group, an arylamino group, a heterocyclic amino group). An acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl or arylsulfonylamino group, a heterocyclic sulfonylamino group, among which a hydrogen atom, a halogen atom, An alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, and an aryl group are preferable, and a methyl group is particularly preferable.

(E) R ₄₅ and R ₄₆ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl group or an arylsulfonyl group, more preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, In particular, a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₅ and R ₄₆ are not simultaneously hydrogen atoms. R ₄₅ and R ₄₆ may combine to form a 5- to 6-membered ring.

  Regarding the preferred combination of substituents of the dye represented by formula (L-4) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  The general formula (L-5) of the present invention will be described in detail.

In the general formula (L-5) of the present invention, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are the same as X ₁ , X _{2 in the} general formula (L-3). , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ , and preferred examples are also the same.

  In General Formula (L-5), W has the same meaning as W in General Formula (L-3), and preferred examples are also the same.

In the general formula (L-5), W ₁₁ has the same meaning as W ₁ in the general formula (L-2), and preferred examples thereof are also the same.

In formula _{(L-5), R 41} , R 42 has the same meaning as _{R 41, R 42} in formula (L-3), and preferred examples thereof are also the same.

_{R 43, R 44} in the general formula (L-5) has the same meaning as _{R 43, R 44} in the formula (L-1), and preferred examples thereof are also the same.

In General Formula (L-5), R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in} General Formula (L-3), and preferred examples are also the same.

  A particularly preferred combination as the compound represented by the general formula (L-5) of the present invention includes the following (a) to (f).

(A) X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an amide group, Ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkoxycarbonyl group, sulfo group (including salts thereof), carboxyl group (including salts thereof) A hydroxyl group (which may be a salt), a phosphono group (which may be a salt) or a quaternary ammonium, and among them, a hydrogen atom, a halogen atom, an alkyl group, a sulfo group (including salts thereof), a carboxyl group (a salt thereof) Including), hydroxyl group (may be a salt) (including salts thereof), hydrogen atom, sulfo group (including salts thereof), carboxyl group (including salts thereof) Including those salts) are preferred, _{X 1, X 2, X 3} , X 4
, X ₅ , X ₆ and X ₇ are preferably sulfo groups (including salts thereof) or carboxyl groups (including salts thereof).

(B) Preferred W is a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, a pyrrole ring, thiophene ring, imidazole ring, thiazole ring, benzothiazole ring, pyridine ring or pyridazine ring) And particularly preferably a substituted phenyl group (particularly a para-substituted phenyl group), a substituted or unsubstituted β-naphthyl group, a pyridine ring or a thiazole ring.

(C) Preferred W ₁₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Among them, an electron-withdrawing group having a σp value of 0.30 or more is preferable, an electron-withdrawing group of 0.45 or more is more preferable, and an electron-withdrawing group of 0.60 or more is particularly preferable. It is desirable not to exceed zero. More specifically, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, A carbamoyl group having 1 to 20 carbon atoms and a halogenated alkyl group having 1 to 20 carbon atoms are preferred. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group.

(D) R ₄₁ and R ₄₂ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group, and more preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, In particular, a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

(E) Preferred examples of R ₄₃ and R ₄₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group , Alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, hydroxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group Represents an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl or arylsulfonylamino group, or a heterocyclic sulfonylamino group, and each group may be further substituted.

More preferred R ₄₃ represents a hydrogen atom, a halogen atom, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a heterocyclic oxycarbonyl group, among which a cyano group, A carboxyl group, a carbamoyl group, and an alkoxycarbonyl group are preferable, and a cyano group is particularly preferable.

R ₄₄ is more preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a hydroxy group, an amino group (an alkylamino group, an arylamino group, a heterocyclic amino group). An acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl or arylsulfonylamino group, a heterocyclic sulfonylamino group, among which a hydrogen atom, a halogen atom, An alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, and an aryl group are preferable, and a methyl group is particularly preferable.

(F) R ₄₅ and R ₄₆ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl group or an arylsulfonyl group, and more preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, In particular, a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₅ and R ₄₆ are not simultaneously hydrogen atoms. R ₄₅ and R ₄₆ may combine to form a 5- to 6-membered ring.

  Regarding the preferred combination of substituents of the dye represented by the general formula (L-5) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  In the present invention, among the compounds represented by the general formula (L-4) and / or (L-5), the compounds represented by the following general formula (L-4-I) and / or (L-5-I) are particularly preferable. Is preferable in that it can exhibit more excellent performance.

In the general formula (L-4-I), R ₁₁ and R ₁₂ each represents an ionic hydrophilic group. Particularly preferred are a sulfo group (including salts thereof) and a carboxyl group (including salts thereof), and among them, a sulfo group is preferred. m and n represent an integer of 1 to 3. Particularly preferably, it represents an integer of 1 to 2, and m = 1 and / or n = 1 is most preferable. W is synonymous with W in the general formula (L-4), and preferred examples are also the same. _{X 1, X 2, X 3} , X 4, X 5, X 6 and _{X 7,} wherein _X 1 in the general formula _{(L-4), X 2} , X 3, X 4, X 5, X 6 and is synonymous preferred examples and X ₇ are the same.

In general formula (L-5-I), R ₁₁ and R ₁₂ represent an ionic hydrophilic group. Particularly preferred are a sulfo group (including salts thereof) and a carboxyl group (including salts thereof), and among them, a sulfo group is preferred. m and n represent an integer of 1 to 3. Particularly preferably, it represents an integer of 1 to 2, and m = 1 and / or n = 1 is most preferable. W is synonymous with W in the general formula (L-5), and preferred examples are also the same. W ₁₁ is synonymous with W _{11 in} formula (L-5), and preferred examples are also the same. _{X 1, X 2, X 3} , X 4, X 5, X 6 and _{X 7,} wherein _X 1 in the general formula _{(L-5), X 2} , X 3, X 4, X 5, X 6 and is synonymous preferred examples and X ₇ are the same.

Specific examples of the azo dye represented by the general formula (L-1) are shown below, but the present invention is not limited to the following examples, and in the following specific examples, a carboxyl group, a phosphono group, and The sulfo group may be in a salt state, and examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic cation (eg, tetramethylammonium ion). Ion, tetramethylguanidinium ion, tetramethylphosphonium). Among these, ammonium ions, organic cations, and lithium ions are preferable, and lithium ions are most preferable.
The ink composition of the present invention preferably contains the counter ion.

  In the present invention, in addition to at least one compound represented by the general formula (L-1) and a salt thereof, or a compound having a naphthalene ring substituted with at least one hydroxyl group and three or more azo groups, It is characterized in that at least one other water-soluble long wave dye L having a different structure is used in combination.

  By using a compound having a naphthalene ring substituted with at least one hydroxyl group and three or more azo groups, it is possible to obtain an image having excellent image fastness and less bleeding under high-humidity storage.

  A compound with a larger number of azo groups has a higher molecular weight and tends to suppress blurring of an image when stored at high humidity. However, the solubility in ink tends to deteriorate, and the storage stability of the ink may become a problem. is there. In order to make them compatible, the number of azo groups is preferably 3-5.

  The compound having a naphthalene ring substituted with at least one hydroxyl group and three or more azo groups preferably has a hydrophilic group.

  The hydrophilic group includes a sulfo group, a carboxyl group, a phosphono group, an amino group, a nitro group, a quaternary ammonium group, and the like. As the hydrophilic group, a carboxyl group, a phosphono group, an amino group, a nitro group, and a sulfo group are preferable. Among them, a carboxyl group and a sulfo group are preferable, and a sulfo group is most preferable from the viewpoint of increasing the solubility in an aqueous solvent.

The hydrophilic group may be in a salt state. Examples of ions having a charge opposite to that of the hydrophilic group and forming a salt (ion pair) (hereinafter referred to as counter salt or counter ion) include ammonium, Alkali metals (eg, lithium, sodium, potassium) and organic cations (eg, tetramethylammonium, tetramethylguanidinium, tetramethylphosphonium) and the like are included. The counter ion is preferably an ion of ammonium, lithium, sodium, or potassium, more preferably sodium ion or lithium ion, and most preferably lithium ion.
Compounds having a naphthalene ring substituted with at least one hydroxyl group and three or more azo groups are represented by the general formulas (L-6), (L-6a), (L-7) and (L-8). It is preferable that it is a compound chosen from the compound to be made.

  In the present invention, in addition to at least one compound represented by the general formula (L-1) and a salt thereof, or a compound having a naphthalene ring substituted with at least one hydroxyl group and three or more azo groups, Use in combination with compounds represented by general formulas (L-1) to (L-5) having different structures, or compounds represented by general formulas (L-1) to (L-5) And the compounds represented by formulas (L-6) to (L-8) are preferably used in combination. The aqueous long wave dye L that can be used in combination is not particularly limited as long as it satisfies the conditions of the water-soluble long wave dye L.

  By using together the compound represented by the general formula (L-1) and the water-soluble long wave dye L having a different structure, a black image having a high density compared to the case where the general formula (L-1) is used alone. And the bronze gloss in the high density part can be suppressed. Although the cause of the effect is not clear, the combined use of the compound represented by formula (L-1), which is an associative dye, and the water-soluble long wave dye L having a different structure, does not impair the image fastness. It is presumed that the association of the compound of the general formula (L-1) is loosened.

  In order not to impair the image fastness, the water-soluble long wave dye L used in combination is preferably fast to light and ozone gas. Further, in order to reduce the hue change when the image is deteriorated by light or ozone, the fading rate constant of the water-soluble long wave dye L used in combination is a value close to the fading rate constant of the general formula (L-1). Specifically, the ratio thereof is more preferably in the range of 0.5 or more and 2.0 or less, but is not limited thereto. The fading rate constant can be determined for each of light resistance and ozone resistance using the method described in JP-A No. 2004-107638 (paragraph numbers [0011] to [0012]).

  The mixing ratio of the compound represented by the general formula (L-1) and the water-soluble long wave dye L used in combination is “addition amount (g) of the general formula (L-1)” / “water soluble long wave used together. The “addition amount (g) of the dye L” is preferably 0.3 to 100, more preferably 0.6 to 20, and still more preferably 1.0 to 10. If it is less than 0.3, the addition amount of the general formula (L-1) is small and the image fastness may be inferior. If it exceeds 100, the amount of the combined dye added is small, and the effect of suppressing the image density and bronze gloss may not be sufficient.

  In this invention, it is also possible to use 2 or more types of compounds represented by general formula (L-1) together. In that case, in the method for judging the associative property from the visible absorption spectrum described in [0031] above, the dye having the strongest associative property is used in combination with the compound represented by the general formula (L-1) and other dyes. The water-soluble long wave dye L is preferably defined as a mixing ratio of the dyes described above.

  From the viewpoint of being robust against light and ozone gas and having the above-mentioned fading rate constant close to that of the general formula (L-1), the water-soluble long wave dye L used in combination is represented by the general formulas (L-4) and (L- 5), (L-6), (L-6a), (L-7) and (L-8) are preferably selected.

  About general formula (L-4) and (L-5), it is synonymous with the said general formula (L-4) and (L-5), and its preferable example is also the same. The compounds represented by the general formulas (L-4) and (L-5) can be preferably used as the compounds of the general formula (L-1), and the compounds represented by the general formula (L-4) As the water-soluble dye L used in combination, a compound of the general formula (L-4) may be used (the same applies to the general formula (L-5)). At this time, the dye used in combination is preferably one having a small degree of association.

  When added as a water-soluble long wave dye L in which the compounds of the general formulas (L-4) and (L-5) are used in combination, the difference in structure from the water-soluble long wave dye L used in combination with the compound of the general formula (L-1) As for, there is no particular limitation as long as it satisfies the general formula, but in particular, it is preferable that the site of B in the general formula (L-1) is different. Examples thereof include a combination of the compound of general formula (L-4) and the compound of general formula (L-5), but are not limited thereto. Moreover, when using together 2 or more types of compounds of general formula (L-4), it is preferable that the structure of the site | part of W in general formula (L-4) differs. When two or more compounds of the general formula (L-5) are used in combination, it is preferable that the structure of the W site is different as in the case of the compound of the general formula (L-4).

In general formula (L-6), R ₁₁ and R ₁₂ are each independently a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a sulfo group, an alkyl group, or a sulfamoyl group that may be substituted with a phenyl group, phosphorus An acid group, a nitro group, an acyl group, a ureido group, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, An alkoxy group having 1 to 4 carbon atoms or an acylamino group which may be substituted with a sulfo group or a carboxyl group; E represents a phenyl group or a naphthyl group; a halogen atom, a cyano group, a carboxyl group, a sulfo group, an alkyl group or Sulfamoyl group, phosphate group, nitro group, acyl group, ureido group, hydroxyl group which may be substituted with phenyl group Or an optionally substituted alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a sulfo group, or a carboxyl group that may be substituted with a carboxyl group. It may be substituted with 1 to 4 alkoxy groups or acylamino groups. n ₁ is 0 or 1.

  Of the compounds represented by the general formula (L-6), a compound represented by the following general formula (L-10) is preferable.

In general formula (L-10), R <_13> , R <_14> and R <_15> are each independently a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a sulfo group, an alkyl group having 1 to 4 carbon atoms or a phenyl group. An optionally substituted sulfamoyl group, a phosphate group, a nitro group, an acyl group, an ureido group, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, An alkoxy group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms which may be substituted with a sulfo group or a carboxyl group, or an acylamino group, and at least one of R ₁₃ , R ₁₄ and R ₁₅ is a sulfo group. Or it is a carboxyl group. n ₁ is 0 or 1.

  Specific examples of preferred compounds of the compound represented by formula (L-6) and salts thereof are shown below, but are not limited thereto. Moreover, although the following specific example is shown with the structure of a free acid, it cannot be overemphasized that you may use as arbitrary salts.

  The detailed description of the compound represented by the general formula (L-6) and a salt thereof is described in JP-A-2005-220211, and the compound described in the above-mentioned publication can be preferably used.

General formula (L-6a):

In general formula (L-6a), A represents the following formula (L-6a-1), the substitution position of A is the m-position or p-position with respect to the azo group, and R ¹ and R ² are Each independently hydrogen atom; halogen atom; cyano group; carboxyl group; sulfo group; sulfamoyl group; N-alkylaminosulfonyl group; N-phenylaminosulfonyl group; phospho group; nitro group; acyl group; ureido group; Or an alkyl group having 1 to 4 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbon atoms; 1 carbon atom which may be substituted with a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a sulfo group or a carboxyl group Represents an alkoxy group having 1 to 4 carbon atoms; an acylamino group which may be substituted with an alkoxy group having 1 to 4 carbon atoms, a sulfo group or a carboxyl group; R ³ and R ⁴ are each independently A hydrogen atom; a halogen atom; a cyano group; a carboxyl group; a sulfo group; a nitro group; an alkyl group having 1 to 4 carbon atoms; a hydroxyl group; a carbon number that may be substituted with an alkoxy group having 1 to 4 carbon atoms or a sulfo group. 1 to 4 alkoxy groups are represented, and n is 0 or 1.

General formula (L-6a-1)

In formula (L-6a-1), R ⁵ represents a cyano group; a carboxyl group; an alkyl group having 1 to 4 carbon atoms; an alkoxycarbonyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁶ , R ⁷ and R ⁸ are each independently substituted with a hydrogen atom; a halogen atom; a cyano group; a carboxyl group; a sulfo group; a nitro group, an alkyl group having 1 to 4 carbon atoms; a hydroxyl group; an alkoxy group having 1 to 4 carbon atoms or a sulfo group. Represents an alkoxy group having 1 to 4 carbon atoms which may be substituted; an acylamino group which may be substituted with a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms or a sulfo group.

  Specific examples of preferred compounds of the compound represented by the general formula (L-6a) and salts thereof are shown below, but are not limited thereto. Moreover, although the following specific examples (compound Nos. 1-27) are shown by the structure of a free acid, it cannot be overemphasized that you may use as arbitrary salts.

  Details of the compound represented by the general formula (L-6a) and a salt thereof are described in WO2005 / 097912, and the compounds described in the above-mentioned publication can be preferably used.

In General Formula (L-7), G and J each independently represent a phenyl group, a naphthyl group, or an azo group, which is a 5-membered or 6-membered aromatic heterocyclic group bonded to a carbon atom. Each component contains at least one carboxyl group or sulfo group. One of X and Y is a hydroxyl group, and the other is an amino group, and l ₂ , m ₂ and n ₂ each independently represent 1 or 2.

  Of the compounds represented by the general formula (L-7), a compound represented by the following general formula (L-11) is preferable.

In general formula (L-11), G and J each independently represent a phenyl group, a naphthyl group, or an azo group, which is a 5-membered or 6-membered aromatic heterocyclic group bonded to a carbon atom; Each component contains at least one carboxyl group or sulfo group. a and b each represent a single bond, the bond position of the bond a is the 2nd or 3rd position, and the bond position of the bond b is the 6th or 7th position. One of X and Y represents a hydroxyl group, the other represents an amino group, and l ₃ , m ₃ , and n ₃ each independently represents 0 or 1.

  In general formula (L-11), it is preferable that G and J are each independently a phenyl group or a naphthyl group which may be substituted with a substituent containing at least one carboxyl group and / or sulfo group. . Examples of substituents for substituting G and J include halogen atoms, hydroxyl groups, amino groups, carboxyl groups, sulfo groups, nitro groups, alkyl groups, alkoxy groups, acyl groups, phenyl groups, ureido groups, hydroxyl groups, alkoxy groups. An alkyl group substituted with a sulfo group or a carboxyl group, a hydroxyl group, an alkoxy group, an alkoxy group substituted with a sulfo group or a carboxyl group, a phenyl group which may be further substituted with a carboxy group or a sulfo group, Examples include an amino group substituted by an alkyl group or an acyl group.

  In the general formula (L-11), G and J are each independently a phenyl group having a sulfo group at the o-position with respect to the azo group, and further substituted with a nitro group, an alkoxy group, or a sulfo group. Preferably there is.

  Specific examples of preferred compounds of the compound represented by formula (L-7) and salts thereof are shown below, but are not limited thereto. Moreover, although the following specific example is shown with the structure of a free acid, it cannot be overemphasized that you may use as arbitrary salts.

Details of the compound represented by the general formula (L-7) and salts thereof are described in JP-A No. 2004-285351, and the compounds described in the above-mentioned publication can be preferably used.

In the formula (L-8), R ₂₁ represents a phenyl group having a substituent or a naphthyl group having a substituent, R ₂₂ represents a phenylene group having a substituent or a naphthylene group having a substituent, and R ₂₃ represents It represents a 5- to 7-membered heterocyclic group having at least one double bond and a substituent. Further, the substituents are independently selected from the group consisting of the R ₂₁ to R _23, with _{OH, SO 3 H, PO 3} H 2, CO 2 H, NO 2, NH 2, alkyl group having 1 to 4 carbon atoms, a substituent It is selected from the group consisting of an alkyl group, an alkoxy group having 1 to 4 carbon atoms, an alkoxy group having a substituent, an amino group, an amino group having a substituent, and a phenyl group having a substituent.

  The compound represented by the general formula (L-8) is preferably a compound selected from the group consisting of the compound represented by the general formula (L-9) and a salt thereof.

In the formula (L-9), R _{31 to} R ₃₉ independently represent a group selected from the group consisting of H, OH, SO ₃ H, PO ₃ H ₂ , CO ₂ H, NO ₂ , and NH _2. Represent.

  Specific examples of preferred compounds of the compounds represented by the general formulas (L-8) and (L-9) and salts thereof are shown below, but are not limited thereto. Moreover, although the following specific example is shown with the structure of a free acid, it cannot be overemphasized that you may use as arbitrary salts.

  Details of the compounds represented by the general formulas (L-8) and (L-9) and salts thereof are described in International Application Publication No. WO03 / 106572 and JP-A-2005-2271. The compounds described in the publication can be preferably used.

  In the present invention, a water-soluble short wave dye S described later can be used in combination as a color correction dye.

(Water-soluble short wave dye S)
The water-soluble shortwave dye S that can be used in the present invention has an absorption spectrum maximum (absorption maximum: λmax) in an aqueous solvent of 400 nm to 540 nm. Furthermore, it is preferable that the half width of the absorption spectrum is 90 nm to 200 nm, and the dye achieves broad absorption.
The absorption spectrum of the water-soluble shortwave dye S is measured using a single compound. That is, when measuring the absorption spectrum in an aqueous solvent, the water-soluble shortwave dye S of the present invention does not exhibit physical properties such as a desired absorption maximum and a half-value width by combining a plurality of compounds, but the physical properties of one compound Is meant to indicate In the present invention, it is obvious that compounds having different structures may be used in combination as long as the water-soluble short wave dye S (hereinafter also referred to as “short wave dye S”) satisfies the absorption spectrum. It is.
Since the short wave dye S has such absorption characteristics, it can absorb a wide range of light from blue to green, which tends to be insufficient in the absorption spectrum of the water-soluble long wave dye L such as disazo dye or trisazo dye. , Have preferable absorption characteristics as a complementary color dye.
The absorption maximum of the short wave dye S is preferably between 400 nm and 540 nm, and particularly preferably between 460 nm and 500 nm.
The full width at half maximum of the absorption maximum of the short wave dye S is preferably between 100 nm and 180 nm, and particularly preferably between 110 nm and 160 nm.

Further, the short wave dye S of the present invention preferably does not have a dissociable phenolic hydroxyl group present in a general pigment. Owing to such a structure, there is little change in color tone depending on the image receiving material to be used. It has preferable performance such as low reactivity with oxidizing gas such as excellent gas resistance.
Here, the dissociable phenolic hydroxyl group means a dissociable hydroxyl group substituted with an aryl group. This aryl group may be substituted with other substituents.
Furthermore, it is preferable that the short wave dye S of the present invention has 2 to 6 azo groups in one molecule, and this structure enhances color developability and also has a fixing property because the dye plane is greatly expanded. Can give a good picture.
Further, the number of the azo groups is more preferably 4 to 6 per molecule from the viewpoint of color developability and fixability.

The short wave dye S is not particularly limited as long as it has the physical properties defined in the present specification and can solve the above-mentioned problems, and examples thereof include polyazo dyes represented by the following general formula.
(D) n-Y
In the above general formula, D represents a dye residue consisting of 1 to 3 azo groups conjugated to each other and 3 to 4 aromatic rings having a total of 20 or more π electrons. , N is 1 or 2, when n is 1, Y represents a hydrogen atom, and when n is 2, Y represents a divalent linking group. The aromatic ring constituting the chromophore may be a hetero ring or a hydrocarbon ring, but is preferably a hydrocarbon ring. When the aromatic ring constituting the chromophore is a condensed ring, the number of π electrons on the aromatic ring is the number of π electrons as the whole condensed ring. For example, a naphthalene ring has 10 π electrons. It is. The divalent linking group represented by Y is an alkylene group, an arylene group, a heterocyclic residue, -CO-, -SOn- (n is 0, 1, 2), -NR- (R is a hydrogen atom, alkyl Group, represents an aryl group), —O—, and a divalent group obtained by combining these linking groups, and further includes an alkyl group, an aryl group, an alkoxy group, an amino group, an acyl group, an acylamino group, and a halogen atom. May have a substituent such as a hydroxyl group, a carboxyl group, a sulfamoyl group, a carbamoyl group, or a sulfonamide group. Particularly preferred examples of the linking group include —NH—CO—NH—, —NH—CS—NH—, and groups having the following general formula.

In the present specification, the alkyl group is a monovalent saturated carbonization obtained by combining linear, branched, cyclic (monocyclic or polycyclic, and in the case of polycyclic, bridged or spiro) or a combination thereof. A hydrogen group means a concept including a cycloalkyl group, a cycloalkylalkyl group, and the like, and further includes a substituted alkyl group when it may be substituted with a substituent.
In the present specification, an alkenyl group excludes an aromatic group obtained by combining linear, branched, cyclic (monocyclic or polycyclic, may be bridged or spiro in the case of polycyclic), or a combination thereof. This is a concept that means a monovalent unsaturated hydrocarbon group containing one or more carbon-carbon double bonds, and when it may be further substituted with a substituent, a substituted alkenyl group is included.
In the present specification, for example, a substituted alkyl group means an alkyl group in which a hydrogen atom of an alkyl group is substituted with another substituent, and the substituent can substitute one or more of each one or more. Other substituted aryl groups and the like are the same as described above.

  In the general formula, X represents a hydroxyl group, a sulfo group, an alkoxy group, an aryloxy group, an amino group (including an alkylamino group or an arylamino group), or an alkyl or arylsulfenyl group, and each group further has a substituent. You may have.

For example, as the short wave dye S, commercially available CIDirect Red 84, Brown 106, and Brown 202 are useful, and among them, it can be used to adjust the color tone of many black dyes.
CIDirect Red 84, which is excellent in fixability, is particularly useful.

Furthermore, although the example of the short wave dye S preferably used by this invention is shown with the structure of a free acid below, it cannot be overemphasized that you may use as arbitrary salts.
Preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, and organic cations (eg, pyridinium, tetramethylammonium, guanidinium).

  Among them, CIDirect Red 84 (sodium salt of the above compound example SB-2) and Brown 106 (sodium salt of the above compound example SB-14) are preferable because they are available as commercially available dyes. CIDirect Red 84, which can be used for color tone adjustment and has excellent color development, fastness, and fixing properties, is particularly useful.

  Examples of counter salts of CIDirect Red84 and Brown 106 include ammonium, alkali metals (eg, lithium, sodium, potassium) and organic cations (eg, tetramethylammonium, tetramethylguanidinium, tetramethylphosphonium). ) And the like. As the counter salt, ammonium, lithium, sodium, and potassium are preferable, and sodium and lithium are more preferable. Sodium salts are preferred because they are available as commercial dyes as described above. Lithium salts have been found to improve the water solubility of the dye and are particularly preferred from the standpoint of stability over time and precipitation in the ink state.

  In addition, the short-wave dye S other than the commercially available dye is also obtained from commercially available raw materials according to the synthesis route of CIDirect Red 84 or Brown 106 described in Color Index Volume 4 (issued by The Society of Dyers and Colorists). Easy to synthesize.

  The black ink composition of the present invention preferably contains 0.1 to 4% by mass, preferably 0.5 to 3.0% by mass, particularly preferably 1.0 to 2.5% by mass of the short-wave dye S. Is also possible.

(Other dyes)
Furthermore, in the present invention, in order to adjust the color tone of the black ink composition, other dyes can be used in combination as long as the light resistance and ozone resistance are not significantly impaired.

  Examples of yellow dyes include phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components; for example, open-chain active methylene compounds as coupling components. Azomethine dyes; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dye species such as quinophthalone dyes, nitro-nitroso dyes And dyes, acridine dyes, acridinone dyes and the like. These dyes may be those that exhibit yellow only after a part of the chromophore is dissociated, in which case the counter cation may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, and further may be a polymer cation having them in a partial structure.

  Examples of magenta dyes include aryl or heteryl azo dyes having phenols, naphthols, and anilines as coupling components; azomethine dyes having pyrazolones and pyrazolotriazoles as coupling components; for example, arylidene dyes, styryl dyes, and merocyanine Dyes, methine dyes such as oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc. And ring dyes. These dyes may exhibit magenta only after part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, and further may be a polymer cation having them in a partial structure.

  Examples of cyan dyes include azomethine dyes such as indoaniline dyes and indophenol dyes; polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; phthalocyanine Dyes; anthraquinone dyes; For example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components, and indigo / thioindigo dyes can be mentioned. These dyes may exhibit cyan only after a part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, and further may be a polymer cation having them in a partial structure.

  Also, black dyes such as polyazo dyes can be used.

  In addition, water-soluble dyes such as direct dyes, acid dyes, food dyes, basic dyes, and reactive dyes can be used in combination. Among these, CI Direct Red 1, 2, 4, 9, 11, 23, 26, 31, 37, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 87, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 219, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, 254, CI Direct Violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101, CI Direct Yellow 4, 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 86, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 120, 130, 132, 142, 144, 157, 161, 163, CI Direct Blue 1, 10, 15, 22, 25, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108 109, 151, 156, 158, 159, 160, 168, 189, 192, 193, 194, 199, 200, 201, 202, 203, 207, 211, 213, 214, 218, 225, 229, 236, 237 , 244, 248, 249, 251, 252, 264, 270, 280, 288, 289, 290, 291, CI Direct Black 9, 17, 19, 22, 32, 51, 56, 62, 69, 77, 80, 91, 94, 97, 108, 112, 113, 114, 117, 118, 121 , 122, 125, 132, 146, 154, 166, 168, 173, 199, CI Acid Red 1, 8, 35, 42, 52, 57, 62, 80, 81, 82, 87, 94, 111, 114, 115, 118, 119, 127, 128, 131, 143, 144, 151, 152, 154, 158, 186, 245, 249, 254, 257, 261, 263, 266, 289, 299, 301, 305, 336, 337, 361, 396, 397, CI Acid Violet 5, 34, 43, 47, 48, 90, 103, 126, CI Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195, 196, 197, 199, 218, 219, 222, 227, CI Acid Blue 9, 25, 40 , 41, 62, 72, 76, 78, 80, 82, 87, 92, 106, 112, 113, 120, 127: 1, 129, 138, 143, 175, 181, 185, 205, 207, 220, 221 , 230, 232, 247, 249, 258, 260, 264, 271, 277, 2 78, 279, 280, 288, 290, 326, CI Acid Black 7, 24, 29, 48, 52: 1, 172, CI Reactive Red 3, 6, 13, 17, 19, 21, 22, 23, 24 29, 35, 37, 40, 41, 43, 45, 49, 55, 63, 106, 107, 112, 113, 114, 126, 127, 128, 129, 130, 131, 137, 160, 161, 174 , 180, CI Reactive Violet 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34, CI Reactive Yellow 2, 3, 13 , 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, CI Reactive Blue 2, 3, 5, 7, 8, 10, 13, 14, 15 , 17, 18, 19, 21, 25, 26, 27, 28, 29, 38, 82, 89, 158, 182, 190, 203, 216, 220, 244, CI Reactive Black 4, 5, 8, 14 , 21, 23, 26, 31, 32, 34, CI Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46, CI Basic Violet 1, 2, 3, 7, 10, 15, 16, 20 21, 25, 27, 28, 35, 37, 39, 40, 48, CI Basic Yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32 , 36, 39, 40, CI Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 45, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71, CI Basic Black 8 etc. are mentioned, but it is not limited to this.

  In addition to the dyes represented above, the dyes described in the following publications may be used in combination. WO01 / 48090, WO2004 / 087815, WO02 / 090441, WO03 / 027185, WO2004 / 088551, JP2003-321627, JP2002-332418, JP2002-332419, WO02 / 059216, WO02 / 059215, WO2004 / 087814, WO00 / 58407, Japanese Patent No. 3558211, Japanese Patent No. 3558212, Japanese Patent No. 3558213, Japanese Patent Application Laid-Open No. 2004-323605, WO04 / 104108, and the like, but are not limited thereto.

  The black ink composition of the present invention preferably contains at least two water-soluble dyes as colorants, and the total amount of the colorants is preferably 0.5 to 12% by weight based on the total weight of the black ink composition. More preferably, the content is 3.0 to 10.0% by weight. Especially preferably, it is 5.0 to 8.0 weight%.

  When the total amount of the above-mentioned dyes contained in the black ink composition is 0.5% by weight or more, when an image or the like is recorded on a recording medium using the ink composition, sufficiently good color development and high image density Can be obtained.

  Further, by setting the total amount of the dyes contained in the black ink composition to 12% by weight or less, the viscosity of the ink composition can be adjusted to a preferable value, and the ink composition from the inkjet head can be adjusted. Can be stabilized, and further, clogging of the ink jet head can be prevented.

The water-miscible organic solvent that can be used in the ink composition of the present invention is a material having functions such as an anti-drying agent, a penetration enhancer, and a wetting agent, and a high-boiling water-miscible organic solvent is mainly used. The Specific examples of such a compound are described in [0419] to [0423] of JP-A-2004-331871.
In the present invention, alcohol-based solvents are particularly preferable among the water-miscible organic solvents. The ink composition of the present invention preferably contains a water-miscible organic solvent having a boiling point of 150 ° C. or higher.
These water-miscible organic solvents are preferably contained in the ink composition in a total amount of 5 to 60% by mass, particularly preferably 10 to 45% by mass.

  For the purpose of improving the ejection stability, print quality, image durability, and the like of the ink composition of the present invention, surfactants, anti-drying agents, penetration enhancers, urea-based agents described in JP-A-2004-331871 and the like Additives, chelating agents, UV absorbers, antioxidants, viscosity modifiers, surface tension modifiers, dispersants, dispersion stabilizers, antiseptics, antifungal agents, rust inhibitors, pH adjusters, antifoaming agents, polymers Additives such as materials and acid precursors can be appropriately selected and used. Preferred amounts of these additives are as described in JP-A-2004-331871.

  Moreover, the black ink composition of the present invention further contains one or more additives selected from the group consisting of a bleeding inhibitor, a bronze improver, and an ozone resistance improver, if necessary, in addition to the above components. It is preferable.

(Anti-bleeding agent)
Examples of anti-bleeding agents include betaine surfactants. As the betaine surfactant, compounds described in [0017] to [0044] of JP-A-2005-111699 can be appropriately selected and used.

(Bronze improver)
The bronze improving agent used in the present invention has a function of weakening or eliminating the bronzing phenomenon seen when solid printing is performed using an ink set containing a black ink composition. For example, as a bronze improving agent, The aromatic compound which has a carboxyl group, or its salt is mentioned.
As the aromatic compound having a carboxyl group or a salt thereof used in the present invention, a compound described in [0044] of JP-A No. 2004-263155 can be appropriately selected and used.

  The total content of the aromatic compound having a carboxyl group and / or a salt thereof is determined by the kind of the aromatic compound having a carboxyl group and / or a salt thereof, the kind of the dye, the kind of the solvent component, and the like.

Further, as another bronze improving agent, a colorless water-soluble planar compound having more than 10 delocalized π electrons in one molecule is preferable.
As the water-soluble planar compound, compounds described in JP-A-2005-105261 [0012] to [0026] can be appropriately selected and used.

  These bronze improvers are preferably in the range of 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total weight of the black ink composition.

(Ozone resistance improver)
The ozone resistance improver is a compound having a function of suppressing dye oxidation, and examples thereof include thiol compounds, amidine compounds, carbazide compounds, hydrazide compounds, and guanidine compounds.

(Thiol compounds)
The thiol compound used in the present invention is a compound having an SH group, preferably an aromatic thiol or an aliphatic thiol, and preferably a compound represented by the general formula (B).
Formula (B):
R ₁₀ -SH
(In the formula, R is an alkyl group, an aryl group, or a heterocyclic group.)
The R _{10 will be} described.
As an alkyl group, Preferably it is C1-C12, More preferably, a C1-C6 thing is mentioned.
As an aryl group, Preferably it is C6-C18, More preferably, a C6-C10 thing is mentioned.
Heterocyclic groups include furyl, pyridyl, pyrimidyl, pyrrolyl, pyrrolinyl, pyrrolidyl, dioxolyl, pyrazolyl, pyrazolinyl, pyrazolidyl, imidazolyl, oxazolyl, thiazolyl, oxadiazolyl, triazolyl , Thiadiazolyl group, pyryl group, pyridyl group, piperidyl group, dioxanyl group, morpholyl group, pyridazyl group, pyrazyl group, piperazyl group, triazyl group, trithianyl group and the like.
The substituent represented by R ₁₀ includes those in which the hydrogen atom is further substituted with any other substituent as described above. Examples of such a substituent include a carboxyl group, an oxo group, an amino group, an amino acid residue (preferably 2 to 8 carbon atoms), an ammonium group, a hydroxyl group, a thiol group, and an alkoxy group (preferably 1 to 12 carbon atoms). ), An acylamino group (preferably having 1 to 12 carbon atoms, a carboxyl group, an amino group or the like may be substituted), a carbamoyl group, or the like. Two or more of these substituents are substituted with the same molecule. It may be.

As a method for synthesizing the compound represented by the general formula (B), for example, a thiol in which R is an aryl group is obtained by a reaction between the corresponding aryl Grignard reagent and elemental sulfur, and a corresponding alkyl halide and sulfide are obtained. Reaction of sodium hydride or thiourea gives a thiol wherein R ₁₀ is an alkyl group.

(Amidine compounds)
The amidine compound used in the present invention means a compound having a structure in which —C (═NH) —NH ₂ group (amidino group) is bonded to a carbon atom of a carbon-containing group, and the above-mentioned —C (═NH) One or more hydrogen atoms of the —NH ₂ group may be substituted with a substituent.
As the amidine-based compound, a compound represented by the general formula (C) is preferable.

(In the formula, R ₅₁ , R ₅₂ , R ₅₃ , or R ₅₄ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and when R ₅₁ contains a nitrogen atom, (It does not bind to C shown in the formula.)
As an alkyl group, Preferably it is C1-C12, More preferably, a C1-C6 thing is mentioned.
As an aryl group, Preferably it is C6-C18, More preferably, a C6-C10 thing is mentioned.
Heterocyclic groups include furyl, pyridyl, pyrimidyl, pyrrolyl, pyrrolinyl, pyrrolidyl, dioxolyl, pyrazolyl, pyrazolinyl, pyrazolidyl, imidazolyl, oxazolyl, thiazolyl, oxadiazolyl, triazolyl , Thiadiazolyl group, pyryl group, pyridyl group, piperidyl group, dioxanyl group, morpholyl group, pyridazyl group, pyrazyl group, piperazyl group, triazyl group, trithianyl group and the like.
In the substituents represented by R _{51 to} R ₅₄ , the hydrogen atom may be further substituted with any other substituent. Examples of such substituents include halogen atoms such as chlorine, nitro groups, amino groups, carboxyl groups, carbamoyl groups, amidino groups, and aryloxy groups (the aryl moiety may be further substituted by the substituents listed here). 2 or more of these substituents may be substituted with the same molecule. In the amino group, carbamoyl group, and amidino group, the hydrogen atom may be substituted with an alkyl group, an aryl group, or a heterocyclic group represented by R _{51 to} R ₅₄ .

  The amidine-based compound may be in the form of a salt such as hydrochloride.

  As a method for synthesizing the compound represented by the general formula (C), for example, the compound can be obtained through at least a step of causing ammonia to act on the hydrochloride of the corresponding imino ether.

(Carbazide compounds)
The carbazide-based compound used in the present invention means carbazide and derivatives thereof, and preferably has the general formula (D) R ₅₅ R ₅₆ NCONHNR ₅₇ R ₅₈ (R _{55 to} R ₅₈ are each independently a hydrogen atom or an organic group. It is a compound represented by.
Examples of the organic group, those listed in the R ₅₁ to R ₅₄ are preferred.
Substituents represented by R ₅₅ to R ₅₈ include those whose hydrogen atom is further substituted with any other substituent. Examples of such substituent include -HNCONHNR ₅₉ R ₆₀ (wherein R ₅₉ and R ₆₀ are organic groups, in addition to those exemplified as those which can be substituted with R _{51 to} R ₅₄ , preferred examples thereof) Is the same as R _{51 to} R ₅₄ ). In the present invention, —HNCONHNR ₅₉ R ₆₀ is referred to as a carbazide structure. The carbazide compound used in the present invention preferably has two or more (more preferably 2 to 6) carbazide structures in the same molecule.

Specifically, the carbazide compound represented by the general formula (D) includes the corresponding isocyanate, diisocyanate, urea derivative and the like, NH ₂ NR ₅₇ R ₅₈ (R ₅₇ and R ₅₈ are as defined above). It can be obtained by a condensation reaction with hydrazine compounds represented by

(Hydrazide compounds)
The hydrazide-based compound used in the present invention means hydrazide and derivatives thereof, preferably the general formula (E) R ₆₁ CONHNR ₆₂ R ₆₃ (R _{61 to} R ₆₃ each independently represents a hydrogen atom, a hydrazino group, Or an organic group, and a ring may be formed by bonding with R ₆₁ and R ₆₂ or R ₆₃ ).
Examples of the organic group, those listed in the R ₅₁ to R ₅₄ in the general formula (C) are preferred.
The substituents represented by R _{61 to} R ₆₃ include those in which the hydrogen atom is further substituted with any other substituent. As such substituents, in addition to those exemplified as those which can be substituted with R _{51 to} R ₅₄ , acyl groups, cyano groups, alkoxy groups, aralkyloxy groups, benzoyl groups, —CONHNR ₆₄ R ₆₅ (wherein , R ₆₄ and R ₆₅ are organic groups, and preferred examples thereof are the same as those of R _{51 to} R _54. ). In the present invention, —CONHNR ₁₄ R _{15 is referred} to as a hydrazide structure. The hydrazide compound used in the present invention preferably has two or more (more preferably 2 to 6) hydrazide structures in the same molecule.

Specifically, the hydrazide compound represented by the general formula (E) includes a corresponding carboxylic acid ester, an acid derivative such as an acid halide, an acid anhydride, etc., and a general formula NH ₂ NR ₆₂ R ₆₃ ( R ₆₂ and R ₆₃ are obtained by a condensation reaction with a hydrazine compound represented by the same formula as above.

Of the ozone resistance improvers, guanidine compounds are particularly preferable. Hereinafter, the guanidine compound will be described in detail.
(Guanidine compounds)
The guanidine compound used in the present invention means a compound having an N—C (═N) —N structure.
As the guanidine compound, a compound represented by the general formula (F) is preferable.

(Wherein R ₇₁ , R ₇₂ , R ₇₃ , or R ₇₄ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, or an amino group, and R ₇₅ represents a hydrogen atom, an alkyl group) A group, an alkoxy group, an aryl group, or a heterocyclic group, and these alkyl group, alkoxy group, aryl group, heterocyclic group, and amino group may be substituted or unsubstituted.)
As an alkyl group, Preferably it is C1-C12, Most preferably, a C1-C6 thing is mentioned.
As an alkoxy group, Preferably it is C1-C12, Most preferably, a C1-C6 thing is mentioned.
As an aryl group, Preferably it is C6-C18, Most preferably, a C6-C10 thing is mentioned.
Heterocyclic groups include furyl, pyridyl, pyrimidyl, pyrrolyl, pyrrolinyl, pyrrolidyl, dioxolyl, pyrazolyl, pyrazolinyl, pyrazolidyl, imidazolyl, oxazolyl, thiazolyl, oxadiazolyl, triazolyl , Thiadiazolyl group, pyryl group, pyridyl group, piperidyl group, dioxanyl group, morpholyl group, pyridazyl group, pyrazyl group, piperazyl group, triazyl group, trithianyl group and the like.
The alkyl group, alkoxy group, aryl group, or heterocyclic group represented by R _{71 to} R ₇₅ includes those in which the hydrogen atom is further substituted with any other substituent. Examples of such substituents include halogen atoms such as chlorine, nitro groups, amino groups, carboxyl groups, hydroxyl groups, carbamoyl groups, amidino groups, guanidino groups, aryloxy groups (the aryl moiety depends on the substituents listed here). Further, two or more of these substituents may be substituted with the same molecule. Further, the amino group, carbamoyl group, amidino group, guanidino group, an alkyl group whose hydrogen atom is represented by R ₇₁ to R _75, alkoxy, aryl, or optionally substituted heterocyclic group.
In the amino group represented by R _{71 to} R ₇₄ , the hydrogen atom may be substituted with an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, or the like represented by R _{71 to} R ₇₅ .

  The guanidine-based compound may be in the form of a salt or a metal complex. For example, hydrochloride, nitrate, phosphate, sulfamate, carbonate, acetate and the like can be mentioned.

  As a method for synthesizing the compound represented by the general formula (F), for example, it can be obtained through at least a step of causing ammonia to act on the hydrochloride of the corresponding imino ether.

  The guanidine-based compound may be a polymer having an N—C (═N) —N structure. Examples of such a polymer include, but are not limited to, compounds containing a repeating unit represented by the following general formula (Fa), general formula (Fb), and general formula (Fc). Is not to be done. The compound containing the repeating unit may be an oligomer. A monomer may be sufficient as the compound containing the repeating unit represented by general formula (Fc). Further, these compounds are preferably salts with acids.

In the general formula (F-a), R ₇₅ is as defined above, R ₇₆ represents any of R ₇₁ , R ₇₂ , R ₇₃ , or R ₇₄ , and n R ₇₅ and R ₇₆ may be the same May be different. n7 is an integer greater than or equal to 2, Preferably it is 2-30, More preferably, it is 2-15. The compound containing the repeating unit represented by the general formula (Fa) may be a homopolymer or a copolymer with another repeating unit such as azetidinium. Moreover, although a terminal structure can be selected suitably, a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, or an amino group is preferable.

In formula (F-b), R ₇₅ and R ₇₆ are as defined above, it may be the same or different each l7 amino R ₇₅ and R _76. l7 is an integer of 2 or more, preferably 2 to 10, and more preferably 2 to 5. m7 is an integer of 1 or more, preferably 1 to 6, and more preferably 1 to 3. The compound containing the repeating unit represented by the general formula (Fb) may be a homopolymer or a copolymer with another repeating unit such as azetidinium. Moreover, although a terminal structure can be selected suitably, a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, or an amino group is preferable.

In the general formula (Fc), R ₇₅ has the same meaning as described above, R ₇₇ has the same meaning as R ₇₁ or R ₇₂ , R ₇₈ has the same meaning as R ₇₃ or R ₇₄ , and p 7 R ₇₅ , R ₇₇ and R ₇₈ may be the same or different. p is an integer greater than or equal to 1, Preferably it is 1-10, More preferably, it is 1-5. The compound containing the repeating unit represented by formula (Fc) may be a homopolymer or a copolymer with another repeating unit such as azetidinium. Moreover, although a terminal structure can be selected suitably, a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, or an amino group is preferable.

  As the ozone resistance improver, the various compounds described above can be used alone or in combination, and the total amount used is preferably 0.1 to 10% by mass in the black ink composition.

  The black ink composition of the present invention preferably has a viscosity of 1 to 20 mPa · s. More preferably, it is 2-15 mPa * s, Most preferably, it is 2-10 mPa * s. If it exceeds 20 mPa · s, the fixing speed of the recorded image becomes slow, and the discharge performance also deteriorates. If it is less than 1 mPa · s, the recorded image is blurred and the quality is lowered. This viscosity is measured at 25 ° C. The viscosity is adjusted by the viscosity modifier. In the case of inkjet recording, the addition amount of the water-miscible organic solvent is preferably used in the range of 5 to 70% by mass and more preferably in the range of 10 to 60% by mass with respect to the black ink composition. preferable. Two or more water-miscible organic solvents can be used in combination.

  The method for measuring the viscosity of the liquid is described in detail in JIS Z8803, but can be easily measured with a commercially available viscometer. For example, the rotary type includes Tokyo Keiki B-type viscometer and E-type viscometer. In this invention, it measured at 25 degreeC by the vibration type VM-100AL type of Yamaichi Electric.

The black ink composition of the present invention preferably has a surface tension of 20 to 50 mN / m, and more preferably 20 to 40 mN / m.
This surface tension means both dynamic surface tension and static surface tension, both of which are measured at 25 ° C. If the surface tension exceeds 50 mN / m, the ejection quality, bleeding at the time of color mixing, print quality such as whiskers, etc. will be significantly reduced. If the surface tension of the ink is 20 mN / m or less, there may be a printing failure due to ink adhesion to the hard surface during ejection. The surface tension can be adjusted by using a surfactant or the like, and those mentioned in the section of the surfactant can be used.

As a static surface tension measuring method, a capillary rising method, a dropping method, a hanging ring method and the like are known. In the present invention, a vertical plate method is used as a static surface tension measuring method.
When a thin plate of glass or platinum is partially immersed in the liquid and suspended vertically, the surface tension of the liquid acts downward along the length of contact between the liquid and the plate. The surface tension can be measured by balancing this force with an upward force.

  Examples of the dynamic surface tension measurement method include “New Experimental Chemistry Course, Vol. 18, Interface and Colloid” [Maruzen Co., Ltd., p. 69-90 (1977)], the vibration jet method, the meniscus dropping method, the maximum bubble pressure method and the like are known, and further, the liquid film breakage as described in JP-A-3-2064 is known. In the present invention, a bubble pressure differential pressure method is used as a dynamic surface tension measurement method. The measurement principle and method will be described below.

  When bubbles are generated in the solution that has become homogeneous by stirring, a new gas-liquid interface is generated, and the surfactant molecules in the solution gather on the surface of the water at a constant rate. When the bubble rate (bubble generation rate) is changed, if the generation rate slows down, more surfactant molecules gather on the surface of the bubble, so the maximum bubble pressure just before the bubble pops is reduced, The maximum bubble pressure (surface tension) relative to the bubble rate can be detected. As a preferable dynamic surface tension measurement, a method is used in which bubbles are generated in a solution using two large and small probes, the differential pressure in the maximum bubble pressure state of the two probes is measured, and the dynamic surface tension is calculated. Can be mentioned.

The black ink composition of the present invention preferably has a conductivity of 0.01 to 10 S / m, and a preferable range is 0.05 to 5 S / m. This conductivity is measured at 25 ° C. By keeping the conductivity in the above range, image storability is ensured.
The conductivity can be measured by an electrode method using commercially available saturated potassium chloride.
The conductivity can be controlled mainly by the ion concentration in the aqueous solution. When the salt concentration is high, desalting can be performed using an ultrafiltration membrane or the like. Moreover, when adjusting conductivity by adding salt etc., it can adjust by adding various organic substance salt and inorganic substance salt.
Inorganic salts include potassium halide, sodium halide, sodium sulfate, potassium sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, sodium nitrate, potassium nitrate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, sodium monohydrogen phosphate, Inorganic compounds such as boric acid, potassium dihydrogen phosphate, sodium dihydrogen phosphate, sodium acetate, potassium acetate, potassium tartrate, sodium tartrate, sodium benzoate, potassium benzoate, sodium p-toluenesulfonate, potassium saccharinate Organic compounds such as potassium phthalate and sodium picolinate can also be used.
The conductivity can also be adjusted by selecting the additive.

The black ink composition of the present invention preferably has a pH of 7 to 9, more preferably 7 to 8. When the pH is less than 7, the solubility of the dye is lowered and the nozzle is easily clogged, and when it exceeds 9, the water resistance tends to deteriorate. As a pH measurement method, a commercially available test paper can be used, and measurement by an electrode method using saturated potassium chloride is also possible.
The pH of the black ink composition is adjusted by using the pH adjuster.

  The black ink composition of the present invention can be used for various image recording because of its high image durability. The dye for imaging can be used, for example, in photographic photosensitive materials, in thermal transfer materials, in thermal and pressure sensitive recording materials, in ink jet recording, etc. Is suitable for use as a black ink composition for inkjet recording.

    In addition, about the preparation method of the inkjet ink composition, Unexamined-Japanese-Patent No. 5-148436, 5-295212, 7-97541, 7-82515, 7-118584, Unexamined-Japanese-Patent No. 2004-331871. Details are described in each of these methods, and can also be used for the preparation of the ink composition of the present invention.

  As the recording paper and the recording film which are printing media suitably used in the present invention, those described in JP-A-2004-331871 (paragraph numbers [0503] to [0627]) are preferably used.

  In the production of ink, as described in Japanese Patent Application Laid-Open No. 2004-331871, ultrasonic vibration can be applied to the dissolution process of additives such as dyes.

  In preparing the ink of the present invention, a step of removing dust that is a solid content by filtration, which is performed after further preparation of liquid, is important. The filtration process is also as described in JP-A-2004-318771.

  Further, the black ink composition of the present invention can be used not only for forming a single color image but also for forming a full color image. In order to form a full-color image, an ink set including at least yellow, magenta and cyan ink compositions is preferable, and a plurality of color ink compositions having the same hue and different densities can be used for each color. Furthermore, ink compositions of intermediate colors such as red, green, blue, and violet can also be used.

  Although the example of the dye as a coloring agent contained in the ink composition which can be preferably used for the ink set of this invention is given below, it is not limited to this.

[Yellow dye]
Examples of the yellow dye include International Patent Publication WO2005 / 075753, JP-A-2004-83903 (paragraph numbers [0024] to [0062]), 2003-277661 (paragraph numbers [0021] to [0050]), 2003. No. 277762 (paragraph numbers [0042] to [0047]), 2003-128953 (paragraph numbers [0025] to [0076]), 2003-41160 (paragraph numbers [0028] to [0064]), US application Examples thereof include those described in Published US 2003/0213405 (paragraph number [0108]) and compounds represented by the following general formula (Y-1).

General formula (Y-1)

  In the formula, G represents a heterocyclic group, and n represents an integer of 1 to 3. When n is 1, R, X, Y, Z, Q, and G represent a monovalent group. When n is 2, R, X, Y, Z, Q, and G each represent a monovalent or divalent substituent, and at least one represents a divalent substituent. When n is 3, R, X, Y, Z, Q, G represents a monovalent, divalent, or trivalent substituent, at least two represent a divalent substituent, or at least one is trivalent. Represents a substituent of

The compound represented by the general formula (Y-1) is represented by the following general formula (Y-2), general formula (Y-3), general formula (Y-4), general formula (Y-5) or general formula (Y It is preferable that it is a compound represented by either of -6).
General formula (Y-2)

In the formula, R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, and G represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle M represents a hydrogen atom or a cation. m ₁ represents an integer of 0 to 3.
General formula (Y-3)

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₁ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₂₁ and m ₂₂ each independently represent an integer of 0 to 3.
General formula (Y-4)

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , and Y ₂ represent a monovalent group, L ₂ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₃₁ and m ₃₂ each independently represents an integer of 0 to 3.
General formula (Y-5)

In the formula, R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₃ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₄₁ and m ₄₂ each independently represents an integer of 0 to 3.
General formula (Y-6)

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₄ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₅₁ and m ₅₂ each independently represents an integer of 0 to 3.

Formula (Y-2), the general formula (Y-3), Formula (Y-4), Formula (Y-5), in the general formula (Y-6), G, composed of _{G 1} and _{G 2} The nitrogen-containing heterocycle is preferably an S-triazine ring.

  It is represented by the general formula (Y-1), the general formula (Y-2), the general formula (Y-3), the general formula (Y-4), the general formula (Y-5), and the general formula (Y-6). Specific examples (exemplified dyes r-1 to 26) of the compounds to be prepared are shown below, but the dyes used in the present invention are not limited to the following examples.

  Moreover, although the structure of the following specific examples is shown with the form of a free acid, it cannot be overemphasized that you may use as arbitrary salts.

  Preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, or organic cations (eg, pyridinium, tetramethylammonium, guanidinium).

[Magenta dye]
As the magenta dye, a heterocyclic azo dye is preferable, and International Patent Publication No. 2002/83795 (pages 35 to 55), 2002-83661 (pages 27 to 42), and JP-A No. 2004-149560 (paragraph number [0046]). To [0059]) and 2004-149561 (paragraph numbers [0047] to [0060]) and azo dyes represented by the following general formula (M-1).
General formula (M-1)

The formula (M-1): A-represents the residue of a 5-membered heterocyclic diazo component A-NH _2.
B ₃₁ and B ₃₂ each represent -CR ₈₁ = or -CR ₈₂ =, or one of them represents a nitrogen atom and the other represents -CR ₈₁ = or -CR ₈₂ =. R ₈₃ and R ₈₄ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. Each group may further have a substituent. R ₈₁ and R ₈₂ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, Hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylamino group, arylamino group, heterocyclic amino group, acylamino Group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl or arylthio group, and alkyl Ku represents an arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group,. Each group may be further substituted. R ₈₁ and R ₈₃ , or R ₈₃ and R ₈₄ may combine to form a 5- or 6-membered ring. a and e each independently represents an alkyl group, an alkoxy group, or a halogen atom. When both a and e are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and May be further substituted. b, c and d are each independently synonymous with R ₈₁ and R ^2, and may be condensed with each other at a and b or e and d. However, General Formula (M-1) has at least one ionic hydrophilic group.
A represents a residue of a 5-membered heterocyclic diazo component A-NH _2. Examples of hetero atoms of the 5-membered heterocyclic ring include N, O, and S. Preferably, it is a nitrogen-containing 5-membered heterocyclic ring, and the heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring.
Examples of a preferable heterocyclic ring for A include a pyrazole ring, an imidazole ring, a triazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a benzothiazole ring, a benzoxazole ring, and a benzoisothiazole ring. Each heterocyclic group may further have a substituent. Of these, a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring, a benzothiazole ring, or a triazole ring is preferable.
The general formula (M-1) azo dye is preferably represented by the following general formula (M-2).

General formula (M-2)

In the general formula (M-2), Z ₁₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ₁₂ represents a hydrogen atom, an acyl group, an aliphatic group, an aromatic group or a heterocyclic group. R ₈₁ , R ₈₂ , R ₈₃ , R ₈₄ , a, b, c, d, and e have the same meanings as in the general formula (M-1). Q ₁₁ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Each of the groups Z ₁₁ , Z ₁₂ and Q ₁₁ may further have a substituent. However, General Formula (M-2) has at least one ionic hydrophilic group.
Specific examples of the azo dye are shown below, but are not limited to the following examples.

[Cyan dye]
As the cyan dye, an associative phthalocyanine dye is preferable as the phthalocyanine dye. As the associative phthalocyanine dye, those having an associative group are preferable. The associative group means a group having at least a binding site (or functional group) capable of hydrogen bonding between molecules in the group. One or more binding sites can be contained in one group. Examples of the bonding site include a hydroxyl group, an amino group, an amide bond, an oxide bond, and the like, and a hydrogen bond is formed between the same species or different species. The associative group may be capable of hydrogen bonding between the phthalocyanine dye and any additive.
In order to reduce the reactivity with ozone, which is an electrophile, for example, a carbon atom of a phthalocyanine skeleton is partially substituted with a heteroatom such as azaphthalocyanine, or an electron withdrawing group is introduced into the phthalocyanine skeleton. Therefore, it is desirable that the oxidation potential is nobler than 1.0 V (vs SCE). The oxidation potential is preferably as noble, more preferably noble than the oxidation potential of 1.1 V (vs SCE), and particularly preferably noble than 1.15 V (vs SCE).

  Examples of associative phthalocyanine dyes include International Publication Nos. 2002/60994, 2003/811, 2003/62324, JP-A 2003-213167, 2004-75986, 2004-323605, 2004- 315758, 2004-315807, and 2005-179469.

The phthalocyanine dye can be synthesized according to JP-A Nos. 2004-315729, 2005-41856, and 2004-323511 in addition to the above-mentioned patents. Further, the starting material, dye intermediate and synthetic route are not limited by these.
The ink set of the present invention can also be used for purposes other than inkjet recording. For example, it can be used for display image materials, image forming materials for interior decoration materials, outdoor decoration materials, and the like described in JP-A-2004-318771 [0727] to [0731].

  In addition to the above dyes, the dyes described in the following publications can also be preferably used for the ink composition of each color. JP-A-10-130557, JP-A-9-255906, JP-A-6-234944, JP-A-7-975541, EP 982371, WO00 / 43450, WO00 / 43451, WO00 / 43452, WO00 / 43453, WO03 / 106572, WO03 / 104332, JP2003-238862, JP2004-83609, JP2002-302619, JP2002-327131, JP2002-265809, WO01 / 48090, WO2004 / 087815, WO02 / 090441, WO03 / 027185, WO2004 / 088551, JP2003-321627, JP2002-332418, JP2002-332419, WO02 / 059216, WO02 / 059215, WO20 4/0887814, WO2004 / 046252, WO2004 / 046265, Patent 3479444, US6652637B, WO03 / 106572, WO03 / 104332, WO00 / 58407, Patent 3558211, Patent 3558212, Patent 3558213, JP2004- 285351, JP2004-323605, WO04 / 104108.

[Recording method]
The recording method of the present invention is characterized by applying the ink composition of the present invention to a recording material. A preferred recording method of the present invention is an ink jet recording method, wherein recording is preferably performed by discharging droplets of the ink composition onto a recording medium, and recording is performed by supplying energy to the ink composition. Known image-receiving materials as materials, that is, plain paper, resin-coated paper, for example, JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, and JP-A-9-323475. No. 1, JP-A-62-238783, JP-A-10-153898, JP-A-10-217473, JP-A-10-235995, JP-A-10-337947, JP-A-10-217597, -Printed paper, film, electrophotographic co-paper, cloth, glass, metal, ceramics, etc. To form. In addition, the description of Paragraph Nos. 0093 to 0105 of JP-A No. 2003-306623 can be applied as the ink jet recording method of the present invention.

In forming an image, a polymer latex compound may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing of applying the latex compound to the image receiving material may be before, after, or simultaneously with the application of the colorant, and therefore the addition location may be in the image receiving paper. It may be in ink or may be used as a liquid material of polymer latex alone.
Specifically, JP 2002-166638 A, JP 2002-121440 A, JP 2002-154201 A, JP 2002-144696 A, JP 2002-080759 A, JP 2002-187342 A. And the method described in JP 2002-172774 A can be preferably used.

Hereinafter, a recording paper and a recording film used for ink jet printing using the ink of the present invention will be described. The support in recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMPMP, CGP, and waste paper pulp such as DIP. Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there. In addition to these supports, either synthetic paper or plastic film sheet may be used, and the thickness of the support is preferably 10 to 250 μm and the basis weight is preferably 10 to 250 g / m ² . The support may be provided with an ink receiving layer and a backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar. In the present invention, as the support, paper and plastic films laminated on both sides with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. It is preferable to add a white pigment (for example, titanium oxide or zinc oxide) or a tinting dye (for example, cobalt blue, ultramarine blue, or neodymium oxide) to the polyolefin.

  The ink receiving layer provided on the support contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. As the white pigment contained in the ink receiving layer, porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either anhydrous silicic acid obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but it is particularly desirable to use hydrous silicic acid.

  The recording method of the present invention is not limited to the ink jet recording system, and is a known system, for example, a charge control system that discharges ink using electrostatic attraction, or an ink jet that forms ink droplets by mechanical deformation of an electrostrictive element. A drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element using a head, an acoustic ink jet method that discharges ink using radiation pressure by irradiating the ink with an electrical signal converted into an acoustic beam, and The ink is heated to form bubbles, and is used in a thermal ink jet system that uses the generated pressure. Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
The black inks B-1 to B-5 and B-7 and the ink sets 1 to 7 are to be read as reference examples.
(Ink stock preparation)
850 g of ultrapure water (specific resistance value of 18 MΩ · cm or more) was added to 50 g of the dye Black-6, and the mixture was stirred for 1 hour while heating at 60 to 65 ° C. After the dye was completely dissolved, it was cooled to room temperature, 100 g of 2-pyrrolidone was added as a viscosity reducing agent, and 1.0 g of PROXEL XL2 was added as a preservative. After stirring for 10 minutes, an ink stock solution was prepared by filtration under reduced pressure through a microfilter having an average pore size of 0.2 μm.
(Preparation of black ink)
After adding ultrapure water (specific resistance value 18 MΩ · cm or more) to the following components to make 100, the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, it filtered under reduced pressure with the micro filter with an average hole diameter of 0.25 micrometer, and prepared the black ink liquid, respectively. In Table 1, the numerical value of each component indicates the weight% of each component when the mass of the ink composition is 100%, and the “residue” indicating the amount of water is the total including the components other than water. The amount to be 100% is shown.

Water-soluble long wave dye L represented by the general formula (L-6a)
(Black-7)

Example 1
These black inks were loaded into a black ink cartridge of an ink jet printer PM-A700 manufactured by Seiko Epson Corporation. A gray image whose density has been changed stepwise from R: 0, G: 0, B: 0 to R: 255, G: 255, B: 255 using Adobe Systems Incorporated image software Photoshop (hereinafter, staircase pattern) And printed in “black” mode to obtain an image printed only with black ink. Epson Co., Ltd. photographic paper <glossy> was used as the image receiving sheet.
(Evaluation)
1) Hue evaluation is a gray staircase pattern in which the color tone of gray at each print density is visually determined. A color tone that exhibits a preferable gray color tone at each density is indicated by A. B, the gray balance of which was lost at most densities was designated C.
2) Regarding the image density, Dvis was measured using a black solid (image data R: 0, G: 0, B: 0 portion) using an X-rite310 density measuring machine.
The case where Dvis is 2.4 or more is A, the case where Dvis is 2.3 or more and less than 2.4 is B, and the case where Dvis is less than 2.3 is C.
3) Regarding image storability, the following 4) to 5) were evaluated using a gray print sample. Image preservation is evaluated by measuring the density of the staircase pattern using an X-rite 310 densitometer equipped with a status A filter, and using the point near Dvis = 1.0 as the reference point, the density change there It was performed by measuring.
4) Light fastness is obtained by obtaining a reflection spectrum from 380 nm to 730 nm obtained by measuring the concentration Ci at the maximum absorption wavelength immediately after printing using a spectroeye made by gretag macbeth, and then using a weather meter made by Atlas to make xenon light ( (85,000 lux) was irradiated for 10 days. Thereafter, the reflection spectrum was measured again, the concentration Cf at the maximum absorption wavelength was measured, and the dye residual ratio (Cf / Ci) × 100 was determined and evaluated.
The case where the dye afterimage rate is 80% or more is A, the case where it is 70 to 80% is B, and the case where it is less than 70% is C.
5) The ozone resistance is 170 in a box in which the ozone gas concentration is set to 5 ppm after obtaining the reflection spectrum at 380 nm to 730 nm obtained by measuring the concentration Ci at the maximum absorption wavelength immediately after printing using a spectroeye manufactured by gretag macbeth. Exposure to ozone gas for hours. Thereafter, the reflection spectrum was measured again, the concentration Cf at the maximum absorption wavelength was measured, and the dye residual ratio Cf / Ci × 100 was determined and evaluated.
The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
The case where the dye afterimage rate is 80% or more is A, the case where it is 70 to 80% is B, and the case where it is less than 70% is C.
6) Regarding hue balance at the time of image deterioration (hereinafter referred to as fading balance), CIEL ^* a ^* b ^* was measured with spectroeye manufactured by gretag macbeth before and after the evaluation of 4) and 5). Determine the ΔEa ^* b ^* from exposure previous value _{^{L i * a i * b i}} * value after exposure _{^{L f * a f * b f}} * from the following equation and evaluated based on the following criteria.
ΔEa ^* b ^* = {(a _i ^* −a _f ^* ) ² + (b _i ^* −b _f ^* ) ² } ^1/2
[Evaluation criteria]
A: ΔEa ^* b ^* is less than 20 in both tests 4) and 5) B: 4) 5) ΔEa ^* b ^* is 20 or more in either or both tests 7) Bronze evaluation Prints a solid black image on Epson's photographic paper CRISPIA <high gloss> under three environmental conditions of 20 ° C., 40% RH, 35 ° C., 60% RH, and 35 ° C., 80% RH. After standing overnight under the conditions, the bronze (the metallic luster of the print surface) was visually evaluated based on the following criteria.
[Criteria]
A: No bronze gloss is observed at all B: Slight bronze gloss is observed at one of the three environmental conditions C: Slight bronze gloss is observed at two or more of the three environmental conditions 8) Clearly bronze gloss is observed under one or more environmental conditions. 8) For image blur under high humidity of black ink, use the image software Photoshop made by Adobe Systems Incorporated. An image of a grid with an interval of 0.2 mm was created. A black / white lattice image sample with black lines (R: 0, G: 0, B: 0) and white lines (R: 255, G: 255, B: 255) is created at 25 ° C and 90 ° C. The image bleeding after storage for 7 days under the condition of% RH was judged visually.
The case where no bleeding was observed in the white background portion between the lattices was designated as A, the case where the thickness of the lattice lines was slightly increased was designated as B, and the case where the black dye oozed out clearly on the white background portion was designated as C.
The evaluation results are shown in Table 2.

Compared with black inks (B-8, B-9, B-10) prepared with only the compound of general formula (L-1), water-soluble long wave dye L is used in combination with general formula (L-1) In the black ink composition of the present invention, it was found that the density of the black solid portion is high and the bronze gloss is suppressed without deteriorating the fading balance. In addition to the water-soluble long wave dye L, the use of the water-soluble short wave dye S has been found to provide a preferable black hue.
The same test was carried out by changing only the image-receiving sheet, Fuji Photo Film Co., Ltd. painting <Photo Finishing Pro>, Fuji Photo Film Co., Ltd. painting <Photo Finishing Advance> Hi Thick, Epson Co., Ltd. photo paper CRISPIA <High gloss>, Epson Co., Ltd. photo paper <Gloss>, Canon Co., Ltd. professional photo paper, Canon Co., Ltd. super photo paper, Konica Minolta Photolike QP <Photo quality> Although the test was conducted, almost the same result as in Table 2 was obtained.

(Example 2)
[Preparation of each ink composition]
Based on the composition shown in Table 3 and Table 4 below, each component was stirred at room temperature for 30 minutes, and then the resulting solution was filtered using a membrane filter having an opening of 1.0 μm to prepare each ink composition. Obtained. In Tables 2 and 3, the numerical value of each component indicates the weight percent of each component when the mass of the ink composition is 100%, and the “residue” indicating the amount of water is combined with components other than water. The total amount is 100%.

(YELLOW-1):

(YELLOW-2):

(YELLOW-3):

Compound (YELLOW-1) can be synthesized by the following method.
(1) Synthesis of compound (YELLOW-1b):
25.5 g of sodium hydrogen carbonate and 150 mL of ion-exchanged water were heated to 40 ° C., and 25.0 g of cyanuric chloride (Tokyo Chemicals) was added in 10 divided portions every 10 minutes and stirred for 1 hour. The solution was added dropwise to a mixed solution (8 ° C.) of 52.8 mL of hydrazine and 47 mL of ion exchange water so that the internal temperature did not exceed 10 ° C. The internal temperature was raised to 50 ° C. and stirred for 30 minutes. The precipitated crystals were filtered to obtain 23.4 g of compound b (YELLOW-1b) (hydrazine derivative: mp> 300 ° C.). The yield was 94.7%.

(2) Synthesis of compound (YELLOW-1c):
35.0 g of the compound (YELLOW-1b) (hydrazine derivative) was suspended in 420 mL of ethylene glycol and stirred at an internal temperature of 50 ° C. Concentrated hydrochloric acid 59 mL, followed by 60.1 g of pivaloylacetonitrile (Tokyo Chemicals) were added and stirred at 50 ° C. for 10 hours. Concentrated hydrochloric acid (95 mL) and methanol (145 mL) were added, and the mixture was further stirred for 8 hours. After cooling to room temperature, the precipitated crystals were separated by filtration to obtain 81.6 g of compound c (5-aminopyrazole derivative: mp = 233-235 ° C.). The yield was 94.2%. ¹ H-NMR (DMSO-d6), δ value TMS standard: 1.2 to 1.3 (18H, s))

(3) Synthesis of compound (YELLOW-1e):
90.57 g of compound d (Tokyo Chemicals) was suspended in 500 ml of H ₂ O, and after cooling with 130 ml of concentrated hydrochloric acid, the internal temperature was cooled to 5 ° C. or lower. Next, 36.23 g of sodium nitrite and 70 ml of an aqueous solution were added dropwise at an internal temperature in the range of 4 to 6 ° C., and the mixture was further stirred at an internal temperature of 5 ° C. or lower for 30 minutes. Next, 159 g of sodium sulfite and 636 ml of H ₂ O were injected while maintaining the internal temperature at 20 ° C. or lower, and further 250 ml of concentrated hydrochloric acid was injected at an internal temperature of 25 ° C., followed by stirring for 1 hour at an internal temperature of 90 ° C. After cooling the internal temperature to room temperature, the mixture was filtered, washed with 200 ml of water and air-dried to obtain 80.0 g of compound e.

(4) Synthesis of compound (YELLOW-1f):
28 ml of triethylamine was added dropwise to 23.3 g of compound e and 209 ml of ethanol suspension at room temperature, and 12.2 g of ethoxymethylenemalononitrile (ALDRICH product) was added in portions, refluxed for 3 hours, cooled to room temperature, filtered, and 400 ml of isopropyl After washing with alcohol and drying, 23.57 g of compound f was obtained.

(5) Synthesis of compound (YELLOW-1):
145.56 mL of acetic acid was injected into 32.4 mL of sulfuric acid at an internal temperature of 4 ° C. or lower, and 15.9 mL of 40% nitrosyl sulfuric acid (ALDRICH product) was added dropwise with stirring at an internal temperature of 7 ° C. or lower.
Compound (YELLOW-1f) (32.4 g) was added in portions, and stirred at the same temperature for 60 minutes while stirring at an internal temperature of 10 ° C. Then, 1.88 g of compound C in which 1.83 g of urea was added to the reaction mixture was added. To a solution suspended in 470 ml of methanol, a diazonium salt was added dropwise at an internal temperature <0 ° C., and the mixture was stirred at the same temperature for 30 minutes, and then the internal temperature of the reaction solution was raised to room temperature, followed by filtration, methanol washing, Washing with H ₂ O gave crude crystals. Subsequently, the crude crystals were suspended in 400 ml of methanol, stirred under reflux for 1 hour, cooled to room temperature, filtered, washed with methanol, washed with water, washed with methanol, dried overnight at 75 ° C., and then free acid form of DYE-11. 34.4 g of crystals were obtained. The obtained crystals were adjusted to 10 wt% aq (at 25 ° C .: pH≈8.3: KOHaq preparation), IPA was added at an internal temperature of 50 ° C., followed by crystallization, cooling, filtration, IPA washing, and drying. 35 g of (YELLOW-1) (potassium salt) was obtained.
λmax = 436.4 nm (H ₂ O), ε: 3.53 × 10 ⁴ (dm ³ .cm / mol)

(YELLOW-4):

(YELLOW-5): C.I. I. Direct yellow 132
(YELLOW-6): C.I. I. Direct yellow-86
(YELLOW-7): C.I. I. Direct yellow 58

  As the magenta dye, the following (MAGENTA-1), (MAGENTA-2), (MAGENTA-3), (MAGENTA-4), and (MAGENTA-5) were used.

(MAGENTA-1):

(MAGENTA-2):

(MAGENTA-3):

The compound (MAGGENTA-1) can be synthesized by the following method.
(1) Synthesis of Compound (MAGGENTA-1a) 5-Amino-3-tert-butyl-4-cyanopyrazole (1) 24.1 g (0.147 mol), concentrated hydrochloric acid 45 ml, acetic acid 30 ml, propionic acid 45 ml The mixture was stirred at 0 ° C., and 10.1 g (0.147 mol) of sodium nitrite dissolved in 20 ml of water was added dropwise over 10 minutes. The mixture was stirred for 30 minutes. 84.7 g (0.147 mol) of coupler component (2) was dissolved in 231 ml of methanesulfonic acid, 147 ml of acetic acid and 221 ml of propionic acid, stirred at 0 ° C., and the diazonium salt was added over 30 minutes. After adding the diazonium salt, the reaction solution was further stirred for 30 minutes, and then 750 g of ice was added to 2250 ml of water and stirred, and then the reaction solution was gradually added, and the precipitated compound (MAGENTA-1a) was suction filtered. Isolated. Yield 73.8 g, 85% yield.

(2) Synthesis of Compound (MAGENTA-1b) 26.6 g (157 mmol) of a heterylating agent (3), 21.7 g of potassium carbonate and 147 ml of DMSO were added to 21 g (35.5 mmol) of the compound (MAGENTA-1a), and nitrogen bubbling was performed. The mixture was heated and stirred at an internal temperature of 92 ° C. for 4 hours. After the stirring, the mixture was cooled to room temperature, and the compound (MAGENTA-1b) precipitated from the reaction system was isolated by suction filtration. Further, this crude crystal was dispersed in 3 L of water, excess potassium carbonate was dissolved, and suction filtration was performed to obtain the target compound (MAGENTA-1b). Yield 20.0 g, yield 63.5%. [lambda] max = 558 nm (DMF solution).
m / Z (POSI) = 858.

(3) Synthesis of Compound (MAGENTA-1) 2 g (2.33 mmol) of Compound (MAGENTA-1b) was dispersed in 7 g of sulfolane manufactured by Tokyo Chemical Industry, and 1.7 g of sodium sulfan (sulfur trioxide) at an internal temperature of 15 ° C. Was dripped. After completion of dropping, the reaction was allowed to proceed for 2 hours at an internal temperature of 70 ° C. After completion of the reaction, the reaction solution was cooled to 20 ° C., and 2 ml of water was added dropwise. The internal temperature was cooled to 5 ° C., 3.3 ml of 25 wt% sodium hydroxide aqueous solution was dropped, and 0.8 ml of sodium methoxide 28 wt% methanol solution was dropped. Further, 4 ml of methanol was added dropwise, and the precipitated inorganic salt was filtered and washed with 2 ml of methanol. To this filtrate, 2 g of potassium acetate and 5.6 ml of methanol were added, and 22.5 ml of ethanol was further added to crystallize the dye, followed by suction filtration and washing with ethanol to obtain a crude crystal compound (MAGENTA-1 ) The crude crystals containing the inorganic salt were desalted and purified by Sephadex LH-20 gel chromatography (Pharmaceutical eluent, water / methanol = 1: 1 (v / v)) from Pharmacia to obtain compound MAGENTA-1. Yield 2g, 66% yield.
λmax (DMSO) = 567.1 nm, ε = 46900

  The compound (MAGENTA-2) and the compound (MAGENTA-3) could also be synthesized by the same synthesis method.

(MAGENTA-4):

(MAGENTA-5):

  In Tables 1 and 2, as cyan dyes, compounds represented by the following (CYAN-1), (CYAN-2), (CYAN-3), (CYAN-4) and (CYAN-5) were used. .

(CYAN-1):

(CYAN-2):

(CYAN-3):

(CYAN-4):

  (CYAN-5); I. Direct blue 199 was used.

  Next, each ink set of the ink sets 1-10 was created with the combination shown in Table 5 using each prepared ink composition.

These inks were filled in the corresponding ink cartridges of an ink jet printer PMG820 manufactured by Seiko Epson Corporation. Ink set 6 uses PMG820 genuine ink as it is except for black ink, and ink set 7 draws out ink of each color of BCI-7, which is ink manufactured by Canon Inc., and fills each corresponding ink cartridge for PMG800. . These ink cartridges were loaded into the PMG 800 and printed.

(Evaluation)
1) Regarding the image storability, a black solid image of R: 0, G: 0, B: 0 was created by using image software Photoshop manufactured by Adobe Systems Incorporated, and a black solid image was printed. The images 2) to 3) were evaluated using the images. The image storage stability was evaluated by measuring the density of the staircase pattern using an X-rite 310 densitometer equipped with a status A filter and measuring the density change.
2) Lightfastness Light fastness is measured by measuring the density (D _B , D _G , D _R ) Ci immediately after printing using an X-rite 310 and then using an Atlas weather meter to display xenon light (8 55,000 lux) was irradiated for 10 days. Thereafter, the concentration Cf was measured again, and the dye residual ratio Cf / Ci × 100 was determined and evaluated.
The case where the dye afterimage ratio is 80% or more in all of D _B , D _G and D _R is A, the case where it is 70-80% at least partly is B, and the case where it is less than 70% is partly C .
3) Ozone resistance The ozone resistance is 170 in a box in which the ozone gas concentration is set to 5 ppm after measuring the concentration (D _B , D _G , D _R ) Ci immediately after printing using the X-rite 310. Exposure to ozone gas for hours. Thereafter, the concentration Cf was measured again, and the dye residual ratio Cf / Ci × 100 was determined and evaluated.
The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
The case where the dye afterimage ratio is 80% or more in all of D _B , D _G and D _R is A, the case where it is 70-80% at least partly is B, and the case where it is less than 70% is partly C .
4) As for image blur under high humidity of black ink, the black / white grid image created in Example 1 and the black / magenta grid created so that the white portion of the image is OD = 1.0 of magenta An image, similarly, a black / cyan grid image in which the white portion was created so that OD = 1.0 of cyan was created, and each image sample was created. Using the image sample, blurring of the image after storage for 7 days under conditions of 25 ° C. and 90% RH was judged visually.
The case where no blur was observed in the lattice spacing was A, the case where the hue of the color correction dye was slightly recognized was B, and the case where the color correction dye oozed out to the white background was clearly C.
5) About bronze evaluation, the obtained printed matter was measured using the gloss meter (PG-1M, Nippon Denshoku Industries Co., Ltd.) (measurement angle 60 degree | times), and glossiness was calculated | required. Printing was performed in two environments of 20 ° C. 40% RH and 35 ° C. 60% RH. Using the obtained glossiness and the increased value calculated based on the following formula as a criterion for determining the degree of occurrence of bronze phenomenon, the determination was made based on the following criterion.
Increase value = Glossiness (printed material)-Glossiness (recording medium)
[Criteria]
Evaluation A: Less than 15 Evaluation B: 15 or more and less than 35 Evaluation C: 35 or more and less than 55 Evaluation D: 55 or more Evaluation results are shown in Table 6.

In the ink set using the black ink composition of the present invention, light resistance, ozone resistance, bronze and image blur are deteriorated even in black solid portions of color prints in which yellow, magenta, and cyan are ejected in addition to black ink. A high-density black printed matter can be obtained without causing it to occur.
For the same test, changing only the image-receiving sheet, Fuji Photo Film Co., Ltd. <Photo Finishing Advance> Hi Thick, Fuji Photo Film Co., Ltd. Painting <Photo Finishing Pro>, Epson Co., Ltd. Photo Paper CRISPIA <High gloss>, Epson Co., Ltd. photo paper <Gloss>, Canon Co., Ltd. professional photo paper, Canon Co., Ltd. super photo paper, Konica Minolta Photolike QP <Photo quality> A test was conducted, and almost the same results as in Table 6 were obtained.

Claims (7)

Maximum wavelength of an absorption spectrum in an aqueous solvent and an ink composition containing at least two water-soluble dyes is a 550 to 700 nm, the following formula as the water-soluble dye (L-1), (L -2), (L-3), (L -4), or contains at least one of the at least one and a compound represented by the following general formula (L-6a) of the compound represented by (L-5) An ink composition characterized by comprising:

In general formula (L-1), A and B each independently represent an optionally substituted aromatic group or an optionally substituted heterocyclic group (A is a monovalent group, B Is a divalent group).
T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one represents a nitrogen atom and the other represents = CR ₄₃ -or -CR ₄₄ =.
V ₁ , R ₄₃ and R ₄₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl Group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group Represents a nitro group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfo group, The group may be further substituted. R ₄₁ and R ₄₂ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group Represents an arylsulfonyl group or a sulfamoyl group, and each group may further have a substituent. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring. However, general formula (L-1) contains at least one ionic hydrophilic group.

In General Formula (L-2), X represents an N atom or = CW _1- . W ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. _{A, V 1, T 1,} T 2, R 41 and _{R 42, A} in the formula (L-1), the same meaning as _{V 1, T 1, T 2} , R 41 and _{R 42.}
W is synonymous with V ₁ in the general formula (L-1) . However, general formula (L-2) contains at least one ionic hydrophilic group.

In the general formula (L-3), V ₁ , W, X, T ₁ , T ₂ , R ₄₁ and R ₄₂ represent V ₁ , W, X, T ₁ , T in the general formula (L-2). ₂ , Synonymous with R ₄₁ and R ₄₂ . X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ represent a monovalent group. However, general formula (L-3) contains at least one ionic hydrophilic group.

In the general formula _{(L-4), R 43} has the same meaning as _{R 43} in formula (L-1). R ₄₄ has the same meaning as _{R 44} in formula (L-1). R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in} formula (L-1) . R ₄₁ and _{R 42} has the same meaning as _{R 41} and _{R 42} in formula (L-1).
W is synonymous with V ₁ in the general formula (L-1) . X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ represent a monovalent group.
However, general formula (L-4) contains at least one ionic hydrophilic group.

In the general formula _{(L-5), R 43} has the same meaning as _{R 43} in formula (L-1). R ₄₄ has the same meaning as _{R 44} in formula (L-1). R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in} formula (L-1) . R ₄₁ and _{R 42} has the same meaning as _{R 41} and _{R 42} in formula (L-1).
W is synonymous with V ₁ in the general formula (L-1) . W ₁₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ represent a monovalent group.
However, general formula (L-5) contains at least one ionic hydrophilic group.
General formula (L-6a):

In general formula (L-6a), A represents the following formula (L-6a-1), the substitution position of A is the m-position or p-position with respect to the azo group, and R ¹ and R ² are Each independently hydrogen atom; halogen atom; cyano group; carboxyl group; sulfo group; sulfamoyl group; N-alkylaminosulfonyl group; N-phenylaminosulfonyl group; phospho group; nitro group; acyl group; ureido group; Or an alkyl group having 1 to 4 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbon atoms; 1 carbon atom which may be substituted with a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a sulfo group or a carboxyl group Represents an alkoxy group having 1 to 4 carbon atoms; an acylamino group which may be substituted with an alkoxy group having 1 to 4 carbon atoms, a sulfo group or a carboxyl group; R ³ and R ⁴ are each independently A hydrogen atom; a halogen atom; a cyano group; a carboxyl group; a sulfo group; a nitro group; an alkyl group having 1 to 4 carbon atoms; a hydroxyl group; a carbon number that may be substituted with an alkoxy group having 1 to 4 carbon atoms or a sulfo group. 1 to 4 alkoxy groups are represented, and n is 0 or 1.
General formula (L-6a-1)

In formula (L-6a-1), R ⁵ represents a cyano group; a carboxyl group; an alkyl group having 1 to 4 carbon atoms; an alkoxycarbonyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁶ , R ⁷ and R ⁸ are each independently substituted with a hydrogen atom; a halogen atom; a cyano group; a carboxyl group; a sulfo group; a nitro group, an alkyl group having 1 to 4 carbon atoms; a hydroxyl group; an alkoxy group having 1 to 4 carbon atoms or a sulfo group. Represents an alkoxy group having 1 to 4 carbon atoms which may be substituted; an acylamino group which may be substituted with a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms or a sulfo group. The ink composition according to claim 1 , comprising at least one water-soluble dye having a maximum absorption spectrum wavelength in a water solvent of 400 nm to 520 nm. 3. The ink composition according to claim 2 , comprising 0.1 to 4% by mass of the water-soluble dye having a maximum wavelength of an absorption spectrum in a water solvent of 400 nm to 520 nm. An ink set comprising at least one ink composition according to any one of claims 1 to 3 . A recording method comprising applying and recording the ink composition according to any one of claims 1 to 3 on a recording medium. A recording method comprising: loading the ink set according to claim 4 into a recording apparatus; and applying ink from the recording apparatus to a recording medium for recording. 7. The recording method according to claim 5 , wherein recording is performed by discharging an ink composition onto a recording medium from an inkjet nozzle.