JP2012193330A - Ink set, ink cartridge, inkjet printer, inkjet recording method and recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink set excellent in ink storage stability.SOLUTION: This ink set includes black ink, yellow ink, magenta ink and cyan ink, in which the black ink contains as a colorant at least one selected from the group consisting of a compound expressed by general formula (1) and a salt thereof, where in the formula, A represents a substituted or nonsubstituted aryl group, or a substituted or nonsubstituted nitrogen-containing five-membered heterocyclic group; G represents a nitrogen atom or -C(R)=; Rrepresents a hydrogen atom, sulfo, carboxy, substituted or nonsubstituted carbamoyl or cyano group; Y, Yand Yeach independently represent a hydrogen atom or a monovalent substituent, and Y, Yand Ymay form a ring by bonding each other, provided that there is no case that all of Y, Yand Yrepresent hydrogen atoms simultaneously; and Ms each independently represent a hydrogen atom or a monovalent counter-cation.

Description

  The present invention relates to an ink set, and more particularly to an ink set that can form an image excellent in light resistance and ozone resistance and has excellent storage stability. Furthermore, the present invention relates to an ink cartridge, an ink jet printer, an ink jet recording method, and a recorded matter using the ink set.

In recent years, inkjet recording methods have been rapidly spread and further developed due to low material costs, high-speed recording, low noise during recording, and ease of color recording. .
Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. There are a method of discharging bubbles, a method of generating bubbles in the ink by heat and discharging droplets, a method of using ultrasonic waves, and a method of sucking and discharging droplets by electrostatic force.
As the ink for ink jet recording, water-based ink, oil-based ink, or solid (melted type) ink is used.

For dyes used in such inks for ink jet recording, the solvent has good solubility or dispersibility, high-density recording is possible, hue is good, light, heat, in the environment Fast against active gases (NOx, ozone and other oxidizing gases, SOx, etc.), excellent fastness to water and chemicals, good fixability to image-receiving materials, and low bleeding. It is required that the ink has excellent storability, has no toxicity, has high purity, and can be obtained at low cost.
For example, Patent Documents 1 and 2 disclose that a specific azo dye can achieve both a good hue and high fastness required for ink jet recording ink.

  In recent years, it has been practiced to form a color image by an ink jet recording method using a plurality of color ink compositions to obtain a recorded matter. In general, a color image is formed by three colors, ie, a yellow ink composition, a magenta ink composition, and a cyan ink composition, and further, if desired, four colors including a black ink composition. There are also cases where color images are formed with six colors obtained by adding a light cyan ink composition and a light magenta ink composition to these four colors, or seven colors obtained by further adding a dark yellow ink composition thereto. A combination of two or more ink compositions is an ink set (see, for example, Patent Documents 3 to 7).

In the ink set used for the formation of the color image described above, the ink composition for each color itself has a good color developability, and a good intermediate color is obtained when a plurality of ink compositions are combined. It is required that color can be developed and that the obtained recorded matter does not discolor during storage.
In addition, when the light resistance / ozone resistance of a specific ink composition is significantly lower than the light resistance / ozone resistance of another ink composition in an ink set, the color formed by the specific ink composition The color fades and discolors faster than the color of the image, and the balance of the color tone of the entire image becomes worse, but the observer can recognize that the image formed by the single ink composition is faded. In addition, it becomes possible to recognize image quality degradation in a short time.
Therefore, in the ink set, in addition to improving the light resistance and ozone resistance of each ink composition constituting the ink set, the light resistance and ozone resistance level of each ink composition, that is, each ink composition. It is preferable that the deterioration rate of the image formed by the light and ozone, for example, the fading rate is as much as possible. In other words, it is preferable that each ink composition constituting the ink set is excellent in light resistance and ozone resistance and that the difference in light resistance and ozone resistance between the ink compositions is small.

  In addition, by configuring an ink set including two types of light and dark ink compositions having different color densities for similar colors, it is possible to form images with various color densities and obtain images without graininess. It was. Such an ink set containing two kinds of ink compositions having different color densities is mainly used for printing a photographic image. In the formation of a photographic image, in order to reduce or eliminate the graininess of the image, generally, the color density is used. Are often used. In the light resistance / ozone resistance evaluation described above, a pattern having an optical density of about 1.0 as an evaluation sample is formed by an ink composition having a low color density. Therefore, in order to improve the light resistance and ozone resistance of photographic images of recorded matter and the light resistance and ozone resistance of the entire ink set, the light resistance and ozone resistance of the ink composition having a low color density is improved. This is very important.

On the other hand, since ink compositions having a high color density are used for printing of images with rich colors and graphic art patterns, it is also necessary to improve the light resistance and ozone resistance of these ink compositions.
Further, since the black ink composition plays an important role from the viewpoint of obtaining image contrast in an image, the black ink composition is often included in the ink set.
Therefore, when the black ink composition is included in the ink set, the black ink composition has excellent light resistance and ozone resistance, and the deterioration rate of the black ink composition due to light and ozone constitutes another ink set. It is desired not to be extremely different from the deterioration rate of the ink composition.

JP 2003-306623 A JP 2005-139427 A JP 2007-138124 A Special table 2009-512737 JP 2007-70573 A JP 2010-37504 A JP 2008-81693 A

As described above, in the ink set, each ink composition itself constituting the ink set has good light resistance and ozone resistance, and a good balance of light resistance and ozone resistance between the ink compositions. It is desirable to prevent certain colors from fading and / or discoloring faster than other colors when exposed to ozone. Thus, since the performance balance between the ink compositions is important in the ink set, a single high-performance ink composition is not always suitable for the ink set.
In the ink sets described in Patent Documents 3 and 4, the light resistance and ozone resistance of each ink composition are improved, but there is room for improvement in the balance of light resistance and ozone resistance between the ink compositions. In addition, further improvement in ink storage stability has been demanded.
Patent Documents 6 and 7 disclose an ink set in which each color dye having a specific structure is combined. Although attention is paid to the performance balance between the ink compositions, the light resistance balance between the ink compositions, All the performances of ozone balance and ink storage stability were not satisfied at the same time, and further improvements were demanded in any performance.

  The present invention has been made to solve the above problems, and provides an ink set having excellent light resistance and ozone resistance, recording an image with excellent color balance, and excellent ink storage stability. Objective. Furthermore, an ink cartridge containing the ink set, an ink jet printer having the ink cartridge loaded therein, a recording method using the ink set, and a recorded matter recorded by the ink set are provided. With the goal.

  The inventors of the present invention have studied in detail a dye having a good hue and solubility, and having high light resistance, ozone resistance, and ink storage stability, and by combining each color dye having a specific structure, The present inventors have found that the problem can be solved and have completed the present invention. Means for solving the above problems are as follows.

（一般式（１）中、Ａは置換若しくは無置換のアリール基、又は置換若しくは無置換の含窒素５員ヘテロ環基を表す。Ｇは窒素原子又は−Ｃ（Ｒ_２）＝を表す。Ｒ_２は、水素原子、スルホ基、カルボキシ基、置換若しくは無置換のカルバモイル基、又はシアノ基を表す。Ｙ_２、Ｙ_３及びＹ_４はそれぞれ独立に、水素原子、又は１価の置換基を表す。Ｙ_２、Ｙ_３及びＹ_４は、互いに結合して環を形成しても良い。Ｙ_２、Ｙ_３及びＹ_４の全てが同時に水素原子を表すことはない。Ｍはそれぞれ独立に水素原子又は一価のカウンターカチオンを表す。）
〔２〕
前記ブラックインク組成物が、更に下記一般式（Ｂ−１４）で表される化合物を含有することを特徴とする〔１〕に記載のインクセット。
一般式（Ｂ−１４）：

一般式（Ｂ−１４）中、Ａ環，Ｂ環，Ｃ環は、それぞれ独立に、置換又は無置換の、アリール基又はヘテロ環基を表す。Ａ_１、Ａ_２、Ａ_３、Ａ_４、Ａ_５、Ａ_１１、Ａ_１２、Ａ_１３、Ａ_１４、Ａ_１５、Ｂ_１、Ｂ_２、Ｂ_３、Ｂ_４、Ｂ_５、Ｂ_６、Ｂ_１１、Ｂ_１２、Ｂ_１３、Ｂ_１４、Ｂ_１５、Ｂ_１６、Ｃ_１、Ｃ_２、Ｃ_３、Ｃ_４、Ｃ_１１、Ｃ_１２、Ｃ_１３、Ｃ_１４は、それぞれ独立に、水素原子又は置換基を表す。Ｑ_１、Ｑ_２は、それぞれ独立に水素原子又は置換基を表す。Ｌ_１２は２価の連結基を表す。但し、一般式（Ｂ−１４）の化合物は、少なくとも一つのイオン性親水性基を有する。
〔３〕
前記ブラックインク組成物中の着色剤の含有量が、該ブラックインク組成物中の総質量に対して０．１〜３０質量％である〔１〕又は〔２〕に記載のインクセット。
〔４〕
前記イエローインク組成物が、着色剤として下記一般式（Ｙ）で表される化合物及び一般式（Ｙ−２）で表される化合物並びにその塩からなる群から選ばれる少なくとも１種の化合物を含有するイエローインク組成物を含む〔１〕〜〔３〕に記載のインクセット。ただし、一般式（Ｙ−２）は一般式（Ｙ）を含まない。
一般式（Ｙ）：

（一般式（Ｙ）中、Ｍはそれぞれ独立に水素原子又はカチオンを表し、Ｍがカチオンを表す場合はＬｉ^＋イオン、Ｎａ^＋イオン、Ｋ^＋イオン又はＮＨ_４ ^＋イオンを表す。）
一般式（Ｙ−２）：

一般式（Ｙ−２）中、Ｒ_４は１価の基を表し、Ｒ_５は−ＯＲ_６又は−ＮＨＲ_７を表し、Ｒ_６及びＲ_７は水素原子又は１価の基を表し、Ｘ_３は２価の連結基を表し、ｎ_３は０又は１であり、Ａｒ_３は２価のヘテロ環基を表し、Ａｒ_４はアルキル基、アリール基又は１価のトリアジン環基を表す。
〔５〕
前記イエローインク組成物中の着色剤の含有量が、該イエローインク組成物中の総質量に対して１．０〜６．０質量％である〔４〕に記載のインクセット。
〔６〕
着色剤として下記式（Ｍ−１）で表される化合物及びその塩からなる群から選ばれる少なくとも一種を含有するマゼンタインク組成物を含む〔１〕〜〔５〕に記載のインクセット。
一般式（Ｍ−１）：

一般式（Ｍ−１）中、Ａ_Ｍは、５員のヘテロ環基を表す。
Ｂ_１及びＢ_２は、各々−ＣＲ_１３＝、−ＣＲ_１４＝を表すか、あるいはいずれか一方が窒素原子，他方が−ＣＲ_１３＝又は−ＣＲ_１４＝を表す。
Ｒ_１１及びＲ_１２は、各々独立に、水素原子、アルキル基、シクロアルキル基、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、又はスルファモイル基を表す。各基は更に置換基を有していてもよい。
Ｇ、Ｒ_１３、Ｒ_１４は、各々独立して、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、アシル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、アシルオキシ基、カルバモイルオキシ基、ヘテロ環オキシ基、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、アルキル基若しくはアリール基若しくはヘテロ環基で置換されたアミノ基、アシルアミノ基、ウレイド基、スルフアモイルアミノ基、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、アルキル又はアリール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、アルキル又はアリールスルホニル基、アルキル又はアリールスルフィニル基、スルファモイル基、ヘテロ環チオ基、又はイオン性親水性基を表す。各基は更に置換されていてもよい。また、Ｒ_１３とＲ_１１、又はＲ_１１とＲ_１２が結合して５又は６員環を形成してもよい。但し、一般式（Ｍ−１）は、少なくとも一つのイオン性親水性基を有する。
〔７〕
マゼンタインク組成物として、色濃度の異なる二種のマゼンタインク組成物を有し、かつ少なくとも一つのマゼンタインク組成物が前記一般式（Ｍ−１）で表される化合物及びその塩からなる群から選ばれる少なくとも一種を着色剤として含有する〔６〕に記載のインクセット。
〔８〕
前記色濃度の異なる二種のマゼンタインク組成物のうち、低い色濃度を有するマゼンタインク組成物が、前記一般式（Ｍ−１）で表される化合物及びその塩からなる群から選ばれる少なくとも一種を着色剤として含み、かつ該着色剤の含有量が前記低い色濃度を有するマゼンタインク組成物の総質量に対して０．５〜３．５質量％である〔７〕に記載のインクセット。
〔９〕
前記色濃度の異なる二種のマゼンタインク組成物のうち、高い色濃度を有するマゼンタインク組成物が、前記一般式（Ｍ−１）で表される化合物及びその塩からなる群から選ばれる少なくとも一種を着色剤として含み、かつ該着色剤の含有量が前記高い色濃度を有するマゼンタインク組成物の総質量に対し３〜１０質量％である〔７〕又は〔８〕に記載のインクセット。
〔１０〕
前記色濃度の異なる二種のマゼンタインク組成物において、低い色濃度を有するマゼンタインク組成物中に含まれる着色剤の濃度（質量％）と高い色濃度を有するマゼンタインク組成物中に含まれる着色剤の濃度（質量％）との比が、１：２〜１：８の範囲にある〔７〕〜〔９〕のいずれか一項に記載のインクセット。
〔１１〕
着色剤として下記式（Ｃ−１）で表される化合物及びその塩からなる群から選ばれる少なくとも一種を含有するシアンインク組成物を含む〔１〕〜〔１０〕のいずれか一項に記載のインクセット。
一般式（Ｃ−１）：

前記一般式（Ｃ−１）中、Ｘ_１、Ｘ_２、Ｘ_３及びＸ_４は、それぞれ独立に、−ＳＯ−Ｚ、−ＳＯ_２−Ｚ、−ＳＯ_２ＮＶ_１Ｖ_２、−ＣＯＮＶ_１Ｖ_２、−ＣＯ_２Ｚ、−ＣＯ−Ｚ又はスルホ基を表す。ここで、Ｚは、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アラルキル基、アリール基、又はヘテロ環基を表す。各基は更に置換基を有していてもよい。Ｖ_１、Ｖ_２は、同一又は異なっていてもよく、水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アラルキル基、アリール基、ヘテロ環基を表す。各基は更に置換基を有していてもよい。
Ｙ_１、Ｙ_２、Ｙ_３及びＹ_４は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシ基、ニトロ基、アミノ基、アルキルアミノ基、アルコキシ基、アリールオキシ基、アミド基、アリールアミノ基、ウレイド基、スルファモイルアミノ基、アルキルチオ基、アリールチオ基、アルコキシカルボニルアミノ基、スルホンアミド基、カルバモイル基、スルファモイル基、アルコキシカルボニル基、ヘテロ環オキシ基、アゾ基、アシルオキシ基、カルバモイルオキシ基、シリルオキシ基、アリールオキシカルボニル基、アリールオキシカルボニルアミノ基、イミド基、ヘテロ環チオ基、ホスホリル基、アシル基、又はイオン性親水性基を表し、各々の基は更に置換基を有していてもよい。
ａ_１〜ａ_４及びｂ_１〜ｂ_４は、それぞれＸ_１〜Ｘ_４及びＹ_１〜Ｙ_４の置換基数を表す。そして、ａ_１〜ａ_４は、それぞれ独立に、０〜４の整数であり、すべてが同時に０になることはない。ｂ_１〜ｂ_４は、それぞれ独立に、０〜４の整数を表す。
Ｍは、金属原子又はその酸化物、水酸化物若しくはハロゲン化物である。
但し、Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４、Ｙ_１、Ｙ_２、Ｙ_３及びＹ_４の内の少なくとも１つは、イオン性親水性基であるか又はイオン性親水性基を置換基として有する基である。
〔１２〕
シアンインク組成物として、色濃度の異なる二種のシアンインク組成物を有し、かつ少なくとも一つのシアンインク組成物が前記一般式（Ｃ−１）で表される化合物及びその塩からなる群から選ばれる少なくとも一種を着色剤として含有する〔１１〕に記載のインクセット。
〔１３〕
前記色濃度の異なる二種のシアンインク組成物のうち、低い色濃度を有するシアンインク組成物が、前記一般式（Ｃ−１）で表される化合物及びその塩からなる群から選ばれる少なくとも一種を着色剤として含み、かつ該着色剤の含有量が前記低い色濃度を有するシアンインク組成物の総質量に対して０．４〜３．０質量％である〔１２〕に記載のインクセット。
〔１４〕
前記色濃度の異なる二種のシアンインク組成物のうち、高い色濃度を有するシアンインク組成物が、前記一般式（Ｃ−１）で表される化合物及びその塩からなる群から選ばれる少なくとも一種を着色剤として含み、かつ該着色剤の含有量が前記高い色濃度を有するシアンインク組成物の総質量に対し２．０〜１０．０質量％である〔１２〕又は〔１３〕に記載のインクセット。
〔１５〕
前記色濃度の異なる二種のシアンインク組成物において、低い色濃度を有するシアンインク組成物中に含まれる着色剤の濃度（質量％）と高い色濃度を有するシアンインク組成物中に含まれる着色剤の濃度（質量％）との比が、１：２〜１：８の範囲にある〔１２〕〜〔１４〕のいずれか一項に記載のインクセット。
〔１６〕
〔１〕〜〔１５〕のいずれか一項に記載のインクセットを用いて記録することを特徴とするインクジェット記録方法。
〔１７〕
〔１〕〜〔１５〕のいずれか一項に記載のインクセットを用いて画像形成することを特徴とするインクジェット記録方法。
〔１８〕
〔１〕〜〔１５〕のいずれか一項に記載のインクセットを用いて記録されたことを特徴とする記録物。 [1]
An ink set comprising at least a black ink composition, a yellow ink composition, a magenta ink composition, and a cyan ink composition,
An ink set in which the black ink composition contains at least one selected from the group consisting of a compound represented by the following general formula (1) and a salt thereof as a colorant.

(In general formula (1), A represents a substituted or unsubstituted aryl group or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group. G represents a nitrogen atom or —C (R ₂ ) ═. ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group, and Y ₂ , Y _3, and Y ₄ each independently represent a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ and Y ₄ may combine with each other to form a ring, and all of Y ₂ , Y ₃ and Y ₄ do not represent a hydrogen atom at the same time, and M independently represents a hydrogen atom. Or represents a monovalent counter cation.)
[2]
The ink set according to [1], wherein the black ink composition further contains a compound represented by the following general formula (B-14).
General formula (B-14):

In general formula (B-14), A ring, B ring, and C ring each independently represent a substituted or unsubstituted aryl group or heterocyclic group. A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₁₁ , A ₁₂ , A ₁₃ , A ₁₄ , A ₁₅ , B ₁ , B ₂ , B ₃ , B ₄ , B ₅ , B ₆ , B ₁₁ , B ₁₂ , B ₁₃ , B ₁₄ , B ₁₅ , B ₁₆ , C ₁ , C ₂ , C ₃ , C ₄ , C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ are each independently a hydrogen atom or a substituent Represents. Q ₁ and Q ₂ each independently represents a hydrogen atom or a substituent. L ₁₂ represents a divalent linking group. However, the compound of the general formula (B-14) has at least one ionic hydrophilic group.
[3]
The ink set according to [1] or [2], wherein the content of the colorant in the black ink composition is 0.1 to 30% by mass with respect to the total mass in the black ink composition.
[4]
The yellow ink composition contains, as a colorant, at least one compound selected from the group consisting of a compound represented by the following general formula (Y), a compound represented by the general formula (Y-2), and a salt thereof. The ink set according to [1] to [3], comprising a yellow ink composition. However, general formula (Y-2) does not include general formula (Y).
General formula (Y):

(In the general formula (Y), each M independently represents a hydrogen atom or a cation. When M represents a cation, each represents a Li ⁺ ion, a Na ⁺ ion, a K ⁺ ion, or an NH ₄ ⁺ ion.)
General formula (Y-2):

In General Formula (Y-2), R ₄ represents a monovalent group, R ₅ represents —OR ₆ or —NHR ₇ , R ₆ and R ₇ represent a hydrogen atom or a monovalent group, and X ₃ Represents a divalent linking group, n ₃ is 0 or 1, Ar ₃ represents a divalent heterocyclic group, and Ar ₄ represents an alkyl group, an aryl group or a monovalent triazine ring group.
[5]
The ink set according to [4], wherein the content of the colorant in the yellow ink composition is 1.0 to 6.0% by mass with respect to the total mass in the yellow ink composition.
[6]
The ink set according to [1] to [5], comprising a magenta ink composition containing at least one selected from the group consisting of a compound represented by the following formula (M-1) and a salt thereof as a colorant.
General formula (M-1):

In General Formula (M-1), A _M represents a 5-membered heterocyclic group.
B ₁ and _{B 2} are each _-CR 13 =, - or represents _{CR 14} =, or either one is a nitrogen atom, the other represents _{-CR 13} = or _{-CR 14} =.
R ₁₁ and R ₁₂ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl. Represents a group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Each group may further have a substituent.
G, R ₁₃ and R ₁₄ 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, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, nitro group, alkyl group substituted by a group or a heterocyclic group A thio group, an arylthio group, an alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a heterocyclic thio group, or an ionic hydrophilic group. Each group may be further substituted. R ₁₃ and R ₁₁ , or R ₁₁ and R ₁₂ may be bonded to form a 5- or 6-membered ring. However, General Formula (M-1) has at least one ionic hydrophilic group.
[7]
The magenta ink composition includes two types of magenta ink compositions having different color densities, and at least one magenta ink composition is selected from the group consisting of the compound represented by the general formula (M-1) and a salt thereof. The ink set according to [6], which contains at least one selected as a colorant.
[8]
Of the two types of magenta ink compositions having different color densities, the magenta ink composition having a low color density is at least one selected from the group consisting of the compound represented by formula (M-1) and a salt thereof. The ink set according to [7], in which the content of the colorant is 0.5 to 3.5% by mass with respect to the total mass of the magenta ink composition having the low color density.
[9]
Of the two types of magenta ink compositions having different color densities, the magenta ink composition having a high color density is at least one selected from the group consisting of the compound represented by formula (M-1) and a salt thereof. The ink set according to [7] or [8], wherein the colorant content is 3 to 10% by mass based on the total mass of the magenta ink composition having the high color density.
[10]
In the two types of magenta ink compositions having different color densities, the colorant contained in the magenta ink composition having a low color density (mass%) and the colorant contained in the magenta ink composition having a high color density. The ink set according to any one of [7] to [9], wherein the ratio to the concentration (mass%) of the agent is in the range of 1: 2 to 1: 8.
[11]
The cyan ink composition containing at least one selected from the group consisting of a compound represented by the following formula (C-1) and a salt thereof as a colorant, according to any one of [1] to [10]. Ink set.
General formula (C-1):

In the general formula (C-1), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NV ₁ V ₂ , —CONV ₁ V. ₂ represents a _-CO 2 Z, -CO-Z, or a sulfo group. Here, Z represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. Each group may further have a substituent. V ₁ and V ₂ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. Each group may further have a substituent.
Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro Group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, Sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group, Or an ionic hydrophilic group , Each group may have a substituent.
a ₁ ~a ₄ and _b 1 ~b ₄ each represent the number of substituents of _X 1 to X ₄ and _Y 1 to Y _4. A _{1 to} a ₄ are each independently an integer of 0 to 4, and all do not become 0 at the same time. b ₁ ~b ₄ each independently represents an integer of 0-4.
M is a metal atom or an oxide, hydroxide or halide thereof.
Provided that at least one of X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y _3, and Y ₄ is an ionic hydrophilic group or a substituent on the ionic hydrophilic group As a group possessed as
[12]
The cyan ink composition includes two cyan ink compositions having different color densities, and at least one cyan ink composition is selected from the group consisting of the compound represented by formula (C-1) and a salt thereof. The ink set according to [11], containing at least one selected as a colorant.
[13]
Of the two cyan ink compositions having different color densities, the cyan ink composition having a low color density is at least one selected from the group consisting of the compound represented by the general formula (C-1) and a salt thereof. The ink set according to [12], in which the content of the colorant is 0.4 to 3.0% by mass with respect to the total mass of the cyan ink composition having the low color density.
[14]
Of the two cyan ink compositions having different color densities, the cyan ink composition having a high color density is at least one selected from the group consisting of the compound represented by formula (C-1) and a salt thereof. [12] or [13], wherein the content of the colorant is 2.0 to 10.0% by mass relative to the total mass of the cyan ink composition having the high color density. Ink set.
[15]
In the two cyan ink compositions having different color densities, the colorant contained in the cyan ink composition having a high color density and the density (mass%) of the colorant contained in the cyan ink composition having a low color density. The ink set according to any one of [12] to [14], wherein the ratio to the concentration (mass%) of the agent is in the range of 1: 2 to 1: 8.
[16]
[1] to [15] An ink jet recording method comprising recording using the ink set according to any one of [15] to [15].
[17]
An ink jet recording method comprising forming an image using the ink set according to any one of [1] to [15].
[18]
A recorded matter recorded using the ink set according to any one of [1] to [15].

  The ink set of the present invention is excellent in ink storage stability by using a specific compound as the colorant of the black ink composition. An image obtained using this ink set is excellent in light resistance and ozone resistance, and can have a good color balance.

[Ink set]
The ink set of the present invention is an ink set including at least a black ink composition, a yellow ink composition, a magenta ink composition, and a cyan ink composition,
The black ink composition contains at least one selected from the group consisting of a compound represented by the general formula (1) and a salt thereof as a colorant.

（一般式（１）中、Ａは置換若しくは無置換のアリール基、又は置換若しくは無置換の含窒素５員ヘテロ環基を表す。Ｇは窒素原子又は−Ｃ（Ｒ_２）＝を表す。Ｒ_２は、水素原子、スルホ基、カルボキシ基、置換若しくは無置換のカルバモイル基、又はシアノ基を表す。Ｙ_２、Ｙ_３及びＹ_４はそれぞれ独立に、水素原子、又は１価の置換基を表す。Ｙ_２、Ｙ_３及びＹ_４は、互いに結合して環を形成しても良い。Ｙ_２、Ｙ_３及びＹ_４の全てが同時に水素原子を表すことはない。Ｍはそれぞれ独立に水素原子又は一価のカウンターカチオンを表す。）

(In general formula (1), A represents a substituted or unsubstituted aryl group or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group. G represents a nitrogen atom or —C (R ₂ ) ═. ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group, and Y ₂ , Y _3, and Y ₄ each independently represent a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ and Y ₄ may combine with each other to form a ring, and all of Y ₂ , Y ₃ and Y ₄ do not represent a hydrogen atom at the same time, and M independently represents a hydrogen atom. Or represents a monovalent counter cation.)

  The inventors of the present invention configured an ink set by combining various ink compositions of a plurality of colors, and studied to improve the ink storage stability and the light resistance / ozone resistance of the formed image. As a result, an ink set including a black ink composition using a colorant having the above specific structure has excellent ink storage stability, and when an image is recorded using the ink set, the recorded image is light-resistant.・ Because it has excellent ozone resistance and the difference in degradation rate due to light and ozone between black ink and other color inks is small, even if the image degradation due to light and ozone progresses to some extent, the observer can degrade the entire image. It was found that an ink set that is difficult to feel can be obtained.

The present invention will be described in detail.
First, in the present invention, the substituent group A ′, the substituent group J, the ionic hydrophilic group, and Hammett's substituent constant σp value are defined.

(Substituent group A ′)
C1-C12 linear or branched alkyl group, C7-C18 linear or branched aralkyl group, C2-C12 linear or branched alkenyl group, C2-C12 linear Or a branched alkynyl group, a C3-C12 cycloalkyl group, a C3-C12 cycloalkenyl group (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl) , T-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), halogen atom (for example, chlorine atom, bromine atom), aryl group (for example, phenyl, 4-t- Butylphenyl, 2,4-di-t-amylphenyl), heterocyclic groups (eg imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thiol) Nyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy), aryloxy Groups (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenyloxy), acylamino groups (for example, acetamide, benzamide, 4 -(3-t-butyl-4-hydroxyphenoxy) butanamide), alkylamino groups (eg methylamino, butylamino, diethylamino, methylbutylamino), arylamino groups (eg phenylamino, 2-chloroanily) ), Ureido groups (eg phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino groups (eg N, N-dipropylsulfamoylamino), alkylthio groups (eg methylthio, octylthio, 2 -Phenoxyethylthio), arylthio groups (eg phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino groups (eg methoxycarbonylamino), alkylsulfonylamino groups and Arylsulfonylamino group (for example, methylsulfonylamino, phenylsulfonylamino, p-toluenesulfonylamino), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl group ( For example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl), a sulfonyl group (eg, methylsulfonyl, octylsulfonyl, phenylsulfonyl, p -Toluenesulfonyl), sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecane) alkyloxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy group (for example, 1 -Phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo) Acyloxy group (for example, acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxy) Carbonylamino), imide group (for example, N-succinimide, N-phthalimide), heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6- Thio, 2-pyridylthio), sulfinyl groups (eg 3-phenoxypropylsulfinyl), phosphonyl groups (eg phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl groups (eg Alkoxycarbonyl), acyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl), an ionic hydrophilic group (carboxyl group, a sulfo group, and quaternary ammonium groups). These substituents may be further substituted, and examples of the further substituent include groups selected from the substituent group A ′ described above.

(Substituent group J)
For example, halogen atom, alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group , Carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group , Mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarboni Examples include groups, alkoxycarbonyl groups, carbamoyl groups, aryl or heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, silyl groups, and ionic hydrophilic groups. . These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group J described above.

  More specifically, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkyl group include linear, branched, and cyclic substituted or unsubstituted alkyl groups, and include cycloalkyl groups, bicycloalkyl groups, and tricyclo structures having many ring structures. An alkyl group (for example, an alkyl group of an alkoxy group or an alkylthio group) in a substituent described below also represents such an alkyl group. Specifically, the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-octyl group, eicosyl. Group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group and the like, and the cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms such as cyclohexyl group, A cyclopentyl group, 4-n-dodecylcyclohexyl group and the like. The bicycloalkyl group is preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a bicycloalkane having 5 to 30 carbon atoms. Monovalent groups from which one hydrogen atom has been removed, for example, bicyclo [1,2,2] heptan-2-yl group, bicycl [2,2,2] octan-3-yl group.

  Examples of the aralkyl group include a substituted or unsubstituted aralkyl group, and the substituted or unsubstituted aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms. For example, a benzyl group and a 2-phenethyl group can be mentioned.

  Examples of the alkenyl group include linear, branched, and cyclic substituted or unsubstituted alkenyl groups, and include cycloalkenyl groups and bicycloalkenyl groups. Specifically, the alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group, and the like. Is preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as 2-cyclopentene-1 -Yl group, 2-cyclohexen-1-yl group and the like, and as the bicycloalkenyl group, a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, That is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond, for example, bicyclo [2 2,1] hept-2-en-1-yl group, a bicyclo [2,2,2] oct-2-en-4-yl group and the like.

  The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms such as an ethynyl group, a propargyl group, and a trimethylsilylethynyl group.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group, and the like. Can be mentioned.

  The heterocyclic group is preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a carbon number. Examples thereof include 3 to 30 5- or 6-membered aromatic heterocyclic groups such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.

  The alkoxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or a 2-methoxyethoxy group. Etc.

  The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as a phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, 3-nitrophenoxy group, 2 -Tetradecanoylaminophenoxy group etc. are mentioned.

  Preferred examples of the silyloxy group include substituted or unsubstituted silyloxy groups having 0 to 20 carbon atoms such as a trimethylsilyloxy group and a diphenylmethylsilyloxy group.

  Preferred examples of the heterocyclic oxy group include substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms, such as a 1-phenyltetrazole-5-oxy group and a 2-tetrahydropyranyloxy group.

  The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as an acetyloxy group, Examples include a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, and a p-methoxyphenylcarbonyloxy group.

  The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N , N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group and the like.

  The alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, or an n-octylcarbonyloxy group. Etc.

  The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxy. Examples include phenoxycarbonyloxy group.

  The amino group includes an alkylamino group, an arylamino group, and a heterocyclic amino group, preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 6 to 30 carbon atoms. Examples of the substituted anilino group include a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, and a triazinylamino group.

  The acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as an acetylamino group, Examples include pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, and the like.

  The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as a carbamoylamino group, N, N-dimethylaminocarbonylamino group, or N, N-diethylaminocarbonylamino group. And a morpholinocarbonylamino group.

  The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino. Group, N-methyl-methoxycarbonylamino group and the like.

  The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxy. Examples thereof include a carbonylamino group.

  The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as a sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn- Examples include octylaminosulfonylamino group.

The alkyl or arylsulfonylamino group is preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as a methylsulfonylamino group. Butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, and the like.
Preferred examples of the alkylthio group include substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, and an n-hexadecylthio group.

  Preferred examples of the arylthio group include substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms such as a phenylthio group, a p-chlorophenylthio group, and an m-methoxyphenylthio group.

  Preferred examples of the heterocyclic thio group include substituted or unsubstituted heterocyclic thio groups having 2 to 30 carbon atoms, such as a 2-benzothiazolylthio group and a 1-phenyltetrazol-5-ylthio group.

  The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfuryl group. Examples include a famoyl group, an N-acetylsulfamoyl group, an N-benzoylsulfamoyl group, and an N- (N′-phenylcarbamoyl) sulfamoyl group.

  The alkyl or arylsulfinyl group is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group, an ethylsulfinyl group, phenyl. Examples thereof include a sulfinyl group and a p-methylphenylsulfinyl group.

  The alkyl or arylsulfonyl group is preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, or a phenyl group. A sulfonyl group, p-methylphenylsulfonyl group, etc. are mentioned.

  The acyl group is preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted group having 2 to 30 carbon atoms. Heterocyclic carbonyl groups bonded to carbonyl groups at substituted carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridyl Examples thereof include a carbonyl group and a 2-furylcarbonyl group.

  The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt- A butylphenoxycarbonyl group etc. are mentioned.

  The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, and an n-octadecyloxycarbonyl group.

  The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, or an N, N-di-n-octyl group. Examples thereof include a carbamoyl group and an N- (methylsulfonyl) carbamoyl group.

  The aryl or heterocyclic azo group is preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo and the like.

  Preferred examples of the imide group include an N-succinimide group and an N-phthalimide group.

  The phosphino group is preferably a substituted or unsubstituted phosphino group having 0 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group, and the like.

  The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 0 to 30 carbon atoms, such as a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, and the like.

  Preferred examples of the phosphinyloxy group include substituted or unsubstituted phosphinyloxy groups having 0 to 30 carbon atoms such as a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group.

  The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 0 to 30 carbon atoms, such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group.

  Preferred examples of the silyl group include substituted or unsubstituted silyl groups having 0 to 30 carbon atoms such as a trimethylsilyl group, a t-butyldimethylsilyl group, and a phenyldimethylsilyl group.

(Ionic hydrophilic group)
A sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, a quaternary ammonium group and the like can be mentioned. Particularly preferred are a sulfo group and a carboxyl group. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. Examples of counter cations that form a salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic. Cation (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) is included, lithium salt, sodium salt, potassium salt, ammonium salt is preferable, lithium salt or mixed salt containing lithium salt as a main component Are more preferred, and lithium salts are most preferred.

The counter cation (monovalent counter cation) of the ionic hydrophilic group contained in the compound represented by the general formula (1) of the present invention preferably contains lithium ions as a main component. The counter cations may not be all lithium ions, but the lithium ion concentration in each of the ink compositions is preferably 50% by mass or more, more preferably based on the total counter cations in each ink composition. Is 75% by mass or more, more preferably 80% by mass, and particularly preferably 95% by mass or more.
Under such conditions, the ink composition contains hydrogen ions, alkali metal ions (for example, sodium ions and potassium ions), alkaline earth metal ions (for example, magnesium ions and calcium ions), 4 A quaternary ammonium ion, a quaternary phosphonium ion, a sulfonium ion, or the like can be included as a counter cation.

About the kind and ratio of the counter cation of the colorant, “New Experimental Chemistry Course 9” edited by the Chemical Society of Japan
Analytical Chemistry "(1977 Maruzen) and the Chemical Society of Japan" 4th edition Experimental Chemistry Course 15 Analysis "(1991 Maruzen) describes various theories about analytical methods and elements, so refer to them for analysis. The method can be selected, analyzed and quantified, among which it is easy to determine by an analytical method such as ion chromatography, atomic absorption, inductively coupled plasma emission spectrometry (ICP).
As a method for obtaining the colorant of the present invention in which the counter cation contains lithium ions, any method may be used. For example, (1) a method of converting a counter cation from another cation to lithium ions using an ion exchange resin, (2) a method of acid precipitation or salting out from a system containing lithium ions, and (3) a counter cation of lithium ions A method of forming a colorant using a raw material and a synthetic intermediate, and (4) a method of introducing an ionic hydrophilic group by functional group conversion of each colorant using a reactive agent whose counter cation is a lithium ion (5) A compound in which the counter cation of the ionic hydrophilic group in the colorant is a silver ion is synthesized, and this is reacted with a lithium halide solution to remove the precipitated silver halide. The method of making it.

The ionic hydrophilic group in each colorant may be any as long as it is an ionic dissociation group. Preferred ionic hydrophilic groups include a sulfo group (may be a salt), a carboxyl group (may be a salt), a hydroxyl group (may be a salt), a phosphono group (may be a salt), a quaternary ammonium group, and an acylsulfamoyl group. (May be a salt), a sulfonylcarbamoyl group (may be a salt), a sulfonylsulfamoyl group (may be a salt), and the like.
A sulfo group, a carboxyl group, or a hydroxyl group (including salts thereof) is preferable. When the ionic hydrophilic group is a salt, a preferable counter cation is lithium or a mixed salt of an alkali metal (for example, sodium, potassium), ammonium, and an organic cation (for example, pyridinium, tetramethylammonium, guanidinium) based on lithium. Among them, lithium or an alkali metal mixed salt containing lithium as a main component is preferable, and a lithium salt of a sulfo group and a lithium salt of a carboxy group are particularly preferable.

(Hammett's substituent constant σp value)
Here, Hammett's substituent constant σp value used in the present specification will be described briefly. Hammett's rule is based on L. 1935 in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it is limited only to a substituent having a known value that can be found in the above-mentioned book. However, it goes without saying that even if the value is unknown, it also includes a substituent that would be included in the range when measured based on Hammett's rule. Although the compound represented by the general formula of the present invention is not a benzene derivative, the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value is hereinafter used in this sense.

  In the present invention, when the compound is a salt, the salt is dissociated into ions in the ink, but is expressed as “contains a salt” for convenience.

Hereinafter, each ink composition contained in the ink set of the present invention will be described.
First, the colorant contained in each ink composition will be described below for each color ink composition.

(Black ink)
The colorant used in the black ink composition constituting the ink set of the present invention will be described.
The black ink composition according to the present invention contains at least one compound represented by the following general formula (1) or a salt thereof used as a black dye as a colorant.

[Dye represented by general formula (1)]
The azo dye used in the ink composition of the present invention is represented by the general formula (1). The azo dye (black dye) represented by the general formula (1) (hereinafter sometimes referred to as “azo compound represented by the general formula (1)”, “azo dye” or “water-soluble dye”) Will be described.

(In general formula (1), A represents a substituted or unsubstituted aryl group or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group. G represents a nitrogen atom or —C (R ₂ ) ═. ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group, and Y ₂ , Y _3, and Y ₄ each independently represent a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ and Y ₄ may combine with each other to form a ring, and all of Y ₂ , Y ₃ and Y ₄ do not represent a hydrogen atom at the same time, and M independently represents a hydrogen atom. Or represents a monovalent counter cation.)

G in the general formula (1) represents a nitrogen atom or —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group. When the carbamoyl group has a substituent, the substituent is an alkyl group (methyl group, ethyl group), An aryl group (phenyl group) can be mentioned.

Y ₂ , Y ₃ and Y ₄ each independently represent a hydrogen atom or a monovalent substituent. At least one of Y ₂ , Y ₃ , and Y ₄ represents a substituent. Examples of the substituent in the case where Y ₂ , Y ₃ , and Y ₄ represent a substituent can include the substituent group J independently.
In the general formula (1), Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, an ionic hydrophilic group, a substituted or unsubstituted amino group, a substituted or unsubstituted carbamoyl group, substituted or unsubstituted. Are preferably any one of the following sulfamoyl groups, substituted or unsubstituted alkylsulfonylamino groups, substituted or unsubstituted arylsulfonylamino groups, and substituted or unsubstituted acylamino groups. In the case of a substituted or unsubstituted amino group, a heterocyclic amino group is preferable.
Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, an ionic hydrophilic group, a substituted or unsubstituted heterocyclic amino group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonyl More preferably an amino group, a substituted or unsubstituted acylamino group, a hydrogen atom, a substituted or unsubstituted heterocyclic amino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted acylamino group It is particularly preferred that

When the heterocyclic amino group, sulfamoyl group, alkylsulfonylamino group, arylsulfonylamino group, or acylamino group represented by Y ₂ , Y ₃ , or Y ₄ has a substituent, each independently represents an ionic hydrophilic group. It is more preferable that it is a sex group (for example, —CO ₂ M, —SO ₃ M: M is a monovalent counter cation).
Y ₂ , Y ₃ , and Y ₄ may further have a substituent, and the further substituent may have a hydroxyl group, a substituted or unsubstituted amino group, or an ionic hydrophilic group. An aryl group and a heterocyclic group which may have an ionic hydrophilic group can be exemplified, and a substituted or unsubstituted amino group is preferable. The substituent of the substituted amino group is preferably, for example, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and substituted with an ionic hydrophilic group. More preferred is an alkyl group or an aryl group substituted with an ionic hydrophilic group.

As the heterocyclic amino group, a substituted or unsubstituted triazinylamino group is preferable, and a triazinylamino group having a substituent is more preferable.
The substituent that the triazinylamino group has is preferably a substituted or unsubstituted amino group, and particularly preferably a substituted or unsubstituted amino group.
As the substituent of the substituted amino group, the above examples are preferably used. Here, the alkyl group in the alkyl group substituted with an ionic hydrophilic group is preferably a methyl group, an ethyl group, or an n-propyl group, and more preferably an ethyl group. The aryl group in the aryl group substituted with an ionic hydrophilic group is preferably a phenyl group.

  As the acylamino group, an alkylcarbonylamino group, an alkylcarbonylamino group having an ionic hydrophilic group as a substituent, and an arylcarbonylamino group having an ionic hydrophilic group as a substituent are preferable. The alkyl group in the alkylcarbonylamino group is preferably a methyl group, an ethyl group, or an n-propyl group, and more preferably an ethyl group. The aryl group in the arylcarbonylacyl group is preferably a phenyl group.

Y ₂ , Y ₃ and Y ₄ do not all represent a hydrogen atom at the same time. Y ₂ , Y ₃ , and Y ₄ may be bonded to each other to form a ring. Examples of the ring formed by combining Y ₂ , Y ₃ , and Y ₄ with each other include a benzene ring and a naphthalene ring. And a benzene ring is preferable.
Among Y ₂ , Y ₃ and Y ₄ , Y ₃ preferably represents a substituent, Y ₂ and Y ₄ represent a hydrogen atom, and Y ₃ represents a substituent.
In particular, Y ₂ and Y ₄ represent a hydrogen atom, and Y ₃ represents a heterocyclic amino group having a substituted or unsubstituted amino group as a substituent, an arylsulfonylamino group having an ionic hydrophilic group as a substituent, or an ion Most preferably, it is an acylamino group having a hydrophilic hydrophilic group as a substituent.

More specific examples of the substituent represented by Y ₂ , Y ₃ and Y ₄ include the following substituent (A1).

(In the substituent (A1), * represents a bond as Y ₂ to Y _4. L ₁ represents a single bond, a carbonyl group, or a sulfonyl group. R ₁ represents a substituted or unsubstituted alkyl group, substituted or unsubstituted. Represents a substituted aryl group or a substituted or unsubstituted heterocyclic group.)

R ₁ is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. In the case of having a substituent, the substituent is an ionic hydrophilic group, aryl An amino group and an alkylamino group are mentioned.

  The substituent (A1) is preferably the following substituent (A2) or (A3).

(In the substituents (A2) and (A3), * represents a bond as Y ₂ to Y _4. L ₂ represents a carbonyl group or a sulfonyl group. R _A2 represents a substituted or unsubstituted alkyl group, or Represents a substituted or unsubstituted aryl group, and R _A3 represents a substituted or unsubstituted heterocyclic group.)

R _A2 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and is preferably an alkyl group. In the case of having a substituent, the substituent is preferably an ionic hydrophilic group.
L ₂ is preferably a carbonyl group.
R _A3 represents a substituted or unsubstituted heterocyclic group, and in the case of having a substituent, the substituent is preferably an alkylamino group or an arylamino group, more preferably an alkylamino group or an arylamino group. These may further have a substituent and are preferably substituted with an ionic hydrophilic group.

  The substituent (A3) is preferably the following substituent (A4).

(In the substituent (A4), * represents a bond as Y ₂ to Y _4. R _A4 independently represents a substituted or unsubstituted alkylamino group or a substituted or unsubstituted arylamino group.)

R _A4 independently represents a substituted or unsubstituted alkylamino group or a substituted or unsubstituted arylamino group, and the substituent in the case of having a substituent is preferably an ionic hydrophilic group.

Specific examples of the alkyl group, aryl group, heterocyclic group alkylamino group, arylamino group and ionic hydrophilic group in the substituents (A1) to (A4) are the same as those in Y ₂ , Y ₃ and Y ₄ . It is.

Specific examples of the substituents (A1) to (A4) are shown below, but are not limited to the following examples. * Represents a bond as Y ₂ to Y ₄ .

A represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group. The aryl group includes a substituted or unsubstituted aryl group. More specifically, an aryl group having substituent group J can be mentioned.
The aryl group represented by A is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted phenyl group. Examples of the substituent include the groups described in the above-mentioned substituent group J, and the ionic hydrophilic group or the electron-withdrawing group having a Hammett's σp value of 0.3 or more is preferable.

  The nitrogen-containing heterocyclic group represented by A includes a substituted or unsubstituted nitrogen-containing heterocyclic group. The heterocyclic group represented by A is preferably a monovalent group obtained by removing one hydrogen atom from a 5-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and has 2 to 4 carbon atoms. The 5-membered aromatic heterocyclic group is more preferable. Examples of the substituent include the groups described in the above-mentioned Substituent group J. Examples of the nitrogen-containing 5-membered heterocyclic group include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a thiazole ring, an isothiazole ring, and a thiadiazole ring when the substitution position is not limited.

  A is preferably an aryl group having a substituent, more preferably an ionic hydrophilic group or an aryl group having a Hammett's σp value of 0.3 or more, and an ionic hydrophilic group. A phenyl group having an electron-attracting group having a group or Hammett σp value of 0.3 or more is more preferable.

As the ionic hydrophilic group in the general formula (1), —SO ₃ M ₁ or —CO ₂ M ₁ is preferable, —SO ₃ M ₁ is more preferable, and —SO ₃ Li is particularly preferable.

M ₁ and M each independently represent a hydrogen atom or a monovalent counter cation. Examples of the monovalent counter cation include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic. And cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). As counter cations other than lithium ions, potassium ions and sodium ions are preferable, and sodium ions are more preferable.

As a salt to be formed, a lithium salt, a sodium salt, a potassium salt, or an ammonium salt is preferable, a lithium salt or a mixed salt containing a lithium salt as a main component is more preferable, and a lithium salt is most preferable.
When the azo compound represented by the general formula (1) is a mixed salt, it is a mixed salt of a lithium salt and a sodium salt from the viewpoints of solubility in water, aqueous solution viscosity, surface tension, and storage stability of a high concentration aqueous solution. It is preferable that a part of a plurality of M represents a lithium ion and the remaining M represents a sodium ion. A mode in which all M in (1) is mixed with a dye representing a sodium ion may be used.
When M is a mixed salt of a lithium salt and a sodium salt, the molar ratio of lithium salt to sodium salt (Li: Na) is preferably 99: 1 to 25:75, particularly 99: 1 to 50:50. 99: 1 to 55:45 are preferable, and 99: 1 to 65:35 is particularly preferable among them. Within this range, the solubility and dissolution rate in water are good, the viscosity and surface tension of the high-concentration aqueous solution can be easily adjusted, and the storage stability of the high-concentration aqueous solution tends to be excellent. In particular, the prescription design of the constituent requirements of the ink composition of the water-soluble ink for ink jet becomes easy, and an excellent raw material (high concentration aqueous solution, ink composition) that satisfies the required performance of the water-soluble ink for ink jet at a high level can be provided. Play.
The ratio of cations of the mixed salt can be measured by ion chromatography analysis.

  A particularly preferable combination as the compound represented by the general formula (1) includes the following (A) to (E).

(A) G represents a nitrogen atom or —C (R ₂ ) ═, and preferably —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group, preferably a carbamoyl group (—CONH ₂ group) or a cyano group, and preferably a cyano group. More preferred.

  (B) A is preferably an aryl group having a substituent, more preferably an ionic hydrophilic group or an aryl group having an electron-withdrawing group having a Hammett's σp value of 0.3 or more. More preferably, it is a phenyl group having two hydrophilic hydrophilic groups.

(C) Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, a substituted or unsubstituted heterocyclic amino group, an ionic hydrophilic group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl. It is preferably any of a group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted acylamino group, and a hydrogen atom, a substituted or unsubstituted amino group is substituted. It is more preferably any of a heterocyclic amino group having, an ionic hydrophilic group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted acylamino group, A hydrogen atom, a heterocyclic amino group having a substituted or unsubstituted amino group as a substituent, and an ionic hydrophilic group are placed. Arylsulfonylamino group having a group, and particularly preferably either an acylamino group having as a substituent an ionic hydrophilic group. As the acylamino group, an alkylcarbonylacyl group, an alkylcarbonylacyl group having an ionic hydrophilic group as a substituent, and an arylcarbonylacyl group having an ionic hydrophilic group as a substituent are preferable. The alkyl group in the alkylcarbonylacyl group is preferably a methyl group, an ethyl group, or an n-propyl group, and more preferably an ethyl group. The aryl group in the arylcarbonylacyl group is preferably a phenyl group.
Y ₂ and Y ₄ represent a hydrogen atom, Y ₃ represents a heterocyclic amino group having a substituted or unsubstituted amino group as a substituent, an arylsulfonylamino group having an ionic hydrophilic group as a substituent, or an ionic hydrophilic Most preferred is an acylamino group having a functional group as a substituent.

(D) As the ionic hydrophilic group, —SO ₃ M ₁ or —CO ₂ M ₁ is preferable, —SO ₃ M ₁ is more preferable, and —SO ₃ Li is particularly preferable.

(E) Each of M ₁ and M independently represents a hydrogen atom or a monovalent counter cation. Examples of the monovalent counter cation include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions). ) And organic cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium), lithium salt, sodium salt, potassium salt, and ammonium salt are preferable, and lithium salt or lithium salt is the main component. The mixed salt is more preferable, and the lithium salt is most preferable.

The reason why this structure is preferable is that the water solubility of the azo compound of the general formula (1) is improved, and an azo dye structure capable of achieving both good hue and coloring power and high storage stability is electronically and sterically. It can be given.
As a result, the storage stability as an ink composition is improved, and the light fastness, thermal stability, wet heat stability, water resistance, gas resistance and / or solvent resistance, which are required ink properties, are greatly improved. Therefore, this is a preferable example.

  The compound represented by the general formula (1) is also preferably a compound represented by the following general formula (2-1).

  Hereinafter, the compound represented by formula (2-1) or a salt thereof will be described in detail.

(In General Formula (2-1), G represents a nitrogen atom or —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group. R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ each independently represent a hydrogen atom or a monovalent substituent, A represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted nitrogen-containing 5 (M represents a hydrogen atom or a monovalent counter cation.)

Examples of G, A, R ₂ and M in the general formula (2-1) are each independently synonymous with examples of G, A, R ₂ and M in the general formula (1), and preferable examples are also included. The same.

Examples of the monovalent substituent represented by R ₁₁ , R ₁₂ , R ₁₃ , and R _{14 in the} general formula (2-1) can include each independently a substituent group A ′, which is substituted or unsubstituted. It is preferably an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, an alkyl group substituted with an ionic hydrophilic group (an alkyl group having 1 to 10 carbon atoms is mentioned, A methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, or a t-butyl group is preferable, and a methyl group, an ethyl group, or an n-propyl group is preferable. Is more preferable, and n-propyl group is further preferable), or an aryl group substituted with an ionic hydrophilic group (an aryl group having 6 to 20 carbon atoms is exemplified, and a phenyl group and a naphthyl group are preferable, and a phenyl group is More preferred It is more preferable have.) A.

The compounds represented by the general formulas (1) and (2-1) are also preferably compounds represented by the following general formula (3-1).
Hereinafter, the compound represented by Formula (3-1) or a salt thereof will be described in detail.

(In General Formula (3-1), G represents a nitrogen atom or —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group. R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ each independently represent a hydrogen atom or a monovalent substituent, and X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ are each independently And represents a hydrogen atom or a monovalent substituent, and M independently represents a hydrogen atom or a monovalent counter cation.)

Examples of G, R ₂ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and M in General Formula (3-1) are each independently G, R ₂ , in General Formula (2-1), It is synonymous with the example of R < ₁₁ >, R < ₁₂ >, R <_13> , R < ₁₄ > and M, and its preferable example is also the same.

In General Formula (3-1), X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ each independently represent a hydrogen atom or a monovalent substituent. Examples of the substituent in the case where X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ represent a substituent include the substituent group J described above.
X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each independently a hydrogen atom, ionic hydrophilic group, cyano group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, nitro Group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, hydrogen atom, ionic hydrophilic group, cyano group, methanesulfonyl group, phenylsulfonyl A group, a nitro group, a methoxycarbonyl group, and a carbamoyl group are more preferable, and a hydrogen atom, an ionic hydrophilic group, or a cyano group is particularly preferable.

In General Formula (3-1), X ₂ and X ₄ are preferably each independently a hydrogen atom or an ionic hydrophilic group. X ₁ , X ₃ , and X ₅ are each independently preferably either a hydrogen atom or substituent group J, and at least one of X ₁ , X _3, and X ₅ has a Hammett σp value It preferably represents an electron withdrawing group of 0.3 or more. The upper limit of Hammett's substituent constant σp value is an electron withdrawing group of 1.0 or less.
If at least one of X ₁ , X ₃ , and X ₅ is an electron-withdrawing group having a σp value in this range, the hue of the azo compound can be adjusted, light fastness and ozone gas fastness can be improved. An effect can be acquired by using as a water-soluble dye for black ink.

  Specific examples of the electron withdrawing group having a σp value of 0.3 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diaryl Phosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated Alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, aryl group substituted with other electron-withdrawing group having σp value of 0.3 or more, nitro group, heterocyclic group, halogen Atom, azo group, or selenocyanate Group. A cyano group, a methylsulfonyl group, a phenylsulfonyl group, a methoxycarbonyl group, a carbamoyl group, and a nitro group are preferable, and a cyano group, a methylsulfonyl group, and a nitro group are more preferable.

From the viewpoints of hue, coloring power, and water-soluble storage stability, among the above, at least one of X ₂ and X ₄ is preferably an ionic hydrophilic group, and X ₁ , X ₃ and X ₅ are A hydrogen atom or Hammett's σp value is preferably an electron withdrawing group having a value of 0.3 or more, X ₁ , X ₃ and X ₅ are hydrogen atoms, and X ₂ and X ₄ are ionic hydrophilic groups. It is more preferable that it is a sex group. The ionic hydrophilic group is preferably —SO ₃ M ₁ or —CO ₂ M ₁ (M ₁ represents a hydrogen atom or a monovalent counter cation), more preferably —CO ₂ M ₁ , and —CO _2. Li is particularly preferred.

  A particularly preferable combination as the compound represented by the general formula (3-1) includes the following (A) to (E).

(A) X ₂ and X ₄ are each independently preferably a hydrogen atom or an ionic hydrophilic group, and at least one of X ₁ , X ₃ and X ₅ has a Hammett's σp value of 0.3 or more It preferably represents an electron withdrawing group, and is a cyano group, a methylsulfonyl group, a phenylsulfonyl group, a methoxycarbonyl group, a carbamoyl group, or a nitro group, more preferably a cyano group, a methylsulfonyl group, or a nitro group, A cyano group is preferable, and it is particularly preferable that X ₁ , X ₂ , X ₃ and X ₄ are hydrogen atoms and X ₅ is a cyano group.

(B) G represents a nitrogen atom or —C (R ₂ ) ═, and preferably —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group, preferably a carbamoyl group (—CONH ₂ group) or a cyano group, and preferably a cyano group. More preferred.

(C) As the monovalent substituent represented by R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ , the substituent group A ′ can be exemplified, and a substituted or unsubstituted alkyl group, substituted or unsubstituted aryl It is preferably a group, a substituted or unsubstituted heterocyclic group, more preferably an alkyl group substituted with an ionic hydrophilic group, or an aryl group substituted with an ionic hydrophilic group.

(D) As the ionic hydrophilic group, —SO ₃ M ₁ or —CO ₂ M ₁ is preferable, —SO ₃ M ₁ is more preferable, and —SO ₃ Li is particularly preferable.

(E) Each of M ₁ and M independently represents a hydrogen atom or a monovalent counter cation. Examples of the monovalent counter cation include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions). ) And organic cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium), lithium salt, sodium salt, potassium salt, and ammonium salt are preferable, and lithium salt or lithium salt is the main component. The mixed salt is more preferable, and the lithium salt is most preferable.

The reason why this structure is preferable is that the water solubility of the azo compound of the general formula (3-1) and the association of the azo dye in the ink composition are remarkably improved, and in particular, the high storage stability in the ink composition is improved. Is mentioned.
As a result, long-term storage stability becomes possible, and the required performance of the ink, such as light fastness, thermal stability, wet heat stability, water resistance, gas resistance, and solvent resistance, is greatly improved. It becomes.

  The compound represented by the general formula (1), (2-1) or (3-1) is preferably a compound represented by the following general formula (4-1).

  Hereinafter, the compound represented by Formula (4-1) or a salt thereof will be described in detail.

(In General Formula (4-1), R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ each independently represent a hydrogen atom or a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ And X ₅ each independently represents a hydrogen atom or a monovalent substituent, and M independently represents a hydrogen atom or a monovalent counter cation.)

Examples of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and M in the general formula (4-1) are each independently R ₁₁ , R ₁₂ , R ₁₃ , R in the general formula (2-1). ₁₄ and M, and preferred examples are also the same.

Examples of X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ in General Formula (4-1) are each independently X ₁ , X ₂ , X ₃ , in General Formula (3-1), X _4, and are the same as examples of X _5, and preferred examples thereof are also the same.

  The reason why this structure is preferable is that the ring containing G in the general formula (1) is not a nitrogen-containing 5-membered hetero ring but a thiophene ring, so that the image fastness of a print using the ink composition of the present invention is improved. As a gray to black ink that can improve storage stability (for example, ozone gas fastness, light fastness), discoloration (color change), and fading (decoloring) at a higher level, and that the discoloration color change is required to be small Improves aptitude.

The compound represented by the general formula (1), (2-1), (3-1) or (4-1) is preferably a compound represented by the following general formula (5).
Hereinafter, the compound represented by the general formula (5) or a salt thereof will be described in detail.

(In General Formula (5), M ₁ , M ₂ , M ₃ , M ₄ , and M ₅ each independently represent a hydrogen atom or a monovalent counter cation, and M ₁ , M ₂ , M ₃ , M ₄ , And when M ₅ represents a monovalent counter cation, it represents a lithium ion, a sodium ion, a potassium ion, or an ammonium ion.)

  The compound represented by the general formula (1) is also preferably a compound represented by the following general formula (2-2).

  Hereinafter, the compound represented by Formula (2-2) or a salt thereof will be described in detail.

(In General Formula (2-2), G represents a nitrogen atom or —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group. R ₃ represents a monovalent substituent, A represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group, and M represents independently a hydrogen atom or a monovalent group. Represents the counter cation.)

Examples of A, G, R ₂ and M in the general formula (2-2) are each independently synonymous with examples of A, G, R ₂ and M in the general formula (1), and preferable examples are also included. The same.

Examples of the monovalent substituent represented by R ₃ in the general formula (2-2) include a substituent group A ′, which includes a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or It is preferably an unsubstituted heterocyclic group, more preferably an alkyl group substituted with an ionic hydrophilic group or an aryl group, and particularly preferably an alkyl group substituted with an ionic hydrophilic group. is there.
In the alkyl group substituted with the ionic hydrophilic group, the alkyl group is preferably a methyl group, an ethyl group, or an n-propyl group, and particularly preferably an ethyl group. The ionic hydrophilic group is preferably —SO ₃ M ₁ or —CO ₂ M ₁ (M ₁ represents a hydrogen atom or a monovalent counter cation), more preferably —CO ₂ M ₁ , and —CO _2. Li is particularly preferred.

  The compounds represented by the general formulas (1) and (2-2) are preferably compounds represented by the following general formula (3-2).

  Hereinafter, the compound represented by formula (3-2) or a salt thereof will be described in detail.

(In General Formula (3-2), G represents a nitrogen atom or —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group. R ₃ represents a monovalent substituent, X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ each independently represent a hydrogen atom or a monovalent substituent, and M represents each independently hydrogen. Represents an atomic or monovalent counter cation.)

Examples of G, R ₂ , R ₃ and M in the general formula (3-2) are each independently synonymous with examples of G, R ₂ , R ₃ and M in the general formula (2-2). The preferred examples are also the same.

In General Formula (3-2), X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ each independently represent a hydrogen atom or a monovalent substituent. Examples of the substituent in the case where X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ represent a substituent include the substituent group J described above.
X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each independently a hydrogen atom, ionic hydrophilic group, cyano group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, nitro Group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, hydrogen atom, ionic hydrophilic group, cyano group, methanesulfonyl group, phenylsulfonyl Group, nitro group, methoxycarbonyl group, carbamoyl group, hydrogen atom, ionic hydrophilic group (-SO ₃ M ₁ or —CO ₂ M ₁ is preferable, —CO ₂ M ₁ is more preferable, —CO ₂ Li is particularly preferred.) Or a cyano group is particularly preferred.

In General Formula (3-2), X ₂ and X ₄ are preferably each independently a hydrogen atom or an ionic hydrophilic group. X ₁ , X ₃ , and X ₅ are each independently preferably either a hydrogen atom or substituent group J, and at least one of X ₁ , X _3, and X ₅ has a Hammett σp value It preferably represents an electron withdrawing group of 0.3 or more. The upper limit of Hammett's substituent constant σp value is an electron withdrawing group of 1.0 or less.
If at least one of X ₁ , X ₃ , and X ₅ is an electron-withdrawing group having a σp value in this range, the hue of the azo compound can be adjusted, light fastness and ozone gas fastness can be improved. An effect can be acquired by using as a water-soluble dye for black ink.

  Specific examples of the electron withdrawing group having a σp value of 0.3 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diaryl Phosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated Alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, aryl group substituted with other electron-withdrawing group having σp value of 0.3 or more, nitro group, heterocyclic group, halogen Atom, azo group, or selenocyanate Group. A cyano group, a methylsulfonyl group, a phenylsulfonyl group, a methoxycarbonyl group, a carbamoyl group, and a nitro group are preferable, and a cyano group, a methylsulfonyl group, and a nitro group are more preferable.

From the viewpoints of hue, coloring power, and water-soluble storage stability, among the above, at least one of X ₂ and X ₄ is preferably an ionic hydrophilic group, and X ₁ , X ₃ , and X ₅ Is preferably a hydrogen atom or an electron-withdrawing group having a Hammett's σp value of 0.3 or more, X ₁ , X ₃ and X ₅ are hydrogen atoms, and X ₂ and X ₄ are ionic. More preferably, it is a hydrophilic group. The ionic hydrophilic group is preferably —SO ₃ M ₁ or —CO ₂ M ₁ (M ₁ represents a hydrogen atom or a monovalent counter cation), more preferably —CO ₂ M ₁ , and —CO _2. Li is particularly preferred.

  A particularly preferable combination as the compound represented by the general formula (3-2) includes the following (A) to (D).

(A) At least one of X ₂ and X ₄ is preferably an ionic hydrophilic group, and X ₁ , X ₃ and X ₅ are hydrogen atoms or electron withdrawing having a Hammett's σp value of 0.3 or more. It is preferable that X ₁ , X ₃ and X ₅ are hydrogen atoms, and X ₂ and X ₄ are more preferably ionic hydrophilic groups.

(B) As the monovalent substituent represented by R ₃ , substituent group A ′ can be mentioned, and a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group is preferable. More preferably an alkyl group or an aryl group substituted with an ionic hydrophilic group.

(C) As the ionic hydrophilic group, —SO ₃ M ₁ or —CO ₂ M ₁ is preferable, —CO ₂ M ₁ is more preferable, and —CO ₂ Li is particularly preferable.

(D) Each of M ₁ and M independently represents a hydrogen atom or a monovalent counter cation, and examples of the monovalent counter cation include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion). ) And organic cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium), lithium salt, sodium salt, potassium salt, and ammonium salt are preferable, and lithium salt or lithium salt is the main component. The mixed salt is more preferable, and the lithium salt is most preferable.

The reason why this structure is preferable is that the water solubility of the azo compound of the general formula (3-2) and the association property of the azo dye in the ink composition are remarkably improved, and in particular, the high storage stability in the ink composition is improved. Is mentioned.
As a result, long-term storage stability becomes possible, and the required performance of the ink, such as light fastness, thermal stability, wet heat stability, water resistance, gas resistance, and solvent resistance, is greatly improved. It becomes.

  The compound represented by the general formula (1), (2-2) or (3-2) is preferably a compound represented by the following general formula (4-2).

  Hereinafter, the compound represented by formula (4-2) or a salt thereof will be described in detail.

(In General Formula (4-2), R ₃ represents a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ each independently represents a hydrogen atom or a monovalent substituent. M represents each independently a hydrogen atom or a monovalent counter cation.)

Examples of R ₃ and M in the general formula (4-2) are each independently synonymous with examples of R ₃ and M in the general formula (2-2), and preferred examples are also the same.

In the general formula _{(4-2), X 1, X} 2, X 3, X 4, and X _{5 X} 1 in the general formula _{(3-2), X 2, X} 3, X 4, and X ₅ It is synonymous with the example of, and a preferable example is also the same.

  A particularly preferable combination as the compound represented by the general formula (4) includes the following (a) to (d).

  (A) A in the general formula (1) is an aryl group having a substituent, and more preferably an ionic hydrophilic group or an aryl group having an electron withdrawing group having a Hammett's σp value of 0.3 or more. Preferably, it is a phenyl group having two ionic hydrophilic groups.

(B) As the monovalent substituent represented by R ₃ , substituent group A ′ can be mentioned, and a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group is preferable. More preferably an alkyl group substituted with an ionic hydrophilic group or an aryl group, particularly preferably an alkyl group substituted with an ionic hydrophilic group (a methyl group, an ethyl group, or an n-propyl group, And n-propyl group is particularly preferable.

(C) As the ionic hydrophilic group, —SO ₃ M ₁ or —CO ₂ M ₁ is preferable, —CO ₂ M ₁ is more preferable, and —CO ₂ Li is particularly preferable.

(D) Each of M ₁ and M independently represents a hydrogen atom or a monovalent counter cation, and examples of the monovalent counter cation include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion). ) And organic cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). As a salt to be formed, a lithium salt, a sodium salt, a potassium salt, or an ammonium salt is preferable, a lithium salt or a mixed salt containing a lithium salt as a main component is more preferable, and a lithium salt is most preferable.

  The reason why this structure is preferable is that the ring containing G in the general formula (1) is not a nitrogen-containing 5-membered hetero ring but a thiophene ring, so that the image fastness of a print using the ink composition of the present invention is improved. As a gray to black ink, storage stability (for example, ozone gas fastness, light fastness), discoloration (color change), fading (decoloring) can be improved at a higher level, and change in discoloration color is required to be small. The aptitude is improved.

  The compound represented by the general formula (1), (2-2), (3-2) or (4-2) is preferably a compound represented by the following general formula (5-2).

(M ₂ independently represents a hydrogen atom or a monovalent counter cation, and when M ₂ represents a monovalent counter cation, it represents a lithium ion, a sodium ion, a potassium ion, or an ammonium ion.)

Examples of M _{2 in} the general formula (5-2) are each independently synonymous with examples of M in the general formula (2-2), and preferred examples are also the same.

The present invention also relates to the azo compound represented by the general formula (1). An aqueous solution and a water-soluble ink composition using the azo compound of the present invention as a coloring agent (colorant) are used as coloring materials such as dyes and pigments. And a dispersant (such as a solvent) thereof, and can be suitably used for image formation.
The compound represented by the general formula (1) is also preferably a compound represented by the following general formula (1-3).

  Hereinafter, the compound represented by formula (1-3) or a salt thereof will be described in detail.

(In General Formula (1-3), G represents a nitrogen atom or —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent, and Y ₂ , Y ₃ and Y ₄ each independently Represents a hydrogen atom or a monovalent substituent, and Y ₂ , Y ₃ , and Y ₄ may be bonded to each other to form a ring, and all of Y ₂ , Y _3, and Y ₄ are simultaneously hydrogen atoms. (M represents each independently a hydrogen atom or a monovalent counter cation.)

Examples of G, R ₂ , Y ₂ , Y ₃ , Y ₄ and M in the general formula (1-3) are each independently G, R ₂ , Y ₂ , Y ₃ , Y ₄ and are the same as examples of M, and preferred examples thereof are also the same.

In General Formula (1-3), X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , and X ₇ each independently represent a hydrogen atom or a monovalent substituent. Examples of the substituent when X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , and X ₇ represent a substituent include the substituent J described above.
X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are each independently a hydrogen atom, ionic hydrophilic group, cyano group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted Preferably an arylsulfonyl group, a nitro group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a hydrogen atom, an ionic hydrophilic group, a cyano group, A methanesulfonyl group, a phenylsulfonyl group, a nitro group, a methoxycarbonyl group, and a carbamoyl group are more preferable, and a hydrogen atom, an ionic hydrophilic group, or a cyano group is particularly preferable.
In the general formula (1-3), X ₁ , X ₃ , X ₅ and X ₇ are each independently preferably either a hydrogen atom or a substituent group J, and further, X ₂ , X ₄ , and It is preferable that at least one of X ₆ represents an electron withdrawing group having a Hammett σp value of 0.3 or more.
If at least one of X ₂ , X ₄ , and X ₆ is an electron-withdrawing group having a σp value in this range, the hue of the azo compound can be adjusted, light fastness and ozone gas fastness can be improved. An effect can be acquired by using as a water-soluble dye for black ink.

X ₂ , X ₄ and X ₆ are each independently a hydrogen atom, ionic hydrophilic group, cyano group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, nitro group, substituted or unsubstituted Are preferably an alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a hydrogen atom, an ionic hydrophilic group, a cyano group, a methanesulfonyl group, a phenylsulfonyl group, a nitro group, and a methoxy group. A carbonyl group or a carbamoyl group is more preferable, and a hydrogen atom, an ionic hydrophilic group, or a cyano group is particularly preferable.

Furthermore, it is preferable that at least one of X ₂ , X ₄ , and X ₆ represents an electron-withdrawing group having a Hammett's σp value of 0.3 or more. More preferably, it is an electron withdrawing group of 0 or less, X ₂ and X ₆ are ionic hydroxyl groups, and X ₄ represents an electron withdrawing group having a Hammett σp value of 0.3 or more.

  Specific examples of the electron withdrawing group having a σp value of 0.3 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diaryl Phosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated Alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, aryl group substituted with other electron-withdrawing group having σp value of 0.3 or more, nitro group, heterocyclic group, halogen Atom, azo group, or selenocyanate Group. A cyano group, a methylsulfonyl group, a phenylsulfonyl group, a methoxycarbonyl group, a carbamoyl group, and a nitro group are preferable, and a cyano group, a methylsulfonyl group, and a nitro group are more preferable.

From the viewpoint of hue, coloring power, and water-soluble storage stability, among the above, at least one of X ₂ , X ₄ , and X ₆ is preferably an ionic hydrophilic group, and X ₂ , X ₄ , And at least one of X ₆ is preferably an electron-withdrawing group having a Hammett's σp value of 0.3 or more, and X ₃ is an electron-withdrawing group having a Hammett's σp value of 0.3 or more. More preferably, X ₂ and X ₆ are ionic hydrophilic groups. The ionic hydrophilic group is preferably —SO ₃ M ₁ or —CO ₂ M ₁ (M ₁ represents a hydrogen atom or a monovalent counter cation), more preferably —SO ₃ M ₁ , and —SO _3. Li is particularly preferred.

  A particularly preferable combination as the compound represented by the general formula (1-3) includes the following (A) to (E).

(A) G represents a nitrogen atom or —C (R ₂ ) ═, and preferably —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group, preferably a carbamoyl group (—CONH ₂ group) or a cyano group, and preferably a cyano group. More preferred.

(B) Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, a substituted or unsubstituted heterocyclic amino group, an ionic hydrophilic group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl. It is preferably any of a group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted acylamino group, and a hydrogen atom, a substituted or unsubstituted amino group is substituted. It is more preferably any of a heterocyclic amino group, an ionic hydrophilic group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted acylamino group as a group. , A hydrogen atom, a heterocyclic amino group having a substituted or unsubstituted amino group as a substituent, an ionic hydrophilic group Arylsulfonylamino group having a substituent group, and particularly preferably either an acylamino group having as a substituent an ionic hydrophilic group. As the acylamino group, an alkylcarbonylamino group, an alkylcarbonylamino group having an ionic hydrophilic group as a substituent, and an arylcarbonylamino group having an ionic hydrophilic group as a substituent are preferable. The alkyl group in the alkylcarbonylamino group is preferably a methyl group, an ethyl group, or an n-propyl group, and more preferably an ethyl group. The aryl group in the arylcarbonylamino group is preferably a phenyl group.
Y ₂ and Y ₄ represent a hydrogen atom, Y ₃ represents a heterocyclic amino group having a substituted or unsubstituted amino group as a substituent, an arylsulfonylamino group having an ionic hydrophilic group as a substituent, or an ionic hydrophilic Most preferred is an acylamino group having a functional group as a substituent.

The (c) an ionic hydrophilic _{group, -SO} 3 _{M 1} or _-CO 2 _{M 1 (M} 1 is. Representing a counter cation of the hydrogen atom or a monovalent) are preferred, _-SO 3 _{M 1} are more preferred, -SO ₃ Li is particularly preferable.

(D) Each of M ₁ and M independently represents a hydrogen atom or a monovalent counter cation, and examples of the monovalent counter cation include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion). ) And organic cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium), lithium salt, sodium salt, potassium salt, and ammonium salt are preferable, and lithium salt or lithium salt is the main component. The mixed salt is more preferable, and the lithium salt is most preferable.

(E) X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , and X ₇ are each independently preferably either a hydrogen atom or substituent group J. It is more preferably a hydrophilic group, a cyano group, a methanesulfonyl group, a phenylsulfonyl group, a nitro group, a methoxycarbonyl group, or a carbamoyl group, and particularly preferably a hydrogen atom, an ionic hydrophilic group, or a cyano group. X ₁ , X ₃ , X ₅ and X ₇ are each independently preferably either a hydrogen atom or a substituent group J, and at least one of X ₂ , X ₄ and X ₆ is Hammett Preferably, it represents an electron withdrawing group having a σp value of 0.3 or more, X ₄ is an electron withdrawing group having a Hammett's σp value of 0.3 or more, and X ₂ and X ₆ are ionic. More preferably, it is a hydrophilic group. The ionic hydrophilic group is preferably —SO ₃ M ₁ or —CO ₂ M ₁ (M ₁ represents a hydrogen atom or a monovalent counter cation), more preferably —SO ₃ M ₁ , and —SO _3. Li is particularly preferred.

The reason why this structure is preferable is that the water solubility of the azo compound represented by the general formula (1-3) is improved, and an azo dye structure that can achieve both good hue, coloring power and high storage stability can be obtained electronically / sterically. It can be mentioned that it can give.
As a result, the storage stability as an ink composition is improved, and the light fastness, thermal stability, wet heat stability, water resistance, gas resistance and / or solvent resistance, which are required ink properties, are greatly improved. Therefore, this is a preferable example.

  The compound represented by the general formula (1-3) is also preferably a compound represented by the following general formula (2-3).

  Hereinafter, the compound represented by Formula (2-3) or a salt thereof will be described in detail.

(In General Formula (2-3), G represents a nitrogen atom or —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent, R ₁₁ , R ₁₂ , R ₁₃ and R _14. Each independently represents a hydrogen atom or a monovalent substituent, and M independently represents a hydrogen atom or a monovalent counter cation.)

Examples of G, R ₂ , X _{1 to} X ₇ , and M in General Formula (2-3) are each independently G, R ₂ , X _{1 to} X ₇ in General Formula (1-3), And examples of M, and preferable examples are also the same.

Examples of the monovalent substituent represented by R ₁₁ , R ₁₂ , R ₁₃ , and R _{14 in the} general formula (2-3) include a substituent group A ′, and a substituted or unsubstituted alkyl group, It is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, an alkyl group substituted with an ionic hydrophilic group, or an aryl group substituted with an ionic hydrophilic group. More preferred.
In R ₁₁ and R ₁₂ , one is preferably a hydrogen atom, and the other is preferably a hydrogen atom or an alkyl group or an aryl group having an ionic hydrophilic group. In R ₁₃ and R ₁₄ , one is preferably a hydrogen atom, and the other is preferably a hydrogen atom or an alkyl group or an aryl group having an ionic hydrophilic group.

In particular, one of the substituents (R ₁₁ and R ₁₂ ) of the amino group on the s-triazine ring is a hydrogen atom and the other is an alkyl group or aryl group having an ionic hydrophilic group, and (R ₁₃ and R ₁₄ ) Is a combination of an alkyl group or an aryl group having one hydrogen atom and the other having an ionic hydrophilic group, thereby improving the water solubility of the dye and the association of the dye in the water solubility (the interaction of the dye molecules It is preferable because the storage stability of the water-soluble ink (prevention of dye precipitation and suppression of dye decomposition), which is required for the coloring composition and the water-soluble ink for inkjet, can be greatly improved.

The compounds represented by the general formulas (1) and (2-3) are preferably compounds represented by the following general formula (3-3).
Hereinafter, the compound represented by Formula (3-3) or a salt thereof will be described in detail.

(In General Formula (3-3), R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ each independently represent a hydrogen atom or a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represents a hydrogen atom or a monovalent substituent, and M independently represents a hydrogen atom or a monovalent counter cation.)

Examples of X _{1 to} X ₇ , R _{11 to} R ₁₄ , and M in General Formula (3-3) are each independently X _{1 to} X ₇ and R _{11 to} R in General Formula (2-3). ₁₄ and M, and preferred examples are also the same.

The compounds represented by the general formulas (1) and (2-3) are preferably compounds represented by the following general formula (4-3).
Hereinafter, the compound represented by Formula (4-3) or a salt thereof will be described in detail.

(In General Formula (4-3), R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ each independently represent a hydrogen atom or a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represents a hydrogen atom or a monovalent substituent, and M independently represents a hydrogen atom or a monovalent counter cation.)

Examples of X _{1 to} X ₇ , R _{11 to} R ₁₄ , and M in General Formula (4-3) are each independently X _{1 to} X ₇ and R _{11 to} R in General Formula (2-3). ₁₄ and M, and preferred examples are also the same.

  Particularly preferred combinations as the compounds represented by the general formulas (2-3), (3-3), and (4-3) include the following (A) to (D).

(I) As the monovalent substituent represented by R _{11 to} R ₁₄ , the substituent group A ′ can be exemplified, and a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group, and the like. It is preferably a heterocyclic group, more preferably an alkyl group substituted with an ionic hydrophilic group, or an aryl group substituted with an ionic hydrophilic group.

(B) The ionic hydrophilic group is preferably —SO ₃ M ₁ or —CO ₂ M ₁ , more preferably —SO ₃ M ₁ , and particularly preferably —SO ₃ Li.

(C) M ₁ and M each independently represent a hydrogen atom or a monovalent counter cation, and examples of the monovalent counter cation include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion). ) And organic cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium), lithium salt, sodium salt, potassium salt, and ammonium salt are preferable, and lithium salt or lithium salt is the main component. The mixed salt is more preferable, and the lithium salt is most preferable.
Preferably _{(d) X} 2, X _4, and at least one of _{X 6} is an ionic hydrophilic _{group, X 2,} X _4, and at least one σp value of Hammett _{X 6} 0.3 The above-mentioned electron-withdrawing group is preferable, X ₄ is an electron-withdrawing group having a Hammett's σp value of 0.3 or more, and X ₂ and X ₆ are ionic hydrophilic groups. Is more preferable.

The reason why this structure is preferable is that the water solubility of the azo compounds of the general formulas (2-3), (3-3), and (4-3) and the association of the azo dyes in the ink composition are remarkably improved. The improvement of the high storage stability in an ink composition is mentioned.
As a result, long-term storage stability becomes possible, and the required performance of the ink, such as light fastness, thermal stability, wet heat stability, water resistance, gas resistance, and solvent resistance, is greatly improved. It becomes.

  The compound represented by the general formula (1-3) is also preferably a compound represented by the following general formula (2-4).

  Hereinafter, the compound represented by formula (2-4) or a salt thereof will be described in detail.

(In General Formula (2-4), G represents a nitrogen atom or —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent, and R ₃ represents a monovalent substituent. Each M independently represents a hydrogen atom or a monovalent counter cation.)

Examples of the general formula (2-4) in the _{G, X 1 ~X 7, R} 2 and M are, _G each independently the above general formula (1-3) in, _{X 1} ~X 7, _{R 2} and M It is synonymous with the example of, and a preferable example is also the same.

Examples of the monovalent substituent represented by R ₃ in the general formula (2-4) include a substituent group A ′, and include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a heterocyclic ring. It is preferably a group, more preferably an alkyl group or an aryl group substituted with an ionic hydrophilic group.

  The compounds represented by the general formulas (1-3) and (2-4) are preferably compounds represented by the following general formula (3-4).

  Hereinafter, the compound represented by formula (3-4) or a salt thereof will be described in detail.

(In General Formula (3-4), R ₃ represents a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are each independently a hydrogen atom or 1 (M represents a hydrogen atom or a monovalent counter cation.)

Examples of M in the general formula (3-4) in, _{R 3,} and _X 1 to X ₇ are, M each independently the above general formula (2-4) in, _{R 3,} and examples of _X 1 to X ₇ And preferred examples are also the same.

  A particularly preferable combination as the compounds represented by the general formulas (2-4) and (3-4) includes the following (A) to (D).

(I) As the monovalent substituent represented by R ₃ , substituent group A ′ can be exemplified, and a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group is preferable. More preferably an alkyl group or an aryl group substituted with an ionic hydrophilic group.

(B) The ionic hydrophilic group is preferably —SO ₃ M ₁ or —CO ₂ M ₁ , more preferably —SO ₃ M ₁ , and particularly preferably —SO ₃ Li.

(C) M ₁ and M each independently represent a hydrogen atom or a monovalent counter cation, and examples of the monovalent counter cation include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion). ) And organic cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium), lithium salt, sodium salt, potassium salt, and ammonium salt are preferable, and lithium salt or lithium salt is the main component. The mixed salt is more preferable, and the lithium salt is most preferable.
Preferably _{(d) X} 2, X _4, and at least one of _{X 6} is an ionic hydrophilic _{group, X 2,} X _4, and at least one σp value of Hammett _{X 6} 0.3 The above-mentioned electron-withdrawing group is preferable, X ₄ is an electron-withdrawing group having a Hammett's σp value of 0.3 or more, and X ₂ and X ₆ are ionic hydrophilic groups. Is more preferable.

The reason why this structure is preferable is that the water solubility of the azo compounds of the general formulas (2-4) and (3-4) and the association of the azo dyes in the ink composition are remarkably improved. The storage stability is improved.
As a result, long-term storage stability becomes possible, and the required performance of the ink, such as light fastness, thermal stability, wet heat stability, water resistance, gas resistance, and solvent resistance, is greatly improved. It becomes.

  The compound represented by the general formula (1-3) or (2-4) is preferably a compound represented by the following general formula (4-4).

  Hereinafter, the compound represented by formula (4-4) or a salt thereof will be described in detail.

(In General Formula (4-4), R ₃ represents a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are each independently a hydrogen atom, Or M represents a hydrogen atom or a monovalent counter cation.

Examples of _{R 3,} X 1 _{~X 7} and M in the general formula (4-4), respectively _{R 3,} X 1 _{~X 7} and M of Example synonymous independently by the general formula (2-4) in The preferred examples are also the same.

  The present invention also relates to the azo compound represented by the general formula (1), and an ink composition using the azo compound of the present invention as a coloring matter (coloring agent) includes a coloring material such as a dye or a pigment and a dispersion thereof. It means a composition containing an agent (such as a solvent) and can be suitably used particularly for image formation.

(In general formula (1), A represents a substituted or unsubstituted aryl group or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group. G represents a nitrogen atom or —C (R ₂ ) ═. ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group, and Y ₂ , Y _3, and Y ₄ each independently represent a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ and Y ₄ may combine with each other to form a ring, and all of Y ₂ , Y ₃ and Y ₄ do not represent a hydrogen atom at the same time, and M independently represents a hydrogen atom. Or represents a monovalent counter cation.)

Examples of G, A, R ₂ , Y ₂ , Y ₃ , Y ₄ and M in the general formula (1) are each independently G, A, R ₂ , Y ₂ , Y _3, is _{Y 4} and same as examples of M, and preferred examples thereof are also the same.

  The azo compound represented by the general formula (1) is also preferably an azo compound represented by the following general formula (3-1).

(In General Formula (3-1), G represents a nitrogen atom or —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group. R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ each independently represent a hydrogen atom or a monovalent substituent, and X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ are each independently And represents a hydrogen atom or a monovalent substituent, and M independently represents a hydrogen atom or a monovalent counter cation.)

Examples of G, R ₂ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and M in the general formula (3-1) are each independently described above. In the general formula (3-1) of G, R ₂ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and M, The preferred examples are also the same.

  It is preferable that the azo compound represented by the general formula (3-1) is an azo compound represented by the following general formula (4-1).

(In General Formula (4-1), R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ each independently represent a hydrogen atom or a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ And X ₅ each independently represents a hydrogen atom or a monovalent substituent, and M independently represents a hydrogen atom or a monovalent counter cation.)

Examples of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and M in the general formula (4-1) are each independently the above-described general formula (4 The same as the examples of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and M in -1), and preferred examples are also the same.

  The azo compound represented by the general formula (4-1) is preferably an azo compound represented by the following general formula (5).

(In General Formula (5), M ₁ , M ₂ , M ₃ , M ₄ , and M ₅ each independently represent a hydrogen atom or a monovalent counter cation, and M ₁ , M ₂ , M ₃ , M ₄ , And when M ₅ represents a monovalent counter cation, it represents a lithium ion, a sodium ion, a potassium ion, or an ammonium ion.)

  The azo compound represented by the general formula (1) is also preferably an azo compound represented by the following general formula (6).

(In General Formula (6), X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ each independently represent a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ , and Y ₄ are Each independently represents a hydrogen atom or a monovalent substituent, Y ₂ , Y ₃ and Y ₄ do not all represent a hydrogen atom at the same time, and M independently represents a hydrogen atom or a monovalent counter cation. )

Examples of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and M in the general formula (6) are each independently X ₁ , X ₂ , X ₃ , X in the general formula (3-1). ₄ , X ₅ and M are the same as the examples, and preferred examples are also the same.
Examples of Y ₂ , Y ₃ , and Y _{4 in} the general formula (6) are each independently synonymous with examples of Y ₂ , Y ₃ , and Y _{4 in} the general formula (1), and preferable examples are also included. The same.

  The azo compound represented by the general formula (1) is also preferably an azo compound represented by the following general formula (7).

(In General Formula (7), X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ each independently represent a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ , Y ₄ are each (Independently represents a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ and Y ₄ do not all represent a hydrogen atom at the same time. M independently represents a hydrogen atom or a monovalent counter cation.)

Examples of Y ₂ , Y ₃ , Y ₄ , X _{1 to} X ₅ and M in the general formula (7) are each independently Y ₂ , Y ₃ , Y ₄ , X _{1 in} the general formula (6). it is the same as examples of to X ₅ and M, and preferred examples thereof are also the same.

  The azo compound represented by the general formulas (1) and (7) is also preferably an azo compound represented by the following formula (8).

  The present invention also relates to an azo compound represented by the general formula (2-3), and an ink composition using the azo compound of the present invention as a coloring matter (coloring agent) includes a coloring material such as a dye or a pigment and the coloring material. In particular, it can be suitably used for image formation.

(In General Formula (2-3), G represents a nitrogen atom or —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent, R ₁₁ , R ₁₂ , R ₁₃ and R _14. Each independently represents a hydrogen atom or a monovalent substituent, and M independently represents a hydrogen atom or a monovalent counter cation.)

Examples of G, R ₂ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , X _{1 to} X ₇ and M in General Formula (2-3) are each independently in General Formula (2-3) above. Are the same as the examples of G, R ₂ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , X _{1 to} X ₇ and M, and preferred examples are also the same.

  The azo compound represented by the general formula (2-3) is preferably an azo compound represented by the following general formula (4-3).

(In General Formula (4-3), R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ each independently represent a hydrogen atom or a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represents a hydrogen atom or a monovalent substituent, and M independently represents a hydrogen atom or a monovalent counter cation.)

Examples of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , X _{1 to} X ₇ and M in the general formula (4-3) are each independently R ₁₁ , R in the general formula (4-3). ₁₂ , R ₁₃ , R ₁₄ , X _{1 to} X ₇ and M are synonymous with examples, and preferred examples are also the same.

  The present invention also relates to the azo compound represented by the general formula (2-4), and an ink composition using the azo compound of the present invention as a coloring matter (coloring agent) includes a coloring material such as a dye or a pigment, and In particular, it can be suitably used for image formation.

(In General Formula (2-4), G represents a nitrogen atom or —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent, and R ₃ represents a monovalent substituent. Each M independently represents a hydrogen atom or a monovalent counter cation.)

  The azo compound represented by the general formula (2-4) is preferably an azo compound represented by the following general formula (3-4).

(In General Formula (3-4), R ₃ represents a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are each independently a hydrogen atom or 1 (M represents a hydrogen atom or a monovalent counter cation.)

  The azo compound represented by the general formula (2-4) is also preferably an azo compound represented by the following general formula (4-4).

(In General Formula (4-4), R ₃ represents a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are each independently a hydrogen atom, Or M represents a hydrogen atom or a monovalent counter cation.

General formula (1), (2-1), (2-2), (2-3), (2-4), (3-1), (3-2), (3-3), (3 -4), (4-1), (4-2), (4-3), (4-4), (5) to (7), and the compound represented by formula (8) is obtained by using water as a solvent. The maximum absorption wavelength (λ _max ) of the absorption spectrum measured as is preferably from 550 nm to 700 nm, more preferably from 580 nm to 650 nm.
In the present invention, the general formulas (1), (2-1), (2-2), (2-3), (2-4), (3-1), (3-2), (3 -3), (3-4), (4-1), (4-2), (4-3), (4-4), (5) to (7), and represented by formula (8) The compound preferably has at least three or more ionic hydrophilic groups. More preferably, it has 3-6 ionic hydrophilic groups, and still more preferably 4-5 ionic hydrophilic groups. As a result, the water solubility and aqueous solution storage stability of the azo compound of the present invention are improved, the required performance as a water-soluble dye for inkjet recording black ink is satisfied at a high level, and the inkjet printed matter when used as an inkjet recording ink is further improved. There is an effect that the image quality can be further improved.
General formula (1), (2-1), (2-2), (2-3), (2-4), (3-1), (3-2), (3-3), (3 -4), (4-1), (4-2), (4-3), (4-4), (5) to (7), and an azo compound represented by formula (8), at least 1 It is preferable that one M is a lithium ion.
In the present invention, the general formulas (1), (2-1), (2-2), (2-3), (2-4), (3-1), (3-2), (3 -3), (3-4), (4-1), (4-2), (4-3), (4-4), (5) to (7), and represented by formula (8) It is applicable even if the compound contains isotopes (eg, 2H, 3H, 13C, 15N).

  The general formulas (1), (2-1), (2-2), (2-3), (2-4), (3-1), (3-2), and (3-3) are described below. Specific examples of the compounds represented by (3-4), (4-1), (4-2), (4-3), (4-4), and (5) to (7) are shown below. However, the compounds used in the present invention are not limited to the following examples. M represents a hydrogen atom or a monovalent counter cation (lithium ion, sodium ion, potassium ion, or ammonium ion).

The dye represented by the general formula (1) may be in a mixed salt state in which a plurality of types of M are present. In the case of a mixed salt, the M of the dye represented by the general formula (1) contained in the ink preferably has a molar fraction of 50 to 100%, more preferably 80 to 100%, and particularly 90 of them. It is preferred that ~ 100% of M is Li ⁺ ions. As M other than Li ⁺ ions, Na ⁺ ions and NH ₄ ⁺ ions are preferable, and Na ⁺ ions are more preferable.

Moreover, it is also preferable that all M of the dye represented by the general formula (1) contained in the ink is not Li but Li. When all M is Li, in a molecular dispersion state dissolved in an aqueous solution or an ink solution, a carboxy group that is an ionic hydrophilic group or a salt thereof (—CO ₂ M) is dissociated and —CO ₂ ^— and An effect that it is easy to suppress the formation of a salt state having a lower solubility in an aqueous solution or an ink solution and precipitation in the state of a colorant salt by exchanging cationic species in an ionized state of M ^+. Is obtained.
The dye represented by the general formula (1) can be synthesized by a general synthesis method, for example, by a coupling reaction between a diazo component and a coupler. Specifically, it can be synthesized by the method described in JP-A No. 2003-306623 or JP-A No. 2005-139427.

  Furthermore, in the present invention, in order to adjust the color tone of the black ink composition, the compound represented by the following formula (B-11), as long as the light resistance and ozone resistance are not significantly impaired, A yellow dye can also be used in combination.

  Examples of the yellow dye used in combination include C.I. I. Direct yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 59, 68, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 142, 144, 161, 163, C.I. I. 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, C.I. I. Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, C.I. I. Basic yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40 and the like can be mentioned, but are not limited thereto. .

  General formula (B-11):

In General Formula (B-11), G ₁ and G ₂ each independently represent an optionally substituted aryl group or an optionally substituted hetero group, and K represents an optional substituent. L represents a divalent linking group. However, General Formula (B-11) has at least one ionic hydrophilic group.
Examples of the aryl group include a benzene ring and a naphthalene ring, and examples of the hetero atom of the hetero ring include N, O, and S. The heterocycle may be condensed with an aliphatic ring, an aromatic ring or another heterocycle. The substituent may be an arylazo group or a heterocyclic azo group.

The compound represented by the general formula (B-11) is preferably a compound represented by the following general formula (B-12).
General formula (B-12):

In General Formula (B-12), G ₁ , G ₂ , G _3, and G ₄ each independently represent an optionally substituted aryl group or an optionally substituted heterocyclic group. L ₁ represents a divalent linking group. However, General Formula (B-12) has at least one ionic hydrophilic group.

The compound represented by the general formula (B-12) is preferably a compound represented by the following general formula (B-13).
General formula (B-13):

In the general formula (B-13), E ₁ , E ₂ , E _3, and E ₄ each independently represent an optionally substituted aryl group or an optionally substituted heterocyclic group. L ₁₁ represents a divalent linking group. However, General Formula (B-13) has at least one ionic hydrophilic group.

The compound represented by the general formula (B-13) is preferably a compound represented by the following general formula (B-14).
General formula (B-14):

In General Formula (B-14), A ring, B ring, and C ring each independently represent an optionally substituted aryl group or an optionally substituted heterocyclic group. A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₁₁ , A ₁₂ , A ₁₃ , A ₁₄ , A ₁₅ , B ₁ , B ₂ , B ₃ , B ₄ , B ₅ , B ₆ , B ₁₁ , B ₁₂ , B ₁₃ , B ₁₄ , B ₁₅ , B ₁₆ , C ₁ , C ₂ , C ₃ , C ₄ , C ₁₁ , C ₁₂ , C ₁₃ , and C ₁₄ each independently represent a hydrogen atom or a substituent. . However, General Formula (B-14) has at least one ionic hydrophilic group. Q ₁ and Q ₂ each independently represents a hydrogen atom or a substituent. L ₁₂ represents a divalent linking group.

General formula (B-14) is demonstrated.
A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₁₁ , A ₁₂ , A ₁₃ , A ₁₄ , A ₁₅ , B ₁ , B ₂ , B ₃ , B ₄ , B ₅ , B ₆ , B ₁₁ , B ₁₂ , B ₁₃ , B ₁₄ , B ₁₅ , B ₁₆ , C ₁ , C ₂ , C ₃ , C ₄ , C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ are each independently a hydrogen atom or a substituent. To express. Preferred examples of the substituent include ionic hydrophilic group, halogen atom, cyano group, nitro group, substituted or unsubstituted acylamino group, substituted or unsubstituted sulfonylamino group, substituted or unsubstituted alkyl group, substituted or unsubstituted Substituted alkoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted sulfamoyl group, substituted or And an unsubstituted carbamoyl group, among which an ionic hydrophilic group, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted acylamino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted sulfamo Le group are preferred, and an ionic hydrophilic group, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted acylamino group, preferably a substituted or unsubstituted alkyl group, and most preferably an ionic hydrophilic group.
Q ₁ and Q ₂ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, more preferably hydrogen. An atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom.
L ₁₂ represents a divalent linking group, preferably a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted phenylene group, a carbonyl group, a substituted or unsubstituted 1,3,5- A triazine-2,4-diyl group, more preferably a carbonyl group, a substituted or unsubstituted 1,3,5-triazine-2,4-diyl group, and particularly preferably a carbonyl group.

  Specific examples of the compounds represented by the general formulas (B-11), (B-12), (B-13), and (B-14) are shown below, but the compounds used in the present invention are: It is not limited to the following example.

The content of the compound represented by the general formula (1) or a salt thereof in the black ink composition of the present invention is preferably 0.1 to 20% by mass with respect to the total mass of the black ink composition. More preferably, it is 0.5-15 mass%, More preferably, it is 1-10 mass%.
Further, the total amount of all the colorants contained in the black ink composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 20%, based on the total mass of the black ink composition. It is 1 mass%, More preferably, it is 1-15 mass%.
When the total amount of the colorant contained in the black ink composition is 0.1% by mass 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 are obtained. Obtainable. In addition, by setting the total amount of the colorant to 30% by mass or less, the viscosity of the ink composition can be adjusted to a preferable value, and the discharge amount of the ink composition from the inkjet head can be stabilized. In addition, clogging of the inkjet head can be prevented.

Since the dye represented by the general formula (1) or a salt thereof is very excellent in light resistance and ozone resistance, an ink set combined with the yellow ink, cyan ink and magenta ink of the present invention is used. Thus, the light resistance and ozone resistance of each color can be dramatically improved, and a good image quality of the image can be maintained for a long time without losing the color balance of the image even after the light / ozone exposure test.
Furthermore, in the black ink composition, the color balance can be further adjusted by combining the dye represented by the general formula (1) or a salt thereof and the compound usable in the present invention. It becomes possible, and the image quality of the printed matter can be kept good for a longer period of time.

(yellow)
Next, the colorant used in the yellow ink composition constituting the ink set of the present invention will be described.

  In the ink set of the present invention, the colorant used in the yellow ink composition is not limited to the colorant having a specific structure, but the light resistance / ozone resistance of the ink composition of other colors and the yellow ink composition It is preferable that the difference between light resistance and ozone resistance is small.

From the above viewpoint, the yellow dye used as a colorant in the yellow ink composition in the present invention is a compound selected from the group consisting of compounds represented by the following general formula (Y) and general formula (Y-2) and salts thereof: It is preferable that However, general formula (Y-2) does not include general formula (Y).
General formula (Y):

(In the general formula (Y), each M independently represents a hydrogen atom or a cation. When M represents a cation, each represents a Li ⁺ ion, a Na ⁺ ion, a K ⁺ ion, or an NH ₄ ⁺ ion.)

M represents a hydrogen atom, Li ⁺ ion, Na ⁺ ion, K ⁺ ion, or NH ₄ ⁺ ion, particularly preferably Na ⁺ ion, K ⁺ ion, or NH ₄ ⁺ ion, and more preferably Na ⁺ ion or K ⁺ ion. Of these, K ⁺ ions are most preferable. In the dye represented by the general formula (Y), it is preferable that the counter cation is K ⁺ ion is the main component of M, and more preferably all M is K ⁺ ion.
The dye represented by formula (Y) may be in the form of a mixed salt in which a plurality of types of M are present. In the case of a mixed salt, the M of the dye represented by formula (Y) contained in the ink preferably has a molar fraction of 50 to 100%, more preferably 80 to 100%, of which 90 It is preferred that ~ 100% of M is K ⁺ ions. As M other than K ⁺ ions, Na ⁺ ions and NH ₄ ⁺ ions are preferable, and Na ⁺ ions are more preferable.

Further, it is most preferable that M of the dye represented by the general formula (Y) contained in the coloring composition, not the mixed salt, is a K ⁺ ion. Since all M is a K ⁺ ion, in a molecular dispersion state dissolved in an aqueous solution or an ink solution, a carboxy group that is an ionic hydrophilic group or a salt thereof (—CO ₂ M) is dissociated to —CO _2. By exchanging cation species in an ionized state of ⁻ and M ⁺ , it is easy to suppress the formation of a salt state that is less soluble in an aqueous solution or ink solution and precipitation in the salt state of the colorant. This is because such an effect is obtained.
Among the compounds of the general formula (Y), it is preferable to use a compound of the following formula (Y-1).

  Formula (Y-1)

  General formula (Y-2):

In general formula (Y-2), R ₄ each independently represents a monovalent group, R ₅ independently represents —OR ₆ or —NHR ₇ , and R ₆ and R ₇ each independently represent a hydrogen atom or Represents a monovalent group, X ₃ represents a divalent linking group, n ₃ represents 0 or 1, Ar ₃ independently represents a divalent heterocyclic group, and Ar ₄ independently represents an alkyl group. Represents an aryl group or a monovalent triazine ring group.

General formula (Y-2) is demonstrated.
(Substituent)
First, the substituent in general formula (Y-2) is demonstrated.
The substituent may be any group that can be substituted, such as a halogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group. , Carboxyl group (may be a salt), alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group) , Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfur Moyl group, sulfo group (may be a salt), alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group Phosphinyloxy group, phosphinylamino group, silyl group and the like.
These substituents may be further substituted, and examples of the further substituent include groups selected from the substituents described above. Examples of the substituent having a further substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Specific examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

In General Formula (Y-2), R ₄ represents a monovalent substituent, R ₅ represents —OR ₆ or —NHR ₇ , and R ₆ and R ₇ represent a hydrogen atom or a monovalent substituent.
Examples of the monovalent group represented by R ₄ , R ₆ and R ₇ 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, and a hydroxyl group. , Nitro group, carboxyl group (may be a salt), alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (anilino group) ), Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, Sul Famoyl group, sulfo group (may be a salt), alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group Phosphinyloxy group, phosphinylamino group, silyl group and the like.

The monovalent group represented by R ₄ , R ₆ and R ₇ will be described in more detail.
Examples of the halogen atom represented by R ₄ , R ₆ and R ₇ include a chlorine atom, a bromine atom and an iodine atom.
The alkyl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted alkyl group. The alkyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group, but include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (may be in the form of a salt), and a carboxyl group (in the form of a salt). May be preferred). Examples of the alkyl group include methyl, ethyl, propyl, n-butyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, hydroxyethyl, cyanoethyl and 4-sulfobutyl.

The cycloalkyl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted cycloalkyl group. The cycloalkyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the cycloalkyl group include cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl and the like.

The aralkyl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted aralkyl group. The aralkyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the aralkyl include benzyl and 2-phenethyl.
The alkenyl group represented by R ₄ , R ₆ and R ₇ includes a linear, branched or cyclic substituted or unsubstituted alkenyl group. The alkenyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the alkenyl group include vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl and the like.

The alkynyl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted alkynyl group. The alkynyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the alkynyl group include ethynyl, propargyl and the like.
The aryl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted aryl group. The aryl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the aryl group include phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl, and the like.
The heterocyclic group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted heterocyclic group. The heterocyclic group represented by R ₄ , R ₆ and R ₇ is a monovalent group in which one hydrogen atom is removed from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. And a 5- to 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms is more preferable. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the heterocyclic group include 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl and the like.

The alkoxy group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted alkoxy group. The alkoxy group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryloxy group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted aryloxy group. The aryloxy group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy and the like.
The silyloxy group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted silyloxy group. The silyloxy group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted silyloxy group having 3 to 20 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the silyloxy group include trimethylsilyloxy and t-butyldimethylsilyloxy.
The heterocyclic oxy group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted heterocyclic oxy group. The heterocyclic oxy group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the heterocyclic oxy group include 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy and the like.

The acyloxy group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted acyloxy group. Examples of the alkyloxy group represented by R ₄ , R ₆ and R ₇ include a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms. Groups are preferred. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the acyloxy group include formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy and the like.
The carbamoyloxy group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted carbamoyloxy group. The carbamoyloxy group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the carbamoyloxy group include N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy and the like. Is mentioned.

The alkoxycarbonyloxy group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted alkoxycarbonyloxy group. The alkoxycarbonyloxy group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy and the like.
The aryloxycarbonyloxy group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted aryloxycarbonyloxy group. The aryloxycarbonyloxy group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, p- (n-hexadecyloxy) phenoxycarbonyloxy and the like.

The amino group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted amino group. The R _4, an amino group represented by _{R 6} and _{R 7,} substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms preferably. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the amino group include amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino and the like.
The acylamino group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted acylamino group. Examples of the acylamino group represented by R ₄ , R ₆ and R ₇ include a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms. Is preferred. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the acylamino group include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino and the like.
The aminocarbonylamino group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted aminocarbonylamino group. The aminocarbonylamino group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the aminocarbonylamino group include carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like.

The alkoxycarbonylamino group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino and the like.
The aryloxycarbonylamino group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m- (n-octyloxy) phenoxycarbonylamino and the like.

The sulfamoylamino group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted sulfamoylamino group. The sulfamoylamino group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the sulfamoylamino group include sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino and the like.
The alkyl or arylsulfonylamino group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted alkyl or arylsulfonylamino group. Examples of the alkyl or arylsulfonylamino group represented by R ₄ , R ₆ and R ₇ include a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms. preferable. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the alkyl or arylsulfonylamino group include methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like.

The alkylthio group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted alkylthio group. The alkylthio group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the alkylthio group include methylthio, ethylthio, n-hexadecylthio and the like.
The arylthio group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted arylthio group. The arylthio group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the arylthio group include phenylthio, p-chlorophenylthio, m-methoxyphenylthio and the like.
The heterocyclic thio group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted heterocyclic thio group. The heterocyclic thio group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the heterocyclic thio group include 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio and the like.

The sulfamoyl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted sulfamoyl group. The sulfamoyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the sulfamoyl group include N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl) and the like.
The alkyl or arylsulfinyl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted alkyl or arylsulfinyl group. The alkyl or arylsulfinyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the alkyl or arylsulfinyl group include methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl and the like.
The alkyl or arylsulfonyl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted alkyl or arylsulfonyl group. As the alkyl or arylsulfonyl group represented by R ₄ , R ₆ and R _7, a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms is preferable. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the alkyl or arylsulfonyl group include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl and the like.

The acyl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted acyl group. Examples of the acyl group represented by R ₄ , R ₆ and R ₇ include a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, and a carbon number A heterocyclic carbonyl group bonded to a carbonyl group with 4 to 30 substituted or unsubstituted carbon atoms is preferred. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the acyl group include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p- (n-octyloxy) phenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl and the like.

The aryloxycarbonyl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted aryloxycarbonyl group. The aryloxycarbonyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p- (t-butyl) phenoxycarbonyl, and the like.
The alkoxycarbonyl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and the like.
The carbamoyl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted carbamoyl group. The carbamoyl group represented by R ₄ , R ₆ and R ₇ is preferably a C 1-30 substituted or unsubstituted carbamoyl group. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl and the like.

The phosphino group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted phosphino group. A substituted or unsubstituted phosphino group having 2 to 30 carbon atoms represented by R ₄ , R ₆ and R ₇ is preferred. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the phosphino group include dimethylphosphino, diphenylphosphino, methylphenoxyphosphino and the like.
The phosphinyl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted phosphinyl group. A substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms represented by R ₄ , R ₆ and R ₇ is preferable. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the phosphinyl group include phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl and the like.
The phosphinyloxy group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted phosphinyloxy group. A substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms represented by R ₄ , R ₆ and R ₇ is preferred. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the phosphinyloxy group include diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.
The phosphinylamino group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted phosphinylamino group. A substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms represented by R ₄ , R ₆ and R ₇ is preferable. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the phosphinylamino group include dimethoxyphosphinylamino and dimethylaminophosphinylamino.
The silyl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted silyl group. A substituted or unsubstituted silyl group having 3 to 30 carbon atoms is preferred. Examples of the substituent include the groups described in the above-mentioned substituent group. Examples of the silyl group include trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl and the like.

In general formula (Y-2), R ₄ is preferably an alkyl group, an aryl group, or a heterocyclic group, more preferably an alkyl group, still more preferably methyl, ethyl, propyl, n-butyl, or t-butyl, and t- Butyl is more preferred.
R ₅ is preferably —NHR ₇ .
R ₆ and R ₇ are preferably a hydrogen atom, an alkyl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, more preferably a hydrogen atom, an alkyl group, or an acyl group, and particularly preferably a hydrogen atom.

In General Formula (Y-2), X ₃ represents a divalent linking group. Examples of the divalent linking group represented by X ₃ include an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene), an alkenylene group (eg, ethenylene, propenylene), an alkynylene group (eg, ethynylene, propynylene). ), Arylene groups (eg, phenylene, naphthylene), divalent heterocyclic groups (eg, 6-chloro-1,3,5-triazine-2,4-diyl group, pyrimidine-2,4-diyl group, quinoxaline) 2,3-diyl group), - O -, - CO -, - NR- (R is a hydrogen atom, an alkyl group or an aryl _{group), - S -, - SO} 2 -, - SO- , or a combination thereof Can be mentioned.
The alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, or alkyl group or aryl group represented by R may have a substituent. Examples of the substituent include the groups described in the above-mentioned substituent group, but include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (may be in the form of a salt), and a carboxyl group (in the form of a salt). May be preferred).
X ₃ is preferably an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, a divalent heterocyclic group, O-, -S-, or a combination thereof.
The total carbon number of the divalent linking group represented by X ₃ is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

n ₃ is 0 or 1, and 1 is preferable.

Ar ₃ represents a divalent heterocyclic group. Heterocycles are preferably 5-membered or 6-membered rings, and they may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. Specifically, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole Benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like.
Among these, aromatic heterocyclic groups are preferable, pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, and thiadiazole are more preferable, and thiadiazole is the most. preferable.
The divalent heterocyclic group represented by Ar ₃ may have a substituent, and examples of the substituent include the groups described in the above-mentioned substituent section.

Ar ₄ represents an alkyl group, an aryl group, or a monovalent triazine ring group.
The alkyl group and aryl group represented by Ar ₄ are synonymous with the alkyl group and aryl group represented by R ₄ , R ₆ and R ₇ , and the preferred range is also the same.
Ar ₄ is preferably an aryl group or a monovalent triazine ring group, more preferably an aryl group, and still more preferably phenyl.
In Ar _4, the alkyl group, aryl group, or monovalent triazine ring group may further have a substituent, and examples of the substituent include the groups described in the above-mentioned substituent group. However, a sulfo group or a carboxyl group is preferable.

In General Formula (Y-2), the plurality of R ₄ , the plurality of R ₅ , the plurality of Ar _4, and the plurality of Ar ₃ may be the same as or different from each other.

The compound represented by the general formula (Y-2) of the present invention is used as a yellow dye. For this reason, from the viewpoint of increasing solubility, R ₄ , R ₆ or R ₇ has an ionic hydrophilic group, or R ₄ , R ₆ , R ₇ , Ar ₄ or Ar ₃ has a ionic hydrophilic group as a substituent. It preferably has a functional group.
Here, the ionic hydrophilic group includes a sulfo group, a carboxyl group, a phosphono group, a quaternary ammonium group, and the like. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and among them, a carboxyl group and a sulfo group are preferable. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. 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, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal salts are preferable. Of the alkali metal salts, potassium ion, sodium ion and lithium ion are preferable, and sodium ion and potassium ion are most preferable.
In general formula (Y-2), it is particularly preferable that Ar ₄ has an ionic hydrophilic group.

  Specific examples of the dye represented by formula (Y-2) are shown below, but the present invention is not limited thereto.

  The dyes represented by the general formula (Y), the formula (Y-1) and the general formula (Y-2) can be synthesized by a general synthesis method. For example, JP-A-2004-083903 [0066] And the method described in [0067].

  When the compound represented by the general formula (Y), formula (Y-1) and general formula (Y-2) is used as a yellow dye, the maximum absorption wavelength of 380 to 490 nm in an aqueous solution from the viewpoint of color reproducibility. (λmax) is preferred, λmax of 400 to 480 nm is further preferred, and λmax is particularly preferred of 420 to 460 nm.

  Furthermore, in the present invention, the general formula (Y), the formula (Y-1) or the general formula (Y) is used within a range that does not significantly impair the light resistance and ozone resistance in order to adjust the color tone of the yellow ink composition. In addition to the compound represented by Y-2), other yellow dyes can be used in combination.

  Examples of the yellow dye used in combination include C.I. I. Direct yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 59, 68, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 142, 144, 161, 163, C.I. I. 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, C.I. I. Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, C.I. I. Basic yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40 and the like can be mentioned, but are not limited thereto.

In the present invention, the content of the colorant in the yellow ink composition (the total amount when a plurality of colorants are used) can be appropriately determined according to the color value of the compound (dye) used as the colorant. However, it is preferably 1.0 to 6.0% by mass relative to the total mass of the yellow ink composition. By making the content of the colorant in the yellow ink composition 1.0% by mass or more, good color developability can be obtained, and by making the content of the colorant 6.0% by mass or less, It is possible to improve the properties such as ejection properties from the nozzles required as an ink composition for use in the ink jet recording method, and to prevent clogging of the ink nozzles.
In particular, the content of the compound represented by formula (Y), formula (Y-1) or formula (Y-2) or a salt thereof in the yellow ink composition is based on the total mass of the yellow ink composition. It is preferable that it is 1.5-5.5 mass% with respect to it, and it is more preferable that it is 2.0-5.5 mass%.

Since the dye represented by the general formula (Y), formula (Y-1) or general formula (Y-2) or a salt thereof is very excellent in light resistance and ozone resistance, the black of the present invention By combining the ink set with ink, cyan ink, and magenta ink, the light resistance and ozone resistance of each color can be dramatically improved, and the color balance of the image is not lost even after the light / ozone exposure test. Therefore, it is possible to maintain a good image quality.
Further, in the yellow ink composition, a dye which is a compound represented by the general formula (Y), formula (Y-1) or general formula (Y-2) or a salt thereof, and the yellow which can be used in the above-described present invention. By using together with a system dye (for example, CI Direct Yellow 58), it becomes possible to adjust to a more preferable color balance, and the image quality of the printed matter can be kept good for a longer period of time.

(Magenta)
Next, the colorant used in the magenta ink composition constituting the ink set of the present invention will be described.

  In the ink set of the present invention, the colorant used in the magenta ink composition is not limited to the colorant having a specific structure, but the light resistance / ozone resistance of the ink composition of other colors and the magenta ink composition It is preferable that the difference between light resistance and ozone resistance is small.

From the above viewpoint, the magenta dye used as a colorant in the magenta ink composition in the present invention is preferably a compound selected from the group consisting of a compound represented by the following general formula (M-1) and a salt thereof.
General formula (M-1):

In the general formula (M-1), A _M represents a 5-membered heterocyclic group.
B ₁ and _{B 2} are each _-CR 13 =, - or represents _{CR 14} =, or either one is a nitrogen atom, the other represents _{-CR 13} = or _{-CR 14} =.
R ₁₁ and R ₁₂ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl. Represents a group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Each group may further have a substituent. However, R ₁₁ and R ₁₂ are not simultaneously hydrogen atoms.
G, R ₁₃ and R ₁₄ 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, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, nitro group, alkyl group substituted by a group or a heterocyclic group A thio group, an arylthio group, an alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a heterocyclic thio group, or an ionic hydrophilic group. Each group may be further substituted with these groups. R ₁₃ and R ₁₁ , or R ₁₁ and R ₁₂ may be bonded to form a 5- or 6-membered ring. However, General Formula (M-1) has at least one ionic hydrophilic group.
Here, the ionic hydrophilic group includes a sulfo group, a carboxyl group, a phosphono group, a quaternary ammonium group, and the like. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and among them, a carboxyl group and a sulfo group are preferable. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. 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, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal salts are preferable. Of the alkali metal salts, potassium ion, sodium ion and lithium ion are preferable, and sodium ion and potassium ion are most preferable.

General formula (M-1) is demonstrated.
A _M represents a 5-membered heterocyclic group. Examples of heteroatoms of the 5-membered heterocycle include N, O, and S. A _M is preferably a nitrogen-containing 5-membered heterocycle, and an aliphatic ring, an aromatic ring or another heterocycle may be condensed to the heterocycle. Examples of preferred heterocycles of A _M can be given pyrazole ring, an imidazole ring, a triazole ring, a thiazole ring, isothiazole ring, thiadiazole ring, benzothiazole ring, benzoxazole ring, or benzisothiazole ring. Each heterocyclic group may further have a substituent. Of these, heterocyclic rings represented by the following general formulas (a) to (i) are preferable.

In formula _{(a) ~ (i),} Rm 1 ~Rm 20 have the same meanings as _{R 13} and _{R 14} in formula (M-1).
Of the general formulas (a) to (i), (a) to (h) are preferable, (a) to (e), (g), and (h) are more preferable, and (a) is particularly preferable.
Rm ₁ is preferably an electron-withdrawing group having a Hammett substituent constant σp value of 0.20 or more, more preferably a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, or a halogen atom, and a cyano group, an alkyl group A sulfonyl group and an arylsulfonyl group are more preferable, and a cyano group is most preferable.
Rm ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, or an acyl group, more preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, carbon atoms 1-6 alkyl groups are particularly preferred.
Rm ₃ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group or a heterocyclic group, more preferably an aryl group or a heterocyclic group substituted with an electron-withdrawing group, A heterocyclic group substituted with an attractive group (preferably an electron-withdrawing group having Hammett's substituent constant σp value of 0.20 or more) is more preferable. As this hetero ring, a benzothiazole ring and a benzoxazole ring are preferable, and a benzothiazole ring is more preferable. Each of these groups may further have a substituent.
Rm _{4 to} Rm ₂₀ are preferably a hydrogen atom, an alkyl group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, or a heterocyclic group, and more preferably a hydrogen atom, an alkyl group, a cyano group, a carboxyl group, or a heterocyclic group. .

In General Formula (M-1), B ₁ and B ₂ each represent -CR ₁₃ =, -CR ₁₄ =, or either one is a nitrogen atom and the other is -CR ₁₃ = or -CR ₁₄ =. To express. The case where B ₁ and B ₂ each represent —CR ₁₃ ═ and —CR ₁₄ ═ is preferable in terms of exhibiting more excellent performance.

R ₁₁ and R ₁₂ are each independently a hydrogen atom, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group, substituted or An unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group is preferred, a hydrogen atom, a substituted aryl group, and a substituted heterocyclic group are more preferred, and among them, a substituted aryl group and a substituted heterocyclic group are particularly preferred. However, R ₁₁ and R ₁₂ are not simultaneously hydrogen atoms. The substituted aryl is preferably a substituted phenyl, and examples of the substituent include an alkyl group (such as a methyl group, an ethyl group, an i-propyl group, and a t-butyl group), a carboxyl group, and a sulfo group. Examples of the hetero ring of the substituted heterocyclic group include pyrazole ring, imidazole ring, triazole ring, thiazole ring, isothiazole ring, thiadiazole ring, benzothiazole ring, benzoxazole ring, benzoisothiazole ring, and benzothiazole ring. Is preferred. Examples of the substituent of the substituted heterocyclic group include an alkyl group, a carboxyl group, and a sulfo group, and a sulfo group is preferable.

G, R ₁₃ and R ₁₄ 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, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, nitro group, alkyl group substituted by a group or heterocyclic group A thio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a heterocyclic thio group, or an ionic hydrophilic group. Each group may be further substituted with these groups.

Halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, alkoxy group, aryl represented by G, R ₁₃ , R ₁₄ Oxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino As the group, alkyl or arylsulfonylamino group, alkylthio group, arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, sulfamoyl group, heterocyclic thio group, Substituents substituent J described can be mentioned.

G represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, a heterocyclic oxy group, an alkyl group, an aryl group, or a heterocyclic ring. Group substituted amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio Group or ionic hydrophilic group is preferred. Each group may be further substituted.
G is more preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group substituted with an alkyl group, an aryl group or a heterocyclic group, or an acylamino group. Among them, an amino group substituted with a hydrogen atom, an aryl group or a heterocyclic group (here, a phenyl group is preferred as the aryl group), an acylamino group is particularly preferred, and the aryl group is substituted with an aryl group having a substituent. Examples of the substituent include a halogen atom, an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), an alkoxy group, and an ionic hydrophilic group. Most preferably, they may combine with each other to form a ring.

R ₁₃ and R ₁₄ are each independently preferably a hydrogen atom, an alkyl group, a cyano group, a carboxyl group, a carbamoyl group, or an alkoxycarbonyl group. Each group may be further substituted. R ₁₃ and R ₁₄ are more preferably a hydrogen atom, an alkyl group, a cyano group, or a carboxyl group. Among them, R ₁₃ is preferably a hydrogen atom and R ₁₄ is an alkyl group, and particularly, R ₁₃ is a hydrogen atom, R ₁₄ Is most preferably a methyl group.

  A particularly preferable combination as the compound represented by the general formula (M-1) includes the following (A) to (D).

(B) As the heterocyclic ring A _M represents a pyrazole ring, an imidazole ring, a triazole ring, a thiazole ring, isothiazole ring, thiadiazole ring, benzothiazole ring, benzoxazole ring, or benzisothiazole ring, more preferably a pyrazole ring , An imidazole ring, a triazole ring, a thiazole ring, an isothiazole ring, and a thiadiazole ring are preferable, and among them, a pyrazole ring, a triazole ring, a thiazole ring, an isothiazole ring, and a thiadiazole ring are preferable, and a pyrazole ring is most preferable.

(B) B ₁ and B ₂ preferably represent —CR ₁₃ ═ and —CR ₁₄ ═, respectively, R ₁₃ is a hydrogen atom (B ₁ is an unsubstituted carbon atom), and R ₁₄ is a hydrogen atom or alkyl. Group (a carbon atom in which B ₂ is unsubstituted or substituted with an alkyl group) is preferred, in particular, R ₁₃ is a hydrogen atom (B ₁ is an unsubstituted carbon atom), R ₁₄ is a methyl group (B ₂ is substituted with a methyl group) Carbon atoms) are most preferred.

(C) R ₁₁ and R ₁₂ are each independently a hydrogen atom, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group A substituted or unsubstituted alkylsulfonyl group and a substituted or unsubstituted arylsulfonyl group are preferable, and a hydrogen atom, a substituted aryl group, and a substituted heterocyclic group are more preferable. Among them, a substituted aryl group and a substituted heterocyclic group are preferable, and An aryl group substituted with a sulfo group and a heterocyclic group substituted with a sulfo group are preferred, and a phenyl group substituted with a sulfo group and a benzothiazole group substituted with a sulfo group are particularly preferred.

  (D) G is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, a heterocyclic oxy group, an alkyl group or an aryl group Or an amino group substituted with a heterocyclic group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, A heterocyclic thio group or an ionic hydrophilic group is preferable, and further substituted with a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an alkyl group, an aryl group, or a heterocyclic group Ami Group and acylamino group are preferable, and among them, an amino group substituted with a hydrogen atom, an aryl group or a heterocyclic group, and an acylamino group are particularly preferable, an amino group substituted with an aryl group having a substituent is more preferable, and a substituent ( Most preferred is an amino group substituted with a phenyl group having a methyl group, an ethyl group, an isopropyl group, a sulfo group, or the like.

  As for the preferred combination of substituents of the compound represented by formula (M-1), a compound in which at least one of various substituents is the above preferred group is preferable, and more various substituents are the above preferred groups. Are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

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

In the general formula _{(M-2), A M} , B 1, B 2, R 11 and _{R 12, A} M in the general formula (M-1), and B _1, B _{2, R 11} and _{R 12} It is synonymous.
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 they may be further substituted.
b, c and d are each independently synonymous with R ₁₃ and R _14, and may be bonded to each other at a and b or e and d to form a ring. However, General Formula (M-2) has at least one ionic hydrophilic group.

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

B _{1, B 2,} the formula (M-1) is _B 1, _{B 2} and synonymous, and preferred examples are also the same.

R _{11, R 12} has the same meaning as _{R 11, R 12} in formula (M-1), and preferred examples thereof are also the same.

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.
More preferably, a and e are each independently preferably a methyl group, an ethyl group or an isopropyl group, more preferably an ethyl group or an isopropyl group, and most preferably a = b = ethyl group or isopropyl group.

b, c and d are each independently synonymous with R ₁₃ and R _{14 in the} general formula (M-1), and a and b or e and d may be bonded to each other to form a ring. Good. However, General Formula (M-2) has at least one ionic hydrophilic group.
More preferably, c is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group.
b and d are preferably a hydrogen atom or an ionic hydrophilic group. Among them, a hydrogen atom, a sulfo group, or a carboxy group is preferable, and a combination of b and d is most preferably a hydrogen atom and a sulfo group.

  A particularly preferable combination as the compound represented by the general formula (M-2) includes the following (A) to (D).

Examples of heterocycles (i) A _M has the same meaning as A _M in formula (M-1), and preferred examples thereof are also the same.

(Ii) _{B 1} and _{B 2} have the same meanings as _{B 1} and _{B 2} in the general formula (M-1), and preferred examples thereof are also the same.

_(C) R _{11, R 12} has the same meaning as _{R 11, R 12} in formula (M-1), and preferred examples thereof are also the same.

  (D) a and e are preferably alkyl groups or halogen atoms. When both a and e are alkyl groups, they are unsubstituted alkyl groups, and the total number of carbon atoms of a and e is 3 or more (preferably 5 or less). And b, c and d are each a hydrogen atom, a halogen atom, an alkyl group or an ionic hydrophilic group (preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an ionic hydrophilic group). Is preferred. More preferably, a and e are each independently preferably a methyl group, an ethyl group or an isopropyl group, more preferably an ethyl group or an isopropyl group, and most preferably a = b = ethyl group or isopropyl group. Furthermore, c is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom or a methyl group. b and d are preferably a hydrogen atom or an ionic hydrophilic group. Among them, a hydrogen atom, a sulfo group, or a carboxy group is preferable, and a combination of b and d is most preferably a hydrogen atom and a sulfo group.

  As for the preferred combination of substituents of the compound represented by the general formula (M-2), a compound in which at least one of various substituents is the above preferred group is preferable, and more various substituents are the above preferred groups. Are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

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

In the general formula (M-3), Z ₁₁ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.2 or more. Z ₁₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group, a heterocyclic group or an acyl group. R ₁₁ , R ₁₂ , a, b, c, d and e have the same meanings as those in the general formula (M-2). R _{13, R 14} has the same meaning as _{R 13, R 14} in formula (M-2). Q represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group or a heterocyclic group. Each of the groups Z ₁₁ , Z ₁₂ and Q may further have a substituent. However, General Formula (M-3) has at least one ionic hydrophilic group.

In general formula (M-3),
R _{13, R 14,} the formula (M-1) have the same meaning as _{R 13, R 14,} and preferable examples thereof are also the same.
R _{11, R 12} has the same meaning as _{R 11, R 12} in formula (M-1), and preferred examples thereof are also the same.
a, b, c, d and e have the same meanings as a, b, c, d and e in formula (M-2), and preferred examples are also the same.

In the general formula (M-3), the electron-withdrawing group of Z _{11 is} an electron-withdrawing group having a Hammett's substituent constant σp value of 0.2 or more, preferably 0.3 or more. The upper limit of the σp value is preferably 1 or less.

  Specific examples of the electron withdrawing group having a σp value of 0.2 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diaryl Phosphono group, diarylphosphinyl group, alkylsulfinyl, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, sulfo group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, Halogenated alkoxy groups, halogenated aryloxy groups, halogenated alkylamino groups, halogenated alkylthio groups, heterocyclic groups, halogen atoms, azo groups, selenocyanate groups, and other electron withdrawing properties with a σp value of 0.2 or more Aryl groups substituted by groups Is mentioned.

Z ₁₁ is preferably a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, or a halogen atom, more preferably a cyano group, an alkylsulfonyl group, or an arylsulfonyl group, and most preferably a cyano group.

Z ₁₂ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, or an acyl group, and more preferably an alkyl group. Each substituent may be further substituted.
More specifically, the alkyl group as Z ₁₂ includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms excluding the carbon atoms of the substituent, and more preferably an alkyl group having 1 to 6 carbon atoms.
Examples of the substituent that Z ₁₂ has include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

Examples of the alkyl group represented by Z ₁₂ include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl, and among them methyl , Ethyl, isopropyl and t-butyl are preferred, isopropyl and t-butyl are particularly preferred, and t-butyl is most preferred.

The cycloalkyl group represented by Z ₁₂ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms excluding the carbon atoms of the substituent. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The aralkyl group represented by Z ₁₂ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms excluding the carbon atom of the substituent is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

The aryl group represented by Z ₁₂ includes an aryl group having a substituent and an unsubstituted aryl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms excluding the carbon atoms of the substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, an amide group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a hydroxyl group, an ester group, and an ionic hydrophilic group. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

The heterocyclic group represented by Z ₁₂ includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent include an amide group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a hydroxyl group, an ester group, and an ionic hydrophilic group. Examples of the heterocyclic group include a 2-pyridyl group, a 2-thienyl group, a 2-thiazolyl group, a 2-benzothiazolyl group, and a 2-furyl group.

The acyl group represented by Z ₁₂ includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 12 carbon atoms excluding the carbon atoms of the substituent. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

In General Formula (M-3), Q represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group, or a heterocyclic group. Each of these substituents may be further substituted. The details of these substituents are the same as those for R ₁₃ and R ₁₄ .
Q is preferably an aryl group or a heterocyclic group substituted with an electron withdrawing group. The electron withdrawing group serving as a substituent for Q is an electron withdrawing group having a Hammett's substituent constant σp value of 0.2 or more, preferably 0.3 or more. The upper limit of the σp value is preferably 1 or less.
Specific examples of the electron withdrawing group having a σp value of 0.2 or more are the same as Z ₁₁ in the general formula (M-3).
More specifically, Q is preferably a heterocyclic group substituted with an electron withdrawing group, and among them, a benzoxazole ring substituted with a sulfo group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, A benzothiazole ring is preferred, and a benzothiazole ring substituted with a sulfo group or a substituted sulfamoyl group is most preferred.

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

(A) Z ₁₁ is an electron withdrawing group having a Hammett's substituent constant σp value of 0.2 or more, preferably 0.3 or more. The upper limit of the σp value is preferably 1 or less. Z ₁₁ is more preferably a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, or a halogen atom, more preferably a cyano group, an alkylsulfonyl group, or an arylsulfonyl group, and most preferably a cyano group.

(B) Z ₁₂ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, or an acyl group, and more preferably an alkyl group. Each substituent may be further substituted. More specifically, the alkyl group as Z ₁₂ includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms excluding the carbon atoms of the substituent, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group. Among them, methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl are preferable, isopropyl and t-butyl are particularly preferable, and t-butyl is preferable. Most preferred.

  (C) Q represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group or a heterocyclic group. Each of these substituents may be further substituted. Furthermore, Q is preferably an aryl group or a heterocyclic group substituted with an electron withdrawing group. The electron withdrawing group serving as a substituent for Q is an electron withdrawing group having a Hammett's substituent constant σp value of 0.2 or more, preferably 0.3 or more. The upper limit of the σp value is preferably 1 or less. More specifically, a heterocyclic group substituted with a Q electron withdrawing group is preferred, and among them, a benzoxazole ring substituted with a sulfo group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, benzothiazole A ring is preferable, and a benzothiazole ring substituted with a sulfo group or a substituted sulfamoyl group is most preferable.

  (D) a, b, c, d and e have the same meanings as a, b, c, d and e in formula (M-2), and preferred examples are also the same.

_{(E) R 13} and _{R 14} have the same meanings as _{R 13} and _{R 14} in the formula (M-2), and preferred examples thereof are also the same.

_(Vi) R _{11, R 12} has the same meaning as _{R 11, R 12} in the above formula (M-2), and preferred examples thereof are also the same.

  As for the preferred combination of substituents of the compound represented by formula (M-3), a compound in which at least one of various substituents is the above preferred group is preferable, and more various substituents are the above preferred groups. Are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

The compounds (azo dyes) represented by the general formulas (M-1), (M-2), and (M-3) have at least one ionic hydrophilic group in the molecule (preferably 3 or more and 6). Or less).
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, and among them, a carboxyl group and a sulfo group are preferable. In particular, at least one is most preferably a sulfo group. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. 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, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal salts are preferable. Among alkali metal salts, potassium ion, sodium ion and lithium ion are preferable, and lithium ion is most preferable. In particular, from the viewpoint of improving solubility and suppressing bronzing in ink jet printing, a combination of an ionic hydrophilic group being a sulfo group and a counter ion being lithium ion is most preferable.

  The compounds represented by the general formulas (M-1), (M-2), and (M-3) preferably have 3 or more and 6 or less ionic hydrophilic groups in the molecule, and have 3 sulfo groups. It is more preferable to have one or more and six or less, and it is even more preferable to have three or more and five or less sulfo groups.

  Specific examples of the compounds represented by the general formulas (B-11), (B-12), (B-13), and (B-14) are shown below, but the compounds used in the present invention are: It is not limited to the following example.

  The magenta ink composition according to the present invention may contain, as a colorant, at least one selected from the compounds represented by the general formulas (M-1), (M-2), and (M-3) and salts thereof. preferable.

  The ink set of the present invention can include inks having different color densities as the magenta ink composition, for example, a dark magenta ink composition and a light magenta ink composition. When both the dark magenta ink composition and the light magenta ink composition are included in the ink set, at least one of the two is a compound of the general formula (M-1), (M-2), (M-3) or a salt thereof. It is preferable to include as a colorant, and it is more preferable that the light magenta ink composition includes a compound of the general formulas (M-1), (M-2), and (M-3)) or a salt thereof as a colorant. By improving the light resistance and ozone resistance of the light magenta ink composition, the light resistance and ozone resistance of the image of the entire recorded matter can be improved. Most preferably, both the dark magenta ink composition and the light magenta ink composition contain the compound of the above general formula (M-1), (M-2), (M-3)) or a salt thereof as a colorant. That is.

  In the ink set of the present invention, the content of the magenta dye in the magenta ink composition is the color value of the compound (dye) of the general formulas (M-1), (M-2), and (M-3) used. Can be appropriately determined based on the above. When only one type of magenta ink composition is included in the ink set, the compound of general formula (M-1), (M-2), (M-3)) or a salt thereof in the magenta ink composition is generally used. The content of is preferably 2.0 to 10% by mass. By setting the content of the dye in the magenta ink composition to 2.0% by mass or more, it is possible to ensure sufficient color developability as an ink, and further to the inkjet recording method by setting the content to 10% by mass or less. As the ink composition to be used, it becomes easy to ensure the dischargeability from the nozzles, prevent nozzle clogging, and the like.

Further, when the dark magenta ink composition and the light magenta ink composition are included in the ink set, the content of the colorant in the light magenta ink composition is represented by the general formulas (M-1) and (M- 2) and can be appropriately selected according to the color value of the compound (dye) of (M-3), but in general, the general formulas (M-1) and (M-2) in the light magenta ink composition The content of the compound (M-3) or a salt thereof is preferably 0.5 to 3.5% by mass, and more preferably 1.0 to 3.0% by mass. By making the content of the dye in the light magenta ink composition 0.5% by mass or more, it is possible to ensure the color developability necessary for the light magenta ink composition, and the content is 3.5% by mass. The graininess in the image of the recorded matter recorded using the light magenta ink composition can be reduced or prevented by the following.
Further, when the dark magenta ink composition and the light magenta ink composition are included in the ink set, the content of the colorant in the dark magenta ink composition is represented by the general formulas (M-1) and (M- 2) and can be appropriately selected according to the color value of the compound (dye) of (M-3), but in general, the general formulas (M-1) and (M-2) in the dark magenta ink composition , (M-3)) or a salt thereof is preferably 3 to 10% by mass. By making the content of the dye in the dark magenta ink composition 3% by mass or more, it is possible to ensure the color developability necessary for the dark magenta ink composition, and making the content 10% by mass or less. Therefore, it is possible to reduce or prevent the graininess in the image of the recorded matter recorded using the light magenta ink composition.

  When a dark magenta ink composition and a light magenta ink composition are included in the ink set, the content (% by mass) of the colorant contained in the light magenta ink composition and the content of the colorant contained in the dark magenta ink composition The ratio to the amount (mass%) is preferably 1: 2 to 1: 8. By configuring the content of the colorant at such a ratio, the graininess of images recorded using these ink compositions can be reduced. Furthermore, by setting the colorant ratio and the ink composition in which the colorant concentration falls within the above-described range, a good color balance can be realized between the dark magenta ink composition and the light magenta ink composition. It is possible to prevent the inkjet nozzle from being clogged.

  The ink set of the present invention is represented by the general formulas (M-1), (M-2), and (M-3) in the magenta ink composition, the dark magenta ink composition, or the light magenta ink composition. The content of the colorant selected from the group consisting of a compound and a salt thereof is determined by the type of each substituent in the general formulas (M-1), (M-2), and (M-3), the type of solvent component, and the like. In the ink composition, including at least one dye selected from compounds of the general formulas (M-1), (M-2), (M-3) and salts thereof contained in the ink composition The total amount of all colorants contained in the ink composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the total mass of the ink composition. By setting the amount of the colorant in the ink composition to 0.1% by mass or more, color developability or image density on the recording medium can be secured, and by adjusting the amount to 10% by mass or less, the viscosity of the ink composition is adjusted. Therefore, characteristics such as ejection reliability and clogging resistance can be easily secured.

  In the magenta ink composition, dark magenta ink composition, or light magenta ink composition of the ink set of the present invention, compounds represented by the general formulas (M-1), (M-2), and (M-3) In addition to the dye selected from the group consisting of salts thereof, other magenta dyes can be used in combination. Examples of magenta dyes that can be used in combination include C.I. I. Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, C.I. I. Direct violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101, C.I. I. Acid Red 35, 42, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 151, 154, 158, 249, 254, 257, 261, 263, 266 289, 299, 301, 305, 336, 337, 361, 396, 397, C.I. I. Acid Violet 5, 34, 43, 47, 48, 90, 103, 126, C.I. I. Reactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55, C.I. I. Reactive violet 1,3,4,5,6,7,8,9,16,17,22,23,24,26,27,33,34, C.I. I. Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46, C.I. I. In addition to basic violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48, etc., a coupling component (hereinafter referred to as coupler component) Heteryl or arylazo dyes (hereinafter referred to as the general formula (M-11)) having phenols, naphthols, anilines, heterocycles such as pyrazine, open-chain active methylene compounds, etc. ); For example, an azomethine dye having an open-chain active methylene compound as a coupler component; an anthrapyridone dye (compound represented by the following general formula (M-12)) (for example, No in Table 1 described in US 2004/023939 A1) 20 compounds and compounds described in WO 04/104108 pamphlet (13) Etc.).

  General formula (M-11):

In the formula, Y represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a phenyl group substituted with OH, SO ₃ H, or COOM, or a naphthyl group. Further, B represents a hydrogen atom or the following formula.

In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms substituted with H, OH, or COOH, and R ₂ is substituted with OH, OCH ₃ , OC ₂ H ₅ , SO ₃ M, or COOM. An alkyl group having 1 to 4 carbon atoms is represented, and M represents H, Li, Na, K, ammonium, or organic amines. R ₃ represents a substituent.

  General formula (M-12):

In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing 5 to 6-membered heterocycle. R ₁ , R ₂ , and R ₃ each independently represent a substituent, and these substituents may further have a substituent. m ₁ represents an integer of 0 to 3, m ₂ represents an integer of 0 to 4, and m ₃ represents an integer of 0 to 2, but m ₁ , m ₂ and m ₃ do not represent 0 at the same time. . When m ₁ is 2 or more, the plurality of R ₁ may be the same as or different from each other. When m ₂ is 2 or more, the plurality of R ₂ may be the same or different from each other, and when m ₃ is 2 or more, the plurality of R ₃ may be the same or different from each other. n represents an integer of 1 to 4. When n is 2 or more, the dye mother nucleus may form a dimer, trimer, or tetramer via R ₁ , R ₂ , or R ₃ .

(cyan)
Hereinafter, the colorant used in the cyan ink composition constituting the ink set of the present invention will be described.

  In the ink set of the present invention, the colorant used in the cyan ink composition is not limited to the colorant having a specific structure, but the light resistance and ozone resistance of the ink composition of other colors and the cyan ink composition It is preferable that the difference between light resistance and ozone resistance is small.

From the above viewpoint, the cyan dye used as a colorant in the cyan ink composition in the present invention is preferably a compound selected from the group consisting of phthalocyanine compounds represented by the following general formula (C-1) and salts thereof. .
General formula (C-1):

In the general formula (C-1), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NV ₁ V ₂ or —CO ₂ NV. _{1 represents} V ₂ , —CO ₂ Z, —CO—Z or a sulfo group. Here, Z represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. Each group may further have a substituent. V ₁ and V ₂ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. Each group may further have a substituent.
Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro Group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, Sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group, Or an ionic hydrophilic group , Each group may have a substituent.
a ₁ ~a ₄ and _b 1 ~b ₄ each represent the number of substituents of _X 1 to X ₄ and _Y 1 to Y _4. A _{1 to} a ₄ are each independently an integer of 0 to 4, and all do not become 0 at the same time. b ₁ ~b ₄ each independently represents an integer of 0-4.
M is a metal atom or an oxide, hydroxide or halide thereof.
Provided that at least one of X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y _3, and Y ₄ is an ionic hydrophilic group or a substituent on the ionic hydrophilic group As a group possessed as

General formula (C-1) is demonstrated.
a ₁ , a ₂ , a ₃ and a ₄ are preferably 0 or 1. a ₁ , a ₂ , a ₃ and a ₄ are 0 or 1, two or more of a ₁ , a ₂ , a ₃ and a ₄ are 1, and b ₁ , b ₂ , b ₃ and b _4. Are preferably integers such that the sum of a ₁ , a ₂ , a ₃ and a ₄ is 4, respectively.

X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NV ₁ V ₂ , —CO ₂ NV ₁ V ₂ , —CO ₂ Z, — It represents either CO-Z or a sulfo group.

Z represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. Each group may further have a substituent. Plural Zs may be the same or different.
Z is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are preferable, Particularly preferred is a substituted alkyl group.

V ₁ and V ₂ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. Each group may further have a substituent.
V ₁ and V ₂ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom, a substituted alkyl group, and a substituted aryl Most preferred is a group or a substituted heterocyclic group.

Examples of the substituent that Z, V ₁ and V ₂ may have include the substituents described in the substituent group A ′.

The substituted or unsubstituted alkyl group represented by Z, V ₁ or V ₂ is preferably an alkyl group having 1 to 30 carbon atoms. In particular, a branched alkyl group is preferred because of increasing the solubility of the dye and the ink stability, and particularly preferred is a case having an asymmetric carbon (use in a racemic form). Examples of the substituent include the substituents that may be possessed by the aforementioned Z, V ₁ and V ₂ , among which a hydroxyl group, an ether group, an ester group, a cyano group, an amino group, an amide group, a sulfone group. An amide group is particularly preferred because it increases the association of the dye and improves the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted cycloalkyl group represented by Z, V ₁ and V ₂ is preferably a cycloalkyl group having 5 to 30 carbon atoms. In particular, the case of having an asymmetric carbon (use in a racemic form) is particularly preferable because of increasing the solubility of the dye and the ink stability. Examples of the substituent include the substituents that may be possessed by the aforementioned Z, V ₁ and V ₂ , among which a hydroxyl group, an ether group, an ester group, a cyano group, an amino group, an amide group, a sulfone group. An amide group is particularly preferred because it increases the association of the dye and improves the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted alkenyl group represented by Z, V ₁ and V ₂ is preferably an alkenyl group having 2 to 30 carbon atoms. In particular, a branched alkenyl group is preferred because it increases the solubility of the dye and the ink stability, and particularly preferred is a case having an asymmetric carbon (use in a racemic form). Examples of the substituent include the substituents that may be possessed by the aforementioned Z, V ₁ and V ₂ , among which a hydroxyl group, an ether group, an ester group, a cyano group, an amino group, an amide group, a sulfone group. An amide group is particularly preferred because it increases the association of the dye and improves the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

_Z, the substituted or unsubstituted alkynyl group represented by _V 1, V _2, is preferably an alkynyl group having 2 to 30 carbon atoms. In particular, a branched alkynyl group is preferred because of increasing the solubility of the dye and the ink stability, and particularly preferred is a case having an asymmetric carbon (use in racemic form). Examples of the substituent include the substituents that may be possessed by the aforementioned Z, V ₁ and V ₂ , among which a hydroxyl group, an ether group, an ester group, a cyano group, an amino group, an amide group, a sulfone group. An amide group is particularly preferred because it increases the association of the dye and improves the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

As the substituted or unsubstituted aralkyl group represented by Z, V ₁ or V ₂ , an alkyl group having 7 to 30 carbon atoms is preferable. In particular, a branched alkyl group is preferred because of increasing the solubility of the dye and the ink stability, and particularly preferred is a case having an asymmetric carbon (use in a racemic form). Examples of the substituent include the substituents that may be possessed by the aforementioned Z, V ₁ and V ₂ , among which a hydroxyl group, an ether group, an ester group, a cyano group, an amino group, an amide group, a sulfone group. An amide group is particularly preferred because it increases the association of the dye and improves the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted aryl group represented by Z, V ₁ and V ₂ is preferably an aryl group having 6 to 30 carbon atoms. Examples of the substituent include the substituents that Z, V ₁ , and V ₂ may have, and among them, the oxidation potential of the dye is noble and the fastness is improved, so the electron withdrawing group. Is particularly preferred.

The heterocyclic group represented by Z, V ₁ and V ₂ is preferably a 5-membered or 6-membered ring, and they may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. The heterocyclic groups represented by Z, V ₁ and V ₂ are exemplified below in the form of a heterocyclic ring with the substitution position omitted, but the substitution position is not limited. It is possible to substitute at position 3, 3 and 4. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole Benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. Among them, an aromatic heterocyclic group is preferable, and preferable examples thereof are exemplified in the same manner as described above. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole And thiadiazole. They may have a substituent, and examples of the substituent include the substituents that Z, V ₁ and V ₂ may have, and the preferred substituent is the aryl group. Substituents and more preferred substituents are the same as the more preferred substituents of the aryl group.

Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro Group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, Sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group, Or an ionic hydrophilic group , Each group may have a substituent.
Among them, hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carbamoyl group, sulfamoyl group, sulfinyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, phosphoryl Group, an acyl group or an ionic hydrophilic group is preferable, and a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a sulfamoyl group, a sulfinyl group, a sulfonyl group and an ionic hydrophilic group are preferable, and a hydrogen atom is particularly preferable.
Y ₁ , Y ₂ , Y ₃ and Y ₄ may have a substituent, if possible. Examples of the substituent are Z, V ₁ , V ₂ in the general formula (C-1) described above. The substituent which may have may be mentioned.

  When the phthalocyanine dye of the present invention is water-soluble, it preferably has an ionic hydrophilic group. 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, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. 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, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal salts are preferable, and lithium salts are particularly preferable because they increase the solubility of the dye and improve the ink stability. The most preferred ionic hydrophilic group is a lithium salt of a sulfo group.

  As the number of ionic hydrophilic groups, those having at least two or more in one molecule of the phthalocyanine dye of the present invention are preferable, and those having at least two sulfo groups and / or carboxyl groups are particularly preferable.

In the general formula (C-1), M is preferably a hydrogen atom or a metal atom, and Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and the like can be given. Examples of the oxide include VO and GeO. Moreover, Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _2, etc. are mentioned as a hydroxide. Moreover, as the _{halide, AlCl, SiCl 2, VCl,} VCl 2, VOCl, FeCl, GaCl, ZrCl , and the like. Among these, M is particularly preferably Cu, Ni, Zn, Al or the like, and Cu is most preferable.

In addition, Pc (phthalocyanine ring) may form a dimer (for example, Pc-MLM-Pc) or a trimer through a divalent linking group L, and M at that time is the same. Or different.
The divalent linking group represented by L includes an oxy group —O—, a thio group —S—, a carbonyl group —CO—, a sulfonyl group —SO ₂ —, an imino group —NH—, a methylene group —CH ₂ —, And a group formed by combining them is preferred.

The chemical structure of the phthalocyanine dye according to the present invention includes a sulfinyl group (—SO—Z); a sulfonyl group (—SO ₂ —Z); a sulfamoyl group (—SO ₂ NV ₁ V ₂ ); a carbamoyl group (—CONV ₁ V). ₂ ); alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group (—CO ₂ Z); acyl group (—CO—Z); an electron-withdrawing group such as sulfo group, and each benzene ring of phthalocyanine It is particularly preferable to introduce at least one each in such a manner that the total of the σp values of the substituents of the entire phthalocyanine skeleton is 1.2 or more. Among them, a sulfinyl group (—SO—Z); a sulfonyl group (—SO ₂ —Z); a sulfamoyl group (—SO ₂ NV ₁ V ₂ ) is preferable, and a sulfonyl group (—SO ₂ —Z); a sulfamoyl group ( -SO ₂ NV ₁ V ₂₎ are preferred, a sulfonyl group _(-SO 2 -Z) is most preferred.

  As for the preferred combination of substituents of the compound represented by the general formula (C-1), a compound in which at least one of various substituents is the preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

In the present invention, the compound represented by the general formula (C-1) is preferably a compound selected from the group consisting of a compound represented by the following general formula (C-2) and a salt thereof.
General formula (C-2):

In General Formula (C-2), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, or cycloalkyl. Group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfa Moylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfinyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, Silyloxy group, aryloxycarbonyl group, aryloxycarbonyl Amino group, an imido group, a heterocyclic thio group, a phosphoryl group, an acyl group or an ionic hydrophilic group. These groups may further have a substituent.
Z ₁ , Z ₂ , Z ₃ , and Z ₄ each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. These groups may further have a substituent, and at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent.
l, m, n, p, q ₁ , q ₂ , q ₃ , and q ₄ each independently represent an integer of 1 or 2.
M is synonymous with the case of general formula (C-1).

  In the present invention, in the general formula (C-2), l, m, n, and p are each independently an integer of 1 or 2, and among them, 2 of l, m, n, and p One or more is preferably 1, and most preferably 1 = m = n = p = 1.

In General Formula (C-2), q ₁ , q ₂ , q ₃ , and q ₄ are each independently an integer of 1 or 2, and among them, q ₁ , q ₂ , q ₃ , and q ₄ Of these, 2 or more are preferably 2, and most preferably q ₁ = q ₂ = q ₃ = q ₄ = 2.

In general formula (C-2), Z ₁ , Z ₂ , Z ₃ , and Z ₄ each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. To express. These groups may further have a substituent, and at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent. Z ₁ , Z ₂ , Z ₃ , and Z ₄ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, A substituted aryl group and a substituted heterocyclic group are preferred, and a substituted alkyl group is most preferred. For example substituents may be mentioned the above-mentioned general formula (C-1) Z _in, V 1, V ₂ has optionally may substituents.

In general formula (C-2), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. A heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a phosphoryl group, an acyl group, or an ionic hydrophilic group, A hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a sulfamoyl group, a sulfinyl group, a sulfonyl group, and an ionic hydrophilic group are preferable, and a hydrogen atom is most preferable.
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ may have a substituent, if possible. (C-1) _{Z in, V 1,} V ₂ can be mentioned substituent which may have.

  In general formula (C-2), M is synonymous with M in general formula (C-1), and preferred examples are also the same.

  As for the preferred combination of substituents of the compound represented by the general formula (C-2), a compound in which at least one of various substituents is the above preferred group is preferable, and more various substituents are the above preferred groups. Are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

In the present invention, the compound represented by the general formula (C-2) is preferably a compound selected from the group consisting of a compound represented by the following general formula (C-3) and a salt thereof.
General formula (C-3):

In the general formula (C-3), Z ₁ , Z ₂ , Z ₃ , Z ₄ , 1, m, n, p and M are the same as Z ₁ , Z ₂ , Z ₃ , Synonymous with Z ₄ , l, m, n, p and M.

  In general formula (C-3), l, m, n, and p are each independently an integer of 1 or 2, and among them, two or more of l, m, n, and p are 1. And preferably 1 = m = n = p = 1.

In the general formula (C-3), Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. Represents. These groups may further have a substituent, and at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent. Z ₁ , Z ₂ , Z ₃ , and Z ₄ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, A substituted aryl group and a substituted heterocyclic group are preferred, and a substituted alkyl group is most preferred. For example substituents may be mentioned the above-mentioned general formula (C-1) Z _in, V 1, V ₂ has optionally may substituents.

More specifically, Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently Z ₁₁ (wherein Z ₁₁ represents — (CH ₂ ) ₃ SO ₃ M ₂ , where M ₂ is an alkali metal) And Z ₁₂ (wherein Z ₁₂ represents — (CH ₂ ) ₃ SO ₂ NHCH ₂ CH (OH) CH ₃ )).
In the cyan dye represented by formula (C-3) in the cyan ink composition, the molar ratio of Z ₁₁ and Z ₁₂ is Z ₁₁ / Z ₁₂ = 4/0, 3/1, 2/2. is preferably a mixture of 1/3 becomes dyes, dye mixtures _Z 11 _{/ Z} 12 = 3/1 among them is the main component, and / or dye _{mixtures Z 11 / Z 12 = 2/} 2 is the main component is Most preferred. Here, the “main component” refers to a component having the largest ratio in the dye mixture.

In — (CH ₂ ) ₃ SO ₄ M ₂ represented by Z ₁₁ , M ₂ is preferably an alkali metal atom, among which lithium, sodium, and potassium ions are preferable, and lithium ion is particularly preferable.

  In general formula (C-3), M is synonymous with M in general formula (C-2), and preferred examples are also the same.

  As for the preferred combination of substituents of the compound represented by formula (C-3), a compound in which at least one of various substituents is the above preferred group is preferable, and more various substituents are the above preferred groups. Are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

  Specific examples of the compounds represented by the general formulas (C-1), (C-2), and (C-3) are shown below, but the compounds used in the present invention are limited to the following examples. It is not something.

  In addition, phthalocyanines represented by M-Pc (Xp1) m (Xp2) n of compounds No. 146 to 192 (M represents Cu, Yq and Yq ′ represent hydrogen atoms, and n + m≈2 to 4). The structure of the compound is as follows.

The phthalocyanine dye can be synthesized according to a known method. The phthalocyanine dye can be synthesized by the methods described in JP-A Nos. 2001-226275, 2001-96610, 2001-47013, and 2001-193638, in addition to the synthesis method described above. it can. Further, the starting material, the dye intermediate and the synthesis route are not limited to these.
The phthalocyanine dye can be used alone, but can be used in combination with other dyes, particularly other phthalocyanine dyes.

In the present invention, the content of the cyan dye contained in the cyan ink composition is, X ₁ to X ₄ and Y ₁ to Y ₄ type in general formula (C-1) used, and the production of ink composition The content of the compound represented by formula (C-1) or the salt thereof in the cyan ink composition is 1 with respect to the total mass of the cyan ink composition. The content is preferably 10 to 10% by mass, and more preferably 2 to 6% by mass.

  When the content of the dye of the formula (C-1) contained in the cyan ink composition is 1% by mass or more, the color development of the ink on the recording medium when printed can be improved and is required. Image density can be secured. Further, by making the total amount of the dye of the formula (C-1) contained in the cyan ink composition 10% by mass or less, the discharge property of the cyan ink composition can be improved when used in the ink jet recording method. In addition, it is possible to obtain an effect such that the inkjet nozzle is not easily clogged.

In the ink set of the present invention, cyan ink compositions having different color densities, such as a cyan ink composition having a high color density (dark cyan ink composition) and a cyan ink composition having a low color density (light Cyan ink composition) can be included in the ink set.
When the dark cyan ink composition and the light cyan ink composition are included in the ink set of the present invention, at least one of the dark cyan ink composition and the light cyan ink composition is represented by the general formulas (C-1) and (C-2). , (C-3) or a salt thereof is preferably contained as a colorant.

Of the two cyan ink compositions having different color densities, the cyan ink composition having a low color density is at least one selected from the group consisting of the compound represented by formula (C-2) and a salt thereof. Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently Z ₁₁ (wherein Z ₁₁ represents — (CH ₂ ) ₃ SO ₃ M ₂ , where M ₂ represents an alkali metal atom) And / or Z ₁₂ (wherein Z ₁₂ represents — (CH ₂ ) ₃ SO ₂ NHCH ₂ CH (OH) CH ₃ )), and in particular, the above general formula (C the molar ratio of the _{Z 11} and the _{Z 12} contained in the entire cyan dye represented by -3) _{is, Z 11 / Z 12 = 4} / 0,3 / 1,2 / 2,1 / 3 becomes dye mixture preferably, the main and _{Z 11 / Z 12 = 2/} 2 among them Min become dye mixture being most preferred.

On the other hand, among the two types of cyan ink compositions having different color densities, the cyan ink composition having a low color density is selected from the group consisting of a compound represented by the following general formula (C-4) and a salt thereof. It is also preferable to use at least one compound.
Formula (C-4):

In General Formula (C-4), Q _{1 to} Q ₄ , P _{1 to} P ₄ , W _{1 to} W ₄ , and R _{1 to} R ₄ are each independently (= C (J ₁ )-or -N = ), (= C (J ₂ )-or -N =), (= C (J ₃ )-or -N =), (= C (J ₄ )-or -N =). J _{1 to} J ₄ each independently represents a hydrogen atom or a substituent. (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ), and at least one of the four rings {ring A: (A), ring B: (B), ring C: (C), ring D: (D)} is a heterocycle . M is a metal atom or an oxide, hydroxide or halide thereof.

General formula (C-4) is demonstrated.
(Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) of the _four rings {ring A: (A), ring B: (B), ring C: (C), ring D: (D)}, at least one heterocycle is nitrogen-containing It is preferably a heterocycle. Among them, the heterocycle is preferably a pyridine ring, a pyrazine ring, a pyrimidine ring or a pyridazine ring, more preferably a heterocycle is a pyridine ring or a pyrazine ring, and most preferably a pyridine ring.

More preferably, in the cyan ink composition represented by the general formula (C-4), (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), Rings including (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) {A ring: (A), B ring: (B), C ring: (C ) And D ring: (D)}, and when it represents an aromatic ring, the following general formula (I) is preferred.
Formula (I):

In general formula (I), * represents a bonding position with the phthalocyanine skeleton. G represents —SO—Z ₁ , —SO ₂ —Z ₁ , —SO ₂ NZ ₂ Z ₃ , —CONZ ₂ Z ₃ , —CO ₂ Z ₁ , —COZ ₁ , or a sulfo group. t represents an integer of 1 to 4.

Z ₁ may be the same or different and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, substituted or unsubstituted An aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group;
Preferred Z ₁ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Among them, a substituted alkyl group or a substituted aryl group is preferable, and a substituted alkyl group is particularly preferable. The group is most preferred.

Z ₂ and Z ₃ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
Preferred examples of Z ₁ and Z ₂ include independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom and a substituted alkyl Group and a substituted aryl group are preferred, and the case where _one of Z ₁ and Z ₂ represents a hydrogen atom and the other represents a substituted alkyl group or a substituted aryl group is most preferred.

G is preferably —SO—Z ₁ , —SO ₂ —Z ₁ , —SO ₂ NZ ₂ Z ₃ , —CONZ ₂ Z ₃ , —CO ₂ Z ₁ , —COZ ₁ , and among them —SO— Z ₁ , —SO ₂ —Z ₁ , and —SO ₂ NZ ₂ Z ₃ are more preferable, and —SO ₂ —Z ₁ is most preferable.
t is preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and most preferably t = 1.

More specifically, in the cyan ink composition represented by the general formula (C-4), when any ring of A ring, B ring, C ring, and D ring is an aromatic ring, at least one It is preferable that an aromatic ring is the following general formula (II).
General formula (II):

In general formula (II), * represents a bonding position with the phthalocyanine skeleton. G is synonymous with the said general formula (I), and its preferable example is also the same. t ₁ is 1 or 2, and t ₁ = 1 is particularly preferable.

  In the ink set of the present invention, both the deep cyan ink composition and the light cyan ink composition are dyes of the general formulas (C-1), (C-2), (C-3), and (C-4). It is particularly preferable to include at least one kind as a colorant.

  As described above, when a dark cyan ink composition and a light cyan ink composition are included in the ink set, the concentration of the colorant in the light cyan ink composition depends on the type of dye used as the colorant. When the composition is combined with the dark cyan ink composition, it can be appropriately determined so as to have a preferable color balance.

  In general, in the light cyan ink composition, the compounds of the general formulas (C-1), (C-2), (C-3), and (C-4) with respect to the total mass of the light cyan ink composition Or it is preferable that 0.4-3.0 mass% of the salt is contained in total. By making the content in the light cyan ink composition 0.4% by mass or more, the color developability can be made excellent, and by making the concentration of the colorant 3.0% by mass or less, The graininess of an image recorded using the light cyan ink composition can be reduced.

On the other hand, in the dark cyan ink composition, the compounds of the general formulas (C-1), (C-2), (C-3), and (C-4) with respect to the total mass of the dark cyan ink composition. Or it is preferable that 2.0-10.0 mass% of the salt is contained in total.
Further, the ratio of the concentration (mass%) of the colorant contained in the light cyan ink composition to the concentration (mass%) of the colorant contained in the dark cyan ink composition is 1: 2 to 1: 8. Preferably there is.

  By satisfying such conditions, a good color balance is realized between the light cyan ink composition and the dark cyan ink composition, and the ink jet nozzle can be prevented from being clogged.

As described above, in the cyan ink composition or the dark cyan ink composition and the light cyan ink composition in the ink set of the present invention, a range in which light resistance and ozone resistance are not greatly impaired for adjusting the color tone of the ink and the like. For example, other cyan dyes represented by dyes or dye mixtures represented by the following general formula (C-5) can be used in combination.
Formula (C-5):

In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent may further have a substituent. a represents an integer of 0 to 5. b represents an integer of 0 to 5. c represents an integer of 0 to 5.

  Further, other cyan dyes used in the present invention include, for example, C.I. I. 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, 291, C.I. I. Acid Blue 9,25,40,41,62,72,76,78,80,82,92,106,112,113,120,127: 1,129,138,143,175,181,205,207, 220, 221, 230, 232, 247, 258, 260, 264, 271, 277, 278, 279, 280, 288, 290, 326, C.I. I. Reactive Blue 2, 3, 5, 8, 10, 13, 14, 15, 17, 18, 19, 21, 25, 26, 27, 28, 29, 38, C.I. I. Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 45, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71, etc. Not.

  In the ink set of the present invention, the total amount of all the colorants contained in the cyan ink composition, dark cyan ink composition, or light cyan ink composition is 0. 0 relative to the total mass of the ink composition. The content is preferably 1 to 10% by mass, and more preferably 0.5 to 5% by mass. By setting the amount of the colorant in the ink composition to 0.1% by mass or more, color developability or image density on the recording medium can be secured, and by adjusting the amount to 10% by mass or less, the viscosity of the ink composition is adjusted. Therefore, characteristics such as ejection reliability and clogging resistance can be easily secured.

(Ink composition)
The colorant used in each ink composition of the present invention and the content of the colorant in the ink composition have been described above, but the other components contained in each ink composition will be described below.

Each ink composition in the present invention can be obtained by dissolving the above-described colorant (dye) in an appropriate solvent. As a solvent for dissolving the colorant in each ink composition, water or a mixed liquid of water and a water-soluble organic solvent is preferably used as a main solvent. As water, ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or the like can be used. From the viewpoint of long-term storage, it is preferable to use water that has been subjected to various chemical sterilization treatments such as ultraviolet irradiation and addition of hydrogen peroxide.
The water content in each ink composition constituting the ink set of the present invention is preferably 40 to 90% by mass, more preferably 50 to 80% by mass of the ink composition.

  As described above, each ink composition in the present invention can use a water-soluble organic solvent as a solvent together with water. As the water-soluble organic solvent, those having the ability to dissolve the dye are preferable, and those having a vapor pressure smaller than that of pure water are preferable.

  Examples of the water-soluble organic solvent used in the present invention include ethylene glycol, propylene glycol, butanediol, pentanediol, 1,3-hexanediol, 1,3-hexanediol, 2-butene-1,4-diol, 2 -Methyl-2,4-pentanediol, glycerin, 1,2,6-hexanetriol, polyhydric alcohols such as diethylene glycol, triethylene glycol and dipropylene glycol, ketones such as acetonyl acetone, γ-butyrolactone, phosphorus Esters such as triethyl acid, furfuryl alcohol, tetrahydrofurfuryl alcohol, thiodiglycol and the like are preferable, but are not limited thereto. By using a water-soluble organic solvent together with water as the solvent of the ink composition, the ejection stability of the ink composition from the ink head can be improved, and the viscosity of the ink composition can be lowered with almost no other change. Etc. can be easily adjusted.

  Further, at least one humectant selected from saccharides can be contained in each ink composition of the present invention. By including a moisturizing agent in the ink composition, when the ink composition is used in the ink jet recording method, it is possible to suppress moisture evaporation from the ink and moisturize the ink. As the saccharide used in the present invention, maltitol, sorbitol, gluconolactone, maltose and the like are preferable. In addition, the water-soluble organic solvent mentioned above may work as a moisturizer.

  The water-soluble organic solvent and / or the humectant can be contained in a total amount of 5 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 5 to 20% by mass in the ink composition. By setting these contents to 5% by mass or more, good ink moisture retention can be obtained, and by adjusting the content to 50% by mass or less, the viscosity of the ink composition is adjusted to a preferable viscosity for use in the inkjet recording method. can do.

  The ink set of the present invention preferably contains a betaine compound in each color ink composition as necessary, and among them, a betaine surfactant having an oil-soluble group is particularly preferable.

The betaine compound preferably used in the present invention is preferably a betaine-type surfactant having surface activity. The betaine compound here refers to a compound having both a cationic site and an anionic site in the molecule.
Examples of the cationic site include an aminic nitrogen atom, a nitrogen atom of a heteroaromatic ring, a boron atom having four bonds with carbon, and a phosphorus atom. Of these, an amine nitrogen atom or a nitrogen atom of a heteroaromatic ring is preferable. Among them, a quaternary nitrogen atom is particularly preferable.
Examples of the anionic site include a hydroxyl group, a thio group, a sulfonamide group, a sulfo group, a carboxyl group, an imide group, a phosphoric acid group, and a phosphonic acid group. Among these, a carboxyl group and a sulfo group are particularly preferable. The charge of the molecule as a whole may be any of cation, anion, and neutral, but is preferably neutral.

  As the betaine compound, compounds described in paragraphs 0033 to 0043 of JP-A-2005-298744 and betaine compounds described in JP-A-2006-56916 can be preferably used.

The betaine compound may be added in any amount as long as the effects of the invention are exerted, but is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass in the ink composition. In addition, two or more betaine compounds can be used in combination, but a combination of compounds represented by general formula W-1, W-2 or W-3 is preferable, and general formulas W-1, W- are particularly preferable. 2 or W-3 preferably includes a compound in which R is an alkyl group having 14 carbon atoms. When this is used, the compound having a C14 alkyl group preferably has a purity (for example, measurable by LC-Mass) of 90% or more, particularly preferably 95% or more, and most preferably 98% or more. is there.
Moreover, when using 2 or more types together, the compound of the maximum usage-amount can be used with a mass ratio of 1 to 10,000 times by mass ratio with respect to the compound of the minimum usage-amount.

In particular, in the present invention, it is preferable to suppress the total mass of inorganic ions mixed in the ink from a betaine compound (particularly a betaine surfactant) to 2% by mass or less with respect to the total mass of the ink.
The inorganic ions here are inorganic ions of counter ions of dyes, inorganic ions derived from inorganic salts that are impurities contained in betaine surfactants, and inorganic ions that become counter ions of ion components that deviate from the ion equivalent of betaine compounds. Represents the sum of inorganic ions introduced from inorganic salts used for pH adjustment, inorganic ions introduced from ink additives such as chelating agents and preservatives. However, in the present invention, ammonium ions are treated as volatile compounds and excluded from these inorganic ions.
The total amount of inorganic ions is preferably 2% by mass or less of the ink, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. For example, NaCl and Na ₂ SO ₄ -derived Cl ⁻ and SO ₄ ²⁻ have a concentration of 20 wt% aq, 100 ppm, preferably 30 ppm, and more preferably 10 ppm (for example, quantification is possible by ion chromatography analysis).

In order to reduce the content of inorganic ions in the ink as much as possible, various methods can be used. For example, the methods described in JP-A-2004-285269, paragraphs 32 and 33 can be used.
First, a method of removing inorganic ions contained in a material (for example, a betaine compound) used in ink at the time of material synthesis can be mentioned. In the case of a water-soluble ink material, many ion dissociable groups are often introduced particularly for the purpose of improving water solubility. At this time, a large amount of an inorganic substance is included at the time of material synthesis, or an inorganic ion is necessarily included as a counter ion. In order to remove the former ions, a desalting purification method by electrolysis dialysis using an ion-selective permeable membrane, a method using an ion exchange resin, a desalting purification by a gel filtration method, and the like can be performed.
In addition, a method of positively exchanging ions during synthesis can be used. For example, a method of exchanging with metal ions by adding excess ammonia or organic amines, or a method of exchanging with organic carboxylic acids in the case of anions can be mentioned. Further, as a desalting method at the time of synthesis, a method of positively depositing a salt with an organic solvent and removing it by filtration can be used.
Second, it is also preferable to carry out the desalting and purification in the state of the ink raw material, that is, a concentrated aqueous solution (ink stock solution) in which various materials are dissolved in a solvent such as water. In some cases, desalting and purification with a finished ink is also possible.

  The ink used in the ink set of the present invention is an ink obtained by dissolving or dispersing a dye in water and a water-soluble organic solvent. Of these, aqueous inks using water-soluble dyes are preferred. In the ink set, the ink having a betaine compound may have any color, and an ink having no color may be prepared for the betaine compound.

When the betaine compound of the present invention is used, bubbles may be generated in the ink. Since the bubbles may cause a printing defect in ink jet recording, this problem can be solved by adding a compound (= antifoaming agent) having an action of eliminating bubbles to the ink.
As an antifoaming agent, various things, such as a pluronic type antifoaming agent (polyoxyethylene-polyoxypropylene type antifoaming agent) and a silicone type antifoaming agent, can be used.

  Next, in the ink set of the present invention, it is also preferable that the cyan and / or magenta ink composition contains at least one selected from a naphthalene-based aromatic compound having a carboxyl group at the 2-position or a salt thereof. By adding at least one selected from the group consisting of a naphthalene-based aromatic compound having a carboxyl group at the 2-position and a salt thereof, the occurrence of bronzing in the cyan ink composition can be prevented, and the magenta ink composition The moisture resistance of can be improved. The above bronze phenomenon generally indicates that a portion of the ink composition containing a cyan dye that has been subjected to high duty printing such as solid printing on an ink jet recording medium (particularly a glossy recording medium) is reddish. Known as a phenomenon. When the bronze phenomenon occurs, the color balance of the entire image becomes non-uniform and the image quality deteriorates, so that a good image cannot be obtained.

  Among the naphthalene-based aromatic compounds having a carboxyl group at the 2-position used in the present invention, particularly preferred are alkali metal salts of naphthalene-based aromatic compounds having a carboxyl group at the 2-position. Further, among the alkali metal salts, it is particularly preferable to use a lithium salt. When lithium salt is used, not only the occurrence of the bronze phenomenon can be prevented, but also an effect that clogging of the ink jet nozzle is less likely to occur.

  Examples of the naphthalene-based aromatic compound having a carboxyl group at the 2-position or a salt thereof include 2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, and 6-hydroxy-2-naphthoic acid. 4-hydroxybenzoic acid, 2,6-naphthalenedicarboxylic acid, 3-methoxy-2-naphthoic acid, 3-ethoxy-2-naphthoic acid, 3-propoxy-2-naphthoic acid, 6-methoxy-2-naphthoic acid , 6-ethoxy-2-naphthoic acid, 6-propoxy-2-naphthoic acid, and the like, and salts thereof, particularly lithium salts. Particularly preferred are 2-naphthoic acid and its lithium salt.

  When a salt of a naphthalene aromatic compound having a carboxyl group at the 2-position is added to the ink composition, a method of adding it to the ink in the form of a salt, or a corresponding naphthalene-based aromatic compound having a carboxyl group at the 2-position And any method of adding it and the base which can form a salt separately to an ink composition can be used. Further, in the present invention, at least one selected from the group consisting of a naphthalene aromatic compound having a carboxyl group at the 2-position and a salt thereof can be used, and a naphthalene aromatic compound having a carboxyl group at the 2-position and a salt thereof can be used. Both can be used together.

  The cyan ink composition and / or magenta ink composition of the present invention comprising the above-mentioned group consisting of a naphthalene-based aromatic compound having a carboxyl group at the 2-position and a salt thereof (hereinafter referred to as a naphthalene-based aromatic compound having a carboxyl group at the 2-position) In the case where at least one selected from the group consisting of naphthalene-based aromatic compounds having a carboxyl group at the 2-position is added, the total amount of these ink compositions is preferably 0.1 to 10% by mass. More preferably, 5-5 mass% is contained. The amount of the naphthalene-based aromatic compound having a carboxyl group at the 2-position contained in the ink composition is the kind of itself, the kind of dye contained in the ink composition, the kind of solvent used in the ink composition, etc. The preferred amount can be determined as appropriate.

  When a naphthalene aromatic compound having a carboxyl group at the 2-position is added to the cyan ink composition, the amount (mass%) of the cyan dye contained in the ink composition and a naphthalene-based aromatic having a carboxyl group at the 2-position The ratio (% by mass) of the group compound is preferably 1: 0.1 to 1:10, and more preferably 1: 0.3 to 1: 6. When the content of the cyan dye in the cyan ink composition is 1, the occurrence of bronzing can be increased by increasing the content of a naphthalene-based aromatic carboxylic acid having a carboxyl group at the 2-position to more than 0.1. Further, by reducing the content of a naphthalene aromatic compound having a carboxyl group at the 2-position to less than 10, clogging of the ink jet nozzle can be prevented.

  On the other hand, when a naphthalene aromatic compound having a carboxyl group at the 2-position is added to the magenta ink composition, the amount (mass%) of the magenta dye contained in the ink composition and a carboxyl group at the 2-position The ratio of the amount (mass%) of the naphthalene aromatic compound or the like is preferably 1: 0.5 to 1:10, and more preferably 1: 1 to 1: 6. When the magenta dye content in the magenta ink composition is 1, the content of a naphthalene-based aromatic compound having a carboxyl group at the 2-position is more than 0.5, so that an image in a high humidity environment is obtained. Degradation of image quality due to bleeding can be reduced, and further, the content of a naphthalene-based aromatic compound having a carboxyl group at the 2-position can be reduced to less than 10 to prevent clogging of the inkjet nozzle. .

  The ink composition constituting the ink set of the present invention preferably contains a nonionic surfactant. By adding a nonionic surfactant, the penetrability of the ink composition into the recording medium is improved, and the ink composition can be quickly fixed on the recording medium during printing. Further, it is preferable that one dot recorded by the ink composition on the recording medium is as close to a perfect circle as possible. However, by containing a nonionic surfactant in the ink composition, an image formed by one dot can be obtained. It is possible to increase the roundness and improve the image quality of the obtained image.

  As a nonionic surfactant used in the present invention, for example, an acetylene glycol surfactant is preferable, but it is not limited thereto.

  Examples of the acetylene glycol surfactant include Surfhinol 465 (trademark), Surfynol 104PG50 (trademark) (trade name, manufactured by Air Products and Chemicals Inc.), Olfine PD001 (trademark), Olfine E1010 (trademark). (The above trade name, manufactured by Nissin Chemical Industry Co., Ltd.) can be exemplified, and it is preferable to add at least one selected from these to the ink composition constituting the ink set of the present invention.

  In the present invention, the nonionic surfactant is contained in the ink composition so that the nonionic surfactant is preferably contained in the ink composition in an amount of 0.1 to 5% by mass, more preferably 0.5 to 2% by mass. An agent should be added. By containing 0.1% by mass or more of the nonionic surfactant in the ink composition, the permeability of each ink composition with respect to the recording medium can be increased. Further, when the content of the nonionic surfactant in the ink composition is 5% by mass or less, an effect that an image formed with the ink composition on the recording medium is difficult to blur can be obtained.

  Furthermore, in addition to nonionic surfactants, the addition of glycol ethers as penetration enhancers to the ink composition improves the penetrability of the ink composition with respect to the recording medium, and when color printing is performed. At the boundary between adjacent color inks, ink bleeding (bleeding) is reduced, and a very clear image can be obtained. Therefore, it is preferable to add a penetration enhancer to the ink composition constituting the ink set of the present invention.

  The glycol ethers used in the present invention as penetration enhancers include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene Glycol monobutyl ether, triethylene glycol monobutyl ether and the like are preferable, but are not limited thereto. These glycol ethers are preferably contained in the ink composition in an amount of 3 to 30% by mass, more preferably 5 to 15% by mass. By making the addition amount of glycol ethers 3% by mass or more, bleeding (bleeding) between adjacent inks during color printing can be effectively prevented, and by making this addition amount 30% by mass or less, image It becomes easy to prevent the occurrence of bleeding, and the storage stability of the ink can be improved.

  Further, the ink composition of the present invention includes a pH adjuster such as triethanolamine or alkali metal hydroxide, a water-soluble polymer such as sodium alginate, a water-soluble resin, a fluorosurfactant, an antiseptic, and an antifungal agent. A material selected from a rust inhibitor, a dissolution aid, an antioxidant, an ultraviolet absorber, and the like can be added as desired. These components can be used alone or in combination of two or more. Moreover, it is not necessary to add, if it is not necessary to add. Those skilled in the art can use the preferable additive selected in a preferable amount as long as the effects of the present invention are not impaired. The dissolution aid is an additive for dissolving the insoluble matter and keeping the ink composition in a uniform solution when the insoluble matter is precipitated from the ink composition.

  Examples of the solubilizer include pyrrolidones such as N-methyl-2-pyrrolidone and 2-pyrrolidone, ureas such as urea, thiourea and tetramethylurea, allophanates such as allophanate and methylallohanate, biuret and dimethylbiuret. And biurets such as tetramethylbiuret can be mentioned, but the invention is not limited to these. Moreover, as an example of the said antioxidant, although L-ascorbic acid and its salt etc. can be illustrated, it is not limited to these.

  Examples of the antiseptic or antifungal agent include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, and 1,2-dibenzisothiazoline-3. -ON (Avexia's Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL2, Proxel TN (trade name) and the like can be exemplified, but not limited thereto.

  Examples of the pH adjuster include amines such as diethanolamine, triethanolamine, propanolamine, morpholine, and modified products thereof, metal hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, Examples thereof include ammonium salts such as quaternary ammonium hydroxide (tetramethylammonium, etc.), carbonates such as potassium carbonate, sodium carbonate, lithium carbonate, and other phosphates, but are not limited thereto.

  The ink composition constituting the ink set of the present invention is prepared by including components appropriately selected from the above-mentioned components, but the viscosity of the obtained ink composition is preferably less than 10 mPa · s at 20 ° C. . Furthermore, in the present invention, the surface tension of the ink composition is preferably 45 mN / m or less at 20 ° C., and particularly preferably in the range of 25 to 45 mN / m. By adjusting the viscosity and the surface tension in this way, an ink composition having desirable characteristics for use in the ink jet recording method can be obtained. The adjustment of the viscosity and the surface tension can be performed by appropriately adjusting and selecting the addition amount of the solvent and various additives to be contained in the ink composition, the kind thereof, and the like.

  The ink composition constituting the ink set of the present invention preferably has a pH of 7.0 to 10.5, more preferably 7.5 to 10.0 at 20 ° C. By making the pH of the ink composition at 20 ° C. 7.0 or more, it is possible to prevent the eutectoid plating of the ink jet head from being peeled off, and to stabilize the ejection characteristics of the ink composition from the ink jet head. Can do. In addition, by setting the pH of the ink composition to 10.5 or less at 20 ° C., it is possible to prevent deterioration of various members that come into contact with the ink composition, for example, members constituting an ink cartridge or an inkjet head. .

  As a method for preparing the ink composition in the present invention, for example, various components contained in the ink composition are sufficiently mixed and dissolved as uniformly as possible, followed by pressure filtration with a membrane filter having a pore size of 0.8 μm. Although the method of preparing the obtained solution by deaeration using a vacuum pump can be illustrated, it is not limited to this.

[Ink cartridge, inkjet printer]
The ink set of the present invention can be used as an ink cartridge that accommodates them integrally or independently, and is preferable from the viewpoint of easy handling. An ink cartridge including an ink set is known in the art, and can be formed into an ink cartridge by appropriately using a known method.
The ink jet printer of the present invention includes the ink cartridge.

  The ink set or ink cartridge of the present invention can be used for general writing instruments, recorders, pen plotters, and the like, but is particularly preferably used for an ink jet recording method.

[Inkjet recording method]
The ink jet recording method in which the ink set or the ink cartridge of the present invention can be used includes any recording method in which the ink composition is ejected as droplets from a thin nozzle and the droplets are attached to a recording medium. Specific examples of the ink jet recording method in which the ink composition of the present invention can be used will be described below.

  The first method is a method called an electrostatic attraction method. In the electrostatic suction method, a strong electric field is applied between the nozzle and the acceleration electrode arranged in front of the nozzle, and droplet-like ink is continuously ejected from the nozzle, and the ink droplet passes between the deflection electrodes. In the meantime, by supplying a printing information signal to the deflection electrode, the ink droplets are blown toward the recording medium and the ink is fixed on the recording medium, or the image is recorded, or the ink droplets are not deflected, In this method, an image is fixed on a recording medium by ejecting ink droplets from a nozzle onto the recording medium in accordance with a print information signal. The ink set or ink cartridge of the present invention is preferably used in a recording method using this electrostatic suction method.

  The second method is a method for forcibly ejecting ink droplets from the nozzles by applying pressure to the ink liquid with a small pump and mechanically vibrating the ink jet nozzles with a quartz vibrator or the like. The ink droplet ejected from the nozzle is charged at the same time as it is ejected, and while the ink droplet passes between the deflection electrodes, a print information signal is given to the deflection electrode to fly the ink droplet toward the recording medium, This is a method for recording an image on a recording medium. The ink set or ink cartridge of the present invention is also preferably used for this recording method.

  The third method is a method in which an image is recorded on a recording medium by simultaneously applying a pressure and a printing information signal to the ink liquid by a piezoelectric element, and ejecting ink droplets from a nozzle toward the recording medium. The ink set or ink cartridge of the present invention is also preferably used for this recording method.

  In the fourth method, the ink liquid is heated and foamed using microelectrodes according to the print signal information, and the bubbles are expanded to eject the ink liquid from the nozzle toward the recording medium, thereby forming an image on the recording medium. It is a method of recording. The ink set or ink cartridge of the present invention is also preferably used for this recording method.

  The ink set or ink cartridge of the present invention is particularly preferable as an ink composition used when an image is recorded on a recording medium using an image recording method based on an ink jet recording method including the four methods described above.

[Recordings]
The recorded matter recorded using the ink set of the present invention has an excellent image quality with good color balance, and is excellent in light resistance and ozone resistance.

  Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to the following examples.

(Synthesis example)
Hereinafter, although the Example demonstrates the preparation method of the dye mixture of this invention in detail, this invention is not limited to these Examples at all.

  The dye BLACK-11 used in the present invention can be derived from, for example, the following synthesis route.

[Synthesis Example 1]
A synthesis scheme of BLACK-11 is shown below.

(1) Synthesis of intermediate (B-5):
After adding 8.5 g of aminoacetophenone (a-2), 4.9 g of malononitrile, 26.5 mL of toluene, 5.0 g of ammonium acetate and 5.9 g of acetic acid at room temperature, the internal temperature was raised to 100 ° C. at the same temperature. Stir for 3 hours. After cooling the reaction solution to 40 ° C., 31.8 mL of methanol was added, and after stirring for 20 minutes, the reaction solution was filtered. It was washed with 42.4 mL of isopropyl alcohol and dried at 60 ° C. for 8 hours. (B-5) 11.1 g was obtained.

(2) Synthesis of intermediate (C-5):
(B-5) 8.0 g, sulfur 2.8 g, sodium bicarbonate 7.4 g, dimethylacetamide 160 mL, acetonitrile 80 mL and water 80 mL were mixed at room temperature, then the temperature was raised to an internal temperature of 40 ° C., and the same temperature for 1 hour. Stir. After cooling the reaction solution to 25 ° C., insoluble matters were filtered off to obtain (C-5) in a solution state.

(3) Synthesis of intermediate (T-1):
100 mL of acetone was cooled to an internal temperature of 0 ° C., and 18.4 g of cyanuric chloride was added. Next, 27.5 g of 2,5-disulfoaniline and 10.6 g of sodium carbonate were dissolved in 95 g of water and added dropwise at an internal temperature of 0-4 ° C. or lower over 30 minutes. After stirring at an internal temperature of 0-5 ° C. for 2.5 hours, 200 mL of methanol and 200 mL of isopropyl alcohol were added dropwise at an internal temperature of 5 ° C. or less, and the precipitated insoluble matter was filtered, and then obtained in the solution state of (T-1). .

(4) Synthesis of intermediate (T-2):
While maintaining (T-1) obtained in Synthesis Example (3) at an internal temperature of 20 ° C., 240.0 g of (C-5) was added dropwise. After dropping, the internal temperature was raised to 30 ° C. and stirred for 2.0 hours. After dropping 2.3 L of isopropyl alcohol at an internal temperature of 30 to 35 ° C. over 1 hour, the mixture was stirred at the same temperature for 30 minutes. The reaction solution was filtered, washed with isopropyl alcohol, and dried to obtain 24.0 g of (T-2).

(5) Synthesis of intermediate (T-3):
8.0 g of taurine and 6.8 g of sodium carbonate were completely dissolved in 650 mL of water at room temperature, and 24.0 g of (T-2) was added in powder form to the solution. The internal temperature was raised to 100 ° C. and stirred at the same temperature for 1.5 hours. The reaction solution was cooled to an internal temperature of 25 ° C. to obtain an intermediate (T-3) in a solution state.

(6) Synthesis of intermediate (f-6):
To 4.4 g of 2-aminobenzonitrile (e-1), 58 mL of water was added and stirred at room temperature. After adding 10.5 mL of 12M aqueous hydrochloric acid dropwise, the reaction mixture was cooled to an internal temperature of 0 ° C. While maintaining the internal temperature at 0-4 ° C, a 25% aqueous solution of 2.8 g of sodium nitrite was added dropwise, and the mixture was stirred at an internal temperature of 0-5 ° C for 1.5 hours. Thereafter, 0.4 g of urea was added and stirred for 15 minutes to obtain a diazonium salt solution. Apart from the diazonium salt solution, 300 mL of water was added to the intermediate (T-3) and cooled to an internal temperature of 2 ° C., and then the diazonium salt solution prepared previously was added dropwise at an internal temperature of 2-4 ° C. over 15 minutes. After maintaining the internal temperature at 2-4 ° C. and stirring for 2 hours, (f-6) was obtained in a solution state.

(7) Synthesis of BLACK-11:
(F-6) obtained in Synthesis Example (6) above was stirred at room temperature, and 17.7 g of Intermediate (G) was completely dissolved in 60 mL of water and added dropwise. 4.5 g of isoamyl nitrite was added dropwise at an internal temperature of 22 ° C., and the mixture was stirred at the same temperature for 30 minutes. Thereafter, 0.2 g of isoamyl nitrite was further added dropwise, and the mixture was stirred at an internal temperature of 22 ° C. for 2 hours. The reaction solution was dedusted and filtered to remove insolubles, then 183 mL of dimethylacetamide was added to the reaction solution, and 1.1 L of isopropyl alcohol was added dropwise over 30 minutes. The slurry-like reaction liquid was filtered and washed with 2 L of methanol to obtain crude (BLACK-11).
To this crude product, 220 mL of water was added and dissolved, and 370 mL of isopropyl alcohol was added dropwise and filtered again to obtain a wet cake. This wet cake was completely dissolved in 220 mL of water, and 1N-lithium hydroxide aqueous solution was added to adjust the pH value to 8.3 (25 ° C.). This solution was heated to an internal temperature of 40 ° C., and 300 mL of saturated LiCl isopropyl alcohol solution was added dropwise at the same temperature, and the precipitated crystals were filtered to obtain wet crystals. To the obtained wet crystals, 170 mL of water and 100 mL of methanol were added, and 430 mL of a saturated LiCl isopropyl alcohol solution was added dropwise with stirring at an internal temperature of 40 ° C., and the precipitated crystals were separated by filtration. After washing with 500 mL of isopropyl alcohol and drying at 40 ° C. for 12 hours, 11.3 g of fine (BLACK-11) M: Li / Na≈70 / 30 (mol / mol) was obtained.

  Also, BLACK-11 (M: Li / Na≈70 / 30 (mol / mol)) obtained as described above was replaced with a Li salt type ion exchange resin (manufactured by Organo Corp., IR-120B converted to Li type). ) To obtain BLACK-11 (M: Li (that is, all M is Li)).

[Synthesis Example 2]
A synthesis scheme of BLACK-32 (M: Li) is shown below.

(1) Synthesis of intermediate (B-11):
40 g of raw material (A-11; Wako Pure Chemicals) was added to 12.5 g of thiourea and 120 ml of water, and stirred at 70 ° C. for 5 hours. The precipitated crystals were separated by filtration, 400 ml of 5% NaOH solution was added, and the mixture was stirred at room temperature for 3 hours and then filtered to obtain 35.5 g of yellow crystals of intermediate (B-11).

(2) Synthesis of intermediate (C-11):
57.0 g of reduced iron, 5.0 g of ammonium chloride, 35 ml of water and 250 ml of isopropyl alcohol were refluxed for 30 minutes, 22.0 g of intermediate (B-11) was added, and the mixture was stirred at reflux for 1 hour. After filtration, the filtrate was concentrated to obtain 15.0 g of yellow crystals of intermediate (C-11).

(3) Synthesis of Intermediate (D-11) 9.6 g of Intermediate (C-11) was added to 125 mL of acetone and stirred at an internal temperature of 50 ° C. for dissolution. After cooling the internal temperature to 4 ° C. in an ice bath, 5.6 g of acetic anhydride was added dropwise over 15 minutes. After raising the temperature to room temperature, 50 mL of water was added, and acetone was distilled off under reduced pressure. The crystals were separated by filtration, washed twice with 50 mL of water, and dried at 80 ° C. for 6 hours to obtain 9.9 g of intermediate (D-11) white crystals.

(4) Synthesis of Intermediate (F-11) 4.3 g of Intermediate (E-11) was added to 43 mL of water and stirred at room temperature. After dropwise addition of 4.0 mL of 12N hydrochloric acid, the internal temperature was cooled to 4 ° C. Thereto, 3 mL of an aqueous solution containing 0.9 g of sodium nitrite was added dropwise and stirred at 5 ° C. or lower for 2 hours. Thereafter, 0.1 g of urea was added and stirred at an internal temperature of 4 ° C. for 15 minutes to obtain a diazonium solution. Separately, 2.4 g of intermediate (D-11) and 8.6 g of lithium acetate were dissolved in 55 mL of methanol and 3.5 mL of dimethylacetamide and cooled to an internal temperature of 5 ° C. or lower. The diazonium solution was added dropwise at an internal temperature of 5 ° C. or less over 5 minutes. After stirring for 1.5 hours, 15.0 g of lithium chloride was added, followed by dropwise addition of 150 mL of isopropyl alcohol. The crystals were separated by filtration and washed with 100 mL of isopropyl alcohol. After drying at 80 ° C., 5.4 g of brown crystals of intermediate (F-11) were obtained.

(5) Synthesis of BLACK-32 Intermediate (F-11) 5.0 g, (G) 3.8 g and 50 mL of water were adjusted to pH 2 or lower with 12N hydrochloric acid, and the internal temperature was 35 to 40 ° C. and isoamyl nitrite. 1.5 g was added dropwise. After stirring for 4 hours at an internal temperature of 40 ° C., 20 g of lithium chloride was added, followed by dropwise addition of 25 mL of isopropyl alcohol. After cooling to an internal temperature of 25 ° C., the crystals were separated by filtration and washed with 50 mL of isopropyl alcohol. 60 mL of water was added to the crystals, and the temperature was raised to an internal temperature of 40 ° C., and then 100 mL of isopropyl alcohol was added dropwise. After cooling to an internal temperature of 25 ° C., the crystals were filtered off. The obtained crystals were added to 35 mL of water, and a 4M aqueous lithium hydroxide solution was added so that the pH was 8.3. To this solution, 250 mL of isopropyl alcohol was added dropwise, and the precipitated crystals were separated by filtration. After washing with 30 mL of isopropyl alcohol, drying at 80 ° C. gave 2.7 g of (BLACK-32) (M: Li) black crystals.

[Synthesis Example 3]
A synthesis scheme of BLACK-31 (M: Li) is shown below.

(1) Synthesis of intermediate (B-12):
20.3 g of p-aminoacetophenone (A-12; Tokyo Chemicals) was added to 150 mL of acetonitrile and completely dissolved by stirring at room temperature. Subsequently, 13.4 mL of pyridine was added, and the internal temperature was kept at 4 ° C. in an ice bath. 11.8 g of acetic anhydride was added dropwise, and the mixture was stirred at an internal temperature of 4 ° C. for 15 minutes. 300 mL of water and then 5 mL of 12N hydrochloric acid were added to the reaction solution, and the crystals were separated by filtration. The crystals were washed with 100 mL of water and dried at 80 ° C. to obtain 18.6 g of intermediate (B-12) white crystals.

(2) Synthesis of intermediate (C-12):
A 100 mL three-necked flask equipped with a Dean-Stark trap was charged with 17.7 g of intermediate (B-12), 7.3 g of malononitrile, 4.6 mL of acetic acid, 1.5 g of ammonium acetate and 20 mL of toluene, and an oil at 125 ° C. Refluxed in bath. After stirring for 1 hour, 4.6 mL of acetic acid and 1.5 g of ammonium acetate were added, and the mixture was stirred for 2 hours under reflux conditions. After allowing to cool, 30 mL of methanol was added, and the mixture was stirred for 30 minutes in an ice bath. The crystals were separated by filtration, washed with 20 mL of cold methanol and dried. 12.1 g of white crystals of intermediate (C-12) was obtained.

(3) Synthesis of Intermediate (D-12) 1.5 g of sulfur was added to a solution of 11.3 g of Intermediate (C-12) and 20 mL of ethanol, followed by dropwise addition of 6.6 mL of triethylamine. After stirring at an internal temperature of 50 ° C. for 30 minutes, 500 mL of ethyl acetate and 300 mL of water were added, followed by liquid separation after shaking. 200 mL of brine was added to the organic layer and the mixture was separated after shaking. Magnesium sulfate was added to the organic layer and dried. After distilling off the organic solvent, 50 mL of isopropanol was added, and the suspension was stirred and the crystals were filtered off. After drying at 80 ° C., 8.1 g of white crystals of intermediate (D-12) were obtained.

(4) Synthesis of intermediate (F-12) 6.0 g of intermediate (E-11) was added to 60 mL of water and stirred at room temperature, and 5.6 mL of 12N hydrochloric acid was added dropwise, and then cooled to an internal temperature of 4 ° C. 4 mL of an aqueous solution of 1.3 g of sodium nitrite was added dropwise at an internal temperature of 5 ° C. or lower. After stirring for 2 hours at an internal temperature of 5 ° C. or less, 0.1 g of urea was added and stirred for 15 minutes to obtain a diazonium solution.
Separately, 3.4 g of the intermediate (D-12) and 12.0 g of lithium acetate were dissolved in 90 mL of methanol and 10 mL of dimethylacetamide at room temperature, cooled to an internal temperature of 4 ° C., and then the diazonium solution at an internal temperature of 5 ° C. or lower. Added dropwise for 15 minutes. After stirring at an internal temperature of 4 ° C. or lower for 1.5 hours, 20.0 g of lithium chloride was added, and 75 mL of acetonitrile was added dropwise. The crystals were separated by filtration and washed with acetonitrile. The isolated crystal was suspended and washed with 75 mL of isopropyl alcohol at an internal temperature of 50 ° C. The crystals were separated by filtration and washed with isopropyl alcohol. After drying at 80 ° C., 6.4 g of brown crystals of intermediate (F-12) were obtained.

(5) Synthesis of BLACK-31 Intermediate (F-12) 5.0 g and (G) 3.7 g and 50 mL of water were adjusted to pH 2 or less with 12N hydrochloric acid water, and nitrous acid at an internal temperature of 35-40 ° C. 1.2 g of isoamyl was added dropwise. After stirring at an internal temperature of 40 ° C. for 3 hours, 50.0 g of lithium chloride was added and the mixture was cooled to an internal temperature of 25 ° C. The crystals were separated by filtration and washed with 150 mL of isopropyl alcohol. The isolated crystals were added to 200 mL of methanol and the temperature was raised to an internal temperature of 40 ° C., and then 800 mL of acetonitrile was added dropwise. After dropping, the mixture was stirred for 15 minutes and cooled to an internal temperature of 25 ° C. The crystals were separated by filtration, added to 150 mL of water, and 450 mL of isopropyl alcohol was added dropwise at room temperature. The crystals were separated by filtration, added to 50 mL of water, and 4M lithium hydroxide aqueous solution was added until pH 8.3. To this solution, 150 mL of isopropyl alcohol was added dropwise, and the precipitated crystals were separated by filtration. After washing with 50 mL of isopropyl alcohol and drying at 80 ° C., 4.3 g of (BLACK-31) (M: Li) black crystals were obtained.

(Synthesis Example 4)
The dye represented by the formula (YELLOW-1) (described as the formula (Y-1) in the following scheme) of the present invention can be derived, for example, from the following synthesis route.
In the following examples, λmax is the absorption maximum wavelength, and εmax is the molar extinction coefficient at the absorption maximum wavelength.

  In 450 mL of DMF (N, N-dimethylformamide) and 24.75 g of 1,2-dichloroethane, compound (a) (2-amino-5-mercapto-1,3,4-thiadiazole (Wako Pure Chemical Industries ( Co., Ltd./Catalog No. 019-11125)) was added to 76.5 g, potassium carbonate 79.5 g was added, the temperature was raised to 70 ° C., and the mixture was stirred at the same temperature for 30 minutes. Subsequently, 375 mL of warm water at 80 ° C. was dropped into the reaction solution over 10 minutes and cooled to an internal temperature of 25 ° C. The precipitated crystals were separated by filtration, washed with 250 mL of ion exchange water and subsequently with 150 mL of methanol, and then dried at 70 ° C. overnight to obtain 65.1 g of compound (b).

  Aminoisophthalic acid (manufactured by Wako Pure Chemical Industries, Ltd./catalog number 322-26175) (A) 181.2 g was suspended in 1000 ml of ion-exchanged water, 257 mL of concentrated hydrochloric acid was added, and the mixture was heated to 5 ° C. in an ice bath. Kept. Thereto was added 116 ml of an aqueous solution of 69.7 g of sodium nitrite (reaction liquid A). 1300 ml of an aqueous solution containing 378.1 g of sodium sulfite was stirred at an internal temperature of 25 ° C., and the reaction solution A was poured therein. After stirring in this state for 30 minutes, the internal temperature was heated to 30 ° C. and stirred for 60 minutes. Hydrochloric acid 500mL was added to this reaction liquid, and it heated up immediately to the internal temperature of 50 degreeC (reaction liquid B). After stirring for 90 minutes in this state, 125.2 g of pivaloyl acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd./catalog number P1112) and 100 mL of isopropanol were added to the reaction solution B, and the internal temperature was raised to 93 ° C. Stir for 240 minutes. After cooling to room temperature, the precipitated crystals (C) were filtered with suction, and the crystals were washed with 1500 mL of ion-exchanged water and then with 1000 mL of isopropanol and dried. Isolated yield 223.5 g. Yield 73.7%.

29.2 g of the compound (b) was added at room temperature to 100 mL of methanesulfonic acid, 120 mL of acetic acid, and 180 mL of propionic acid, the internal temperature was raised to 45 ° C. to obtain a homogeneous solution, and then the internal temperature was cooled to 0 ° C. Subsequently, a solution of 14.7 g of NaNO ₂ and 27 mL of ion-exchanged water was added dropwise to the homogeneous solution while maintaining the internal temperature of 0 to 10 ° C., and stirred for 15 minutes at an internal temperature of 5 ° C. to prepare a diazonium salt. The diazonium salt solution was added dropwise to a solution prepared in advance from 60.6 g of the coupler component (C) prepared in Synthesis Example 2, 600 mL of methanol, and 600 mL of ethylene glycol at a rate maintaining the internal temperature of 0 to 10 ° C. Subsequently, the mixture was stirred at an internal temperature of 25 ° C. for 30 minutes. The precipitated crystals were filtered and washed with 250 mL of methanol, and then the crude crystals were dispersed in 650 mL of water, then stirred for 30 minutes at an internal temperature of 80 ° C., cooled to room temperature, filtered, washed with 300 mL of water, and then washed at 60 ° C. Drying overnight gave 64.47 g of dye (D).

In a solution of 16.5 g of KOH (tablet) prepared in advance and 414.9 mL of ion-exchanged water, 46.1 g of the dye (D) prepared in Synthesis Example 3 was added and dissolved at an internal temperature of 20 to 30 ° C.
Subsequently, potassium acetate 40. A solution of og and methanol (200 mL) was dropped into the dye aqueous solution at an internal temperature of 25 ° C., followed by stirring at the same temperature for 10 minutes. Thereafter, 2488 mL of IPA (isopropanol) was added dropwise for salt formation, followed by stirring at the same temperature for 30 minutes, followed by filtration, washing with 500 mL of IPA, and drying at 70 ° C. overnight to obtain 44 g of crude crystals of dye (YELLOW-1). It was.

After dissolving 8.7 g of crude crystals (YELLOW-1) in 78.3 mL of ion-exchanged water at room temperature, the pH value of the aqueous solution was adjusted to 8.5 using 0.1 N hydrochloric acid, and filtered through a 0.2 μm membrane filter. Thereafter, 391.5 mL of IPA was added dropwise to the filtrate at an internal temperature of 25 ° C. The precipitated crystal was filtered, washed with 100 mL of IPA, and dried overnight at 80 ° C. to obtain 7.8 g of a fine crystal of dye (YELLOW-1). {Λmax: 428 nm (H ₂ O), εmax: 4.20 × 10 ⁴ }

  (YELLOW-2) and (YELLOW-3) can also be synthesized by the same method as (YELLOW-1).

[Preparation of each ink composition]
Based on the composition shown in the following Tables 1 to 6, after stirring each component at room temperature for 30 minutes, each ink composition was obtained by filtering the obtained solution using a membrane filter having an opening of 1.0 μm. It was. In Tables 1 to 6, the numerical value of each component indicates the mass% of each component when the mass of the ink composition is 100%, and the “residue” indicating the amount of water is combined with the components other than water. The total amount is 100%.

Details of the compounds used in each ink composition are shown below.
-TEGmBE: Triethylene glycol monobutyl ether-DEGmBE: Diethylene glycol monobutyl ether-Acetylenol E100: Acetylene glycol surfactant, manufactured by Kawaken Fine Chemical Co., Ltd.-Olphine E1010: Acetylene glycol surfactant, manufactured by Nisshin Chemical Co., Ltd. Acetylene glycol surfactant, manufactured by Nissin Chemical Co., Ltd. Surfynol 104PG50: Acetylene glycol surfactant, manufactured by Air Products and Chemicals Inc. Proxel XL2: 1,2-dibenzisothiazolin-3-one Made by Arch ・ YELLOW-R1: C.I. I. Direct yellow 132
YELLOW-R2: C.I. I. Direct yellow 86
・ C. I. Acid Red 289: manufactured by Tokyo Chemical Industry Co., Ltd. I. Acid Blue 9: manufactured by Tokyo Chemical Industry Co., Ltd.

  Using the ink compositions having the compositions shown in Tables 1 to 6, ink sets of Examples 1 to 9 and Comparative Examples 1 and 2 were prepared based on combinations of the ink compositions shown in Table 7 below.

For the ink sets shown in Table 7, the ink storage stability of each ink composition in the ink set was evaluated as follows.
In addition, an ink jet printer Stylus Color 880 (trademark) (trade name, manufactured by Seiko Epson Corporation) was used, and an ink set shown in Table 7 was used, and an ink jet recording medium {photo paper <gloss> (trade name, Seiko Epson Co., Ltd.)} in yellow (Y), magenta (M), cyan (Cy), and black (Bk), and the OD value of each color is 0.7 to 1.8. Each color single-color image pattern in which the density changed in a shape and green, red, and gray image patterns were printed.

[Ink storage stability]
The ink composition was stored in a sealed container, and the storage stability for 1 month at room temperature (18 to 20 ° C.) was confirmed. The pigment content (dye content) in the ink before and after storage was measured by high performance liquid chromatography (LC20 manufactured by Shimadzu Corporation) and evaluated as the pigment residual ratio. The dye residual ratio was evaluated in three stages, with A being 90% or more, B being 80% or more and less than 90%, and C being less than 80%. The higher the dye residual ratio, the better the ink storage stability. The evaluation results are shown in Table 8.

[Light resistance]
Glossy paper on which images are formed is irradiated with xenon light (100,000 lux) for 28 days, the image density before and after the xenon irradiation is measured using a reflection densitometer (X-Rite 310TR), and the OD value of each color monochromatic image is measured. did. The reflection density was measured at three points of 0.7, 1.0, and 1.8. From the obtained results, the optical density residual ratio (ROD) was determined using the following formula: ROD (%) = (D / D ₀ ) × 100 (where D is the OD value after light irradiation, D ₀ Represents the OD value before light irradiation.)
At any concentration, ROD is 85% or more, A when any one point's ROD is less than 85%, B when any two points' concentration is less than 85%, C, all concentrations The case where ROD was less than 85% was evaluated as D and evaluated in four stages.
Even if exposed to light for a long time, the lower the decrease in ROD, the better the light resistance. The evaluation results are shown in Table 8.

Also, from the results of the light resistance evaluation of each color, the light resistance ranking of each ink set was performed using the following criteria. The obtained evaluation results are shown in Table 9 as “light resistance” of the ink set.
A: Light resistance evaluation is A for all four colors.
B: The light resistance evaluation is B for one or more of the four colors, and A for all the remaining colors.
C: Light resistance evaluation is C for one or more of the four colors, and A or B for the remaining colors.
D: Light resistance evaluation is D for one or more of the four colors.

Furthermore, the difference in ROD change (color balance) between the colors of the printed matter caused by exposure to light was evaluated for each ink set using the following criteria.
A: Even after 28 days from the start of light irradiation, the difference between the maximum value and the minimum value of the ROD of each color (hereinafter simply referred to as “ROD difference” in the description of this evaluation method) is 15 points (15%). Is less than.
B: 15 to 28 days after the start of light irradiation, the ROD difference becomes 15 points.
C: The difference in ROD becomes 15 points from 8 to 14 days from the start of light irradiation.
D: Within 7 days from the start of light irradiation, the ROD difference becomes 15 points.
In this evaluation, a small difference in ROD is excellent as a recorded material. Table 9 shows the evaluation results obtained as “Color balance 1”.

[Ozone resistance]
The glossy paper on which the image has been formed is allowed to stand for 14 days under conditions set to an ozone gas concentration of 5 pm (25 ° C., 60% RH), and the image density before and after being left under ozone gas is measured using a reflection densitometer (X-Rite 310TR). Then, the OD value of each color single color image was measured. The reflection density was measured at three points of 0.7, 1.0, and 1.8. The optical density residual ratio (ROD) was calculated from the obtained results using the following formula: ROD (%) = (D / D ₀ ) × 100 (where D is the OD value after standing under ozone gas, D ₀ represents the OD value before standing under ozone gas.)
At any concentration, ROD is 85% or more, A when any one point's ROD is less than 85%, B when any two points' concentration is less than 85%, C, all concentrations The case where ROD was less than 85% was evaluated as D and evaluated in four stages.
Even if exposed to ozone gas for a long time, the lower the ROD, the better the ozone resistance. The evaluation results are shown in Table 8.

In addition, from the results of the ozone resistance evaluation of each color, the following determination criteria were used to rank the ozone resistance as each ink set. The obtained evaluation results are shown in Table 9 as “ozone resistance of ink set”.
A: The ozone resistance evaluation is A for all four colors.
B: The ozone resistance evaluation is B for one or more of the four colors, and A for all the remaining colors.
C: The ozone resistance evaluation is C for one or more of the four colors, and A or B for the remaining colors.
D: The ozone resistance evaluation is D for one or more of the four colors.

Further, the difference in ROD change (color balance) between the colors of the printed matter caused by exposure to ozone was evaluated for each ink set using the following criteria.
A: Even after 15 days from the start of standing under ozone gas, the difference between the maximum value and the minimum value of the ROD of each color (hereinafter simply referred to as “ROD difference” in the description of this evaluation method) is 15 points (15%). ).
B: The difference in ROD becomes 15 points from 8 to 14 days from the start of standing under ozone gas.
C: The difference in ROD becomes 15 points from 4 to 7 days from the start of standing under ozone gas.
D: The difference in ROD becomes 15 points within 3 days from the start of standing under ozone gas.
In this evaluation, a small difference in ROD is excellent as a recorded material. Table 9 shows the evaluation results obtained as “Color balance 2”.

  Using the ink compositions having the compositions shown in Tables 1 to 6, ink sets of Examples 10 to 35 and Comparative Examples 3 to 4 were prepared based on combinations of the ink compositions shown in Table 10 below.

  The ink storage stability, ozone resistance, and light resistance evaluation (including color balance) of each ink composition in the ink sets of Examples 10 to 35 and Comparative Examples 3 to 5 were evaluated in Examples 1 to 9 and Comparative Example 1. And 2.

[Preparation of recorded matter with dark and light mixed inks]
Using the ink compositions having the compositions shown in Tables 1 to 6, yellow (Y), magenta (M), cyan (Cy), light cyan (LC), light magenta (LM), shown in Table 13 below, And ink sets of Examples 36 to 50 and Comparative Examples 6 to 8 were prepared based on the combination of the black (Bk) ink compositions.

Each ink composition in the ink sets of Examples 36 to 50 and Comparative Examples 6 to 8 was evaluated.
Also, using each ink set and an ink jet printer PM930C (trade name, manufactured by Seiko Epson Corporation), yellow (Y) on an inkjet dedicated recording medium {photographic paper <gloss> (trade name, manufactured by Seiko Epson Corporation)} ), Magenta (M), cyan (Cy), light cyan (LC), light magenta (LM), and black (Bk), and the OD value of each color is set to 0.7 to 1.8. Each color single-color image pattern in which the density changed in a shape and green, red, and gray image patterns were printed.
Evaluation of ozone resistance and light resistance (including color balance) for each color single-color image was performed in the same manner as in Examples 1 to 9 and Comparative Examples 1 and 2. However, the evaluation criteria for light resistance and ozone resistance were as follows.
The evaluation results are shown in Tables 14-15.

[Light resistance]
A: Light resistance evaluation is A for all six colors.
B: Light resistance evaluation is B for one or more of the six colors, and A for all the remaining colors.
C: Light resistance evaluation is C for one or more of the six colors, and A or B for the remaining colors.
D: Light resistance evaluation is D for one or more of the six colors.

[Ozone resistance]
A: The ozone resistance evaluation is A for all six colors.
B: The ozone resistance evaluation is B for one or more of the six colors, and A for all the remaining colors.
C: The ozone resistance evaluation is C for one or more of the six colors, and is A or B for the remaining colors.
D: The ozone resistance evaluation is D for one or more of the six colors.

  From the above results, it can be seen that the ink set of the present invention provides an image (recorded material) having excellent ink storage stability, good color balance, and excellent light resistance and ozone resistance. In particular, Example 9 (an ink using BLACK-11 (M: Li) as a dye compound) unexpectedly had a higher print density and a clearer black color than the others.

Claims (18)

An ink set comprising at least a black ink composition, a yellow ink composition, a magenta ink composition, and a cyan ink composition,
An ink set in which the black ink composition contains at least one selected from the group consisting of a compound represented by the following general formula (1) and a salt thereof as a colorant.

(In general formula (1), A represents a substituted or unsubstituted aryl group or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group. G represents a nitrogen atom or —C (R ₂ ) ═. ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group, and Y ₂ , Y _3, and Y ₄ each independently represent a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ and Y ₄ may combine with each other to form a ring, and all of Y ₂ , Y ₃ and Y ₄ do not represent a hydrogen atom at the same time, and M independently represents a hydrogen atom. Or represents a monovalent counter cation.) The ink set according to claim 1, wherein the black ink composition further contains a compound represented by the following general formula (B-14).
General formula (B-14):

In general formula (B-14), A ring, B ring, and C ring each independently represent a substituted or unsubstituted aryl group or heterocyclic group. A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₁₁ , A ₁₂ , A ₁₃ , A ₁₄ , A ₁₅ , B ₁ , B ₂ , B ₃ , B ₄ , B ₅ , B ₆ , B ₁₁ , B ₁₂ , B ₁₃ , B ₁₄ , B ₁₅ , B ₁₆ , C ₁ , C ₂ , C ₃ , C ₄ , C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ are each independently a hydrogen atom or a substituent Represents. Q ₁ and Q ₂ each independently represents a hydrogen atom or a substituent. L ₁₂ represents a divalent linking group. However, the compound of the general formula (B-14) has at least one ionic hydrophilic group.   The ink set according to claim 1 or 2, wherein the content of the colorant in the black ink composition is 0.1 to 30% by mass with respect to the total mass in the black ink composition. A yellow ink composition containing at least one compound selected from the group consisting of a compound represented by the following general formula (Y), a compound represented by the general formula (Y-2) and a salt thereof as a colorant is included. The ink set according to claim 1. However, general formula (Y-2) does not include general formula (Y).
General formula (Y):

(In the general formula (Y), each M independently represents a hydrogen atom or a cation. When M represents a cation, each represents a Li ⁺ ion, a Na ⁺ ion, a K ⁺ ion, or an NH ₄ ⁺ ion.)
General formula (Y-2):

In General Formula (Y-2), R ₄ represents a monovalent group, R ₅ represents —OR ₆ or —NHR ₇ , R ₆ and R ₇ represent a hydrogen atom or a monovalent group, and X ₃ Represents a divalent linking group, n ₃ is 0 or 1, Ar ₃ represents a divalent heterocyclic group, and Ar ₄ represents an alkyl group, an aryl group or a monovalent triazine ring group.   The ink set according to claim 4, wherein the content of the colorant in the yellow ink composition is 1.0 to 6.0 mass% with respect to the total mass in the yellow ink composition. The ink set according to claim 1, comprising a magenta ink composition containing at least one selected from the group consisting of a compound represented by the following formula (M-1) and a salt thereof as a colorant.
General formula (M-1):

In General Formula (M-1), A _M represents a 5-membered heterocyclic group.
B ₁ and _{B 2} are each _-CR 13 =, - or represents _{CR 14} =, or either one is a nitrogen atom, the other represents _{-CR 13} = or _{-CR 14} =.
R ₁₁ and R ₁₂ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl. Represents a group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Each group may further have a substituent. However, R ₁₁ and R ₁₂ are not simultaneously hydrogen atoms.
G, R ₁₃ and R ₁₄ 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, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, nitro group, alkyl group substituted by a group or a heterocyclic group A thio group, an arylthio group, an alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a heterocyclic thio group, or an ionic hydrophilic group. Each group may be further substituted. R ₁₃ and R ₁₁ , or R ₁₁ and R ₁₂ may be bonded to form a 5- or 6-membered ring. However, General Formula (M-1) has at least one ionic hydrophilic group.   The magenta ink composition includes two types of magenta ink compositions having different color densities, and at least one magenta ink composition is selected from the group consisting of the compound represented by the general formula (M-1) and a salt thereof. The ink set according to claim 6, comprising at least one selected as a colorant.   Of the two types of magenta ink compositions having different color densities, the magenta ink composition having a low color density is at least one selected from the group consisting of the compound represented by formula (M-1) and a salt thereof. The ink set according to claim 7, wherein the content of the colorant is 0.5 to 3.5% by mass based on the total mass of the magenta ink composition having the low color density.   Of the two types of magenta ink compositions having different color densities, the magenta ink composition having a high color density is at least one selected from the group consisting of the compound represented by formula (M-1) and a salt thereof. The ink set according to claim 7 or 8, wherein the content of the colorant is 3 to 10% by mass based on the total mass of the magenta ink composition having the high color density.   In the two types of magenta ink compositions having different color densities, the colorant contained in the magenta ink composition having a low color density (mass%) and the colorant contained in the magenta ink composition having a high color density. The ink set according to any one of claims 7 to 9, wherein a ratio with the concentration (mass%) of the agent is in the range of 1: 2 to 1: 8. The ink set according to any one of claims 1 to 10, comprising a cyan ink composition containing at least one selected from the group consisting of a compound represented by the following formula (C-1) and a salt thereof as a colorant. .
General formula (C-1):

In the general formula (C-1), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NV ₁ V ₂ , —CONV ₁ V. ₂ represents a _-CO 2 Z, -CO-Z, or a sulfo group. Here, Z represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. Each group may further have a substituent. V ₁ and V ₂ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. Each group may further have a substituent.
Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro Group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, Sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group, Or an ionic hydrophilic group , Each group may have a substituent.
a ₁ ~a ₄ and _b 1 ~b ₄ each represent the number of substituents of _X 1 to X ₄ and _Y 1 to Y _4. A _{1 to} a ₄ are each independently an integer of 0 to 4, and all do not become 0 at the same time. b ₁ ~b ₄ each independently represents an integer of 0-4.
M is a metal atom or an oxide, hydroxide or halide thereof.
Provided that at least one of X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y _3, and Y ₄ is an ionic hydrophilic group or a substituent on the ionic hydrophilic group As a group possessed as   The cyan ink composition includes two cyan ink compositions having different color densities, and at least one cyan ink composition is selected from the group consisting of the compound represented by formula (C-1) and a salt thereof. The ink set according to claim 11, comprising at least one selected as a colorant.   Of the two cyan ink compositions having different color densities, the cyan ink composition having a low color density is at least one selected from the group consisting of the compound represented by the general formula (C-1) and a salt thereof. The ink set according to claim 12, wherein the content of the colorant is 0.4 to 3.0% by mass with respect to the total mass of the cyan ink composition having the low color density.   Of the two cyan ink compositions having different color densities, the cyan ink composition having a high color density is at least one selected from the group consisting of the compound represented by formula (C-1) and a salt thereof. 14. The ink set according to claim 12, wherein the content of the colorant is 2.0 to 10.0% by mass based on the total mass of the cyan ink composition having the high color density. .   In the two cyan ink compositions having different color densities, the colorant contained in the cyan ink composition having a high color density and the density (mass%) of the colorant contained in the cyan ink composition having a low color density. The ink set according to any one of claims 12 to 14, wherein a ratio to the concentration (mass%) of the agent is in the range of 1: 2 to 1: 8.   An ink jet recording method comprising: recording using the ink set according to claim 1.   An ink jet recording method comprising forming an image using the ink set according to claim 1.   A recorded matter recorded using the ink set according to any one of claims 1 to 15.