JP5602387B2 - Ink jet ink, ink jet recording method, ink cartridge, recording unit, and ink jet recording apparatus - Google Patents

Description

  The present invention relates to an inkjet ink, an inkjet recording method, an ink cartridge, a recording unit, and an inkjet recording apparatus.

  The problem of the ink jet recording method is that the obtained recorded matter is inferior in image storability. In general, the recorded matter obtained by the ink jet recording method has lower image storage stability than the silver salt photograph. Specifically, when the recorded material is exposed to light, humidity, heat, or environmental gases that exist in the air for a long time, the color material on the recorded material deteriorates, causing a change in color tone or fading of the image. There is a problem that it is easy to do.

  Many proposals have heretofore been made in order to improve the light fastness of an image, particularly among image storability. For example, among the cyan, magenta, and yellow inks, a color material that can improve the light resistance of the image and can form an image with excellent color developability, particularly in a yellow ink with low image light resistance. Has been proposed (see Patent Document 1). In addition, there is a proposal for improving the light resistance of an image by using an ink using a plurality of different color materials that are considered to have excellent image fastness (see Patent Document 2).

  On the other hand, in the mechanism of the ink jet recording apparatus, there is a problem of ink contamination that occurs when substances eluted from ink cartridges that come into contact with ink or members constituting the ink supply path are mixed into the ink as impurities. That is, there is a problem that stable image formation is impaired by impurities mixed in the ink. For this problem, for example, there is a proposal relating to defining the amount of silicon eluted from the ink absorber in the ink cartridge and the conditions for performing stable ink jet recording (see Patent Document 3).

International Publication No. 2006/082669 Pamphlet JP 2005-146244 A JP-A-11-198399

However, as a result of the study by the present inventors, it has been found that there are the following problems even when the techniques described in the patent literature as mentioned above are used.
In recent years, the demand for image storability has been particularly increased, and even if the ink containing the color material described in Patent Document 1 is used, the light resistance of the formed image is no longer sufficient. It is coming. Furthermore, the color material described in Patent Document 1 gives a high optical density, while the color tone of the image is tinged with green, and when used in combination with cyan or magenta ink, the color reproduction range of red is large. There was another issue of loss. Further, when the present inventors examined the technique described in Patent Document 2, even if the color material described in Patent Document 1 and a different color material are used in combination, the formed image is still green. I found it tasted. This is because the conventional technology has not yet solved the problem of a large loss of the color reproduction range of red when used in combination with cyan or magenta ink, and has not yet provided ink with excellent color tone. It is shown that.

  In addition, there are impurities in the ink that are derived from substances that cannot be removed during the production of coloring materials, etc., and impurities that are believed to have eluted into the ink from members that make up the ink cartridge or ink supply path. There is a case. These substances mixed in the ink cause clogging of the ink supply path, ink supply characteristics, and a decrease in ink storage stability. This is a problem to be solved from the viewpoint of reliability. However, in general, it is difficult to remove such substances, and even if it can be removed, it is very expensive. It becomes a serious problem in practical use.

  Contamination of impurities into ink has been recognized as a problem to be solved in the past, and a countermeasure has been proposed, but it is not always a sufficient solution. In particular, with the recent high-definition ink jet recording methods in which ink is ejected as small droplets, for example, 5 pL (picoliter) or less, this problem has become more prominent. Under such circumstances, even if the technique described in Patent Document 3 mentioned above is used, it is not always a sufficient solution. This is presumably because, in the invention described in Patent Document 3, the idea is to keep the content of the causative substance in the ink below a certain level.

  Accordingly, an object of the present invention is to provide a yellow ink-jet ink that can give an image excellent in light resistance, can form an image excellent in color tone, and can sufficiently satisfy the reliability as an ink. There is. Another object of the present invention is to provide an ink jet recording method, an ink cartridge, a recording unit, and an ink jet recording apparatus using the ink jet ink.

（一般式（Ｉ）中、Ｒ ₁ 、Ｒ ₂ 、Ｙ ₁ 、及びＹ ₂ はそれぞれ独立に、一価の基であり、Ｘ ₁ 及びＸ ₂ はそれぞれ独立に、ハメットのσｐ値が０．２０以上の電子吸引性基であり、Ｚ ₁ 及びＺ ₂ はそれぞれ独立に、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアラルキル基、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ヘテロ環基であり、Ｍ ₁ は、水素原子、アルカリ金属、アンモニウム、又は有機アンモニウムである。）

（一般式（II）中、Ｒ ₃ 及びＹ ₃ はそれぞれ独立に、一価の基であり、Ｘ ₃ はハメットのσｐ値が０．２０以上の電子吸引性基であり、Ｚ ₃ は、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアラルキル基、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ヘテロ環基である。）

（一般式（III）中、Ｒ ₄ 及びＹ ₄ はそれぞれ独立に、一価の基であり、Ｘ ₄ はハメットのσｐ値が０．２０以上の電子吸引性基であり、Ｚ ₄ 及びＺ ₅ はそれぞれ独立に、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアラルキル基、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ヘテロ環基であり、Ｍ ₂ は、水素原子、アルカリ金属、アンモニウム、又は有機アンモニウムである。） The above object is achieved by the present invention described below. That is, the ink-jet ink according to the present invention is an ink-jet ink containing at least two color materials, that is, a first color material and a second color material. a compound of formula (I), the second coloring material is a compound represented by the following formula the compound represented by及beauty under following general formula in (II) (III), wherein the The content (mass%) of the color material 2 in the ink is 0.002 times or more and 0.50 times or less in terms of mass ratio with respect to the content (mass%) of the first color material in the ink. It is characterized by being.

(In the general formula (I), R ₁ , R ₂ , Y ₁ , and Y ₂ are each independently a monovalent group, and X ₁ and X ₂ are each independently a Hammett σp value of 0.20. These electron-withdrawing groups, Z ₁ and Z ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, substituted or unsubstituted And an aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and M ₁ is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

(In the general formula (II), R ₃ and Y ₃ are each independently a monovalent group, X ₃ is an electron-withdrawing group having a Hammett's σp value of 0.20 or more, and Z ₃ is hydrogen. Atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted heterocycles Group.)

(In general formula (III), R ₄ and Y ₄ are each independently a monovalent group, X ₄ is an electron-withdrawing group having a Hammett's σp value of 0.20 or more, and Z ₄ and Z ₅ Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted group Or an unsubstituted heterocyclic group, and M ₂ is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

  According to the present invention, it is possible to provide a yellow inkjet ink that can give an image excellent in light resistance, can form an image excellent in color tone, and can sufficiently satisfy the reliability as an ink. it can. Moreover, according to another embodiment of the present invention, an ink jet recording method, an ink cartridge, a recording unit, and an ink jet recording apparatus using the ink jet ink can be provided.

It is a perspective view of an inkjet recording device. It is a perspective view of the mechanism part of an inkjet recording device. It is sectional drawing of an inkjet recording device. FIG. 4 is a perspective view of a state where an ink cartridge is mounted on a head cartridge. It is a disassembled perspective view of a head cartridge. FIG. 6 is a front view showing a recording element substrate in the head cartridge.

Hereinafter, preferred embodiments of the present invention will be described in detail.
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. Further, in the following description, the compound represented by the general formula (I) and the compound represented by the general formula (IV), which are the first coloring material, are respectively “compound of general formula (I)”, And may be abbreviated as “compound of general formula (IV)”. In addition, the compound represented by the general formula (II) and the compound represented by the general formula (III), which are the second coloring material, are respectively “compound of general formula (II)” and “general formula (II)”. It may be abbreviated as “compound of III)”. Furthermore, the compound represented by the general formula (V) and the compound represented by the general formula (VI), which are the second coloring material, are respectively “compound of general formula (V)” and “general formula ( It may be abbreviated as “compound of VI)”.

In light of the above-described problems of the prior art, the present inventors have considered that it is necessary to conduct a detailed study on the color material used for yellow ink.
As described above, among yellow, magenta, and cyan inks that are widely used as inkjet inks, yellow ink tends to be inferior in light resistance of an image to be formed. Accordingly, the present inventors have made various studies on the color material used for the yellow ink. As a result, the compound of the following general formula (I) described in the above-mentioned Patent Document 1 and the compound of the following general formula (IV), among others, were noted to be excellent in light resistance and color developability.

  Furthermore, the present inventors prepared an ink containing only the compound of the general formula (I) as a coloring material, and examined various images formed using the ink and reliability as the ink. As a result, the image storability of the recorded matter obtained using the ink containing only the compound of the general formula (I) as the coloring material has a certain performance or more, but particularly in the light resistance of the image in recent years. It has been concluded that it is still insufficient to satisfy the high demands of Japan. In particular, the color tone of a yellow image formed using the ink is tinged with green, and the color reproduction range in an image formed by combining the ink with cyan ink and magenta ink having various hue angles, particularly Also found that the red area lost a lot. Furthermore, it has been found that if the ink is mounted on the ink jet recording apparatus and left for a long period of time without using the ink jet recording apparatus, the discharge performance and the storage stability of the ink may decrease depending on the ink jet recording apparatus. .

  As a result of detailed studies by the present inventors on these phenomena, it was found that an ink having a relatively small content of the compound of the general formula (I) is inferior in image storage stability, particularly light resistance, of the formed image. On the other hand, when the ink containing a large amount of the compound of the general formula (I) is relatively excellent in light resistance of the formed image, the color tone is tinged with green, and when used in combination with cyan or magenta ink In addition, there is a problem that the red area is largely lost. Further, when the ink having a large content of the compound of the general formula (I) is mounted on the ink jet recording apparatus and left for a long time without using the ink jet recording apparatus, the recording head is observed. There was something happening. As a result of examining the foreign matter, it was found that the foreign matter was eluted from members constituting the ink cartridge and the ink supply path, or originated from ions such as metal and silicon which are considered to be contained in the coloring material. It has been found that when a recording head in which such foreign matter is generated is used, the ejection performance is lowered due to the foreign matter, and the storage stability of the ink is lowered due to the foreign matter.

  That is, for an image formed using an ink containing the compound of the general formula (I), it has been conventionally possible to achieve both excellent light resistance, color reproduction range, and all the performances that satisfy the reliability as an ink. The technology of was insufficient. More specifically, the provision of ink that simultaneously satisfies the following three performances cannot be sufficiently achieved by the conventional technology. The color reproduction range of red of an image formed by improving the light fastness of an ink image containing the specific color material until a high level required in recent years is satisfied, and using the ink together with cyan or magenta ink To satisfy the reliability of ink.

  The present inventors have studied to solve the above technical problem that occurs when the compound of the general formula (I) is used, and have made the present invention. That is, in the present invention, the compound represented by the following general formula (I) as the first color material, the compound represented by the following general formula (II) as the second color material, and / or the following general formula. The above technical problem is solved by an ink containing the compound represented by (III) at a specific mass ratio.

（一般式（Ｉ）中、Ｒ₁、Ｒ₂、Ｙ₁、及びＹ₂はそれぞれ独立に、一価の基であり、Ｘ₁及びＸ₂はそれぞれ独立に、ハメットのσｐ値が０．２０以上の電子吸引性基である。また、Ｚ₁及びＺ₂はそれぞれ独立に、水素原子及び下記の置換基からなる群から選ばれる。置換基の群は、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアラルキル基、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ヘテロ環基である。また、Ｍ₁は、水素原子、アルカリ金属、アンモニウム、又は有機アンモニウムである。）

(In the general formula (I), R ₁ , R ₂ , Y ₁ , and Y ₂ are each independently a monovalent group, and X ₁ and X ₂ are each independently a Hammett σp value of 0.20. In addition, each of Z ₁ and Z ₂ is independently selected from the group consisting of a hydrogen atom and the following substituents, wherein the substituent group includes a substituted or unsubstituted alkyl group, a substituted group Or an unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and M ₁ represents hydrogen. Atom, alkali metal, ammonium, or organic ammonium.)

（一般式（II）中、Ｒ₃及びＹ₃はそれぞれ独立に、一価の基であり、Ｘ₃はハメットのσｐ値が０．２０以上の電子吸引性基である。また、Ｚ₃は、水素原子及び下記の置換基からなる群から選ばれる。置換基の群は、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアラルキル基、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ヘテロ環基である。）

(In General Formula (II), R ₃ and Y ₃ are each independently a monovalent group, X ₃ is an electron-withdrawing group having a Hammett's σp value of 0.20 or more, and Z ₃ is Selected from the group consisting of a hydrogen atom and the following substituents: The substituted group is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted group. An aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.)

（一般式（III）中、Ｒ₄及びＹ₄はそれぞれ独立に、一価の基であり、Ｘ₄はハメットのσｐ値が０．２０以上の電子吸引性基である。また、Ｚ₄及びＺ₅はそれぞれ独立に、水素原子及び下記の置換基からなる群から選ばれる。置換基の群は、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアラルキル基、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ヘテロ環基である。また、Ｍ₂は、水素原子、アルカリ金属、アンモニウム、又は有機アンモニウムである。）

(In the general formula (III), each R ₄ and Y ₄ independently a monovalent group, X ₄ is σp value of Hammett's of 0.20 or more electron withdrawing group. Also, Z ₄ and Each Z ₅ is independently selected from the group consisting of a hydrogen atom and the following substituents: a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group; A substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and M ₂ is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

  In the present invention, in particular, a compound represented by the following general formula (IV) is used as the first color material, and a compound represented by the following general formula (V) as the second color material and / or It is preferable to use a compound represented by the following general formula (VI).

（一般式（IV）中、Ｒ₅、Ｒ₆、Ｙ₁及びＹ₂はそれぞれ独立に、一価の基であり、Ｘ₁及びＸ₂はそれぞれ独立に、ハメットのσｐ値が０．２０以上の電子吸引性基であり、ｎは１以上の整数である。また、Ｍ₁は、水素原子、アルカリ金属、アンモニウム、又は有機アンモニウムである。）

(In the general formula (IV), R ₅ , R ₆ , Y ₁ and Y ₂ are each independently a monovalent group, and X ₁ and X ₂ are each independently having a Hammett σp value of 0.20 or more. And n is an integer of 1 or more, and M ₁ is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

（一般式（Ｖ）中、Ｒ₇及びＹ₃はそれぞれ独立に、一価の基であり、Ｘ₃はハメットのσｐ値が０．２０以上の電子吸引性基であり、ｎは１以上の整数である。）

(In the general formula (V), R ₇ and Y ₃ are each independently a monovalent group, X ₃ is an electron-withdrawing group having a Hammett σp value of 0.20 or more, and n is 1 or more. (It is an integer.)

（一般式（VI）中、Ｒ₈及びＹ₄はそれぞれ独立に、一価の基であり、Ｘ₄はハメットのσｐ値が０．２０以上の電子吸引性基であり、ｎは１以上の整数である。また、Ｚは、水素原子及び下記の置換基からなる群から選ばれる。置換基の群は、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアラルキル基、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ヘテロ環基である。また、Ｍ₂は、水素原子、アルカリ金属、アンモニウム、又は有機アンモニウムである。）

(In General Formula (VI), R ₈ and Y ₄ are each independently a monovalent group, X ₄ is an electron-withdrawing group having a Hammett's σp value of 0.20 or more, and n is 1 or more. Z is selected from the group consisting of a hydrogen atom and the following substituents: The group of substituents is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group. An alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and M ₂ is a hydrogen atom, an alkali metal, ammonium, or organic ammonium. .)

  As described above, the effects of the present invention can be obtained particularly remarkably by combining the color materials used in the ink with a combination of compounds having a specific structure and including these color materials in the ink at a specific mass ratio. . Hereinafter, the ink-jet ink of the present invention will be described in detail.

<Ink>
Hereinafter, components constituting the ink-jet ink according to the present invention (hereinafter sometimes simply referred to as ink), physical properties of the ink, and the like will be described in detail.

(Color material)
[First coloring material: compound represented by general formula (I) and compound represented by general formula (IV)]
The ink of the present invention needs to contain a compound of the following general formula (I) having the characteristics of excellent light resistance and color development as the first coloring material. Among the compounds of the following general formula (I), it is particularly preferable to use a compound of the following general formula (IV). Hereinafter, these general formulas will be described.

（一般式（Ｉ）中、Ｒ₁、Ｒ₂、Ｙ₁、及びＹ₂はそれぞれ独立に、一価の基であり、Ｘ₁及びＸ₂はそれぞれ独立に、ハメットのσｐ値が０．２０以上の電子吸引性基である。また、Ｚ₁及びＺ₂はそれぞれ独立に、水素原子及び下記の置換基からなる群から選ばれる。置換基の群は、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアラルキル基、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ヘテロ環基である。また、Ｍ₁は、水素原子、アルカリ金属、アンモニウム、又は有機アンモニウムである。）

(In the general formula (I), R ₁ , R ₂ , Y ₁ , and Y ₂ are each independently a monovalent group, and X ₁ and X ₂ are each independently a Hammett σp value of 0.20. In addition, each of Z ₁ and Z ₂ is independently selected from the group consisting of a hydrogen atom and the following substituents, wherein the substituent group includes a substituted or unsubstituted alkyl group, a substituted group Or an unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and M ₁ represents hydrogen. Atom, alkali metal, ammonium, or organic ammonium.)

（一般式（IV）中、Ｒ₅、Ｒ₆、Ｙ₁及びＹ₂はそれぞれ独立に、一価の基であり、Ｘ₁及びＸ₂はそれぞれ独立に、ハメットのσｐ値が０．２０以上の電子吸引性基であり、ｎは１以上の整数である。また、Ｍ₁は、水素原子、アルカリ金属、アンモニウム、又は有機アンモニウムである。）

(In the general formula (IV), R ₅ , R ₆ , Y ₁ and Y ₂ are each independently a monovalent group, and X ₁ and X ₂ are each independently having a Hammett σp value of 0.20 or more. And n is an integer of 1 or more, and M ₁ is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

R ₁ , R ₂ , Y ₁ and Y ₂ in the general formula (I) and R ₅ , R ₆ , Y ₁ and Y ₂ in the general formula (IV) are each independently a monovalent group. Specifically, it can be any of the following substituents. Hydrogen atom, halogen atom, alkyl group, cycloalkyl 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. An amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonylamino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group; Alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group. Examples thereof include an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a silyl group, an azo group, and an imide group. These groups may further have a substituent.

  Among those described above, those selected from the following groups are particularly preferable. As a preferred group, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an amide group, a ureido group, an alkylsulfonylamino group, and an arylsulfonylamino group. And a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, and an alkoxycarbonyl group. Among these, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic group are more preferable. Further, a hydrogen atom, an alkyl group, an aryl group, a cyano group, or an alkylsulfonyl group is particularly preferable.

Hereinafter, R ₁ , R ₂ , Y ₁ and Y ₂ in the general formula (I) and those constituting R ₅ , R ₆ , Y ₁ and Y ₂ in the general formula (IV) will be described in more detail. .

  Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom. Among them, a chlorine atom or a bromine atom is preferable, and a chlorine atom is particularly preferable.

  Examples of the alkyl group include substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms. Specific examples include methyl, ethyl, butyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, hydroxyethyl, cyanoethyl, and 4-sulfobutyl.

  Examples of the cycloalkyl group include substituted or unsubstituted cycloalkyl groups having 5 to 30 carbon atoms. Specific examples include cyclohexyl, cyclopentyl, and 4-n-dodecylcyclohexyl.

  Examples of the aralkyl group include substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms. Specific examples include benzyl and 2-phenethyl.

  Examples of the alkenyl group include substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms. Specific examples include vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, and the like.

  Examples of the alkynyl group include substituted or unsubstituted alkynyl groups having 2 to 30 carbon atoms. Specific examples include ethynyl and propargyl.

  Examples of the aryl group include substituted or unsubstituted aryl groups having 6 to 30 carbon atoms. Specific examples include phenyl, p-tolyl, naphthyl, m-chlorophenyl, and o-hexadecanoylaminophenyl.

  A heterocyclic group is a 5-membered or 6-membered ring, and is a monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. It may be condensed. Among these, an aromatic heterocyclic group having a 5- or 6-membered ring having 3 to 50 carbon atoms is preferable. Specific examples of the heterocyclic group include the followings when exemplified without limiting the substitution position. Pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene. Pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole. Thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole. And isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, and thiazoline.

  Examples of the alkoxy group include substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms. Specific examples include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy, and 3-carboxypropoxy.

  Examples of the aryloxy group include substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms. Specific examples include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy and the like.

  Examples of the silyloxy group include silyloxy groups having 3 to 20 carbon atoms. Specific examples include trimethylsilyloxy and t-butyldimethylsilyloxy.

  Examples of the heterocyclic oxy group include substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms. Specific examples include 1-phenyltetrazole-5-oxy and 2-tetrahydropyranyloxy.

  Examples of the acyloxy group 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. Specific examples include formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, and p-methoxyphenylcarbonyloxy.

  Examples of the carbamoyloxy group include substituted or unsubstituted carbamoyloxy groups having 1 to 30 carbon atoms. Specific examples include N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy and the like. It is done.

  Examples of the alkoxycarbonyloxy group include substituted or unsubstituted alkoxycarbonyloxy groups having 2 to 30 carbon atoms. Specific examples include methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, and n-octylcarbonyloxy.

  Examples of the aryloxycarbonyloxy group include substituted or unsubstituted aryloxycarbonyloxy groups having 7 to 30 carbon atoms. Specific examples include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, and pn-hexadecyloxyphenoxycarbonyloxy.

  Examples of the amino group include a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms and a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. Specific examples include amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, hydroxyethylamino, carboxyethylamino, sulfoethylamino, and 3,5-dicarboxyanilino. Can be mentioned.

  Examples of the acylamino group 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. Specific examples include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino, and the like.

  Examples of the aminocarbonylamino group include substituted or unsubstituted aminocarbonylamino groups having 1 to 30 carbon atoms. Specific examples include carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like.

  Examples of the alkoxycarbonylamino group include substituted or unsubstituted alkoxycarbonylamino groups having 2 to 30 carbon atoms. Specific examples include methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino and the like.

  Examples of the aryloxycarbonylamino group include substituted or unsubstituted aryloxycarbonylamino groups having 7 to 30 carbon atoms. Specific examples include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, and mn-octyloxyphenoxycarbonylamino.

  Examples of the sulfamoylamino group include substituted or unsubstituted sulfamoylamino groups having 0 to 30 carbon atoms. Specific examples include sulfamoylamino, N, N-dimethylaminosulfonylamino, and Nn-octylaminosulfonylamino.

  Examples of the alkylsulfonylamino group and arylsulfonylamino group include substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms and substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms. Specific examples include methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, and p-methylphenylsulfonylamino.

  Examples of the alkylthio group include substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms. Specific examples include methylthio, ethylthio, and n-hexadecylthio.

  Examples of the arylthio group include substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms. Specific examples include phenylthio, p-chlorophenylthio, and m-methoxyphenylthio.

  Examples of the heterocyclic thio group include substituted or unsubstituted heterocyclic thio groups having 2 to 30 carbon atoms. Specific examples include 2-benzothiazolylthio and 1-phenyltetrazol-5-ylthio.

  Examples of the sulfamoyl group include substituted or unsubstituted sulfamoyl groups having 0 to 30 carbon atoms. Specific examples include the following. That is, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, and N- (N′- Phenylcarbamoyl) sulfamoyl and the like.

  Examples of the alkylsulfinyl group and arylsulfinyl group include substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms and substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms. Specific examples include methylsulfinyl, ethylsulfinyl, phenylsulfinyl, and p-methylphenylsulfinyl.

  Examples of the alkylsulfonyl group and arylsulfonyl group include substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms and substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms. Specific examples include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, and p-toluenesulfonyl.

  The following are mentioned as an acyl group. That is, a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms. And a heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms. Specific examples include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl, and the like.

  Examples of the aryloxycarbonyl group include substituted or unsubstituted aryloxycarbonyl groups having 7 to 30 carbon atoms. Specific examples include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl, and the like.

  Examples of the alkoxycarbonyl group include substituted or unsubstituted alkoxycarbonyl groups having 2 to 30 carbon atoms. Specific examples include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, and n-octadecyloxycarbonyl.

  Examples of the carbamoyl group include substituted or unsubstituted carbamoyl groups having 1 to 30 carbon atoms. Specific examples include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, and N- (methylsulfonyl) carbamoyl.

  Examples of the phosphino group include substituted or unsubstituted phosphino groups having 2 to 30 carbon atoms. Specific examples include dimethylphosphino, diphenylphosphino, and methylphenoxyphosphino.

  Examples of the phosphinyl group include substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms. Specific examples include phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl and the like.

  Examples of the phosphinyloxy group include substituted or unsubstituted phosphinyloxy groups having 2 to 30 carbon atoms. Specific examples include diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.

  Examples of the phosphinylamino group include substituted or unsubstituted phosphinylamino groups having 2 to 30 carbon atoms. Specific examples include dimethoxyphosphinylamino and dimethylaminophosphinylamino.

  Examples of the silyl group include substituted or unsubstituted silyl groups having 3 to 30 carbon atoms. Specific examples include trimethylsilyl, t-butyldimethylsilyl, and phenyldimethylsilyl.

  Specific examples of the azo group include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, and 2-hydroxy-4-propanoylphenylazo.

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

  Each of the substituents listed above may be further substituted. The substituent in this case may be selected from the group consisting of the substituents listed below, for example. Straight chain or branched alkyl group having 1 to 12 carbon atoms, straight chain or branched aralkyl group having 7 to 18 carbon atoms, straight chain or branched chain alkenyl group having 2 to 12 carbon atoms, straight chain having 2 to 12 carbon atoms Or a branched alkynyl group. And a linear or branched cycloalkyl group having 3 to 12 carbon atoms and a linear or branched cycloalkenyl group having 3 to 12 carbon atoms. These substituents are preferably those having a branched chain, and more preferably those having an asymmetric carbon, in order to improve the solubility of the dye and the stability of the ink.

R ₁ , R ₂ , Y ₁ and Y ₂ in the general formula (I) of the present invention, and the general formula (IV), which are exemplified as substituents included in the above substituent group and other usable substituents. Specific examples of the substituent in R ₅ , R ₆ , Y ₁ and Y ₂ in the following include the following. A substituted or unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, and cyclopentyl; a chlorine atom; And halogen atoms such as bromine atom; aryl groups such as phenyl, 4-t-butylphenyl, and 2,4-di-t-amylphenyl; imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl And heterocyclic groups such as 2-benzothiazolyl; cyano group; hydroxyl group; nitro group; carboxy group; amino group; alkyloxy groups such as methoxy, ethoxy, 2-methoxyethoxy, and 2-methylsulfonylethoxy; phenoxy, 2 -Methylphenoxy, 4-t- Aryloxy groups such as tilphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, and 3-methoxycarbonylphenyloxy; acetamide, benzamide, and 4- (3-t-butyl-4-hydroxyphenoxy) butanamide Acylamino groups such as; methylamino, butylamino, diethylamino, and alkylamino groups such as methylbutylamino; phenylamino and anilino groups such as 2-chloroanilino; phenylureido, methylureido, and N, N-dibutylureido Ureido groups; sulfamoylamino groups such as N, N-dipropylsulfamoylamino; alkylthio groups such as methylthio, octylthio, and 2-phenoxyethylthio; phenylthio, 2-butoxy-5-t- Arylthio groups such as octylphenylthio and 2-carboxyphenylthio; alkyloxycarbonylamino groups such as methoxycarbonylamino; alkyl or arylsulfonylamino groups such as methylsulfonylamino, phenylsulfonylamino, and p-toluenesulfonylamino; N Carbamoyl groups such as ethylcarbamoyl and N, N-dibutylcarbamoyl; sulfamoyl groups such as N-ethylsulfamoyl, N, N-dipropylsulfamoyl and N-phenylsulfamoyl; methylsulfonyl, octylsulfonyl, Sulfonyl groups such as phenylsulfonyl and p-toluenesulfonyl; alkyloxycarbonyl groups such as methoxycarbonyl and butyloxycarbonyl; 1-phenyltetrazole- Heterocyclic oxy groups such as 5-oxy and 2-tetrahydropyranyloxy; azo groups such as phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, and 2-hydroxy-4-propanoylphenylazo Acyloxy groups such as acetoxy; carbamoyloxy groups such as N-methylcarbamoyloxy and N-phenylcarbamoyloxy; silyloxy groups such as trimethylsilyloxy and dibutylmethylsilyloxy; aryloxycarbonylamino groups such as phenoxycarbonylamino; N An imide group such as succinimide and N-phthalimide; a heterocyclic thio group such as 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, and 2-pyridylthio; 3-pheno Sulfinyl groups such as cypropylsulfinyl; phosphonyl groups such as phenoxyphosphonyl, octyloxyphosphonyl, and phenylphosphonyl; aryloxycarbonyl groups such as phenoxycarbonyl; acyl groups such as acetyl, 3-phenylpropanoyl, and benzoyl; Examples thereof include ionic hydrophilic groups such as a carboxyl group, a sulfonic acid group, a phosphono group, and a quaternary ammonium group.

R ₅ and R ₆ in the general formula (IV) are each independently a monovalent group. However, in order for the compound of the general formula (IV) to have hydrophilicity, these groups are ionic hydrophilic groups. Preferably there is. Specific examples of such ionic hydrophilic groups include sulfonic acid groups, carboxyl groups, hydroxyl groups, or phosphono groups, or salts thereof, or quaternary ammonium salts. Among these, a sulfonic acid group, a carboxyl group, or a hydroxyl group is particularly preferable. Examples of counter ions of these ionic hydrophilic groups include alkali metal ions, ammonium ions, or organic ammonium ions. Among these, an alkali metal ion is particularly preferable. When the ionic hydrophilic group is a sulfonic acid group, it is a lithium salt, and when the ionic hydrophilic group is a carboxyl group, it is a sodium salt or a potassium salt. preferable.

X ₁ and X ₂ in the general formula (I), and X ₁ and X ₂ in the general formula (IV), .sigma.p value of Hammett is 0.20 or more electron withdrawing groups.

  Here, Hammett's rule and Hammett's substituent constant σp value (hereinafter referred to as “Hammett σp value”) will be described. Hammett's rule is an empirical rule proposed by L.P. Hammett in 1935 to quantitatively discuss the influence of substituents on the reaction and equilibrium of benzene derivatives, and is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values are described in many general books. For example, there is a detailed description in J.A. Dean, Lange's Handbook of Chemistry, 12th edition, 1979, McGraw-Hill, Chemistry, Special Issue, 122, 96-103, 1979, Nankodo.

  In the present invention, each substituent is defined by Hammett's σp value. However, the present invention is not limited to only the substituents whose σp values are specifically described in the above-mentioned literature. In the present invention, even if the σp value is not described in the literature as described above, when the σp value is calculated based on the Hammett rule, the substituent that will be included in the range is also included. Including. Neither the compound of the general formula (I) nor the compound of the general formula (IV) is a benzene derivative. However, in the present invention, the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. To do. Specific examples of the substituent that can be used as an electron-withdrawing group having a Hammett's σp value of 0.20 or more in the substituent of the compound of the general formula (I) or the compound of the general formula (IV) of the present invention are as follows. Examples are listed for each range of Hammett σp values.

  Examples of the electron-withdrawing group having a Hammett σp value of 0.60 or more include the following. A cyano group, a nitro group, an alkylsulfonyl group (for example, methanesulfonyl group), an arylsulfonyl group (for example, benzenesulfonyl group).

In addition to the above, examples of the electron withdrawing group having a Hammett σp value of 0.45 or more include the following.
An acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, m-chlorophenoxycarbonyl group). An alkylsulfinyl group (for example, n-propylsulfinyl group), an arylsulfinyl group (for example, phenylsulfinyl group); A sulfamoyl group (for example, N-ethylsulfamoyl group, N, N-dimethylsulfamoyl group), a halogenated alkyl group (for example, trifluoromethyl group).

In addition to the above, examples of the electron-withdrawing group having a Hammett's σp value of 0.30 or more include the following.
Acyloxy group (for example, acetoxy group), carbamoyl group (for example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group). A halogenated alkoxy group (for example, trifluoromethyloxy group), a halogenated aryloxy group (for example, pentafluorophenyloxy group); Sulfonyloxy group (for example, methylsulfonyloxy group), halogenated alkylthio group (for example, difluoromethylthio group). An aryl group substituted with an electron-withdrawing group having two or more σp values of 0.15 or more (for example, 2,4-dinitrophenyl group, pentachlorophenyl group). Heterocycle (for example, 2-benzoxazolyl group, 2-benzothiazolyl group, 1-phenyl-2-benzimidazolyl group).

  Examples of the electron-withdrawing group having a Hammett σp value of 0.20 or more include halogen atoms (for example, fluorine, chlorine, bromine) and the like.

Z ₁ and Z ₂ in the general formula (I) are each independently any of the substituents listed below. That is, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group Any one of the heterocyclic groups.

Examples of the alkyl group include R ₁ , R ₂ , Y ₁ and Y ₂ in the general formula (I), and alkyls mentioned in the description of R ₅ , R ₆ , Y ₁ and Y _{2 in} the general formula (IV). The same thing as a group is mentioned. Examples of the alkenyl group include R ₁ , R ₂ , Y ₁ and Y ₂ in the general formula (I), and alkenyl mentioned in the description of R ₅ , R ₆ , Y ₁ and Y _{2 in} the general formula (IV). The same thing as a group is mentioned. Examples of the alkynyl group include R ₁ , R ₂ , Y ₁ and Y ₂ in the general formula (I) and R ₅ , R ₆ , Y ₁ and Y _{2 in} the general formula (IV). The same thing as a group is mentioned. As the aralkyl group, R ₁ , R ₂ , Y ₁ and Y ₂ in the general formula (I), and the aralkyl mentioned in the description of R ₅ , R ₆ , Y ₁ and Y _{2 in} the general formula (IV). The same thing as a group is mentioned. Examples of the aryl group include R ₁ , R ₂ , Y ₁ and Y ₂ in the general formula (I), and aryls mentioned in the description of R ₅ , R ₆ , Y ₁ and Y _{2 in} the general formula (IV). The same thing as a group is mentioned. Examples of the heterocyclic group include R ₁ , R ₂ , Y ₁ and Y ₂ in the general formula (I), and R ₅ , R ₆ , Y ₁ and Y _{2 in} the general formula (IV). The same thing as the heterocyclic group mentioned.

Moreover, these substituents may be further substituted. The substituents in this case are R ₁ , R ₂ , Y ₁ and Y ₂ in the general formula (I), and R ₅ , R ₆ , Y ₁ and Y _{2 in} the general formula (IV). And the same groups as those mentioned as the group for further substituting the substituents mentioned in the above.

M ₁ in the general formula (I) and the general formula (IV) is each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the organic ammonium include acetamide, benzamide, methylamino, butylamino, diethylamino, and phenylamino. Each n in the general formula (IV) is independently an integer of 1 or more, preferably an integer of 1 to 5, and more preferably 2.

  Preferable specific examples of the compound of the general formula (I) or the compound of the general formula (IV) include the following exemplified compounds 1 to 14. In addition, the following exemplary compounds are described in the form of a free acid. Of course, the present invention is not limited to the following exemplary compounds as long as they are included in the structure of the general formula (I) or the general formula (IV) and the definition thereof. In the present invention, it is particularly preferable to use the exemplified compound 5 among the following exemplified compounds.

[Second colorant: a compound represented by general formula (II), a compound represented by general formula (III), a compound represented by general formula (V), and a general formula (VI) Compound)
The ink of the present invention has a feature that it has excellent color developability in addition to the compound of the general formula (I) or the compound of the general formula (IV) described above used as the first color material. It is necessary to contain a coloring material. In the present invention, a compound of the following general formula (II) and / or a compound of the following general formula (III) is used as the second coloring material. Among the compounds of the following general formula (II), it is particularly preferable to use the compounds of the following general formula (V), and among the compounds of the following general formula (III), particularly the compounds of the following general formula (VI).

  In the present invention, as the second coloring material, a compound of the general formula (II) and / or a compound of the general formula (III), particularly preferably a compound of the general formula (V) and / or a compound of the general formula (VI) May be used alone or in combination. In the present invention, it is further preferable to use a compound of the general formula (II) and a compound of the general formula (III), particularly preferably a compound of the general formula (V) and a compound of the general formula (VI).

  In addition, the compound of the following general formula (II) and the compound of the following general formula (III) exhibit a synergistic effect when used in combination with the compound of the general formula (I), and can obtain the following effects. it can. That is, by containing these color materials, not only can the ink have a preferable yellow color tone, but also an image with excellent light resistance can be provided, and in addition, the reliability as the ink can be sufficiently satisfied. Can do. Hereinafter, these general formulas will be described.

（一般式（II）中、Ｒ₃及びＹ₃はそれぞれ独立に、一価の基であり、Ｘ₃はハメットのσｐ値が０．２０以上の電子吸引性基である。また、Ｚ₃は、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアラルキル基、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ヘテロ環基である。）

(In General Formula (II), R ₃ and Y ₃ are each independently a monovalent group, X ₃ is an electron-withdrawing group having a Hammett's σp value of 0.20 or more, and Z ₃ is , Hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted It is a heterocyclic group.)

（一般式（III）中、Ｒ₄及びＹ₄はそれぞれ独立に、一価の基であり、Ｘ₄はハメットのσｐ値が０．２０以上の電子吸引性基である。また、Ｚ₄及びＺ₅はそれぞれ独立に、下記に挙げる群から選ばれる。すなわち、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアラルキル基、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ヘテロ環基から選ばれる。また、Ｍ₂は、水素原子、アルカリ金属、アンモニウム、又は有機アンモニウムである。）

(In the general formula (III), each R ₄ and Y ₄ independently a monovalent group, X ₄ is σp value of Hammett's of 0.20 or more electron withdrawing group. Also, Z ₄ and Z ₅ is independently selected from the following groups: hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aralkyl Selected from a group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and M ₂ is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

（一般式（Ｖ）中、Ｒ₇及びＹ₃はそれぞれ独立に、一価の基であり、Ｘ₃はハメットのσｐ値が０．２０以上の電子吸引性基であり、ｎは１以上の整数である。）

(In the general formula (V), R ₇ and Y ₃ are each independently a monovalent group, X ₃ is an electron-withdrawing group having a Hammett σp value of 0.20 or more, and n is 1 or more. (It is an integer.)

（一般式（VI）中、Ｒ₈及びＹ₄はそれぞれ独立に、一価の基であり、Ｘ₄はハメットのσｐ値が０．２０以上の電子吸引性基であり、ｎは１以上の整数である。また、Ｚは、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基、置換若しくは無置換のアラルキル基、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ヘテロ環基である。また、Ｍ₂は、水素原子、アルカリ金属、アンモニウム、又は有機アンモニウムである。）

(In General Formula (VI), R ₈ and Y ₄ are each independently a monovalent group, X ₄ is an electron-withdrawing group having a Hammett's σp value of 0.20 or more, and n is 1 or more. Z is a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl Or a substituted or unsubstituted heterocyclic group, and M ₂ is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

Y ₃ and R _{3 in} the general formula (II), Y ₄ and R ₄ in the general formula (III), Y ₃ and R ₇ in the general formula (V), and Y ₄ and R ₈ in the general formula (VI) are Each is independently a monovalent group. Specific examples of these groups include specific examples of R ₁ , R ₂ , Y ₁ and Y ₂ in the general formula (I), and R ₅ , R ₆ , Y ₁ and Y _{2 in} the general formula (IV). The same as those mentioned above. When these groups further have a substituent, R ₁ , R ₂ , Y ₁ and Y ₂ in the above general formula (I) and R ₅ , R ₆ , Y ₁ and Y ₂ in the general formula (IV) The same as those mentioned as the substituents for.

R ₇ in the general formula (V) and R ₈ in the general formula (VI) are each independently a monovalent group. However, in order for the compound to have hydrophilicity, these are ionic hydrophilic groups. It is preferable. Specific examples of the ionic hydrophilic group include a sulfonic acid group, a carboxyl group, a hydroxyl group, or a phosphono group, a salt thereof, or a quaternary ammonium salt. Among these, a sulfonic acid group, a carboxyl group, or a hydroxyl group is particularly preferable. Examples of counter ions of these ionic hydrophilic groups include alkali metal ions, ammonium ions, or organic ammonium ions. Among these, an alkali metal ion is particularly preferable. When the ionic hydrophilic group is a sulfonic acid group, it is a lithium salt, and when the ionic hydrophilic group is a carboxyl group, it is a sodium salt or a potassium salt. preferable.

X ₃ in the formula (II), the general formula (III) X ₄ in, X _3, and X ₄ are each independently in the general formula (IV) in the general formula (V), σp value of Hammett's 0.20 It is an electron-withdrawing group. Specific examples of these groups include the same X ₁ and X ₂ in the general formula (I) and the same examples as X ₁ and X ₂ in the general formula (IV).

Z _{3 in} the general formula (II), Z ₄ and Z ₅ in the general formula (III), and Z in the general formula (VI) are each independently selected from the following groups. That is, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group A heterocyclic group. Specific examples of these groups are the same as those given as specific examples of Z ₁ and Z ₂ in the general formula (I). N in the general formula (V) and n in the general formula (VI) are each independently an integer of 1 or more, preferably an integer of 1 to 5, and more preferably 2.

M ₂ are each independently in the general formula (III) in M ₂ and general formula (VI), a hydrogen atom, an alkali metal, ammonium or organic ammonium. Examples of these may be the same as those listed as specific examples of M ₁ M ₁ and Formula in (IV) in the general formula (I).

  Preferable specific examples of the compound of the general formula (II) or the compound of the general formula (V) include the following exemplified compounds 15 to 28. The following exemplary compounds are described in the form of free acid. Of course, the present invention is not limited to the following exemplary compounds as long as they are included in the structure of the general formula (II) or the general formula (V) and the definition thereof. In the present invention, it is particularly preferable to use the exemplified compound 19 among the following exemplified compounds.

  Preferable specific examples of the compound of the general formula (III) or the compound of the general formula (VI) include the following exemplified compounds 29 to 45. The following exemplary compounds are described in the form of free acid. Of course, the present invention is not limited to the following exemplary compounds as long as they are included in the structure of the general formula (III) or the general formula (VI) and the definition thereof. In the present invention, it is particularly preferable to use the exemplified compound 33 among the following exemplified compounds.

[Color material verification method]
To verify whether or not the color material used in the present invention is contained in the ink, the following verification methods (1) to (3) using high performance liquid chromatography (HPLC) can be applied.
(1) Peak retention time (2) Maximum absorption wavelength for peak at (1) (3) M / Z (posi), M / Z (nega) of mass spectrum for peak at (1)

The analysis conditions of high performance liquid chromatography are as follows. A liquid (ink) diluted about 1,000 times with pure water was used as a measurement sample. And the analysis by a high performance liquid chromatography was performed on the following conditions, and the retention time (retention time) of a peak and the maximum absorption wavelength of a peak were measured.
Column: SunFire C ₁₈ (Nippon Waters) 2.1 mm x 150 mm
-Column temperature: 40 ° C
・ Flow rate: 0.2 mL / min
PDA: 200 nm to 700 nm
-Mobile phase and gradient conditions: Table 1 below

The analysis conditions of the mass spectrum are as shown below. About the obtained peak, a mass spectrum is measured on condition of the following, and M / Z detected most strongly is measured with respect to each of posi and negative.
・ Ionization method ・ ESI
Capillary voltage: 3.5 kV
Desolvent gas: 300 ° C
Ion source temperature: 120 ° C
Detector posi: 40V 200-1500amu / 0.9sec
nega: 40V 200-1500amu / 0.9sec

  Under the method and conditions described above, as representative examples of the respective color materials, exemplary compound 5 which is a specific example of the first color material, exemplary compound 19 and exemplary compound 33 which are specific examples of the second color material are measured. Went. As a result, the obtained retention time, maximum absorption wavelength, M / Z (posi), and M / Z (negative) values are shown in Table 2. When the unknown ink is measured under the same method and conditions as described above and corresponds to the values shown in Table 2, it can be determined that it corresponds to the compound used in the present invention.

[Content of coloring material]
The content (mass%) of the second color material, based on the total mass of the ink, is a mass ratio with respect to the content (mass%) of the first color material (second color material / second 1 colorant) = 0.002 times or more and 0.50 times or less. More specifically, {[content of compounds of general formula (II), general formula (III), general formula (V), and general formula (VI)] / [general formula (I), and general formula ( Content of compound IV)]} = 0.02 times or more and 0.50 times or less. If the mass ratio is less than 0.002 times , ink storage stability cannot be obtained, and if it exceeds 0.50 times , recording durability cannot be obtained. By configuring the color material content mass ratio to be in the above range, it exceeds the performance predicted from the combination of the light resistance of the first color material and the light resistance of the second color material. An image having a high level of light resistance can be formed. Further, an image having a preferable color tone can be obtained, and the reliability as an ink can be satisfied.

  By using the first color material and the second color material at a specific mass ratio, the present inventors have the following reason why a synergistic effect is exhibited and an image having light resistance exceeding prediction can be formed. I guess. Since the first color material tends to have a low solubility in an aqueous medium from the beginning, when an ink containing these compounds is applied to a recording medium, the color material associates and aggregates immediately after that. The association or aggregation tends to improve the fastness of the color material on the recording medium on which the image is formed. On the other hand, however, excessive association or aggregation may reduce the light fastness inherent in the molecular structure. On the other hand, by causing the first color material and the second color material to coexist, the first color material forms an optimal association or aggregation state with respect to light resistance on the recording medium. It is considered that the light resistance of the image has been improved.

  In addition, the inventors presume why the synergistic effect is achieved and the ink reliability is achieved by using the first color material and the second color material at a specific mass ratio as follows. doing. As described above, impurities that are considered to have eluted from the ink cartridge and the members constituting the ink supply path are mixed in the ink, and the ink supply path is clogged, the ink supply characteristics are degraded, and the ink storage stability is improved. May cause a drop. The main components of such impurities are ions such as metal and silicon, and once the ions such as metal and silicon dissolved in the ink are deposited for some reason and adhere to the inside of the nozzle or its vicinity, ink supply It is considered that the characteristics deteriorate. In addition, it is considered that the storage stability of the ink is lowered due to the instability of the dissolved state of the ink component due to precipitation of ions of metal, silicon, and the like. As a result of the study by the present inventors, it has been found that by adding the second color material into the ink, such precipitation of ions such as metal and silicon is effectively suppressed. When these compounds form a complex with a metal or silicon ion mixed in the ink to chelate, the metal or silicon ion can be stably dissolved in the ink. As a result, it is considered that precipitation of ions such as metal and silicon is suppressed, ink supply characteristics are stabilized, and ink storage stability is also improved. In other words, with regard to the reliability of the ink, which was difficult to achieve by using only the first color material as the color material, the combined use of the second color material provides an effect that exceeds the expectation, and sufficient reliability. Sex can be achieved.

  The content (% by mass) of the first colorant [the compound of general formula (I), preferably the compound of general formula (IV)] in the ink is 1.0% by mass or more and 8% by mass or more based on the total mass of the ink. It is preferable that it is 0.0 mass% or less. In addition, the content of the second colorant [the compound of general formula (II) and / or general formula (III), preferably the compound of general formula (V) and / or general formula (VI)] in the ink is The following is preferable. That is, the content (% by mass) of the second color material is preferably 0.004% by mass to 3.5% by mass based on the total mass of the ink. Furthermore, it is 0.01% by mass or more and 1.0% by mass or less, particularly 0.01% by mass or more and 0.86% by mass or less, and most preferably 0.01% by mass or more and 0.24% by mass or less. Like that. In this case, the content of the second color material is more preferably as follows in relation to other color materials. When any one of the compounds of general formula (II), general formula (III), general formula (V) and general formula (VI) is used alone, the content thereof is also used in combination of two or more selected from these When it does, it is preferable to comprise so that the total content may satisfy said range, respectively. By setting the content of the first color material and / or the second color material in the above range, not only the light resistance and color tone of the image are satisfied, but also the ink reliability such as storage stability and recording durability. It is possible to satisfy this point.

  Further, the total content (% by mass) of the first color material and the second color material in the ink is 1.10% by mass or more and 9.00% by mass or less based on the total mass of the ink. It is preferable. If the total content is less than 1.10% by mass, sufficient light resistance and color developability may not be obtained. If the total content exceeds 9.00% by mass, ink jet such as anti-sticking property may be obtained. Characteristics may not be obtained.

Further, in the present invention, the content (mass%) of the second color material is a mass ratio with respect to the content (mass%) of the first color material (second color material / first Colorant) = 0.002 times or more and 0.43 times or less is preferable. By configuring the mass ratio of the color material content to be in the above range, the performance predicted from the combination of the light resistance of the first color material and the light resistance of the second color material is far greater. Images with higher levels of lightfastness can be formed. In addition, an image having a more preferable color tone can be obtained. In particular, the content (mass%) of the second color material is a mass ratio with respect to the content (mass%) of the first color material (second color material / first color material) = It is preferably 0.002 times or more and 0.25 times or less, and particularly preferably 0.002 times or more and 0.12 times or less. By setting the mass ratio of the content of the color material within this range, an image having a particularly high level of light resistance can be formed even in the mass ratio of the content described above. Furthermore, an image having a particularly preferable color tone can be obtained, and in addition, the reliability as an ink can be sufficiently satisfied.

  When the inkjet ink of the present invention is a yellow ink, the preferred color tone for the yellow ink means the following two things. That is, it means that an image formed using only yellow ink is not reddish or greenish. In addition to this, when forming a secondary color image formed using yellow ink, that is, a red or green image, a color tone that does not greatly lose the red and green color reproduction ranges. It means having. More specifically, the hue angle of an image formed using only yellow ink is preferably 85 ° or more and 92 ° or less, and more preferably 88 ° or more and 90 ° or less.

(Ink pH)
The ink of the present invention preferably has a pH of 7.0 or more and 10.0 or less. This is because if the pH of the ink exceeds 10.0, the following problems may occur depending on the type of the material constituting the member in contact with the ink in the ink cartridge or the ink jet recording apparatus. That is, impurities may elute into the ink and the ink performance may be reduced. Moreover, the material which comprises the member which contacts ink may deteriorate. Furthermore, when recording is performed continuously for a long period of time, deterioration (dissolution) of the heat-generating portion of the recording head may occur, or wiring may be disconnected. On the other hand, when the pH of the ink is less than 7.0, the solubility of the compound of the general formula (I) or the compound of the general formula (IV) is lowered, so that the storage stability of the ink may be lowered.

(Aqueous medium)
In the ink of the present invention, water or an aqueous medium that is a mixed solvent of water and a water-soluble organic solvent can be used. It is preferable to use deionized water (ion exchange water) as the water. The content (% by mass) of water in the ink is preferably 10.0% by mass or more and 90.0% by mass or less based on the total mass of the ink.

  The water-soluble organic solvent is not particularly limited as long as it is water-soluble, and alcohol, polyhydric alcohol, polyglycol, glycol ether, nitrogen-containing polar solvent, sulfur-containing polar solvent and the like can be used. The content (% by mass) of the water-soluble organic solvent in the ink is 5.0% by mass or more and 90.0% by mass or less, and further 10.0% by mass or more and 50.0% by mass or less based on the total mass of the ink. It is preferable that When the content of the water-soluble organic solvent is less than the above range, reliability such as ejection stability may not be obtained when the ink is used in an ink jet recording apparatus. Further, if the content of the water-soluble organic solvent is larger than the above range, the viscosity of the ink is increased and ink supply failure may occur.

  Specific examples of the water-soluble organic solvent include the following. Alkyl alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol; Amides such as dimethylformamide and dimethylacetamide. Ketones or ketoalcohols such as acetone and diacetone alcohol. Ethers such as tetrahydrofuran and dioxane. Polyalkylene glycols such as polyethylene glycol and polypropylene glycol. Glycols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, hexylene glycol, and thiodiglycol. 2 alkylene groups such as 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,2,6-hexanetriol Alkylene glycols having 6 to 6 carbon atoms. Bis (2-hydroxyethyl) sulfone. Lower alkyl ether acetates such as polyethylene glycol monomethyl ether acetate. Alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether. N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. Of course, the present invention is not limited to these. These water-soluble organic solvents can be used alone or in combination of two or more as required.

(Other additives)
In addition to the components described above, the ink of the present invention contains a water-soluble organic compound that is solid at room temperature, such as polyhydric alcohols such as trimethylolpropane and trimethylolethane, and urea derivatives such as ethyleneurea, as necessary. You may contain. Further, the ink of the present invention is optionally provided with a surfactant, a pH adjuster, a rust inhibitor, an antiseptic, an antifungal agent, an antioxidant, a reduction inhibitor, an evaporation accelerator, a chelating agent, and a water-soluble agent. You may contain various additives, such as a polymer.

<Other inks>
The ink of the present invention is suitably used for an ink jet recording method or the like, but in order to form a full color image, the ink of the present invention is used in combination with an ink having a color tone different from that of the ink of the present invention. Can do. The ink of the present invention is preferably used together with at least one kind of ink selected from, for example, black ink, cyan ink, magenta ink, yellow ink, red ink, green ink and blue ink. Further, so-called light ink having substantially the same color tone as these inks can be used in combination. The color material of these inks or light inks may be a known dye or a newly synthesized color material.

<Inkjet recording method>
The ink jet recording method of the present invention is an ink jet recording method of performing recording on a recording medium by ejecting ink by an ink jet method, wherein the ink is the ink jet ink of the present invention described above. . The ink jet recording method of the present invention can be applied to a recording method in which ink is ejected by applying mechanical energy to ink, a recording method in which ink is ejected by applying thermal energy to ink, and the like. In particular, in the present invention, it is preferable to apply an ink jet recording method using thermal energy.

<Ink cartridge>
The ink cartridge of the present invention is an ink cartridge provided with an ink storage portion that stores ink, and the stored ink is the ink-jet ink of the present invention described above.

<Recording unit>
The recording unit of the present invention is a recording unit that includes an ink storage portion that stores ink and a recording head for ejecting ink, and the ink stored in the recording unit of the present invention described above. It is an inkjet ink. As a suitable recording unit of the present invention, a recording unit in which the recording head ejects ink by applying thermal energy corresponding to the recording signal to the ink can be mentioned. Further, in the present invention, a more preferable effect can be obtained in the case of a recording head having a heat generating part wetted surface containing metal, silicon, and oxides thereof. Specific examples of the metal and / or metal oxide constituting the heat generating part wetted surface include, for example, metals such as Ta, Zr, Ti, Ni, and Al, or oxides of these metals.

<Inkjet recording apparatus>
The ink jet recording apparatus of the present invention is an ink jet recording apparatus provided with an ink containing portion containing ink and a recording head for discharging ink, and the ink contained therein is the book described above. It is an ink-jet ink of the invention. As a preferable example of the ink jet recording apparatus of the present invention, a method in which the recording head ejects ink by applying thermal energy corresponding to a recording signal to the ink can be mentioned.

  Hereinafter, a schematic configuration of the mechanism part of the ink jet recording apparatus according to an example of the present invention will be described. The ink jet recording apparatus is composed of a paper feed unit, a transport unit, a carriage unit, a paper discharge unit, a cleaning unit, and an exterior unit that protects these parts and provides design properties in accordance with the role of each mechanism.

  FIG. 1 is a perspective view of the ink jet recording apparatus. 2 and 3 are diagrams for explaining the internal mechanism of the ink jet recording apparatus. FIG. 2 is a perspective view from the upper right part, and FIG. 3 is a side sectional view of the ink jet recording apparatus.

  When paper is fed, only a predetermined number of recording media are fed to a nip portion composed of a paper feed roller M2080 and a separation roller M2041 in a paper feed unit including a paper feed tray M2060. The recording medium is separated at the nip portion, and only the uppermost recording medium is conveyed. The recording medium conveyed to the conveyance unit is guided by the pinch roller holder M3000 and the paper guide flapper M3030, and conveyed to the roller pair of the conveyance roller M3060 and the pinch roller M3070. The roller pair of the conveyance roller M3060 and the pinch roller M3070 is rotated by driving of the LF motor E0002, and the recording medium is conveyed on the platen M3040 by this rotation.

  When forming an image on a recording medium, the carriage unit arranges a recording head H1001 (FIG. 4; a detailed configuration will be described later) at a position where a target image is formed, and follows a signal from the electric board E0014. Ink is ejected onto the recording medium. An image is formed on the recording medium by alternately repeating main scanning in which the carriage M4000 scans in the column direction while recording is performed by the recording head H1001 and sub-scanning in which the recording medium is conveyed in the row direction by the conveyance roller M3060. The recording medium on which the image is formed is conveyed in a state sandwiched between the nips of the first paper discharge roller M3110 and the spur M3120 at the paper discharge unit, and is discharged to the paper discharge tray M3160.

  The cleaning unit cleans the recording head H1001 before and after forming an image. When the pump M5000 is operated with the cap M5010 capping the ejection port of the recording head H1001, unnecessary ink or the like is sucked from the ejection port of the recording head H1001. In addition, by sucking ink remaining in the cap M5010 with the cap M5010 open, sticking due to the remaining ink and other problems do not occur.

(Configuration of recording head)
The configuration of the head cartridge H1000 will be described. FIG. 4 is a diagram showing the configuration of the head cartridge H1000, and is a diagram showing how the ink cartridge H1900 is mounted on the head cartridge H1000. The head cartridge H1000 has a recording head H1001, means for mounting the ink cartridge H1900, and means for supplying ink from the ink cartridge H1900 to the recording head, and is detachably mounted on the carriage M4000.

  The ink jet recording apparatus forms an image with yellow, magenta, cyan, black, light magenta, light cyan, and green inks. Therefore, the ink cartridge H1900 is also prepared for seven colors independently. In the above, the ink of the present invention is used as at least one ink. As shown in FIG. 4, each ink cartridge H1900 is detachable from the head cartridge H1000. The ink cartridge H1900 can be attached and detached even when the head cartridge H1000 is mounted on the carriage M4000.

  FIG. 5 is an exploded perspective view of the head cartridge H1000. The head cartridge H1000 includes a recording element substrate, a plate, an electric wiring substrate H1300, a cartridge holder H1500, a flow path forming member H1600, a filter H1700, a seal rubber H1800, and the like. The recording element substrate is composed of a first recording element substrate H1100 and a second recording element substrate H1101, and the plate is composed of a first plate H1200 and a second plate H1400.

  The first recording element substrate H1100 and the second recording element substrate H1101 are Si substrates, and a plurality of recording elements (nozzles) for ejecting ink are formed on one side thereof by a photolithography technique. Electric wiring such as Al for supplying electric power to each recording element is formed by a film forming technique, and a plurality of ink flow paths corresponding to individual recording elements are formed by a photolithography technique. Further, an ink supply port for supplying ink to the plurality of ink flow paths is formed to open on the back surface.

  FIG. 6 is an enlarged front view illustrating the configuration of the first recording element substrate H1100 and the second recording element substrate H1101. H2000 to H2600 are arrays of printing elements corresponding to different ink colors (hereinafter also referred to as nozzle arrays). On the first recording element substrate H1100, nozzle rows for three colors, a nozzle row H2000 for yellow ink, a nozzle row H2100 for magenta ink, and a nozzle row H2200 for cyan ink, are formed. On the second recording element substrate H1101, nozzle rows for four colors, a light cyan ink nozzle row H2300, a black ink nozzle row H2400, a green ink nozzle row H2500, and a light magenta ink nozzle row H2600, are formed. ing.

Each nozzle row is composed of 768 nozzles arranged at an interval of 1,200 dpi (dot / inch; reference value) in the recording medium conveyance direction (sub-scanning direction). Each nozzle ejects about 2 picoliters of ink. For this reason, the opening area in each discharge port is set to about 100 μm ² . The ejection of the head of the present invention is preferably 5 picoliters or less in accordance with recent high image quality. However, it is not limited to this.

  Hereinafter, a description will be given with reference to FIGS. The first recording element substrate H1100 and the second recording element substrate H1101 are bonded and fixed to the first plate H1200. Here, an ink supply port H1201 for supplying ink to the first recording element substrate H1100 and the second recording element substrate H1101 is formed. Further, a second plate H1400 having an opening is bonded and fixed to the first plate H1200. The second plate H1400 holds the electrical wiring substrate H1300 so that the electrical wiring substrate H1300 is electrically connected to the first recording element substrate H1100 and the second recording element substrate H1101.

  The electrical wiring substrate H1300 applies an electrical signal for ejecting ink from each nozzle formed on the first recording element substrate H1100 and the second recording element substrate H1101. The electric wiring board H1300 is arranged on the electric wiring corresponding to the first recording element substrate H1100 and the second recording element substrate H1101, and an external part for receiving an electric signal from the ink jet recording apparatus. And a signal input terminal H1301. The external signal input terminal H1301 is positioned and fixed on the back side of the cartridge holder H1500.

  A flow path forming member H1600 is fixed to the cartridge holder H1500 that holds the ink cartridge H1900, for example, by ultrasonic welding, and forms an ink flow path H1501 that communicates from the ink cartridge H1900 to the first plate H1200. A filter H1700 is provided at the ink cartridge side end of the ink flow path H1501 that engages with the ink cartridge H1900, and can prevent dust from entering from the outside. Further, a seal rubber H1800 is attached to the engaging portion with the ink cartridge H1900 so that the ink can be prevented from evaporating from the engaging portion.

  Furthermore, as described above, the head cartridge H1000 is configured by bonding the cartridge holder portion and the recording head portion H1001 by bonding or the like. The cartridge holder portion includes a cartridge holder H1500, a flow path forming member H1600, a filter H1700, and a seal rubber H1800. The recording head portion H1001 includes a first recording element substrate H1100, a second recording element substrate H1101, a first plate H1200, an electric wiring substrate H1300, and a second plate H1400.

  Here, as an embodiment of the recording head, a thermal ink jet recording head that performs recording using an electrothermal transducer (recording element) that generates thermal energy for causing ink to cause film boiling in accordance with an electrical signal. Said. About this typical structure and principle, for example, what is performed using the basic principle disclosed in US Pat. Nos. 4,723,129 and 4,740,796 is preferable. . This method can be applied to both a so-called on-demand type and a continuous type.

  The thermal ink jet method is particularly effective when applied to an on-demand type. In the case of the on-demand type, at least one drive that applies a rapid temperature rise exceeding nucleate boiling corresponding to the recording information to the electrothermal transducer disposed corresponding to the liquid flow path holding the ink Apply a signal. As a result, thermal energy is generated in the electrothermal transducer, and film boiling occurs in the ink. As a result, bubbles in the ink corresponding to the drive signal on a one-to-one basis can be formed. At least one droplet is formed by ejecting ink through the ejection port by the growth and contraction of the bubbles. It is more preferable that the driving signal has a pulse shape, since the bubble grows and contracts immediately and appropriately, so that ink discharge with particularly excellent response can be achieved.

  The ink of the present invention is not limited to the thermal ink jet method, and can be preferably used in an ink jet recording apparatus using mechanical energy as described below. An ink jet recording apparatus having such a configuration includes a nozzle forming substrate having a plurality of nozzles, a pressure generating element made of a piezoelectric material and a conductive material disposed to face the nozzles, and ink filling the periphery of the pressure generating element. Become. Then, the pressure generating element is displaced by the applied voltage, and ink is ejected from the nozzle.

  As described above, the ink jet recording apparatus is not limited to one in which the recording head and the ink cartridge are separated from each other. Further, the ink cartridge is integrated with the recording head in a separable or non-separable manner and mounted on the carriage, and is provided at a fixed portion of the ink jet recording apparatus via an ink supply member such as a tube. An ink may be supplied to the recording head. Further, when the ink cartridge is provided with a configuration for applying a preferable negative pressure to the recording head, the following configuration can be adopted. That is, a mode in which an absorber is disposed in the ink storage portion of the ink cartridge, or a mode in which a flexible ink storage bag and a spring portion that applies a biasing force in the direction of expanding the inner volume of the flexible ink storage bag are provided. It can be. The ink jet recording apparatus may take the form of a line printer in which recording elements are aligned over a range corresponding to the entire width of the recording medium, in addition to the serial type recording method described above.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, this invention is not limited at all by the following Example, unless the summary is exceeded. In the description, “parts” and “%” are based on mass unless otherwise specified.

<Preparation of coloring material>
[Synthesis of Exemplary Compound 5]
Exemplified Compound 5 (potassium salt) was synthesized according to the following synthesis flow and procedure.

(1) Synthesis of Compound b 25.5 g of sodium hydrogen carbonate and 150 mL of ion-exchanged water were mixed and heated to 40 ° C., and 25.0 g of cyanuric chloride (manufactured by Tokyo Chemical Industry; compound a) was added to this every 5 minutes. Added in equal portions and stirred for 1 hour to prepare a solution. The obtained solution was dropped into a mixed liquid (8 ° C.) of 52.8 mL of hydrazine monohydrate and 47 mL of ion-exchanged water so that the internal temperature did not exceed 10 ° C. Thereafter, the internal temperature was raised to 50 ° C. and stirred for 30 minutes. The precipitated crystals were filtered to obtain 23.4 g of compound b (hydrazine derivative, melting point> 300 ° C.). The yield was 94.7%.

(2) Synthesis of Compound c 35.0 g of the compound b (hydrazine derivative) obtained above was suspended in 420 mL of ethylene glycol, and stirred at an internal temperature of 50 ° C. To this, 59 mL of concentrated hydrochloric acid was added, and then 60.1 g of pivaloyl acetonitrile (manufactured by Tokyo Chemical Industry) was added and stirred at a temperature of 50 ° C. for 10 hours. To this, 95 mL of concentrated hydrochloric acid and 145 mL of methanol were added, and the mixture was further stirred for 8 hours. After cooling to room temperature, the precipitated crystals were collected by filtration to obtain 81.6 g of compound c (5-aminopyrazole derivative, melting point = 233-235 ° C.). The yield was 94.2%.

(3) Synthesis of Compound e 90.57 g of Compound d (manufactured by Tokyo Chemical Industry) was suspended in 500 mL of water, and 130 mL of concentrated hydrochloric acid was added thereto, and cooled until the internal temperature after addition was 5 ° C. or lower. did. Next, 70 mL of an aqueous solution containing 36.23 g of sodium nitrite was added dropwise in the range of the internal temperature of 4 to 6 ° C., and the internal temperature was kept at 5 ° C. or lower and stirred for 30 minutes. Next, 159 g of sodium sulfite and 636 mL of water were added while keeping the internal temperature at 20 ° C. or less, 250 mL of concentrated hydrochloric acid was added at an internal temperature of 25 ° C., and then the internal temperature was 90 ° C. for 1 hour. Stir. Thereafter, the internal temperature was cooled to room temperature, followed by filtration, washing with 200 mL of water, and then air drying to obtain 80.0 g of compound e.

(4) Synthesis of Compound f 23.3 g of Compound e obtained above was suspended in 209 mL of ethanol, and 28 mL of triethylamine was added dropwise thereto at room temperature. Thereafter, 12.2 g of ethoxymethylenemalononitrile (manufactured by ALDRICH) was added in several portions thereto. The mixture was further refluxed for 3 hours, cooled to room temperature, filtered, washed with 400 mL of isopropyl alcohol, and dried to obtain 23.57 g of compound f.

(5) Synthesis of Exemplified Compound 5 Acetic acid (145.56 mL) was added to sulfuric acid (32.4 mL) at an internal temperature of 4 ° C. or lower, and the internal temperature was maintained at 7 ° C. or lower, and 15.9 mL of 40 mass% nitrosyl sulfuric acid (manufactured by ALDRICH ) Was added dropwise. To this, 32.4 g of the compound f obtained above was added in several portions, and the internal temperature was 10 ° C., followed by stirring for 60 minutes. Thereafter, a diazonium salt of compound f was added dropwise to a solution obtained by suspending 18.8 g of compound c added with 1.83 g of urea in 470 mL of methanol with an internal temperature of less than 0 ° C., and the internal temperature was reduced to less than 0 ° C. For 30 minutes. Thereafter, the internal temperature of the reaction solution was raised to room temperature, followed by filtration, washing with methanol, and further washing with water to obtain crude crystals. The obtained crude crystals were suspended in 400 mL of methanol, stirred for 60 minutes under reflux, then cooled to room temperature, filtered, washed with methanol, water, and methanol in this order, and then overnight at 75 ° C. Drying gave 34.4 g of free acid crystals of exemplary compound 5. The obtained crystals were dissolved in water to form a 10% by mass aqueous solution (25 ° C .: pH≈8.3: adjusted with KOH aqueous solution), and then crystallized by adding isopropanol at an internal temperature of 50 ° C., followed by cooling. Then, it was filtered, washed with isopropanol and dried. In this way, 35.0 g of Exemplified Compound 5 (potassium salt) was obtained.

[Synthesis of Exemplified Compound 19]
Exemplified compound 19 (potassium salt) was synthesized according to the following synthesis flow and procedure.

(1) Synthesis of Compound i Hydrochloric acid was added to 5-amino-3-tert-butylpyrazole (Compound h) to obtain Compound i.

(2) Synthesis of Compound e 90.57 g of Compound d (manufactured by Tokyo Chemical Industry) was suspended in 500 mL of water, and 130 mL of concentrated hydrochloric acid was added thereto, and cooled until the internal temperature after addition was 5 ° C. or lower. did. Next, 70 mL of an aqueous solution containing 36.23 g of sodium nitrite was added dropwise in the range of the internal temperature of 4 to 6 ° C., and the internal temperature was kept at 5 ° C. or lower and stirred for 30 minutes. Next, 159 g of sodium sulfite and 636 mL of water were added while keeping the internal temperature at 20 ° C. or less, 250 mL of concentrated hydrochloric acid was added at an internal temperature of 25 ° C., and then the internal temperature was 90 ° C. for 1 hour. Stir. Thereafter, the internal temperature was cooled to room temperature, followed by filtration, washing with 200 mL of water, and then air drying to obtain 80.0 g of compound e.

(3) Synthesis of Compound f 23.3 g of Compound e obtained above was suspended in 209 mL of ethanol, and 28 mL of triethylamine was added dropwise thereto at room temperature. Thereafter, 12.2 g of ethoxymethylenemalononitrile (manufactured by ALDRICH) was added in several portions thereto. The mixture was further refluxed for 3 hours, cooled to room temperature, filtered, washed with 400 mL of isopropyl alcohol, and dried to obtain 23.57 g of compound f.

(4) Synthesis of Exemplified Compound 19 15.5 mL of 40% by mass nitrosylsulfuric acid (manufactured by ALDRICH) was added under stirring while adding 145.56 mL of acetic acid to 32.4 mL of sulfuric acid at an internal temperature of 4 ° C. or lower. ) Was added dropwise. To this, 32.4 g of the compound f obtained above was added in several portions, and the internal temperature was 10 ° C., followed by stirring for 60 minutes. Thereafter, a diazonium salt of compound f was added dropwise to a solution in which 7.00 g of compound i to which 1.83 g of urea was added was suspended in 470 mL of methanol and the internal temperature was less than 0 ° C., and the internal temperature was less than 0 ° C. For 30 minutes. Thereafter, the internal temperature of the reaction solution was raised to room temperature, followed by filtration, washing with methanol, and further washing with water to obtain crude crystals. The obtained crude crystals were suspended in 400 mL of methanol, stirred for 60 minutes under reflux, then cooled to room temperature, filtered, washed with methanol, water, and methanol in this order, and then overnight at 75 ° C. By drying, 25.8 g of free acid crystals of Exemplified Compound 19 were obtained. The obtained crystals were dissolved in water to form a 10% by mass aqueous solution (25 ° C .: pH≈8.3: adjusted with KOH aqueous solution), and then crystallized by adding isopropanol at an internal temperature of 50 ° C., followed by cooling. Then, it was filtered, washed with isopropanol and dried. In this way, 24.0 g of Exemplified Compound 19 (potassium salt) was obtained.

[Synthesis of Exemplified Compound 33]
Exemplified Compound 33 (potassium salt) was synthesized according to the following synthesis flow and procedure.

(1) Synthesis of Compound j 51.0 g of sodium bicarbonate and 150 mL of ion exchange water were mixed and heated to 40 ° C., and an aqueous sodium hydroxide solution was added thereto to adjust the pH of the liquid to 8.0 (40 ° C. ). To this, 25.0 g of cyanuric chloride (manufactured by Tokyo Chemical Industry; compound a) was added in 5 equal portions every 10 minutes, and stirred for 1 hour to prepare a solution. The obtained solution was dropped into a mixed solution (8 ° C.) of 26.4 mL of hydrazine monohydrate and 47 mL of ion exchange water so that the internal temperature did not exceed 10 ° C. Thereafter, the internal temperature was raised to 50 ° C. and stirred for 30 minutes. The precipitated crystals were filtered to obtain 20.5 g of compound j (hydrazine derivative, melting point> 300 ° C.).

(2) Synthesis of Compound k 30.0 g of the compound j (hydrazine derivative) obtained above was suspended in 420 mL of ethylene glycol and stirred at an internal temperature of 50 ° C. To this, 59 mL of concentrated hydrochloric acid was added, and then 60.1 g of pivaloyl acetonitrile (manufactured by Tokyo Chemical Industry) was added and stirred at a temperature of 50 ° C. for 10 hours. To this, 95 mL of concentrated hydrochloric acid and 145 mL of methanol were added, and the mixture was further stirred for 8 hours. After cooling to room temperature, the precipitated crystals were filtered off to obtain 60.6 g of compound k (5-aminopyrazole derivative, melting point> 200 ° C.).

(3) Synthesis of Compound e 90.57 g of Compound d (manufactured by Tokyo Chemical Industry) was suspended in 500 mL of water, and 130 mL of concentrated hydrochloric acid was added thereto, and cooled until the internal temperature after addition was 5 ° C. or lower. did. Next, 70 mL of an aqueous solution containing 36.23 g of sodium nitrite was added dropwise in the range of the internal temperature of 4 to 6 ° C., and the internal temperature was kept at 5 ° C. or lower and stirred for 30 minutes. Next, 159 g of sodium sulfite and 636 mL of water were added while keeping the internal temperature at 20 ° C. or less, 250 mL of concentrated hydrochloric acid was added at an internal temperature of 25 ° C., and then the internal temperature was 90 ° C. for 1 hour. Stir. Thereafter, the internal temperature was cooled to room temperature, followed by filtration, washing with 200 mL of water, and then air drying to obtain 80.0 g of compound e.

(4) Synthesis of Compound f 23.3 g of Compound e obtained above was suspended in 209 mL of ethanol, and 28 mL of triethylamine was added dropwise thereto at room temperature. Thereafter, 12.2 g of ethoxymethylenemalononitrile (manufactured by ALDRICH) was added in several portions thereto. The mixture was further refluxed for 3 hours, cooled to room temperature, filtered, washed with 400 mL of isopropyl alcohol, and dried to obtain 23.57 g of compound f.

(5) Synthesis of Exemplified Compound 33 145.56 mL of acetic acid was added to 32.4 mL of sulfuric acid at an internal temperature of 4 ° C. or lower, and 15.9 mL of 40% by mass nitrosylsulfuric acid with stirring at an internal temperature of 7 ° C. or lower (produced by ALDRICH). ) Was added dropwise. To this, 32.4 g of the compound f obtained above was added in several portions, and the internal temperature was 10 ° C., followed by stirring for 60 minutes. Then, a diazonium salt of compound f was added dropwise to a solution in which 9.0 g of compound k added with 1.83 g of urea was suspended in 470 mL of methanol with an internal temperature of less than 0 ° C., and the internal temperature was less than 0 ° C. For 30 minutes. Thereafter, the internal temperature of the reaction solution was raised to room temperature, followed by filtration, washing with methanol, and further washing with water to obtain crude crystals. The obtained crude crystals were suspended in 400 mL of methanol, stirred for 60 minutes under reflux, then cooled to room temperature, filtered, washed with methanol, water, and methanol in this order, and then overnight at 75 ° C. By drying, 29.1 g of free acid crystals of Exemplified Compound 33 were obtained. The obtained crystals were dissolved in water to form a 10% by mass aqueous solution (25 ° C .: pH≈8.3: adjusted with KOH aqueous solution), and then crystallized by adding isopropanol at an internal temperature of 50 ° C., followed by cooling. Then, it was filtered, washed with isopropanol and dried. In this way, 27.8 g of Exemplified Compound 33 (potassium salt) was obtained.

<Preparation of ink>
Exemplary compounds 5, 19, and 33, which are yellow color materials obtained above, and C.I. I. Each ink was prepared using Direct Yellow 132 as follows. First, the components shown in Table 3 below were mixed and sufficiently stirred. Thereafter, pressure filtration was performed with a filter having a pore size of 0.2 μm to prepare inks of Examples , Reference Examples and Comparative Examples. Further, the mass ratio (second color material / first color material) of the content (% by mass) of the second color material in the ink to the content (% by mass) of the first color material in the ink. The results are shown in Table 3 below.

<Evaluation>
(1) Light resistance Each of the inks obtained above was mounted on an ink jet recording apparatus (trade name: PIXUS iP8600; manufactured by Canon) using thermal energy. The recording conditions were a temperature of 23 ° C., a relative humidity of 55%, a recording density of 2,400 dpi × 1,200 dpi, and a discharge amount of 2.5 pL. Here, a recording medium used for producing a recorded material was produced as follows. First, a resin composition containing 70 parts of low density polyethylene, 20 parts of high density polyethylene, and 10 parts of titanium oxide is applied to both sides of a base paper having a basis weight of 155 g / m ² so as to be 25 g / m ^2. A support coated with resin was prepared. Then, an ink receiving layer mainly composed of alumina hydrate and polyvinyl alcohol was formed on the support. In this way, a gap type ink receiving layer was provided, and the JAPAN TAPPI paper pulp test method no. A recording medium having a surface pH of 5.0 after 3 minutes measured according to 49-1.

ＡＡ：光学濃度の残存率が９５％以上。
Ａ：光学濃度の残存率が９０％以上９５％未満。
Ｂ：光学濃度の残存率が８０％以上９０％未満。
Ｃ：光学濃度の残存率が８０％未満。 An image with a recording duty of 50% was formed on the obtained recording medium, and the image was naturally dried for 24 hours at a temperature of 23 ° C. and a relative humidity of 55%. The optical density of the image portion of the recorded matter thus obtained was measured (referred to as “optical density before test”). Further, this recorded matter was exposed for 72 hours at an irradiation intensity of 100 kilolux, a bath temperature of 24 ° C., and a relative humidity of 60% using a super xenon tester (trade name: SX-75; manufactured by Suga Test Instruments). Thereafter, the optical density of the image portion of the recorded matter was measured (referred to as “optical density after test”). The optical density was measured using a spectrophotometer (Spectorolino; manufactured by Gretag Macbeth) under the conditions of light source: D50 and field of view: 2 °. From the obtained values of the optical density before the test and the optical density after the test, the residual ratio of the optical density was calculated based on the following formula, and the light resistance was evaluated. The criteria for light resistance are as follows. The evaluation results are shown in Table 4. In the present invention, AA, A and B are acceptable levels and C is not acceptable according to the following evaluation criteria.

AA: The residual ratio of optical density is 95% or more.
A: The residual ratio of the optical density is 90% or more and less than 95%.
B: The residual ratio of the optical density is 80% or more and less than 90%.
C: The residual ratio of optical density is less than 80%.

(2) Color tone Each of the inks obtained above was mounted on an ink jet recording apparatus (trade name: PIXUS iP8600; manufactured by Canon) using thermal energy. The recording conditions were a temperature of 23 ° C., a relative humidity of 55%, a recording density of 2,400 dpi × 1,200 dpi, and a discharge amount of 2.5 pL. An image with a recording duty of 60% was formed on the same recording medium as described above, and the image was naturally dried for 24 hours at a temperature of 23 ° C. and a relative humidity of 55%. The hue of the image portion of the recorded matter thus obtained was measured using a spectrophotometer (Spectorolino; manufactured by Gretag Macbeth) to evaluate the color tone. The evaluation criteria for the color tone are as follows. The evaluation results are shown in Table 4. In the present invention, AA, A and B are acceptable levels and C is not acceptable according to the following evaluation criteria.
AA: Hue angle is 88 ° or more and 90 ° or less.
A: The hue angle is 85 ° or more and less than 88 °, or greater than 90 ° and 92 ° or less.
B: The hue angle is 83 ° or more and less than 85 °, or greater than 92 ° and 94 ° or less.
C: Hue angle is less than 83 ° or greater than 94 °.

(3) Storage stability Each ink obtained above is filled in an ink cartridge for an ink jet recording apparatus (trade name: PIXUS iP8600; manufactured by Canon Inc.), and an ink supply port is provided so that the ink in the ink cartridge does not evaporate. Closed. This ink cartridge was put in a sealed container and stored in a thermostatic bath at a temperature of 60 ° C. for 3 months. Thereafter, the ink cartridge was taken out from the thermostat and attached to the head cartridge of the ink jet recording apparatus. Then, it was stored for 2 weeks at a temperature of 35 ° C. and a humidity of 10% with the discharge port of the head cartridge exposed. Thereafter, the head cartridge was mounted on the same ink jet recording apparatus as described above, and suction was performed a predetermined number of times, and the recoverability was confirmed to evaluate the storage stability of the ink. The suction means “print head cleaning” which is one of functions provided in the ink jet recording apparatus (trade name: PIXUS iP8600; manufactured by Canon Inc.). The evaluation criteria for storage stability are as follows. The evaluation results are shown in Table 4. In the present invention, AA and A are acceptable levels and B and C are unacceptable levels according to the following evaluation criteria.
AA: All the discharge ports recovered to a state where they could be discharged without any problem by suctioning 4 times or less.
A: All the discharge ports recovered to a state where they could be discharged without problems after 5 suctions.
B: It recovered to the state which can discharge all the discharge ports without a problem by 6 times of attraction | suction.
C: There were discharge ports that could not be discharged even after 7 or more times of suction.

(4) Recording durability Each of the inks obtained above was mounted at the position of magenta ink in an ink jet recording apparatus (trade name: BJ F890; manufactured by Canon) using thermal energy. An image with a recording duty of 100% was recorded on the entire surface of an A4 size recording medium (trade name: office planner: manufactured by Canon), and the recording durability was evaluated. Evaluation criteria for recording durability are as follows. The evaluation results are shown in Table 4. In the present invention, AA and A are acceptable levels and B and C are unacceptable levels according to the following evaluation criteria.
AA: Even when 20,000 sheets were recorded, no twist or blur occurred.
A: When recording from 15,000 to 19,999 sheets, slight blurring due to minute twist occurred.
B: When 10,000 to 14,999 sheets were recorded, slight blurring due to minute deviation occurred.
C: Before reaching 10,000 sheets, blurring occurred or non-ejection due to disconnection occurred.

  Note that the inks of Examples 5 and 6 were both ranked A in terms of recording durability, but the ink of Example 6 was slightly inferior in the degree of recording blur. The inks of Examples 9 and 10 both had a recording durability evaluation of A rank, but the ink of Example 10 was slightly inferior in recording blur. In addition, the inks of Examples 14 to 17 all had an evaluation of recording durability of rank A. However, the inks of Examples 16 and 17 were faint compared to the inks of Examples 14 and 15. The degree of was slightly inferior. Further, the color tone of the image formed with the ink of Example 15 was slightly inferior to those of other AA ranks.

Claims (10)

An ink-jet ink containing at least two colorants, a first colorant and a second colorant,
Wherein the first coloring material is a compound represented by the following formula (I), the second coloring material, the compound represented by及beauty under following general formula by the following general formula (II) (III) The content (% by mass) in the ink of the second color material is a mass ratio with respect to the content (% by mass) in the ink of the first color material, An ink-jet ink, wherein the ink is from 0.002 times to 0.50 times.

(In the general formula (I), R ₁ , R ₂ , Y ₁ , and Y ₂ are each independently a monovalent group, and X ₁ and X ₂ are each independently a Hammett σp value of 0.20. These electron-withdrawing groups, Z ₁ and Z ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, substituted or unsubstituted And an aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and M ₁ is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

(In the general formula (II), R ₃ and Y ₃ are each independently a monovalent group, X ₃ is an electron-withdrawing group having a Hammett's σp value of 0.20 or more, and Z ₃ is hydrogen. Atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted heterocycles Group.)

(In general formula (III), R ₄ and Y ₄ are each independently a monovalent group, X ₄ is an electron-withdrawing group having a Hammett's σp value of 0.20 or more, and Z ₄ and Z ₅ Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted group Or an unsubstituted heterocyclic group, and M ₂ is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.) The compound represented by the general formula (I) is a compound represented by the following general formula (IV), and the compound represented by the general formula (II) is represented by the following general formula (V). The inkjet ink according to claim 1, which is a compound and the compound represented by the general formula (III) is a compound represented by the following general formula (VI).

(In the general formula (IV), R ₅ , R ₆ , Y ₁ and Y ₂ are each independently a monovalent group, and X ₁ and X ₂ are each independently having a Hammett σp value of 0.20 or more. And n is an integer of 1 or more, and M ₁ is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

(In the general formula (V), R ₇ and Y ₃ are each independently a monovalent group, X ₃ is an electron-withdrawing group having a Hammett σp value of 0.20 or more, and n is 1 or more. (It is an integer.)

(In General Formula (VI), R ₈ and Y ₄ are each independently a monovalent group, X ₄ is an electron-withdrawing group having a Hammett's σp value of 0.20 or more, and n is 1 or more. Z is an integer, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, Or a substituted or unsubstituted heterocyclic group, and M ₂ is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)   The inkjet ink according to claim 1 or 2, wherein a content (% by mass) of the first color material is 1.0% by mass or more and 8.0% by mass or less based on the total mass of the ink.   4. The inkjet according to claim 1, wherein the content (% by mass) of the second color material is 0.004% by mass to 3.5% by mass based on the total mass of the ink. For ink.   The content (mass%) of the second color material in the ink is 0.002 times or more and 0.43 in mass ratio with respect to the content (mass%) of the first color material in the ink. The inkjet ink according to any one of claims 1 to 4, wherein the inkjet ink is less than or equal to 2 times.   The content (mass%) of the second color material in the ink is 0.002 times or more and 0.12 in mass ratio with respect to the content (mass%) of the first color material in the ink. The inkjet ink according to any one of claims 1 to 5, wherein the inkjet ink is twice or less.   7. An ink jet recording method for recording on a recording medium by ejecting ink by an ink jet method, wherein the ink is the ink jet ink according to any one of claims 1 to 6.   An ink cartridge comprising an ink containing portion containing ink, wherein the ink is the ink jet ink according to any one of claims 1 to 6.   7. The inkjet ink according to claim 1, wherein the recording unit includes an ink storage unit configured to store ink and a recording head for ejecting ink. 7. A recording unit characterized by.   7. The ink jet recording apparatus according to claim 1, wherein the ink is an ink jet recording apparatus including an ink containing portion configured to contain ink and a recording head for ejecting the ink. 8. An ink jet recording apparatus.

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