JP2014001284A - Color material set, ink, ink set, ink cartridge and ink jet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color material set that enables preparation of an ink and an ink set suppressing the occurrence of stains in a recording device inside and a recording medium even in the case of borderless recording performed.SOLUTION: A color material set for ink jet has a combination of a first color material and a second color material. The first color material is a compound represented by general formula (I), and the second color material is at least one of a trisazo compound having a tricyclic condensed ring including two N containing heterocyclic compounds as a heteroatom, and a disazo compound having one N containing heterocyclic compound as a heteroatom.

Description

  The present invention relates to a color material set, an ink, an ink set, an ink cartridge, and an ink jet recording method.

  The ink jet recording method is a recording method in which an ink droplet is applied to a recording medium such as plain paper to form an image, and is rapidly spreading due to its low price and an increase in recording speed. The demand for color materials and ink is increasing, and there is a higher demand for improving the optical density and fastness of recorded images. For example, there is a proposal regarding a polyazo compound as a black dye (see Patent Document 1).

  On the other hand, in the ink jet recording method, by applying ink to a region slightly larger than the size of the recording medium, an image is recorded over the entire surface of the recording medium, and no margin is generated at the edge of the recording medium (edgeless). Recording). When performing borderless recording, an ink absorbing member that absorbs ink ejected to the outside of the recording medium is provided with a predetermined amount so that the ink ejected to the outside of the recording medium does not contaminate the inside of the recording apparatus or the recording medium. There is known a method of arranging at a location (see Patent Documents 2 and 3). As the material of the ink absorbing member, urethane foam or the like is widely used.

  Further, in the case of using an ink that easily aggregates, a technique for impregnating the ink absorbing member with an organic solvent has been proposed in order to prevent the ink applied to the ink absorbing member from aggregating and depositing due to evaporation of moisture. (See Patent Document 4). Furthermore, it has been proposed to suppress the accumulation by adding the ink that is difficult to accumulate aggregates to the ink that easily accumulates aggregates and mixing the inks (see Patent Document 5).

JP 2008-169374 A JP 2001-260391 A JP 2002-337405 A JP 2004-174978 A JP 2011-051135 A

  The present inventors have examined the ink containing the black color material described in Patent Document 1. However, it has been found that the fastness of images recorded using this ink has not reached the level required in recent years. As a result of further studies, it has been found that when a color material having a specific structure is used, an image having high fastness and good optical density can be recorded.

  However, when the methods described in Patent Documents 2 and 3 are adopted and borderless recording is performed with the ink containing the color material having the specific structure, the ink deposited on the ink absorbing member comes into contact with the recording medium. A new problem has arisen in that dirt is generated by doing. To solve this problem, it has been found that the method described in Japanese Patent Laid-Open No. 2004-228620 can reduce the smearing of the recording medium when the number of borderless recordings is increased, although the ink accumulation is reduced. In addition, although the method described in Patent Document 5 can suppress ink accumulation, it has not been possible to improve the contamination of the recording medium when the number of borderless recordings is increased.

  Accordingly, an object of the present invention is to provide a color material set capable of preparing an ink and an ink set in which the occurrence of contamination of the inside of the recording apparatus and the recording medium is suppressed even when borderless recording is performed. is there. Another object of the present invention is to provide an ink using the color material set, an ink set, an ink cartridge, and an ink jet recording method.

  The above object is achieved by the present invention described below. That is, according to the present invention, an inkjet color material set having a combination of a first color material and a second color material, wherein the first color material is represented by the following general formula (I): A color material set, wherein the second color material is at least one of a compound represented by the following general formula (II) and a compound represented by the following general formula (III): Is provided.

（前記一般式（Ｉ）中、Ｒ₁は、炭素数１乃至４のアルキル基；カルボキシ基で置換された炭素数１乃至４のアルキル基；フェニル基；スルホン酸基で置換されたフェニル基；又はカルボキシ基を表し、Ｒ₂は、シアノ基；カルバモイル基；又はカルボキシ基を表し、Ｒ₃及びＲ₄は、それぞれ独立に、水素原子；炭素数１乃至４のアルキル基；ハロゲン原子；炭素数１乃至４のアルコキシ基；又はスルホン酸基を表し、Ｒ₅及びＲ₇は、それぞれ独立に、炭素数１乃至４のアルキルチオ基；又はヒドロキシ基、スルホン酸基及びカルボキシ基からなる群より選択される少なくとも１種の基で置換された炭素数１乃至４のアルキルチオ基を表し、Ｒ₆及びＲ₈は、それぞれ独立に、炭素数１乃至４のアルキルカルボニルアミノ基を表し、Ｒ₉及びＲ₁₀は、それぞれ独立に、水素原子；カルボキシ基；スルホン酸基；アセチルアミノ基；塩素原子；炭素数１乃至４のアルキル基；炭素数１乃至４のアルコキシ基；又はヒドロキシ基、炭素数１乃至４のアルコキシ基、スルホン酸基及びカルボキシ基からなる群より選択される少なくとも１種の基で置換された炭素数１乃至４のアルコキシ基を表し、Ｒ₁₁、Ｒ₁₂及びＲ₁₃は、それぞれ独立に、水素原子；カルボキシ基；スルホン酸基；ヒドロキシ基；アセチルアミノ基；塩素原子；シアノ基；ニトロ基；スルファモイル基；炭素数１乃至４のアルキル基；炭素数１乃至４のアルコキシ基；ヒドロキシ基、炭素数１乃至４のアルコキシ基、スルホン酸基及びカルボキシ基からなる群より選択される少なくとも１種の基で置換された炭素数１乃至４のアルコキシ基；炭素数１乃至４のアルキルスルホニル基；又はヒドロキシ基、スルホン酸基及びカルボキシ基からなる群より選択される少なくとも１種の基で置換された炭素数１乃至４のアルキルスルホニル基を表す）

(In the general formula (I), R ₁ represents an alkyl group having 1 to 4 carbon atoms; an alkyl group having 1 to 4 carbon atoms substituted with a carboxy group; a phenyl group; a phenyl group substituted with a sulfonic acid group; Or a carboxy group, R ₂ represents a cyano group; a carbamoyl group; or a carboxy group, and R ₃ and R ₄ each independently represent a hydrogen atom; an alkyl group having 1 to 4 carbon atoms; a halogen atom; Represents an alkoxy group having 1 to 4; or a sulfonic acid group, and R ₅ and R ₇ are each independently selected from the group consisting of an alkylthio group having 1 to 4 carbon atoms; or a hydroxy group, a sulfonic acid group, and a carboxy group. R ₆ and R ₈ each independently represents a C 1 to C 4 alkylcarbonylamino group substituted with at least one kind of group, R ₉ and R ₁₀ each independently represent a hydrogen atom; a carboxyl group; a sulfonic group; an acetylamino group; a chlorine atom; an alkoxy group having 1 to 4 carbon atoms; an alkyl group having 1 to 4 carbon atoms or hydroxy groups, 1 to carbon atoms 4 represents an alkoxy group having 1 to 4 carbon atoms substituted with at least one group selected from the group consisting of 4 alkoxy groups, sulfonic acid groups and carboxy groups, wherein R ₁₁ , R ₁₂ and R ₁₃ are each independently Carboxy group; sulfonic acid group; hydroxy group; acetylamino group; chlorine atom; cyano group; nitro group; sulfamoyl group; alkyl group having 1 to 4 carbon atoms; alkoxy group having 1 to 4 carbon atoms; 1 to 4 carbon atoms substituted with at least one group selected from the group consisting of a group, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, and a carboxy group An alkoxy group; an alkylsulfonyl group having 1 to 4 carbon atoms; or an alkylsulfonyl group having 1 to 4 carbon atoms substituted with at least one group selected from the group consisting of a hydroxy group, a sulfonic acid group, and a carboxy group; )

（前記一般式（II）中、Ｒ₁₄は、置換基を有するフェニル基を表し、前記置換基は、カルボキシ基；スルホン酸基；塩素原子；シアノ基；ニトロ基；スルファモイル基；炭素数１乃至４のアルキル基；ヒドロキシ基、炭素数１乃至４のアルコキシ基、スルホン酸基、又はカルボキシ基で置換されていてもよい炭素数１乃至４のアルコキシ基；及びヒドロキシ基、スルホン酸基、又はカルボキシ基で置換されていてもよい炭素数１乃至４のアルキルスルホニル基からなる群より選択される少なくとも１種の基である。Ｒ₁₅及びＲ₁₆は、それぞれ独立に、置換基を有するパラフェニレン基を表し、前記置換基は、カルボキシ基；スルホン酸基；炭素数１乃至４のアルキル基；ヒドロキシ基、炭素数１乃至４のアルコキシ基、スルホン酸基、又はカルボキシ基で置換されていてもよい炭素数１乃至４のアルコキシ基；及びヒドロキシ基、スルホン酸基、又はカルボキシ基で置換されていてもよい炭素数１乃至４のアルキルスルホニル基からなる群より選択される少なくとも１種の基である。Ｒ₁₇は、カルボキシ基で置換されていてもよい炭素数１乃至４のアルキル基、スルホン酸基で置換されていてもよいフェニル基、又はカルボキシ基を表し、Ｒ₁₈は、シアノ基、カルバモイル基、又はカルボキシ基を表し、Ｒ₁₉及びＲ₂₀は、それぞれ独立に、水素原子、メチル基、塩素原子、又はスルホン酸基を表す）

(In the general formula (II), R ₁₄ represents a phenyl group having a substituent, and the substituent is a carboxy group; a sulfonic acid group; a chlorine atom; a cyano group; a nitro group; a sulfamoyl group; An alkyl group having 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms which may be substituted with a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, or a carboxy group; and a hydroxy group, sulfonic acid group, or carboxy And at least one group selected from the group consisting of alkylsulfonyl groups having 1 to 4 carbon atoms which may be substituted with a group R ₁₅ and R ₁₆ are each independently a paraphenylene group having a substituent. And the substituent is a carboxy group; a sulfonic acid group; an alkyl group having 1 to 4 carbon atoms; a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, or a carboxyl group; Selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms which may be substituted with a boxy group; and an alkylsulfonyl group having 1 to 4 carbon atoms which may be substituted with a hydroxy group, a sulfonic acid group or a carboxy group R ₁₇ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a carboxy group, a phenyl group which may be substituted with a sulfonic acid group, or a carboxy group. , R ₁₈ represents a cyano group, a carbamoyl group, or a carboxy group, and R ₁₉ and R ₂₀ each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a sulfonic acid group)

（前記一般式（III）中、Ｒ₂₁は、置換されていてもよい芳香族基又は複素環基を表し、−Ｒ₂₂−は下記一般式（ｉ）乃至（ｖ）のいずれかの基を表し、Ｍは、それぞれ独立に、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を表す）

(In the general formula (III), R ₂₁ represents an optionally substituted aromatic group or heterocyclic group, and —R ₂₂ — represents any one of the following general formulas (i) to (v). And each M independently represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium)

（前記一般式（ｉ）乃至（ｖ）中、Ｒ₂₃乃至Ｒ₃₁は、それぞれ独立に、水素原子、ハロゲン原子、脂肪族基、芳香族基、複素環基、カルボキシ基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環オキシカルボニル基、アシル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、複素環オキシ基、シリルオキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基、アシルアミノ基、ウレイド基、スルファモイルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、複素環スルホニルアミノ基、シアノ基、ニトロ基、アルキルチオ基、アリールチオ基、複素環チオ基、アルキルスルホニル基、アリールスルホニル基、複素環スルホニル基、アルキルスルフィニル基、アリールスルフィニル基、複素環スルフィニル基、スルファモイル基、又はスルホン酸基を表し、これらの基はさらに置換されていてもよい）

(In the general formulas (i) to (v), R _{23 to} R ₃₁ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a carboxy group, a carbamoyl group, or an alkoxycarbonyl group. Group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, cyano group, nitro group, Alkylthio group, aryl Represents a thio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfonic acid group, and these groups are further substituted May be)

  According to the present invention, it is possible to provide a color material set capable of preparing an ink and an ink set in which the occurrence of contamination of the inside of the recording apparatus and the recording medium is suppressed even when borderless recording is performed. Further, according to the present invention, it is possible to provide an ink, an ink set, an ink cartridge, and an ink jet recording method using this color material set.

It is sectional drawing which shows typically one Embodiment of the ink cartridge of this invention. FIG. 2 is a diagram schematically illustrating an example of an ink jet recording apparatus used in the ink jet recording method of the present invention, in which (a) is a perspective view of a main part of the ink jet recording apparatus, and (b) is a perspective view of a head cartridge.

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. 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.

  The present inventors have used as a coloring material for ink jet inks a compound represented by general formula (I) (first coloring material), a compound represented by general formula (II), and a general formula ( A combination with at least one of the compounds represented by III) (second coloring material) was found. It was also found that the occurrence of smudges in the recording apparatus and in the recording medium is suppressed when borderless recording is performed using the ink and ink set prepared with the color material set having this combination. The inventors presume the reason why such an effect is obtained as follows.

  When borderless recording was performed with an ink using only the compound represented by the general formula (I) as a coloring material, the compound represented by the general formula (I) aggregated and deposited on the ink absorbing member to which the ink was applied. As a result, it was found that the inside of the recording apparatus and the recording medium were soiled. The reason why the compound represented by the general formula (I) is likely to aggregate is considered to be because the structure has a carbonylamino group having high hydrogen bonding property. On the other hand, when the compound represented by the general formula (II) is present together with the compound represented by the general formula (I), the structures are similar to each other. The molecule of the compound represented by the general formula (II) enters between the molecules of the compound to be produced. For this reason, it is estimated that aggregation of the compound represented by general formula (I) is suppressed. In addition, when the compound represented by the general formula (III) is present together with the compound represented by the general formula (I), two secondary amino groups in the structure of the compound represented by the general formula (III) are formed. Inhibiting hydrogen bonding by the carbonylamino group between the compounds represented by formula (I). For this reason, it is estimated that aggregation of the compound represented by general formula (I) is inhibited.

  The color material set of the present invention having a combination of the first color material and the second color material can be suitably used as an ink or a component for constituting the ink set. That is, it may be an ink containing both the first color material and the second color material, and the first ink containing the first color material and the second ink containing the second color material It is good also as an ink set containing. Hereinafter, the color material set of the present invention, the ink and ink set using the color material set, the components other than the color material constituting the ink, and the physical properties of the ink will be described in detail.

<Color material set>
Hereinafter, each color material constituting the color material set of the present invention will be described in detail.

(First colorant: compound represented by formula (I))
The color material set of the present invention is a color material set for inkjet having a combination of a first color material and a second color material. The first color material constituting the color material set is a compound represented by the following general formula (I).

In the general formula (I), R ₁ is an alkyl group having 1 to 4 carbon atoms; an alkyl group having 1 to 4 carbon atoms substituted with a carboxy group; a phenyl group; a phenyl group substituted with a sulfonic acid group; or Represents a carboxy group. R ₂ represents a cyano group; a carbamoyl group; or a carboxy group. R ₃ and R ₄ each independently represents a hydrogen atom; an alkyl group having 1 to 4 carbon atoms; a halogen atom; an alkoxy group having 1 to 4 carbon atoms; or a sulfonic acid group. R ₅ and R ₇ are each independently an alkylthio group having 1 to 4 carbon atoms; or 1 to 1 carbon atoms substituted with at least one group selected from the group consisting of a hydroxy group, a sulfonic acid group, and a carboxy group. 4 represents an alkylthio group. R ₆ and R ₈ each independently represents an alkylcarbonylamino group having 1 to 4 carbon atoms. R ₉ and R ₁₀ are each independently a hydrogen atom; a carboxy group; a sulfonic acid group; an acetylamino group; a halogen atom; an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms; It represents an alkoxy group having 1 to 4 carbon atoms substituted with at least one group selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, and a carboxy group. R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom; a carboxy group; a sulfonic acid group; a hydroxy group; an acetylamino group; a halogen atom; a cyano group; a nitro group; a sulfamoyl group; A group having 1 to 4 carbon atoms; a group having 1 to 4 carbon atoms substituted with at least one group selected from the group consisting of a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, and a carboxy group; An alkylsulfonyl group having 1 to 4 carbon atoms; or an alkylsulfonyl group having 1 to 4 carbon atoms substituted with at least one group selected from the group consisting of a hydroxy group, a sulfonic acid group and a carboxy group; Represent.

The compound represented by the general formula (I) has tautomers. As tautomers, compounds represented by the following general formulas (IV) and (V) can be considered in addition to the compounds represented by the general formula (I). In the present invention, these compounds (tautomers) and salts are also included in the compound represented by the general formula (I). In general formula (IV) and (V) R ₁ to R ₁₃ in is synonymous with R ₁ through R ₁₃ in the general formula (I).

In general formula (I), examples of the alkyl group having 1 to 4 carbon atoms represented by R ₁ include a linear or branched unsubstituted alkyl group. Among these, a linear unsubstituted alkyl group is preferable. Specific examples of the alkyl group having 1 to 4 carbon atoms include linear alkyl groups such as methyl, ethyl, n-propyl, and n-butyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl. Can be mentioned. Among these, a methyl group and an n-propyl group are preferable, and a methyl group is more preferable.

In the general formula (I), the alkyl group having 1 to 4 carbon atoms substituted by the carboxy group represented by R ₁ is _{one in} which any of the above-mentioned unsubstituted alkyl groups is substituted with a carboxy group. Can be mentioned. The substitution position of the carboxy group is preferably the terminal of the alkyl group. Further, the number of substitutions of the carboxy group is preferably 1 or 2, and more preferably 1. Specific examples of the alkyl group having 1 to 4 carbon atoms substituted with a carboxy group include carboxymethyl and 2-carboxyethyl. Among these, a carboxymethyl group is preferable.

In the general formula (I), examples of the phenyl group substituted with the sulfonic acid group represented by R ₁ include a phenyl group substituted with 1 to 3, preferably 1 or 2 sulfonic acid groups. . Specific examples of the phenyl group substituted with a sulfonic acid group include 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, and 3,5-disulfophenyl. Among these, a 4-sulfophenyl group is preferable.

R ₁ in the general formula (I) is an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms substituted with a carboxy group, a phenyl group, or a phenyl group substituted with a sulfonic acid group. It is preferable. R ₁ is more preferably a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a sulfonic acid group, and more preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group. preferable. R ₁ is particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.

R ₂ in the general formula (I) is preferably a cyano group or a carbamoyl group, and more preferably a cyano group.

In general formula (I), examples of the alkyl group having 1 to 4 carbon atoms represented by R ₃ and R ₄ include those exemplified for the alkyl group having 1 to 4 carbon atoms represented by R ₁ , and preferred ones. The same thing can be mentioned including.

In the general formula (I), examples of the halogen atom represented by R ₃ and R ₄ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a chlorine atom is preferable.

In the general formula (I), examples of the alkoxy group having 1 to 4 carbon atoms represented by R ₃ and R ₄ include linear or branched alkoxy groups. Among these, a linear alkoxy group is preferable. The alkoxy group may have a substituent, but an unsubstituted alkoxy group is preferable. Specific examples of the alkoxy group having 1 to 4 carbon atoms include straight-chain alkoxy groups such as methoxy, ethoxy, n-propoxy, and n-butoxy; branched-chain alkoxy groups such as isopropoxy, isobutoxy, sec-butoxy, and tert-butoxy And so on. Of these, a methoxy group is particularly preferable.

R ₃ and R ₄ in the general formula (I) are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a sulfonic acid group. A combination in which one of R ₃ and R ₄ is a hydrogen atom and the other is a sulfonic acid group is more preferable. In the case where one of R ₃ and R ₄ is a hydrogen atom and the other is a sulfonic acid group, the substitution position of the sulfonic acid group is two adjacent to any nitrogen atom constituting the benzimidazolopyrrolidone ring. Preferably they are either carbon atoms. The compound represented by the general formula (I) may be a mixture containing at least two kinds of positional isomers having different substitution positions of R ₃ and R ₄ from the viewpoint of ease of synthesis and cost.

Preferred combinations of R _{1 to} R _{4 in} the general formula (I) are as shown below.
R ₁ : an alkyl group having 1 to 4 carbon atoms or a phenyl group (preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group)
R ₂ : cyano group or carbamoyl group (preferably cyano group)
R ₃ : hydrogen atom, methyl group, or methoxy group (preferably methoxy group)
R ₄ : sulfonic acid group

In the general formula (I), examples of the alkylthio group having 1 to 4 carbon atoms represented by R ₅ and R ₇ include a linear or branched unsubstituted alkylthio group represented by alkyl. Of these, a straight-chain unsubstituted alkylthio group is preferable. Specific examples of the alkylthio group having 1 to 4 carbon atoms include linear alkylthio groups such as methylthio, ethylthio, n-propylthio, and n-butylthio; branched chain alkylthio such as isopropylthio, isobutylthio, sec-butylthio, and tert-butylthio. Examples include groups.

In the general formula (I), the alkylthio group having 1 to 4 carbon atoms substituted with a specific substituent represented by R ₅ and R ₇ is any carbon constituting the alkylthio group having 1 to 4 carbon atoms. The thing which the specific substituent couple | bonded with the atom can be mentioned. The specific substituent is at least one group selected from the group consisting of a hydroxy group, a sulfonic acid group, and a carboxy group. The number of substituents is preferably 1 or 2, and more preferably 1. The position of the substituent is preferably a carbon atom other than the carbon atom to which the sulfur atom constituting the alkylthio group is bonded. Specific examples of the alkylthio group having 1 to 4 carbon atoms substituted with a specific substituent include hydroxyalkylthio groups such as 2-hydroxyethylthio, 2-hydroxypropylthio, and 3-hydroxypropylthio; 2-sulfoethylthio And sulfoalkylthio groups such as 3-sulfopropylthio; carboxyalkylthio groups such as 2-carboxyethylthio, 3-carboxypropylthio and 4-carboxybutylthio.

R ₅ and R _{7 in} general formula (I) are each independently preferably a sulfoalkylthio group or a carboxyalkylthio group, more preferably a sulfoalkylthio group, and particularly preferably a sulfopropylthio group. preferable.

In the general formula (I), examples of the alkylcarbonylamino group having 1 to 4 carbon atoms represented by R ₆ and R ₈ include a linear or branched alkylcarbonylamino group having an alkyl group. Of these, a linear alkylcarbonylamino group is preferred. The alkylcarbonylamino group may have a substituent, but an unsubstituted alkylcarbonylamino group is preferable. Specific examples of the alkylcarbonylamino group having 1 to 4 carbon atoms include straight-chain unsubstituted groups such as acetylamino (methylcarbonylamino), propionylamino (ethylcarbonylamino), n-propylcarbonylamino, and n-butylcarbonylamino. An alkylcarbonylamino group; branched-chain unsubstituted alkylcarbonylamino groups such as isopropylcarbonylamino, isobutylcarbonylamino, sec-butylcarbonylamino, and pivaloylamino (tert-butylcarbonylamino). Among these, a linear unsubstituted alkylcarbonylamino group is preferable, and an acetylamino group is more preferable.

As a combination of R ₅ and R _{6 in} the general formula (I), it is preferable that R ₅ is a sulfoalkylthio group having 1 to 4 carbon atoms and R ₆ is an acetylamino group. More preferably, R ₅ is a sulfopropylthio group and R ₆ is an acetylamino group.

As a combination of R ₇ and R _{8 in} the general formula (I), it is preferable that R ₇ is a sulfoalkylthio group having 1 to 4 carbon atoms and R ₈ is an acetylamino group. More preferably, R ₇ is a sulfopropylthio group and R ₈ is an acetylamino group.

In the general formula (I), examples of the halogen atom represented by R ₉ and R ₁₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a chlorine atom is preferable.

In general formula (I), examples of the alkyl group having 1 to 4 carbon atoms represented by R ₉ and R ₁₀ include those exemplified for the alkyl group having 1 to 4 carbon atoms represented by R ₁ and preferred ones. The same thing can be mentioned including.

In the general formula (I), examples of the alkoxy group having 1 to 4 carbon atoms represented by R ₉ and R ₁₀ include those exemplified for the alkoxy group having 1 to 4 carbon atoms represented by R ₃ and R _4. The same thing can be mentioned including a preferable thing.

In the general formula (I), the alkoxy group having 1 to 4 carbon atoms substituted by a specific substituent represented by R ₉ and R ₁₀ is any carbon constituting the alkoxy group having 1 to 4 carbon atoms. The thing which the specific substituent couple | bonded with the atom can be mentioned. The specific substituent is at least one group selected from the group consisting of a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, and a carboxy group. The number of substituents is preferably 1 or 2, and more preferably 1. The position of the substituent is preferably a carbon atom other than the carbon atom to which the oxygen atom constituting the alkoxy group is bonded. Specific examples of the alkoxy group having 1 to 4 carbon atoms substituted with a specific substituent include hydroxyalkoxy groups such as 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy; 2-sulfoethoxy, 3-sulfo Examples thereof include sulfoalkoxy groups such as propoxy and 4-sulfobutoxy; carboxyalkoxy groups such as 2-carboxyethoxy, 3-carboxypropoxy and 4-carboxybutoxy.

R ₉ is preferably a sulfoalkoxy group or a carboxyalkoxy group, more preferably a sulfoalkoxy group, and particularly preferably a sulfopropoxy group or a sulfobutoxy group. R ₁₀ is preferably an alkyl group, an alkoxy group, a sulfoalkoxy group, a carboxyalkoxy group, or an acetylamino group, more preferably an alkyl group, and particularly preferably a methyl group.

As a combination of R ₉ and R _{10 in} the general formula (I), it is preferable that R ₉ is a sulfoalkoxy group and R ₁₀ is an alkyl group. More preferably, R ₉ is a sulfopropoxy group (particularly 3-sulfopropoxy group) or a sulfobutoxy group (particularly 4-sulfobutoxy group), and R ₁₀ is a methyl group.

In the general formula (I), examples of the halogen atom represented by R ₁₁ , R ₁₂ and R ₁₃ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a chlorine atom is preferable.

In the general formula (I), examples of the alkyl group having 1 to 4 carbon atoms represented by R ₁₁ , R ₁₂ and R ₁₃ include those exemplified for the alkyl group having 1 to 4 carbon atoms represented by R _1. The same thing can be mentioned including a preferable thing.

In the general formula (I), the alkoxy group having 1 to 4 carbon atoms represented by R ₁₁ , R ₁₂ and R ₁₃ is exemplified for the alkoxy group having 1 to 4 carbon atoms represented by R ₃ and R _4. The same thing including what was preferable and what was preferable can be mentioned.

In the general formula (I), the alkoxy group having 1 to 4 carbon atoms substituted by a specific substituent represented by R ₁₁ , R ₁₂ and R ₁₃ is represented by R ₉ and R ₁₀ . The thing similar to what was illustrated about the C1-C4 alkoxy group substituted by the specific substituent can be mentioned. Preferred examples of the alkoxy group having 1 to 4 carbon atoms substituted with a specific substituent are the same as those exemplified for R ₉ and R ₁₀ . The specific substituent is at least one group selected from the group consisting of a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, and a carboxy group.

In the general formula (I), examples of the alkylsulfonyl group having 1 to 4 carbon atoms represented by R ₁₁ , R _12, and R ₁₃ include linear or branched unsubstituted alkylsulfonyl groups. Of these, a straight-chain unsubstituted alkylsulfonyl group is preferred. Specific examples of the alkylsulfonyl group having 1 to 4 carbon atoms include linear alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, and n-butylsulfonyl; branched alkyl such as isopropylsulfonyl and isobutylsulfonyl. A sulfonyl group can be mentioned. Among these, a methylsulfonyl group, an ethylsulfonyl group, or an isopropylsulfonyl group is preferable, and a methylsulfonyl group is more preferable.

In the general formula (I), the alkylsulfonyl group having 1 to 4 carbon atoms substituted with a specific substituent represented by R ₁₁ , R ₁₂ and R ₁₃ is the alkylsulfonyl group having 1 to 4 carbon atoms. In which a specific substituent is bonded to an arbitrary carbon atom that constitutes. The specific substituent is at least one group selected from the group consisting of a hydroxy group, a sulfonic acid group, and a carboxy group. The number of substituents is preferably 1 or 2, and more preferably 1. Specific examples of the alkylsulfonyl group having 1 to 4 carbon atoms substituted with a specific substituent include hydroxyethylsulfonyl, 2-hydroxypropylsulfonyl, 2-sulfoethylsulfonyl, 3-sulfopropylsulfonyl, and 2-carboxyethylsulfonyl. , 3-carboxypropylsulfonyl and the like.

R ₁₁ is preferably a hydrogen atom, a carboxy group, a sulfonic acid group, a chlorine atom, a nitro group, a methyl group, a methoxy group, or an alkylsulfonyl group having 1 to 4 carbon atoms. Further, it is more preferably a hydrogen atom; an electron-withdrawing group such as a carboxy group, a sulfonic acid group, a chlorine atom, a nitro group, an alkylsulfonyl group having 1 to 4 carbon atoms; a methyl group; or a methoxy group, and a hydrogen atom Or it is especially preferable that it is a chlorine atom.

R ₁₂ represents a hydrogen atom, a carboxy group, a sulfonic acid group, a chlorine atom, a nitro group, a sulfamoyl group, a methyl group, a methoxy group, an alkylsulfonyl group having 1 to 4 carbon atoms, or a carboxyalkylsulfonyl group (the carbon number of alkyl is 1). To 4) and a sulfoalkylsulfonyl group having 1 to 4 carbon atoms (the alkyl has 1 to 4 carbon atoms). In addition, a hydrogen atom; an electron-withdrawing group such as a carboxy group, a sulfonic acid group, a chlorine atom, a nitro group, a sulfamoyl group, an alkylsulfonyl group having 1 to 4 carbon atoms, or a carboxyalkylsulfonyl group (the alkyl has 1 to 4), a sulfoalkylsulfonyl group having 1 to 4 carbon atoms (the alkyl has 1 to 4 carbon atoms); a methyl group; or a methoxy group, more preferably a sulfonic acid group, a nitro group, a sulfamoyl group, a methyl group, A methoxy group, a sulfopropylsulfonyl group, or a carboxyethylsulfonyl group is particularly preferable, and a sulfonic acid group is most preferable.

R ₁₃ is preferably a hydrogen atom, a carboxy group, a sulfonic acid group, a methoxy group, a chlorine atom, a nitro group, or an alkylsulfonyl group having 1 to 4 carbon atoms. Further, a hydrogen atom; an electron-withdrawing group such as a carboxy group, a sulfonic acid group, a chlorine atom, a nitro group, an alkylsulfonyl group having 1 to 4 carbon atoms; or a methoxy group is more preferable, and a hydrogen atom. Is particularly preferred.

Preferred combinations of R ₁₁ , R ₁₂ and R _{13 in} the general formula (I) are (a), (b) and (c) shown below. Among these, the combination (c) is particularly preferable.
(A) R ₁₁ is a hydrogen atom, R ₁₂ is a sulfonic acid group, R ₁₃ is a combination of hydrogen atoms (b) R ₁₁ is a hydrogen atom, R ₁₂ is a sulfamoyl group, R ₁₃ is a combination of hydrogen atoms (c) R ₁₁ Is a hydrogen atom, R ₁₂ is a chlorine atom, R ₁₃ is a sulfonic acid group combination

  Among the compounds represented by the general formula (I), compounds represented by the following general formula (VI) are preferable.

R ₁ to R ₁₃ in the general formula (VI), the general formula (I) in the same meanings as those of R ₁ to R ₁₃ of the same as if preferred groups and combinations thereof also general formula (I). Further, in the benzene ring substituted by R ₁₁ , R ₁₂ and R ₁₃ in the general formula (VI), when the substitution position of the azo group is 1-position, the substitution position of R ₁₁ is 2-position or 3-position, R The substitution position of ₁₂ is preferably 4-position, and the substitution position of R ₁₃ is preferably 5-position or 6-position. Preferred combinations of R _{1 to} R _{13 in} the general formula (I) are (i) and (ii) shown below. The combination (ii) is more preferable than the combination (i).

(I)
R ₁ : methyl group R ₂ : cyano group or carbamoyl group R ₃ : hydrogen atom, methyl group, or methoxy group R ₄ : sulfonic acid group R ₅ : sulfoalkylthio group having 1 to 4 carbon atoms R ₆ : 1 to carbon atoms 4 alkylcarbonylamino group R ₇ : sulfoalkylthio group having 1 to 4 carbon atoms R ₈ : alkylcarbonylamino group (alkyl has 1 to 4 carbon atoms)
R ₉ : C 1 -C 4 sulfoalkoxy group R ₁₀ : C 1 -C 4 alkyl group or acetylamino group R ₁₁ , R ₁₂ and R ₁₃ : each independently a hydrogen atom, sulfonic acid group, methyl group, Methoxy group, chlorine atom, nitro group, or sulfamoyl group

(Ii)
R ₁ : methyl group R ₂ : cyano group R ₃ : hydrogen atom or methoxy group R ₄ : sulfonic acid group R ₅ : sulfoalkylthio group having 1 to 4 carbon atoms R ₆ : acetylamino group R ₇ : 1 to 4 carbon atoms sulfoalkyl thio group R _8: an acetylamino group R _9: sulfopropoxy group or sulfobutoxy group R _10: alkyl group having 1 to 4 carbon atoms R _11: a hydrogen atom or a sulfonic acid group R _12: a sulfonic acid group or a chlorine atom R ₁₃ : Hydrogen atom or sulfonic acid group

  Preferable specific examples of the compound represented by the general formula (I) include Exemplified Compounds 1 to 96 shown in Table 1. In Table 1, exemplary compounds are shown as the free acid form (H form) in the form of the following general formula (VI '). Of course, in the present invention, the compounds shown in Table 1 are not limited as long as they are included in the structure of the general formula (I) and the definition thereof. In the present invention, among the exemplary compounds shown in Table 1, exemplary compounds 1 to 12, 19 and 20 are preferable, exemplary compounds 7 to 12, 19 and 29 are more preferable, and exemplary compounds 7 to 12 are particularly preferable.

The compound represented by the general formula (I) can be synthesized, for example, according to the method shown below. Hereinafter, the structural formula of the compound in each step is expressed as a free acid type. Incidentally, R ₁ through R ₁₃ in the following general formula (1) to (8) has the same meaning as R ₁ to R ₁₃ in the general formula (I).

  A diazo compound obtained by diazotizing a compound represented by the following general formula (1) according to a conventional method and a compound represented by the following general formula (2) are subjected to a coupling reaction according to a conventional method. A compound represented by the formula (3) is obtained.

  A diazo compound obtained by diazotizing a compound represented by the general formula (3) according to a conventional method and a compound represented by the following general formula (4) are subjected to a coupling reaction according to a conventional method. A compound represented by the formula (5) is obtained.

  A diazo compound obtained by diazotizing a compound represented by the general formula (5) according to a conventional method and a compound represented by the following general formula (6) are subjected to a coupling reaction according to a conventional method. A compound represented by the formula (7) is obtained.

  If a diazo compound obtained by diazotizing the compound represented by the general formula (7) according to a conventional method and a compound represented by the following general formula (8) are subjected to a coupling reaction according to a conventional method, The compound represented by the general formula (I) can be obtained.

  The diazotization of the compound represented by the general formula (1) is performed by a known method. For example, diazotization is performed using nitrite in an inorganic acid medium at -5 to 30 ° C, preferably 0 to 15 ° C. As the nitrite, alkali metal nitrites such as sodium nitrite can be used. A coupling reaction between the diazotized compound of the compound represented by the general formula (1) and the compound represented by the general formula (2) is also carried out by a known method. For example, the coupling reaction is carried out in water or an aqueous organic medium at −5 to 30 ° C., preferably 0 to 25 ° C., at an acidic to neutral pH value, preferably pH 1 to 6. The diazotization reaction liquid is acidic. Further, since the coupling reaction proceeds, the reaction solution is further acidified. For this reason, the pH of the reaction solution is adjusted to a preferred value by adding a base. Examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; alkali metal acetates such as sodium acetate; Ammonia; organic amines can be used. Moreover, what is necessary is just to use the compound represented by General formula (1), and the compound represented by General formula (2) in a substantially stoichiometric amount.

  The diazotization of the compound represented by the general formula (3) is performed by a known method. For example, diazotization is performed using nitrite in an inorganic acid medium at −5 to 40 ° C., preferably 5 to 30 ° C. Coupling of the diazotized product of the compound represented by the general formula (3) and the compound represented by the general formula (4) is also carried out by a known method. The coupling reaction is carried out in water or an aqueous organic medium at −5 to 40 ° C., preferably 10 to 30 ° C., at an acidic to neutral pH value, preferably pH 2 to 7. The diazotization reaction liquid is acidic. Further, since the coupling reaction proceeds, the reaction solution is further acidified. For this reason, the pH of the reaction solution is adjusted to a preferred value by adding a base. The same base as described above can be used. Moreover, what is necessary is just to use the compound represented by General formula (3) and the compound represented by General formula (4) in a substantially stoichiometric amount.

  The diazotization of the compound represented by the general formula (5) is performed by a known method. For example, diazotization is performed using nitrite in an inorganic acid medium at −5 to 50 ° C., preferably 5 to 40 ° C. Coupling of the diazotized product of the compound represented by the general formula (5) and the compound represented by the general formula (6) is also performed by a known method. The coupling reaction is carried out in water or an aqueous organic medium at −5 to 50 ° C., preferably 10 to 40 ° C., at an acidic to neutral pH value, preferably pH 2 to 7. The diazotization reaction liquid is acidic. Further, since the coupling reaction proceeds, the reaction solution is further acidified. For this reason, the pH of the reaction solution is adjusted to a preferred value by adding a base. The same base as described above can be used. Moreover, what is necessary is just to use the compound represented by General formula (5), and the compound represented by General formula (6) in a substantially stoichiometric amount.

  The diazotization of the compound represented by the general formula (7) is performed by a known method. For example, diazotization is performed using nitrite in an inorganic acid medium at −5 to 50 ° C., preferably 10 to 40 ° C. Coupling of the diazotized product of the compound represented by the general formula (7) and the compound represented by the general formula (8) is also carried out by a known method. The coupling reaction is carried out in water or an aqueous organic medium at −5 to 50 ° C., preferably 10 to 40 ° C., at a slightly acidic to alkaline pH value, preferably pH 5 to 10. The diazotization reaction liquid is acidic. Further, since the coupling reaction proceeds, the reaction solution is further acidified. For this reason, the pH of the reaction solution is adjusted to a preferred value by adding a base. The same base as described above can be used. Further, the compound represented by the general formula (7) and the compound represented by the general formula (8) may be used in a substantially stoichiometric amount.

  The salt of the compound represented by the general formula (I) is a salt of the compound represented by the general formula (I) and an inorganic or organic cation. Specific examples of the inorganic salt include alkali metal salts, alkaline earth metal salts, and ammonium salts. Of these, lithium, sodium, potassium and ammonium salts are preferred. Moreover, as an organic cation, the quaternary ammonium ion represented by following General formula (9) can be mentioned, for example. In addition, the compound represented by the general formula (1) may be a mixture containing the free acid of the compound represented by the general formula (I), tautomers thereof, and various salts thereof. Specifically, any combination such as a mixture of sodium salt and ammonium salt, a mixture of free acid and sodium salt, a mixture of lithium salt, sodium salt and ammonium salt may be used. Depending on the type of salt, the physical properties such as solubility may differ. For this reason, the mixture which has the physical property suitable for the objective can also be obtained by selecting the kind of salt suitably as needed, or changing the ratio, when a some salt etc. are included.

In the general formula (9), Z _{1 to} Z ₄ each independently represent a group selected from the group consisting of a hydrogen atom, an unsubstituted alkyl group, a hydroxyalkyl group, and a hydroxyalkoxyalkyl group. However, at least one of Z _{1 to} Z ₄ is a group other than a hydrogen atom.

Specific examples of the unsubstituted alkyl group represented by Z _{1 to} Z ₄ in the general formula (9) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. And an unsubstituted alkyl group having 1 to 4 carbon atoms. Specific examples of the hydroxyalkyl group include hydroxyalkyl groups having 1 to 4 carbon atoms such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, and 2-hydroxybutyl. Can be mentioned. Specific examples of the hydroxyalkoxyalkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxy. Examples thereof include hydroxyalkoxyalkyl groups such as butyl (the number of carbon atoms of alkoxy and alkyl is 1 to 4 respectively). Of these, a hydroxyethoxyalkyl group (alkyl having 1 to 4 carbon atoms) is preferable.

Z _{1 to} Z ₄ in the general formula (9) are each independently a hydrogen atom (provided that at least one of Z _{1 to} Z ₄ is a group other than a hydrogen atom); methyl; hydroxymethyl, hydroxyethyl, C1-C4 hydroxyalkyl groups such as 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl; hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxy It is preferably a hydroxyethoxyalkyl group (alkyl has 1 to 4 carbon atoms) such as propyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl and 2-hydroxyethoxybutyl.

  Specific examples of the quaternary ammonium ion represented by the general formula (9) include the exemplified compounds a to l shown in Table 2.

Examples of the method for synthesizing the salt of the compound represented by the general formula (I) include the following methods (a) and (b). The target salt of the compound represented by the general formula (I) can be obtained in the form of a solution or a precipitated solid by the method shown below.
(A) After completion of the final step in the synthesis reaction of the compound represented by the general formula (I), an inorganic salt or a quaternary ammonium salt is added to the reaction solution and salted out.
(B) An inorganic salt adhered after washing the free acid of the azo compound isolated by adding a mineral acid such as hydrochloric acid to the reaction solution as described above, with water, acidic water, or an aqueous organic medium, if necessary. Remove impurities such as. Again, the desired inorganic base or organic base corresponding to the quaternary ammonium salt is added to the free acid in an aqueous medium (preferably in water).
Acidic water refers to, for example, mineral acids such as sulfuric acid and hydrochloric acid; and organic acids such as acetic acid dissolved in water to make them acidic. The aqueous organic medium refers to a mixture of water and an organic compound that is miscible with water. Specific examples of the “organic compound miscible with water” include water-soluble organic solvents described later.

  Specific examples of the inorganic salt used when the azo compound represented by the general formula (I) is used as a desired salt include alkali metal halides such as lithium chloride, sodium chloride and potassium chloride; lithium carbonate, sodium carbonate, Alkali metal carbonates such as potassium carbonate; Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Ammonium halides such as ammonium chloride and ammonium bromide; Ammonium hydroxide (ammonia water), etc. Can be mentioned. Specific examples of the organic cation salt include halogen salts of quaternary ammonium ions represented by the general formula (9) such as diethanolamine hydrochloride and triethanolamine hydrochloride.

(First color material verification method)
In order to verify whether or not the first color material used in the present invention is contained in each ink, the following verification methods (1) to (3) using high performance liquid chromatography (HPLC) are applied. be able to.
(1) Peak retention time (2) Maximum absorption wavelength for peak of (1) (3) M / Z (posi), M / Z (negative) of mass spectrum for peak of (1)

The analysis conditions of high performance liquid chromatography are as follows. A liquid (ink) diluted about 1,000 times with pure water is used as a measurement sample. Then, an analysis by high performance liquid chromatography is performed under the following conditions, and a peak retention time and a peak maximum absorption wavelength are measured.
Column: SunFire C18 (Nippon Waters) 2.1mm x 150mm
-Column temperature: 40 ° C
・ Flow rate: 0.2 mL / min
PDA: 200 nm to 700 nm
Mobile phase and gradient conditions: Table 3

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, M / Z detected most strongly is measured with respect to each of posi and nega.
・ 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 above-mentioned method and conditions, the measurement was performed on the exemplified compound 7 which is a specific example of the compound represented by the general formula (I). As a result, the obtained retention time, maximum absorption wavelength, M / Z (posi), and M / Z (negative) values are shown in Table 4. For an unknown ink, measurement is performed under the same method and conditions as described above, and when the obtained measurement value corresponds to the value shown in Table 4, it can be determined that the compound contains the compound used in the ink of the present invention. .

(Second coloring material: compound represented by formula (II))
The second color material constituting the color material set of the present invention is at least one of the compound represented by the general formula (II) and the compound represented by the general formula (III). The compound represented by the following general formula (II) is described in JP-A-2009-030023.

In the general formula (II), R ₁₄ represents a phenyl group having a substituent. The substituent is a carboxy group; a sulfonic acid group; a chlorine atom; a cyano group; a nitro group; a sulfamoyl group; an alkyl group having 1 to 4 carbon atoms; a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, or Selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms which may be substituted with a carboxy group; and an alkylsulfonyl group having 1 to 4 carbon atoms which may be substituted with a hydroxy group, a sulfonic acid group or a carboxy group Is at least one group.

In the general formula (II), R ₁₅ and R ₁₆ each independently represents a paraphenylene group having a substituent. The substituent is a carboxy group; a sulfonic acid group; an alkyl group having 1 to 4 carbon atoms; a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, or a carboxy group, which may be substituted with 1 carbon atom. Or at least one group selected from the group consisting of an alkylsulfonyl group having 1 to 4 carbon atoms which may be substituted with a hydroxy group, a sulfonic acid group, or a carboxy group.

In the general formula (II), R ₁₇ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a carboxy group, a phenyl group which may be substituted with a sulfonic acid group, or a carboxy group. In general formula (II), R ₁₈ represents a cyano group, a carbamoyl group, or a carboxy group. In general formula (II), R ₁₉ and R ₂₀ each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a sulfonic acid group.

In the general formula (II), R ₁₄ is preferably a phenyl group having a sulfonic acid group or a carboxy group. Furthermore, in the general formula (II), R ₁₅ and R ₁₆ are preferably each independently a group represented by the following general formula (vi).

（前記一般式（vi）中、Ｒ₃₂は、スルホン酸基又はスルホプロポキシ基を表し、Ｒ₃₃は、水素原子、メチル基、エチル基、メトキシ基、又はエトキシ基を表す）

(In the general formula (vi), R ₃₂ represents a sulfonic acid group or a sulfopropoxy group, and R ₃₃ represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group)

(Second coloring material: compound represented by general formula (III))
The second color material constituting the color material set of the present invention is at least one of the compound represented by the general formula (II) and the compound represented by the general formula (III). The compound represented by the following general formula (III) is described in JP2009-030023A.

In the general formula (III), R ₂₁ represents an optionally substituted aromatic group or heterocyclic group. In the general formula (III), -R _22- represents any one of the following general formulas (i) to (v). Moreover, in general formula (III), M represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium each independently.

In general formulas (i) to (v), R _{23 to} R ₃₁ each independently represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a carboxy group, a carbamoyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, cyano group, nitro group, alkylthio group , Arylthio Represents a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, alkylsulfinyl group, arylsulfinyl group, heterocyclic sulfinyl group, a sulfamoyl group, or a sulfonic acid group. These groups may be further substituted.

<Ink>
The ink of the present invention is an ink-jet ink containing a plurality of types of color materials, and the plurality of types of color materials constitute the first color material and the second color material constituting the color material set of the present invention described above. Includes coloring material. As long as the effect of the present invention is obtained, a color material other than the first color material and the second color material may be further used.

  The content (% by mass) of the first color material in the ink is preferably 0.2% by mass or more and 8.0% by mass or less based on the total mass of the ink. The content (% by mass) of the second color material in the ink is preferably 0.1% by mass or more and 6.0% by mass or less based on the total mass of the ink. The total content (% by mass) of the first color material and the second color material in the ink is preferably 0.3% by mass or more and 10.0% by mass or less based on the total mass of the ink. .

  When the compound represented by the general formula (II) is used as the second color material, the content (% by mass) of the second color material based on the total mass of the ink is the content of the first color material. The mass ratio with respect to the amount (% by mass) is preferably 0.05 times or more. When the compound represented by the general formula (III) is used as the second color material, the content (% by mass) of the second color material based on the total mass of the ink is the same as that of the first color material. The mass ratio with respect to the content (mass%) is preferably 0.10 times or more. In any case, if the mass ratio is less than the above, the effect of suppressing the ink deposition on the ink absorbing member in the borderless recording may not be sufficiently obtained at a high level. On the other hand, the content (% by mass) of the second color material based on the total mass of the ink is preferably 10.0 times or less in mass ratio with respect to the content (% by mass) of the first color material. . When the mass ratio is exceeded, a high level of optical density may not be obtained sufficiently.

<Ink set>
The ink set of the present invention is an ink jet ink set having a combination of a first ink and a second ink. And the 1st ink contains the 1st color material which comprises the color material set of this invention demonstrated above. Further, the second ink contains the second color material constituting the color material set of the present invention described above. As long as the effect of the present invention is obtained, a color material other than the first color material and the second color material may be further used.

  The content (% by mass) of the first color material in the first ink is preferably 0.2% by mass or more and 8.0% by mass or less based on the total mass of the ink. Further, the content (% by mass) of the second color material in the second ink is preferably 0.1% by mass or more and 6.0% by mass or less based on the total mass of the ink.

<Ingredients other than coloring materials>
Next, components other than the color material used in the ink of the present invention and the first and second inks constituting the ink set of the present invention will be described. Hereinafter, the “ink” of the present invention and the “first ink” and “second ink” constituting the ink set of the present invention will be referred to as “ink” of the present invention for convenience.

(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.

(Other additives)
In addition to the components described above, the ink of the present invention is a water-soluble organic substance that is solid at room temperature, such as polyhydric alcohols such as trimethylolpropane and trimethylolethane, and urea derivatives such as urea and ethyleneurea, if necessary. A compound may be contained. Furthermore, the ink of the present invention contains a surfactant, a pH adjuster, a rust inhibitor, an antiseptic, an antifungal agent, an antioxidant, an anti-reduction agent, an evaporation accelerator, a chelating agent, and a water-soluble agent as necessary. Various additives such as a functional resin may be contained.

(Other inks)
Further, in order to form a full-color image or the like, the ink of the present invention can be used in combination with another ink having a hue different from the ink of the present invention. Examples of the other ink include at least one ink selected from the group consisting of black ink, cyan ink, magenta ink, yellow ink, red ink, green ink, and blue ink. Further, a so-called light ink having substantially the same hue as these inks can be used in combination. The coloring material used for other inks and light inks may be a known dye or a newly synthesized dye.

<Ink cartridge>
The ink cartridge of the present invention includes ink and an ink storage unit that stores the ink. And the ink accommodated in this ink accommodating part is the ink of this invention demonstrated above. FIG. 1 is a cross-sectional view schematically showing an embodiment of the ink cartridge of the present invention. As shown in FIG. 1, an ink supply port 12 for supplying ink to the recording head is provided on the bottom surface of the ink cartridge. The inside of the ink cartridge is an ink storage portion for storing ink. The ink storage portion is composed of an ink storage chamber 14 and an absorber storage chamber 16, which communicate with each other via a communication port 18. The absorber housing chamber 16 communicates with the ink supply port 12. Liquid ink 20 is stored in the ink storage chamber 14, and absorbers 22 and 24 that hold the ink in an impregnated state are stored in the absorber storage chamber 16. The ink storage unit may have a form in which the entire amount of ink stored is held by an absorber without having an ink storage chamber for storing liquid ink. Further, the ink storage portion may have a form that does not have an absorber and stores the entire amount of ink in a liquid state. Further, the ink cartridge may be configured to have an ink storage portion and a recording head.

<Inkjet recording method>
The ink jet recording method of the present invention is a method of recording an image on a recording medium by discharging the ink of the present invention described above from an ink jet recording head. Examples of the method for ejecting ink include a method for imparting mechanical energy to the ink and a method for imparting thermal energy to the ink. In the present invention, it is particularly preferable to employ a method in which thermal energy is applied to the ink and the ink is ejected. Other than using the ink of the present invention, the steps of the ink jet recording method may be known.

  2A and 2B are diagrams schematically showing an example of an ink jet recording apparatus used in the ink jet recording method of the present invention. FIG. 2A is a perspective view of a main part of the ink jet recording apparatus, and FIG. 2B is a perspective view of a head cartridge. It is. The ink jet recording apparatus is provided with a conveying means (not shown) for conveying the recording medium 32 and a carriage shaft 34. A head cartridge 36 can be mounted on the carriage shaft 34. The head cartridge 36 includes recording heads 38 and 40, and is configured such that an ink cartridge 42 is set. While the head cartridge 36 is conveyed along the carriage shaft 34 in the main scanning direction, ink (not shown) is ejected from the recording heads 38 and 40 toward the recording medium 32. Then, the recording medium 32 is conveyed in the sub-scanning direction by a conveying unit (not shown), whereby an image is recorded on the recording medium 32.

  On the platen (not shown), an ink absorbing member is provided that absorbs ink applied to the outside of the recording medium when borderless recording is performed. As the ink absorbing member, a material having ink absorbability such as urethane foam is used.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited at all by the following Example, unless the summary is exceeded. In addition, what is described as “parts” and “%” with respect to the component amounts is based on mass unless otherwise specified.

<Synthesis of first color material>
A first color material was synthesized according to the following procedure. Using water as a solvent, the maximum absorption wavelength (λmax) of the absorption spectrum of the obtained colorant was measured under the following conditions.
・ Spectrophotometer: Self-recording spectrophotometer (trade name “U-3300”, manufactured by Hitachi, Ltd.)
・ Measurement cell: 1 cm quartz cell ・ Sampling interval: 0.1 nm
・ Scanning speed: 30nm / min

(Synthesis of Compound A)
(A)
41.8 parts of 4-chloro-3-nitroaniline was dissolved in 60.0 parts of N-methyl-2-pyrrolidone, and 35.2 parts of acetic anhydride was added dropwise thereto over about 15 minutes. After making it react at 40-50 degreeC for 2 hours, the reaction liquid was added to 400.0 parts of water. After stirring at room temperature for 30 minutes, the precipitated solid was filtered. The obtained solid was washed with 100.0 parts of water, and fractionated and dried to obtain 63.0 parts of a compound represented by the following formula (10).

(B)
42.9 parts of the compound represented by the formula (10) obtained in the procedure (a) was dissolved in 115.0 parts of N-methyl-2-pyrrolidone, and 40.9 parts of sodium 3-mercaptopropanesulfonate was dissolved therein. And 29.0 parts of potassium carbonate were added. Then, it heated at 130-140 degreeC and made it react at the same temperature for 2 hours. After further adding 3.6 parts of sodium 3-mercaptopropanesulfonate, the mixture was reacted at 130 to 140 ° C. for 1 hour. After cooling to 60 ° C., the reaction solution was added to 700.0 parts of 2-propanol, cooled to room temperature, and the produced solid was filtered to obtain a wet cake. The obtained wet cake was dissolved in 300.0 parts of water, and 35% hydrochloric acid was added to adjust the pH to 3.0 to 4.0. Thereafter, sodium chloride was added for salting out, and the precipitated solid was collected by filtration to obtain 205.3 parts of a wet cake of a compound represented by the following formula (11).

(C)
In 150.0 parts of water, 102.6 parts of a wet cake of the compound represented by the formula (11) obtained in the procedure (b), 1.6 parts of activated carbon, and 0.4 parts of anhydrous iron (III) chloride are added. After addition and heating to 60 ° C., 15.9 parts of 80% hydrazine hydrate was added dropwise over about 30 minutes. After heating to 90 ° C., the reaction was carried out at the same temperature for 1.5 hours. After cooling to 40 ° C., insoluble matters were removed by filtration, and the filtrate was cooled to room temperature. 50% sulfuric acid was added to adjust the pH to 1.0 to 1.5. The precipitated solid was collected by filtration to obtain 62.3 parts of a wet cake of a compound represented by the following formula (12).

(D)
After adding 12.6 parts of 5-amino-2-chlorobenzenesulfonic acid represented by the following formula (13) to 40.0 parts of water, a 25% aqueous sodium hydroxide solution is added to adjust the pH to 4.0 to 5.0. An aqueous solution of was obtained. After adding 25.0 parts of 35% hydrochloric acid to the obtained aqueous solution, 12.6 parts of 40% aqueous sodium nitrite solution was added and reacted for about 30 minutes. To this, 1.5 parts of sulfamic acid was added and stirred for 5 minutes to obtain a diazo reaction liquid. On the other hand, after adding 32.4 parts of a wet cake of the compound represented by the formula (12) obtained in the procedure (c) to 200.0 parts of water, a 25% aqueous sodium hydroxide solution was added to adjust the pH to 4. An aqueous solution of 0-5.0 was obtained. The obtained aqueous solution was added dropwise to the diazo reaction solution over about 5 minutes. After dropping, a 15% aqueous sodium carbonate solution was added to react for 3 hours while maintaining the pH at 2.0 to 2.5. Thereafter, sodium chloride was added for salting out, and the precipitated solid was collected by filtration to obtain 31.5 parts of a wet cake of a compound represented by the following formula (14).

(E)
After adding the total amount of the wet cake of the compound represented by the formula (14) obtained in the procedure (d) to 40.0 parts of water, a 25% aqueous sodium hydroxide solution was added to adjust the pH to 6.0 to 7.0. An aqueous solution of was obtained. After adding 24.8 parts of 35% hydrochloric acid, 9.8 parts of 40% aqueous sodium nitrite solution was added and allowed to react for about 30 minutes. 2.0 parts of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid. On the other hand, after adding 30.8 parts of a wet cake of the compound represented by the formula (12) obtained in the procedure (c) to 250.0 parts of water, a 25% aqueous sodium hydroxide solution was added to adjust the pH to 4. An aqueous solution of 0-5.0 was obtained. This aqueous solution was added dropwise to the diazo reaction solution over about 5 minutes. After dropping, a 15% aqueous sodium carbonate solution was added to react for 3 hours while maintaining the pH at 2.0 to 2.5. Thereafter, sodium chloride was added for salting out, and the precipitated solid was collected by filtration to obtain 90.0 parts of a wet cake of a compound represented by the following formula (15).

(F)
To 250.0 parts of water, 45.0 parts of a wet cake of the compound represented by the formula (14) obtained in the procedure (d) was added, and dissolved by stirring. After adding 16.5 parts of 35% hydrochloric acid, 4.7 parts of 40% aqueous sodium nitrite solution was added and stirred for about 30 minutes. 2.0 parts of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid. On the other hand, 5.5 parts of a compound represented by the following formula (16) was added to 60.0 parts of water, and a 25% aqueous sodium hydroxide solution was added to obtain an aqueous solution having a pH of 4.5 to 5.5. The obtained aqueous solution was added dropwise to the diazo reaction solution over about 5 minutes. After the dropwise addition, a 15% aqueous sodium carbonate solution was added to react for 3 hours while maintaining the pH at 2.0 to 3.0. A 15% aqueous sodium carbonate solution was added to adjust the pH to 4.5, and then 350.0 parts of methanol was added. The precipitated solid was collected by filtration to obtain 6.0 parts of a wet cake of a compound represented by the following formula (17).

(G)
To 170.0 parts of water, 32.2 parts of a wet cake of the compound represented by the formula (17) obtained in the procedure (f) was added and stirred to dissolve. After adding 5.2 parts of 35% hydrochloric acid, 1.5 parts of 40% aqueous sodium nitrite solution was added and stirred for about 30 minutes. 1.0 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid. On the other hand, 2.2 parts of a compound represented by the following formula (18) was added to 60.0 parts of water, and a 25% aqueous sodium hydroxide solution was added to obtain an aqueous solution having a pH of 7.5 to 8.5. The diazo reaction liquid was added dropwise over about 30 minutes while maintaining the obtained aqueous solution at 15 to 30 ° C. At this time, an aqueous sodium carbonate solution was added to maintain the pH of the reaction solution at 7.5 to 8.5, and the reaction was further continued for 2 hours while maintaining the same temperature and pH. Thereafter, sodium chloride was added for salting out, and the precipitated solid was separated by filtration to obtain 29.5 parts of a wet cake. The obtained wet cake was dissolved in 100.0 parts of water, the pH was adjusted to 7.0 to 7.5 with 35% hydrochloric acid, 80.0 parts of methanol was added, and the precipitated solid was collected by filtration. . The obtained wet cake was again dissolved in 60.0 parts of water, and then 90.0 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain 6.3 parts of a compound represented by the following formula (19) as a sodium salt.

(H)
To 140.0 parts of water, 6.3 parts of the compound represented by the formula (10) obtained in the procedure (g) and 14 parts of lithium chloride were added and stirred. To this, 400.0 parts of 2-propanol was added, and the precipitated solid was filtered to obtain a wet cake. The obtained wet cake and 12.5 parts of lithium chloride were added to 150.0 parts of water and stirred. To this, 350.0 parts of 2-propanol was added, and the precipitated solid was filtered to obtain a wet cake. The obtained wet cake was added to 80.0 parts of water, 150.0 parts of 2-propanol was added thereto, and the precipitated solid was filtered to obtain a wet cake. The obtained wet cake was added to 40 parts of water, 100.0 parts of 2-propanol was added thereto, the precipitated solid was filtered, and then dried to obtain 4.5 parts of Compound A. The obtained compound A is a mixture of a lithium salt and a sodium salt (80%: 20%) of the compound represented by the formula (19) as a free acid form. Further, the maximum absorption wavelength λmax of the absorption spectrum of the obtained compound A was 590 nm.

(Synthesis of Compound B)
(I)
15.2 parts of 2-methyl-6-nitroaniline were dissolved in 300.0 parts of methanol. The obtained solution was transferred into an autoclave, 2.0 parts of 5% Pd / carbon was added, and the reaction was continued under pressure in a hydrogen atmosphere of 0.2 to 0.5 MPa at 20 to 30 ° C. until no hydrogen was absorbed. I let you. Further reaction was performed at the same temperature for 30 minutes. The catalyst (5% Pd / carbon) was separated by filtration to obtain a solution (filtrate) containing a compound represented by the following formula (20).

(J)
13.0 parts of methyl cyanoacetate was added to 200.0 parts of the solution containing the compound represented by the formula (20) obtained in the procedure (i), and the mixture was refluxed for 30 minutes. After methanol was distilled off under reduced pressure and concentrated, 100.0 parts of water and sodium carbonate were added to adjust the pH to 7.0 to 7.5. The precipitated solid was separated by filtration and then dried to obtain 8.3 parts of a compound represented by the following formula (21).

(K)
To 100.0 parts of ethanol were added 8.3 parts of the compound represented by the formula (21) obtained in the procedure (j), 12.0 parts of 28% sodium methoxide, and 7.2 parts of methyl acetoacetate, Refluxed for 30 minutes. Ethanol was distilled off under reduced pressure and concentrated, and then 100.0 parts of water and 35% hydrochloric acid were added to adjust the pH to 7.0 to 7.5. The precipitated solid was separated by filtration and dried to obtain 11.1 parts of a compound represented by the following formula (22). The obtained compound represented by the following formula (22) was a mixture of a compound having a methoxy group substituted with b and a compound substituted with c.

(L)
After slowly adding 5.6 parts of the compound represented by the formula (22) obtained in the step (k) to 77.0 parts of 8% fuming sulfuric acid at 5 to 10 ° C., the reaction is performed at the same temperature for 1.5 hours. I let you. The reaction solution was dropped into 150.0 parts of ice water over about 10 minutes, stirred at 65 to 70 ° C. for 30 minutes, and then the precipitated solid was separated by filtration, whereby the compound represented by the following formula (23) 24.4 parts of a wet cake was obtained. The compound represented by the following formula (23) is obtained by (i) a compound in which a methoxy group is substituted by b and a sulfonic acid group is substituted by a, c or d, and (ii) a methoxy group is substituted by c. And a mixture with a compound in which the sulfonic acid group was substituted with a, b or d.

(M)
Instead of 2.2 parts of the compound represented by the formula (18), 7.2 parts of a wet cake of the compound represented by the formula (23) obtained in the procedure (l) was used. Otherwise in the same manner as in the above-mentioned procedure (g) of “Synthesis of Compound A”, 6.3 parts of a compound represented by the following formula (24) was obtained as a sodium salt. The compound represented by the following formula (24) is obtained by replacing (A) a methoxy group with b and a sulfonic acid group with a, c or d, and (B) a methoxy group with c. It was a mixture composed of 2 to 6 kinds of compounds including a compound in which a sulfonic acid group was substituted with a, b or d.

(N)
Procedure (h) of “Synthesis of Compound A” described above, except that the compound represented by formula (15) obtained in the procedure (m) was used instead of the compound represented by formula (10). In the same manner as in the above, Compound B was obtained. The obtained compound B is a mixture of a lithium salt and a sodium salt (80%: 20%) of the compound represented by the formula (24) as a free acid form. Further, the maximum absorption wavelength λmax of the absorption spectrum of the obtained compound B was 592 nm.

<Preparation of second coloring material>
As the second colorant, compounds C to F represented by the following formulas (25) to (28) were used as the free acid type. These compounds C to F are all black dyes. The pH of these compounds C to F was adjusted using an aqueous sodium hydroxide solution, and the acidic group was used as a sodium salt form for ink preparation. All of these compounds C to F are described in JP-A-2009-030023.

<Preparation of ink>
Each component (unit:%) shown in Tables 5-1 and 5-2 was mixed and sufficiently stirred, and then each ink was prepared by pressure filtration with a filter having a pore size of 0.20 μm. In addition, "acetylenol E100" in Tables 5-1 and 5-2 is a trade name of a nonionic surfactant (manufactured by Kawaken Fine Chemicals).

<Evaluation>
Each ink obtained above was filled in an ink cartridge and mounted on an ink jet recording apparatus (trade name “PIXUS iP8600”, manufactured by Canon Inc.) that discharges ink from the recording head by the action of thermal energy. In this embodiment, a solid image recorded by applying 22 ng of ink to a unit area of 1/600 inch × 1/600 inch is defined as “recording duty is 100%”.

A solid image with an ink recording duty of 100% was recorded on a recording medium (trade name “Canon Photo Paper / Glossy Professional PR-201L; manufactured by Canon) for 1,000 sheets with borderless recording. In the case of evaluation, the recording duty of the first ink was 50%, the recording duty of the second ink was 50%, and the total recording duty was 100%. The members were visually checked, and the suppression of deposition in the borderless recording was evaluated according to the following evaluation criteria: In the present invention, the following evaluation criteria allowed C to be unacceptable, and levels A and B allowed. The ink evaluation results are shown in Table 6. The ink set evaluation results are shown in Table 7.
A: There was no accumulation on the ink absorbing member, and the ink penetrated into the ink absorbing member.
B: Although there was no accumulation on the ink absorbing member, ink was accumulated on the surface of the ink absorbing member.
C: There was deposition on the ink absorbing member.

Claims (10)

A color material set for inkjet having a combination of a first color material and a second color material,
The first colorant is a compound represented by the following general formula (I):
The color material set, wherein the second color material is at least one of a compound represented by the following general formula (II) and a compound represented by the following general formula (III).

(In the general formula (I), R ₁ represents an alkyl group having 1 to 4 carbon atoms; an alkyl group having 1 to 4 carbon atoms substituted with a carboxy group; a phenyl group; a phenyl group substituted with a sulfonic acid group; Or a carboxy group, R ₂ represents a cyano group; a carbamoyl group; or a carboxy group, and R ₃ and R ₄ each independently represent a hydrogen atom; an alkyl group having 1 to 4 carbon atoms; a halogen atom; Represents an alkoxy group having 1 to 4; or a sulfonic acid group, and R ₅ and R ₇ are each independently selected from the group consisting of an alkylthio group having 1 to 4 carbon atoms; or a hydroxy group, a sulfonic acid group, and a carboxy group. R ₆ and R ₈ each independently represents a C 1 to C 4 alkylcarbonylamino group substituted with at least one kind of group, R ₉ and R ₁₀ each independently represent a hydrogen atom; a carboxyl group; a sulfonic group; an acetylamino group; a halogen atom; an alkoxy group having 1 to 4 carbon atoms; an alkyl group having 1 to 4 carbon atoms or hydroxy groups, 1 to carbon atoms 4 represents an alkoxy group having 1 to 4 carbon atoms substituted with at least one group selected from the group consisting of 4 alkoxy groups, sulfonic acid groups and carboxy groups, wherein R ₁₁ , R ₁₂ and R ₁₃ are each independently Carboxy group; sulfonic acid group; hydroxy group; acetylamino group; halogen atom; cyano group; nitro group; sulfamoyl group; alkyl group having 1 to 4 carbon atoms; alkoxy group having 1 to 4 carbon atoms; The number of carbon atoms substituted by at least one group selected from the group consisting of a group, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, and a carboxy group An alkoxysulfonyl group having 1 to 4 carbon atoms; an alkylsulfonyl group having 1 to 4 carbon atoms; or an alkylsulfonyl group having 1 to 4 carbon atoms substituted with at least one group selected from the group consisting of a hydroxy group, a sulfonic acid group, and a carboxy group Represents a group)

(In the general formula (II), R ₁₄ represents a phenyl group having a substituent, and the substituent is a carboxy group; a sulfonic acid group; a chlorine atom; a cyano group; a nitro group; a sulfamoyl group; An alkyl group having 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms which may be substituted with a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, or a carboxy group; and a hydroxy group, sulfonic acid group, or carboxy And at least one group selected from the group consisting of alkylsulfonyl groups having 1 to 4 carbon atoms which may be substituted with a group R ₁₅ and R ₁₆ are each independently a paraphenylene group having a substituent. And the substituent is a carboxy group; a sulfonic acid group; an alkyl group having 1 to 4 carbon atoms; a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, or a carboxyl group; Selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms which may be substituted with a boxy group; and an alkylsulfonyl group having 1 to 4 carbon atoms which may be substituted with a hydroxy group, a sulfonic acid group or a carboxy group R ₁₇ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a carboxy group, a phenyl group which may be substituted with a sulfonic acid group, or a carboxy group. , R ₁₈ represents a cyano group, a carbamoyl group, or a carboxy group, and R ₁₉ and R ₂₀ each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a sulfonic acid group)

(In the general formula (III), R ₂₁ represents an optionally substituted aromatic group or heterocyclic group, and —R ₂₂ — represents any one of the following general formulas (i) to (v): And M represents each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium)

(In the general formulas (i) to (v), R _{23 to} R ₃₁ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a carboxy group, a carbamoyl group, or an alkoxycarbonyl group. Group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, cyano group, nitro group, Alkylthio group, aryl Represents a thio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfonic acid group, and these groups are further substituted May be) In the general formula (I), R ₁ is a methyl group, R ₂ is a cyano group or a carbamoyl group, R ₃ is a hydrogen atom, a methyl group, or a methoxy group, R ₄ is a sulfonic acid group, R ₅ and R ₇ are Each independently a sulfoalkylthio group having 1 to 4 carbon atoms, R ₆ and R ₈ are each independently an alkylcarbonylamino group having 1 to 4 carbon atoms, R ₉ is a sulfoalkoxy group having 1 to 4 carbon atoms, R ₁₀ is an alkyl group having 1 to 4 carbon atoms or an acetylamino group, R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, carboxy group, sulfonic acid group, halogen atom, nitro group, methyl group, methoxy group Or a colorant set according to claim 1, which is a sulfamoyl group. In the general formula (I), R ₁ is a methyl group, R ₂ is a cyano group, R ₃ is a hydrogen atom or a methoxy group, R ₄ is a sulfonic acid group, and R ₅ and R ₇ are each independently a carbon number of 1 1 to 4 sulfoalkylthio groups, R ₆ and R ₈ are acetylamino groups, R ₉ is a sulfopropoxy group or sulfobutoxy group, R ₁₀ is an alkyl group having 1 to 4 carbon atoms, R ₁₁ is a hydrogen atom or a sulfonic acid group, The color material set according to claim 1, wherein R ₁₂ is a sulfonic acid group or a halogen atom, and R ₁₃ is a hydrogen atom or a sulfonic acid group. In the general formula (II), R ₁₄ is a phenyl group having a sulfonic acid group or a carboxy group, and R ₁₅ and R ₁₆ are each independently a group represented by the following general formula (vi): The color material set according to any one of 1 to 3.

(In the general formula (vi), R ₃₂ represents a sulfonic acid group or a sulfopropoxy group, and R ₃₃ represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group) An ink jet ink containing a plurality of kinds of coloring materials,
5. The ink according to claim 1, wherein the plurality of kinds of color materials include the first color material and the second color material constituting the color material set according to claim 1. An ink set for inkjet having a combination of a first ink and a second ink,
The first ink contains the first color material constituting the color material set according to any one of claims 1 to 4,
An ink set comprising the second color material constituting the color material set according to any one of claims 1 to 4. An ink cartridge comprising ink and an ink containing portion for containing the ink,
An ink cartridge according to claim 5, wherein the ink is an ink according to claim 5. An ink cartridge comprising ink and an ink containing portion for containing the ink,
An ink cartridge, wherein the ink is the first ink or the second ink constituting the ink set according to claim 6. An inkjet recording method for recording on a recording medium by discharging ink by an inkjet method,
An ink jet recording method, wherein the ink is the ink according to claim 5. An inkjet recording method for recording on a recording medium by discharging ink by an inkjet method,
An ink jet recording method, wherein the ink is the first ink or the second ink constituting the ink set according to claim 6.

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