JP4390290B2 - Ink, ink jet recording method, ink cartridge, recording unit, and ink jet recording apparatus - Google Patents

Description

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

  The ink jet recording method is a recording method in which an ink droplet is applied to a recording medium such as plain paper or glossy media to form an image, and is rapidly spreading due to its low cost and high recording speed. In addition, the ink jet recording method has become widespread as an image output method comparable to a silver salt photograph with the rapid spread of digital cameras, in addition to the progress of image quality improvement of images obtained by this method. ing.

  In recent years, with the widespread use of inkjet recording devices, recorded matter having an image quality comparable to silver salt photography, particularly a recorded matter having a graininess reduced and excellent gradation, and an even better image quality than before. Is required to be output.

  In order to solve such a problem, a gray ink having a neutral color tone is used in addition to the conventional cyan, magenta, and yellow inks. By using gray ink in addition to conventional ink, for example, graininess in dark areas such as skin color and background, and gradation when connecting gradation from light to dark areas are improved, resulting in higher image quality. It is known that a recorded material can be obtained. The meaning of the ink having a neutral color tone will be described later.

  In general, the gray ink can be produced by toning using cyan, magenta, and yellow color materials. Then, it has been proposed to improve the image quality using a gray ink produced by using such a color material together. For example, it has been proposed that light gray ink, medium gray ink, and dark gray ink are prepared as the toned gray ink, and gradation recording is performed by a combination thereof (see Patent Document 1). Furthermore, Patent Document 1 discloses that a black color material and an appropriate color material are mixed to obtain a gray ink.

  On the other hand, the above-described gray ink using a combination of cyan, magenta, and yellow has a problem that the image storage stability of the obtained recorded matter is lower than that of a silver salt photograph. Specifically, when a recorded material formed using gray ink is exposed to light, humidity, heat, environmental gases present in the air for a long time, the color material on the recorded material deteriorates, and the image It is a problem that color tone changes and fading easily occur. Among these image storability, many proposals have hitherto been made in order to improve especially the ozone resistance and light resistance of images.

Further, the fading of the image is caused mainly by cyan ink having low ozone resistance among cyan, yellow, and magenta inks. For this reason, there are many proposals for improving the ozone resistance of cyan ink (see Patent Documents 2 to 8). There is also a proposal for improving the ozone resistance of an image by introducing a nitrogen-containing heteroaromatic ring into the skeleton of a phthalocyanine-based color material that is widely used as a color material for cyan ink (see Patent Document 9). This phthalocyanine color material may have (SO ₃ D) _m or (SO ₂ NHR) _n (m = 1 to 4, n = 0 to 3) as a substituent, and the SO ₂ NHR is SO ₂ It is described that it is a sulfonamide residue capable of forming a complex with NH ₂ or copper ion. The D is a monovalent alkali metal, ammonium, or organic ammonium.

The Patent Document _9, as the SO 2 NHR, are described as SO ₂ NH ₂ are preferred. However, three of the five examples in Patent Document 9 do not have SO ₂ NHR, that is, n = 0. As a result of fading test by ozone gas in the case of SO ₂ NH ₂ and sulfonamide residues as SO ₂ NHR was used phthalocyanine colorant was replaced are respectively described. However, despite The SO ₂ NHR it is described as preferably SO ₂ NH ₂ in Patent Document 9 as described above, the result of fading test in the case of using these phthalocyanine type coloring material is n = 0 It is disclosed as inferior.

  The performance required for ozone resistance of recorded matter obtained by the ink jet recording method has been increasing year by year, and color materials conventionally used for cyan ink have ozone resistance at a level that satisfies the above requirements. It has not yet reached the image which has. For example, in the inventions described in Patent Documents 2 to 9, attempts are made to improve the ozone resistance of an image by introducing various substituents into the color material. However, there is a limit to improving the ozone resistance of the image.

JP 2006-526062 A Japanese Patent Laid-Open No. 2002-249677 JP 2002-275386 A JP 2002-294097 A JP 2002-302623 A JP 2002-327132 A JP 2003-3099 A JP 2003-213168 A JP 2003-34758 A

  As described above, there has never been a gray ink that has the performance required as a gray ink and that provides an image having a high level of ozone resistance and light resistance. Accordingly, the first object of the present invention is to provide a gray ink that has the performance required as a gray ink and gives an image having a high level of ozone resistance and light resistance.

  In addition, a recorded matter formed using a gray ink produced by combining the above-described cyan, magenta, and yellow color materials has a problem that a color difference is increased by a light source (reflected light), that is, metamerism is inferior. is doing. Metamerism (conditional color) refers to a phenomenon in which colors having different spectral distributions appear to be the same color under certain observation conditions. However, in the present invention, metamerism refers to the same recorded matter as a light source (transmitted light). It refers to a phenomenon in which the color looks different depending on the reflected light). And when metamerism is inferior in a recorded matter, there is a problem that the same recorded matter appears to change color, for example, under sunlight or under a fluorescent lamp. Therefore, the second problem of the present invention is to provide a gray ink that can eliminate or reduce the problem of metamerism in reflected light.

  In response to the above problems, the inventors of the present invention can obtain a gray ink prepared by using various cyan dyes, magenta dyes, yellow dyes, and the like that are considered to be excellent in ozone resistance and light resistance of an image. The image was examined. As a result, the following was found. In general, phthalocyanine dyes widely used as cyan dyes applied to ink-jet inks tend to be present in the vicinity of the surface of the recording medium when the ink is applied to the recording medium. For this reason, it has been found that phthalocyanine dyes are susceptible to attack by oxidizing gases such as ozone gas in the air, and tend to be more deteriorated than dyes of other colors. Based on this finding, the present inventors have further studied and found the following. Specifically, it was found that when an image obtained with a gray ink toned with a cyan dye, a magenta dye, a yellow dye, or the like is exposed to ozone gas, the cyan component is significantly deteriorated as compared with other components.

  Therefore, the present inventors have used dyes such as cyan, magenta, and yellow as main elements that suppress deterioration of the cyan component and enable achievement of a high level of ozone resistance when used in image formation. Explored. As a result, it was found that the combined use of a specific cyan dye and a specific yellow dye markedly changed the behavior of the cyan dye in the recording medium as compared with the conventional cyan dye. Furthermore, it has been found that the combined use of such specific dyes can suppress the deterioration of the cyan component, thereby achieving a high level of ozone resistance of the image. Therefore, the third object of the present invention is to analyze a behavior of a cyan dye in a recording medium, and to obtain a specific cyan dye and a specific yellow dye, which provide an image capable of achieving a high level of ozone resistance. The object is to provide a combined ink.

  The present inventors further found that a gray ink having excellent ozone resistance and color tone can be obtained by using a specific magenta dye in addition to the specific cyan dye and yellow dye. . In addition to the above-described dye, a specific dye is used in combination to give an image having excellent ozone resistance and light resistance, giving an image having a preferable color tone as a gray ink, and obtaining a gray ink excellent in image metamerism. I found out.

  As can be understood from the above problem recognition, the object of the present invention is to provide each invention that solves each of the above problems. Specifically, an object of the present invention is to provide an ink excellent in ozone resistance and giving an image having a neutral gray color tone. Another object of the present invention is to provide an ink that gives an image excellent in light resistance. Another object of the present invention is to provide an ink that gives an image excellent in metamerism. Furthermore, 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.

（一般式（Ｉ）中、Ａ、Ｂ、Ｃ、及びＤはそれぞれ独立に、芳香性を有する６員環であり、かつ、Ａ、Ｂ、Ｃ、及びＤの少なくとも１つが含窒素複素芳香環であり、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であり、Ｅはアルキレン基である。また、Ｘは、スルホ置換アニリノ基、カルボキシル置換アニリノ基、又はホスホノ置換アニリノ基であり、該置換アニリノ基はさらに、スルホン酸基、カルボキシル基、ホスホノ基、スルファモイル基、カルバモイル基、水酸基、アルコキシ基、アミノ基、アルキルアミノ基、ジアルキルアミノ基、アリールアミノ基、ジアリールアミノ基、アセチルアミノ基、ウレイド基、アルキル基、ニトロ基、シアノ基、ハロゲン、アルキルスルホニル基、及びアルキルチオ基からなる群から選ばれる少なくとも１つの置換基を１乃至４個有してもよい。また、Ｙは水酸基又はアミノ基であり、ｌ（エル）、ｍ、及びｎは、０≦ｌ（エル）≦２、０≦ｍ≦３、０．１≦ｎ≦３であり、かつｌ（エル）＋ｍ＋ｎ＝１乃至４である。）

（一般式（II）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り、Ｚ₁及びＺ₂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（III）中、Ｒはそれぞれ独立に、水素原子、アルキル基、ヒドロキシアルキル基、シクロヘキシル基、又はモノ若しくはジアルキルアミノアルキル基であり、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であり、Ｘは連結基である。）

（一般式（IV）中、Ｒ ₁ は水素原子又はアルキル基であり、ｍは１乃至３の整数であり、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である。）

（一般式（Ｖ）中、Ｒ ₂ 、Ｒ ₃ 、Ｒ ₄ 、及びＲ ₅ はそれぞれ独立にアルキル基であり、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である。） The means for solving the above problems correspond to each purpose. That is, the ink according to the present invention is an ink containing at least three color materials of the first color material , the second color material, and the third color material, and the first color material . There is a compound represented by the following formula (I), the second color material, Ri compound der represented by the following formula (II), said third coloring material is a compound represented by the following general formula compounds represented by (III), wherein at least one compound der Rukoto selected from the group consisting of compounds represented by compounds represented by the following general formula (IV), and formula (V) And

(In the general formula (I), A, B, C and D are each independently a 6-membered aromatic ring, and at least one of A, B, C and D is a nitrogen-containing heteroaromatic ring. in it, M are each independently a hydrogen atom, an alkali metal, ammonium or organic ammonium,, E is an alkylene group. in addition, X is a sulfo-substituted anilino group, carboxyl-substituted anilino group, or a phosphono-substituted anilino group The substituted anilino group is further sulfonic acid group, carboxyl group, phosphono group, sulfamoyl group, carbamoyl group, hydroxyl group, alkoxy group, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, Acetylamino, ureido, alkyl, nitro, cyano, halogen, alkylsulfonyl, and alkyl It may have 1 to 4 substituents selected from the group consisting of a kirthio group, Y is a hydroxyl group or an amino group, and l (el), m, and n are 0 ≦ l ( L) ≦ 2, 0 ≦ m ≦ 3, 0.1 ≦ n ≦ 3, and l (L) + m + n = 1 to 4.

(In general formula (II), R ₁ , R ₂ , Y ₁ and Y ₂ are each independently a monovalent group, and X ₁ and X ₂ are each independently having a Hammett's σp value of 0.20 or more. 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, a substituted or unsubstituted group An aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and M is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

(In the general formula (III), each R is independently a hydrogen atom, an alkyl group, a hydroxyalkyl group, a cyclohexyl group, or a mono- or dialkylaminoalkyl group, and each M is independently a hydrogen atom, an alkali metal, or ammonium. Or an organic ammonium, and X is a linking group.)

(In General Formula (IV), R ₁ is a hydrogen atom or an alkyl group, m is an integer of 1 to 3, and M is each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

(In General Formula (V), R ₂ , R ₃ , R ₄ , and R ₅ are each independently an alkyl group, and M is each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

（一般式（VI）中、Ｒ₁₀はそれぞれ独立に、水素原子、ヒドロキシル基、カルボキシル基、ヒドロキシル基若しくは炭素数１乃至４のアルコキシ基によって置換されていてもよい炭素数１乃至４のアルキル基、ヒドロキシル基若しくは炭素数１乃至４のアルコキシ基によって置換されていてもよい炭素数１乃至４のアルコキシル基、ヒドロキシル基若しくは炭素数１乃至４のアルコキシ基によって置換されていてもよい炭素数１乃至４のアルキルアミノ基、カルボキシル−炭素数１乃至５のアルキルアミノ基、ビス−〔カルボキシ−炭素数１乃至５のアルキル〕アミノ基、ヒドロキシル基若しくは炭素数１乃至４のアルコキシ基によって置換されていてもよい炭素数１乃至４のアルカノイルアミノ基、カルボキシル基若しくはスルホン酸基若しくはアミノ基で置換されていてもよいフェニルアミノ基、スルホン酸基、ハロゲン原子、又はウレイド基であり、〔Ｃ〕はカルボキシル基又はスルホン酸基を有する脂肪族アミン残基であり、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である。）

（一般式（VII）中、Ａは置換されていてもよい芳香族基又は複素環基であり、Ｂは下記一般式（１）乃至（５）で表されるいずれかの基であり、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である。）

（一般式（１）乃至（５）中、Ｒ₁乃至Ｒ₉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、カルボキシル基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環オキシカルボニル基、アシル基、ヒドロキシル基、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、アルキル若しくは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、アルキル若しくはアリールチオ基、複素環チオ基、アルキル若しくはアリールスルホニル基、複素環スルホニル基、アルキル若しくは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、又はスルホン酸基であり、各基はさらに置換されていてもよい。） The ink according to another aspect of the present invention may further include at least one compound selected from a compound represented by the following general formula (VI) and a compound represented by the following general formula (VII) as the fourth colorant: It is characterized by containing.

(In General Formula (VI), each R ₁₀ independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms which may be substituted by an alkoxy group having 1 to 4 carbon atoms. 1 to 4 carbon atoms which may be substituted by a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, 1 to 4 carbon atoms which may be substituted by a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms Substituted by 4 alkylamino groups, carboxyl-alkylamino groups having 1 to 5 carbon atoms, bis- [carboxy-alkyl having 1 to 5 carbon atoms] amino groups, hydroxyl groups or alkoxy groups having 1 to 4 carbon atoms. C1-C4 alkanoylamino group, carboxyl group or sulfonic acid group Or a phenylamino group optionally substituted with an amino group, a sulfonic acid group, a halogen atom, or a ureido group, [C] is an aliphatic amine residue having a carboxyl group or a sulfonic acid group, and M is Each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

(In General Formula (VII), A is an optionally substituted aromatic group or heterocyclic group, B is any group represented by the following General Formulas (1) to (5), M Are each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

(In the general formulas (1) to (5), R _{1 to} R ₉ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxyl 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, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, cyano group, nitro group, alkyl or arylthio group, Heterocycle A thio group, an alkyl or arylsulfonyl group, a heterocyclic sulfonyl group, an alkyl or arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfonic acid group, and each group may be further substituted.

  Another embodiment of the present invention is an ink jet recording method, an ink cartridge, a recording unit, and an ink jet recording apparatus characterized by using the ink described above.

  According to the present invention that solves the first problem, it is possible to provide an ink that has the performance required as a gray ink and that provides an image having a high level of ozone resistance and light resistance. Moreover, according to the present invention that solves the second problem, it is possible to provide an ink that can eliminate or reduce the problem of metamerism in reflected light. Furthermore, according to the present invention that solves the third problem, an ink that uses a specific cyan dye and a specific yellow dye in combination is excellent while suppressing association and aggregation of a cyan dye, particularly a phthalocyanine dye. An ink capable of forming an image can be provided.

  In particular, according to the best mode of the present invention, there is provided an ink that is excellent in ozone resistance and light resistance, can give an image having a neutral gray color tone, and can give an image excellent in metamerism. Is done. According to another embodiment of the present invention, there are provided an ink jet recording method, an ink cartridge, a recording unit, and an ink jet recording apparatus capable of providing the above-described excellent image.

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. In the following description, the “compounds represented by general formulas (I) to (VII)” may be abbreviated as “compounds of general formulas (I) to (VII)”, respectively. Further, values such as the number of substituents of each compound in the ink have a meaning as an average value unless otherwise specified. Further, in the above description, each form corresponding to each problem of the present invention is described separately, but in the following description, it may be simply referred to as “ink according to the present invention”. In the following description, the above compounds and color materials may be simply referred to as “first color material” and “second color material”. Color materials and compounds not included in the present invention are simply referred to as “general”. Sometimes called "special" dyes, colorants, and compounds.

<Ink>
The components constituting the ink according to the present invention and the physical properties of the ink will be described in detail below.
(Color material)
The main feature of the present invention is that by combining a compound represented by the following general formula (I) as the first colorant and a compound represented by the following general formula (II) as the second colorant, an ink colorant is obtained. It is that excellent ozone resistance is achieved in the formed image.

（一般式（Ｉ）中、Ａ、Ｂ、Ｃ、及びＤはそれぞれ独立に、芳香性を有する６員環であり、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であり、Ｅはアルキレン基である。また、Ｘは、スルホ置換アニリノ基、カルボキシル置換アニリノ基、又はホスホノ置換アニリノ基である。該置換アニリノ基は、さらに、スルホン酸基、カルボキシル基、ホスホノ基、スルファモイル基、カルバモイル基、水酸基、アルコキシ基、アミノ基、アルキルアミノ基、ジアルキルアミノ基、アリールアミノ基、ジアリールアミノ基、アセチルアミノ基。ウレイド基、アルキル基、ニトロ基、シアノ基、ハロゲン、アルキルスルホニル基、及びアルキルチオ基からなる群から選ばれる少なくとも１つの置換基を１乃至４個有してもよい。また、Ｙは水酸基又はアミノ基であり、ｌ（エル）、ｍ、及びｎは、０≦ｌ（エル）≦２、０≦ｍ≦３、０．１≦ｎ≦３であり、かつ、ｌ（エル）＋ｍ＋ｎ＝１乃至４である。） [First coloring material: compound represented by formula (I)]
The ink of the present invention needs to contain a compound of the following general formula (I) as the first color material (dye).

(In General Formula (I), A, B, C, and D are each independently a six-membered aromatic ring, and M is each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium. , E is an alkylene group, and X is a sulfo-substituted anilino group, a carboxyl-substituted anilino group, or a phosphono-substituted anilino group, which further includes a sulfonic acid group, a carboxyl group, a phosphono group, and a sulfamoyl group. Group, carbamoyl group, hydroxyl group, alkoxy group, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acetylamino group, ureido group, alkyl group, nitro group, cyano group, halogen, alkylsulfonyl group , And at least one substituent selected from the group consisting of alkylthio groups. Y is a hydroxyl group or an amino group, and l (el), m, and n are 0 ≦ l (el) ≦ 2, 0 ≦ m ≦ 3, and 0.1 ≦ n ≦ 3. And l (el) + m + n = 1 to 4.)

  A, B, C, and D in the general formula (I) are each independently a 6-membered ring having aromaticity. Examples of the aromatic six-membered ring include a benzene ring and a nitrogen-containing heteroaromatic ring. The nitrogen-containing heteroaromatic ring includes a pyridine ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring, preferably a pyridine ring or a pyrazine ring, and more preferably a pyridine ring. Specific examples of the general formula (I) that can be suitably used in the present invention include the following. Compounds in which A, B, C and D are all benzene rings or all nitrogen-containing heteroaromatic rings, or 1 to 3 of A, B, C and D are nitrogen-containing heteroaromatic rings, and the rest are benzene rings The compound which is is mentioned. According to the study by the present inventors, the compound of the general formula (I) improves the ozone resistance of the recorded material when the number of nitrogen-containing heteroaromatic rings in the structure increases, but conversely, the bronze resistance (Suppression of occurrence of bronze phenomenon) tends to decrease. For this reason, it is preferable to adjust the number of nitrogen-containing heteroaromatic rings in consideration of the balance between ozone resistance and bronze resistance.

  E in the general formula (I) is an alkylene group, and the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms. Specifically, ethylene group, propylene group, butylene group, pentylene group, hexylene group, cyclopropylenediyl group, 1,2- or 1,3-cyclopentylenediyl group, 1,2-, 1,3-, Or a cyclohexylene group, such as 1, 4-, etc. are mentioned. Among these, an ethylene group, a propylene group, and a butylene group are preferable.

  X in the general formula (I) is a sulfo-substituted anilino group, a carboxyl-substituted anilino group, or a phosphono-substituted anilino group. The substituted anilino group may further have 1 to 4, preferably 1 to 2, at least one substituent selected from the following substituent group. Substituent group: sulfonic acid group, carboxyl group, phosphono group, sulfamoyl group, carbamoyl group, hydroxyl group, alkoxy group. Amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acetylamino group, ureido group, alkyl group, nitro group, cyano group, halogen, alkylsulfonyl group, and alkylthio group. Specific examples of X in the general formula (I) include the following. 2,5-disulfoanilino group, 2-sulfoanilino group, 3-sulfoanilino group, 4-sulfoanilino group, 2-carboxyanilino group, 2-methoxy-5-sulfoanilino group, 4-ethoxy-2-sulfoanilino group, 2-methyl -5-sulfoanilino group. 2-nitro-4-sulfoanilino group, 2-methoxy-4-nitro-5-sulfoanilino group, 2-chloro-5-sulfoanilino group, 2-carboxy-4-sulfoanilino group, 3-carboxy-4-hydroxyanilino group . 3-carboxy-4-hydroxy-5-sulfoanilino group, 2-hydroxy-5-nitro-3-sulfoanilino group, 4-acetylamino-2-sulfoanilino group, 4-anilino-3-sulfoanilino group, 3,5-di Carboxyanilino group. 2-carboxy-4-sulfamoylanilino group, 2,5-dichloro-4-sulfoanilino group, 3-phosphonoanilino group and the like.

  Y in general formula (I) is a hydroxyl group or an amino group.

  M in general formula (I) is a hydrogen atom, an alkali metal, ammonium, or organic ammonium each independently. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the organic ammonium include acetamide, benzamide, methylamino, butylamino, diethylamino, and phenylamino.

  The sulfonic acid group, carboxyl group, phosphono group, etc. mentioned in the description of X in the compound of the general formula (I) may be in the form of a salt. Examples of counter ions that form salts include ions of alkali metals, ammonium, and organic ammonium. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the organic ammonium include the following. Alkylamines having 1 to 3 carbon atoms such as methylamine and ethylamine; Examples include onium salts of mono-, di-, or tri- (C1-C4 alkanol) amines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine. The counter ion may be an alkaline earth metal such as calcium and magnesium.

（一般式（Ａ）中、Ａ、Ｂ、Ｃ、及びＤはそれぞれ独立に芳香性を有する６員環である。） The compound of general formula (I) can be synthesized as follows.
First, a compound of the following general formula (A) (copper porphyrazine compound) is synthesized.

(In General Formula (A), A, B, C, and D are each independently a 6-membered aromatic ring.)

  The compound of the general formula (A) is obtained, for example, by reacting an aromatic nitrogen-containing heteroaromatic dicarboxylic acid derivative with a phthalic acid derivative in the presence of a catalyst and a copper compound. The number of nitrogen-containing heteroaromatic rings and the number of benzene rings of A, B, C, and D are adjusted by changing the molar ratio of the reaction between the aromatic nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative. be able to.

  Examples of the nitrogen-containing heteroaromatic dicarboxylic acid derivative having aromaticity used in this case include the following. Dicarboxylic acid compounds such as quinolinic acid, 3,4-pyridinedicarboxylic acid, and 2,3-pyrazinedicarboxylic acid, or acid anhydrides thereof. Dicarboxyamide compounds such as pyridine-2,3-dicarboxamide. Dicarboxylic acid monoamide compounds such as pyrazine-2,3-dicarboxylic acid monoamide. Acid imide compounds such as quinolinic acid imide. Dicarbonitrile compounds such as pyridine-2,3-dicarbonitrile and pyrazine-2,3-dicarbonitrile. Examples of the phthalic acid derivative include phthalic acid, phthalic anhydride, phthalamide, phthalamic acid, phthalimide, phthalonitrile, 1,3-diiminoisoindoline, and 2-cyanobenzamide.

  General methods for synthesizing copper compounds include a nitrile method and a Weiler method, each having different reaction conditions. The nitrile method is a method of synthesizing a copper compound using a dicarbonitrile compound such as 2,3-pyridinedicarbonitrile, 2,3-pyrazinedicarbonitrile, or phthalonitrile as a raw material. The Weiler method is a method of synthesizing a copper compound using the following compounds as raw materials. Examples of compounds that can be used as the raw material for the Weiler method include the following. Dicarboxylic acid compounds such as phthalic acid, quinolinic acid, 3,4-pyridinedicarboxylic acid, 2,3-pyrazinedicarboxylic acid, or acid anhydrides thereof. Dicarboxyamide compounds such as phthalamide and 2,3-pyridinedicarboxamide. Dicarboxylic acid monoamide compounds such as phthalamic acid and 2,3-pyrazinedicarboxylic acid monoamide. Acid imide compounds such as phthalimide and quinolinic acid imide. In addition, when synthesizing a copper compound by the Weiler method, urea is necessary, and the amount of urea used is a total of 1 mol of a nitrogen-containing heteroaromatic dicarboxylic acid derivative having aromaticity and a phthalic acid derivative. It is preferably 5 to 100 mole times.

  Usually, the synthesis reaction of a copper compound is performed in the presence of an organic solvent. In the nitrile method, an organic solvent having a boiling point of 100 ° C. or higher, preferably 130 ° C. or higher is used. Examples of the organic solvent that can be used in the nitrile method include the following. Alcohols such as n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 1-octanol, 2-ethylhexanol, N, N-dimethylaminoethanol and benzyl alcohol. Glycols such as ethylene glycol and propylene glycol. Trichlorobenzene, chloronaphthalene, nitrobenzene, quinoline sulfolane, urea, etc. In the Weiler method, an aprotic organic solvent having a boiling point of 150 ° C. or higher, preferably 180 ° C. or higher is used. Examples of the organic solvent that can be used in the Weiler method include trichlorobenzene, chloronaphthalene, nitrobenzene, quinoline, sulfolane, and urea. The amount of the organic solvent used is preferably 1 to 100 times the mass of the total mass of the aromatic nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative.

  Moreover, as a catalyst which can be used by a nitrile method, the following are mentioned, for example. Quinolin, 1,8-diazabicyclo [5,4,0] -7-undecene, tributylamine, ammonia, amines such as N, N-dimethylaminoethanol, alkali metal alcoholates such as sodium ethoxide and sodium methoxide. Examples of the catalyst that can be used in the Weiler method include ammonium molybdate and boric acid. The amount of these catalysts used is preferably 0.001 to 1 mole times the total of 1 mole of the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative.

  Examples of the copper compound used in the above synthesis include metal copper, copper halide, copper carboxylate, copper sulfate, copper nitrate, copper acetylacetonate, and a copper complex. Specific examples include copper chloride, copper bromide, copper acetate, copper acetylacetonate, and the like. The amount of the copper compound used is preferably 0.15 mol times to 0.35 mol times with respect to a total of 1 mol of the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative.

  The reaction temperature in the nitrile method is usually 100 ° C. to 200 ° C., more preferably 130 ° C. to 170 ° C. In addition, the reaction temperature in the Weiler method is usually 150 ° C. to 300 ° C., more preferably 170 ° C. to 220 ° C. In addition, although reaction time changes with reaction conditions, it is preferable that it is normally 1 to 40 hours. After completion of the reaction, the copper porphyrazine compound represented by the general formula (A) can be obtained by filtering, washing and drying.

  A compound (copper dibenzobis (2,3-pyrido) porphyrazine) in which two of A, B, C, and D in the general formula (A) are pyridine rings and the remaining two are benzene rings is used as an example. The method for synthesizing the compound of formula (I) will be described in more detail.

  First, quinolinic acid (0.5 mol), phthalic anhydride (0.5 mol), copper (II) chloride (0.25 mol), ammonium phosphomolybdate (0.004 mol), urea (6 mol) The reaction is carried out at 200 ° C. for 5 hours in sulfolane, which is an organic solvent. In this way, copper dibenzobis (2,3-pyrido) porphyrazine in which two of A, B, C, and D in the general formula (A) are pyridine rings and the remaining two are benzene rings is obtained. Note that quinolinic acid, phthalic anhydride, metal compounds, organic solvents, catalysts, and the like are not limited to these because the reactivity varies depending on the type and amount used.

  The main product obtained in the above synthesis flow is copper dibenzobis (2,3-pyrido) porphyrazine, which includes five types of isomers having different positions of the pyridine ring and the nitrogen atom of the pyridine ring (described below). Structural formulas 1A, 1B, 1C, 1D, and 1E). At the same time, copper tribenzo (2,3-pyrido) porphyrazine and copper benzotris (2,3-pyrido) porphyrazine are produced as by-products. The copper tribenzo (2,3-pyrido) porphyrazine is a compound in which one of A, B, C and D in the general formula (A) is a pyridine ring and the remaining three are benzene rings (the following structural formula 2 ). The copper benzotris (2,3-pyrido) porphyrazine is a compound in which three of A, B, C and D in the general formula (A) are pyridine rings and the remaining one is a benzene ring. These compounds also have pyridine ring positional isomers (the following structural formulas 3A, 3B, 3C, and 3D). In addition, copper tetrakis (2,3-pyrido) porphyrazine and copper phthalocyanine (copper tetrabenzoporphyrazine) are also produced in small amounts. That is, what is obtained by the above synthesis flow is a mixture of these compounds.

  Usually, it is very difficult to isolate only the target compound from these mixtures. For this reason, these mixtures are almost always used as “copper dibenzobis (2,3-pyrido) porphyrazine having two pyridine rings and two remaining benzene rings as an average value”.

（一般式（Ｂ）中、Ａ、Ｂ、Ｃ、及びＤはそれぞれ独立に、芳香性を有する６員環であり、ｘは１乃至４である。） Next, the compound of the following general formula (B) (copper chlorosulfonylporphyrazine compound) is synthesized.

(In General Formula (B), A, B, C, and D are each independently a 6-membered aromatic ring, and x is 1 to 4.)

  The compound of the general formula (B) can be obtained by chlorosulfonating the compound of the general formula (A) obtained as described above in chlorosulfonic acid. Alternatively, it can be obtained by sulfonating a compound of the general formula (A) in sulfuric acid or fuming sulfuric acid, and then derivatizing a sulfonic acid group to a chlorosulfonic acid group with a chlorinating agent. The chlorosulfonic acid group or sulfonic acid group thus obtained is introduced onto the benzene ring when A, B, C and D in the general formula (A) are benzene rings. , C, and D are not introduced when they are nitrogen-containing heteroaromatic rings. That is, among A, B, C, and D in the general formula (A), the chlorosulfonic acid group or the sulfonic acid group is introduced only into the benzene ring.

  The reaction for chlorosulfonating the compound of the general formula (A) generally uses chlorosulfonic acid as a solvent. The amount of chlorosulfonic acid used is preferably 3 to 20 times, more preferably 5 to 10 times the mass of the compound of general formula (A). In general, the reaction temperature is preferably 100 ° C. to 150 ° C., more preferably 120 ° C. to 150 ° C. The reaction time varies depending on the reaction temperature and other conditions, but is generally preferably 1 hour to 10 hours. In the compound of the general formula (B) obtained, the chlorosulfonic acid group and the sulfonic acid group are substituted, but the ratio of the chlorosulfonic acid group can be improved by adding a chlorinating agent to the reaction system. . Examples of the chlorinating agent include chlorosulfonic acid, thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, and phosphorus oxychloride. Of course, the present invention is not limited to these.

  In addition to the above, the compound represented by the general formula (B) can also be obtained by the following method. First, a sulfophthalic acid having a sulfonic acid group, or a sulfophthalic acid having a sulfonic acid group and quinolinic acid are condensed and ring-closed, whereby a compound of the following general formula (C) (a copper porphyrazine compound having a sulfonic acid group) is obtained. Synthesize. And the compound of general formula (B) can also be obtained by introduce | transducing the sulfonic acid group in the compound of general formula (C) obtained in this way into the chlorosulfonic acid group.

（一般式（Ｃ）中、Ａ、Ｂ、Ｃ、及びＤはそれぞれ独立に芳香性を有する６員環であり、ｐは１乃至４である。）

(In General Formula (C), A, B, C, and D are each independently a 6-membered aromatic ring, and p is 1 to 4.)

  Moreover, the sulfonic acid group in the compound of the general formula (C) can be converted into a chlorosulfonic acid group by reacting the compound of the general formula (C) with a chlorinating agent. Examples of the solvent used in the reaction for chlorination include sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, benzene, toluene, nitrobenzene, chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide and the like. Examples of the chlorinating agent include chlorosulfonic acid, thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, and phosphorus oxychloride. Of course, the present invention is not limited to these.

（一般式（Ｄ）中、Ｅはアルキレン基であり、Ｘはスルホ置換アニリノ基、カルボキシル置換アニリノ基、又はホスホノ置換アニリノ基であり、これらの置換アニリノ基は、さらに、下記の置換基群から選ばれる少なくとも１つの置換基を１乃至４個有してもよい。置換基群：スルホン酸基、カルボキシル基、ホスホノ基、スルファモイル基、カルバモイル基、水酸基、アルコキシ基。アミノ基、アルキルアミノ基、ジアルキルアミノ基、アリールアミノ基、ジアリールアミノ基、アセチルアミノ基、ウレイド基、アルキル基、ニトロ基、シアノ基、ハロゲン、アルキルスルホニル基、及びアルキルチオ基からなる。また、Ｙは水酸基又はアミノ基である。） Finally, the compound of the general formula (B) obtained as described above, the compound of the following general formula (D) (organic amine), and ammonia are reacted to obtain the target compound of the general formula (I). Is synthesized.

(In General Formula (D), E is an alkylene group, X is a sulfo-substituted anilino group, a carboxyl-substituted anilino group, or a phosphono-substituted anilino group, and these substituted anilino groups are further represented by the following substituent group: It may have 1 to 4 substituents selected from 1 to 4. Substituent groups: sulfonic acid group, carboxyl group, phosphono group, sulfamoyl group, carbamoyl group, hydroxyl group, alkoxy group, amino group, alkylamino group, It consists of a dialkylamino group, arylamino group, diarylamino group, acetylamino group, ureido group, alkyl group, nitro group, cyano group, halogen, alkylsulfonyl group, and alkylthio group, and Y is a hydroxyl group or an amino group. .)

  Specifically, the compound of the general formula (I) used in the present invention can be synthesized by the following procedure using each compound described above. That is, in water, the compound of the general formula (B) obtained above, the compound of the general formula (D) and the ammonia (aminating agent) are generally subjected to conditions of pH 8 to 10 and temperature 5 ° C. to 70 ° C. It can be obtained by reacting for 1 to 20 hours. Examples of ammonia used at this time include ammonium salts such as ammonium chloride and ammonium sulfate, urea, aqueous ammonia, and ammonia gas. And by using these, it can introduce into a reaction system. In addition, reaction of the compound of general formula (B), the compound of general formula (D), and an aminating agent is generally performed in water. Moreover, although the usage-amount of the compound of general formula (D) is preferable 1 mol times or more of theoretical values with respect to 1 mol of compounds of general formula (B), reaction of the compound of general formula (D) Depends on sex and reaction conditions.

  The compound of the general formula (D) used above can be synthesized as follows. First, 0.95 to 1.1 mol of a substituted aniline corresponding to X in the general formula (D) and 1 mol of 2,4,6-trichloro-S-triazine (cyanuric chloride) in water, The reaction is carried out for 2 hours to 12 hours under conditions of pH 3 to 7 and temperature 5 ° C to 40 ° C. Thereby, a primary condensate is obtained. In the case of obtaining the compound of the general formula (D) having a structure in which Y in the formula is an amino group, next, the primary condensate obtained above and 0.95 mol to 2.0 mol of ammonia are added at pH 4 to 10 The reaction is carried out at 5 to 80 ° C. for 0.5 to 12 hours. Moreover, when obtaining the compound of the said general formula (D) of the structure whose Y is a hydroxyl group in a formula next, hydroxide of alkali metals, such as sodium hydroxide, is added to the primary condensate obtained above. Then, the reaction is performed for 0.5 to 8 hours under conditions of pH 4 to 10 and temperature 5 to 80 ° C. By such a procedure, the compound of the general formula (D) can be obtained. For the pH adjustment during the condensation, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and the like can be used. The order of condensation can be appropriately determined according to the reactivity of each compound.

As described above, the compound of the general formula (I) used in the present invention is synthesized from the compound of the general formula (B) and the compound of the general formula (D) in the presence of ammonia. Therefore, theoretically, a part of the chlorosulfonyl group of the compound of the general formula (B) is hydrolyzed by water present in the reaction system, and a compound converted into sulfonic acid is generated as a by-product, It can be considered that it is mixed in the compound of the general formula (I). However, in mass spectrometry, it is difficult to distinguish an unsubstituted sulfamoyl group from a sulfonic acid group. Therefore, in the present invention, all chlorosulfonyl groups in the compound of the general formula (B) other than those reacted with the compound of the general formula (D) (organic amine) are all unsubstituted sulfamoyl groups (—SO ₂ —NH _2). ) Are described as converted.

When the compound of the general formula (I) is synthesized by the above method, the copper porphyrazine ring (Pz) is dimer (Pz-L-Pz) or trimer via the divalent linking group (L). Impurities forming (Pz-L-Pz-L-Pz) may be mixed in the reaction product as a by-product. Examples of the divalent linking group (L) in this case include —SO ₂ —, —SO ₂ —NH—SO ₂ —, and the like. In the case of a trimer, a by-product formed by combining these two Ls may be produced.

  The compound of the general formula (I) can be taken out from the reaction system as described above by filtration or the like after aciding out or salting out. The salting out can be performed in an acidic to alkaline manner, and is preferably performed in a pH range of 1 to 11. The salting out is preferably performed by heating to 40 ° C. to 80 ° C., more preferably 50 ° C. to 70 ° C., and then adding salt.

  The compound of the general formula (I) synthesized by the method as described above can be obtained in a free acid form or a salt form thereof. In order to convert the compound of the general formula (I) into the free acid form, for example, acid precipitation may be performed. Further, in order to make the compound of the general formula (I) into a salt form, salting out may be performed. When a desired salt cannot be obtained by salting out, for example, after making into a free acid form, a desired organic Or the normal salt exchange method which adds an inorganic base should just be utilized.

  Preferable specific examples of the compound of the general formula (I) include exemplified compounds I-1 to I-25 shown in Table 1 below. Table 1 shows portions A, B, C, D, E, X, and Y in the general formula (I). 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) and the definition thereof. When A, B, C, and D in the general formula (I) are pyridine rings, there are positional isomers of nitrogen atoms as described above. Therefore, when synthesizing a compound, these positional isomers are used. A mixture of It is difficult to isolate these isomers, and it is also difficult to analyze and identify these isomers. Therefore, the compound of general formula (I) is usually used as a mixture. However, even in a state containing isomers, the effects of the present invention can be obtained without any change, and therefore, isomers are described without distinction. In the present invention, among A, B, C, and D in formula (I), the number of pyridine rings is preferably 1 to 3, and more preferably 1 to 2. In this case, an image having better ozone resistance can be obtained, and the absorption wavelength becomes broad, so that the color difference due to the difference in the light source is reduced and the metamerism is improved. Specifically, among the following exemplified compounds, it is particularly preferable to use exemplified compounds I-1 to I-3, I-10 to I-12, I-21 to I-23, and I-25. In addition, exemplary compound I-25 is a compound in which M in general formula (I) is sodium.

（一般式（II）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。Ｚ₁及びＺ₂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る。Ｍ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。） [Second coloring material: compound represented by formula (II)]
The ink of the present invention needs to contain a compound represented by the following general formula (II) as the second color material (dye) together with the first color material described above.

(In general formula (II), R ₁ , R ₂ , Y ₁ and Y ₂ are each independently a monovalent group, and X ₁ and X ₂ are each independently having a Hammett's σp value of 0.20 or more. 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, a substituted or unsubstituted group An aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and M is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

R ₁ , R ₂ , Y ₁ and Y ₂ in the general formula (II) are each independently a monovalent group, and specifically can be 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 ring Oxy group and acyloxy group. Carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, 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. An alkylsulfonyl group, an arylsulfonyl group, an acyl group, an aryloxycarbonyl group, and an alkoxycarbonyl group; Examples thereof include 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 the above, the following substituents are particularly preferable. Hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amide group; Ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, 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, and a hydrogen atom, an alkyl group, an aryl group, a cyano group, and an alkyl group are more preferable. A sulfonyl group is particularly preferred.

Hereinafter, R ₁ , R ₂ , Y ₁ and Y ₂ in the general formula (II) 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, and 2-cyclohexen-1-yl.

  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. Examples of the heterocyclic group are pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, and benzofuran. Thiophene, benzothiophene. Pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole. Examples include 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-phenyltetrazol-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, p-methoxyphenylcarbonyloxy, and the like.

  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.

  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, pn-hexadecyloxyphenoxycarbonyloxy, and the like.

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

  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, and 3,4,5-tri-n-octyloxyphenylcarbonylamino.

  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, Nn-octylaminosulfonylamino and the like.

  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, p-methylphenylsulfonylamino and the like.

  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. Specifically, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl. N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl and the like can be mentioned.

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

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

  The acyl group is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms. Examples thereof include 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, and 2-furylcarbonyl.

  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, N- (methylsulfonyl) carbamoyl, and the like.

  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, and diethoxyphosphinyl.

  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, 2-hydroxy-4-propanoylphenylazo, and the like.

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

  These substituents may be further substituted. Examples of the substituent in this case include the following. 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. 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.

  Specific examples of the substituent include the following. Substituted or unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, and cyclopentyl. Halogen atoms such as chlorine atom and bromine atom. Aryl groups such as phenyl, 4-t-butylphenyl, and 2,4-di-t-amylphenyl; Heterocyclic groups such as imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, and 2-benzothiazolyl. Cyano group. Hydroxyl group. Nitro group. Carboxy group. Amino group. Alkyloxy groups such as methoxy, ethoxy, 2-methoxyethoxy, and 2-methylsulfonylethoxy; Aryloxy groups such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, and 3-methoxycarbonylphenyloxy; Acylamino groups such as acetamide, benzamide, and 4- (3-t-butyl-4-hydroxyphenoxy) butanamide. Alkylamino groups such as methylamino, butylamino, diethylamino, and methylbutylamino; Anilino groups such as phenylamino and 2-chloroanilino. Ureido groups such as phenylureido, methylureido, and N, N-dibutylureido. Sulfamoylamino groups such as N, N-dipropylsulfamoylamino. Alkylthio groups such as methylthio, octylthio, and 2-phenoxyethylthio; Arylthio groups such as phenylthio, 2-butoxy-5-t-octylphenylthio, and 2-carboxyphenylthio; Alkyloxycarbonylamino groups such as methoxycarbonylamino; Alkyl or arylsulfonylamino groups such as methylsulfonylamino, phenylsulfonylamino, and p-toluenesulfonylamino; Carbamoyl groups such as N-ethylcarbamoyl and N, N-dibutylcarbamoyl. Sulfamoyl groups such as N-ethylsulfamoyl, N, N-dipropylsulfamoyl, and N-phenylsulfamoyl. Sulfonyl groups such as methylsulfonyl, octylsulfonyl, phenylsulfonyl, and p-toluenesulfonyl. Alkyloxycarbonyl groups such as methoxycarbonyl and butyloxycarbonyl; Heterocyclic oxy groups such as 1-phenyltetrazol-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; Imido groups such as N-succinimide and N-phthalimide. Heterocyclic thio groups such as 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, and 2-pyridylthio. Sulfinyl groups such as 3-phenoxypropylsulfinyl. Phosphonyl groups such as phenoxyphosphonyl, octyloxyphosphonyl, and phenylphosphonyl. Aryloxycarbonyl groups such as phenoxycarbonyl. Acyl groups such as acetyl, 3-phenylpropanoyl, and benzoyl; Examples include ionic hydrophilic groups such as a carboxyl group, a sulfonic acid group, a phosphono group, and a quaternary ammonium group.

In the second colorant represented by the general formula (II) used in the present invention, X ₁ and X ₂ in the general formula (II) each independently have a Hammett σp value of 0.20 or more. It is necessary to be an electron-withdrawing group. Here, Hammett's rule and Hammett's substituent constant σp value (hereinafter referred to as “Hammett σp value”) will be described. Hammett's rule was established in 1935 by L. L. in order to quantitatively discuss the effect of substituents on the reaction and equilibrium of benzene derivatives. P. This is an empirical rule proposed by Hammett 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 JADean edition, Langes Handbook of Chemistry 12th edition, 1979, McGraw-Hill, Chemistry domain, extra number 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. Needless to say. Although the compound of the general formula (II) is not a benzene derivative, in the present invention, the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. Specific examples of the substituent that can be used as the electron-withdrawing group having a Hammett's σp value of 0.20 or more in the substituent of the compound of the general formula (II) used in the present invention are as follows. List each value range.

  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 (II) 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 the same alkyl groups as those described above for R ₁ , R ₂ , Y ₁ and Y ₂ . Examples of the alkenyl group include the same alkenyl groups as those described above for R ₁ , R ₂ , Y ₁ and Y ₂ . Examples of the alkynyl group include the same alkynyl groups as mentioned above in the description of R ₁ , R ₂ , Y ₁ and Y ₂ . Examples of the aralkyl group include the same aralkyl groups as mentioned above in the description of R ₁ , R ₂ , Y ₁ and Y ₂ . Examples of the aryl group include the same aryl groups as those described above for R ₁ , R ₂ , Y ₁ and Y ₂ . Examples of the heterocyclic group include the same heterocyclic groups as those described above for R ₁ , R ₂ , Y ₁ and Y ₂ . Further, these substituents may be further substituted, and in this case, the substituents are listed as groups for further substituting the substituents previously mentioned in the description of R ₁ , R ₂ , Y ₁ and Y ₂ . The same as the group.

  M in general formula (II) is a hydrogen atom, an alkali metal, ammonium, or organic ammonium each independently. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the organic ammonium include acetamide, benzamide, methylamino, butylamino, diethylamino, and phenylamino.

  Preferred specific examples of the compound of the general formula (II) include the following exemplified compounds II-1 to II-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 (II) and the definition thereof. In the present invention, it is particularly preferable to use the exemplified compounds II-5, II-6, II-7, II-8, and II-10 among the following exemplified compounds.

[Contents of first color material and second color material]
The content (% by mass) of the first coloring material (compound of general formula (I)) in the ink is preferably 0.1% by mass or more and 10.0% by mass or less based on the total mass of the ink. . Further, the content (% by mass) of the second color material (the compound of the general formula (II)) in the ink is 0.1% by mass or more and 10.0% by mass or less based on the total mass of the ink. Is preferred.

  Further, the total content (% by mass) of the first color material and the second color material in the ink is 1.0% by mass or more and 10.0% by mass or less based on the total mass of the ink. Is preferred. Furthermore, the total (mass%) of these contents is particularly preferably 1.5% by mass or more and 7.0% by mass or less. If the total content is less than 1.0% by mass, the ozone resistance and color developability of the formed image may not be sufficiently obtained. If the total content exceeds 10.0% by mass, Ink jet characteristics such as adhesion may not be obtained.

  The content (mass%) of the first color material, based on the total mass of the ink, is a mass ratio with respect to the content (mass%) of the second color material (first color material / first 2 coloring material) = 0.1 times or more and 15.0 times or less is preferable. More specifically, {content of compound of general formula (I) / content of compound of general formula (II)} is preferably 0.1 times or more and 15.0 times or less. By making the mass ratio of the content within the above range, the ozone resistance of the image to be formed can be made particularly excellent. In the present invention, the mass ratio is more preferably 1.0 times or more and 8.0 times or less. By making the mass ratio of the content within the above range, the interaction between the first color material and the second color material (details will be described later) is exerted particularly strongly, thereby further improving ozone resistance. The image which has can be obtained.

[Study on the effect of improving the ozone resistance of an image by using both the first color material and the second color material]
As described above, in the image using the ink containing the second color material excellent in ozone resistance and light resistance of the image and the first color material, the cyan component significantly deteriorated in the image using the conventional ink. The remarkable fall of the ozone resistance resulting from was suppressed. This result can be explained from the relative relationship between the first color material and the second color material in the ink and analysis of the formed image.

  The present inventors first conducted the following investigation on an image formed using the ink of the present invention, another color material combination, or an image formed using an ink containing each color material alone. It was. Specifically, the position (penetration depth) where the color material is present in the thickness direction of the ink receiving layer of the recording medium was measured by cutting each image and observing the cross section, and compared. As a result, the position where each color material is present in the ink receiving layer includes an image formed using an ink containing only a general cyan dye, and also contains a general cyan dye and a compound of the general formula (II). The same result was obtained in an image formed using the ink. That is, the positions where general cyan dyes exist are concentrated in the vicinity of the surface of the ink receiving layer and are shallow in the thickness direction. In contrast, in an image formed using an ink containing a compound of general formula (I) and a compound of general formula (II), the compound of general formula (I) is contained in the ink receiving layer of the recording medium. It penetrated and was dispersed to a relatively deep position from the surface. In other words, it has been found that the ink containing the first color material and the second color material allows the first color material to penetrate deeper than the conventional ink.

  Next, the inventors analyzed the state of the dye in the ink, investigated the aggregation state or association state of the dye in the ink, and the adsorption rate of each dye with respect to the components constituting the ink receiving layer. It was. When examining the adsorption rate, general alumina hydrates and silica particles were examined as components constituting the ink receiving layer.

<Dye aggregation state or association state in ink>
The aggregation state or association state of the dye can be measured by a small angle X-ray scattering method. Small-angle X-ray scattering is used in colloidal solutions as described in “Latest Colloid Chemistry” (Kodansha Scientific Fumio Kitahara, Kunio Furusawa) and “Surface State and Colloidal State” (Tokyo Chemical Doujin Masayuki Nakagaki). This is a general-purpose method for calculating the distance between particles. The present inventors measured the aggregation state or association state of the dye by this small angle X-ray scattering method. As a result, the first colorant and the second colorant are compared with a dye aqueous solution containing a general cyan dye and a compound of the general formula (II) or a dye aqueous solution containing only a general cyan dye. It was found that the aggregation state or association state of the dye in the aqueous dye solution containing Specifically, it was found that in the dye aqueous solution containing the first color material and the second color material, the aggregation state or association state of the cyan color material was slightly suppressed. Furthermore, it was found that the aggregation state of the dye in the ink of the present invention is remarkably suppressed. Therefore, when used in combination with the compound of the general formula (II), the compound of the general formula (I) is more suppressed in aggregation than the general cyan dye. For this reason, it has been found that the penetration of the dye into the ink-receiving layer of the formed image penetrates deeper in the compound of the general formula (I) and brings about the above effect.

<Adsorption rate of dye to components constituting ink receiving layer>
When a general cyan dye and a compound of the general formula (II) are used in combination, the adsorption rate of the cyan dye to the components constituting the ink receiving layer is the same as when this general cyan dye is used alone. The adsorption rate was almost the same. In any case, the adsorption rate was close to 100%. However, it has been found that when the compound of the general formula (I) is used in combination with the compound of the general formula (II), the adsorption rate changes. Specifically, when the compound of general formula (I) was used alone, the adsorption rate was close to 100%, whereas the compound of general formula (I) and the compound of general formula (II) were used in combination. In this case, the adsorption rate of the compound of the general formula (I) was reduced to about 40%.

  The “adsorption rate” in the present invention is a ratio of adsorbing a coloring material to a material constituting an ink receiving layer of a recording medium such as aluminum oxide. This adsorption rate can be calculated, for example, by measuring the absorbance of the aqueous solution after measuring the absorbance in advance to the aqueous solution containing the alumina dispersion and adding the aqueous solution containing the dye and stirring for a certain time. .

  As a result of the study by the present inventors, the phenomenon as described above in the compound of the general formula (I) constitutes an ink receiving layer such as a silica type as well as a case where the component constituting the ink receiving layer is an alumina type. It has been found that the same tendency is observed in other materials that are general as components. From the above examination results, it can be understood that a decrease in ozone resistance of an image formed by the ink of the present invention can be remarkably suppressed.

  Furthermore, the present inventors conducted a separate examination of each element in order to confirm a dominant element for obtaining the above-described effect from each structure of the first color material and the second color material. The technology of the present invention was established. First, a description will be given with reference to FIG. 7, which is a schematic diagram showing the position of each color material in the ink receiving layer of the recording medium when ink containing each color material is applied to the recording medium.

  As shown in FIG. 7A, when an ink containing a general cyan dye O1002 alone as a coloring material is applied to a recording medium, the dye O1002 is in the thickness direction of the ink receiving layer O1001 of the recording medium. It exists in a shallow position (near the surface). As shown in FIG. 7B, when an ink containing the compound O1003 of the general formula (I) alone is applied to the recording medium, the compound O1003 of the general formula (I) is an ink of the recording medium as described above. It exists in a shallow position (near the surface) in the thickness direction of the receiving layer O1001.

  As shown in FIG. 7C, when an ink containing a general cyan dye O1002 and another general dye O1004 is applied to the recording medium, these dyes are also included in the ink receiving layer O1001 of the recording medium. It exists in a shallow position (near the surface) in the thickness direction. In addition, as shown in FIG. 7 (d), when an ink containing a general cyan dye O1002 and a compound O1005 of the general formula (II) is applied to a recording medium, these dyes are also recorded on the recording medium in the same manner as described above. The ink receiving layer O1001 exists in a shallow position (near the surface) in the thickness direction. Hereinafter, the shallow position in the thickness direction of the ink receiving layer O1001 of the recording medium is referred to as “near the surface of the ink receiving layer”.

  When the coloring material is present in the ink receiving layer of the recording medium as described above, when an oxidizing gas such as ozone gas in the air causes a reaction that deteriorates the coloring material, the vicinity of the surface of the ink receiving layer The degree of deterioration of the cyan component present in the image becomes larger. When the compound of general formula (I), which is a cyan dye used in the present invention, is also an ink containing the compound alone as a colorant, the adsorption rate of the compound with respect to the components constituting the ink receiving layer of the recording medium is Since it is high, it exists near the surface of the ink receiving layer.

  However, as shown in FIG. 7 (e), the ink containing the compound O1003 of the general formula (I) and the compound O1005 of the general formula (II) as the coloring material is used in the ink receiving layer of the recording medium. The location of each color material is as follows. That is, by using these color materials in combination, as described above, the adsorption rate of the compound O1003 of the general formula (I) to the ink receiving layer O1001 becomes relatively low. Therefore, the compound O1003 of the general formula (I) is present at a position where it penetrates to some extent in the thickness direction of the ink receiving layer O1001 as compared with the case of FIG. 7B. As a result, when the color material is used in combination as described above, the contact between the compound of general formula (I) and an oxidizing gas such as ozone gas in the air is alleviated, the deterioration of the cyan component is suppressed, and the image resistance is reduced. It is estimated that the ozone is improved.

  In the case of a general cyan dye O1002, the adsorption rate to the components constituting the ink receiving layer O1001 remains high even when used in combination with the compound O1005 of the general formula (II). For this reason, as shown in FIG. 7D, there is no significant difference in the position where the color material exists.

  When an ink in which the compound of general formula (I) and the compound of general formula (II) coexist is used, the position of the compound of general formula (I) in the ink-receiving layer of the recording medium is as described above. The present inventors presume the reason for the specific behavior as follows.

  Using software that can perform molecular orbital calculations (WinMOPAC 3.9Pro; manufactured by Fujitsu), the following was found when the stabilized structure of the compound of general formula (II) was determined. Specifically, in the compound of the general formula (II), nitrogen atoms on a pyrazole ring having no amino group face each other and exist as a circular structure. Thus, the compound of the general formula (II) existing as a circular structure interacts with the triazine ring of the compound of the general formula (I), so that the compound of the general formula (II) and the general formula ( The compound of I) comes to be in an overlapping state. The compound of the general formula (I) taking such a state has a larger interaction with the compound of the general formula (II) than the adsorptive power to the components constituting the ink receiving layer. On the other hand, the compound of the general formula (I) has a low adsorption rate with respect to the ink receiving layer, and exists in a position where it penetrates to some extent in the thickness direction of the ink receiving layer together with the compound of the general formula (II). Thus, it is considered that an image formed by using an ink in which the compound of the general formula (I) and the compound of the general formula (II) coexist is particularly remarkably suppressed by ozone.

  Further, as a result of the study by the present inventors, as a result of using a combination of a phthalocyanine-based color material having a triazine ring as a substituent and a compound having a skeleton in which (a plurality of) nitrogen-containing heteroaromatic rings are directly bonded to the triazine ring. It was found that the following phenomenon occurred. Specifically, it was found that the ozone resistance of the image is improved by reducing the adsorption rate of the phthalocyanine color material to the ink receiving layer. Hereinafter, a compound having a partial element structure of the compound represented by the general formula (I) as the first color material may be referred to as a “phthalocyanine color material”. In addition, the compound having a partial element structure of the compound represented by the general formula (II) as the second colorant is referred to as “a compound having a skeleton in which (a plurality of) nitrogen-containing heteroaromatic rings are directly bonded to a triazine ring”. Sometimes called.

  When the present inventors performed molecular orbital calculation in order to analyze the cause, it was found that the following phenomenon occurred. Specifically, the triazine ring in the phthalocyanine color material, the triazine ring in the other compound, and the nitrogen-containing heteroaromatic ring approach each other, so that the distance (distance) between the molecules of the phthalocyanine color material exists. I was allowed to spread. As a result, it has been found that the phthalocyanine-based coloring material is difficult to be associated. As a result, it is considered that the interaction between the phthalocyanine color material and the compound is strong, and the adsorption rate of the phthalocyanine color material to the ink receiving layer is lowered. Furthermore, it has been found that the synergistic action of the phthalocyanine-based colorant is further increased by having a nitrogen-containing heteroaromatic ring in the phthalocyanine skeleton. In particular, it was also found that the synergistic effect is significantly increased when the nitrogen-containing heteroaromatic ring is a pyridine ring or a pyrazine ring. In this case, since the nitrogen-containing heteroaromatic ring in the compound has an amino group, the solubility of the compound does not depend on pH, and the synergistic action with the phthalocyanine colorant can be kept more stable. Particularly preferred. Further, when the compound has a skeleton in which a plurality of nitrogen-containing heteroaromatic rings are directly bonded to the triazine ring, the interval (distance) at which the molecules of the phthalocyanine dye are present can be further increased. For this reason, the range in which the distribution of the phthalocyanine dye in the thickness direction of the recording medium can be further expanded, which is particularly preferable. Further, it is particularly preferable that the nitrogen-containing heteroaromatic ring of the compound has an amino group, so that the solubility of the compound does not depend on pH as described above. In the present invention, if the compound is a compound of the general formula (II) having all these conditions simultaneously, the effect is great.

  From the above, an ink having the above-described effects of the present invention can be obtained by using an ink having the following configurations. (1) A phthalocyanine-based coloring material having a pyridine ring or a pyrazine ring in a phthalocyanine skeleton and having a triazine ring as a substituent, and a compound having a skeleton in which a triazine ring and a nitrogen-containing heteroaromatic ring are directly bonded Ink. (2) containing a phthalocyanine-based coloring material having a nitrogen-containing heteroaromatic ring in the phthalocyanine skeleton and having a triazine ring as a substituent, and a compound having a skeleton in which the triazine ring and the nitrogen-containing heteroaromatic ring are directly bonded Ink. (3) A phthalocyanine-based coloring material having a nitrogen-containing heteroaromatic ring in the phthalocyanine skeleton and a substituent containing a triazine ring, and a compound having a skeleton in which a plurality of nitrogen-containing heteroaromatic rings are directly bonded to the triazine ring. Contains ink. (4) An ink comprising a phthalocyanine color material having a nitrogen-containing heteroaromatic ring in the phthalocyanine skeleton and having a triazine ring as a substituent, and the compound represented by the general formula (II). In the inks having the configurations (1), (2), and (3), it is more preferable that the nitrogen-containing heteroaromatic ring of the compound has an amino group.

[Third coloring material: compound represented by general formula (III), compound represented by general formula (IV), and compound represented by general formula (V)]
The ink of the present invention preferably further contains a third color material in addition to the first color material and the second color material described above. The third colorant is selected from the group consisting of a compound represented by the following general formula (III), a compound represented by the following general formula (IV), and a compound represented by the following general formula (V). At least one compound is used. In the following description, the compound is selected from the group consisting of a compound represented by the following general formula (III), a compound represented by the following general formula (IV), and a compound represented by the following general formula (V). At least one compound is referred to as a third color material. By using the third color material in combination with the first color material and the second color material described above, a gray ink excellent in ozone resistance and color tone of the image can be obtained.

（一般式（III）中、Ｒはそれぞれ独立に、水素原子、アルキル基、ヒドロキシアルキル基、シクロヘキシル基、又はモノ若しくはジアルキルアミノアルキル基である。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である。Ｘは連結基である。）

(In general formula (III), each R is independently a hydrogen atom, an alkyl group, a hydroxyalkyl group, a cyclohexyl group, or a mono- or dialkylaminoalkyl group. M is independently a hydrogen atom, an alkali metal, or an ammonium salt. Or X is a linking group.)

  R in the general formula (III) is each independently a hydrogen atom, an alkyl group, a hydroxyalkyl group, a cyclohexyl group, or a mono- or dialkylaminoalkyl group.

  Examples of the alkyl group include alkyl groups having 1 to 8 carbon atoms. Specifically, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, iso-butyl, n-pentyl, n-hexyl, n-heptyl, and n- Examples include octyl.

  Examples of the hydroxyalkyl group include a hydroxyalkyl group having 1 to 4 carbon atoms. Specific examples include hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl. Examples of the alkyl in the hydroxyalkyl group include linear, branched, and cyclic alkyl, and linear alkyl is particularly preferable. Moreover, any position may be sufficient as the substitution position of the hydroxy in the said alkyl, However, The hydroxy substituted at the terminal, for example, 2-hydroxyethyl, 3-hydroxypropyl, and 4-hydroxybutyl are especially preferable.

  Examples of the monoalkylaminoalkyl group include a mono-carbon number 1 to 4 alkylamino-carbon number 1 to 4 alkyl group. Specific examples include monomethylaminopropyl and monoethylaminopropyl.

  Examples of the dialkylaminoalkyl group include a di-carbon number 1 to 4 alkylamino-carbon number 1 to 4 alkyl group. Specific examples include dimethylaminopropyl and diethylaminoethyl.

  In the present invention, R in the general formula (III) is preferably a hydrogen atom, an alkyl group, or cyclohexyl, more preferably a hydrogen atom or an alkyl group, and particularly preferably a methyl group.

  X in the general formula (III) is a linking group. Examples of the linking group include the following linking groups 1 to 7. In the linking groups 1 to 7, a bond marked with “*” is a bond of each nitrogen atom, and each nitrogen atom and two different triazine rings in the general formula (III) are directly bonded. Of the following linking groups, the linking group 1 is particularly preferably used.

（連結基１中、ｎは２乃至８、好ましくは２乃至６、さらに好ましくは２であり、＊はそれぞれ異なる２つのトリアジン環との結合部位である。）

(In linking group 1, n is 2 to 8, preferably 2 to 6, more preferably 2, and * is a bonding site with two different triazine rings.)

（連結基２中、Ｒ_aはそれぞれ独立に、水素原子又はメチル基であり、＊はそれぞれ異なる２つのトリアジン環との結合部位である。）

(In the linking group 2, each R _a is independently a hydrogen atom or a methyl group, and * is a bonding site with two different triazine rings.)

（連結基３中、＊はそれぞれ異なる２つのトリアジン環との結合部位である。）

(In linking group 3, * is a bonding site with two different triazine rings.)

（連結基４中、＊はそれぞれ異なる２つのトリアジン環との結合部位である。）

(In the linking group 4, * is a bonding site with two different triazine rings.)

（連結基５中、＊はそれぞれ異なる２つのトリアジン環との結合部位である。）

(In the linking group 5, * is a bonding site with two different triazine rings.)

（連結基６中、ｍは２乃至４であり、＊はそれぞれ異なる２つのトリアジン環との結合部位である。）

(In the linking group 6, m is 2 to 4, and * is a bonding site with two different triazine rings.)

（連結基７中、＊はそれぞれ異なる２つのトリアジン環との結合部位である。）

(In the linking group 7, * is a bonding site with two different triazine rings.)

  M in general formula (III) is a hydrogen atom, an alkali metal, ammonium, or organic ammonium each independently. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the organic ammonium include acetamide, benzamide, methylamino, butylamino, diethylamino, phenylamino, and triethanolamino.

（一般式（IV）中、Ｒ₁は水素原子又はアルキル基であり、ｍは１乃至３の整数であり、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である。）

(In General Formula (IV), R ₁ is a hydrogen atom or an alkyl group, m is an integer of 1 to 3, and M is each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

R ₁ in the general formula (IV) is a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 3 carbon atoms from the viewpoint of solubility in an aqueous medium constituting the ink, and specifically includes a methyl group, an ethyl group, a primary propyl group, and a secondary group. A propyl group is mentioned. When the alkyl group has 4 or more carbon atoms, the coloring material becomes more hydrophobic and the coloring material may not dissolve in the aqueous medium constituting the ink.

  M in 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, phenylamino, and triethanolamino.

（一般式（Ｖ）中、Ｒ₂、Ｒ₃、Ｒ₄、及びＲ₅はそれぞれ独立にアルキル基であり、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である。）

(In General Formula (V), R ₂ , R ₃ , R ₄ , and R ₅ are each independently an alkyl group, and M is each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

R ₂ , R ₃ , R ₄ and R ₅ in the general formula (V) are each independently an alkyl group. The alkyl group preferably has 1 to 3 carbon atoms from the viewpoint of solubility in an aqueous medium constituting the ink, and specifically includes a methyl group, an ethyl group, a primary propyl group, and a secondary group. A propyl group is mentioned. When the alkyl group has 4 or more carbon atoms, the coloring material becomes more hydrophobic and the coloring material may not dissolve in the aqueous medium constituting the ink.

  M in general formula (V) is a hydrogen atom, an alkali metal, ammonium, or organic ammonium each independently. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the organic ammonium include acetamide, benzamide, methylamino, butylamino, diethylamino, phenylamino, and triethanolamino.

  Preferred specific examples of the compound of the general formula (III), the compound of the general formula (IV), and the compound of the general formula (V) include the following Exemplified Compounds III-1, III-2, IV-1, IV- 2 and V-1 to V-3. 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 structures of the general formula (III), general formula (IV), and general formula (V) and the definitions thereof. In the present invention, among the following exemplary compounds, exemplary compound III-1, exemplary compound IV-1, or exemplary compound V-2 is preferably used, and more preferably exemplary compound V-2 is used.

[Content of third color material]
The preferred ink of the present invention is at least selected from the group consisting of the compounds of the general formula (III), the general formula (IV), and the general formula (V) as described above as the third color material. Contains one compound. In this case, the content (% by mass) of the third color material in the ink is preferably 0.1% by mass or more and 10.0% by mass or less based on the total mass of the ink.

  Further, the total (mass%) of the content of the first color material, the content of the second color material, and the content of the third color material in the ink is 1 based on the total mass of the ink. It is preferable that it is 0.0 mass% or more and 10.0 mass% or less. Furthermore, the total (mass%) of these contents is particularly preferably 1.5% by mass or more and 7.0% by mass or less. When the total content of the color materials is less than 1.0% by mass, the ozone resistance and color developability of the image formed with the ink may not be sufficiently obtained, and the total content of the color materials is 10%. If it exceeds 0.0 mass%, ink jet characteristics such as anti-sticking property may not be obtained.

  The content (mass%) of the third color material based on the total mass of the ink is mass relative to the total (mass%) of the content of the first color material and the content of the second color material. The ratio is preferably (total of first color material and second color material / third color material) = 0.5 times or more and 5.0 times or less. Furthermore, the mass ratio is particularly preferably 1.0 to 3.0 times. By setting the mass ratio of the content within the above range, in addition to excellent ozone resistance and light resistance of an image, a color tone preferable as a gray ink can be obtained.

  When the first color material, the second color material, and the third color material are used in combination, the mass ratio between the first color material and the second color material based on the total mass of the ink (the first color material) A preferable range of (one color material / second color material) is as described above.

[Preferred color tone for gray ink]
The color tone that is preferable as the gray ink in the present invention, that is, the neutral color tone that gives a preferable image specifically means the following. For an image having gradation that is formed using a gray ink with a recording duty reduced from 100%, a ^* and b in an L ^* a ^* b ^* display system defined by the CIE (International Commission on Illumination) Measure ^* . An ink having values of a ^* and b ^* of −5 ≦ a ^* ≦ 10 and −10 ≦ b ^* ≦ 1 at least in a portion where the recording duty is 100% is preferable as a gray ink in the present invention. It is said that the ink has Furthermore, an ink satisfying the following rules is an ink having a more preferable color tone as a gray ink in the present invention. That is, it is preferable that the values of a ^* and b ^* in the portion where the recording duty is 100% are −0.5 ≦ a ^* ≦ 5 and −6.5 ≦ b ^* ≦ 0. The values of a ^* and b ^* can be measured using, for example, a spectrophotometer (trade name: Spectrolino; manufactured by Gretag Macbeth). Of course, the present invention is not limited to this.

  In the present invention, the gray ink is prepared so as to have a color tone preferable as the gray ink within the range of the mass ratio of the first color material, the second color material, and the third color material. It is preferable to do. In addition, adjusting to the preferable color tone range as the gray ink can be performed by appropriately determining the content of each color material within the above-described mass ratio range. In order to obtain a color tone preferable as a gray ink, it is particularly preferable to use the compound of the general formula (V) as the third color material.

[Fourth Color Material: Compound Represented by General Formula (VI) and / or Compound Represented by General Formula (VII)]
The ink of the present invention further contains at least one compound selected from the following general formula (VI) and the following general formula (VII) as a fourth coloring material in addition to the above-described coloring material. It may be. Specifically, an ink containing a fourth color material in addition to the first color material and the second color material, or the first color material, the second color material, and the third color material. In addition, an ink containing a fourth coloring material can be used. In particular, an ink containing a fourth color material in addition to the first color material, the second color material, and the third color material is preferable.

（一般式（VI）中、Ｒ₁₀は、それぞれ独立に、水素原子、ヒドロキシル基、カルボキシル基、ヒドロキシル基若しくは炭素数１乃至４のアルコキシ基によって置換されていてもよい炭素数１乃至４のアルキル基。ヒドロキシル基若しくは炭素数１乃至４のアルコキシ基によって置換されていてもよい炭素数１乃至４のアルコキシル基、ヒドロキシル基若しくは炭素数１乃至４のアルコキシ基によって置換されていてもよい炭素数１乃至４のアルキルアミノ基。カルボキシル−炭素数１乃至５のアルキルアミノ基、ビス−〔カルボキシ−炭素数１乃至５のアルキル〕アミノ基、ヒドロキシル基若しくは炭素数１乃至４のアルコキシ基によって置換されていてもよい炭素数１乃至４のアルカノイルアミノ基。カルボキシル基若しくはスルホン酸基若しくはアミノ基で置換されていてもよいフェニルアミノ基、スルホン酸基、ハロゲン原子、又はウレイド基である。〔Ｃ〕は、カルボキシル基又はスルホン酸基を有する脂肪族アミン残基である。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である。）

(In General Formula (VI), each R ₁₀ independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbon atoms. A group which may be substituted by a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a carbon group which may be substituted by a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms An alkylamino group having 1 to 4 carbon atoms, substituted by a carboxyl-alkyl group having 1 to 5 carbon atoms, a bis- [carboxy-alkyl having 1 to 5 carbon atoms] amino group, a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms. C1-C4 alkanoylamino group which may be a carboxyl group or a sulfonic acid group Or phenylamino group, sulfonic acid group, halogen atom or ureido group which may be substituted with amino group [C] is an aliphatic amine residue having a carboxyl group or sulfonic acid group. Are each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

R ₁₀ in the general formula (VI) is each independently a hydrogen atom, a hydroxyl group, a carboxyl group, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbon atoms. 1 to 4 carbon atoms which may be substituted by a hydroxyl group or an alkoxyl group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group or an alkoxy group which has 1 to 4 carbon atoms An alkylamino group. 1 to 5 carbon atoms optionally substituted by a carboxyl-alkyl group having 1 to 5 carbon atoms, a bis- [carboxy-alkyl having 1 to 5 carbon atoms] amino group, a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms 4 alkanoylamino groups. A phenylamino group, a sulfonic acid group, a halogen atom, or a ureido group which may be substituted with a carboxyl group, a sulfonic acid group, or an amino group.

  Specific examples of the alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms include the following groups. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl. Examples include methoxyethyl, ethoxyethyl, nT propoxyethyl, isopropoxyethyl, n-butoxyethyl, sec-butoxyethyl, tert-butoxyethyl, and 2-hydroxyethyl.

  Specific examples of the alkoxyl group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms include the following groups. Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy. Methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy. Examples include methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy, and 2-hydroxyethoxyethoxy.

  Specific examples of the alkylamino group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms include the following groups. Methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino. N, N-dimethylamino, N, N-diethylamino, N, N-di (n-propyl) amino, N, N-di (isopropyl) amino, hydroxyethylamino. Examples include 2-hydroxypropylamino, 3-hydroxypropylamino, bis (hydroxyethyl) amino, methoxyethylamino, ethoxyethylamino, bis (methoxyethyl) amino, and bis (2-ethoxyethyl) amino.

  Specific examples of the carboxy-C 1-5 alkylamino group include carboxymethylamino, carboxyethylamino, carboxypropylamino, carboxy-n-butylamino, and carboxy-n-pentylamino.

  Specific examples of the bis- [carboxy-alkyl having 1 to 5 carbon atoms] amino group include bis- (carboxymethyl) amino group, bis- (carboxyethyl) amino group, and bis- (carboxypropyl) amino group. Etc.

  Specific examples of the alkanoylamino group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms include the following groups. Acetylamino, n-propionylamino, isopropionylamino, hydroxyacetylamino, 2-hydroxy-n-propionylamino, 3-hydroxy-n-propionylamino, 2-methoxy-n-propionylamino. Examples include 3-methoxy-n-propionylamino, 2-hydroxy-n-butyrylamino, 3-hydroxy-n-butyrylamino, 2-methoxy-n-butyrylamino, and 3-methoxy-n-butyrylamino.

  Specific examples of the phenylamino group optionally substituted with a carboxyl group, a sulfonic acid group, or an amino group include the following groups. Examples include phenylamino, sulfophenylamino, carboxyphenylamino, biscarboxyphenylamino, aminophenylamino, diaminophenylamino, and diaminosulfophenylamino.

  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.

  Specific examples of the ureido group include 3-methylureido group, 3,3-dimethylureido group, and 3-phenylureido group.

  [C] in the general formula (VI) is an aliphatic amine residue having a carboxyl group or a sulfonic acid group. As the aliphatic amine residue, an alkylamine residue having 1 to 5 mono-carbons or an alkylamine residue having 1 to 5 di-carbons having a carboxyl group or a sulfonic acid group is preferable. Specific examples of the aliphatic amine residue having a carboxyl group or a sulfonic acid group include the following. Amino-C1-C5 alkylsulfonic acid, diimino-C1-C5 alkylsulfonic acid, amino-C1-C5 alkyl carboxylic acid, diimino-C1-C5 alkyl carboxylic acid, etc. are mentioned. It is done. Among these, aliphatic carbon number is preferably 1 or 2. As the aliphatic amine residue having a carboxyl group or a sulfonic acid group, a sulfoethylamino group and a dicarboxymethylimino group are particularly preferable, and a sulfoethylamino group is more preferable.

  M in the general formula (VI) is each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium. Specific examples of the alkali metal include lithium, sodium, and potassium. Examples of the organic ammonium include acetamide, benzamide, methylamino, butylamino, diethylamino, and phenylamino.

In the compound of the general formula (VI) used in the present invention, R ₁₀ is preferably an alkyl group having 1 to 4 carbon atoms, and R ₁₀ is more preferably a methyl group.

Moreover, it is preferable that the compound of general formula (VI) used by this invention is 400 nm or more and 440 nm or less of the maximum absorption wavelength ((lambda) _max ) of the absorption spectrum measured using water as a solvent.

  Preferable specific examples of the compound of the general formula (VI) include the following exemplified compounds VI-1 to VI-12. Exemplified compounds VI-1 to VI-12 are compounds in which [C] in the following general formula (VIII) is an aliphatic amine residue shown in Table 2 below. The present invention is not limited to the following exemplified compounds as long as they are included in the structure of the general formula (VI). In the present invention, it is particularly preferable to use exemplified compounds VI-1, VI-5, and VI-9 among the following exemplified compounds.

（一般式（VIII）中、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である。）

(In general formula (VIII), each M is independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

（一般式（VII）中、Ａは置換されていてもよい芳香族基又は複素環基であり、Ｂは下記一般式（１）乃至（５）で表されるいずれかの基であり、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である。） Next, the compound of the following general formula (VII) used as the fourth coloring material in the ink of the present invention will be described in detail.

(In General Formula (VII), A is an optionally substituted aromatic group or heterocyclic group, B is any group represented by the following General Formulas (1) to (5), M Are each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

（一般式（１）乃至（５）中、Ｒ₁乃至Ｒ₉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、カルボキシル基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環オキシカルボニル基、アシル基。ヒドロキシル基、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、アルキル若しくは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、アルキル若しくはアリールチオ基。複素環チオ基、アルキル若しくはアリールスルホニル基、複素環スルホニル基、アルキル若しくは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、又はスルホン酸基であり、各基はさらに置換されていてもよい。）

(In the general formulas (1) to (5), R _{1 to} R ₉ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxyl 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, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, cyano group, nitro group, alkyl or arylthio group. Heterocycle A thio group, an alkyl or arylsulfonyl group, a heterocyclic sulfonyl group, an alkyl or arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfonic acid group, and each group may be further substituted.

  A in the general formula (VII) is an optionally substituted aromatic group or heterocyclic group, and specifically, the following substituents can be used. Examples include a benzene ring, naphthalene ring, pyridine ring, imidazole ring, pyrazole ring, thiazole ring, isothiazole ring, thiadiazole ring, benzothiazole ring, and benzoisothiazole ring. Among these, a benzene ring, a naphthalene ring, a pyridine ring, a pyrazole ring, an imidazole ring, an isothiazole ring, or a benzothiazole ring is preferable, and a benzene ring or a naphthalene ring is more preferable.

B in the general formula (VII) is any group represented by the general formulas (1) to (5) shown above. R _{1 to} R ₉ in formulas (1) to (5) are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxy A carbonyl group, a heterocyclic oxycarbonyl group, and an acyl group. Hydroxyl 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, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, cyano group, nitro group, alkyl or arylthio group. A heterocyclic thio group, an alkyl or arylsulfonyl group, a heterocyclic sulfonyl group, an alkyl or arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfonic acid group, and each group may be further substituted.

  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.

  Aliphatic groups include alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, alkynyl groups, substituted alkynyl groups, aralkyl groups, and substituted aralkyl groups. These aliphatic groups may have a branch or may form a ring. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms. The aryl moiety of the aralkyl group and substituted aralkyl group is preferably phenyl or naphthyl, more preferably phenyl. Specific examples of the aliphatic group include the following groups. Examples include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl, cyclohexyl, benzyl, 2-phenethyl, vinyl, and allyl.

  Examples of the aromatic group include a monovalent or divalent aryl group and a substituted aryl group. Examples of the monovalent aromatic group include an aryl group and a substituted aryl group. The aryl group is preferably phenyl or naphthyl, and more preferably phenyl. The monovalent aromatic group preferably has 6 to 20 carbon atoms, and more preferably 6 to 16 carbon atoms. Specific examples of the monovalent aromatic group include phenyl, p-phenylphenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl, p-chlorophenyl, p-acetylaminophenyl, and m- (3- Sulfopropylamino) phenyl. Examples of the divalent aromatic group include those obtained by divalentizing these monovalent aromatic groups. Specific examples include phenylene, p-tolylene, p-methoxyphenylene, o-chlorophenylene, m- (3-sulfopropylamino) phenylene, and naphthylene.

  Examples of the heterocyclic group include a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring, or another heterocyclic ring. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group, and examples of the hetero atom of the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. Specific examples of the substituent include aliphatic groups, halogen atoms, alkyl or arylsulfonyl groups, acyl groups, acylamino groups, sulfamoyl groups, carbamoyl groups, and ionic hydrophilic groups. Examples of the monovalent heterocyclic group include 2-pyridyl group, 3-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group, and 2-furyl group. It is done. Examples of the divalent heterocyclic group include groups in which a hydrogen atom in the monovalent heterocyclic group is removed to form a bond.

  Examples of the carbamoyl group include a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Specific examples of the substituent include an alkyl group. Specific examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

  Examples of the alkoxycarbonyl group include an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms is preferable. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  Examples of the aryloxycarbonyl group include a substituted aryloxycarbonyl group and an unsubstituted aryloxycarbonyl group. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 20 carbon atoms. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

  Examples of the heterocyclic oxycarbonyl group include a substituted heterocyclic oxycarbonyl group and an unsubstituted heterocyclic oxycarbonyl group. As the heterocyclic oxycarbonyl group, a heterocyclic oxycarbonyl group having 2 to 20 carbon atoms is preferable. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the heterocyclic oxycarbonyl group include a 2-pyridyloxycarbonyl group.

  Examples of the acyl group include a substituted acyl group and an unsubstituted acyl group. As the acyl group, an acyl group having 1 to 20 carbon atoms is preferable. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the acyl group include an acetyl group and a benzoyl group.

  Examples of the alkoxy group include a substituted alkoxy group and an unsubstituted alkoxy group. As the alkoxy group, an alkoxy group having 1 to 20 carbon atoms is preferable. Specific examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

  Examples of the aryloxy group include a substituted aryloxy group and an unsubstituted aryloxy group. As the aryloxy group, an aryloxy group having 6 to 20 carbon atoms is preferable. Specific examples of the substituent include an alkoxy group and an ionic hydrophilic group. Specific examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

  Examples of the heterocyclic oxy group include a heterocyclic oxy group having a substituent and an unsubstituted heterocyclic oxy group. As the heterocyclic oxy group, a heterocyclic oxy group having 2 to 20 carbon atoms is preferable. Specific examples of the substituent include an alkyl group, an alkoxy group, and an ionic hydrophilic group. Specific examples of the heterocyclic oxy group include a 3-pyridyloxy group and a 3-thienyloxy group.

  As the silyloxy group, an aliphatic group having 1 to 20 carbon atoms and a silyloxy group substituted with an aromatic group are preferable. Specific examples of the silyloxy group include trimethylsilyloxy and diphenylmethylsilyloxy.

  Examples of the acyloxy group include a substituted acyloxy group and an unsubstituted acyloxy group. As the acyloxy group, an acyloxy group having 1 to 20 carbon atoms is preferable. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

  Examples of the carbamoyloxy group include a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Specific examples of the substituent include an alkyl group. Specific examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

  Examples of the alkoxycarbonyloxy group include an alkoxycarbonyloxy group having a substituent and an unsubstituted alkoxycarbonyloxy group. As the alkoxycarbonyloxy group, an alkoxycarbonyloxy group having 2 to 20 carbon atoms is preferable. Specific examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group and an isopropoxycarbonyloxy group.

  Examples of the aryloxycarbonyloxy group include an aryloxycarbonyloxy group having a substituent and an unsubstituted aryloxycarbonyloxy group. The aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having 7 to 20 carbon atoms. Specific examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group.

  Examples of the amino group include an amino group substituted with an alkyl group, an aryl group, or a heterocyclic group, and the alkyl group, the aryl group, and the heterocyclic group may further have a substituent. The alkylamino group is preferably an alkylamino group having 1 to 20 carbon atoms. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the alkylamino group include a methylamino group and a diethylamino group. Examples of the arylamino group include an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 20 carbon atoms. Specific examples of the substituent include a halogen atom and an ionic hydrophilic group. Specific examples of the arylamino group include an anilino group and a 2-chlorophenylamino group. Examples of the heterocyclic amino group include a heterocyclic amino group having a substituent and an unsubstituted heterocyclic amino group. As the heterocyclic amino group, a heterocyclic amino group having 2 to 20 carbon atoms is preferable. Specific examples of the substituent include an alkyl group, a halogen atom, and an ionic hydrophilic group.

  Examples of the acylamino group include a substituted acylamino group and an unsubstituted acylamino group. The acylamino group is preferably an acylamino group having 2 to 20 carbon atoms. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-disulfobenzoylamino group.

  Examples of the ureido group include a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 20 carbon atoms. Specific examples of the substituent include an alkyl group and an aryl group. Specific examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

  Examples of the sulfamoylamino group include a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. Specific examples of the substituent include an alkyl group. Specific examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino group.

  Examples of the alkoxycarbonylamino group include a substituted alkoxycarbonylamino group and an unsubstituted alkoxycarbonylamino group. As the alkoxycarbonylamino group, an alkoxycarbonylamino group having 2 to 20 carbon atoms is preferable. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

  Examples of the aryloxycarbonylamino group include an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

  Examples of the alkyl or arylsulfonylamino group include a substituted alkyl or arylsulfonylamino group and an unsubstituted alkyl or arylsulfonylamino group. As the sulfonylamino group, a sulfonylamino group having 1 to 20 carbon atoms is preferable. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the sulfonylamino group include a methylsulfonylamino group, an N-phenyl-methylsulfonylamino group, a phenylsulfonylamino group, and a 3-carboxyphenylsulfonylamino group.

  Examples of the heterocyclic sulfonylamino group include a heterocyclic sulfonylamino group having a substituent and an unsubstituted heterocyclic sulfonylamino group. The heterocyclic sulfonylamino group is preferably a heterocyclic sulfonylamino group having 1 to 12 carbon atoms. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the heterocyclic sulfonylamino group include a 2-thiophenesulfonylamino group and a 3-pyridinesulfonylamino group.

  Examples of the alkyl or arylthio group include a substituted alkyl or arylthio group and an unsubstituted alkyl or arylthio group. As the alkyl or arylthio group, those having 1 to 20 carbon atoms are preferable. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the alkyl or arylthio group include a methylthio group and a phenylthio group.

  Examples of the heterocyclic thio group include a heterocyclic thio group having a substituent and an unsubstituted heterocyclic thio group. As the heterocyclic thio group, those having 1 to 20 carbon atoms are preferable. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the heterocyclic thio group include a 2-pyridylthio group.

  Examples of the alkyl or arylsulfonyl group include a substituted alkyl or arylsulfonyl group and an unsubstituted alkyl or arylsulfonyl group. Specific examples of the alkyl or arylsulfonyl group include a methylsulfonyl group and a phenylsulfonyl group.

  Examples of the heterocyclic sulfonyl group include a substituted heterocyclic sulfonyl group and an unsubstituted heterocyclic sulfonyl group. As the heterocyclic sulfonyl group, a heterocyclic sulfonyl group having 1 to 20 carbon atoms is preferable. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the heterocyclic sulfonyl group include a 2-thiophenesulfonyl group and a 3-pyridinesulfonyl group.

  Examples of the alkyl or arylsulfinyl group include a substituted alkyl or arylsulfinyl group and an unsubstituted alkyl or arylsulfinyl group. Specific examples of the alkyl or arylsulfinyl group include a methylsulfinyl group and a phenylsulfinyl group.

  Examples of the heterocyclic sulfinyl group include a heterocyclic sulfinyl group having a substituent and an unsubstituted heterocyclic sulfinyl group. As the heterocyclic sulfinyl group, a heterocyclic sulfinyl group having 1 to 20 carbon atoms is preferable. Specific examples of the substituent include an ionic hydrophilic group. Specific examples of the heterocyclic sulfinyl group include a 4-pyridinesulfinyl group.

  Examples of the sulfamoyl group include a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Specific examples of the substituent include an alkyl group. Specific examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

  M in general formula (VII) is respectively independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium. Specific examples of the alkali metal include lithium, sodium, and potassium. Specific examples of the organic ammonium include acetamide, benzamide, methylamino, butylamino, diethylamino, phenylamino, and triethanolamino.

In the compound of the general formula (VII) used in the present invention, A is an optionally substituted naphthyl group, and B is preferably a group represented by the above general formula (2). R ₃ in Formula (2) is more preferably an aryl group or a pyridyl group. Specific examples of the aryl group or pyridyl group are as follows. Phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group and the like. Also, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, etc. . In addition, 2,4,6-trimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group and the like. Moreover, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group and the like. In addition, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, and the like. Moreover, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 1-naphthyl group, 2-naphthyl group and the like. Among these, phenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 2-pyridyl group, 4-pyridyl group, 1-naphthyl group, 2-naphthyl group, etc. Is preferred.

In addition, the compound of the general formula (VII) used in the present invention preferably has a maximum absorption wavelength (λ _max ) of 590 nm or more and 620 nm or less of an absorption spectrum measured using water as a solvent.

  Preferable specific examples of the compound of the general formula (VII) include the following exemplified compounds VII-1 to VII-12. The present invention is not limited to the following exemplary compounds as long as they are included in the structure of the general formula (VII). In the present invention, among the following exemplary compounds, exemplary compounds VII-3, VII-5, VII-6, VII-8, VII-9, VII-10, VII-11, and VII-12 are used. It is preferable. Furthermore, it is more preferable to use exemplary compounds VII-3, VII-5, and VII-10.

[Content of Fourth Colorant]
A preferred ink of the present invention contains at least one compound selected from the compound of the general formula (VI) and the compound of the general formula (VII) as described above as the fourth coloring material. In this case, the content (% by mass) of the fourth color material in the ink is preferably 0.05% by mass or more and 10.0% by mass or less based on the total mass of the ink.

  In addition, the total (mass%) of the contents of the first color material and the second color material in the ink, and the third color material and the fourth color material to be contained as necessary, represents the total mass of the ink. As a reference, it is preferably 1.0% by mass or more and 10.0% by mass or less. Furthermore, the total (mass%) of these contents is particularly preferably 1.5% by mass or more and 7.0% by mass or less. When the total content of the color materials is less than 1.0% by mass, the ozone resistance and color developability of the image to be formed may not be sufficiently obtained, and the total content of the color materials is 10.0 masses. If it exceeds 50%, ink jet characteristics such as anti-sticking property may not be obtained.

  The content (mass%) of the fourth color material based on the total mass of the ink is preferably contained within a specific range with respect to the other color materials. For example, with respect to the total (mass%) of the content of the first color material, the content of the second color material, and the content of the third color material in the ink, The total of the color material, the second color material, and the third color material) / (fourth color material) = 1.0 times or more and 70.0 times or less is preferable. In the present invention, the mass ratio is more preferably 5.0 times or more and 45.0 times or less. By setting the mass ratio of the content within the above range, it is possible to obtain a color tone that is more neutral and preferable as a gray ink. By setting the mass ratio of the content within the above range, in addition to the excellent ozone resistance and light resistance of the image, it is possible to more effectively obtain a color tone preferable as a gray ink, and further, to improve the metamerism of the image. Can be improved.

  When the first color material, the second color material, the third color material, and the fourth color material are used in combination, the first color material and the second color material based on the total mass of the ink. And the preferred range of the mass ratio to the third color material (the sum of the first color material and the second color material / the third color material) is as described above. Further, when the first color material, the second color material, and the third color material are used in combination, the mass ratio between the first color material and the second color material based on the total mass of the ink (the first color material) The preferable range of (1 color material / second color material) is also as described above.

  The preferred color tone for the gray ink is as described above. In the present invention, within the range of the mass ratio of the first color material, the second color material, the third color material, and the fourth color material described above, a color tone preferable as the gray ink is provided. It is particularly preferable to prepare a gray ink. The adjustment of the color tone range that is preferable for the gray ink can be performed by appropriately determining the content of each color material within the above-described mass ratio range. In order to obtain a color tone preferable as a gray ink, it is particularly preferable to use the compound of the general formula (VII) as the fourth color material.

[Mechanism for improving metamerism of an image by using a first color material, a second color material, and a third color material added as necessary, and a fourth color material]
As described above, the ink containing the first color material, the second color material, and the third color material added as necessary further contains the fourth color material, so that the metamerism in the obtained image is obtained. The present inventors presume a mechanism for improving the following.

  In order to improve the metamerism of the image, it is important that the ink has absorption over the entire visible light region (region of 380 nm to 780 nm) and that the absorption spectrum is flat. Since each absorption spectrum of the first color material, the second color material, and the third color material used in the present invention has a relatively sharp shape, it is maximum in the wavelength region sandwiched between the maximum absorption wavelengths of the color materials. The absorption intensity is smaller than the absorption wavelength. As a result, since the absorption spectrum of the ink containing the first color material, the second color material, and the third color material has a difference in absorption intensity, it has absorption over the entire visible light region, And it is not easy to make the absorption spectrum flat.

  The fourth color material used in the present invention has absorption in a wavelength region sandwiched between the maximum absorption wavelengths of the first color material, the second color material, and the third color material. For this reason, when the ink containing the first color material, the second color material, and, if necessary, the third color material further contains the fourth color material, absorption is performed in a wide region of the visible light region. The ink has a flat absorption spectrum. Such a mechanism is considered to improve the metamerism of the image.

[Mechanism for improving light resistance of image when compound of general formula (VII) is used as fourth colorant]
An ink containing the first color material, the second color material, and, if necessary, the third color material can be obtained by further containing the compound of the general formula (VII) as the fourth color material. Since both metamerism and light resistance can be improved in an image, it is particularly preferable. The present inventors presume the mechanism of improving both metamerism and light resistance as follows.

  According to the study by the present inventors, the first color material, the second color material, the third color material used as necessary, and the compound of the general formula (VII) as the fourth color material In addition to the metamerism of the image, the light resistance is improved by the ink containing. Generally, when a recorded matter is irradiated with light, the yellow component in the recorded matter is particularly deteriorated. On the other hand, the compound of the general formula (VII) has a characteristic that its color tone changes in the yellow direction when irradiated with light. Therefore, the mechanism by which the light resistance of the image is improved by using the ink that is a combination of the above coloring materials is that the yellow component in the recorded matter deteriorated by the light irradiation is changed in the yellow direction of the compound of the general formula (VII). This is thought to be due to the change in color tone.

[Color material verification method]
The following verification methods (1) to (3) using high performance liquid chromatography (HPLC) can be applied to verify whether the color material used in the present invention is contained in the liquid (ink).
(1) Peak retention time (2) Maximum absorption wavelength for peak (1) (3) M / Z (posi), M / Z (negative) of mass spectrum for peak (1)

The analysis conditions of high performance liquid chromatography are as follows. First, a liquid (ink) diluted about 1,000 times with pure water was prepared and used as a measurement sample. Then, the sample was analyzed by high performance liquid chromatography under the following conditions, and the peak retention time and the peak maximum absorption wavelength 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 3 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, Exemplified Compound II-5 as a representative example of the second coloring material, Exemplified Compounds III-1, IV-1, and V-2 as representative examples of the third coloring material, and the fourth As representative examples of the coloring material, Exemplified Compounds VI-1 and VII-5 were measured. As a result, the obtained retention time, maximum absorption wavelength, M / Z (posi), and M / Z (negative) values are shown in Table 4. An unknown ink is measured under the same method and conditions as described above, and when the measured value corresponds to the value shown in Table 4, it contains a compound corresponding to the compound used in the present invention. It can be judged.

(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.

  Specifically, for example, the following water-soluble organic solvents can be used. 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 and 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. 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 2 to 6 carbon atoms. Bis (2-hydroxyethyl) sulfone. 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)
In addition, in order to form a full-color image, the ink of the present invention is used in combination with an ink having substantially the same color tone as the ink of the present invention or an ink having a color tone different from 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.

<Recording medium>
As the recording medium used for forming an image using the ink of the present invention, any recording medium can be used as long as the recording medium is provided with ink. In the present invention, it is preferable to use an ink jet recording medium in which a coloring material such as a dye or a pigment is adsorbed to fine particles forming the porous structure of the ink receiving layer. In particular, it is preferable to use a recording medium having a so-called gap absorption type ink receiving layer that absorbs ink by voids formed in the ink receiving layer on the support. The gap absorption type ink receiving layer is composed mainly of fine particles, and may further contain a binder and other additives as necessary.

  Specifically, the following fine particles can be used. Inorganic pigments such as aluminum oxide such as silica, clay, talc, calcium carbonate, kaolin, alumina or alumina hydrate, diatomaceous earth, titanium oxide, hydrotalcite, or zinc oxide. Organic pigments such as urea formalin resin, ethylene resin, styrene resin. These fine particles can be used alone or in combination of two or more as required.

  Examples of the binder include water-soluble polymers and latex. Specifically, the following can be used. Polyvinyl alcohol, starch, gelatin, or modified products thereof. Arabic gum. Cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, or hydroxypropylmethylcellulose. Vinyl-based copolymer latex such as SBR latex, NBR latex, methyl methacrylate-butadiene copolymer latex, functional group-modified polymer latex, or ethylene vinyl acetate copolymer. Polyvinyl pyrrolidone. Maleic anhydride or a copolymer thereof, or an acrylate copolymer. These binders can use 1 type (s) or 2 or more types as needed.

  In addition, additives can be used as necessary. For example, dispersants, thickeners, pH adjusters, lubricants, fluidity modifiers, surfactants, antifoaming agents, mold release agents, optical brighteners, ultraviolet absorbers, antioxidants, dye fixing agents, etc. Can be used.

  In particular, when an image is formed using the ink of the present invention, it is preferable to use a recording medium in which an ink receiving layer is formed mainly of fine particles having an average particle diameter of 1 μm or less. Specific examples of the fine particles include silica fine particles and aluminum oxide fine particles. A preferable silica fine particle is a silica fine particle typified by colloidal silica. Although a colloidal silica can also use a commercial item, it is preferable to use especially the colloidal silica described in patent 2803134, 2881847, for example. Further, preferable examples of the aluminum oxide fine particles include alumina hydrate fine particles (alumina pigments).

Among the alumina pigments, an alumina hydrate such as pseudoboehmite represented by the following formula can be particularly preferable.
AlO _3-n (OH) _2n · mH ₂ O
(In the formula, n is an integer of 1 to 3, and m is 0 to 10, preferably 0 to 5. However, m and n are not 0 at the same time.)

mH ₂ O often also represents a detachable aqueous phase that is not involved in the formation of the mH ₂ O crystal lattice. For this reason, m can take an integer or a non-integer value. Also, when this type of alumina hydrate is heated, m can reach zero.

  Alumina hydrate can be produced by the following known methods. For example, it can be produced by hydrolysis of aluminum alkoxide or hydrolysis of sodium aluminate described in US Pat. No. 4,242,271 and US Pat. No. 4,202,870. Moreover, it can manufacture by the method of adding aqueous solution, such as sodium sulfate and aluminum chloride, to aqueous solution, such as sodium aluminate described in Japanese Patent Publication No.57-44605.

  The recording medium preferably has a support for supporting the ink receiving layer. The support is not particularly limited as long as the ink receiving layer can be formed of the above-described porous fine particles and gives rigidity that can be transported by a transport mechanism such as an ink jet recording apparatus. Can also be used. For example, a paper support composed of a pulp raw material mainly composed of natural cellulose fibers can be used. In addition, a plastic support made of a material such as polyester (for example, polyethylene terephthalate), cellulose triacetate, polycarbonate, polyvinyl chloride, polypropylene, or polyimide can be used. Furthermore, a resin-coated paper (eg, RC paper) having a polyolefin resin coating layer added with a white pigment or the like on at least one surface of the base paper can be used.

<Inkjet recording method>
The ink of the present invention is particularly preferably used for the ink jet recording method of the present invention in which the ink is ejected by an ink jet method to perform recording on a recording medium. Ink jet recording methods include a recording method in which ink is ejected by applying mechanical energy to the ink, and a recording method in which ink is ejected by applying thermal energy to the ink. In particular, in the present invention, an ink jet recording method using thermal energy can be preferably used.

<Ink cartridge>
As an ink cartridge suitable for performing recording using the ink of the present invention, the ink cartridge of the present invention provided with an ink storage portion for storing such ink can be mentioned.

<Recording unit>
As a recording unit suitable for performing recording using the ink of the present invention, there is a recording unit of the present invention provided with an ink storage portion for storing such ink and a recording head for discharging the ink. In particular, a recording unit in which the recording head ejects ink by applying thermal energy corresponding to the recording signal to the ink can be preferably used. In particular, in the present invention, it is preferable to use a recording head having a heat generating part wetted surface containing a metal and / or a metal oxide. 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>
As an ink jet recording apparatus suitable for performing recording using the ink of the present invention, an ink jet recording apparatus of the present invention including an ink storage portion for storing such ink and a recording head for discharging the ink can be cited. It is done. In particular, there is an ink jet recording apparatus that ejects ink by applying thermal energy corresponding to a recording signal to ink inside a recording head having an ink storage portion that stores the ink.

  Below, the schematic structure of the mechanism part of an inkjet recording device is demonstrated. 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 structure 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 1200 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 .

  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 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 , a reference example, and a comparative example, this invention is not limited at all by the following Example , unless the summary is exceeded. Unless otherwise specified, “parts” and “%” in color material preparation and ink preparation are based on mass.

<Preparation of coloring material>
The compounds of general formula (I) obtained by the synthesis of the coloring materials described below are all mixtures, and unless otherwise specified, the following isomers and the like are described as “compounds”. That is, the compound is a positional isomer of a compound, a positional isomer of a nitrogen atom of a nitrogen-containing heteroaromatic ring, a ratio of benzo ring / nitrogen-containing heteroaromatic ring of A, B, C, and D of the general formula (I) As well as α / β positional isomers of substituted or unsubstituted sulfamoyl groups on the benzo ring. As mentioned above, it is extremely difficult to isolate a specific compound from a mixture of these isomers and determine the structure, so for convenience, an example of possible isomers is given as a representative example. Its structural formula is described. About the compound obtained when synthesize | combining the compound of general formula (I), the analysis by mass spectrometry, ICP emission spectroscopy, and an absorbance measurement was performed, and the synthesis | combination of each compound was confirmed.

(Mass spectrometry)
About each compound, DI-MS (direct mass) measurement was performed. The analysis conditions of DI-MS are as shown below.
-EI method-Mass spectrometer: SSQ-7000
-Ion source temperature: 230 ° C
・ Degree of vacuum: about 8mT

(ICP emission spectroscopy)
For each compound containing copper, the copper content was analyzed by ICP emission spectroscopy. Specifically, the analysis was performed as follows. About 0.1 g of an analytical sample was precisely weighed and dissolved in pure water, and then the volume was measured in a 100 mL volumetric flask. 1 ml of this liquid was weighed into a 50 ml volumetric flask using a whole pipette, a certain amount of Y (yttrium) was added as an internal standard substance, and the volume was adjusted to 50 ml with pure water, and then copper was measured by ICP emission spectroscopy. The content was quantified. The apparatus used at this time is an ICP emission spectroscopic apparatus SPS3100 (manufactured by SII Nanotechnology).

(Absorbance measurement)
Absorbance measurement was performed for each compound. Absorbance measurement conditions are shown below.
・ 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
・ Number of measurements: average of 5 measurements

Compounds 1-1 to 1-7, which are the first coloring materials used in Examples and Reference Examples , and Compound 2 used in Reference Examples were respectively synthesized as follows. Moreover, the comparative compound 1 which is the cyan dye used for the comparative example was synthesize | combined.

[Synthesis of Compound 1-1]
(1) Synthesis of compound (1)

  To 2,000 parts of ice water, 7.2 parts of ROTAT OH104-K (manufactured by Lion) and 239.9 parts of cyanuric chloride were added and stirred for 30 minutes. To this, 411.6 parts of aniline-2,5-disulfonic acid monosodium salt (purity 91.2%) was added, and while adding a 25% aqueous sodium hydroxide solution, the pH of the reaction solution was adjusted to 2.7 to 2.7. The mixture was kept at 3.0 and reacted at 10 to 15 ° C. for 1 hour and then at 27 to 30 ° C. for 2 hours. Next, after cooling the reaction liquid to 10 ° C. or lower, a 25% aqueous sodium hydroxide solution was added to adjust the pH of the reaction liquid to 7.0 to 7.5. To this, 118.4 parts of 28% aqueous ammonia was added, and the temperature was adjusted to 10 to 15 ° C. and the pH was adjusted to 9.5 to 10.0 and maintained for 3 hours. Thereafter, concentrated hydrochloric acid was added to adjust the pH of the reaction solution to 6.0 to 7.0. Next, 2,000 parts of ice was added, cooled to 0 ° C., and 780 parts of ethylenediamine was added dropwise while maintaining the temperature at 5 ° C. or lower. Thereafter, the temperature of the reaction solution was kept at 10 to 15 ° C. for 1 hour. Subsequently, concentrated hydrochloric acid was added dropwise thereto to adjust the pH of the reaction solution to 0.9 to 1.0. During this time, the temperature of the reaction solution was kept at 10 to 15 ° C. by adding ice so that the temperature did not rise. Furthermore, ice was added thereto, and the temperature of the reaction solution was cooled to 10 ° C. or lower. The liquid volume at this time was 13,000 parts. To this reaction liquid, 2,600 parts of sodium chloride (20% with respect to the liquid amount) was added and stirred for 1 hour to precipitate crystals. The precipitated crystals were collected by filtration and washed with 3,000 parts of a 20% aqueous sodium chloride solution to obtain 743.0 parts of a wet cake (purity: 59.3%, HPLC purity: 93.3%).

(2) Copper tribenzo (2,3-pyrido) porphyrazine [the following compound (2): one of A, B, C and D in the general formula (A) is a pyridine ring and the remaining three are benzene rings Of a certain mixture]

  In a four flask, 250 parts sulfolane, 22.1 parts phthalimide, 8.4 parts quinolinic acid, 72.0 parts urea, 8.8 parts copper (II) chloride dihydrate (purity 97.0%), 1.0 part of ammonium molybdate was added, and the reaction solution was heated to 200 ° C. and kept for 5 hours. After completion of the reaction, the reaction solution was cooled to 75 ° C., 200 parts of methanol was added, and the precipitated crystals were filtered. The obtained crystal was washed with 250 parts of methanol and subsequently with 500 parts of hot water to obtain 61.9 parts of a wet cake. The obtained wet cake was added to 500 parts of 5% hydrochloric acid, and the liquid was heated to 60 ° C. and kept for 1 hour. The obtained crystals were filtered and washed with 300 parts of water. Subsequently, the obtained wet cake was added to 500 parts of 10% ammonia water, and the temperature of the liquid was adjusted to 25 to 30 ° C. and maintained for 1 hour. Thereafter, the obtained crystals were filtered and washed with 300 parts of water to obtain 64.9 parts of a wet cake. The obtained wet cake was dried at 80 ° C. to obtain 20.9 parts of blue crystals. As a result of analyzing this blue crystal, the following measured values were obtained. As a result, it was confirmed that the obtained blue crystals were the compound (2) having the above structure.

Maximum absorption wavelength (λ _max ): 670.5 nm (in pyridine)
Elemental analysis results: C ₃₁ H ₁₅ N ₉ Cu

(3) Copper tribenzo (2,3-pyrido) porphyrazine trisulfonyl chloride [the following compound (3): a mixture in which one of the outermost aromatic rings of the main component in the mixture is a pyridine ring and the remaining three are benzene rings ]

  Slowly add 5.8 parts of copper tribenzo (2,3-pyrido) porphyrazine obtained in (2) above to 46.2 parts of chlorosulfonic acid while maintaining the temperature of the liquid at 60 ° C. or lower. And then reacted at 140 ° C. for 4 hours. Next, the reaction solution was cooled to 70 ° C., 17.9 parts of thionyl chloride was added dropwise over 30 minutes, and the mixture was reacted at 70 ° C. for 3 hours. The reaction solution is cooled to 30 ° C. or lower, slowly poured into 500 parts of ice water, the precipitated crystals are filtered, washed with 200 parts of cold water, and wet with copper tribenzo (2,3-pyrido) porphyrazine trisulfonyl chloride. 71.1 parts of cake were obtained.

(4) The following compound (4) [mixture containing exemplary compound I-1: one of the outermost aromatic rings of the main component in the mixture is a pyridine ring and the remaining three are benzene rings, b is 2.4, of the mixture in which c is 0.6]

To 200 parts of ice water, 71.1 parts of a wet cake of copper tribenzo (2,3-pyrido) porphyrazine trisulfonyl chloride (compound (3)) obtained in (3) above was added and suspended by stirring. I let you. Next, what melt | dissolved 20.5 parts of compounds (1) (purity: 59.3%) obtained by said (1) in 3.0 parts of aqueous ammonia and 100 parts of warm water was added. To this, the pH of the reaction solution was maintained at 9.0 to 9.3 by adding 28% ammonia water, and the reaction solution was allowed to react at a temperature of 17 to 20 ° C. for 6 hours. Thereafter, the temperature of the reaction solution was raised to 60 ° C. The liquid volume at this time was 500 parts. To this, 100 parts of sodium chloride (20% with respect to the liquid volume) was added, and 35% hydrochloric acid aqueous solution was added to adjust the pH of the liquid to 1.0 to precipitate crystals. The precipitated crystals were collected by filtration and washed with 100 parts of a 20% aqueous sodium chloride solution to obtain 47.7 parts of a wet cake. The obtained wet cake was dissolved again in water to adjust the pH of the liquid to 9.0, then the total amount was adjusted to 300 parts, and the temperature of the liquid was raised to 60 ° C. The liquid volume at this time was 320 parts. To this, 48 parts of sodium chloride (15% with respect to the liquid amount) was added, and a 35% hydrochloric acid aqueous solution was added to adjust the pH of the liquid to 1.0 to precipitate crystals. The precipitated crystals were separated by filtration and washed with 100 parts of a 15% aqueous sodium chloride solution to obtain 47.8 parts of a wet cake. 47.8 parts of the obtained wet cake was added to 250 parts of methanol and suspended by stirring at 60 ° C. for 1 hour, followed by filtration, washing with 100 parts of methanol, and drying to obtain blue crystals (compound (4)). ) Was obtained 10.7 parts. As a result of analyzing the blue crystal, the maximum absorption wavelength (λ _max ) was 611 nm (in an aqueous solution). The obtained compound (4) was ion-exchanged by a conventional method to obtain a sodium salt type compound 1-1.

[Synthesis of Compound 1-2]
(1) Copper dibenzobis (2,3-pyrido) porphyrazine [the following compound (5): two of A, B, C and D in the general formula (A) are pyridine rings and the remaining two are benzene rings Of a certain mixture]

  In a four flask, 250 parts sulfolane, 14.7 parts phthalimide, 16.7 parts quinolinic acid, 72.0 parts urea, 8.8 parts copper (II) chloride dihydrate (purity 97.0%), 1.0 part of ammonium molybdate was added, and the reaction solution was heated to 200 ° C. and kept for 5 hours. After completion of the reaction, the reaction solution was cooled to 85 ° C., 200 parts of methanol was added, and the precipitated crystals were filtered. The obtained crystals were washed with 200 parts of methanol and subsequently with 500 parts of hot water and then dried to obtain 24.1 parts of crude copper dibenzobis (2,3-pyrido) porphyrazine (mixture) as blue crystals. 24.1 parts of the obtained crude copper dibenzobis (2,3-pyrido) porphyrazine (mixture) was added to 500 parts of 5% hydrochloric acid, and this liquid was heated to 60 ° C. and kept for 1 hour. Thereafter, the crystals were filtered and washed with 100 parts of water to obtain a wet cake. Next, the obtained wet cake was added to 500 parts of 10% ammonia water, and the temperature of the liquid was adjusted to 25 to 30 ° C. and maintained for 1 hour. The obtained crystals were filtered and washed with 200 parts of water to obtain 44.4 parts of a wet cake. The obtained wet cake was dried at 80 ° C. to obtain 17.7 parts of copper dibenzobis (2,3-pyrido) porphyrazine (mixture) as blue crystals. As a result of analyzing this blue crystal, the following measured values were obtained. As a result, it was confirmed that the obtained blue crystals were the compound (5) having the above structure.

Maximum absorption wavelength (λ _max ): 662.5 nm (in pyridine)
Elemental analysis: C ₃₀ H ₁₄ N ₁₀ Cu

(2) Copper dibenzobis (2,3-pyrido) porphyrazine disulfonyl chloride [the following compound (6): two of the outermost aromatic rings of the main components in the mixture are pyridine rings and the remaining two are benzene rings Of mixture]

  To 46.2 parts of chlorosulfonic acid, 5.8 parts of copper dibenzobis (2,3-pyrido) porphyrazine obtained in (1) above was gradually added with stirring while maintaining the liquid temperature at 60 ° C. or lower. And then reacted at 140 ° C. for 4 hours. Next, the reaction solution was cooled to 70 ° C., 17.9 parts of thionyl chloride was added dropwise over 30 minutes, and the mixture was reacted at 70 ° C. for 3 hours. The reaction solution is cooled to 30 ° C. or lower, slowly poured into 500 parts of ice water, the precipitated crystals are filtered, washed with 200 parts of cold water, and wet with copper dibenzobis (2,3-pyrido) porphyrazine disulfonyl chloride. 46.0 parts of cake were obtained.

(3) The following compound (7) [mixture containing exemplary compounds I-2 and I-3: two of the outermost aromatic rings of the main components in the mixture are pyridine rings and the remaining two are benzene rings, and b is Of 1.6, a mixture in which c is 0.4]

To 250 parts of ice water, 46.0 parts of a wet cake of copper dibenzobis (2,3-pyrido) porphyrazine disulfonyl chloride (compound (6)) obtained in (2) above was added and suspended by stirring. I let you. Next, a solution obtained by dissolving 20.5 parts of the compound (1) (purity: 59.3%) obtained in the synthesis of the compound 1-1 was added to 4.0 parts of ammonia water and 100 parts of warm water. did. To this, the pH of the reaction solution was maintained at 9.0 to 9.3 by adding 28% aqueous ammonia, and the reaction solution was reacted at a temperature of 17 to 20 ° C. for 4 hours. Thereafter, the temperature of the reaction solution was raised to 60 ° C. The liquid volume at this time was 480 parts. To this, 48 parts of sodium chloride (10% with respect to the liquid amount) was added, 35% aqueous hydrochloric acid was added to adjust the pH of the liquid to 1.0, and crystals were precipitated. The precipitated crystals were collected by filtration and washed with 100 parts of a 15% aqueous sodium chloride solution to obtain 86.1 parts of a wet cake. The obtained wet cake was dissolved again in water to adjust the pH of the liquid to 9.0, then the total amount was adjusted to 400 parts, and the temperature of the liquid was raised to 60 ° C. The liquid volume at this time was 410 parts. To this, 41 parts of sodium chloride (10% with respect to the liquid amount) was added, 35% aqueous hydrochloric acid was added to adjust the pH of the liquid to 1.0, and crystals were precipitated. The precipitated crystals were separated by filtration and washed with 100 parts of a 10% aqueous sodium chloride solution to obtain 65.7 parts of a wet cake. 65.7 parts of the obtained wet cake was added to 330 parts of methanol and suspended by stirring at 60 ° C. for 1 hour, followed by filtration, washing with 100 parts of methanol, and drying to obtain blue crystals (compound (7)). 9.3 parts) was obtained. As a result of analyzing this blue crystal, the maximum absorption wavelength (λ _max ) was 602 nm (in an aqueous solution). The obtained compound (7) was ion-exchanged by a conventional method to obtain a sodium salt type compound 1-2.

[Synthesis of Compound 1-3]
(1) Copper benzotris (2,3-pyrido) porphyrazine [the following compound (8): three of A, B, C and D in the general formula (A) are pyridine rings and the remaining one is a benzene ring Of a certain mixture]

  In a four-flask flask, sulfolane 250 parts, phthalimide 7.4 parts, quinolinic acid 25.1 parts, urea 72.0 parts, copper chloride (II) dihydrate (purity 97.0%) 8.8 parts, 1.0 part of ammonium molybdate was added, and the temperature of the reaction solution was raised to 200 ° C. and kept for 5 hours. After completion of the reaction, the reaction solution was cooled to 70 ° C., 200 parts of methanol was added, and the precipitated crystals were filtered. The obtained crystals were washed with 200 parts of methanol and subsequently with 500 parts of hot water and then dried to obtain 20.5 parts of crude copper benzotris (2,3-pyrido) porphyrazine (mixture) as blue crystals. 14.5 parts of the obtained crude copper benzotris (2,3-pyrido) porphyrazine (mixture) was added to 500 parts of 5% hydrochloric acid, and this liquid was heated to 60 ° C. and kept for 1 hour. Thereafter, the crystals were filtered and washed with 100 parts of water to obtain a wet cake. Next, the obtained wet cake was added to 500 parts of 10% ammonia water, and the temperature of the liquid was adjusted to 25 to 30 ° C. and maintained for 1 hour. The obtained crystals were filtered and washed with 100 parts of water to obtain 23.5 parts of a wet cake. The obtained wet cake was dried at 80 ° C. to obtain 9.7 parts of copper benzotris (2,3-pyrido) porphyrazine (mixture) as blue crystals. As a result of analyzing this blue crystal, the following measured values were obtained. As a result, it was confirmed that the obtained blue crystals were the compound (8) having the above structure.

λ _max : 655 nm (in pyridine)
Elemental analysis: C ₂₉ H ₁₃ N ₁₁ Cu

(2) Copper benzotris (2,3-pyrido) porphyrazinesulfonyl chloride (the following compound (9): a mixture in which three of the outermost aromatic rings of the main component in the mixture are pyridine rings and the remaining one is a benzene ring) Synthesis of

  In 46.2 parts of chlorosulfonic acid, 5.8 parts of the copper benzotris (2,3-pyrido) porphyrazine obtained in (1) above was gradually stirred while maintaining the temperature of the liquid at 60 ° C. or lower. Then, the mixture was reacted at 140 ° C. for 4 hours. Next, the reaction solution was cooled to 70 ° C., 17.9 parts of thionyl chloride was added dropwise over 30 minutes, and the mixture was reacted at 70 ° C. for 3 hours. The reaction solution is cooled to 30 ° C. or lower, slowly poured into 500 parts of ice water, the precipitated crystals are filtered, washed with 200 parts of cold water, and a wet cake of copper benzotris (2,3-pyrido) porphyrazine sulfonyl chloride. 33.0 parts were obtained.

(3) The following compound (10) [a mixture in which three of the outermost aromatic rings of the main component in the mixture are pyridine rings and the remaining one is a benzene ring, b is 0.9, and c is 0.1] Synthesis of

Add 33.0 parts of a wet cake of copper benzotris (2,3-pyrido) porphyrazinesulfonyl chloride (compound (9)) obtained in (2) above to 250 parts of ice water, and stir to suspend. It was. Next, a solution obtained by dissolving 20.5 parts of the compound (1) (purity: 59.3%) obtained in the synthesis of the compound 1-1 in 4.0 parts of ammonia water and 90 parts of warm water was added. did. To this, the pH of the reaction solution was maintained at 9.0 to 9.3 by adding 28% aqueous ammonia, and the reaction solution was reacted at a temperature of 17 to 20 ° C. for 3 hours. Thereafter, the temperature of the reaction solution was raised to 60 ° C. The liquid volume at this time was 450 parts. To this, 67.5 parts of sodium chloride (15% with respect to the liquid amount) was added, and 35% aqueous hydrochloric acid solution was added to adjust the pH of the liquid to 1.0 to precipitate crystals. The precipitated crystals were collected by filtration and washed with 100 parts of a 15% aqueous sodium chloride solution to obtain 42.6 parts of a wet cake. The obtained wet cake was dissolved again in water to adjust the pH of the liquid to 9.0, then the total amount was adjusted to 300 parts, and the temperature of the liquid was raised to 60 ° C. The liquid volume at this time was 310 parts. To this, 31 parts of sodium chloride (10% with respect to the liquid amount) was added, and a 35% aqueous hydrochloric acid solution was added to adjust the pH of the liquid to 1.0 to precipitate crystals. The precipitated crystals were separated by filtration and washed with 100 parts of a 10% aqueous sodium chloride solution to obtain 42.8 parts of a wet cake. 42.8 parts of the obtained wet cake was added to 220 parts of methanol and suspended by stirring at 60 ° C. for 1 hour, followed by filtration, washing with 100 parts of methanol, and drying to obtain blue crystals (compound (10)). ) Was obtained. As a result of analyzing this blue crystal, the maximum absorption wavelength (λ _max ) was 584 nm (in an aqueous solution). The obtained compound (10) was ion-exchanged by a conventional method to obtain a sodium salt type compound 1-3.

[Synthesis of Compound 1-4]
(1) Sodium copper tribenzo (2,3-pyrido) porphyrazine trisulfonate [the following compound (11): one of the outermost aromatic rings of the main component in the mixture is a pyridine ring and the remaining three are benzene rings Of sodium salt of mixture]

To a four-flask, 250 parts of sulfolane, 4-sulfophthalic acid (50% aqueous solution, manufactured by Pilot Chemical, containing 20% 3-sulfophthalic acid) 73.8 parts, 28% ammonia water 27.3 parts are added, and water is added. While distilling off, the temperature of the reaction solution was raised to 160 ° C. After completion of the reaction, the reaction solution was cooled to 100 ° C., 8.4 parts of quinolinic acid, 72.0 parts of urea, 8.8 parts of copper (II) chloride dihydrate (purity 97.0%), molybdic acid 1.0 part of ammonium was added, and the reaction solution was heated to 200 ° C. and kept for 5 hours. After completion of the reaction, the reaction solution was cooled to 90 ° C., 200 parts of methanol was added, and the precipitated crystals were filtered. The obtained crystal was washed with 750 parts of methanol to obtain a wet cake. The obtained wet cake was added to a liquid in which 900 parts of 28.6% saline and 100 parts of concentrated hydrochloric acid were mixed, and the liquid was heated to 60 ° C. and kept for 1 hour. The obtained crystals were filtered and then washed with a liquid in which 225 parts of 28.6% saline and 25 parts of concentrated hydrochloric acid were mixed. Next, the obtained wet cake is added to 500 parts of methanol, and further 50 parts of 28% ammonia water is added. The liquid is heated to 60 ° C. and kept for 1 hour, and the crystals are filtered and washed with 200 parts of methanol. To obtain 78.1 parts of a wet cake. The obtained wet cake is added to 500 parts of methanol, then 30 parts of 25% aqueous sodium hydroxide solution is added, the liquid is heated to 60 ° C. and kept for 1 hour, the crystals are filtered and washed with 200 parts of methanol. , 72.6 parts of a wet cake was obtained. The obtained wet cake was dried at 80 ° C. to obtain 32.4 parts of copper tribenzo (2,3-pyrido) porphyrazine sodium trisulfonate as blue crystals. As a result of analyzing this blue crystal, the maximum absorption wavelength (λ _max ) was 625 nm (in an aqueous solution). As a result, it was confirmed that the obtained blue crystals were the compound (11) having the above structure.

(2) Copper tribenzo (2,3-pyrido) porphyrazine trisulfonyl chloride [the following compound (12): a mixture in which one of the outermost aromatic rings of the main component in the mixture is a pyridine ring and the remaining three are benzene rings ]

  In 70.6 parts of chlorosulfonic acid, while maintaining the temperature of the liquid at 60 ° C. or lower, 8.8 parts of copper tribenzo (2,3-pyrido) porphyrazine sodium trisulfonate obtained in (1) above was stirred. Was gradually added, and then reacted at 120 ° C. for 4 hours. Next, the reaction solution was cooled to 70 ° C., 17.9 parts of thionyl chloride was added dropwise over 30 minutes, and the mixture was reacted at 70 ° C. for 3 hours. The reaction solution is cooled to 30 ° C. or lower, slowly poured into 500 parts of ice water, the precipitated crystals are filtered, washed with 100 parts of cold water, and copper tribenzo (2,3-pyrido) porphyrazine trisulfonyl chloride (mixture). ) 61.2 parts of a wet cake.

(3) The following compound (13) [mixture containing exemplary compound I-1: one of the outermost aromatic rings of the main component in the mixture is a pyridine ring and the remaining three are benzene rings, b is 2, and c is Of a mixture of 1]

To 250 parts of ice water, 61.2 parts of a wet cake of copper tribenzo (2,3-pyrido) porphyrazine trisulfonyl chloride (compound (12)) obtained in (2) above was added, and the mixture was stirred and suspended. Made cloudy. Next, a solution obtained by dissolving 20.5 parts of the compound (1) (purity: 59.3%) obtained in the synthesis of the compound 1-1 was added to 3.0 parts of ammonia water and 90 parts of warm water. did. To this, the pH of the reaction solution was maintained at 9.0 to 9.3 by adding 28% aqueous ammonia, and the reaction solution was reacted at a temperature of 17 to 20 ° C. for 4 hours. Thereafter, the temperature of the reaction solution was raised to 60 ° C. The liquid volume at this time was 500 parts. To this, 100 parts of sodium chloride (20% with respect to the liquid volume) was added, and 35% hydrochloric acid aqueous solution was added to adjust the pH of the liquid to 1.0 to precipitate crystals. The precipitated crystals were collected by filtration and washed with 100 parts of a 20% aqueous sodium chloride solution to obtain 37.0 parts of a wet cake. The obtained wet cake was dissolved again in water to adjust the pH of the liquid to 9.0, then the total amount was adjusted to 400 parts, and the temperature of the liquid was raised to 60 ° C. The liquid volume at this time was 400 parts. To this, 80 parts of sodium chloride (20% with respect to the liquid amount) was added, and 35% hydrochloric acid aqueous solution was added to adjust the pH of the liquid to 1.0 to precipitate crystals. The precipitated crystals were separated by filtration and washed with 100 parts of a 20% aqueous sodium chloride solution to obtain 39.2 parts of a wet cake. 39.2 parts of the obtained wet cake was added to 200 parts of methanol and suspended by stirring at 60 ° C. for 1 hour, followed by filtration, washing with 200 parts of methanol, and drying to obtain blue crystals (compound (13)). 9.8 parts) were obtained. As a result of analyzing this blue crystal, the maximum absorption wavelength (λ _max ) was 614 nm (in an aqueous solution). The obtained compound (13) was ion-exchanged by a conventional method to obtain a sodium salt type compound 1-4.

[Synthesis of Compound 1-5]
(1) Copper dibenzobis (2,3-pyrido) porphyrazine disulfonate sodium [the following compound (14): a mixture in which two of the outermost aromatic rings of the main component in the mixture are pyridine rings and the remaining two are benzene rings Of sodium salt]

To a four-flask, add 250 parts of sulfolane, 49.2 parts of 4-sulfophthalic acid (50% aqueous solution, manufactured by Pilot Chemical, containing 20% of 3-sulfophthalic acid), 18.2 parts of 28% aqueous ammonia, and add water. While distilling off, the temperature of the reaction solution was raised to 160 ° C. After completion of the reaction, the reaction solution was cooled to 110 ° C., 16.7 parts of quinolinic acid, 72.0 parts of urea, 8.8 parts of copper (II) chloride dihydrate (purity 97.0%), molybdic acid 1.0 part of ammonium was added, and the reaction solution was heated to 200 ° C. and kept for 5 hours. After completion of the reaction, the reaction solution was cooled to 70 ° C., 100 parts of methanol was added, and the precipitated crystals were filtered. The obtained crystals were washed with 150 parts of methanol and then dried to obtain 36.9 parts of blue crystals. The obtained blue crystals were added to a liquid obtained by mixing 1,000 parts of 20% saline and 10 parts of concentrated hydrochloric acid, and the liquid was heated to 60 ° C. and kept for 1 hour. Thereafter, a 25% aqueous sodium hydroxide solution was added to adjust the pH of the liquid to 7 to 8, and the precipitated crystals were collected by filtration to obtain a wet cake. The obtained wet cake was added to 1,000 parts of water, the temperature of the liquid was kept at 60 ° C. for 1 hour, and 600 parts of methanol was added to precipitate crystals. The obtained crystals were filtered and washed with 100 parts of methanol to obtain 110.7 parts of a wet cake. The obtained wet cake was dried at 80 ° C. to obtain 28.9 parts of copper dibenzobis (2,3-pyrido) porphyrazine sodium disulfonate as blue crystals. As a result of analyzing this blue crystal, the maximum absorption wavelength (λ _max ) was 607.5 nm (in an aqueous solution). As a result, it was confirmed that the obtained blue crystals were the compound (14) having the above structure.

(2) Copper dibenzobis (2,3-pyrido) porphyrazine disulfonyl chloride [the following compound (15): a mixture in which two of the outermost aromatic rings of the main component in the mixture are pyridine rings and the remaining two are benzene rings ]

  To 62.6 parts of chlorosulfonic acid, while maintaining the temperature of the liquid at 60 ° C. or lower, 7.8 parts of sodium copper dibenzobis (2,3-pyrido) porphyrazine disulfonate obtained in (1) above was stirred. The mixture was gradually added and then reacted at 120 ° C. for 4 hours. Next, the reaction solution was cooled to 70 ° C., 17.9 parts of thionyl chloride was added dropwise over 30 minutes, and the mixture was reacted at 70 ° C. for 3 hours. The reaction solution is cooled to 30 ° C. or lower, slowly poured into 500 parts of ice water, the precipitated crystals are filtered, washed with 200 parts of cold water, and copper dibenzobis (2,3-pyrido) porphyrazine disulfonyl chloride (mixture). ) 44.3 parts of a wet cake was obtained.

(3) The following compound (16) [mixture containing exemplary compounds I-2 and I-3: two of the outermost aromatic rings of the main components in the mixture are pyridine rings and the remaining two are benzene rings, and b is 1.7, a mixture in which c is 0.3]

44.3 parts of a wet cake of copper dibenzobis (2,3-pyrido) porphyrazine disulfonyl chloride (compound (15)) obtained in (2) above was added to 250 parts of ice water, and the mixture was stirred and suspended. Made cloudy. Next, a solution obtained by dissolving 25.3 parts of the compound (1) (purity: 59.3%) obtained in the synthesis of the compound 1-1 was added to 5.0 parts of ammonia water and 100 parts of warm water. did. To this, the pH of the reaction solution was maintained at 9.0 to 9.3 by adding 28% aqueous ammonia, and the reaction solution was allowed to react at 17 to 20 ° C. for 3 hours. Thereafter, the temperature of the reaction solution was raised to 60 ° C. The liquid volume at this time was 520 parts. To this, 104 parts of sodium chloride (20% with respect to the liquid amount) was added, and a 35% hydrochloric acid aqueous solution was added to adjust the pH of the liquid to 1.0 to precipitate crystals. The precipitated crystals were collected by filtration and washed with 100 parts of a 20% aqueous sodium chloride solution to obtain 27.6 parts of a wet cake. The obtained wet cake was dissolved again in water to adjust the pH of the liquid to 9.0, then the total amount was adjusted to 300 parts, and the temperature of the liquid was raised to 60 ° C. The liquid volume at this time was 310 parts. To this, 62 parts of sodium chloride (20% with respect to the liquid amount) was added, and a 35% hydrochloric acid aqueous solution was added to adjust the pH of the liquid to 1.0 to precipitate crystals. The precipitated crystals were separated by filtration and washed with 100 parts of a 20% aqueous sodium chloride solution to obtain 32.0 parts of a wet cake. 32.0 parts of the obtained wet cake was added to 160 parts of methanol, suspended by stirring at 60 ° C. for 1 hour, filtered, washed with 100 parts of methanol and dried to obtain blue crystals (compound (16)). 7.6 parts) was obtained. As a result of analyzing this blue crystal, the maximum absorption wavelength (λ _max ) was 609 nm (in an aqueous solution). The obtained compound (16) was ion-exchanged by a conventional method to obtain a sodium salt type compound 1-5.

[Synthesis of Compound 1-6]
(1) Copper dibenzobis (2,3-pyrazino) porphyrazine disulfonate sodium [the following compound (17): a mixture in which two of the outermost aromatic rings of the main component in the mixture are pyrazine rings and the remaining two are benzene rings Of sodium salt]

To a four-flask, add 250 parts of sulfolane, 49.2 parts of 4-sulfophthalic acid (50% aqueous solution, manufactured by Pilot Chemical, containing 20% of 3-sulfophthalic acid), 18.2 parts of 28% aqueous ammonia, and add water. While distilling off, the temperature of the reaction solution was raised to 160 ° C. After completion of the reaction, the reaction solution was cooled to 100 ° C., and 16.8 parts of pyrazinedicarboxylic acid, 72.0 parts of urea, 8.8 parts of copper (II) chloride dihydrate (purity 97.0%), molybdenum 1.0 part of ammonium acid was added, and the reaction solution was heated to 200 ° C. and kept for 5 hours. After completion of the reaction, the reaction solution was cooled to 70 ° C., 200 parts of methanol was added, and the resulting crystals were filtered. The obtained crystals were washed with 400 parts of methanol to obtain 55.0 parts of a wet cake. The obtained wet cake was added to a liquid in which 900 parts of 28.6% saline and 100 parts of concentrated hydrochloric acid were mixed, and the liquid was heated to 60 ° C. and kept for 1 hour. The obtained crystals were filtered and then washed with a liquid in which 225 parts of 28.6% saline and 25 parts of concentrated hydrochloric acid were mixed. Next, the obtained wet cake is added to 500 parts of methanol, and further 50 parts of 28% ammonia water is added. The liquid is heated to 60 ° C. and kept for 1 hour, and the crystals are filtered and washed with 200 parts of methanol. , 34.8 parts of a wet cake was obtained. The obtained wet cake is added to 500 parts of methanol, then 30 parts of 25% aqueous sodium hydroxide solution is added, the liquid is heated to 60 ° C. and kept for 1 hour, the crystals are filtered and washed with 200 parts of methanol. 31.5 parts of a wet cake was obtained. The obtained wet cake was dried at 80 ° C. to obtain 22.2 parts of copper dibenzobis (2,3-pyrazino) porphyrazine sodium disulfonate (mixture) as blue crystals. As a result of analyzing this blue crystal, the maximum absorption wavelength (λ _max ) was 610.5 nm (in an aqueous solution). As a result, it was confirmed that the obtained blue crystals were the compound (17) having the above structure.

(2) Copper dibenzobis (2,3-pyrazino) porphyrazine disulfonyl chloride [the following compound (18): a mixture in which two of the outermost aromatic rings of the main component in the mixture are pyrazine rings and the remaining two are benzene rings ]

  While maintaining the temperature of the liquid at 62.7 parts of chlorosulfonic acid, 7.8 parts of sodium copper dibenzobis (2,3-pyrazino) porphyrazine disulfonate obtained in (2) above was stirred. The mixture was gradually added and then reacted at 120 ° C. for 4 hours. Next, the reaction solution was cooled to 70 ° C., 17.9 parts of thionyl chloride was added dropwise over 30 minutes, and the mixture was reacted at 70 ° C. for 3 hours. The reaction solution is cooled to 30 ° C. or lower, slowly poured into 500 parts of ice water, the precipitated crystals are filtered, washed with 200 parts of cold water, and copper dibenzobis (2,3-pyrazino) porphyrazine disulfonyl chloride (mixture) ) 44.1 parts of a wet cake.

(3) The following compound (19) [mixture containing exemplary compounds I-11 and I-12: two of the outermost aromatic rings of the main components in the mixture are pyrazine rings and the remaining two are benzene rings, and b is 1.2, a mixture in which C is 0.8]

To 200 parts of ice water, 44.1 parts of a wet cake of copper dibenzobis (2,3-pyrazino) porphyrazine disulfonyl chloride (compound (18)) obtained in (2) above was added, and the mixture was stirred and suspended. Made cloudy. Next, a solution obtained by dissolving 20.5 parts of the compound (1) (purity: 59.3%) obtained in the synthesis of the compound 1-1 was added to 3.0 parts of ammonia water and 100 parts of warm water. did. To this, the pH of the reaction solution was maintained at 9.0 to 9.3 by adding 28% aqueous ammonia, and the reaction solution was reacted at a temperature of 17 to 20 ° C. for 2 hours. Thereafter, the temperature of the reaction solution was raised to 60 ° C. The liquid volume at this time was 450 parts. To this, 90 parts of sodium chloride (20% with respect to the liquid amount) was added, and 35% aqueous hydrochloric acid was added to adjust the pH of the liquid to 1.0, thereby precipitating crystals. The precipitated crystals were collected by filtration and washed with 100 parts of a 20% aqueous sodium chloride solution to obtain 31.7 parts of a wet cake. The obtained wet cake was dissolved again in water to adjust the pH of the liquid to 9.0, then the total amount was adjusted to 300 parts, and the temperature of the liquid was raised to 60 ° C. The liquid volume at this time was 320 parts. To this, 64 parts of sodium chloride (20% with respect to the liquid amount) was added, and a 35% hydrochloric acid aqueous solution was added to adjust the pH of the liquid to 1.0 to precipitate crystals. The precipitated crystals were separated by filtration and washed with 100 parts of a 20% aqueous sodium chloride solution to obtain 38.1 parts of a wet cake. 38.1 parts of the obtained wet cake was added to 210 parts of methanol and suspended by stirring at 60 ° C. for 1 hour, followed by filtration, washing with 200 parts of methanol, and drying to obtain blue crystals (compound (19)). 8.8 parts) was obtained. As a result of analyzing this blue crystal, the maximum absorption wavelength (λ _max ) was 614.5 nm (in an aqueous solution). The obtained compound (19) was ion-exchanged by a conventional method to obtain a sodium salt type compound 1-6.

[Synthesis of Compound 1-7]
(1) A mixture of copper tribenzo (2,3-pyrido) porphyrazine and copper dibenzobis (2,3-pyrido) porphyrazine (the pyridine ring and benzene among A, B, C and D in the general formula (A)) Synthesis of a mixture having an average ring ratio of 1.5: 2.5) In a four-flask flask, 250 parts of sulfolane, 18.4 parts of phthalimide, 12.5 parts of quinolinic acid, 72.0 parts of urea, chloride Copper (II) dihydrate (purity 97.0%) 8.8 parts and ammonium molybdate 1.0 part were added, and the reaction solution was heated to 200 ° C. and kept for 5 hours. After completion of the reaction, the reaction solution was cooled to 65 ° C., 200 parts of methanol was added, and the precipitated crystals were filtered. The obtained crystal was washed with 150 parts of methanol and subsequently with 200 parts of warm water and dried to obtain 72.2 parts of a wet cake. The obtained wet cake was added to 500 parts of 5% hydrochloric acid, and the liquid was heated to 60 ° C. and kept for 1 hour. The obtained crystals were filtered and washed with 200 parts of water. Next, the obtained wet cake was added to 500 parts of 10% aqueous ammonia, and the temperature of the liquid was set to 60 ° C. and maintained for 1 hour. Thereafter, the obtained crystals were filtered and then washed with 300 parts of water and subsequently with 100 parts of methanol to obtain 33.6 parts of a wet cake. The obtained wet cake was dried at 80 ° C. to obtain 19.8 parts of a mixture of copper tribenzo (2,3-pyrido) porphyrazine and copper dibenzobis (2,3-pyrido) porphyrazine as blue crystals. As a result of analysis of this blue crystal, the maximum absorption wavelength (λ _max ) was 663.5 nm (in pyridine).

(2) Mixture of copper tribenzo (2,3-pyrido) porphyrazine trisulfonyl chloride and copper dibenzobis (2,3-pyrido) porphyrazine disulfonyl chloride [mixture containing the above compound (3) and compound (5): Synthesis of a mixture of A, B, C, and D in the general formula (B) in which the ratio of the pyridine ring to the benzene ring is 1.5: 2.5 and x is 2.5 on average The copper tribenzo (2,3-pyrido) porphyrazine and the copper dibenzobis (2,3-pyrido) porphyl obtained in the above (1) were kept in 46.2 parts of chlorosulfonic acid at a liquid temperature of 60 ° C. or lower. 5.8 parts of a mixture of azines were added slowly with stirring. Then, it was made to react at 140 degreeC for 4 hours. Next, the reaction solution was cooled to 70 ° C., 17.9 parts of thionyl chloride was added dropwise over 30 minutes, and the mixture was reacted at 70 ° C. for 3 hours. The reaction solution was cooled to 30 ° C. or lower, slowly poured into 500 parts of ice water, and the precipitated crystals were filtered and washed with 200 parts of cold water. In this manner, 59.3 parts of a wet cake of a mixture of copper tribenzo (2,3-pyrido) porphyrazine trisulfonyl chloride and copper dibenzobis (2,3-pyrido) porphyrazine disulfonyl chloride was obtained.

(3) A mixture of the above compound (4) and compound (16) [mixture containing exemplary compounds I-2, I-3, and I-4: A, B, C, and D in the general formula (I) The ratio of the pyridine ring to the benzene ring is 1.5: 2.5 on average, E is ethylene, X is a 2,5-disulfoanilino group, Y is an amino group, l is 0, and m is 1. 7. Mixture in which n is 0.8] In 350 parts of ice water, 59.3 parts of a wet cake of copper benzo (2,3-pyrido) porphyrazine sulfonyl chloride obtained in (2) above was added. And suspended by stirring. Next, a solution obtained by dissolving 20.5 parts of the compound (1) (purity: 59.3%) obtained in the synthesis of the compound 1-1 was added to 3.0 parts of ammonia water and 100 parts of warm water. did. To this, the pH of the reaction solution was maintained at 9.0 to 9.3 by adding 28% aqueous ammonia, and the reaction solution was reacted at a temperature of 17 to 20 ° C. for 4 hours. Thereafter, the temperature of the reaction solution was raised to 60 ° C. The liquid volume at this time was 560 parts. To this, 112 parts of sodium chloride (20% with respect to the liquid amount) was added, and a 35% hydrochloric acid aqueous solution was added to adjust the pH of the liquid to 1.0 to precipitate crystals. The precipitated crystals were collected by filtration and washed with 100 parts of a 20% aqueous sodium chloride solution to obtain 73.6 parts of a wet cake. The obtained wet cake was dissolved again in water to adjust the pH of the liquid to 9.0, then the total amount was adjusted to 360 parts, and the temperature of the liquid was raised to 60 ° C. The liquid volume at this time was 380 parts. To this, 76 parts of sodium chloride (20% with respect to the liquid amount) was added, and a 35% hydrochloric acid aqueous solution was added to adjust the pH of the liquid to 1.0 to precipitate crystals. The precipitated crystals were separated by filtration and washed with 100 parts of a 20% aqueous sodium chloride solution to obtain 48.4 parts of a wet cake. 48.4 parts of the obtained wet cake was added to 250 parts of methanol, and the mixture was stirred and suspended at 60 ° C. for 1 hour, followed by filtration, washing with 200 parts of methanol, and drying to obtain 10.7 parts of blue crystals. Obtained. As a result of analyzing this blue crystal, the maximum absorption wavelength (λ _max ) was 606 nm (in an aqueous solution). The obtained blue crystals were ion-exchanged by a conventional method to obtain sodium salt type compound 1-7.

[Compound 2]
As the compound 2, the sodium salt of the exemplified compound I-25 synthesized with reference to JP-A-2006-45535 was used.

[Comparative Compound 1]
As the following comparative compound 1, which is a comparative compound of the first coloring material, the following cyan dye synthesized with reference to Japanese Patent No. 3851569 was used.

Compound 3 as the second colorant used in Examples and Reference Examples was synthesized as follows.

[Compound 3]
Compound 3 (the potassium salt of Exemplified Compound II-5) was synthesized according to the following synthesis flow and procedure. Details of each flow will be described.

(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 filtered off 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 Compound 3 145.56 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 (manufactured by ALDRICH). Was dripped. 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 compound 3. 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. Thus, 35.0 g of compound 3 (potassium salt of Exemplified Compound II-5) was obtained.

(Comparative Compound 2)
Comparative compound 2 was used as a comparative compound for the second coloring material. The comparative compound 2 is a commercially available yellow dye (Y104; manufactured by Ilford Imaging) having the following structure.

Compound 4 which is the third coloring material used in the examples was synthesized by the following procedures (A) to (G). Compound 4 was obtained as the sodium salt of Exemplified Compound III-1. Further, compounds 5 and 6 as the third coloring material used in Examples and Reference Examples were synthesized by the method described later. Compound 5 was synthesized as the sodium salt of Exemplified Compound IV-1, and Compound 6 was synthesized as the lithium salt of Exemplified Compound V-2. Further, Comparative Compounds 3 and 4 which are magenta dyes used in Comparative Examples were synthesized by the method described later.

[Compound 4]
(A) In 360 parts of xylene, 94.8 parts of the compound of the following formula (1), 3.0 parts of sodium carbonate, and 144.0 parts of benzoylacetic acid ethyl ester are sequentially added with stirring, and the temperature of the liquid is adjusted to 140 to The temperature was raised to 150 ° C. and reacted for 8 hours. Meanwhile, ethanol and water produced by the reaction were distilled out of the system while azeotroping with xylene to complete the reaction. The reaction solution was cooled to 30 ° C., 240 parts of methanol was added, and the mixture was stirred for 30 minutes. Thereafter, the precipitated solid was collected by filtration. The obtained solid was washed with 360 parts of methanol and then dried to obtain 124.8 parts of a compound of the following formula (2) as pale yellow needle-like crystals.

  (B) In 300.0 parts of N, N-dimethylformamide, 88.8 parts of the compound of the formula (2) obtained above, 75.0 parts of metaaminoacetanilide, 24.0 parts of copper acetate monohydrate , And 12.8 parts of sodium carbonate were added sequentially with stirring. And the temperature of the liquid was raised to 120-130 degreeC, and was made to react for 3 hours. The reaction solution was cooled to about 50 ° C., 120 parts of methanol was added, and the mixture was stirred for 30 minutes. Thereafter, the precipitated solid was collected by filtration. The obtained solid was washed with 500 parts of methanol and then with warm water of 80 ° C. and then dried to obtain 79.2 parts of a compound of the following formula (3) as bluish red crystals.

  (C) To 130 parts of 98% sulfuric acid, 170 parts of 28% fuming sulfuric acid was added with stirring under water to prepare 300 parts of 12% fuming sulfuric acid. While cooling with water, 51.3 parts of the compound of the formula (3) obtained above was added at a temperature of 50 ° C. or lower, and then the temperature of the liquid was raised to 85 to 90 ° C. and reacted for 4 hours. The reaction solution was added to 600 parts of ice water, and while the ice was added, the rise in the solution temperature due to heat generation was suppressed, and the solution temperature was kept at 40 ° C. or lower. Further, water was added to bring the amount of the reaction solution to 1,000 parts, followed by filtration to remove undissolved substances. Warm water was added to the obtained mother liquor to make 1,500 parts, while maintaining the liquid temperature at 60 to 65 ° C., 300 parts of sodium chloride was added and stirred for 2 hours, and the precipitated crystals were collected by filtration. The obtained crystals were washed with 300 parts of a 20% aqueous sodium chloride solution and thoroughly squeezed to obtain 100.3 parts of a wet cake containing 59.2 parts of the compound of the following formula (4) as red crystals.

  (D) In 60 parts of water, 67.7 parts of the wet cake of the compound of the formula (4) obtained above was added. Next, 24 parts of 25% aqueous sodium hydroxide solution was added thereto and stirred, and further dissolved by adjusting the pH of the liquid to 3 to 4 by adding 25% aqueous sodium hydroxide solution. On the other hand, 0.4 parts of Lipar OH (trade name, anionic surfactant; manufactured by Lion) was added to 60 parts of ice water, and 8.9 parts of cyanuric chloride was added thereto, followed by stirring for 30 minutes. Got. The resulting suspension was added to the solution containing formula (4) obtained above. Then, a compound of the following formula (5) is obtained by reacting at a temperature of 25 to 30 ° C. for 4 hours while maintaining the pH of the liquid at 2.7 to 3.0 using a 10% aqueous sodium hydroxide solution. A reaction solution containing was obtained.

  (E) 9.5 parts of sodium p-phenolsulfonate dihydrate was added to the reaction solution containing the compound of the formula (5) obtained above. Next, 25% aqueous sodium hydroxide solution was added thereto, and while maintaining the pH of the liquid at 6.5 ± 0.3, the temperature of the liquid was raised to 50 to 55 ° C., and the reaction was performed at that temperature for 1 hour. To obtain a reaction solution containing a compound of the following formula (6).

  (F) 1.2 parts of ethylenediamine was added to the reaction solution containing the compound of the formula (6) obtained above. Next, 25% aqueous sodium hydroxide solution was added thereto, and while maintaining the pH of the liquid at 7.8-8.2, the temperature of the liquid was raised to 78-82 ° C. and kept at that temperature for 1 hour. Reacted. Thereafter, water was added to bring the liquid volume to about 350 parts, followed by filtration to remove undissolved substances. After adding water to the obtained mother liquor to make the liquid volume 400 parts, concentrated hydrochloric acid was added while maintaining the liquid temperature at 55 ± 2 ° C. to adjust the pH of the liquid to 3. Next, 40 parts of sodium chloride was added to this liquid over 15 minutes, stirred for 30 minutes, and concentrated hydrochloric acid was added to adjust the pH of the liquid to 2. The obtained acidic aqueous solution was stirred for 1 hour, the precipitated crystals were collected by filtration, and the obtained crystals were washed with 100 parts of a 20% aqueous sodium chloride solution to obtain a red wet cake.

  (G) The wet cake obtained above was added to 500 parts of methanol, and the temperature of the liquid was raised to 60 to 65 ° C. and stirred for 1 hour. The precipitated crystals were collected by filtration, washed with methanol, and then dried to obtain a free acid type compound 4. And the free acid type compound 4 was ion-exchanged by a conventional method to obtain compound 4 (sodium salt of the exemplified compound III-1).

[Compound 5]
Compound 5 used was the sodium salt of Exemplified Compound IV-1, which was synthesized with reference to the description in Example 4 of WO 2004/104108.

[Compound 6]
As the compound 6, a lithium salt of the exemplified compound V-2 synthesized with reference to the description of the compound d-5 in JP-A-2006-143989 was used.

[Comparative Compound 3]
The following comparative compound 3, which is a comparative compound of the third coloring material, used the following magenta dye synthesized with reference to JP-A-2002-80765.

[Comparative Compound 4]
The following magenta dye synthesized with reference to JP-A-8-73791 was used as the comparative compound 4 for the third colorant comparative compound.

The fourth coloring material used in Examples and Reference Examples , Compound 7 and Compound 8, were synthesized by the following methods, respectively. Compound 7 is the sodium salt of Exemplified Compound VI-1, and Compound 8 is the sodium salt of Exemplified Compound VII-5. Moreover, the comparative compound 5 which is the black dye used by the comparative example was synthesize | combined by the below-mentioned method.

[Compound 7]
As the compound 7, the sodium salt of the exemplified compound VI-1 synthesized with reference to Example 1 of WO 2006/001274 was used.

[Compound 8]
As the compound 8, the lithium salt of the exemplified compound VII-5 synthesized with reference to JP-A-2005-139427 was used.

[Comparative Compound 5]
As the following comparative compound 5 which is a comparative compound of the fourth coloring material, the following black dye synthesized with reference to US Pat. No. 6,302,949 was used.

<Evaluation of combination of cyan dye and yellow dye>
(Preparation of inks of Reference Examples 1 to 15 and Comparative Examples 1 to 5)
The inks of Reference Examples 1 to 15 and Comparative Examples 1 to 5 were prepared as follows by changing the combination of coloring materials. The compounds 1-1 to 1-7 synthesized above and the compound 2 were used as reference examples as the first coloring material, and the synthesized comparative compound 1 and C.I. I. Direct Blue 199 was used. Compound 3 synthesized above as the second colorant and its comparative example include C.I. I. Direct Yellow 132 and C.I. I. Direct yellow 86 was used. Preparation of ink, first, by mixing respective components shown in Table 5, sufficiently stirred, then, subjected to pressure filtration through a filter having a pore size of 0.2 [mu] m, the ink of Reference Example and Comparative Example It was. In Table 5, the cyan dyes of compounds 1-1 to 1-7 and compound 2 correspond to the first color material, and the yellow dye of compound 3 corresponds to the second color material.

(Evaluation)
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 2400 dpi × 1200 dpi, and a discharge amount of 2.5 pL. Then, an image was formed on a recording medium (Professional Photo Paper PR-101; manufactured by Canon) with the recording duty changed from 0% to 100% in increments of 10%.

The brightness (L) and color tone (a and b) in the L ^* a ^* b ^* display system defined by the CIE (International Lighting Commission) for the image portion of the recorded matter obtained above with a recording duty of 50% Was measured (“Lab value before ozone resistance test”). Further, this recorded matter was exposed to an ozone test apparatus (trade name: OMS-H; manufactured by Suga Test Instruments Co., Ltd.) with an ozone gas concentration of 2.5 ppm, a relative humidity of 50%, and a tank temperature of 23 ° C. for 16 hours as one cycle. Two cycles of ozone exposure were performed. Thereafter, the lightness (L) and the color tone (a and b) were measured in the same manner as described above for an image portion having a recording duty of 50% in the recorded matter (referred to as “Lab value after ozone resistance test”). The lightness (L) and color tone (a and b) were measured using a spectrophotometer (trade name: Spectrolino; manufactured by Gretag Macbeth) under the conditions of light source: D50 and field of view: 2 °. From the obtained Lab value before the ozone resistance test and the Lab value after the ozone resistance test, the color difference (ΔE) was calculated based on the following formula (A) to evaluate the ozone resistance. The standard of ozone resistance is as follows. The evaluation results are shown in Table 6. Table 6 also shows the ratio of the content of the first color material and the second color material.

ＡＡ：ΔＥが５未満
Ａ：ΔＥが５以上７未満
Ｂ：ΔＥが７以上１０未満
Ｃ：ΔＥが１０以上 In the following evaluation criteria, AA, A, and B are levels that are not problematic as ozone resistance, A is an excellent level, AA is a particularly excellent level, and C is an unacceptable level as ozone resistance.

AA: ΔE is less than 5 A: ΔE is 5 or more and less than 7 B: ΔE is 7 or more and less than 10 C: ΔE is 10 or more

(D value)
The scattering angle profiles of each of the inks of Reference Examples 1 and 2 and Comparative Example 4 obtained above, Compound 1-1, Compound 2, and Comparative Compound 1 were measured by the small-angle X-ray scattering method. The measurement for each ink was carried out by preparing a model ink in which the water-soluble organic solvent or surfactant was replaced with water from the ink composition, and therefore, among the actual ink composition, cyan dye and yellow dye were measured. The measurement was performed on an aqueous dye solution containing the combination. Moreover, the measurement about each dye was performed by preparing dye aqueous solution so that dye density | concentration might be 3.5 mass%.

The measurement conditions of the scattering angle profile are as shown below.
・ Device: Nano Viewer (Rigaku)
・ X-ray source: Cu-Kα
・ Output: 45kV-60mA
・ Effective focus: 0.3mmφ + Confocal Max-Flux Mirror
-1st Slit: 0.5mm, 2nd Slit: 0.4mm, 3rd Slit: 0.8mm
・ Irradiation time: 240 min
・ Beam stopper: 3.0mmφ
・ Measurement method: Transmission method ・ Detector: Blue Imaging Plate

（式（Ａ）中、λはＸ線の波長、ｄは粒子間の距離、θは散乱角である。） From the obtained scattering angle profile, the X-ray diffraction data processing software JADE (manufactured by Material Data Inc.) is used to calculate the d value (nm) based on the following formula (A) from the 2θ value of the scattering angle peak top. did. The d value is an index representing the cohesiveness or dispersibility of the color material.

(In the formula (A), λ is the X-ray wavelength, d is the distance between particles, and θ is the scattering angle.)

The obtained d value is as follows.
-Ink of Reference Example 1 5.89 nm
-Ink of Reference Example 2. 5.68 nm
-Ink of Comparative Example 4 6.09 nm
Compound 1-1 6.77 nm
Compound 2 6.98 nm
Comparative compound 1 6.84 nm

<Evaluation of gray ink>
(Preparation of inks of Examples 16 to 22 , 24 to 29, 31 to 35, 37 to 46, Reference Examples 23, 30, 36, and Comparative Examples 6 to 12)
Compounds 1-1 to 1-7, compounds 2 to 8, compounds 1 to 5, and comparative compounds 1 to 5 obtained by synthesis as described above. I. Using Direct Yellow 86, each ink of Examples , Reference Examples and Comparative Examples was prepared as follows. First, each component shown in Table 7 was mixed and sufficiently stirred. Thereafter, pressure filtration was performed with a filter having a pore size of 0.2 μm to prepare each ink.

In Tables 7-1 to 7-6, (* 1) to (* 4) indicate annotations, and their contents are as follows. In Tables 7-1 to 7-6, “remainder” means that the composition of the ink as a whole was adjusted to 100% with ion-exchanged water. Specifically, The amount obtained by subtracting the value of each ink component in Table 7 from 100 is the amount of water.
(* 1) Acetylene glycol ethylene oxide adduct (surfactant; manufactured by Kawaken Fine Chemicals)
(* 2) First color material content / second color material content (* 3) (first color material content + second color material content) / third color material Content (* 4) (1st color material content + 2nd color material content + 3rd color material content added as needed) / 4th color material content In addition, in the comparative example, when each color material prescribed | regulated by this invention is used, the content rate of the applicable color material was computed and shown. In Table 7, compounds 1-1 to 1-7, which are cyan dyes, and compound 2 correspond to the first color material, and compound 3, which is a yellow dye, corresponds to the second color material. Further, compounds 4 to 6 which are magenta dyes correspond to the third color material, and compounds 7 and 8 which are black dyes correspond to the fourth color material.

(Evaluation)
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 2400 dpi × 1200 dpi, and a discharge amount of 2.5 pL. Then, an image was formed on a recording medium (Professional Photo Paper PR-101; manufactured by Canon) with the recording duty changed from 0% to 100% in increments of 10%.

[Ozone resistance]
The brightness (L) and color tone (a and b) in the L ^* a ^* b ^* display system defined by the CIE (International Lighting Commission) for the image portion of the recorded matter obtained above with a recording duty of 50% Was measured (“Lab value before ozone resistance test”). Further, this recorded matter was exposed to an ozone test apparatus (trade name: OMS-H; manufactured by Suga Test Instruments Co., Ltd.) with an ozone gas concentration of 2.5 ppm, a relative humidity of 50%, and a tank temperature of 23 ° C. for 16 hours as one cycle. Two cycles of ozone exposure were performed. Thereafter, the lightness (L) and the color tone (a and b) were measured in the same manner as described above for an image portion having a recording duty of 50% in the recorded matter (referred to as “Lab value after ozone resistance test”). The lightness (L) and color tone (a and b) were measured using a spectrophotometer (trade name: Spectrolino; manufactured by Gretag Macbeth) under the conditions of light source: D50 and field of view: 2 °. From the obtained Lab value before the ozone resistance test and the Lab value after the ozone resistance test, the color difference (ΔE) was calculated based on the following formula (A) to evaluate the ozone resistance.

Ａ：ΔＥが８．５未満
Ｂ：ΔＥが８．５以上１０未満
Ｃ：ΔＥが１０以上 The standard of ozone resistance is as follows. The evaluation results are shown in Table 8. In Table 8, the content in each combination of the first to fourth color materials in the inks of Examples and Reference Examples is shown together. In the following evaluation criteria, A and B are levels that are not problematic for ozone resistance, A is an excellent level, and C is an unacceptable level for ozone resistance.

A: ΔE is less than 8.5 B: ΔE is 8.5 or more and less than 10 C: ΔE is 10 or more

[Light resistance]
The brightness (L) and color tone (a and b) in the L ^* a ^* b ^* display system defined by the CIE (International Lighting Commission) for the image portion of the recorded matter obtained above with a recording duty of 50% Was measured (“Lab value before light resistance test”). Further, this recorded matter was exposed for 220 hours at an irradiation intensity of 50 kilolux, a relative humidity of 50%, and an in-tank temperature of 23 ° C. using a low-temperature xenon tester (trade name: SL-75; manufactured by Suga Test Instruments). Thereafter, the lightness (L) and the color tone (a and b) were measured in the same manner as described above for an image portion having a recording duty of 50% in the recorded matter (referred to as “Lab value after light resistance test”). The lightness (L) and color tone (a and b) were measured using a spectrophotometer (trade name: Spectrolino; manufactured by Gretag Macbeth) under the conditions of light source: D50 and field of view: 2 °. From the obtained Lab value before the light resistance test and the Lab value after the light resistance test, the color difference (ΔE) was calculated based on the following formula (B) to evaluate the light resistance.

ＡＡ：ΔＥが５未満
Ａ：ΔＥが５以上７未満
Ｂ：ΔＥが７以上１０未満
Ｃ：ΔＥが１０以上 The criteria for light resistance are as follows. The evaluation results are shown in Table 8. In the following evaluation criteria, AA, A, and B are levels that do not cause problems with light resistance, A is an excellent level, AA is a particularly excellent level, and C is an unacceptable level for light resistance.

AA: ΔE is less than 5 A: ΔE is 5 or more and less than 7 B: ΔE is 7 or more and less than 10 C: ΔE is 10 or more

[Color tone]
For the portion of the image having a recording duty of 100% in the recorded matter obtained above, the color tone is measured by measuring a ^* and b ^* in the L ^* a ^* b ^* display system defined by the CIE (International Lighting Commission). Was evaluated. Note that a ^* and b ^* were measured using a spectrophotometer (trade name: Spectrolino; manufactured by Gretag Macbeth) under conditions of a light source: D50 and a visual field: 2 °.

The standard of the color tone is as follows. The evaluation results are shown in Table 8. In the following evaluation criteria, A and B are levels that have no problem with color tone, A is an excellent level, and C is a level that is not acceptable as a color tone.
A: −0.5 ≦ a ^* ≦ 5 and −6.5 ≦ b ^* ≦ 0 is satisfied B: −5 ≦ a ^* ≦ 10 and −10 ≦ b ^* ≦ 1 is satisfied, and −0.5 ≦ a ^* ≦ 5, −6.5 ≦ b ^* ≦ 0 not satisfied C: −5 <a ^* <10 and −10 <b ^* <1 not satisfied

[Metamerism]
L ^* , a ^* , and b ^* in the L ^* a ^* b ^* display system defined by the CIE (International Lighting Commission) are measured for the image portion of the recorded matter obtained above with a recording duty of 100%. did. L ^* , a ^* , and b ^* are spectrophotometers (trade name: Spectrolino; manufactured by Gretag Macbeth), light sources: D50, D65, A, C, and F1-F12, field of view: 2 °. The reflection absorption spectrum was measured under the conditions. At this time, when the light source is D50, the values of L ^* , a ^* , and b ^* are “Lab values in the light source D50”, and the light sources are D65, A, C, and F1 to F12 (15 in total). The value of L ^* , a ^* , and b ^* of “Species” was defined as “Lab value in each light source”. Then, based on the values of L ^* , a ^* , and b ^* when the light source is D50, the deviation of the values of L ^* , a ^* , and b ^* in each of the 15 types of light sources is expressed by the following formula (C). Was calculated as a color difference (ΔE). Then, metamerism was evaluated from the average value of color differences (average value of ΔE) obtained with each of these 15 light sources.

Ａ：０．０≦ΔＥの平均値≦４．０
Ｂ：４．０＜ΔＥの平均値≦５．０
Ｃ：５．０＜ΔＥの平均値 The standard of metamerism is as follows. The evaluation results are shown in Table 8. In the following evaluation criteria, A and B are image levels that are not problematic as metamerism, A is an excellent level, and C is an image level that is not acceptable as metamerism.

A: 0.0 ≦ ΔE average value ≦ 4.0
B: 4.0 <average value of ΔE ≦ 5.0
C: Average value of 5.0 <ΔE

Of the examples and reference examples in which the evaluation result of ozone resistance was B, the ozone resistance of Examples 24 and 44 to 46 was lower than that of the other B rank Examples and Reference Examples. It was. Among the examples and reference examples in which the light resistance evaluation result was B, the light resistance of Example 24 had a lower ΔE value than the other examples and reference examples of B rank.

  In addition, although the specific example of each substituent included in the said compound other than the said specific Example and a structure is not mentioned here, the effect acquired by the said Example was able to be acquired similarly.

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. 6 is a perspective view illustrating a state where an ink cartridge is mounted on the 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. FIG. 4 is a schematic diagram showing the position of each color material in the ink receiving layer of the recording medium when ink containing each color material is applied to the recording medium.

Explanation of symbols

M2041: separation roller M2060: paper feed tray M2080: paper feed roller M3000: pinch roller holder M3030: paper guide flapper M3040: platen M3060: transport roller M3070: pinch roller M3110: paper discharge roller M3120: spur M3160: paper discharge tray M4000: Carriage M5000: Pump M5010: Cap M7030: Access cover E0002: LF motor E0014: Electric substrate H1000: Head cartridge H1001: Recording head H1100: First recording element substrate H1101: Second recording element substrate H1200: First plate H1201 : Ink supply port H1300: Electric wiring board H1301: External signal input terminal H1400: Second plate H1500: Tank holder (cartridge Dah)
H1501: Ink flow path H1600: Flow path forming member H1700: Filter H1800: Seal rubber H1900: Ink cartridge H2000: Yellow nozzle array H2100: Magenta nozzle array H2200: Cyan nozzle array H2300: Light cyan nozzle array H2400: Black nozzle array H2500: Green Nozzle array H2600: Light magenta nozzle array O1001: Ink receiving layer O1002 of recording medium: General cyan dye O1003: Compound of general formula (I) O1004: General dye O1005: Compound of general formula (II)

Claims (12)

An ink containing at least three colorants of a first colorant , a second colorant , and a third colorant,
The first colorant is a compound represented by the following general formula (I):
Said second color material, Ri compound der represented by the following formula (II),
The third coloring material is selected from the group consisting of a compound represented by the following general formula (III), a compound represented by the following general formula (IV), and a compound represented by the following general formula (V). ink, wherein at least one compound der Rukoto.

(In the general formula (I), A, B, C and D are each independently a 6-membered aromatic ring, and at least one of A, B, C and D is a nitrogen-containing heteroaromatic ring. in it, M are each independently a hydrogen atom, an alkali metal, ammonium or organic ammonium,, E is an alkylene group. in addition, X is a sulfo-substituted anilino group, carboxyl-substituted anilino group, or a phosphono-substituted anilino group The substituted anilino group is further sulfonic acid group, carboxyl group, phosphono group, sulfamoyl group, carbamoyl group, hydroxyl group, alkoxy group, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, Acetylamino, ureido, alkyl, nitro, cyano, halogen, alkylsulfonyl, and alkyl It may have 1 to 4 substituents selected from the group consisting of a kirthio group, Y is a hydroxyl group or an amino group, and l (el), m, and n are 0 ≦ l ( L) ≦ 2, 0 ≦ m ≦ 3, 0.1 ≦ n ≦ 3, and l (L) + m + n = 1 to 4.

(In general formula (II), R ₁ , R ₂ , Y ₁ and Y ₂ are each independently a monovalent group, and X ₁ and X ₂ are each independently having a Hammett's σp value of 0.20 or more. 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, a substituted or unsubstituted group An aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and M is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

(In the general formula (III), each R is independently a hydrogen atom, an alkyl group, a hydroxyalkyl group, a cyclohexyl group, or a mono- or dialkylaminoalkyl group, and each M is independently a hydrogen atom, an alkali metal, or ammonium. Or an organic ammonium, and X is a linking group.)

(In General Formula (IV), R ₁ is a hydrogen atom or an alkyl group, m is an integer of 1 to 3, and M is each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

(In General Formula (V), R ₂ , R ₃ , R ₄ , and R ₅ are each independently an alkyl group, and M is each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.) The ink according to claim 1, wherein the nitrogen-containing heteroaromatic ring in the general formula (I) is a pyridine ring or a pyrazine ring.   The content (mass%) of the first color material in the ink is 0.1 times or more and 15.0 by mass ratio with respect to the content (mass%) of the second color material in the ink. The ink according to claim 1, wherein the ink is twice or less. The content (mass%) of the first color material in the ink and the content (mass%) of the second color material in the ink with respect to the content (mass%) of the third color material in the ink. 4) The ink according to any one of claims 1 to 3, wherein the sum of (%) is 0.5 to 5.0 times in terms of mass ratio. The ink according to any one of claims 1 to 4, wherein the third color material is a compound represented by the general formula (V). Further, as a fourth coloring material, according to claim 1 to 5 comprising at least one compound selected from compounds represented by a compound represented by the following general formula by the following general formula (VI) (VII) The ink according to any one of the above.

(In General Formula (VI), each R ₁₀ independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms which may be substituted by an alkoxy group having 1 to 4 carbon atoms. 1 to 4 carbon atoms which may be substituted by a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, 1 to 4 carbon atoms which may be substituted by a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms Substituted by 4 alkylamino groups, carboxyl-alkylamino groups having 1 to 5 carbon atoms, bis- [carboxy-alkyl having 1 to 5 carbon atoms] amino groups, hydroxyl groups or alkoxy groups having 1 to 4 carbon atoms. C1-C4 alkanoylamino group, carboxyl group or sulfonic acid group Or a phenylamino group optionally substituted with an amino group, a sulfonic acid group, a halogen atom, or a ureido group, [C] is an aliphatic amine residue having a carboxyl group or a sulfonic acid group, and M is Each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

(In General Formula (VII), A is an optionally substituted aromatic group or heterocyclic group, B is any group represented by the following General Formulas (1) to (5), M Are each independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

(In the general formulas (1) to (5), R _{1 to} R ₉ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxyl 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, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, cyano group, nitro group, alkyl or arylthio group, Heterocycle A thio group, an alkyl or arylsulfonyl group, a heterocyclic sulfonyl group, an alkyl or arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfonic acid group, and each group may be further substituted. Amount contained in the ink of the fourth coloring material with respect to (mass%), the content in the content (mass%) and the ink in the second coloring material in the ink of the first color material (mass% ) and the total content (mass%) in the ink of the third coloring material, at mass ratio, ink according to claim 6 or less 70.0 × 1.0 times or more. The ink according to claim 6 or 7 , wherein the fourth color material is a compound represented by the general formula (VII). 9. An ink jet recording method in which ink is ejected by an ink jet method to perform recording on a recording medium, wherein the ink is the ink according to any one of claims 1 to 8 . 9. An ink cartridge comprising an ink containing portion for containing ink, wherein the ink is the ink according to any one of claims 1 to 8 . 9. A recording unit comprising an ink containing portion for containing ink and a recording head for ejecting ink, wherein the ink is the ink according to any one of claims 1 to 8. Recording unit. An ink jet recording apparatus comprising an ink containing portion for containing ink and a recording head for ejecting ink, wherein the ink is the ink according to any one of claims 1 to 8. Inkjet recording apparatus.

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