JP4471397B2 - 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. Moreover, in addition to the progress of high image quality of images obtained by the ink jet recording method, with the rapid spread of digital cameras, it has become widely used as an image output method comparable to silver salt photography.

  In recent years, image quality has been improved more than ever due to the minimization of ink droplets and the improvement of the color gamut accompanying the introduction of multicolor ink. On the other hand, however, demands for color materials and inks are increasing, and more stringent characteristics are required in terms of reliability such as improved color development, clogging, and ejection stability.

  On the other hand, the problem of the ink jet recording method is that the obtained recorded matter is inferior in image storability. In general, the recorded matter obtained by the ink jet recording method has lower image storage stability than silver salt photographs. Specifically, when the recorded material is exposed to environmental gases such as light, humidity, heat, and ozone gas that exists in the air for a long time, the color material on the recorded material deteriorates, causing a change in color tone or fading of the image. There is a problem that is likely to occur.

  Many proposals have heretofore been made in order to improve ozone resistance, particularly among image storability. For example, many techniques for improving the fastness of an image, particularly the ozone resistance, have been proposed for color materials used in ink jet inks. However, it has not yet achieved the higher level of robustness that has been required in recent years.

  Furthermore, in recent years, there has been an increasing demand for displaying a recorded material on a wall or a bulletin board without putting it in a frame or the like. On the other hand, with the fastness obtained by the inks that are widely used at present, the color material in the image is noticeably faded by an oxidizing gas in the air, especially ozone, and therefore it is at an unacceptable level as an image. May deteriorate (fading).

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 1 to 7). 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 8). 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 NH. ₂ or a sulfonamide residue capable of forming a complex with a copper ion. The D is a monovalent alkali metal, ammonium, or organic ammonium. Furthermore, in order to improve the ozone resistance of an image, there is a proposal relating to an ink containing a combination of a plurality of phthalocyanine color materials (see Patent Document 9).

In addition, as a technique paying attention to the cohesiveness of the color material, there is also a proposal for achieving both ozone resistance and bronze resistance by defining the _d75 value of the phthalocyanine color material (see Patent Document 10). However, current user demand levels are increasing day by day, and further improvements are needed.
As described above, a fundamental solution that can dramatically improve the ozone resistance of an image has not yet been proposed.

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 JP 2006-328129 A Japanese Patent Laid-Open No. 2006-45534

  As described above, the performance required for ozone resistance of the recorded matter obtained by the ink jet recording method has been increasing year by year, and the color materials conventionally used for cyan ink have a high level that satisfies the above requirements. An image showing ozone resistance has not yet been obtained. For example, in the inventions described in Patent Documents 1 to 7, an attempt is made to improve the ozone resistance of an image by introducing various substituents into the color material. Therefore, there is a limit to improving the ozone resistance only by the characteristics of such a single color material.

Patent Document 8 describes that SO ₂ NH ₂ is preferable as SO ₂ NHR. However, three of the five examples in Patent Document 8 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, as described above, although Patent Document 8 describes that SO ₂ NH ₂ is preferable as SO ₂ NHR, the result of the fading test using these phthalocyanine color materials is n = 0. It is disclosed as inferior. In other words, it can be said that the ozone resistance of images obtained with these color materials is insufficient. Furthermore, since the color tone of the ink is biased in the red direction by using this color material, there is another problem that a color tone preferable for cyan ink cannot be obtained.

  Furthermore, the method of combining a plurality of phthalocyanine color materials described in Patent Document 9 improves the bronze resistance, which becomes a problem when using phthalocyanine color materials, and at the same time improves the ozone resistance of images. Has been. However, even in this case, the present situation has not yet reached the high level of ozone resistance required for images in recent years. Therefore, the present inventors considered that it is necessary to conduct a detailed study on the color material used for cyan ink.

  Accordingly, an object of the present invention is to provide a cyan ink that achieves a high level of ozone resistance and gives an image having a preferable color tone. 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 that enable the above-described excellent image formation by using such an ink.

  The above object is achieved by the present invention described below. That is, the ink according to the present invention is an ink containing at least two color materials, ie, a first color material and a second color material, and the first color material is represented by the following general formula (I): The second colorant is a compound represented by the following general formula (II).

（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のうち少なくとも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。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。）

(In 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. a ring, M is 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 The substituted anilino group further includes a sulfonic acid group, a carboxyl group, a phosphono group, a sulfamoyl group, a carbamoyl group, a hydroxyl group, an alkoxy group, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, and a diarylamino group. Acetylamino group, ureido group, alkyl group, nitro group, cyano group, halogen, alkylsulfonyl group, and It may have 1 to 4 substituents 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, 0.1 ≦ n ≦ 3, and l (el) + m + n = 1 to 4.

（一般式（II）中、Ｘ₁、Ｘ₂、Ｘ₃、及びＸ₄はそれぞれ独立に、−ＳＯ−Ｚ、−ＳＯ₂−Ｚ、−ＳＯ₂ＮＲ₁Ｒ₂、又は−ＣＯＮＲ₁Ｒ ₂ である。ここで、Ｚはそれぞれ独立に、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シクロアルキル基、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複素環基であり、Ｒ₁及びＲ₂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シクロアルキル基、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複素環基である。また、一般式（II）中、Ｙ₁、Ｙ₂、Ｙ₃、Ｙ₄、Ｙ₅、Ｙ₆、Ｙ₇、及びＹ₈はそれぞれ水素原子であり、ａ１、ａ２、ａ３、及びａ４はそれぞれ、Ｘ₁、Ｘ₂、Ｘ₃、及びＸ₄の置換基の数を示し、それぞれ独立に１又は２の整数である。）

(In General Formula (II), X ₁ , X ₂ , X ₃ , and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , or —CONR ₁ R _2. it. here, Z is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted An aryl group or a substituted or unsubstituted heterocyclic group, wherein R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group An alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and in formula (II), Y ₁ , Y ₂ , Y ₃ , Y _{4, 5,} Y _6, Y _7, and Y ₈ are, respectively it water MotoHara child, a1, a2, a3, respectively, and a4 is X _1, the number of substituents of X _2, X _3, and X ₄ was shown, an integer of 1 or 2 independently.)

  An ink jet recording method according to another embodiment of the present invention is 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 an ink having the above-described configuration. .

  An ink cartridge according to another embodiment of the present invention is an ink cartridge including an ink storage portion that stores ink, wherein the ink is ink having the above-described configuration.

  According to another embodiment of the present invention, there is provided a recording unit comprising an ink storage portion for storing ink and a recording head for discharging ink, wherein the ink is ink having the above-described configuration. It is characterized by that.

  An ink jet recording apparatus according to another embodiment of the present invention is an ink jet recording apparatus including an ink containing portion for containing ink and a recording head for ejecting ink. It is characterized by being.

  According to the present invention, it is possible to provide a cyan ink that has a high level of ozone resistance and gives an image having a preferable color tone. According to another embodiment of the present invention, an ink jet recording method, an ink cartridge, a recording unit, and an ink jet recording apparatus using the ink can be provided.

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. Further, in the following description, the compound represented by the general formula (I) and the compound represented by the general formula (II) are represented by the “compound of the general formula (I)” and “ It may be abbreviated as “compound”.

  As a result of the study by the present inventors, it has been found that an image excellent in ozone resistance having a preferable color tone can be obtained by a constitution of an ink containing a combination of two kinds of compounds having a specific structure as a colorant. . Further, it was found that the recorded matter is particularly excellent in ozone resistance by using these compounds at a specific mass ratio. Furthermore, the important knowledge in the case of combining two types of compounds having a specific structure was obtained. Specifically, the present inventors have found an element that appropriately controls the structure of compounds involved in the cohesiveness of each other or the properties of aggregation and association that occur when two types of compounds having a specific structure are combined. .

  In the present invention, a compound of the following general formula (I) is used as the first color material, and a compound of the following general formula (II) is used as the second color material in combination. Hereinafter, these color materials will be described in detail.

[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).

（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。）

(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, and the substituted anilino group further includes a sulfonic acid group, a carboxyl group, a phosphono group, and a 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 1 to 4 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.)

  In addition, when the color material of the general formula (I) is mixed with the color material of the general formula (II) described later, the mixed color material is more easily aggregated or the mixed color material is more easily associated. What is in the state is preferred. For example, when the surface energy of the color material of the general formula (I) and the color material of the general formula (II) are closer, it is considered that the above state is likely to occur.

  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. Examples of the nitrogen-containing heteroaromatic ring include a pyridine ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring, and among them, a pyridine ring is particularly preferable. 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 ( The suppression of the 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, 4-ethoxy-2-sulfoanilino group, 2-methyl-5-sulfoanilino group, 2-methoxy-4-nitro-5-sulfoanilino group, 2-chloro-5-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-dicarboxyanilino 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.
In addition, the sulfonic acid group, carboxyl group, phosphono group and the like 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, triisopropanolamine. The counter ion may be an alkaline earth metal such as calcium and magnesium.

（一般式（III）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 (III) (copper porphyrazine compound) is synthesized.

(In general formula (III), A, B, C, and D are each independently a six-membered aromatic ring.)

  The compound of the general formula (III) can be obtained, for example, by reacting a nitrogen-containing heteroaromatic dicarboxylic acid derivative having aromaticity with a phthalic acid derivative in the presence of a catalyst and a copper compound. By changing the molar ratio of the reaction of the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative, the number of nitrogen-containing heteroaromatic rings of A, B, C, and D and the number of benzene rings can be adjusted.

  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.

  Common 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 5 mol times to 1 mol of the total of 1 mol of the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative. It is preferably 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 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. Specifically, copper chloride, copper bromide, copper acetate, copper acetylacetonate and the like can be used. 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 (III) can be obtained by filtration, washing and drying.

  Taking as an example a compound (copper dibenzobis (2,3-pyrido) porphyrazine) in which two of A, B, C and D in the general formula (III) are pyridine rings and the remaining two are benzene rings, The synthesis method of the compound of general 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 (III) 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 kinds of isomers having different pyridine ring positions and pyridine ring nitrogen atom positions (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 (III) 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 (III) 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（IV）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, a compound of the following general formula (IV) (copper chlorosulfonylporphyrazine compound) is synthesized.

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

  The compound of general formula (IV) can be obtained by chlorosulfonating the compound of general formula (III) obtained as described above in chlorosulfonic acid. Alternatively, the compound of general formula (III) can be obtained by sulfonating in sulfuric acid or fuming sulfuric acid, and then derivatizing the sulfonic acid group to 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 (III) are benzene rings. , C and D are not introduced when they are heteroaromatic ring groups. That is, among A, B, C, and D in the general formula (III), 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 (III) 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 (III). 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. The substituent of the compound of the general formula (IV) obtained is a mixture of chlorosulfonic acid and sulfonic acid group, but the ratio of chlorosulfonic acid 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 of the general formula (IV) can 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 a quinolinic acid are condensed and ring-closed to obtain a compound of the following general formula (V) (a copper porphyrazine compound having a sulfonic acid group). Synthesize. And the compound of general formula (IV) can also be obtained by guide | inducing the sulfonic acid group in the compound of general formula (V) obtained in this way to the chloro sulfone group.

（一般式（Ｖ）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 (V), 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 (V) can be converted into a chlorosulfonic acid group by reacting the compound of the general formula (V) 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（VI）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。また、Ｙは、水酸基又はアミノ基である。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。） Finally, the compound of the general formula (IV) obtained as described above, the compound of the following general formula (VI) (organic amine), and ammonia are reacted to obtain the target compound of the general formula (I). Is synthesized.

(In General Formula (VI), E is an alkylene group, X is a sulfo-substituted anilino group, a carboxyl-substituted anilino group, or a phosphono-substituted anilino group. These substituted anilino groups are further represented by the following substituent group: It may have at least one selected substituent of 1 to 4. Y is a hydroxyl group or an amino group Substituent group: sulfonic acid group, carboxyl group, phosphono group, sulfamoyl group, carbamoyl group, Hydroxyl group, alkoxy group, from 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 Become.)

  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 (IV) obtained above, the compound of the general formula (VI) 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 (IV), the compound of general formula (VI), and an aminating agent is generally performed in water. Further, the amount of the compound of the general formula (IV) used is preferably 1 mol times or more of the theoretical value with respect to 1 mol of the compound of the general formula (IV), but the reaction of the compound of the general formula (IV) Depends on sex and reaction conditions.

  The compound of the general formula (VI) 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 (VI) 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 (VI) 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. In addition, when obtaining the compound of the general formula (VI) having a structure in which Y in the formula is a hydroxyl group, an alkali metal hydroxide such as sodium hydroxide is then 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 (VI) 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 (IV) and the compound of the general formula (VI) in the presence of ammonia. Therefore, theoretically, a part of the chlorosulfonyl group of the compound of the general formula (IV) 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 (IV) other than those reacted with the compound of the general formula (VI) (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.

  Preferred 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, more preferably 1 to 2, Since the effect of invention can be acquired more effectively, it is especially preferable. 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.

（一般式（II）中、Ｘ₁、Ｘ₂、Ｘ₃、及びＸ₄はそれぞれ独立に、−ＳＯ−Ｚ、−ＳＯ₂−Ｚ、−ＳＯ₂ＮＲ₁Ｒ₂、スルホン酸基、−ＣＯＮＲ₁Ｒ₂、又はＣＯ₂Ｒ₁である。ここで、Ｚはそれぞれ独立に、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シクロアルキル基、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複素環基であり、Ｒ₁及びＲ₂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シクロアルキル基、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複素環基である。また、一般式（II）中の、Ｙ₁、Ｙ₂、Ｙ₃、Ｙ₄、Ｙ₅、Ｙ₆、Ｙ₇、及びＹ₈はそれぞれ独立に、水素原子、ハロゲン原子、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リール基、シアノ基、置換若しくは無置換のアルコキシ基、アミド基、ウレイド基、スルホンアミド基、置換若しくは無置換のカルバモイル基、置換若しくは無置換のスルファモイル基、置換若しくは無置換のアルコキシカルボニル基、カルボキシル基、又はスルホン酸基であり、ａ１、ａ２、ａ３、及びａ４はそれぞれ、Ｘ₁、Ｘ₂、Ｘ₃、及びＸ₄の置換基の数を示し、それぞれ独立に１又は２の整数である。） [Second coloring material: compound represented by formula (II)]
The ink of the present invention needs to contain a compound of the following general formula (II) as the second color material (dye).

(In General Formula (II), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , a sulfonic acid group, —CONR. ₁ R ₂ or CO ₂ R ₁ , where Z is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted An aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, wherein R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group, A cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and in the general formula (II) _{, Y 1, Y 2, Y} 3, Y 4, Y 5, Y 6, Y 7, and Y ₈ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl Group, cyano group, substituted or unsubstituted alkoxy group, amide group, ureido group, sulfonamido group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, substituted or unsubstituted alkoxycarbonyl group, carboxyl group Or a sulfonic acid group, and a1, a2, a3, and a4 each represent the number of substituents of X ₁ , X ₂ , X ₃ , and X ₄ and are each independently an integer of 1 or 2. )

  In addition, when the color material of the general formula (II) is mixed with the color material of the above general formula (I), the mixed color material is more easily aggregated, or the mixed color material is more easily associated. What is in the state is preferred. For example, when the surface energy of the color material of the general formula (I) and the color material of the general formula (II) are closer, it is considered that the above state is likely to occur.

X ₁ , X ₂ , X ₃ and X ₄ in the general formula (II) are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , a sulfonic acid group, —CONR ₁ R. ₂ or CO ₂ R ₁ . Among them, —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , and CONR ₁ R ₂ are preferable, —SO ₂ —Z and SO ₂ NR ₁ R ₂ are more preferable, and —SO ₂ is particularly preferable. _2- Z is preferred. _{X 1, X 2, X 3} , and a1 represents the number of substituents X _4, a2, when a3, and any a4 is _{2, X 1, X 2,} X 3, and of the X ₄ A plurality of them may be the same or different and are each independently any of the substituents listed above. X ₁ , X ₂ , X ₃ and X ₄ may all be the same or different substituents. In the case of different substituents, for example, when X ₁ , X ₂ , X ₃ , and X ₄ are all —SO ₂ —Z and each Z is different, the type of substituent is It may contain the same but partially different substituents. Or, for example, as in the case of containing a -SO ₂ -Z and -SO ₂ NR ₁ R _2, it may comprise different substituents.

  Each Z is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or substituted or unsubstituted An unsubstituted heterocyclic group. Among these, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferable, and a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group is more preferable.

R ₁ and R ₂ are each independently a hydrogen atom or a group selected from the group consisting of substituted or unsubstituted groups listed below. That is, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted complex Selected from the group consisting of cyclic groups. Among them, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferable, and further a hydrogen atom, a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic ring Groups are preferred. However, it is not preferable that both R ₁ and R ₂ are hydrogen atoms.

Hereinafter, R ₁ , R ₂ and Z in the general formula (II) will be described in more detail. In addition, the carbon number of each group demonstrated below is a number which does not contain the carbon atom of a substituent.
Examples of the alkyl group include substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms. Of these, branched alkyl groups are preferred from the viewpoint of solubility of the coloring material and ink stability, and more preferred are alkyl groups having asymmetric carbon (used as racemates). The alkyl group may further have a substituent, and specific examples of the substituent include a substituent when Z, R ₁ , R ₂ , and Y _{1 to} Y ₈ described later can further have a substituent. The same can be mentioned. Among them, a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group is particularly preferable because it can improve the association property of the coloring material and improve the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

Examples of the cycloalkyl group include substituted or unsubstituted cycloalkyl groups having 5 to 30 carbon atoms. Among these, a cycloalkyl group having an asymmetric carbon (used as a racemate) is particularly preferable from the viewpoint of the solubility of the coloring material and the stability of the ink. The cycloalkyl group may further have a substituent, and specific examples of the substituent include a substituent when Z, R ₁ , R ₂ , and Y _{1 to} Y ₈ described later can further have a substituent. The same thing is mentioned. Among them, a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group is particularly preferable because it can improve the association property of the coloring material and improve the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

Examples of the alkenyl group include substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms. Of these, branched alkenyl groups are preferred from the viewpoint of solubility of the coloring material and ink stability, and alkenyl groups having an asymmetric carbon (used as a racemate) are particularly preferred. The alkenyl group may further have a substituent, and specific examples of the substituent include a substituent when Z, R ₁ , R ₂ , and Y _{1 to} Y ₈ described later can further have a substituent. The same can be mentioned. Among them, a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group is particularly preferable because it can improve the association property of the coloring material and improve the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

Examples of the aralkyl group include substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms. Of these, branched aralkyl groups are preferable from the viewpoint of the solubility of the colorant and the stability of the ink, and more preferable are aralkyl groups having an asymmetric carbon (used as a racemate). The aralkyl group may further have a substituent, and specific examples of the substituent include a substituent when Z, R ₁ , R ₂ , and Y _{1 to} Y ₈ described later can further have a substituent. The same can be mentioned. Among them, a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group is particularly preferable because it can improve the association property of the coloring material and improve the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

Examples of the aryl group include substituted or unsubstituted aryl groups having 6 to 30 carbon atoms. The aryl group may further have a substituent, and specific examples of the substituent include a substituent when Z, R ₁ , R ₂ , and Y _{1 to} Y ₈ described later can further have a substituent. The same can be mentioned. Among them, an electron-withdrawing group is particularly preferable because fastness can be improved when the oxidation potential of the coloring material is noble. Examples of the electron-withdrawing group include those having a positive Hammett's substituent constant σp value. Of these, a halogen atom, heterocyclic group, cyano group, carboxyl group, acylamino group, sulfonamido group, sulfamoyl group, carbamoyl group, sulfonyl group, imide group, acyl group, sulfonic acid group, or quaternary ammonium group is preferable. Furthermore, a cyano group, a carboxyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an imide group, an acyl group, a sulfonic acid group, or a quaternary ammonium group is particularly preferable.

The heterocyclic group is a 5-membered or 6-membered ring, and includes a substituted or unsubstituted aromatic or non-aromatic heterocyclic ring, which may be further condensed. Hereinafter, specific examples in the case where R ₁ , R ₂ , and Z are heterocyclic groups are given as heterocyclic rings with the substitution positions omitted. The substitution position is not limited to the following description. For example, in the case of pyridine, substitution can be performed at the 2-position, the 3-position, and the 4-position. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole. Furan, benzofuran, thiophene, benzothiophene. Pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole. Examples include pyrrolidine, piperidine, piperazine, imidazolidine, and thiazoline. Of these, an aromatic heterocyclic group is preferable. Furthermore, pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, and thiadiazole are particularly preferable.

These heterocyclic groups may further have a substituent, and specific examples of the substituent include a case where Z, R ₁ , R ₂ and Y _{1 to} Y ₈ described later can further have a substituent. The same thing as a substituent is mentioned. Among them, an electron-withdrawing group is particularly preferable because fastness can be improved when the oxidation potential of the coloring material is noble. Examples of the electron-withdrawing group include those having a positive Hammett's substituent constant σp value. Of these, a halogen atom, heterocyclic group, cyano group, carboxyl group, acylamino group, sulfonamido group, sulfamoyl group, carbamoyl group, sulfonyl group, imide group, acyl group, sulfonic acid group, or quaternary ammonium group is preferable. Furthermore, a cyano group, a carboxyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an imide group, an acyl group, a sulfonic acid group, or a quaternary ammonium group is particularly preferable.

Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , and Y ₈ in the general formula (II) are each independently a hydrogen atom, a halogen atom, or a group consisting of the groups listed below. The group to be selected. That is, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a cyano group, a substituted or unsubstituted alkoxy group. An amide group, a ureido group, a sulfonamido group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted alkoxycarbonyl group, a carboxyl group, or a sulfonic acid group. Among these, a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, or a sulfonic acid group is preferable, and a hydrogen atom is particularly preferable.

Hereinafter, Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , and Y ₈ in the general formula (II) will be described more specifically. In addition, the carbon number of each group demonstrated below is a number which does not contain the carbon atom of a substituent.

  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 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.

  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 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 sulfamoyl group include substituted or unsubstituted sulfamoyl groups having 1 to 30 carbon atoms. Specifically, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, and N-benzoylsulfamoyl, N- ( N'-phenylcarbamoyl) sulfamoyl 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.

When Z, R ₁ , R ₂ , Y _{1 to} Y ₈ are groups that can further have a substituent, they may further have the following substituents. 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. Examples thereof include 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 branch from the viewpoint of the solubility of the coloring material and the stability of the ink, and more preferably those having an asymmetric carbon.

  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-methanesulfonylethoxy; Aryloxy groups such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, and 3-methoxycarbamoyl; 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; Sulfonamide groups such as methanesulfonamide, benzenesulfonamide, and p-toluenesulfonamide. 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 methanesulfonyl, octanesulfonyl, benzenesulfonyl, and 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 thereof include ionic hydrophilic groups such as a carboxyl group, a sulfo group, a phosphono group, and a quaternary ammonium group. In addition, it is preferable that the number of ionic hydrophilic groups in the general formula (II) is at least two in one molecule, and it is particularly preferable that there are at least two sulfonic acid groups and / or carboxyl groups.

In the general formula (II), a1, a2, a3, and a4 are the number of substituents X _{1 to} X ₈ , respectively. a1, a2, a3, and a4 are each independently an integer of 1 or 2. When at least one of a1, a2, a3, and a4 is 2, at least one of X ₁ , X ₂ , X ₃ , and X ₄ is present in plural. In this case, a plurality of substituents may be the same or different. In the present invention, it is particularly preferable that a1, a2, a3, and a4 are 1.

In the compound represented by the general formula (II), the phthalocyanine ring (Pc) is dimer (Pc-Cu-L-Cu-Pc) or trimer (Pc) via the divalent linking group (L). Pc-Cu-L-Cu-L-Cu-Pc) or the like may be formed. L is a divalent linking group, and includes an oxy group (—O—), a thio group (—S—), a carbonyl group (—CO—), a sulfonyl group (—SO ₂ —), and an imino group (—NH—). , A methylene group (—CH ₂ —) or a combination thereof.

  In the present invention, it is preferable that at least one of the substituents in the general formula (II) is the substituent specifically exemplified above, and more substituents are specifically exemplified above. It is preferably a substituent. In particular, it is preferable that all the substituents in the general formula (II) are the substituents mentioned above. Furthermore, the compound represented by the general formula (II) preferably has water solubility, and in this case, the substituent in the general formula (II) preferably contains an ionic hydrophilic group. Examples of the ionic hydrophilic group include a sulfonic acid group, a carboxyl group, a phosphono group, and a quaternary ammonium group. Among them, a carboxyl group, a phosphono group, or a sulfonic acid group is preferable, and further a carboxyl group or a sulfonic acid group. The group is particularly preferred. The carboxyl group, phosphono group, and sulfonic acid group may be in the form of a salt. Examples of the counter ion that forms the salt include alkali metal ions, ammonium ions, and organic cations. Examples of alkali metal ions include lithium ions, sodium ions, and potassium ions. Examples of organic cations include tetramethylammonium ion, tetramethylguanidinium ion, and tetramethylphosphonium. Among these, alkali metal salts are preferable, and lithium salts are particularly preferable from the viewpoints of solubility of the coloring material and ink stability.

  In the present invention, the compound of the general formula (II) is used in combination with the compound of the general formula (I) described above. For this reason, the compound of the general formula (II) has a site capable of forming a hydrogen bond with the compound of the general formula (I), for example, a hydroxyl group in a state mixed with the compound of the general formula (I). Is particularly preferred.

  Further, the compound of the general formula (II) is preferably formed by introducing at least one electron-withdrawing group such as a sulfinyl group, a sulfonyl group, and a sulfamoyl group into each of the four benzene rings of the phthalocyanine skeleton. Furthermore, it is particularly preferable to have a structure in which the sum of Hammett's substituent constants σp values of all the electron-withdrawing groups substituted on the phthalocyanine skeleton in the general formula (II) is 1.60 or more.

  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 are detailed descriptions in J.A. Dean, Langes Handbook of Chemistry 12th edition, 1979, McGraw-Hill, Chemistry, Special Issue, 122, 96-103, 1979, Nankodo.

  In the present invention, each substituent is defined by Hammett's σp value. However, the present invention is not limited to only the substituents whose σp values are specifically described in the literature as described above. 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. Specific examples of the substituent that can be used as the electron-withdrawing group having a positive Hammett σp value in the compound of the general formula (II) of the present invention are shown below together with the Hammett σp value.

The σp value of 0.60 or more electron withdrawing group with a Hammett's substituent constant, a cyano group, a nitro group, an alkylsulfonyl group (e.g., methanesulfonyl group), an arylsulfonyl group (e.g., benzenesulfonyl group) and the like .

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

  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 groups. 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). And a heterocyclic ring (for example, 2-benzoxazolyl group, 2-benzothiazolyl group, 1-phenyl-2-benzimidazolyl group) and the like. Moreover, the aryl group substituted by two or more electron withdrawing groups whose (sigma) p value is 0.15 or more is mentioned.

  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.

Here, the α-position and β-position in the phthalocyanine compound will be described using the following structural formula. The α-position is the 1-position and / or 4-position, 5-position and / or 8-position, 9-position and / or 12-position, 13-position and / or 16-position, and the α-position-substituted phthalocyanine compounds are these A phthalocyanine compound having a specific substituent at at least one of the positions. The β-position means the 2-position and / or the 3-position, the 6-position and / or the 7-position, the 10-position and / or the 11-position, the 14-position and / or the 15-position, Is a phthalocyanine compound having a specific substituent at at least one of these positions. That is, in the compound of the general formula (II), X ₁ , X ₂ , X ₃ , and X ₄ are in the β- position, and Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , And Y ₈ are phthalocyanine compounds each substituted at the α- position.

  As described above, when a large number of electron withdrawing groups such as sulfamoyl groups are introduced into the phthalocyanine skeleton, the oxidation potential becomes more noble and the ozone resistance of an image formed with such an ink can be improved. However, when the synthesis is carried out by the method described above, it is inevitable that a phthalocyanine compound having a small number of electron withdrawing groups, that is, having a lower oxidation potential is mixed. Therefore, in order to improve the ozone resistance of an image formed with ink, it is particularly preferable to perform the synthesis by a method that suppresses the generation of a phthalocyanine compound having a lower oxidation potential.

  The compound of general formula (II) can be synthesized, for example, according to the following two synthesis flows. By reacting a phthalonitrile derivative and / or a diiminoisoindoline derivative with a copper derivative, a compound of formula (II) (β-substituted type) can be synthesized. Moreover, the compound (β-substituted type) of the general formula (II) can be synthesized by deriving from a tetrasulfophthalocyanine compound obtained by reacting a 4-sulfophthalonitrile derivative with a copper derivative.

In the above synthesis flow, X _m corresponds to X ₁ , X ₂ , X ₃ , or X ₄ in the general formula (II). Y _n represents Y ₁ , Y ₃ , Y ₅ , or Y ₇ in the general formula (II), and Y _{n ′} represents Y ₂ , Y ₄ , Y ₆ , or Y ₈ in the general formula (II). Equivalent to. M in the 4-sulfophthalonitrile derivative is a cation, and specific examples include alkali metal ions such as Li, Na, and K, or organic cations such as triethylammonium ion and pyridinium ion. Y in the copper derivative (Cu (Y) _d ) is a monovalent or divalent ligand, and specific examples include a halogen atom, an acetate anion, acetylacetonate, oxygen, and the like. An integer from 4 to 4.

  According to the synthesis flow described above, a desired number of desired substituents can be introduced into the copper phthalocyanine skeleton. In particular, when a large number of electron withdrawing groups are to be introduced into the copper phthalocyanine skeleton in order to make the oxidation potential noble as in the present invention, the above-described synthesis flow is extremely effective.

  Preferable specific examples of the compound of the general formula (II) include the following exemplified compounds II-1 to II-102. Of course, the present invention is not limited to the following exemplified compounds as long as they are included in the structure of the general formula (II) and the definition thereof. In the present invention, among the following exemplary compounds, it is preferable to use an exemplary compound having a hydroxyl group, and it is particularly preferable to use exemplary compound II-66.

The following is exemplified compound II-13~II-57 below shows in tabular set of X _m in Table 2, and (Y _n, Y _{n ')} sets of, included in the general formula (II) Each substituent in the general formula shown in FIG. These groups are independently in any order in the following general formula.

Table 2-1: Exemplary compounds having the structure of general formula (II)

Table 2-2: Exemplary compounds having the structure of general formula (II)

Table 2-3: Exemplary compounds having the structure of general formula (II)

In the following, Exemplified Compounds II-58 to II-102 represented by the following formulas included in the general formula (II) are shown in the table. In Table 2, X _pr is each independently P ₁ or P ₂ , the number of P ₁ substituting for the copper phthalocyanine skeleton is m, the number of P ₂ is n, and Y _q is a hydrogen atom. In addition, each substituent of P ₁ and P ₂ is substituted at the β position of the copper phthalocyanine skeleton, and the substitution positions at the β position are in no particular order.

Table 2-4: Exemplary compounds having the structure of general formula (II)

Table 2-5: Exemplary compounds having the structure of general formula (II)

[Color material verification method]
For verifying whether or not the color material of the general formula (II) used in the present invention is contained in the liquid (ink), the following verifications (1) to (3) using high performance liquid chromatography (HPLC) The method is applicable.
(1) Peak retention time (2) Maximum absorption wavelength by peak absorbance detector of (1) (3) Mass spectrum M / Z (posi, negative) by mass spectrometry for peak of (1)

The analysis conditions of high performance liquid chromatography are as follows. A liquid diluted approximately 1,000 times with pure water was used as a measurement sample, and the sample was analyzed by high performance liquid chromatography under the following conditions. And the retention time (retention time) of a peak and the maximum absorption wavelength of the peak by a visible light absorbance detector were measured.
Column: SunFire C ₁₈ 2.1mm x 150mm
-Column temperature: 40 ° C
・ Flow rate: 0.2 mL / min
PDA: 200 nm to 700 nm
-Mobile phase and gradient conditions: Table 3 below

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

  Table 3 shows the retention time, maximum absorption wavelength, M / Z (posi), and M / Z (negative) values for Example Compound II-66, which is a specific example of the second color material. As a result of performing the same analysis as described above for the unknown ink, when each value corresponds to the value shown in Table 4, it can be determined that the coloring material corresponding to the compound used in the present invention is contained.

[Content of coloring 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.

  The total content (% by mass) of the first color material (compound of general formula (I)) and the second color material (compound of general formula (II)) in the ink is based on the total mass of the ink. The content is preferably 0.1% by mass or more and 20.0% by mass or less. Furthermore, the total content (% by mass) of the content is particularly preferably 0.5% by mass or more and 10.0% by mass or less. If the total content is less than 0.1% by mass, sufficient ozone resistance and color developability may not be obtained. If the total content exceeds 20.0% by mass, such as anti-sticking property. Ink jet characteristics may not be obtained.

  The content (mass%) of the first color material (compound of general formula (I)) based on the total mass of the ink is the content (mass of the second color material (compound of general formula (II)). %) In terms of mass ratio, (first color material / second color material) = 1.25 times or more and 5.0 times or less is preferable. Furthermore, the mass ratio is particularly preferably 1.5 times or more and 3.0 times or less. As a result of the study by the present inventors, when mixing with the first color material and the second color material, there is a correlation between these mass ratios and ozone resistance, and the effect of improving ozone resistance is particularly noticeable. It was found that the mass ratio of the content is in the above range. That is, when this mass ratio is satisfied, a particularly excellent ozone resistance is obtained that far exceeds the performance predicted from the ozone resistance possessed by the compound of general formula (I) or the compound of general formula (II). be able to. In addition, by setting the mass ratio of the content within the above range, it is possible to obtain a color tone preferable as a cyan ink. When the mass ratio exceeds 5.0, the influence of mixing of the color materials on the cohesiveness is small, and the ozone resistance may be close to the performance when these color materials are used alone. In addition, since the color tone of the ink is also biased toward the red direction, a color tone preferable as a cyan ink may not be obtained. On the other hand, if the mass ratio is less than 1.25, the influence of mixing of coloring materials on the cohesiveness is small, and ozone resistance may be close to the performance when these coloring materials are used alone. . Further, since the color tone of the ink is also biased toward the green direction, a color tone preferable as a cyan ink may not be obtained. In other words, in the present invention, by mixing the first color material and the second color material at a specific mass ratio, the ozone resistance of the image far exceeding the predicted level and the color tone preferable as the cyan ink are obtained. Can be achieved particularly remarkably.

In the present invention, the preferable color tone for the cyan ink means the following. For an image formed using cyan ink at a recording duty of 100%, a ^* and b ^* in the L ^* a ^* b ^* display system defined by the CIE (International Lighting Commission) are measured. Then, from the obtained values of a ^* and b ^* , an ink having a hue angle (H °) calculated based on the following formula (1) of 237 ° or more and 244 ° or less is referred to as cyan ink in the present invention. The ink has a preferable color tone. 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.

Formula (1)
When a ^* ≧ 0 and b ^* ≧ 0 (first quadrant), H ° = tan ⁻¹ (b ^* / a ^* )
When a ^* ≦ 0 and b ^* ≧ 0 (second quadrant), H ° = 180 + tan ⁻¹ (b ^* / a ^* )
For a ^* ≦ 0 and b ^* ≦ 0 (third quadrant), H ° = 180 + tan ⁻¹ (b ^* / a ^* )
When a ^* ≧ 0 and b ^* ≦ 0 (fourth quadrant), H ° = 360 + tan ⁻¹ (b ^* / a ^* )

[Mechanism to improve ozone resistance]
As described above, the combination of the first colorant and the second colorant produces a synergistic effect that improves the ozone resistance of the image far beyond the expected level. The present inventors speculate as follows.

  As a result of the study by the present inventors, it has been found that there is a correlation between the cohesiveness of the coloring material and the ozone resistance. That is, ozone resistance is higher when the specific color material is mixed than when the color material is present alone in the ink, that is, when the color material is present in an aggregate. It was found that the performance was improved. From this, it is possible to control the cohesiveness in the aggregate of the color material formed by mixing a specific color material, and this further aggregates than when each color material is present alone in the ink. It will be in the state. As a result, it is considered that particularly excellent ozone resistance exceeding the predicted level was obtained. Note that controlling the cohesiveness of the colorant present in the ink is considered to have the same effect as controlling the cohesiveness of the aggregate of the colorant applied to the recording medium.

  As described above, when ink having a cohesive property controlled and easily aggregated is applied to the recording medium, the aggregate of the color materials aggregates on the recording medium, thereby forming a larger aggregate. When an oxidizing gas such as ozone gas in the air causes a reaction that deteriorates the color material on the recording medium, molecules near the surface layer of the aggregates deteriorate. However, since the molecules inside the aggregate are not easily deteriorated by the oxidizing gas, the ratio of the color material remaining without being deteriorated as a whole increases. In the present invention, ozone resistance can be particularly remarkably improved by such a mechanism.

  On the other hand, in an ink containing only one type of color material, the cohesiveness is determined by the inherent performance of the color material, so it is difficult to arbitrarily control the cohesiveness depending only on the characteristics of the color material. There are many cases. In addition, it is conceivable to select one type of color material having a high cohesiveness of the color material itself, but at this time, it is often difficult to achieve both a preferable cyan color tone and cohesiveness. Even when two or more kinds of color materials are mixed, in conventional color materials, the state of aggregation often depends on the inherent cohesiveness of each color material. However, it was difficult to control the cohesiveness.

  However, as a result of the study by the present inventors, when two or more color materials are used in combination, the two or more color materials are specifically aggregated by using a color material having a specific substituent. I found out that One colorant preferably has a substituted sulfamoyl group in the compound of the general formula (I) described above, and more preferably the substituted sulfamoyl group has an alkylene group. Since the alkylene group in the substituted sulfamoyl group of the compound of the general formula (I) has an effect of lowering the solubility of the coloring material in an aqueous medium, it is considered that the coloring material is more easily aggregated and the ozone resistance is improved. It is done. The other colorant preferably has a group capable of forming a hydrogen bond with the substituted sulfamoyl group, and it has been found that ozone resistance is particularly remarkably improved particularly when it has a hydroxyl group.

  That is, in the present invention, by selecting a color material having a specific structure that causes aggregation specifically, particularly a color material having each of the above-mentioned substituents, by using these color materials in combination, The effect is obtained. That is, ozone resistance far exceeding the performance in the case of combining these predicted from the ozone resistance of each color material can be obtained. This is because the cohesiveness when using a combination of colorants is higher than the cohesiveness of each colorant, making it easier to form larger aggregates on the recording medium and suppressing the deterioration rate of the colorant. It is thought that it is because it can do. In the present invention, when (first color material / second color material) = 1.25 times to 5.0 times, further 1.5 times to 3.0 times In particular, it is particularly preferable because an excellent ozone resistance of an image can be realized.

[Color material cohesion]
The small angle X-ray scattering method can be applied to the measurement of the cohesiveness of the color material. 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.

  An outline of the small-angle X-ray scattering apparatus will be described with reference to FIG. 1 which is a measurement principle diagram of the small-angle X-ray scattering method. The X-ray generated from the X-ray source is focused on the sample solution to the extent of several mm or less while passing through the first to third slits, and irradiated to the sample solution. X-rays irradiated to the sample solution are scattered on the sample solution and then detected on the imaging plate. Since the scattered X-rays interfere with each other due to the difference in optical path difference, the distance d value between particles can be obtained from the obtained θ value by the Bragg equation (the following equation (A)). In addition, d value calculated | required here can be considered as the distance of the center from the center of the particle | grains arranged at a fixed space | interval.

（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。）

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

  Generally, when the particles in the solution are not regularly arranged, no peak occurs in the scattering angle profile. In the case of an aqueous solution of a compound in which all of the aromatic rings corresponding to A, B, C, and D of the general formula (I) used in the present invention are benzo rings, a strong value has a maximum value in the range of 2θ = 0 ° to 5 °. A peak is detected. Therefore, it can be seen that particles (molecular aggregates) formed by aggregation of phthalocyanine colorant molecules are arranged according to a certain rule. FIG. 2 shows 10 masses of each of the following compound (A), which is a triphenylmethane-based color material, and a compound in which the aromatic rings corresponding to A, B, C, and D in the general formula (I) are all benzo rings. The scattering angle profile in% aqueous solution is shown. From FIG. 2, it can be seen that even if the color material has the same cyan hue, the phthalocyanine color material has a specific scattering angle peak. In other words, in the case of phthalocyanine-based colorants, several phthalocyanine molecules aggregate in the aqueous solution to form molecular aggregates, and the distance between the molecular aggregates has a certain distribution as shown by the scattering angle profile. become.

  FIG. 3 is a conceptual diagram of a dispersion distance of a molecular aggregate of a phthalocyanine color material. As shown in FIG. 3, the radius of a molecular assembly of a certain phthalocyanine color material is r1, and the distance between the molecular assemblies is d1. Assuming that d1 is always constant, as the radius of the molecular assembly formed by the phthalocyanine-based colorant increases from r1 → r2, the d value measured by the small angle X-ray scattering method also changes from d2 → d3. It is thought to grow. Therefore, the d value measured by the above method is considered to be an index representing the size of the molecular aggregate of the phthalocyanine color material, and the larger the d value, the larger the size of the molecular aggregate formed by the color material molecules. It is thought that it has become. In this way, the cohesiveness of the color material, that is, the size of the aggregate can be represented by the d value.

  As a result of the study by the present inventors, the d value when the compound of the general formula (I) and the compound of the general formula (II) are mixed at a certain ratio is only the compound of the general formula (I) or the general formula It turned out that it becomes larger than each d value of only the compound of (II). Further, in this way, a synergistic effect is exhibited in the combination of color materials in which the d value in the mixed state is larger than the d value of each compound, and ozone resistance is particularly remarkably improved. I found out that However, there was no correlation between the magnitude of the d value in the mixed state and the ozone resistance performance.

That is, the ink according to another aspect of the present invention is an ink containing at least the coloring material A and the coloring material B, and the dispersion distance d value of the molecular aggregate in the ink obtained by the small angle X-ray scattering method is The following conditions are preferably satisfied. In this case, when the compound of general formula (I) and the compound of general formula (II) are combined rather than the ozone resistance of each of the compound of general formula (I) or the compound of general formula (II) only Synergistic effects are exhibited and ozone resistance is significantly improved. Here, the compound of general formula (I) is referred to as “coloring material A”, and the compound of general formula (II) is referred to as “coloring material B”.
d _{A + B} > d _A and d _{A + B} > d _B
(In the above formula, d _A (nm) is the d value of the color material A, d _B (nm) is the d value of the color material B, and d _{A + B} (nm) is the color material A and the color material B. D value when mixing.)

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

(Other additives)
In addition to the components described above, the ink of the present invention is a water-soluble organic substance that is solid at room temperature, such as polyhydric alcohols such as trimethylolpropane and trimethylolethane, and urea derivatives such as urea and ethyleneurea, if necessary. A compound may be contained. 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>
Further, in order to form a full-color image or the like, the ink of the present invention can be used in combination with an ink having a color tone different from that of the ink of the present invention. 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 the aqueous solution of sodium aluminate etc. which are 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 used in the ink jet recording method of the present invention in which recording is performed on a recording medium by ejecting the ink by an ink jet method. 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, and 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. 4 is a perspective view of the ink jet recording apparatus. 5 and 6 are diagrams for explaining the internal mechanism of the ink jet recording apparatus. FIG. 5 is a perspective view from the upper right part, and FIG. 6 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 an image is formed on a recording medium, the carriage unit arranges a recording head H1001 (FIG. 7; 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 performing recording 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. 7 is a diagram showing the configuration of the head cartridge H1000, and also shows how the ink cartridge H1900 is attached to 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. 7, 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. 8 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. 9 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 recording elements corresponding to different ink colors (hereinafter also referred to as nozzle arrays). On the first recording element substrate H1100, nozzle rows for three colors, a nozzle row H2000 for yellow ink, a nozzle row H2100 for magenta ink, and a nozzle row H2200 for cyan ink, are formed. On the second recording element substrate H1101, nozzle rows for four colors, a light cyan ink nozzle row H2300, a black ink nozzle row H2400, a green ink nozzle row H2500, and a light magenta ink nozzle row H2600, are formed. ing.

Each nozzle row is composed of 768 nozzles arranged at an interval of 1,200 dpi (dot / inch; reference value) in the recording medium conveyance direction (sub-scanning direction). Each nozzle ejects about 2 picoliters of ink. For this reason, the opening area in each discharge port is set to about 100 μm ² .

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

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

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

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

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

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

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

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

EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example , 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, the ink components in Examples , Reference Examples , and Comparative Examples mean “parts by 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, dissolved in pure water, and then fixed 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

(Synthesis of Compound A)
(1) Synthesis of compound (1)

  To 2,000 parts of ice water, 7.2 parts of Rotat OH-104K (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 reaction was carried out 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 was added 118.4 parts of 28% aqueous ammonia, and the mixture was kept at 10-15 ° C. and pH 9.5-10.0 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 to this, and the temperature of the reaction liquid was 10 degrees C or less. 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 (III) 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 crystals were filtered. The obtained crystals were 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. 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 crystal was a compound 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 ]

  Into 46.2 parts of chlorosulfonic acid, 5.8 parts of copper tribenzo (2,3-pyrido) porphyrazine obtained above was gradually charged with stirring while maintaining the temperature of the liquid at 60 ° C. or lower, and then 140 The reaction was carried out at 4 ° 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 reaction was performed 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 obtained above was added and suspended by stirring. Next, a solution obtained by dissolving 20.5 parts of the compound (1) (purity: 59.3%) obtained above in 3.0 parts of aqueous ammonia and 100 parts of warm water was added, and 28% aqueous ammonia was added. By adding, the pH of the reaction solution was maintained at 9.0 to 9.3, and the reaction was performed at 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 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 A). 10.7 parts were obtained. As a result of analyzing this blue crystal, the following measured values were obtained.
Maximum absorption wavelength (λ _max ): 611 nm (in aqueous solution)

(Synthesis of Compound B)
(1) Copper dibenzobis (2,3-pyrido) porphyrazine [the following compound (5): two of A, B, C and D in the general formula (III) 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 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 the 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 crystal was a compound 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): 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 ]

  Into 46.2 parts of chlorosulfonic acid, 5.8 parts of the copper dibenzobis (2,3-pyrido) porphyrazine obtained above was gradually charged with stirring while maintaining the temperature of the liquid at 60 ° C. or less. The reaction was carried out at 4 ° 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 reaction was performed 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 the wet cake of copper dibenzobis (2,3-pyrido) porphyrazine disulfonyl chloride obtained above was added and suspended by stirring. Next, what melt | dissolved 20.5 parts of compounds (1) (purity: 59.3%) obtained by the synthesis | combination of the said compound A in 4.0 parts of ammonia water 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% aqueous ammonia, and the reaction was performed at 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 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, suspended by stirring at 60 ° C. for 1 hour, filtered, washed with 100 parts of methanol and dried to obtain blue crystals (compound B). 9.3 parts were obtained. As a result of analyzing this blue crystal, the following measured values were obtained.
Maximum absorption wavelength (λ _max ): 602 nm (in aqueous solution)

(Synthesis of Compound C)
(1) Copper benzotris (2,3-pyrido) porphyrazine [the following compound (8): three of A, B, C and D in the general formula (III) 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 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 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 the liquid was heated to 60 ° C. and kept for 1 hour. Thereafter, the crystals were filtered and washed with 100 parts of water. Subsequently, the obtained wet cake was added to 500 parts of 10% ammonia water, and the temperature of the liquid was set 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 crystal was a compound 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 crude copper benzotris (2,3-pyrido) porphyrazine obtained above was gradually charged with stirring while maintaining the temperature of the liquid at 60 ° C. or lower. The reaction was carried out 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 reaction was performed 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) [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

To 250 parts of ice water, 33.0 parts of the copper benzotris (2,3-pyrido) porphyrazine sulfonyl chloride wet cake obtained above was added and suspended by stirring. Next, what melt | dissolved 20.5 parts of compounds (1) (purity: 59.3%) obtained by the synthesis | combination of the said compound A in 4.0 parts of ammonia water and 90 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% aqueous ammonia, and the reaction was performed 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 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 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 C). 5.0 parts were obtained. As a result of analyzing this blue crystal, the following measured values were obtained.
Maximum absorption wavelength (λ _max ): 584 nm (in aqueous solution)

(Synthesis of Compound D)
(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 reaction solution was heated 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 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, then 50 parts of 28% aqueous ammonia 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. 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 following measured values were obtained.
Maximum absorption wavelength (λ _max ): 625 nm (in aqueous solution)

(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 ]

  To 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 above was gradually stirred. Then, the reaction was carried out 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 reaction was performed 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 the wet cake of copper tribenzo (2,3-pyrido) porphyrazine trisulfonyl chloride obtained above was added and suspended by stirring. Next, what melt | dissolved 20.5 parts of compounds (1) (purity: 59.3%) obtained by the synthesis | combination of the said compound A in 3.0 parts of aqueous ammonia and 90 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% aqueous ammonia, and the reaction was performed at 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 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 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 blue crystals (compound D). 9.8 parts were obtained. As a result of analyzing this blue crystal, the following measured values were obtained.
Maximum absorption wavelength (λ _max ): 614 nm (in aqueous solution)

(Synthesis of Compound E)
(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. The temperature was raised to 160 ° C. while distilling off. Thereafter, 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%), ammonium molybdate 1 0.0 part was added and the temperature was raised 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 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 in which 1000 parts of 20% saline and 10 parts of concentrated hydrochloric acid were mixed, 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 1000 parts of water, 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 following measured values were obtained.
Maximum absorption wavelength (λ _max ): 607.5 nm (in aqueous solution)

(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, 7.8 parts of copper dibenzobis (2,3-pyrido) porphyrazine sodium disulfonate obtained above is gradually charged with stirring while maintaining the liquid temperature at 60 ° C. or lower. Thereafter, the reaction was carried out 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 reaction was performed 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 the wet cake of copper dibenzobis (2,3-pyrido) porphyrazine disulfonyl chloride obtained above was added to 250 parts of ice water, and suspended by stirring. Next, what melt | dissolved 25.3 parts of compounds (1) (purity: 59.3%) obtained by the synthesis | combination of the said compound A in 5.0 parts of ammonia water 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% aqueous ammonia, and the reaction was performed 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 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 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 E). 7.6 parts were obtained. As a result of analyzing this blue crystal, the following measured values were obtained.
Maximum absorption wavelength (λ _max ): 609 nm (in aqueous solution)

(Synthesis of Compound F)
(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. The temperature was raised to 160 ° C. while distilling off. Thereafter, the mixture was cooled to 100 ° C., 16.8 parts of pyrazine dicarponic acid, 72.0 parts of urea, 8.8 parts of copper (II) chloride dihydrate (purity 97.0%), ammonium molybdate 1. 0 parts 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 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, then 50 parts of 28% aqueous ammonia 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. , 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 following measured values were obtained.
Maximum absorption wavelength (λ _max ): 610.5 nm (in aqueous solution)

(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 ]

To 2.7 parts of chlorosulfonic acid, 7.8 parts of sodium copper dibenzobis (2,3-pyrazino) porphyrazine disulfonate obtained above was gradually charged with stirring while maintaining the liquid temperature at 60 ° C. or lower. Thereafter, the reaction was carried out at 120 ° C. for 4 hours. Then, the reaction solution was cooled to 70 ° C., thionyl chloride 17. Nine parts were added dropwise over 30 minutes and reacted at 70 ° C. for 3 hours. The reaction was cooled to 30 ° C. or lower, and gradually poured into 500 parts of ice water, and the precipitated crystals were filtered and washed with 200 parts of cold water, copper dibenzobis (2,3-pyrazino) porphyrazine sulfonyl chloride (a 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]

In 200 parts of ice water, 44.1 parts of the wet cake of copper dibenzobis (2,3-pyrazino) porphyrazine disulfonyl chloride obtained above was added and suspended by stirring. Next, what melt | dissolved 20.5 parts of compounds (1) (purity: 59.3%) obtained by the synthesis | combination of the said compound A in the ammonia water 3.0 parts and warm water 100 parts was added. To this, the pH of the reaction solution was kept at 9.0 to 9.3 by adding 28% aqueous ammonia, and the reaction was carried out at 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 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 8 crystals of blue crystals (Compound F). .8 parts were obtained. As a result of analyzing this blue crystal, the following measured values were obtained.
Maximum absorption wavelength (λ _max ): 614.5 nm (in aqueous solution)

(Synthesis of Compound G)
(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 (III)) 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 crystals were filtered. The obtained crystals were 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, 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. The obtained crystals were filtered and washed with 300 parts of water and 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 analyzing this blue crystal, the following measured values were obtained.
Maximum absorption wavelength (λ _max ): 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 (IV) in which the ratio of the pyridine ring to the benzene ring is 1.5: 2.5 on average and x is 2.5] In 46.2 parts of chlorosulfonic acid, maintaining the temperature of the liquid at 60 ° C. or lower, the copper tribenzo (2,3-pyrido) porphyrazine and copper dibenzobis (2,3-pyrido) porphyrazine obtained above 5.8 parts of the mixture were gradually charged under stirring. In this state, the reaction was carried out 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 reaction was performed at 70 ° C. for 3 hours. Next, 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) Mixture of the above-mentioned compound (4) and compound (16) [mixture of exemplary compounds I-2, I-3, and I-4: A, B, C, and D in the general formula (I) Among them, 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. , N is 0.8] In 350 parts of ice water, 59.3 parts of the wet cake of copper benzo (2,3-pyrido) porphyrazinesulfonyl chloride obtained above is added and stirred. And suspended. Next, what melt | dissolved 20.5 parts of compounds (1) (purity: 59.3%) obtained by the synthesis | combination of the said compound A in the ammonia water 3.0 parts and warm water 100 parts was added. To this, the pH of the reaction solution was maintained at 9.0 to 9.3 by adding 28% aqueous ammonia, and the reaction was performed at 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 separated by liquid 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 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 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 G). 10.7 parts were obtained. As a result of analyzing this blue crystal, the following measured values were obtained.
Maximum absorption wavelength (λ _max ): 606 nm (in aqueous solution)

(Compound H)
As compound H, exemplified compound I-25 described in Table 1-2 was used.

(Synthesis of Comparative Compound I)
As the comparative compound I which is a comparative compound of the compound of the general formula (I), the following comparative compound I synthesized according to the method for synthesizing the compound of Example 1 described in JP-A-2006-328129 was used.

(Synthesis of Compound J)
As compound J, Exemplified Compound II-66 described in Table 2-4 synthesized with reference to Japanese Patent No. 3851569 was used.

(Comparative Compound K)
As a comparative compound K which is a comparative compound of the compound of general formula (II), C.I. I. Direct blue 199 was used.

<Preparation of ink>
The components having the compositions shown in Tables 5 to 8 were mixed and sufficiently stirred. Then, pressure filtration was performed with a filter having a pore size of 0.20 μm to prepare inks of Examples 1 to 7 , 9 to 20 , Reference Example 8, and Comparative Examples 1 to 16.

<Preparation of recording medium>
By applying a resin composition containing 70 parts of low density polyethylene, 20 parts of high density polyethylene, and 10 parts of titanium oxide to both sides of a base paper having a basis weight of 155 g / m ² , the resin composition is 25 g / m ^2. A support coated with was prepared. Then, an ink receiving layer mainly composed of alumina hydrate and polyvinyl alcohol was formed on the support. In this way, a gap type ink receiving layer was provided, and the JAPAN TAPPI paper pulp test method no. A recording medium having a surface pH of 5.0 after 3 minutes measured according to 49-1.

<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. An image with the recording duty varied from 0% to 100% in increments of 10% was formed on the recording medium obtained above.

(Ozone resistance)
The image density of the image portion having a recording duty of 50% in the recorded matter obtained above was measured (referred to as “image density D ₁ before the ozone resistance test”). Further, this recorded matter was exposed for 4 hours at an ozone gas concentration of 10 ppm, a relative humidity of 60%, and an in-tank temperature of 23 ° C. using an ozone test apparatus (trade name: OMS-H; manufactured by Suga Test Instruments). Thereafter, the image density of the image portion of the recorded matter having a recording duty of 50% was measured (referred to as “image density D ₂ after the ozone resistance test”). The image density was 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 image density before the ozone resistance test and image density after the ozone resistance test, the residual density ratio was calculated based on the following formula (B), and the ozone resistance was evaluated. The standard of ozone resistance is as follows. The evaluation results are shown in Table 9. In the following evaluation criteria, AA to B are levels that are not problematic as ozone resistance, AA and A are particularly excellent levels, and C and D are levels that are insufficient in ozone resistance.

A: The residual concentration ratio is 95% or more A: The residual concentration ratio is 92% or more and less than 95% B: The residual concentration ratio is 90% or more and less than 92% C: The residual concentration ratio is 85% or more and less than 90% D: The residual concentration ratio Is less than 85%

(D value)
About each ink obtained above, the scattering angle profile was measured by the small angle X-ray scattering method. 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: 0.5 mm, 2nd Slit: 0.4 mm, 3rd Slit: 0.8 mm
・ Irradiation time: 240 min
・ Beam stopper: 3.0mmφ
・ Measurement method: Transmission method ・ Detector: Blue Imaging Plate

  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 results are shown in Table 9. In addition, d value represents the cohesiveness of a color material or a mixture of color materials.

When compound A and compound J were combined as (first color material / second color material) = 1.26 (Example 16), the d _{A + B} value was 6.94 nm. This value is larger than each of the d _A value of 6.76 nm in the case of Compound A alone and the d _B value of 6.69 nm in the case of Compound J alone. That is, it shows that the cohesiveness when the color materials are used in combination becomes higher than the cohesiveness of each color material. Further, when the compound J and the compound H are combined as (first color material / second color material) = 2.33 ( Reference Example 8), the d _{A + B} value is 6.79 nm. In this case as well, than the d value of each of the coloring material (d _A value and d _B value), it can be confirmed that d value in the case of using a combination of color material is increased. However, when the compound A and the comparative compound K were combined with (first color material / second color material) = 1.50 (Comparative Example 12), the d _{A + B} value was 6.26 nm. This value is an intermediate value between the d _A value of 6.76 nm in the case of only Compound A and the d _B value of 5.32 nm in the case of only Comparative Compound K. This is because the compound A and the comparative compound K are not a combination that specifically improves the aggregation property.

  Further, it has been considered that an equivalent effect can be obtained by selecting a color material having high cohesion as a single color material, that is, a color material having a large d value. However, as a result of the study by the present inventors, simply selecting a color material having a large d value often causes the color tone of the ink to deviate significantly from the color tone preferred as a cyan ink, and is used as an ink having a cyan hue. Can be said to have a problem.

  From the above, when the compound A and the compound J are combined, the substituted sulfamoyl group of the compound A interacts with the substituent of the compound J, so that a larger aggregate than the case of the compound A alone or the compound J alone. It can be said that is formed. And since an aggregate becomes large and the deterioration rate of a coloring material is suppressed, it turns out that ozone resistance improves. Similarly, when the compound J and the compound H are combined, larger aggregates are formed than in the case of the compound J alone or the compound H alone, so that the ozone resistance is improved. However, it was found that when a compound having a sulfone urea group, such as Comparative Compound I, was combined, ozone resistance was not improved and the effects of the present invention could not be obtained.

  In this way, a combination of compounds that can increase the cohesiveness is selected, and a larger aggregate is formed on the recording medium, so that it deteriorates due to an attack from an oxidizing gas in the air, particularly ozone. The proportion of the color material can be reduced. As a result, particularly excellent ozone resistance can be obtained in the present invention. At the same time, a preferable color tone can be obtained.

It is a measurement principle figure of a small angle X-ray scattering method. It is a small angle X-ray scattering profile of a triphenylmethane color material and a phthalocyanine color material. It is a conceptual diagram of the dispersion distance of the molecular aggregate of a phthalocyanine color material. 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.

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 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 H1501: Ink channel H1600: Channel type Member H1700: filter H1800: seal rubber H1900: ink cartridge H2000: yellow nozzle row H2100: magenta nozzle row H2200: cyan nozzle row H2300: light cyan nozzle row H2400: black nozzle row H2500: green nozzle row H2600: light magenta nozzle row

Claims (7)

An ink containing at least two colorants, a first colorant and a second colorant,
The first colorant is a compound represented by the following general formula (I):
The ink, wherein the second color material is a compound represented by the following general formula (II).

(In 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. Each ring is independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium, and E is an alkylene group, and X is a sulfo-substituted anilino group, a carboxyl-substituted anilino group, or a phosphono-substituted anilino group. The substituted anilino group further includes a sulfonic acid group, a carboxyl group, a phosphono group, a sulfamoyl group, a carbamoyl group, a hydroxyl group, an alkoxy group, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, and a diarylamino group. Acetylamino group, ureido group, alkyl group, nitro group, cyano group, halogen, alkylsulfonyl group, and It may have 1 to 4 substituents 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 ( L) ≦ 2, 0 ≦ m ≦ 3, 0.1 ≦ n ≦ 3, and l (L) + m + n = 1 to 4.

(In General Formula (II), X ₁ , X ₂ , X ₃ , and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , or —CONR ₁ R _2. it. here, Z is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted An aryl group or a substituted or unsubstituted heterocyclic group, wherein R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group An alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and Y ₁ , Y ₂ , Y ₃ , Y _{4 Y 5, Y 6, Y 7} , and Y ₈ are, respectively it water MotoHara child, a1, a2, a3, and a4 are _{respectively, X 1, X 2, X} 3, and the substituents X ₄ Number, each independently an integer of 1 or 2.)   The ink according to claim 1, wherein the nitrogen-containing heteroaromatic ring is a pyridine ring or a pyrazine ring.   The content (mass%) of the first color material in the ink is 1.25 to 5.0 times the content (mass%) of the second color material in the ink. The ink according to claim 1 or 2.   4. An ink jet recording method for recording on a recording medium by ejecting ink by an ink jet method, wherein the ink is the ink according to any one of claims 1 to 3.   4. An ink cartridge comprising an ink container for containing ink, wherein the ink is the ink according to any one of claims 1 to 3.   4. A recording unit comprising an ink storage portion for storing ink and a recording head for ejecting ink, wherein the ink is the ink according to claim 1. 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 3. Inkjet recording apparatus.

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