JP2013221054A - Ink, ink cartridge and inkjet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide ink enabling an image having excellent coloring property and ozone resistance to be recorded.SOLUTION: Ink contains a first coloring material and a second coloring material. The first coloring material is a compound expressed by general formula (1) (in the formula, each of rings A, B, C and D independently expresses benzene ring or a heterocyclic aromatic ring. Rexpresses alkyl group, Rexpresses alkylene group and X expresses an anilino group having one or more sulfonic acid group. (m) is more than 0.0 and <3.9 in average, (n) is ≥0.1 and <4.0 in average and the sum of (m) and (n) is ≥0.1 and <4.0 in average), the second coloring material is a compound having triphenyl methane skeleton, and (content of first coloring material):(content of second coloring material) is 5.0-40.0 in the ratio by mass, based on total mass of the ink.

Description

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

  The ink jet recording method is a recording method in which an ink droplet is applied to a recording medium such as plain paper to form an image, and is rapidly spreading due to its low price and an increase in recording speed. In general, the recorded matter obtained by the ink jet recording method has lower image storage stability than silver salt photographs. In particular, when the recorded material is exposed to environmental gases such as light, humidity, heat, or ozone gas present in the air for a long time, the color material of the recorded material deteriorates, and the color tone of the image or fading easily occurs. There is a problem.

  The change in color tone or dark blue of the image is mainly caused by cyan ink having low ozone resistance among cyan, yellow, and magenta inks. Therefore, improving the ozone resistance of cyan ink to the level of yellow ink or magenta ink is one of the important issues in the ink jet recording system.

  Of the dyes contained in the inkjet ink as colorants, compounds having a cyan hue are roughly divided into two basic skeletons, a phthalocyanine skeleton and a triphenylmethane skeleton. Examples of the compound having a phthalocyanine skeleton include C.I. I. Direct blue 86, 87, 199 and the like can be mentioned. Examples of the compound having a triphenylmethane skeleton include C.I. I. Acid Blue 9 etc. are mentioned. In general, a compound having a phthalocyanine skeleton is characterized by being excellent in light resistance as compared with a compound having a triphenylmethane skeleton. In addition, it is a compound widely used as a coloring material for ink-jet inks because of its high fastness to humidity and heat and good color developability.

  However, compounds having a phthalocyanine skeleton have low fastness to ozone gas in the air. For example, this is conspicuous in a recorded matter using a recording medium having an ink receiving layer formed of an inorganic material such as alumina or silica, and when such a recorded matter is left in a room for a long time, it is markedly faded. There is a problem. On the other hand, a compound having a triphenylmethane skeleton is characterized by excellent color developability as compared with a compound having a phthalocyanine skeleton. Therefore, for the purpose of recording an image having excellent color developability, a phthalocyanine compound and C.I. I. A cyan ink containing a compound having a triphenylmethane skeleton such as Acid Blue 9 as a coloring material has been proposed (see Patent Document 1).

JP-A-11-158424

  The demand for color developability and ozone resistance of images recorded by the ink jet recording method is increasing year by year, and inks using conventional color materials for cyan ink have not reached a level that can satisfy the above requirements. is the current situation. In addition, the ozone resistance of the triphenylmethane compound is extremely lower than that of the phthalocyanine compound. For this reason, even with the cyan ink proposed in Patent Document 1, it has been difficult to record an image having both color developability and ozone resistance.

  Accordingly, an object of the present invention is to provide an ink capable of recording an image excellent in color development and ozone resistance. Another object of the present invention is to provide an ink cartridge and an ink jet recording method using the ink.

  The above object is achieved by the present invention described below. That is, according to the present invention, an ink containing a first color material and a second color material, wherein the first color material is a compound represented by the following general formula (1), The second color material is a compound having a triphenylmethane skeleton, and the content (% by mass) of the first color material based on the total mass of the ink is the content of the second color material ( The ink is characterized by having a mass ratio with respect to (mass%) of 5.0 times or more and 40.0 times or less.

（前記一般式（１）中、破線で表される環Ａ、Ｂ、Ｃ及びＤは、それぞれ独立に、ベンゼン環又は複素芳香環を表し、かつ、前記複素芳香環の個数は平均値で０．０より大きく３．０以下であるとともに残りはベンゼン環である。Ｒ₁はアルキル基を表し、Ｒ₂はアルキレン基を表し、Ｘは１以上のスルホン酸基を有するアニリノ基を表す。Ｘはカルボキシ基、リン酸基、ヒドロキシ基、アルコキシ基、アルキルカルボニルアミノ基、ウレイド基、ニトロ基、及びハロゲン原子からなる群より選択される１以上の置換基をさらに有してもよい。ｍは平均値で０．０より大きく３．９未満であり、ｎは平均値で０．１以上４．０未満であり、かつ、ｍ及びｎの和は平均値で１．０以上４．０未満である）

(In the general formula (1), the rings A, B, C and D represented by broken lines each independently represent a benzene ring or a heteroaromatic ring, and the number of heteroaromatic rings is 0 on average. 0.0 to 3.0 and the remainder is a benzene ring, R ₁ represents an alkyl group, R ₂ represents an alkylene group, and X represents an anilino group having one or more sulfonic acid groups. May further have one or more substituents selected from the group consisting of a carboxy group, a phosphate group, a hydroxy group, an alkoxy group, an alkylcarbonylamino group, a ureido group, a nitro group, and a halogen atom. The average value is greater than 0.0 and less than 3.9, n is an average value of 0.1 or more and less than 4.0, and the sum of m and n is an average value of 1.0 or more and less than 4.0 Is)

  ADVANTAGE OF THE INVENTION According to this invention, the ink which can record the image excellent in coloring property and ozone resistance can be provided. In addition, according to the present invention, it is possible to provide an ink cartridge and an ink jet recording method using this ink.

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

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. In the present invention, when the compound is a salt, the salt is dissociated into ions in the ink, but is expressed as “contains a salt” for convenience.

<Ink>
The ink of the present invention contains the first color material and the second color material at a specific mass ratio. The first color material is a compound represented by the general formula (1), and the second color material is a compound having a triphenylmethane skeleton. Hereinafter, each component constituting the ink of the present invention will be described in detail.

(First color material)
The ink of the present invention contains a compound represented by the following general formula (1) as a first color material. The compound represented by the general formula (1) is a mixture as described later, but for convenience, the general formula (1) is shown as a typical structure of the mixture, and the number of rings and the number of substituents are as follows. The average value is shown. This color material is a water-soluble dye exhibiting a cyan color and can be suitably used as a color material for cyan ink. In the present specification, for the sake of convenience, the compound represented by the general formula (1) may be collectively referred to as “first color material”.

（前記一般式（１）中、破線で表される環Ａ、Ｂ、Ｃ及びＤは、それぞれ独立に、ベンゼン環又は複素芳香環を表し、かつ、前記複素芳香環の個数は平均値で０．０より大きく３．０以下であるとともに残りはベンゼン環である。Ｒ₁はアルキル基を表し、Ｒ₂はアルキレン基を表し、Ｘは１以上のスルホン酸基を有するアニリノ基を表す。Ｘはカルボキシ基、リン酸基、ヒドロキシ基、アルコキシ基、アルキルカルボニルアミノ基、ウレイド基、ニトロ基、及びハロゲン原子からなる群より選択される１以上の置換基をさらに有してもよい。ｍは平均値で０．０より大きく３．９未満であり、ｎは平均値で０．１以上４．０未満であり、かつ、ｍ及びｎの和は平均値で１．０以上４．０未満である）

(In the general formula (1), the rings A, B, C and D represented by broken lines each independently represent a benzene ring or a heteroaromatic ring, and the number of heteroaromatic rings is 0 on average. 0.0 to 3.0 and the remainder is a benzene ring, R ₁ represents an alkyl group, R ₂ represents an alkylene group, and X represents an anilino group having one or more sulfonic acid groups. May further have one or more substituents selected from the group consisting of a carboxy group, a phosphate group, a hydroxy group, an alkoxy group, an alkylcarbonylamino group, a ureido group, a nitro group, and a halogen atom. The average value is greater than 0.0 and less than 3.9, n is an average value of 0.1 or more and less than 4.0, and the sum of m and n is an average value of 1.0 or more and less than 4.0 Is)

  In the general formula (1), preferred specific examples of the heteroaromatic ring represented by the rings A, B, C and D represented by broken lines include heteroaromatic rings having at least one nitrogen atom as a ring constituent atom, A nitrogen-containing heteroaromatic ring can be mentioned. The number of nitrogen atoms contained as a ring-constituting atom in the nitrogen-containing heteroaromatic ring is usually 1 or 2, preferably 1. Specific examples of the nitrogen-containing heteroaromatic ring include pyridine having one nitrogen atom; pyrazine, pyridazine and pyrimidine having two nitrogen atoms. Of these, a pyridine ring is particularly preferable.

  The condensed ring site with the porphyrazine ring in the heteroaromatic ring is not particularly limited. For example, when the heteroaromatic ring of rings A, B, C and D is a pyridine ring, a ring condensed at the 2-position and 3-position or 3-position and 4-position with the position of the nitrogen atom as the 1-position Preferred are those condensed at the 3- and 4-positions. The number of heteroaromatic rings among the rings A, B, C and D is an average value of more than 0.0 and 3.0 or less, preferably 0.2 or more and 2.0 or less, more preferably 0.5. It is 1.7 or more and particularly preferably 0.7 or more and 1.5 or less. The remainder of rings A, B, C and D is a benzene ring. The number of benzene rings among rings A, B, C and D is 1.0 or more and less than 4.0 on average, preferably 2.0 or more and 3.8 or less, more preferably 2.3 or more and 3.5. Hereinafter, it is particularly preferably 2.5 or more and 3.3 or less.

  In the present specification, unless otherwise specified, the number of heteroaromatic rings is rounded off to the first digit after the second decimal place. However, for example, when the number of pyridine rings is 1.35 and the number of benzene rings is 2.65, when both are rounded off, the former becomes 1.4 and the latter becomes 2.7, and the sum of both is 4. It becomes larger than 0. In such a case, for the sake of convenience, the second decimal place of the number of heteroaromatic rings is rounded down, and only the number of benzene rings is rounded off to describe the former as 1.3 and the latter as 2.7. As for m and n in the general formula (1), in principle, the second decimal place is rounded off to the first digit. However, when the sum of both exceeds the theoretical value, the second decimal place of m is rounded down and only n is rounded off.

In the general formula (1), examples of the alkylene group represented by R ₂ include a linear, branched or cyclic alkylene group. Of these, a linear or cyclic alkylene group is preferable, and a linear alkylene group is more preferable. The carbon number of the alkylene group is usually 2 or more and 12 or less, preferably 2 or more and 6 or less, more preferably 2 or more and 4 or less, and particularly preferably 2 or more and 3 or less. Specific examples of the alkylene group include linear alkylene groups such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, and dodecylene; branched chain alkylene such as 2-methylethylene; cyclopropylene diyl, Examples thereof include cyclic alkylene groups such as 1,2- or 1,3-cyclopentylenediyl and cyclohexylenediyl such as 1,2-, 1,3- or 1,4-.

In general formula (1), examples of the alkyl group represented by R ₁ include linear, branched or cyclic alkyl groups. Of these, a linear or branched alkyl group is preferable, and a linear alkyl group is more preferable. The carbon number of the alkyl group is usually 1 or more and 6 or less, preferably 1 or more and 4 or less, and more preferably 1 or more and 3 or less. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl; isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, isohexyl and the like And a branched alkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Among these, a methyl group, an ethyl group, or an isopropyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is particularly preferable.

  In the general formula (1), the anilino group having one or more sulfonic acid groups represented by X is usually 1 or more and 3 or less, preferably 1 or 2, more preferably an anilino group having two sulfonic acid groups. Can be mentioned. Specific examples of the anilino group having one or more sulfonic acid groups include anilino groups having one sulfonic acid group such as 2-sulfoanilino, 3-sulfoanilino, and 4-sulfoanilino; 2,3-disulfoanilino and 2,4-disulfoanilino , 2,5-disulfoanilino, 3,4-disulfoanilino, 3,5-disulfoanilino and other anilino groups having two sulfonic acid groups; 2,3,4-trisulfoanilino, 2,3,5-trisulfoani Examples thereof include an anilino group having three sulfonic acid groups such as lino, 2,3,6-trisulfoanilino, and 3,4,5-trisulfoanilino. Of these, a 2,5-disulfoanilino group is particularly preferable.

  In the general formula (1), when the anilino group having one or more sulfonic acid groups represented by X further has a substituent other than the sulfonic acid group, the number of substituents other than the sulfonic acid group is usually 1 Or 2, preferably 1. The kind of substituent may be single or plural. Examples of the substituent other than the sulfonic acid group include a carboxy group, a phosphoric acid group, a hydroxy group, an alkoxy group, an alkylcarbonylamino group, a ureido group, a nitro group, and a halogen atom.

  Examples of the alkoxy group include a straight chain, branched chain or cyclic alkoxy group, a straight chain or branched chain alkoxy group is preferred, and a straight chain alkoxy group is more preferred. The number of carbon atoms of the alkoxy group is usually 1 or more and 6 or less, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less. Specific examples of the alkoxy group include linear alkoxy groups such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy; isopropoxy, isobutoxy, sec-butoxy, t-butoxy, isopentyloxy And branched chain alkoxy groups such as isohexyloxy; cyclic alkoxy groups such as cyclopropoxy, cyclopentoxy, cyclohexyloxy and the like. Among these, a methoxy group, an ethoxy group, or an isopropoxy group is preferable, and a methoxy group is more preferable.

  Examples of the alkylcarbonylamino group include a linear or branched alkylcarbonylamino group, and a linear alkylcarbonylamino group is preferred. The carbon number of the alkyl moiety of the alkylcarbonylamino group is usually 1 or more and 6 or less, preferably 1 or more and 4 or less, and more preferably 1 or more and 3 or less. Specific examples of the alkylcarbonylamino group include linear alkylcarbonylamino groups such as methylcarbonylamino (acetylamino), ethylcarbonylamino, n-propylcarbonylamino, and n-butylcarbonylamino; branched alkyl such as isopropylcarbonylamino. Examples thereof include a carbonylamino group. Among these, an acetylamino group is preferable.

  Examples of the ureido group include an unsubstituted ureido group, an alkyl ureido group, and an aryl ureido group. Specific examples of the alkyl or arylureido group include alkylureido groups such as methylureido, ethylureido, N, N-dimethylureido and N, N-dibutylureido; arylureido groups such as phenylureido and the like. Of these, unsubstituted ureido groups are particularly preferred.

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

  In the general formula (1), m and n, and the sum of m and n are all average values. m is greater than 0.0 and less than 3.9. n is 0.1 or more and less than 4.0. The sum of m and n is 1.0 or more and less than 4.0. When the number of heteroaromatic rings in the rings A, B, C, and D is 0.2 to 2.0 and the number of benzene rings is 2.0 to 3.8, m is 1.8. It is preferable that it is 3.6 or less, n is 0.2 or more and 2.0 or less, and the sum of m and n is 2.0 or more and 3.8 or less. When the number of heteroaromatic rings in the rings A, B, C, and D is 0.3 to 1.5 and the number of benzene rings is 2.5 to 3.7, m is 2 2 or more and 3.0 or less, n is 0.3 or more and 1.5 or less, and the sum of m and n is preferably 2.5 or more and 3.7 or less. Further, when the number of heteroaromatic rings in the rings A, B, C and D is 0.5 or more and 1.2 or less and the number of benzene rings is 2.8 or more and 3.5 or less, m is 2 It is preferable that n is 0.4 or more and 1.4 or less, and the sum of m and n is 2.8 or more and 3.5 or less.

  As the value of m increases, the ozone resistance of the recorded image tends to improve, while the bronze phenomenon tends to occur. For this reason, the ratio of m and n may be adjusted as appropriate while considering the ozone resistance and bronze resistance of the recorded image, and a well-balanced ratio may be selected. The unsubstituted sulfamoyl group and the substituted sulfamoyl group, each of which is represented by m and n, are groups introduced into the benzene ring among the rings A, B, C, and D. That is, the unsubstituted sulfamoyl group and the substituted sulfamoyl group are not introduced into the heteroaromatic ring among the rings A, B, C, and D.

The compound represented by the general formula (1) may be a free acid type (H type), or may form a salt with an acidic group such as a sulfonic acid group in the molecule. Examples of counter ions in the case of forming a salt include alkali metals; ammonia (NH ₃ ); cations such as organic ammonium. Specific examples of the alkali metal include lithium, sodium and potassium. Specific examples of organic ammonium include alkylamines having 1 to 3 carbon atoms such as methylamine and ethylamine; carbon numbers such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine. Mention may be made of organic ammonium such as 1 to 4 mono-, di- or trialkanolamines.

Preferred specific examples of the salt of the compound represented by the general formula (1) include salts with alkali metals such as sodium, potassium, and lithium; monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanol Examples thereof include salts with mono-, di- or trialkanolamines having 1 to 4 carbon atoms, such as amines and triisopropanolamine; ammonium (NH ₄ ⁺ ) salts.

  Further, when the compound represented by the general formula (1) is a salt type, depending on the type of the counter ion of the salt, physical properties such as solubility and the performance of the ink containing the salt as a coloring material ( In particular, the performance related to the robustness of the recorded image may change. For this reason, it is also preferable to select the kind of salt according to the performance of the target ink. In order to change the compound from the free acid form to the salt form, the above-mentioned substances that generate cations (alkali metal hydroxides, etc.) are added to bring the pH of the liquid containing the compound into the alkaline region. Adjust it. In order to change the compound from the salt form to the free acid form, an acid may be added to adjust the pH of the liquid containing the compound to the acidic region. In addition, ion exchange or the like may be performed to change from a specific salt type to another salt type.

  As a more preferable specific example of the first color material contained in the ink of the present invention, a compound represented by the following general formula (2) can be given.

（前記一般式（２）中、破線で表される環Ａ、Ｂ、Ｃ及びＤは、それぞれ独立に、ベンゼン環又は複素芳香環を表し、かつ、前記複素芳香環の個数は平均値で０．０より大きく３．０以下であるとともに残りはベンゼン環である。Ｍは、それぞれ独立に、水素原子、アルカリ金属、アンモニウム、又は有機アンモニウムを表す。ｍは平均値で０．０より大きく３．９未満であり、ｎは平均値で０．１以上４．０未満であり、かつ、ｍ及びｎの和は平均値で１．０以上４．０未満である）

(In the general formula (2), the rings A, B, C and D represented by broken lines each independently represent a benzene ring or a heteroaromatic ring, and the number of heteroaromatic rings is 0 on average. Greater than 0.0 and less than or equal to 3.0 and the remainder is a benzene ring, each M independently represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium, and m is an average value greater than 0.0 and 3 Less than 0.9, n is an average value of 0.1 or more and less than 4.0, and the sum of m and n is an average value of 1.0 or more and less than 4.0)

  Table 1 shows preferred specific examples of the compound represented by the general formula (1). Of course, the compound represented by the general formula (1) used as the coloring material in the ink of the present invention is an exemplary compound shown in Table 1 as long as it is included in the structure of the general formula (1) and its definition. It is not limited. As is well known to those skilled in the art, a phthalocyanine-based porphyrazine compound such as the compound represented by the general formula (1) usually exists in a complex mixture containing a plurality of isomers. Even if it is used in, it is effective. However, in this specification, for convenience, a typical structural formula is described without distinguishing a plurality of isomers. In addition, in order to avoid complexity for the values of m and n in Table 1, the first decimal place is rounded off. For this reason, m in Table 1 is described as “0” for the sake of convenience, but this is a problem of calculation processing, meaning that m in the general formula (1) is larger than 0.0. There is no change.

  The compound represented by the general formula (1) is, for example, a compound represented by the following general formula (II) and an organic amine represented by the following general formula (III) in the presence of ammonia or an ammonia generation source. It can synthesize | combine by making it react with. A compound represented by the following general formula (II) can be obtained, for example, by chlorosulfonylating a compound represented by the following general formula (I).

（一般式（Ｉ）中、破線で表される環Ａ、Ｂ、Ｃ及びＤは、それぞれ独立に、ベンゼン環又は複素芳香環を表し、かつ、複素芳香環の個数は平均値で０．０より大きく３．０以下であるとともに残りはベンゼン環である）

(In general formula (I), rings A, B, C and D represented by broken lines each independently represent a benzene ring or a heteroaromatic ring, and the average number of heteroaromatic rings is 0.0. Greater than 3.0 and the rest are benzene rings)

（一般式（ＩＩ）中、破線で表される環Ａ、Ｂ、Ｃ及びＤは、前記一般式（Ｉ）中の環Ａ、Ｂ、Ｃ及びＤと同義である。ｎは平均値で１．０以上４．０未満である）

(In general formula (II), rings A, B, C and D represented by broken lines have the same meanings as rings A, B, C and D in general formula (I). 0.0 or more and less than 4.0)

（一般式（ＩＩＩ）中、Ｒ₁はアルキル基を表し、Ｒ₂はアルキレン基を表し、Ｘは１以上のスルホン酸基を有するアニリノ基を表す。Ｘはカルボキシ基、リン酸基、ヒドロキシ基、アルコキシ基、アルキルカルボニルアミノ基、ウレイド基、ニトロ基、及びハロゲン原子からなる群より選択される１以上の置換基をさらに有してもよい）

(In the general formula (III), R ₁ represents an alkyl group, R ₂ represents an alkylene group, X represents an anilino group having one or more sulfonic acid groups. X represents a carboxy group, a phosphoric acid group, or a hydroxy group. 1 or more substituents selected from the group consisting of an alkoxy group, an alkylcarbonylamino group, a ureido group, a nitro group, and a halogen atom)

  Any of the compounds represented by formula (I) can be obtained according to a known method or a method analogous thereto. Known methods include, for example, methods disclosed in International Publication No. 2007/091631, International Publication No. 2007/116933, and International Publication No. 2008/111635.

  As a suitable method for chlorosulfonylating the compound represented by the general formula (I), a compound represented by the general formula (I) is added to chlorosulfonic acid and reacted, and then a chlorinating agent is further added. The method of making it react can be mentioned. When a compound represented by the general formula (I) is reacted with chlorosulfonic acid, a compound in which a chlorosulfonyl group and a sulfonic acid group are mixed and substituted is obtained, and the target general formula (II) It is difficult to obtain the represented compound with high selectivity. For this reason, after reacting the compound represented by the general formula (I) with chlorosulfonic acid, it is preferable to add a chlorinating agent to convert the substituted sulfonic acid group into a chlorosulfonyl group.

  When the compound represented by the general formula (I) is chlorosulfonylated, the chlorosulfonic acid is usually 3 to 20 times by mass, preferably 5 to 10 masses, relative to the compound represented by the general formula (I). Use twice. The reaction temperature is usually 100 to 150 ° C., preferably 120 to 150 ° C. The reaction time varies depending on the reaction temperature and other conditions, but is usually 1 to 10 hours.

  Examples of the chlorinating agent include thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like. Of these chlorinating agents, thionyl chloride is preferred. The addition amount of the chlorinating agent varies depending on the type, but is usually 6 to 40 mol, preferably 9 to 20 mol, per 1 mol of the compound represented by the general formula (I). The reaction temperature is usually 30 to 100 ° C., preferably 50 to 90 ° C. The reaction time varies depending on the reaction temperature and other conditions, but is usually 1 to 10 hours.

The organic amine represented by the general formula (III) can be synthesized by the following method. First, 5 to 60 mol of alcohols represented by the general formula “R ₁ —OH”, ₁ mol of 2,4,6-trichloro-S-triazine (cyanuric chloride), and 0.8 to 1 of sodium bicarbonate .2 moles are reacted to obtain a reaction solution containing the primary condensate. The reaction temperature is usually 5 to 70 ° C. The reaction time is usually 2 to 12 hours. The primary condensate isolated as a solid such as a wet cake from the obtained primary condensate reaction solution by an appropriate method such as salting out may be used in the next reaction.

  Next, the reaction solution or wet cake (preferably the reaction solution) of the obtained primary condensate is added to an aqueous solution of 0.9 to 1.5 mol of aniline having one or more sulfonic acid groups corresponding to X. Then, the pH of the reaction solution is adjusted to about 4 to 10 with an alkali metal hydroxide such as sodium hydroxide and reacted to obtain a secondary condensate. The reaction temperature is usually 5 to 80 ° C., preferably 5 to 40 ° C. The reaction time is usually 0.5 to 12 hours.

By reacting 1 mol of the obtained secondary condensate with 1 to 50 mol of alkylenediamine represented by the general formula of “H ₂ N—R ₂ —NH ₂ ”, the above general formula (III) The organic amine represented can be obtained. The pH during the reaction is usually 4-7. The reaction temperature is usually 5 to 90 ° C, preferably 40 to 90 ° C. The reaction time is usually 0.5 to 8 hours.

  For the pH adjustment in each condensation reaction, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate can be used. In addition, what is necessary is just to determine the order of a condensation reaction suitably according to the reactivity of the compound made to react with cyanuric chloride.

  By reacting the compound represented by the general formula (II) with the organic amine represented by the general formula (III) in the presence of ammonia or an ammonia generation source, for example, in water, the target general formula (1) ) Can be obtained. The pH during the reaction is usually 8 to 10. The reaction temperature is usually 5 to 70 ° C., preferably 5 to 40 ° C. The reaction time is usually 1 to 20 hours. As the ammonia, ammonia water, a water-miscible organic solvent containing ammonia gas, or the like can be used. Specific examples of the water-soluble organic solvent used for the water-miscible organic solvent containing ammonia gas include dimethylformamide and dimethylacetamide. As the water miscible organic solvent containing ammonia water or ammonia gas, those prepared by a known method such as blowing ammonia gas into water or water miscible organic solvent, or those obtained as a commercial product can be used. .

  As the ammonia generation source, a chemical substance that generates ammonia by neutralization or decomposition can be used. Examples of such chemical substances include ammonium salts that generate ammonia by neutralization of ammonium chloride and ammonium sulfate; substances that generate ammonia by thermal decomposition of urea and the like. Among the above, it is preferable to use ammonia, and it is preferable to use it as ammonia water. In particular, it is preferable to use concentrated aqueous ammonia (which is commercially available as about 28% by mass aqueous ammonia), or ammonia water obtained by diluting this concentrated aqueous ammonia with water as necessary. Furthermore, it is preferable to use concentrated aqueous ammonia because the amount of the reaction solution can be reduced.

  The amount of the organic amine represented by the general formula (III) is usually a theoretical value (a value intended for n in the general formula (1) with respect to 1 mol of the compound represented by the general formula (II). About 1 molar equivalent of the number of moles of the organic amine represented by the general formula (III) necessary for the above. However, it is appropriately adjusted depending on the reactivity of the organic amine and the reaction conditions. Usually, it is 1 to 3 molar equivalents of the theoretical value, preferably 1 to 2 molar equivalents.

When the compound represented by the general formula (II) and the organic amine represented by the general formula (III) are reacted in water, a part of the chlorosulfonyl group in the general formula (II) is converted into a sulfonic acid group. It is theoretically considered to be hydrolyzed. That is, it is theoretically that a compound in which a part of the “—SO ₂ NH ₂ ” group in the general formula (1) becomes a sulfonic acid group is mixed into the target compound represented by the general formula (1). Conceivable. However, it is usually difficult to distinguish a “—SO ₂ NH ₂ ” group from a sulfonic acid group by mass spectrometry, which is one of the general analytical means of phthalocyanine-based porphyrazine compounds. For this reason, all chlorosulfonyl groups in the general formula (II) other than those reacted with the organic amine represented by the general formula (III) in this specification are all converted to “—SO ₂ NH ₂ ” groups. It is described as converted.

  As a method of isolating the compound represented by the general formula (1) from the reaction solution in the final step of the synthesis method, acid precipitation (method of precipitating the compound by adding an acid), salting out, or a combination thereof A method such as acid precipitation may be mentioned. The salting out is preferably performed in the acidic to alkaline range, and more preferably in the range of pH 1 to 11. The temperature at the time of salting out is not particularly limited, but is usually 40 to 80 ° C, preferably 40 to 60 ° C. It is preferable to salt out by adding sodium chloride after heating. As a method for isolating the compound represented by the general formula (1), acid salting out in which salting out is performed under strong acidic pH 1 is preferable.

  As is well known to those skilled in the art, phthalocyanine-based porphyrazine compounds are classified into one of three types: α-substituted type, β-substituted type, and αβ-position mixed substituted type, depending on the substitution position of the substituent. . The compound represented by the general formula (1) has a specific number (average value) of benzene rings as the rings A, B, C and D. For this reason, the compound represented by the general formula (1) can also be classified into any of the three types of substitution depending on the position of the substituent on the benzene ring, like the phthalocyanine-based porphyrazine compound. And the compound represented by the general formula (1) can be classified into αβ-position mixed substitution type.

(Second color material)
The second color material combined with the above compound represented by the general formula (1) used as the first color material is a compound having a triphenylmethane skeleton. Any compound having a triphenylmethane skeleton corresponds to the second colorant in the present invention. Examples of the compound having a triphenylmethane skeleton with a color index include C.I. I. Acid Blue: 1, 3, 5, 7, 9, 11, 13, 15, 17, 22, 24, 26, 34, 48, 75, 83, 84, 86, 88, 90, 91, 93, 99, 100 , 103, 104, 108, 109, 110, 119, 147, and 269.

(Coloring material content)
The ink of the present invention can record an image realized at a high level of color developability and ozone resistance by containing the first color material and the second color material at a specific mass ratio. . In the present invention, the content (mass%) of the first color material based on the total mass of the ink is 5.0 times or more by the mass ratio with respect to the content (mass%) of the second color material. 0 times or less, preferably 20.0 times or more and 35.0 times or less. That is, “content of first color material (% by mass)” / “content of second color material (% by mass)” = 5.0 to 40.0 times, preferably 20.0 2 times or more and 35.0 times or less. When the above-mentioned mass ratio is less than 5.0 times, the excellent effect of improving ozone resistance of the first coloring material is not exhibited. On the other hand, when the above-mentioned mass ratio is more than 40.0 times, the excellent coloring property improving effect of the second coloring material is not exhibited.

  The present inventors presume the mechanism by which an image having both high color developability and high ozone resistance can be recorded when the ink of the present invention is used. In general, phthalocyanine compounds are inferior in color developability of recorded images as compared to triphenylmethane compounds, but are excellent in ozone resistance. In particular, regarding the ozone resistance, the “compound represented by the general formula (1)” is very excellent among the phthalocyanine compounds. Furthermore, since the “compound represented by the general formula (1)” is a compound having a highly planar molecular structure, it is likely to remain on the surface of the recording medium or in the vicinity thereof, rather than a compound having a triphenylmethane skeleton. . That is, in the depth direction of the recording medium, the compound represented by the general formula (1) tends to exist at a shallow position and the compound having a triphenylmethane skeleton easily exists at a deep position. For this reason, depending on the positional relationship of each color material in the recording medium, the compound having a triphenylmethane skeleton is protected by the compound represented by the general formula (1), and the probability of contact with ozone is reduced. High ozone resistance can be obtained. On the other hand, since the color developability is not greatly affected by the positional relationship of each color material in the recording medium, even if a compound having a triphenylmethane skeleton is present at a deep position, its characteristics are not impaired. Excellent color developability can be obtained.

  The content (% by mass) of the first color material in the ink is preferably 0.10% by mass or more and 10.00% by mass or less based on the total mass of the ink. The content (% by mass) of the second color material in the ink is preferably 0.01% by mass or more and 5.00% by mass or less based on the total mass of the ink. The ink of the present invention may contain a color material other than the first color material and the second color material. The total content (mass%) of the coloring material in the ink is not particularly limited as long as it satisfies the reliability as an inkjet ink such as ejection characteristics, but is 0.01 mass% or more and 10.00 mass% or less. Preferably there is.

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

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

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

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

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

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

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

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

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

<Synthesis of coloring materials>
The compound represented by the general formula (1) obtained by the synthesis method described below is a mixture containing a plurality of isomers, but unless otherwise specified, it is a mixture containing a plurality of isomers. Are described as “compounds”. That is, “compound” includes a positional isomer; a positional isomer of a nitrogen atom of a heteroaromatic ring; a ratio of benzene ring / heteroaromatic ring represented by rings A, B, C and D in the general formula (1) Different isomers; α / β positional isomers on the benzene ring of substituted or unsubstituted sulfamoyl groups. As mentioned earlier, it is very difficult to isolate a specific compound from a mixture of these isomers and determine the structure. For this reason, for convenience, one of the possible isomers is taken as a representative example, and the structural formula is described.

About the compound obtained by the synthesis method described below, mass spectrometry, ICP emission spectroscopy, and absorbance measurement were performed to confirm the structure. In addition, each operation, such as reaction and crystallization, was performed under stirring unless otherwise specified. “Leocol” used in the synthesis reaction is a surfactant (trade name “Leocor TD-90”, manufactured by Lion). The maximum absorption wavelength (λ _max ) is a measured value measured in an aqueous solution having a pH of 6 to 9, and a sodium hydroxide aqueous solution was used for pH adjustment. In addition, when the required amount of the target compound was not obtained by one synthesis, the same operation was repeated until the required amount of the target compound was obtained.

(Mass spectrometry)
About each compound synthesize | combined, mass spectrometry was performed on condition of the following.
-Ionization method: EI method-Mass spectrometer: Trade name "SSQ-7000" (manufactured by ThermoQuest)
-Ion source temperature: 230 ° C
・ Degree of vacuum: about 8mTorr

(ICP emission spectroscopy)
For each compound containing copper, the copper content was analyzed by ICP emission spectroscopy. Specifically, the analysis was performed as follows. About 0.1 g of an analytical sample was precisely weighed and dissolved in pure water, and then the volume was measured in a 100 mL volumetric flask. Using a whole pipette, 1 mL of this liquid was measured, put into a 50 mL volumetric flask, and a certain amount of Y (yttrium) was added as an internal standard substance. After the volume was adjusted to 50 mL with pure water, the copper content was quantified by ICP emission spectroscopy. An ICP emission spectrometer (trade name “SPS3100”, manufactured by SII Nanotechnology) was used as the analyzer.

(Absorbance measurement)
Absorbance was measured for each synthesized 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: 30 nm / min ・ Number of measurements: Average of 5 measurements

<Synthesis of Compound A>
(Synthesis of Compound (a-1))
To 400 parts of sulfolane, 44.4 parts of phthalic anhydride, 16.7 parts of cinchomeronic acid, 144 parts of urea, 13.4 parts of copper (II) chloride and 2.0 parts of ammonium molybdate are added, and the temperature is raised to 200 ° C. And reacted at the same temperature for 5 hours. After completion of the reaction, the mixture was cooled to 65 ° C., 80 parts of DMF (N, N-dimethylformamide) was added, and the precipitated solid was obtained by filtration. The obtained solid was washed with 220 parts of DMF to obtain 112.1 parts of a wet cake. The obtained wet cake was added to 340 parts of DMF, the temperature was raised to 110 ° C., and the mixture was stirred at the same temperature for 1 hour, and then the solid was separated by filtration and washed with 300 parts of water to obtain a wet cake. The obtained wet cake was added to 300 parts of 5% hydrochloric acid, heated to 60 ° C. and stirred at the same temperature for 1 hour, and then the solid was separated by filtration and washed with 300 parts of water to obtain a wet cake. The obtained wet cake was added to 300 parts of 5% aqueous ammonia and stirred at 60 ° C. for 1 hour, and then the solid was separated by filtration and washed with 300 parts of water to obtain 138.2 parts of a wet cake. The obtained wet cake was dried at 80 ° C. to obtain 46.3 parts of compound (a-1) as a blue solid.

(Synthesis of Compound (a-2))
Under room temperature, 5.8 parts of compound (a-1) was gradually added to 46.2 parts of chlorosulfonic acid so as not to exceed 60 ° C., and then reacted at 140 ° C. for 4 hours to obtain a reaction solution. After cooling the obtained reaction liquid to 70 ° C., 17.9 parts of thionyl chloride was added dropwise over 30 minutes, and the mixture was further reacted at 70 ° C. for 3 hours. After cooling the reaction solution to 30 ° C. or lower, it is slowly poured into 800 parts of ice water, the precipitated solid is separated by filtration, washed with 200 parts of cold water, and 33.0 parts of the wet cake of compound (a-2) is added. Obtained.

(Synthesis of Compound (a-3))
To 160 parts of methanol, 36.8 parts of cyanuric chloride, 4 parts of leocol, and 16.8 parts of sodium hydrogen carbonate were added and reacted at 30 ° C. or lower for 1 hour to obtain a reaction liquid containing a primary condensate. To 280 parts of water, 56.1 parts of 2,5-disulfoaniline and 32 parts of 25% aqueous sodium hydroxide solution were added to adjust the pH to 3-5. The reaction solution containing the primary condensate obtained as described above is gradually added to this liquid, and further reacted overnight at room temperature while adjusting the pH to 6 to 7 with a 25% aqueous sodium hydroxide solution to contain the secondary condensate. A reaction solution was obtained. To the obtained reaction solution, 360 parts of hydrochloric acid and 125 parts of ice water were added and cooled to 0 ° C., and then 120 parts of ethylenediamine was further added dropwise. While adjusting the pH to 5 to 6 by adding 25% aqueous sodium hydroxide, the mixture was reacted at 80 ° C. for 2.5 hours to obtain a reaction solution containing a tertiary condensate.

  To the resulting reaction solution, 55 parts of hydrochloric acid was added to adjust the pH to 1.0. The liquid volume at this time was 1000 parts. To the obtained liquid, 200 parts of sodium chloride was added and stirred for 30 minutes, and the precipitated solid was separated by filtration to obtain 183 parts of a wet cake. The obtained wet cake was added to 1000 parts of water, and adjusted to pH 9.0 with 25% aqueous sodium hydroxide solution to obtain a liquid. The resulting liquid was adjusted to pH 1.0 by adding 55 parts of hydrochloric acid. At this time, the liquid volume was 1400 parts. To this liquid was added 280 parts of sodium chloride, and the mixture was stirred at room temperature for 30 minutes and further at 0 ° C. for 30 minutes, and the precipitated solid was separated by filtration to obtain 60 parts of a wet cake. The obtained wet cake was added to a mixed liquid of 224 parts of methanol and 56 parts of water to form a suspension, stirred at 50 ° C. for 1 hour, and then the solid was separated by filtration to obtain 51.3 parts of a wet cake. . The obtained wet cake was dried to obtain 37.0 parts of compound (a-3) as a white powder.

(Synthesis of Compound A)
To 120 parts of ice water, 33.0 parts of the wet cake of compound (a-2) was added and stirred at 5 ° C. or lower for 10 minutes to obtain a suspension. On the other hand, 2.1 parts of white powder of compound (a-3) was dissolved in a mixed solution of 1 part of 28% ammonia water and 40 parts of water to obtain a liquid. The obtained liquid was added to the above suspension while maintaining at 10 ° C. or lower, and reacted while maintaining pH 9.0 with 28% aqueous ammonia. While maintaining the same pH, the temperature was raised to 20 ° C. over 1 hour, and the reaction was further continued at the same temperature for 8 hours. The liquid volume of the reaction liquid was 225 parts. The reaction solution was heated to 50 ° C., 33.8 parts of sodium chloride was added and stirred for 30 minutes, and then concentrated hydrochloric acid was added to adjust the pH to 1.0 over 20 minutes. The precipitated solid was separated by filtration and washed with 100 parts of a 10% aqueous sodium chloride solution to obtain 62.3 parts of a wet cake. The obtained wet cake was added to 200 parts of water and adjusted to pH 9.0 with a 25% aqueous sodium hydroxide solution to obtain a liquid. The liquid volume at this time was 275 parts. The liquid was heated to 50 ° C., 22.5 parts of sodium chloride was added and stirred for 30 minutes, then adjusted to pH 1.0 with concentrated hydrochloric acid over 20 minutes, and the precipitated solid was separated by filtration. The wet cake was washed with 100 parts of a 10% sodium chloride aqueous solution to obtain 37.1 parts of a wet cake. The obtained wet cake was added to a mixed liquid of 160 parts of ethanol and 40 parts of water to form a suspension. After stirring this liquid at 50 ° C. for 1 hour, the solid was separated by filtration to obtain 32.0 parts of a wet cake. Obtained. The obtained wet cake was dried to obtain 10.0 parts of a free acid of Compound A represented by the following formula (A) as a blue powder. The obtained compound A had a λ _max of 605 nm. Further, in compound A, the average value of the number of benzene rings is 3.0, the average value of the number of heteroaromatic rings is 1.0, and m, n, and m + n are average values of 0 <m <3. 9, 0.1 ≦ n <4.0 and 1.0 ≦ m + n <4.0. Combined with other analysis results, the average value of m is about 2.8, the average value of n is about 0.2, and the average value of m + n is about 3.0, which is close to the synthesized compound A (mixture). it is conceivable that. The obtained compound A was used for the preparation of an ink by using an aqueous sodium hydroxide solution to change the acidic group counter ion to sodium ion.

<Synthesis of Compound B>
(Synthesis of Compound (b-1))
To 220 parts of ethanol, 36.8 parts of cyanuric chloride, 4 parts of leocol, and 16.8 parts of sodium hydrogen carbonate were added and reacted at 30 ° C. or lower for 1 hour to obtain a reaction liquid containing a primary condensate. On the other hand, to 280 parts of water, 56.1 parts of 2,5-disulfoaniline and 32 parts of 25% aqueous sodium hydroxide solution were added to adjust the pH to 3-5. To this liquid, the reaction solution containing the primary condensate obtained as described above is gradually added, and further reacted overnight at room temperature while adjusting the pH to 6 to 7 with a 25% aqueous sodium hydroxide solution to contain the secondary condensate. A reaction solution was obtained. To the obtained reaction liquid, 360 parts of hydrochloric acid and 125 parts of ice water were added and cooled to 0 ° C., and 120 parts of ethylenediamine was further added dropwise. The resulting liquid was reacted at 80 ° C. for 2.5 hours while adding a 25% aqueous sodium hydroxide solution to adjust the pH to 5 to 6 to obtain a reaction solution containing a tertiary condensate.

  To the resulting reaction solution, 55 parts of hydrochloric acid was added to adjust the pH to 1.0. The liquid volume at this time was 1000 parts. To the obtained liquid, 200 parts of sodium chloride was added and stirred for 30 minutes, and the precipitated solid was separated by filtration to obtain 183 parts of a wet cake. The obtained wet cake was added to 1000 parts of water, and adjusted to pH 9.0 with 25% aqueous sodium hydroxide solution to obtain a liquid. To this liquid, 55 parts of hydrochloric acid was added to adjust the pH to 1.0. At this time, the liquid volume was 1400 parts. To this liquid was added 280 parts of sodium chloride, and the mixture was stirred at room temperature for 30 minutes and further at 0 ° C. for 30 minutes, and the precipitated solid was separated by filtration to obtain 60 parts of a wet cake. The obtained wet cake was added to a mixed liquid of 224 parts of methanol and 56 parts of water to form a suspension, stirred at 50 ° C. for 1 hour, and then the solid was separated by filtration to obtain 51.3 parts of a wet cake. . The obtained wet cake was dried to obtain 37.0 parts of compound (b-1) as a white powder.

(Synthesis of Compound B)
Except that the compound (a-3) was replaced with the compound (b-1), 10.0 parts of the compound B represented by the following formula (B) was obtained in the same manner as the synthesis of the compound A described above. Λ _max of the obtained compound B was 607 nm. Further, in compound B, the average value of the number of benzene rings is 3.0, the average value of the number of heteroaromatic rings is 1.0, and m, n, and m + n are average values, 0 <m <3. 9, 0.1 ≦ n <4.0 and 1.0 ≦ m + n <4.0. Combined with other analysis results, the average value of m is about 2.8, the average value of n is about 0.2, and the average value of m + n is about 3.0, which is close to the synthesized compound B (mixture). it is conceivable that. The obtained compound B was used for the preparation of ink by using an aqueous sodium hydroxide solution to change the counter ion of the acidic group to sodium ion.

(Synthesis of Compound C)
Compound C represented by the following formula (C) was synthesized according to the method for synthesizing the compound of formula (16) described on page 35 of WO2007 / 091631. In compound C, m was 2.4, and n was 0.6. This compound C is a comparative compound of the compound represented by the general formula (1). The obtained compound C was used for the preparation of ink by using an aqueous sodium hydroxide solution to change the acidic group counter ion to sodium ion.

<Preparation of Inks (Examples 1-6, Comparative Examples 1-6)>
Each component (unit:%) shown in the upper part of Tables 2-1 and 2-2 was mixed and stirred sufficiently, and each ink was prepared by pressure filtration with a filter having a pore size of 0.20 μm. In Tables 2-1 and 2-2, “acetylenol E100” is a trade name of a nonionic surfactant (manufactured by Kawaken Fine Chemicals). Further, in the lower part of Tables 2-1 and 2-2, the content (%) of the first color material, the content (%) of the second color material, and the first color material in the ink are shown. The value of the content (%) / the content (%) of the second color material is shown as “first / second mass ratio (times)”.

<Evaluation>
Each ink obtained above was filled in an ink cartridge and mounted on an ink jet recording apparatus (trade name “PIXUS Pro 9000 Mark II”, manufactured by Canon Inc.) that discharges ink from the recording head by the action of thermal energy. Using this inkjet recording apparatus, a solid image having a recording duty of 100% was recorded on a recording medium (trade name “Canon Photo Paper / Glossy Pro [Platinum Grade] PT101”, manufactured by Canon) to obtain a recorded matter. . In this embodiment, a solid image recorded by applying 22 ng of ink to a unit area of 1/600 inch × 1/600 inch is defined as “recording duty is 100%”. For the solid image of the obtained recorded matter, the optical density of the cyan component was measured using a spectrophotometer (trade name “Spectrolino”, manufactured by Gretag Macbeth) under the conditions of a light source: D50 and a visual field: 2 °. In the present invention, the evaluation criteria for the following items are such that B is not acceptable and A is acceptable. The evaluation results are shown in Table 3.

(Color development)
The optical density of the cyan component of the solid image in the obtained recorded matter was measured, and the color developability was evaluated according to the following criteria.
A: The optical density was 2.20 or more.
B: The optical density was less than 2.20.

(Ozone resistance)
The optical density of the cyan component of the solid image in the obtained recorded matter was measured. This recorded material was placed in an ozone tester (trade name “OMS-H”, manufactured by Suga Test Instruments Co., Ltd.), and exposed to ozone for 4 hours under the conditions of a tank temperature of 40 ° C., a relative humidity of 55%, and an ozone gas concentration of 10 ppm. It was. Thereafter, the optical density of the cyan component of the same solid image as previously measured was measured again. The residual ratio of optical density (%) = (optical density after exposure / optical density before exposure) × 100 was calculated, and ozone resistance was evaluated according to the criteria shown below.
A: The residual ratio of the optical density was 75% or more.
B: The residual ratio of the optical density was less than 75%.

Claims (5)

An ink containing a first color material and a second color material,
The first colorant is a compound represented by the following general formula (1):
The second colorant is a compound having a triphenylmethane skeleton;
The content (mass%) of the first color material based on the total mass of the ink is a mass ratio with respect to the content (mass%) of the second color material, and is 5.0 times or more and 40.0 times. Ink characterized by:

(In the general formula (1), the rings A, B, C and D represented by broken lines each independently represent a benzene ring or a heteroaromatic ring, and the number of heteroaromatic rings is 0 on average. 0.0 to 3.0 and the remainder is a benzene ring, R ₁ represents an alkyl group, R ₂ represents an alkylene group, and X represents an anilino group having one or more sulfonic acid groups. May further have one or more substituents selected from the group consisting of a carboxy group, a phosphate group, a hydroxy group, an alkoxy group, an alkylcarbonylamino group, a ureido group, a nitro group, and a halogen atom. The average value is greater than 0.0 and less than 3.9, n is an average value of 0.1 or more and less than 4.0, and the sum of m and n is an average value of 1.0 or more and less than 4.0 Is) The ink according to claim 1, wherein the first color material is a compound represented by the following general formula (2).

(In the general formula (2), the rings A, B, C and D represented by broken lines each independently represent a benzene ring or a heteroaromatic ring, and the number of heteroaromatic rings is 0 on average. Greater than 0.0 and less than or equal to 3.0 and the remainder is a benzene ring, each M independently represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium, and m is an average value greater than 0.0 and 3 Less than 0.9, n is an average value of 0.1 or more and less than 4.0, and the sum of m and n is an average value of 1.0 or more and less than 4.0)   The second color material is C.I. I. Acid Blue: 1, 3, 5, 7, 9, 11, 13, 15, 17, 22, 24, 26, 34, 48, 75, 83, 84, 86, 88, 90, 91, 93, 99, 100 The ink according to claim 1, wherein the ink is at least one selected from the group consisting of:, 103, 104, 108, 109, 110, 119, 147, and 269. An ink cartridge comprising ink and an ink containing portion for containing the ink,
The ink cartridge according to claim 1, wherein the ink is an ink according to claim 1. An inkjet recording method for recording an image on a recording medium by discharging ink from an inkjet recording head,
An ink jet recording method, wherein the ink is the ink according to any one of claims 1 to 3.

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