JP2018048308A - Ink, and inkjet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous ink excellent in ozone gas resistance.SOLUTION: The ink contains a compound represented by formula (1), a tautomer of the same, or a salt of these, and at least one coloring agent selected from the group consisting of a coloring agent (A) comprising a compound having a λmax of 500-700 nm, and a half value width of 100-500 nm, and a coloring agent (B) comprising a compound having a λmax of 350-450 nm, and a half value width of 50-250 nm.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous ink, an ink jet recording method using the ink, and a recording medium to which the ink is attached.

  A recording method using an ink jet printer (ink jet recording method) is one of color recording methods. In the ink jet recording method, ink droplets are generated and attached to various recording media (paper, film, fabric, etc.) for recording. This method is quiet because it does not generate sound because the recording head and the recording medium are not in direct contact. In addition, the ink jet printer can be easily downsized and increased in speed. For this reason, the ink jet recording method has been rapidly spread in recent years, and is expected to greatly expand in the future. As a water-based ink for writing instruments and inkjet recording applications, an ink in which a colorant is dissolved in an aqueous medium is generally used. A water-soluble organic solvent is usually added to these water-based inks in order to prevent clogging of the ink at the pen tip or the ink discharge nozzle. With these inks, it is possible to provide a recording image with sufficient density, no clogging of the pen tip and nozzles, good drying on the recording medium, less bleeding, and storage stability. Performance such as excellence is required. Moreover, as a coloring agent, a thing with the high solubility to the water-soluble organic solvent added to water and ink is desirable. Furthermore, various fastnesses, such as water resistance, light resistance, gas resistance (especially ozone gas resistance), moisture resistance, etc. are calculated | required by the image recorded with the water-based ink.

  Black ink is an important ink used for both monocolor and full color images. However, there are many technical difficulties in developing pigments that are neutral in hue and light color gamut, high in color density, and excellent in fastness. There are few things with sufficient performance. Therefore, generally, a black ink is prepared by mixing a plurality of various pigments. However, when an ink is prepared by mixing a plurality of pigments, problems such as different hues depending on the recording material and particularly large discoloration due to bleeding due to water are more likely to occur than when an ink is prepared with a single pigment.

  Inks containing at least one colorant are disclosed in Patent Documents 1-12.

JP 2013-249332 A Japanese Patent Laying-Open No. 2015-34207 JP 2012-177073 A JP 2012-177074 A JP 2012-177079 A JP 2012-177080 A JP 2012-177082 A Japanese Patent Laid-Open No. 2006-89113 International Publication No. 2016/021730 Gazette International Publication No. 2008/053776 Gazette International Publication 2006/001274 Gazette International Publication No. 2007/077931 Gazette

  An object of the present invention is to provide a water-based ink having good ozone gas resistance.

  As a result of intensive studies to solve the above problems, the present inventors have found that the compound represented by the formula (1) or a tautomer thereof, or a salt thereof, a specific colorant (A) and The inventors have found that the above-mentioned problems can be solved by an ink containing at least one colorant selected from the colorants (B), and have completed the present invention.

That is, the present invention relates to the following 1) to 10).
1)
A compound represented by the following formula (1) or a tautomer thereof, or a salt thereof, and at least one colorant selected from the following colorant (A) and colorant (B) ink.

[In Formula (1),
R ¹¹ represents an alkyl group, an aryl group, or a carboxy group,
R ¹² represents a cyano group, a carbamoyl group, or a carboxy group,
R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a sulfo group,
R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represents an alkylthio group; an alkoxy group; or a group represented by the following formula (2):
R ¹⁸ , R ¹⁹ and R ¹¹⁰ each independently represent a hydrogen atom; a carboxy group; a sulfo group; an alkylcarbonylamino group; a halogen atom; an alkyl group; an alkoxy group; or a group represented by the following formula (2):
R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; an alkylcarbonylamino group; a halogen atom; a cyano group; a nitro group; a sulfamoyl group; an alkyl group; Or represents an alkylsulfonyl group.
Any of the above groups can further have a substituent.
However, at least one of R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ¹¹⁰ is a group represented by the following formula (2).
Moreover, it can have a benzene ring represented by a broken line.

[In Formula (2),
R ¹¹⁶ represents a sulfoanilino group or a sulfonaphthylamino group.
The group represented by R ¹¹⁶ further includes a carboxy group, a phosphate group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkoxy group, an amino group, an alkylamino group, an arylamino group, an alkylcarbonylamino group, a ureido group, One or more substituents selected from the group consisting of an alkyl group, a cyano group, a halogen atom, an alkylsulfonyl group, and an alkylthio group can be included.
R ¹¹⁷ represents an anilino group, a naphthylamino group, an alkylamino group, an arylamino group, an amino group, an alkylthio group, an arylthio group, a phenoxy group, an alkoxy group, or a hydroxy group.
The group represented by R ¹¹⁷ further includes a sulfo group, a carboxy group, a phosphate group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkoxy group, an amino group, an alkylamino group, an arylamino group, an alkylcarbonylamino group, It may have one or more groups selected from the group consisting of a ureido group, an alkyl group, an aryl group, a furyl group, a pyridyl group, a cyano group, a halogen atom, an alkylsulfonyl group, and an alkylthio group.
Further, “*” in the formula (2) represents a bonding position. ].
Colorant (A):
A compound having λmax of 500 nm to 700 nm and a half width of 100 nm to 500 nm.
Colorant (B):
A compound having λmax of 350 nm to 450 nm and a half width of 50 nm to 250 nm.
2)
In the formula (1),
R ¹¹ is an alkyl group,
R ¹⁵ is an alkylthio group, an alkoxy group, or a group represented by the formula (2),
The ink according to 1), wherein R ¹⁶ and R ¹⁷ are each independently an alkylthio group or a group represented by the formula (2).
3)
In the formula (1),
R ¹¹ is an alkyl group,
R ¹² is a cyano group,
R ¹³ and R ¹⁴ are each independently a hydrogen atom, an alkoxy group, or a sulfo group,
R ¹⁵ is an alkoxy group,
R ¹⁶ and R ¹⁷ are each independently an alkylthio group,
R ¹⁸ and R ¹¹⁰ are each independently an alkyl group or an alkylcarbonylamino group,
R ¹⁹ is a group represented by the formula (2),
The ink according to 1), wherein R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom, a sulfo group, or a nitro group.
4)
1) The colorant (A) is at least one colorant selected from the group of the compounds represented by the following formulas (3) to (5), tautomers thereof, or salts thereof. The ink described.

[In Formula (3),
A ³ group is a carboxy group; a sulfo group; a halogen atom; a cyano group; a nitro group; a sulfamoyl group; an alkyl group; an alkoxy group; and an aryl group having at least one group selected from the group consisting of: And
The B ³ group and the C ³ group are each independently a paraphenylene group having at least one group selected from the group consisting of a carboxy group; a sulfo group; an alkyl group; an alkoxy group; and an alkylthio group;
R ³¹ represents an alkyl group, an aryl group, or a carboxy group,
R ³² represents a cyano group, a carbamoyl group, or a carboxy group,
R ³³ and R ³⁴ each independently represent a hydrogen atom, an alkyl group, a halogen atom, or a sulfo group.
Any of the above groups can further have a substituent. ].

[In Formula (4),
R ⁴¹ , R ⁴² , R ⁴⁵ , R ⁴⁶ and R ⁴⁷ are each independently a hydrogen atom; a halogen atom; a cyano group; a hydroxy group; a carboxy group; a sulfo group; a sulfamoyl group; an N-alkylaminosulfonyl group; Sulfonyl group; alkylcarbonyl group; arylcarbonyl group; ureido group; alkyl group; alkoxy group; alkylcarbonylamino group; arylcarbonylamino group; alkylsulfonylamino group; Represents a group selected from the group consisting of:
R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom; a halogen atom; a cyano group; a carboxy group; a sulfo group; a nitro group; an alkyl group; an alkoxy group; an alkylcarbonylamino group; an alkylsulfonylamino group; Represents at least one group selected from the group consisting of:
n represents 0 or 1, respectively.
Any of the above groups can further have a substituent. ].

[In Formula (5),
A ⁵ group represents an aryl group or a heterocyclic group,
G represents a nitrogen atom or —C (R ⁵⁶ ) ═.
R ⁵⁶ represents a hydrogen atom, a sulfo group, a carboxy group, a carbamoyl group, or a cyano group.
R ⁵¹ , R ⁵⁴ and R ⁵⁵ each independently represents an aryl group,
R ⁵² and R ⁵³ each independently represent a substituent. ]
5)
The colorant (B) has at least two ionic hydrophilic groups in one molecule, and is a compound represented by the following formulas (6) to (8) or a tautomer thereof, or a salt thereof: The ink according to 1), which is at least one colorant selected from the group.

[In Formula (6),
A ⁶ group and D ⁶ group each independently represent an aryl group,
B ⁶ group and C ⁶ group each independently represent an arylene group,
R ⁶¹ represents a group represented by the following formula (9) or a carbonyl group. ]

[In Formula (7),
A ⁷¹ group and A ⁷² group each independently represent an aryl group,
B ⁷¹ group, C ⁷¹ group, B ⁷² group, and C ⁷² group each independently represent an arylene group,
R ⁷¹ represents a group represented by the following formula (10) or formula (11). ]

[In Formula (8),
The A ⁸ group and the B ⁸ group each independently represent an aryl group or a heterocyclic group, but both do not represent an aryl group at the same time. ]

[In Formula (9), R ⁹¹ represents a substituent, and * represents a binding site. ]

[In formula (10), R ⁹¹ represents the same meaning as in formula (9), and * represents a binding site with C ⁷¹ group and C ⁷² group. ]

In formula (11), * represents a bonding site to the ^{C 71} group, and ^{C 72} groups. ]
6)
Furthermore, the ink as described in any one of 1) -5) containing a water-soluble organic solvent.
7)
An ink jet recording method for forming an image using the ink described in 6).
8)
A recording medium to which the ink according to any one of 1) to 6) is attached.
9)
An ink jet printer cartridge filled with the ink according to 6).
10)
An inkjet printer having the inkjet printer cartridge according to 9).

  According to the present invention, an aqueous ink having good ozone gas resistance can be provided.

  In this specification, “CI” means “color index”. In the present specification, “%” and “parts” including examples and the like are described on a mass basis unless otherwise specified.

  The compound represented by the formula (1) or a tautomer thereof, or a salt thereof is substantially a colorant. That is, the ink is an ink containing at least two kinds of colorants. As the colorant, a water-soluble colorant is preferable. In the present specification, the water-soluble colorant means a colorant having a solubility in 1 liter of water at 25 ° C. of usually 5 g or more, preferably 10 g or more, more preferably 20 g or more. Although there is no upper limit in particular, it is about 500g.

[Compounds represented by Formula (1), Formula (3), and Formula (4), or tautomers thereof, or salts thereof]
The compound represented by the formula (1), the formula (3), or the formula (4) or a tautomer thereof, or a salt thereof (hereinafter referred to as “compound or a tautomer thereof, or a salt thereof” Each of the “compounds”) may be a tautomeric organism or a mixture of salts thereof. All such compounds are included in the compound represented by the formula (1), formula (3), or formula (4). Hereinafter, groups that these compounds can have will be described. Moreover, the term of these groups has the same meaning also in the group represented by Formula (2).

  As an alkyl group, C1-C12, Preferably it is 1-8, More preferably, it is 1-6, More preferably, a linear, branched or cyclic alkyl group of 1-4 is mentioned. Among these, a straight chain or a branched chain is preferable, and a linear alkyl group is more preferable. Specific examples thereof include, for example, linear alkyl groups such as methyl, ethyl, n-propyl and n-butyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, t-butyl and 2-ethylhexyl; cyclopropyl And cyclic alkyl groups such as cyclopentyl. Among these, methyl or n-propyl is preferable, and methyl is more preferable.

  Examples of the alkyl group substituted with a carboxy group include the above alkyl groups substituted with one or two, preferably one carboxy group. The substitution position of the carboxy group is not particularly limited, but it is preferably substituted at the end of the alkyl group. Specific examples thereof include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl and the like.

  Examples of the aryl group include aryl groups having 6 to 30 carbon atoms, preferably 6 to 10 carbon atoms. Specific examples thereof include a phenyl group and a naphthyl group. Of these, a phenyl group is preferred.

  The aryl group substituted with a sulfo group is usually an aryl group substituted with 1 to 5, preferably 1 to 3, more preferably 1 or 2, and even more preferably 1 sulfo group. It is done.

  As an alkoxy group, C1-C12, Preferably it is 1-8, More preferably, it is 1-6, More preferably, a linear, branched, or cyclic alkoxy group of 1-4 is mentioned. Among these, a straight chain or a branched chain is preferable, and a linear alkoxy group is more preferable. Specific examples thereof include, for example, linear alkoxy groups such as methoxy, ethoxy, n-propoxy, and n-butoxy; branched-chain alkoxy groups such as isopropoxy, isobutoxy, sec-butoxy, t-butoxy, and 2-ethylhexyloxy A cyclic alkoxy group such as cyclopropoxy, cyclopentyloxy and the like; Of these, methoxy is preferred.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In these, a fluorine atom and a chlorine atom are preferable.

  Examples of the alkylthio group include straight-chain, branched-chain, or cyclic alkylthio groups having 1 to 12, preferably 1 to 8, more preferably 1 to 6, more preferably 1 to 4, carbon atoms. Among these, a straight chain or a branched chain is preferable, and a linear alkylthio group is more preferable. Specific examples thereof include, for example, linear alkylthio groups such as methylthio, ethylthio, n-propylthio, and n-butylthio; branched alkylthio groups such as isopropylthio, isobutylthio, sec-butylthio, t-butylthio, and 2-ethylhexylthio. A cyclic alkylthio group such as cyclopropylthio and cyclopentylthio; Among these, methylthio or n-propylthio is preferable, and methylthio is more preferable.

  The alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group is usually one or two, preferably one substituted with the aforementioned group, An alkylthio group is mentioned. Although the substitution position of the above group in the alkylthio group is not particularly limited, it is preferably substituted with a carbon atom other than the carbon atom to which the sulfur atom in the alkylthio group is bonded. Among the above groups, a sulfo group and a carboxy group are preferable, and a sulfo group is more preferable. Specific examples thereof include, for example, 2-hydroxyethylthio, 3-hydroxypropylthio, 2-sulfoethylthio, 3-sulfopropylthio, 2-carboxyethylthio, 3-carboxypropylthio, 4-carboxybutylthio, 2-hydroxy-3-sulfopropylthio, 2-hydroxy-3-carboxypropylthio, 2,2-disulfoethylthio, 2,2-dicarboxyethylthio, 3-carboxy-3-sulfopropylthio and the like It is done.

  The alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group is usually one or two, preferably one substituted with the aforementioned group, An alkoxy group is mentioned. Although the substitution position of the above group in the alkoxy group is not particularly limited, it is preferably substituted with a carbon atom other than the carbon atom to which the oxygen atom in the alkoxy group is bonded. Among the above groups, a sulfo group and a carboxy group are preferable, and a sulfo group is more preferable. Specific examples thereof include, for example, 2-hydroxyethoxy, 2-hydroxypropoxy, 2-sulfoethoxy, 3-sulfopropoxy, 2-carboxyethoxy, 3-carboxypropoxy, 4-carboxybutoxy, 2-hydroxy-3-sulfo Examples include propoxy, 2-hydroxy-3-carboxypropoxy, 2,2-disulfoethoxy, 2,2-dicarboxyethoxy, 3-carboxy-3-sulfopropoxy and the like.

  The alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, an alkoxy group, a sulfo group, and a carboxy group is selected from the group consisting of the above-mentioned “hydroxy group, sulfo group, and carboxy group”. Examples of the configuration of the “alkoxy group substituted with at least one kind of group” include an alkoxy group added as a substituent option. Specific examples thereof include 2-methoxyethoxy, 3-methoxypropoxy, 2-ethoxyethoxy, 3-ethoxypropoxy and the like in addition to the same as described above.

  As the alkylcarbonylamino group, a linear, branched, or cyclic alkylcarbonylamino having a carbon number of the alkyl moiety of usually 1 to 12, preferably 1 to 8, more preferably 1 to 6, and further preferably 1 to 4. Groups. Among these, a straight chain or a branched chain is preferable, and a linear alkyl group is more preferable. Specific examples thereof include, for example, linear alkylcarbonylamino groups such as methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, n-butylcarbonylamino; isopropylcarbonylamino, isobutylcarbonylamino, sec-butylcarbonylamino, Examples include branched alkylcarbonylamino groups such as t-butylcarbonylamino and 2-ethylhexylcarbonylamino; and cyclic alkylcarbonylamino groups such as cyclopropylcarbonylamino and cyclopentylcarbonylamino. Of these, methylcarbonylamino is preferred.

  As the alkylsulfonyl group, a linear, branched, or cyclic alkylsulfonyl group having 1 to 12, preferably 1 to 8, more preferably 1 to 6, more preferably 1 to 4, carbon atoms in the alkyl moiety is usually used. Can be mentioned. In these, a linear or branched chain is preferable and a linear alkylsulfonyl group is more preferable. Specific examples thereof include, for example, linear alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, n-butylsulfonyl; isopropylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, t-butylsulfonyl, 2-ethylhexyl. Examples include branched alkylsulfonyl groups such as sulfonyl; cyclic alkylsulfonyl groups such as cyclopropylsulfonyl and cyclopentylsulfonyl. Of these, methylsulfonyl is preferred.

  The alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group is usually substituted with one or two, preferably one of the aforementioned groups. Examples include the alkylsulfonyl group. Among the above groups, a sulfo group and a carboxy group are preferable, and a sulfo group is more preferable. Specific examples thereof include, for example, 2-hydroxyethylsulfonyl, 3-hydroxypropylsulfonyl, 2-sulfoethylsulfonyl, 3-sulfopropylsulfonyl, 2-carboxyethylsulfonyl, 3-carboxypropylsulfonyl, 4-carboxybutylsulfonyl, Examples include 2-hydroxy-3-sulfopropylsulfonyl, 2-hydroxy-3-carboxypropylsulfonyl, 2,2-disulfoethylsulfonyl, 2,2-dicarboxyethylsulfonyl, 3-carboxy-3-sulfopropylsulfonyl, and the like. It is done.

  Examples of the sulfoanilino group include an aryl group substituted with usually 1 to 5, preferably 1 to 3, more preferably 1 or 2 sulfo groups.

  Examples of the sulfoanilino group include a naphthyl group substituted with usually 1 to 7, preferably 1 to 3 sulfo groups.

  As the alkylamino group, a linear, branched, or cyclic monoalkylamino group in which the alkyl moiety usually has 1 to 12, preferably 1 to 8, more preferably 1 to 6, more preferably 1 to 4 carbon atoms. And dialkylamino groups. Among these, a straight chain or a branched chain is preferable, and a linear alkyl group is more preferable. Specific examples of monoalkylamino groups include, for example, linear alkylamino groups such as methylamino, ethylamino, n-propylamino, n-butylamino; isopropylamino, isobutylamino, sec-butylamino, t-butylamino Branched alkylamino groups such as 2-ethylhexylamino; cyclic alkylamino groups such as cyclopropylamino and cyclopentylamino. Specific examples of the dialkylamino group include an amino group having two alkyl groups independently exemplified as the monoalkylamino group, such as methylethylamino.

  Examples of the arylamino group include a monoarylamino group having 6 to 30 carbon atoms, preferably 6 to 10 carbon atoms, or a diarylamino group. Specific examples thereof include monoarylamino groups such as phenylamino group, 1-naphthylamino group and 2-naphthylamino group; and diarylamino groups such as diphenylamino group.

  As the N-alkylaminosulfonyl group, a linear, branched, or cyclic monovalent alkyl group having usually 1 to 12, preferably 1 to 8, more preferably 1 to 6, more preferably 1 to 4 carbon atoms. Examples thereof include an alkylaminosulfonyl group and a dialkylaminosulfonyl group. Among these, a straight chain or a branched chain is preferable, and a linear alkyl group is more preferable. Specific examples of the monoalkylaminosulfonyl group include, for example, linear alkylaminosulfonyl groups such as methylaminosulfonyl, ethylaminosulfonyl, n-propylaminosulfonyl, n-butylaminosulfonyl; isopropylaminosulfonyl, isobutylaminosulfonyl, sec Examples include branched alkylaminosulfonyl groups such as -butylaminosulfonyl, t-butylaminosulfonyl, 2-ethylhexylaminosulfonyl; and cyclic alkylaminosulfonyl groups such as cyclopropylaminosulfonyl and cyclopentylaminosulfonyl. Specific examples of the dialkylaminosulfonyl group include an aminosulfonyl group having two alkyl groups independently exemplified as the monoalkylaminosulfonyl group, such as methylethylaminosulfonyl.

  Examples of the arylaminosulfonyl group include a monoarylaminosulfonyl group having 6 to 30 carbon atoms, preferably 6 to 10 carbon atoms, or a diarylaminosulfonyl group. Specific examples thereof include monoarylaminosulfonyl groups such as phenylaminosulfonyl group, 1-naphthylaminosulfonyl group and 2-naphthylaminosulfonyl group; and diarylaminosulfonyl groups such as diphenylaminosulfonyl group.

  As the alkylsulfonylamino group, a linear, branched, or cyclic alkylsulfonylamino group in which the alkyl moiety has usually 1 to 12, preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4. Groups. In these, a linear or branched chain is preferable and a linear alkylsulfonylamino group is more preferable. Specific examples thereof include, for example, linear alkylsulfonylamino groups such as methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, n-butylsulfonylamino; isopropylsulfonylamino, isobutylsulfonylamino, sec-butylsulfonylamino, Examples include branched alkylsulfonylamino groups such as t-butylsulfonylamino and 2-ethylhexylsulfonylamino; and cyclic alkylsulfonylamino groups such as cyclopropylsulfonylamino and cyclopentylsulfonylamino. Of these, methylsulfonylamino is preferred.

  Examples of the arylsulfonylamino group include arylsulfonylamino groups having 6 to 30 carbon atoms, preferably 6 to 10 carbon atoms. Specific examples thereof include a phenylsulfonylamino group, a 1-naphthylsulfonylamino group, and a 2-naphthylsulfonylamino group.

  All the groups described above may further have one or two groups selected from the substituent group 1 described later.

Of these, R ¹¹ is preferably an alkyl group, an alkyl group substituted with a carboxy group, an aryl group, an aryl group substituted with a sulfo group, or a carboxy group. R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently an alkylthio group; an alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; an alkoxy group; a hydroxy group And an alkoxy group substituted with at least one group selected from the group consisting of a sulfo group and a carboxy group; or a group represented by the formula (2). R ¹⁸ , R ¹⁹ and R ¹¹⁰ each independently comprise a hydrogen atom; a carboxy group; a sulfo group; an alkylcarbonylamino group; a halogen atom; an alkyl group; an alkoxy group; a hydroxy group, an alkoxy group, a sulfo group, and a carboxy group. An alkoxy group substituted with at least one group selected from the group; or a group represented by the formula (2) is preferred. R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; an alkylcarbonylamino group; a halogen atom; a cyano group; a nitro group; a sulfamoyl group; an alkyl group; An alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, an alkoxy group, a sulfo group, and a carboxy group; an alkylsulfonyl group; or a group consisting of a hydroxy group, a sulfo group, and a carboxy group Alkylsulfonyl groups substituted with at least one selected group are preferred.

As the compound represented by the formula (1), among the above, the compounds of the following combinations (1-i) to (1-V) are preferable. Further, the preference increases sequentially from (1-i) to (1-V), and the compound of (1-V) is most preferable.
(1-i)
R ¹¹ is an alkyl group,
R ¹⁵ is an alkylthio group, an alkoxy group, or a group represented by the formula (2),
A compound in which R ¹⁶ and R ¹⁷ are each independently an alkylthio group or a group represented by the formula (2).
(1-ii)
R ¹¹ is an alkyl group,
R ¹² is a cyano group,
R ¹³ and R ¹⁴ are each independently a hydrogen atom, an alkoxy group, or a sulfo group,
R ¹⁵ is an alkoxy group,
R ¹⁶ and R ¹⁷ are each independently an alkylthio group,
R ¹⁸ and R ¹¹⁰ are each independently an alkyl group or an alkylcarbonylamino group,
R ¹⁹ is a group represented by the formula (2),
A compound in which R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom, a sulfo group or a nitro group.
(1-iii)
R ¹¹ is an alkyl group,
R ¹² is a cyano group,
One of R ¹³ and R ¹⁴ is a hydrogen atom or an alkoxy group, the other is a sulfo group,
R ¹⁵ is an alkoxy group substituted with a sulfo group or a carboxy group,
R ¹⁶ and R ¹⁷ are each independently an alkylthio group substituted with a sulfo group or a carboxy group,
R ¹⁸ and R ¹¹⁰ are each independently an alkyl group or an alkylcarbonylamino group,
R ¹⁹ is a group represented by the formula (2),
A compound in which R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom, a sulfo group or a nitro group.
(1-iV)
R ¹¹ is an alkyl group,
R ¹² is a cyano group,
One of R ¹³ and R ¹⁴ is a hydrogen atom or an alkoxy group, the other is a sulfo group,
R ¹⁵ is an alkoxy group substituted with a sulfo group,
R ¹⁶ and R ¹⁷ are each independently an alkylthio group substituted with a sulfo group,
R ¹⁸ is an alkyl group,
R ¹⁹ is a group represented by the formula (2),
A compound in which R ¹¹⁰ is an alkylcarbonylamino group, and R ¹¹¹ , R ¹¹² , R ^113, and R ¹¹⁴ are each independently a hydrogen atom, a sulfo group, or a nitro group.
(1-V)
R ¹¹ is an alkyl group,
R ¹² is a cyano group,
One of R ¹³ and R ¹⁴ is a hydrogen atom or an alkoxy group, the other is a sulfo group,
R ¹⁵ is an alkoxy group substituted with a sulfo group,
R ¹⁶ and R ¹⁷ are each independently an alkylthio group substituted with a sulfo group,
R ¹⁸ is an alkyl group,
R ¹⁹ is a group represented by the formula (2),
R ¹¹⁰ is an alkylcarbonylamino group, R ¹¹¹ is a sulfo group,
R ¹¹² is a nitro group,
A compound in which R ¹¹³ and R ¹¹⁴ are a hydrogen atom.

The compound represented by the formula (1) preferably does not have a benzene ring represented by a broken line. The substitution position of R ^{15 to} R ¹⁷ is preferably the 2-position, with the substitution position of the azo group on the right side of the benzene ring to be substituted as the 1-position. Similarly, the substitution position of R ¹⁸ , R ¹⁹ and R ¹¹⁰ is preferably the 5-position. The substitution positions of R ¹¹¹ and R ¹¹² are preferably the 2-position and the 4-position, respectively, with the substitution position of the azo group of the benzene ring to be substituted as the 1-position.

Specific examples of the compound represented by the formula (1) are shown below, but the compound represented by the formula (1) is not limited to the following examples.
The abbreviations in the following Tables 1 to 18 have the following meanings.
Ac: Acetyl.
Et: ethyl.
n-Pr: n-propyl.

The compound represented by the formula (1) can be synthesized, for example, by the following method. Moreover, the structural formula of the compound in each process shall be represented with the form of a free acid. In the following formulas (1-74) to (1-81), R ^{11 to} R ¹⁹ and R ^{110 to} R ¹¹⁴ represent the same meaning as in formula (1). A compound represented by the following formula (1-74) is diazotized by a conventional method, and the resulting diazo compound and a compound represented by the following formula (1-75) are subjected to a coupling reaction by a conventional method. 1-76) is obtained.

  The compound represented by the formula (1-76) thus obtained is diazotized by a conventional method, and then the resulting diazo compound and a compound represented by the following formula (1-77) are subjected to a coupling reaction by a conventional method. To obtain a compound represented by the following formula (1-78).

  The compound represented by the formula (1-78) thus obtained is diazotized by a conventional method, and then the resulting diazo compound and a compound represented by the following formula (1-79) are subjected to a coupling reaction by a conventional method. To obtain a compound represented by the following formula (1-80). The compound represented by the formula (1-80) thus obtained is diazotized by a conventional method, and then the obtained diazo compound and a compound represented by the following formula (1-81) are subjected to a coupling reaction by a conventional method. By this, the compound represented by the above formula (1) can be obtained. In addition, the compound represented by Formula (1-81) is compoundable according to the method as described in patent document 12.

  The diazotization of the compound represented by the formula (1-74) is carried out by a method known per se, for example, nitrite in an inorganic acid medium, for example, at a temperature of -5 to 30 ° C, preferably 0 to 15 ° C. For example, using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of the compound represented by the formula (1-74) and the compound represented by the formula (1-75) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 0 to 25 ° C, and at an acidic to neutral pH value, for example pH 1-6. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. Examples of the base that can be used include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate, acetates such as sodium acetate, ammonia, and organic amines. . The compound represented by the formula (1-74) and the compound represented by the formula (1-75) are used in a substantially stoichiometric amount.

  The diazotization of the compound represented by the formula (1-76) is carried out by a method known per se, for example, nitrite in an inorganic acid medium, for example, at a temperature of -5 to 40 ° C, preferably 5 to 30 ° C. For example, using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of the compound represented by the formula (1-76) and the compound represented by the formula (1-77) is also carried out under conditions known per se. It is advantageous to carry out the reaction in water or an aqueous organic medium, for example at a temperature of -5 to 40 ° C, preferably 10 to 30 ° C, and at an acidic to neutral pH value, for example pH 2-7. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. The same base as described above can be used. The compound represented by the formula (1-76) and the compound represented by the formula (1-77) are used in a substantially stoichiometric amount.

  The diazotization of the compound of the formula (1-78) is carried out in a manner known per se, for example nitrite, for example in an inorganic acid medium, for example at a temperature of -5 to 50 ° C., preferably 5 to 40 ° C. It is carried out using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of the compound represented by the formula (1-78) and the compound represented by the formula (1-79) is also carried out under conditions known per se. It is advantageous to carry out the reaction in water or an aqueous organic medium, for example at a temperature of -5 to 50 ° C, preferably 10 to 40 ° C, and at an acidic to neutral pH value, for example pH 2-7. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. The same base as described above can be used. The compound represented by formula (1-78) and the compound represented by formula (1-79) are used in approximately stoichiometric amounts.

  The diazotization of the compound represented by the formula (1-80) is also carried out by a method known per se, for example, a nitrite, for example It is carried out using an alkali metal nitrite such as sodium nitrate. Coupling of the diazotized compound of the compound represented by the formula (1-80) with the compound represented by the formula (1-81) is also carried out under conditions known per se. It is advantageous to carry out the reaction in water or an aqueous organic medium, for example at a temperature of -5 to 50 ° C, preferably 10 to 40 ° C, and at a weakly acidic to alkaline pH value. It is preferably carried out at a weakly acidic to weakly alkaline pH value, for example, pH 5 to 10, and the pH value is adjusted by adding a base. The same base as described above can be used. The compound represented by the formula (1-80) and the compound represented by the formula (1-81) are used in a substantially stoichiometric amount.

In the formula (2), the sulfoanilino group of R ¹¹⁶ or the sulfonaphthylamino group is preferably a sulfoanilino group. R ¹¹⁶ preferably further includes one or more substituents selected from the group consisting of a carboxy group, a hydroxy group, an alkoxy group, an alkyl group, a cyano group, a halogen atom, an alkylsulfonyl group, and an alkylthio group. Or you can have two.
Among them, R ¹¹⁶ is usually a sulfoanilino group having usually 1 to 5, preferably 1 to 3, more preferably 1 or 2 sulfo groups, more preferably a sulfoanilino group having 2 sulfo groups. Particularly preferred. Among these, a 2,5-disulfoanilino group is particularly preferable.

In the formula (2), R ¹¹⁷ is preferably an alkylamino group or a hydroxy group, and more preferably an alkylamino group. When R ¹¹⁷ is an alkylamino group, preferably a sulfo group, a carboxy group, a phosphate group, a hydroxy group, an alkoxy group, an alkylcarbonylamino group, a ureido group, an alkyl group, an aryl group, a cyano group, a halogen atom, an alkyl group A sulfonyl group and an alkylthio group; more preferably, a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, an alkyl group, an aryl group, a halogen atom, an alkylsulfonyl group, and an alkylthio group; It can have one or two of the above substituents. Among these, an alkylamino group having one or two or more substituents selected from the group consisting of a sulfo group, a carboxy group, and a phosphate group is more preferable, and an alkylamino group having one sulfo group Is particularly preferred.

In the formula (3), the A ³ group is a carboxy group; a sulfo group; a halogen atom; a cyano group; a nitro group; a sulfamoyl group; an alkyl group; an alkoxy group; an alkylsulfonyl group; An alkylsulfonyl group substituted with at least one group selected from the group consisting of groups; an aryl group having at least one group selected from the group consisting of groups is preferred. B ³ group and C ³ group are each independently a carboxy group; a sulfo group; an alkyl group; an alkoxy group; and at least one kind selected from the group consisting of a hydroxy group, an alkoxy group, a sulfo group, and a carboxy group An alkoxy group substituted with a group; an alkylthio group; an alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group; at least one group selected from the group consisting of And having two paraphenylene groups is preferred. R ³¹ is preferably an alkyl group that can have a carboxy group, an aryl group that can have a sulfo group, or a carboxy group.

  All the groups described above may further have one or two groups selected from the substituent group 1 described later.

Among the compounds represented by the formula (3), the A ³ group includes a carboxy group; a sulfo group; a cyano group; a nitro group; a sulfamoyl group; an alkoxy group; an alkylsulfonyl group; and a hydroxy group, a sulfo group, and a carboxy group An alkylsulfonyl group substituted with at least one group selected from the group consisting of: an aryl group having 1 to 5 groups selected from the group consisting of: Similarly, a carboxy group; a sulfo group; a cyano group; a nitro group; a sulfamoyl group; an alkoxy group; and an alkylsulfonyl group substituted with at least one group selected from a hydroxy group and a sulfo group; An aryl group having 1 to 3 selected groups is more preferable. Similarly, a group selected from the group consisting of: a carboxy group; a sulfo group; an alkoxy group; an alkylsulfonyl group; and an alkylsulfonyl group substituted with at least one group selected from a hydroxy group and a sulfo group; An aryl group having 1 to 3 is more preferable. Similarly, an aryl group having one or two groups selected from a carboxy group and a sulfo group is particularly preferred.

Among the compounds represented by the formula (3), the B ³ group and the C ³ group are selected from the group consisting of a sulfo group; an alkyl group; an alkoxy group; and a hydroxy group, an alkoxy group, a sulfo group, and a carboxy group. Preferred is a phenylene group having one or two groups selected from the group consisting of an alkoxy group substituted with at least one group selected from the group consisting of: Similarly, a phenylene group having one or two groups selected from the group consisting of a sulfo group; an alkyl group; an alkoxy group; and an alkoxy group substituted with a sulfo group; These substitution positions are preferably substitution at the 2-position and / or 5-position with the substitution position of the azo group substituted on the right side of each of the B ³ group and the C ³ group as the 1-position.

Among the compounds represented by the formula (3), R ³¹ is preferably an alkyl group that can have a carboxy group, and more preferably an unsubstituted alkyl group. R ³² is preferably a cyano group or a carbamoyl group. As R ³³ and R ³⁴ , one is preferably a hydrogen atom, the other is preferably an alkyl group, a halogen atom or a sulfo group; one is more preferably a hydrogen atom, the other is an alkyl group or a sulfo group; one is a hydrogen atom and the other is More preferably, it is a sulfo group.

  The compound represented by the formula (3) can be synthesized, for example, according to the description in Patent Document 1 or in accordance therewith. Although the specific example is shown below, the compound represented by Formula (3) is not limited to the following example.

In the formula (4), R ⁴¹ , R ⁴² , R ⁴⁵ , R ⁴⁶ and R ⁴⁷ each independently represent a hydrogen atom; a halogen atom; a cyano group; a hydroxy group; a carboxy group; a sulfo group; a sulfamoyl group; N-arylaminosulfonyl group; alkylsulfonyl group; alkylsulfonyl group substituted with at least one group selected from the group consisting of hydroxy group, sulfo group and carboxy group; phosphate group; nitro group Alkylcarbonyl group; arylcarbonyl group; ureido group; alkyl group; alkyl group substituted with at least one group selected from hydroxy group and alkoxy group; alkoxy group; hydroxy group, alkoxy group, sulfo group, and At least one selected from the group consisting of carboxy groups Substituted with at least one group selected from the group consisting of a halogen atom, an alkyl group, and a nitro group; an alkylcarbonylamino group; an arylcarbonylamino group; an arylsulfonylamino group; Preferred is a group selected from the group consisting of: R ⁴³ and R ⁴⁴ are each independently substituted with at least one group selected from a hydrogen atom; a halogen atom; a cyano group; a carboxy group; a sulfo group; a nitro group; an alkyl group; a hydroxy group, and an alkoxy group. Alkoxy group; alkoxy group; alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, an alkoxy group, a sulfo group, and a carboxy group; an alkylcarbonylamino group; an alkylsulfonylamino group; Arylsulfonylamino group; arylsulfonylamino group substituted with at least one group selected from the group consisting of halogen atoms, alkyl groups, and nitro groups; alkylthio groups; groups consisting of hydroxy groups, sulfo groups, and carboxy groups With at least one group selected from Alkylthio group; at least one group selected from the group consisting of is preferred.

  All the groups described above may further have one or two groups selected from the substituent group 1 described later.

Among the compounds represented by the formula (4), R ⁴¹ and R ⁴² each independently represent a hydrogen atom; a halogen atom; a cyano group; a carboxy group; a sulfo group; a sulfamoyl group; an N-alkylaminosulfonyl group; An alkylsulfonyl group; an alkylsulfonyl group substituted with a hydroxy group; a phosphoric acid group; a nitro group; an alkylcarbonyl group; an arylcarbonyl group; an ureido group; an alkyl group; an alkoxy group; a hydroxy group, an alkoxy group, A group selected from the group consisting of an alkoxy group substituted with one or two groups selected from the group consisting of a sulfo group and a carboxy group; an alkylcarbonylamino group; an arylcarbonylamino group; Similarly, a group selected from the group consisting of a hydrogen atom; a halogen atom; a cyano group; a sulfamoyl group; an alkylcarbonylamino group; a nitro group; a carboxy group; and a sulfo group; As R ⁴¹ and R ⁴² , one is preferably a hydrogen atom or a sulfo group, and the other is more preferably a carboxy group, a sulfo group or an alkoxy group; one is a hydrogen atom and the other is preferably a carboxy group or a sulfo group; It is particularly preferred that one is a hydrogen atom and the other is a sulfo group. The substitution position of R ⁴¹ , R ⁴² and the nitro group is not particularly limited, but the substitution position of the azo group is the first position, R ⁴¹ is the second position, the nitro group is the fourth position, and R ⁴² is the fifth position; ^{2-position, R 41} is ^4-position, it is preferred that ^{R 42} is 5-position.
However, both R ⁴¹ and R ⁴² do not represent a hydrogen atom at the same time.

Among the compounds represented by the formula (4), R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom; a cyano group; a carboxy group; a sulfo group; a nitro group; an alkyl group; an alkoxy group; a hydroxy group, an alkoxy group, An alkoxy group substituted with at least one group selected from the group consisting of a sulfo group and a carboxy group; and a group selected from the group consisting of an alkylcarbonylamino group are preferred. Similarly, a group selected from the group consisting of a hydrogen atom; a carboxy group; a sulfo group; an alkyl group; an alkoxy group; an alkoxy group substituted with a sulfo group; As R ⁴³ and R ⁴⁴ , one is more preferably a sulfo group or an alkoxy group substituted with a sulfo group, and the other is a hydrogen atom, a sulfo group, or an alkyl group.
R ⁴³ is particularly preferably a sulfo group.
R ⁴⁴ is particularly preferably a hydrogen atom.
The substitution position of R ⁴³ and R ⁴⁴ is not particularly limited, but it is preferred that the substitution position of the right azo group is the 1st position, the left azo group is the 4th position, R ⁴³ is the 3rd position, and R ⁴⁴ is the 6th position. .

Of the compounds represented by formula (4), R ⁴⁵ , R ⁴⁶ and R ⁴⁷ each independently represent a hydrogen atom; a halogen atom; a cyano group; a carboxy group; a sulfo group; a sulfamoyl group; an N-alkylaminosulfonyl group; N-arylaminosulfonyl group; alkylsulfonyl group; alkylsulfonyl group substituted by hydroxy group; phosphate group; nitro group; alkylcarbonyl group; arylcarbonyl group; ureido group; alkyl group; alkoxy group; hydroxy group, alkoxy group An alkoxy group substituted with at least one group selected from the group consisting of: a sulfo group and a carboxy group; an alkylcarbonylamino group; an arylcarbonylamino group; an arylsulfonylamino group substituted with an alkyl group; A group selected from is preferred. As R ⁴⁵ , R ⁴⁶ and R ⁴⁷ , any one is a hydrogen atom; a carboxy group; a sulfo group; or a group selected from the group consisting of an alkyl group, and any one of the other is a hydrogen atom; a hydroxy group; a carboxy group A sulfo group; a sulfamoyl group; a nitro group; an alkylcarbonylamino group; an arylsulfonylamino group substituted with an alkyl group, the remaining one consisting of a hydrogen atom; a carboxy group; a sulfo group; and an alkoxy group substituted with a sulfo group More preferred are groups selected from the group. Among these, it is more preferable that R ⁴⁵ is a hydrogen atom; a carboxy group; or a sulfo group, R ⁴⁶ is a sulfo group, and R ⁴⁷ is a hydrogen atom. The substitution position of R ⁴⁵ , R ⁴⁶ and R ⁴⁷ is not particularly limited. Preferably, ^{R 45} substitution position of the azo group as the 1-position 2-position or ^{3-position, R 46} is ^4-position, it is preferred that ^{R 47} is 5-position.
However, in the compound represented by the formula (4), all of R ⁴⁵ , R ⁴⁶ and R ⁴⁷ do not represent hydrogen atoms at the same time.

In formula (4), the substitution position of the sulfo group whose substitution position is not specified is not particularly limited. Preferred substitution positions of this sulfo group include the substitution position of the right azo group at position 1, the amino group at position 2, the hydroxy group at position 3, the left azo group at position 4, and the sulfo group whose substitution position is specified. 7th place as 5th place.
N is preferably 1.

  The compound represented by the formula (4) can be synthesized, for example, according to the description in Patent Document 1 or in accordance therewith. Although the specific example is shown below, the compound represented by Formula (4) is not limited to the following example.

[Compound represented by Formula (5)]
Below, the compound represented by Formula (5) is demonstrated. In the compound represented by the formula (5), the following substituent group 1, substituent group 2, ionic hydrophilic group, and Hammett's substituent constant σp value are used.

[Substituent group 1]
C1-C12 linear or branched alkyl group, C7-C18 linear or branched aralkyl group, C2-C12 linear or branched alkenyl group, C2-C12 linear Or a branched alkynyl group, a C3-C12 cycloalkyl group, a C3-C12 cycloalkenyl group (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl) , T-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), halogen atom (for example, chlorine atom, bromine atom), aryl group (for example, phenyl, 4-t- Butylphenyl, 2,4-di-t-amylphenyl), heterocyclic groups (eg imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thiol) Nyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy), aryloxy group (For example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenyloxy, acylamino groups (for example, acetamide, benzamide, 4- ( 3-tert-butyl-4-hydroxyphenoxy) butanamide), alkylamino groups (eg methylamino, butylamino, diethylamino, methylbutylamino), arylamino groups (eg phenylamino, 2-chloroanilino), u Id group (for example, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, 2-phenoxy) Ethylthio), arylthio groups (eg, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkoxycarbonylamino groups (eg, methoxycarbonylamino), alkylsulfonylamino groups, and arylsulfonylamino Groups (for example, methylsulfonylamino, phenylsulfonylamino, p-toluenesulfonylamino), carbamoyl groups (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl groups (for example, N- Ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), sulfonyl group (eg, methylsulfonyl, octylsulfonyl, phenylsulfonyl, p-toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl) , Butyloxycarbonyl), heterocyclic oxy group (eg 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo group (eg phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenyl) Azo, 2-hydroxy-4-propanoylphenylazo), alkylcarbonyloxy group (for example, acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group ( For example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide group (for example, N-succinimide, N-phthalimide), heterocyclic thio group (for example, 2-benzothiazolyl). Ruthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (eg 3-phenoxypropylsulfinyl), phosphonyl group (eg phenoxyphosphonyl, octyloxy) Phosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic group (carboxy group, sulfo group, etc.) It is done. These groups can further have a substituent. Examples of the further substituent include one or two groups selected from the substituent group 1 described above. Specific examples of groups in parentheses include examples in which each of these groups has a further substituent.

[Substituent group 2]
Halogen atom, alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyl Oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto Group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, Job aryloxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a silyl group, an ionic hydrophilic group mentioned as an example. These substituents may be further substituted. Examples of the further substituent include one or two groups selected from the substituent group 2 described above.

  Below, each group in the substituent group 1 and the substituent group 2 is demonstrated in more detail.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned, for example.

  Examples of the alkyl group include linear, branched, and cyclic substituted or unsubstituted alkyl groups, and include cycloalkyl groups, bicycloalkyl groups, and tricyclo structures having many ring structures. An alkyl group (for example, an alkyl group of an alkoxy group or an alkylthio group) in a substituent described below also represents such an alkyl group. Specifically, the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-octyl group, eicosyl. Group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group and the like, and the cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms such as cyclohexyl group, A cyclopentyl group, 4-n-dodecylcyclohexyl group and the like. The bicycloalkyl group is preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a bicycloalkane having 5 to 30 carbon atoms. Monovalent groups from which one hydrogen atom has been removed, for example, bicyclo [1,2,2] heptan-2-yl group, bicycl [2,2,2] octan-3-yl group.

  Examples of the aralkyl group include a substituted or unsubstituted aralkyl group, and the substituted or unsubstituted aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms. For example, a benzyl group and a 2-phenethyl group can be mentioned.

  Examples of the alkenyl group include linear, branched, and cyclic substituted or unsubstituted alkenyl groups, and include cycloalkenyl groups and bicycloalkenyl groups. Specifically, the alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group, and the like. Is preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as 2-cyclopentene-1 -Yl group, 2-cyclohexen-1-yl group and the like, and as the bicycloalkenyl group, a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, That is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond, for example, bicyclo [2 2,1] hept-2-en-1-yl group, a bicyclo [2,2,2] oct-2-en-4-yl group and the like.

  The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms such as an ethynyl group, a propargyl group, and a trimethylsilylethynyl group.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group, and the like. Can be mentioned.

  The heterocyclic group is preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a carbon number. Examples thereof include 3 to 30 5- or 6-membered aromatic heterocyclic groups such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.

  The alkoxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or a 2-methoxyethoxy group. Etc.

  The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as a phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, 3-nitrophenoxy group, 2 -Tetradecanoylaminophenoxy group etc. are mentioned.

  Preferred examples of the silyloxy group include substituted or unsubstituted silyloxy groups having 0 to 20 carbon atoms such as a trimethylsilyloxy group and a diphenylmethylsilyloxy group.

  Preferred examples of the heterocyclic oxy group include substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms, such as a 1-phenyltetrazole-5-oxy group and a 2-tetrahydropyranyloxy group.

  The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as an acetyloxy group, Examples include a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, and a p-methoxyphenylcarbonyloxy group.

  The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N , N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group and the like.

  The alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, or an n-octylcarbonyloxy group. Etc.

  The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxy. Examples include phenoxycarbonyloxy group.

  The amino group includes an alkylamino group, an arylamino group, and a heterocyclic amino group, preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 6 to 30 carbon atoms. Examples of the substituted anilino group include a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, and a triazinylamino group.

  The acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as an acetylamino group, Examples include pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, and the like.

  The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as a carbamoylamino group, N, N-dimethylaminocarbonylamino group, or N, N-diethylaminocarbonylamino group. And a morpholinocarbonylamino group.

  The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino. Group, N-methyl-methoxycarbonylamino group and the like.

  The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxy. Examples thereof include a carbonylamino group.

  The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as a sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn- Examples include octylaminosulfonylamino group.

  The alkyl or arylsulfonylamino group is preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as a methylsulfonylamino group. Butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, and the like.

  Preferred examples of the alkylthio group include substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, and an n-hexadecylthio group.

  Preferred examples of the arylthio group include substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms such as a phenylthio group, a p-chlorophenylthio group, and an m-methoxyphenylthio group.

  Preferred examples of the heterocyclic thio group include substituted or unsubstituted heterocyclic thio groups having 2 to 30 carbon atoms, such as a 2-benzothiazolylthio group and a 1-phenyltetrazol-5-ylthio group.

  The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfuryl group. Examples include a famoyl group, an N-acetylsulfamoyl group, an N-benzoylsulfamoyl group, and an N- (N′-phenylcarbamoyl) sulfamoyl group.

  The alkyl or arylsulfinyl group is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group, an ethylsulfinyl group, phenyl. Examples thereof include a sulfinyl group and a p-methylphenylsulfinyl group.

  The alkyl or arylsulfonyl group is preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, or a phenyl group. A sulfonyl group, p-methylphenylsulfonyl group, etc. are mentioned.

  The acyl group is preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted group having 2 to 30 carbon atoms. Heterocyclic carbonyl groups bonded to carbonyl groups at substituted carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridyl Examples thereof include a carbonyl group and a 2-furylcarbonyl group.

  The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt- A butylphenoxycarbonyl group etc. are mentioned.

  The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, and an n-octadecyloxycarbonyl group.

  The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, or an N, N-di-n-octyl group. Examples thereof include a carbamoyl group and an N- (methylsulfonyl) carbamoyl group.

  The aryl or heterocyclic azo group is preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo and the like.

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

  The phosphino group is preferably a substituted or unsubstituted phosphino group having 0 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group, and the like.

  The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 0 to 30 carbon atoms, such as a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, and the like.

  Preferred examples of the phosphinyloxy group include substituted or unsubstituted phosphinyloxy groups having 0 to 30 carbon atoms such as a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group.

  The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 0 to 30 carbon atoms, such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group.

  Preferred examples of the silyl group include substituted or unsubstituted silyl groups having 0 to 30 carbon atoms such as a trimethylsilyl group, a t-butyldimethylsilyl group, and a phenyldimethylsilyl group.

[Ionic hydrophilic group]
Sulfo group, carboxy group, thiocarboxy group, sulfino group, phosphono group, dihydroxyphosphino group, hydroxy group, phosphate group and quaternary ammonium group, acylsulfamoyl group, sulfonylcarbamoyl group, sulfonylsulfamoyl group, etc. Can be mentioned. Particularly preferred are a sulfo group and a carboxy group. The carboxy group, phosphono group and sulfo group may be in the form of a salt. Examples of counter cations that form a salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic. Cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) are included, and lithium salts, sodium salts, potassium salts, and ammonium salts are preferable.

  The counter cation (monovalent counter cation) of the ionic hydrophilic group contained in the compound represented by the formula (5) preferably contains lithium ions as a main component. The counter cations may not be all lithium ions, but the lithium ion concentration in each ink composition is preferably 50% or more, more preferably, relative to the total counter cations in each ink composition. It is 75% or more, more preferably 80%, and particularly preferably 95% or more. Under such conditions, hydrogen ions, alkali metal ions (for example, sodium ions, potassium ions), alkaline earth metal ions (for example, magnesium ions, calcium ions, etc.), quaternary ammonium ions, quaternary phosphoniums Ions, sulfonium ions, and the like can be included as counter cations.

[Hammett's substituent constant σp value]
Hammett's rule is a method described in 1935 in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, but this means that it is limited to only a substituent having a value known in the literature, which can be found in the above-mentioned book. Needless to say, even if the value is unknown, it includes a substituent that would be included in the range when measured based on Hammett's rule. The compound represented by the formula (5) is not a benzene derivative, but the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value will be used in this sense.

In the formula (5), R ⁵¹ represents an aryl group, and is a benzene ring group having R ⁵¹¹ , R ⁵¹² and R ⁵¹³ like the structure represented by the following formula (5-1) described later. Is preferred. Examples of R ⁵² include an alkyl group, an alkyl group substituted with a carboxy group, an aryl group, an aryl group substituted with a sulfo group, or a carboxy group. Among these, an alkyl group is preferable. R ⁵³ includes a cyano group, a carbamoyl group, or a carboxy group. Of these, a cyano group is preferred. R ⁵⁴ and R ⁵⁵ are preferably each independently an aryl group substituted with an ionic hydrophilic group, and more preferably an aryl group substituted with a sulfo group. The number of substitutions of the ionic hydrophilic group is usually 1 to 5, preferably 1 to 3, more preferably 1 or 2, and still more preferably 1. When the number of substitutions of the ionic hydrophilic group is 1, the 4-position is preferred with the carbon atom of R ⁵⁴ and R ⁵⁵ bonded to the nitrogen atom as the 1-position. G represents a nitrogen atom or —C (R ⁵⁶ ) ═. R ⁵⁶ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group. When the carbamoyl group has a substituent, the substituent is an alkyl group (methyl group, ethyl group), aryl And a group (phenyl group).

  As the compound represented by the formula (5), a compound represented by the following formula (5-1) is preferable.

In formula (5-1), A ⁵ group, G, and R ^{52 to} R ⁵⁵ have the same meaning as in formula (5), including preferred ones. R ⁵¹¹ , R ⁵¹² and R ⁵¹³ each independently represent a hydrogen atom or a monovalent substituent. R ⁵¹¹ , R ⁵¹² and R ⁵¹³ may be bonded to each other to form a ring. R ⁵¹¹ , R ⁵¹² and R ⁵¹³ do not all represent a hydrogen atom at the same time.

As the substituent in the case where R ⁵¹¹ , R ⁵¹² and R ⁵¹³ represent a substituent, the substituent group 2 can be exemplified independently. In the general formula (1), R ⁵¹¹ , R ⁵¹² and R ⁵¹³ are each independently a hydrogen atom, an ionic hydrophilic group, a substituted or unsubstituted heterocyclic amino group, a substituted or unsubstituted carbamoyl group, substituted or unsubstituted It is preferably a substituted sulfamoyl group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted acylamino group, a hydrogen atom, an ionic hydrophilic group, A heterocyclic amino group having a substituted or unsubstituted amino group as a substituent, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted acylamino group And more preferably a heterocyclic group having a hydrogen atom, a substituted or unsubstituted amino group as a substituent. A mino group, an arylsulfonylamino group having an ionic hydrophilic group as a substituent, or an acylamino group having an ionic hydrophilic group as a substituent is particularly preferable. As the acylamino group, an alkylcarbonylamino group, an alkylcarbonylamino group having an ionic hydrophilic group as a substituent, and an arylcarbonylamino group having an ionic hydrophilic group as a substituent are preferable. The alkyl group in the alkylcarbonylamino group is preferably a methyl group, an ethyl group, or an n-propyl group, and more preferably an ethyl group. The aryl group in the arylcarbonylamino group is preferably a phenyl group. When the heterocyclic amino group, sulfamoyl group, alkylsulfonylamino group, arylsulfonylamino group, or acylamino group represented by R ⁵¹¹ , R ^{512, or} R ⁵¹³ has a substituent, each independently has an ionic hydrophilic property More preferably, it is a group (for example, —CO ₂ M, —SO ₃ M: M is a monovalent counter cation). R ⁵¹¹ , R ⁵¹² and R ⁵¹³ may combine with each other to form a ring, and examples of the ring formed by combining R ⁵¹¹ , R ⁵¹² and R ⁵¹³ with each other include a benzene ring and a naphthalene ring. A benzene ring is preferred. R ⁵¹¹ , R ⁵¹² and R ⁵¹³ may further have a substituent, and as a further substituent, an aryl which may have a hydroxyl group, a substituted or unsubstituted amino group or an ionic hydrophilic group A heterocyclic group optionally having an ionic hydrophilic group, and a substituted or unsubstituted amino group. The substituent of the substituted amino group is preferably, for example, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and substituted with an ionic hydrophilic group. More preferred is an alkyl group or an aryl group substituted with an ionic hydrophilic group.

R ⁵¹¹ , R ⁵¹² and R ⁵¹³ each independently represent a hydrogen atom or a monovalent substituent. As the substituent in the case where R ⁵¹¹ , R ⁵¹² and R ⁵¹³ represent a substituent, the substituent group 2 can be exemplified independently. In the general formula (1), R ⁵¹¹ , R ⁵¹² and R ⁵¹³ are each independently a hydrogen atom, an ionic hydrophilic group, a substituted or unsubstituted amino group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted group. It is preferably any one of a sulfamoyl group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, and a substituted or unsubstituted acylamino group. In the case of a substituted or unsubstituted amino group, a heterocyclic amino group is preferable. R ⁵¹¹ , R ⁵¹² and R ⁵¹³ are each independently a hydrogen atom, an ionic hydrophilic group, a substituted or unsubstituted heterocyclic amino group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino More preferably a group, a substituted or unsubstituted acylamino group, a hydrogen atom, a substituted or unsubstituted heterocyclic amino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted acylamino group. It is particularly preferable that either one is used.

When the heterocyclic amino group, sulfamoyl group, alkylsulfonylamino group, arylsulfonylamino group, or acylamino group represented by R ⁵¹¹ , R ^{512, or} R ⁵¹³ has a substituent, each independently has an ionic hydrophilic property More preferably, it is a group (for example, —CO ₂ M, —SO ₃ M: M is a monovalent counter cation). R ⁵¹¹ , R ⁵¹² and R ⁵¹³ may further have a substituent, and as the further substituent, an aryl which may have a hydroxyl group, a substituted or unsubstituted amino group or an ionic hydrophilic group And a heterocyclic group which may have an ionic hydrophilic group, and a substituted or unsubstituted amino group is preferable. The substituent of the substituted amino group is preferably, for example, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and substituted with an ionic hydrophilic group. More preferred is an alkyl group or an aryl group substituted with an ionic hydrophilic group.

  As the heterocyclic amino group, a substituted or unsubstituted triazinylamino group is preferable, and a triazinylamino group having a substituent is more preferable. The substituent that the triazinylamino group has is preferably a substituted or unsubstituted amino group, and particularly preferably a substituted or unsubstituted amino group. As the substituent of the substituted amino group, the above examples are preferably used. Here, the alkyl group in the alkyl group substituted with an ionic hydrophilic group is preferably a methyl group, an ethyl group, or an n-propyl group, and more preferably an ethyl group. The aryl group in the aryl group substituted with an ionic hydrophilic group is preferably a phenyl group.

  As the acylamino group, an alkylcarbonylamino group, an alkylcarbonylamino group having an ionic hydrophilic group as a substituent, and an arylcarbonylamino group having an ionic hydrophilic group as a substituent are preferable. The alkyl group in the alkylcarbonylamino group is preferably a methyl group, an ethyl group, or an n-propyl group, and more preferably an ethyl group. The aryl group in the arylcarbonylacyl group is preferably a phenyl group.

R ⁵¹¹ , R ⁵¹² and R ⁵¹³ do not all represent a hydrogen atom at the same time. R ⁵¹¹ , R ⁵¹² and R ⁵¹³ may combine with each other to form a ring, and examples of the ring formed by combining R ⁵¹¹ , R ⁵¹² and R ⁵¹³ with each other include a benzene ring and a naphthalene ring. A benzene ring is preferred. Among R ⁵¹¹ , R ⁵¹² and R ⁵¹³ , R ⁵¹² preferably represents a substituent, R ⁵¹¹ and R ⁵¹³ represent a hydrogen atom, and R ⁵¹² represents a substituent. In particular, R ⁵¹¹ and R ⁵¹³ represent a hydrogen atom, R ⁵¹² represents a heterocyclic amino group having a substituted or unsubstituted amino group as a substituent, an arylsulfonylamino group having an ionic hydrophilic group as a substituent, or an ion Most preferably, it is an acylamino group having a hydrophilic hydrophilic group as a substituent.

Specific examples of the substituent represented by R ⁵¹¹ , R ⁵¹² and R ⁵¹³ include the following substituent (A5-1).

In the substituent (A5-1), * represents a bond as R ^{511 to} R ⁵¹³ . L ^A511 represents a single bond, a carbonyl group, or a sulfonyl group. R ^A511 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

R ^A511 is ^preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. In the case of having a substituent, the substituent is an ionic hydrophilic group, aryl An amino group and an alkylamino group are mentioned.

  The substituent (A5-1) is preferably the following substituent (A5-2) or (A5-3).

In the substituents (A5-2) and (A5-3), * represents a bond as R ^{511 to} R ⁵¹³ . L ^A521 represents a carbonyl group or a sulfonyl group. R ^A521 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ^A531 represents a substituted or unsubstituted heterocyclic group.

R ^A521 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and the substituent in the case of having a substituent is preferably an ionic hydrophilic group. R ^A531 represents a substituted or unsubstituted heterocyclic group, and in the case of having a substituent, the substituent is preferably an alkylamino group or an arylamino group, more preferably an alkylamino group or an arylamino group. These may further have a substituent and are preferably substituted with an ionic hydrophilic group.

  The substituent (A5-3) is preferably the following substituent (A5-4).

In the substituent (A5-4), * represents a bond as R ^{511 to} R ⁵¹³ . R ^A541 independently represents a substituted or unsubstituted alkylamino group or a substituted or unsubstituted arylamino group.

R ^A541 independently represents a substituted or unsubstituted alkylamino group or a substituted or unsubstituted arylamino group, and the substituent in the case of having a substituent is preferably an ionic hydrophilic group.

Specific examples of the substituents (A5-1) to (A5-4) are shown below, but are not limited to the following examples. * Represents a bond as R ^{511 to} R ⁵¹³ .

The A ⁵ group represents a substituted phenyl group or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group. Examples of the substituted phenyl group include a phenyl group having the substituent group 2, and more preferably an ionic hydrophilic group or a phenyl group having an electron withdrawing group having a Hammett's σp value of 0.3 or more.

Nitrogen-containing heterocyclic group A ⁵ groups represented include heterocyclic group substituted or unsubstituted nitrogen-containing. The heterocyclic group represented by A is preferably a monovalent group obtained by removing one hydrogen atom from a 5-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and has 2 to 4 carbon atoms. The 5-membered aromatic heterocyclic group is more preferable. Examples of the substituent include the groups described in the section of the substituent group 2 described above. Examples of the nitrogen-containing 5-membered heterocyclic group include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a thiazole ring, an isothiazole ring, and a thiadiazole ring when the substitution position is not limited.

  As the compound represented by the formula (5), a compound represented by the following formula (5-2) is also preferable.

In formula (5-2), A ⁵ group, G, and R ^{52 to} R ⁵⁵ have the same meaning as in formula (5), including preferred ones. R ⁵²¹ , R ⁵²² , R ⁵²³ , and R ⁵²⁴ each independently represent a hydrogen atom or a monovalent substituent. A ⁵² represents a substituted phenyl group or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group.

Examples of the monovalent substituent represented by R ⁵²¹ , R ⁵²² , R ⁵²³ , and R ^{524 in} formula (5-2) can include, independently, substituent group 1, substituted or unsubstituted alkyl. A group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and an alkyl group substituted with an ionic hydrophilic group (an alkyl group having 1 to 10 carbon atoms is exemplified by methyl, Ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, or t-butyl is preferred, methyl, ethyl, or n-propyl is more preferred, and n-propyl is still more preferred). Alternatively, it is more preferably an aryl group substituted with an ionic hydrophilic group (an aryl group having 6 to 20 carbon atoms is mentioned, phenyl and naphthyl are preferred, and phenyl is more preferred). That's right.

  As the compound represented by the formula (5) or the formula (5-2), a compound represented by the following formula (5-3) is preferable.

In formula (5-3), G and R ^{52 to} R ⁵⁵ have the same meaning as in formula (5), including preferred ones. R ⁵²¹ , R ⁵²² , R ⁵²³ , and R ⁵²⁴ have the same meaning as in formula (5-2), including preferred ones. X ⁵²¹ , X ⁵²² , X ⁵²³ , X ⁵²⁴ and X ⁵²⁵ each independently represent a hydrogen atom or a monovalent substituent. ^Examples of the substituent in the case where X ⁵²¹ , X ⁵²² , X ⁵²³ , X ⁵²⁴ and X ⁵²⁵ represent a substituent include the substituent group 2 described above. X ⁵²¹ , X ⁵²² , X ⁵²³ , X ⁵²⁴ and X ⁵²⁵ each independently represent a hydrogen atom, an ionic hydrophilic group, a cyano group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, nitro Group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, hydrogen atom, ionic hydrophilic group, cyano group, methanesulfonyl group, phenylsulfonyl A group, a nitro group, a methoxycarbonyl group, and a carbamoyl group are more preferable, and a hydrogen atom, an ionic hydrophilic group, or a cyano group is particularly preferable.

In formula (5-3), X ⁵²² and X ⁵²⁴ are preferably each independently a hydrogen atom or an ionic hydrophilic group. X ⁵²¹ , X ⁵²³ and X ⁵²⁵ are preferably each independently a hydrogen atom or substituent group 2, and at least one of X ⁵²¹ , X ⁵²³ and X ⁵²⁵ has a Hammett σp value. It preferably represents an electron withdrawing group of 0.3 or more. The upper limit of Hammett's substituent constant σp value is an electron withdrawing group of 1.0 or less.

  Specific examples of the electron withdrawing group having a σp value of 0.3 or more include an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, and a diarylphospho group. Group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy Group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, aryl group substituted with other electron-withdrawing group having σp value of 0.3 or more, nitro group, heterocyclic group, halogen atom , An azo group, or a selenocyanate group Is mentioned. A cyano group, a methylsulfonyl group, a phenylsulfonyl group, a methoxycarbonyl group, a carbamoyl group, and a nitro group are preferable, and a cyano group, a methylsulfonyl group, and a nitro group are more preferable.

  Particularly preferred combinations as the compound represented by the formula (5-3) include the following (5-3-i) to (5-3-v).

(5-3-i)
X ⁵²² and X ⁵²⁴ are preferably each independently a hydrogen atom or an ionic hydrophilic group, and at least one of X ⁵²¹ , X ⁵²³ and X ⁵²⁵ is an electron withdrawing having a Hammett's σp value of 0.3 or more. A cyano group, a methylsulfonyl group, a phenylsulfonyl group, a methoxycarbonyl group, a carbamoyl group, and a nitro group, more preferably a cyano group, a methylsulfonyl group, and a nitro group, and even more preferably a cyano group. X ⁵²¹ , X ⁵²² , X ⁵²³ and X ⁵²⁴ are hydrogen atoms and X ⁵²⁵ is a cyano group

(5-3-ii)
G represents a nitrogen atom or —C (R ⁵⁶ ) ═, R ⁵⁶ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group, and a carbamoyl group (—CONH ₂ group) or A cyano group is preferred, and a cyano group is more preferred.

(5-3-iii)
^{Examples of} the monovalent substituent represented by R ⁵²¹ , R ⁵²² , R ⁵²³ , and R ⁵²⁴ include the substituent group 1. A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or An unsubstituted heterocyclic group is preferred, and an alkyl group substituted with an ionic hydrophilic group or an aryl group substituted with an ionic hydrophilic group is more preferred. Among these, an alkyl group in which one of R ⁵²¹ and R ⁵²² is substituted with a hydrogen atom and the other with an ionic hydrophilic group is preferable. Similarly, an aryl group in which one of R ⁵²³ and R ⁵²⁴ is substituted with one hydrogen atom and the other with an ionic hydrophilic group is preferred, and the other is more preferably an aryl group substituted with 1 to 3 ionic hydrophilic groups. Preferred is a phenyl group substituted with two ionic hydrophilic groups. At this time, the substitution position of the ionic hydrophilic group is not particularly limited, but the 2-position and 5-position are preferred, with the position of the nitrogen atom to which R ⁵²³ or R ⁵²⁴ is bonded as the 1-position.

(5-3-iv)
R ⁵² is preferably an alkyl group, R ⁵³ is preferably a cyano group, and R ⁵⁴ and R ⁵⁵ are each preferably an aryl group substituted with an ionic hydrophilic group. R ⁵⁴ and R ⁵⁵ are more preferably a phenyl group substituted with an ionic hydrophilic group, and even more preferably a phenyl group substituted with an ionic hydrophilic group. At this time, the substitution position of the ionic hydrophilic group is not particularly limited, but the 4-position is preferred with the position of the nitrogen atom to which R ⁵⁴ and R ⁵⁵ are bonded as the 1-position.

(5-3-v)
As the ionic hydrophilic group, a sulfo group or a carboxy group is preferable, and a sulfo group is more preferable.

  As the compound represented by the formula (5), a compound represented by the following formula (5-4) is also preferable.

In formula (5-4), R ⁵⁴¹ represents a monovalent substituent, and G, R ^{52 to} R ⁵⁵ and A ⁵ groups have the same meaning as in formula (5), including preferred ones. L ^A521 has the same meaning as in formula (A5-2).

Examples of the monovalent substituent represented by R ⁵⁴¹ in Formula (5-4) include Substituent Group 1. A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group can be given. It is preferably a heterocyclic group, more preferably an alkyl group substituted with an ionic hydrophilic group, or an aryl group, and particularly preferably an alkyl group substituted with an ionic hydrophilic group. In the alkyl group substituted with an ionic hydrophilic group, the alkyl group is preferably a methyl group, an ethyl group, or an n-propyl group, and particularly preferably an ethyl group. As the ionic hydrophilic group, a sulfo group or a carboxy group is preferable, and a carboxy group is more preferable.

  As the compound represented by the formula (5-4), a compound represented by the following formula (5-5) is preferable.

In formula (5-5), R ⁵⁴¹ , G and R ^{52 to} R ⁵⁵ have the same meaning as in formula (5) or formula (5-4), including preferred ones. L ^A521 has the same meaning as in formula (A5-2). X ⁵⁵¹ , X ⁵⁵² , X ⁵⁵³ , X ⁵⁵⁴ and X ⁵⁵⁵ each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the substituent group 2 described above. X ⁵⁵¹ , X ⁵⁵² , X ⁵⁵³ , X ⁵⁵⁴ and X ⁵⁵⁵ are each independently a hydrogen atom, ionic hydrophilic group, cyano group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, nitro group Preferably a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a hydrogen atom, an ionic hydrophilic group, a cyano group, a methanesulfonyl group, a phenylsulfonyl group , A nitro group, a methoxycarbonyl group, and a carbamoyl group, more preferably a hydrogen atom, an ionic hydrophilic group, or a cyano group. As the ionic hydrophilic group, a sulfo group or a carboxy group is preferable, and a carboxy group is more preferable.

In general formula (5-5), it is preferable that ^X552 and ^X554 each independently represent a hydrogen atom or an ionic hydrophilic group. X ⁵⁵¹ , X ⁵⁵³ and X ⁵⁵⁵ are preferably each independently a hydrogen atom or any one of substituent group 2, and at least one of X ⁵⁵¹ , X ⁵⁵³ and X ⁵⁵⁵ has a Hammett's σp value of 0. It is preferable to represent 3 or more electron withdrawing groups. The upper limit of Hammett's substituent constant σp value is an electron withdrawing group of 1.0 or less. Specific examples thereof are the same as described above.

  Particularly preferred combinations as the compound represented by the general formula (5-5) include the following (5-5-i) to (5-5-v).

(5-5-i)
At least one of X ⁵⁵² and X ⁵⁵⁴ is preferably an ionic hydrophilic group, and X ⁵⁵¹ , X ⁵⁵³ and X ⁵⁵⁵ are a hydrogen atom or an electron-withdrawing group having a Hammett's σp value of 0.3 or more. It is preferable that ^X551 , ^X553, and ^X555 are hydrogen atoms, and it is more preferable that ^X552 and ^X554 are ionic hydrophilic groups. More ^{specifically,} X 551 ^{to X 554} is a hydrogen ^{atom, X 555} is Hammett σp value of 0.3 or more electron withdrawing group electron withdrawing group, preferably cyano group; ^or, X ^{551, X 553} And X ⁵⁵⁵ is a hydrogen atom, and X ⁵⁵² and X ⁵⁵⁴ are ionic hydrophilic groups, preferably a carboxy group.

(5-5-ii)
G represents a nitrogen atom or —C (R ⁵⁶ ) ═, R ⁵⁶ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group, and a carbamoyl group (—CONH ₂ group) or A cyano group is preferred, and a cyano group is more preferred.

(5-5-iii)
^Examples of the monovalent substituent represented by ^R541 include Substituent Group 1, which is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group, and has an ionic hydrophilic property. An alkyl group and an aryl group substituted with a functional group are more preferable. More specifically, R ⁵⁴¹ is an alkyl group (particularly preferably methyl), an alkyl group (particularly preferably carboxyethyl) substituted with a carboxy group, a sulfonyl group (particularly preferably methylsulfonyl), or an ionic hydrophilic group. A substituted aryl group (preferably substituted with one to three, more preferably one or two ionic hydrophilic groups, more preferably one or two ionic hydrophilic groups; And phenyl group). When R ⁵⁴¹ is one or two phenyl groups substituted with an ionic hydrophilic group, although the substitution positions of the ionic hydrophilic group is not particularly limited, as one of the bonding position of the L ^A521, 2-position and The 4th position is preferred.

(5-5-iv)
R ⁵² is preferably an alkyl group, R ⁵³ is preferably a cyano group, and R ⁵⁴ and R ⁵⁵ are each preferably an aryl group substituted with an ionic hydrophilic group. R ⁵⁴ and R ⁵⁵ are more preferably a phenyl group substituted with an ionic hydrophilic group, and even more preferably a phenyl group substituted with an ionic hydrophilic group. At this time, the substitution position of the ionic hydrophilic group is not particularly limited, but the 4-position is preferred, with the position of the carbon atom where R ⁵⁴ and R ⁵⁵ are bonded to the nitrogen atom being the 1-position.

(5-5-v)
As the ionic hydrophilic group, a sulfo group or a carboxy group is preferable, and a carboxy group is more preferable.

  As the compound represented by the formula (5-4), a compound represented by the following formula (5-6) is also preferable.

In formula (5-6), R ⁵⁴¹ , G, R ⁵² , R ⁵⁴ and R ⁵⁵ have the same meaning as in formula (5) or formula (5-4), including preferred ones. R ⁵³ independently has the same meaning as in formula (5) or formula (5-4), including preferred ones. L ^A521 has the same meaning as in formula (A5-2). R ⁵⁶¹ is an aryl group substituted with an ionic hydrophilic group, preferably one to three, more preferably an aryl group substituted with one or two ionic hydrophilic groups, more preferably two ions. Represents an aryl group substituted with an ionic hydrophilic group, particularly preferably a phenyl group substituted with two ionic hydrophilic groups. When R ⁵⁶¹ is a phenyl group substituted with two ionic hydrophilic groups, the substitution position of the ionic hydrophilic group is not limited. Preferably, ^R561 is in the 3rd and 5th positions, with the position of the carbon atom bonded to the nitrogen atom as the 1st position.

  Particularly preferred combinations as the compound represented by the formula (5-6) include the following (5-6-i) to (5-6-v).

(5-6-i)
G represents a nitrogen atom or —C (R ⁵⁶ ) ═, R ⁵⁶ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group, and a carbamoyl group (—CONH ₂ group) or A cyano group is preferred, and a cyano group is more preferred.

(5-6-ii)
^Examples of the monovalent substituent represented by ^R541 include Substituent Group 1, which is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group, and has an ionic hydrophilic property. More preferred are an alkyl group and an aryl group substituted with an ionic group, and further preferred is an aryl group substituted with an ionic hydrophilic group. More specifically, R ⁵⁴¹ is an alkyl group (particularly preferably methyl), an alkylcarbonyl group substituted with a carboxy group (particularly preferably carboxyethylcarbonyl), a sulfonyl group (particularly preferably methylsulfonyl), ionic hydrophilicity An aryl group substituted with a group (preferably an aryl group substituted with one to three, more preferably one or two ionic hydrophilic groups, more preferably one or two ionic hydrophilic groups Substituted phenyl group). When R ⁵⁴¹ is one or two phenyl groups substituted with an ionic hydrophilic group, although the substitution positions of the ionic hydrophilic group is not particularly limited, as one of the bonding position of the L ^A521, 2-position and The 4th position is preferred.

(5-6-iii)
R ⁵² is preferably an alkyl group, R ⁵³ is preferably a cyano group, and R ⁵⁴ and R ⁵⁵ are each preferably an aryl group substituted with an ionic hydrophilic group. R ⁵⁴ and R ⁵⁵ are more preferably a phenyl group substituted with an ionic hydrophilic group, and even more preferably a phenyl group substituted with an ionic hydrophilic group. At this time, the substitution position of the ionic hydrophilic group is not particularly limited, but the 4-position is preferred with the position of the nitrogen atom to which R ⁵⁴ and R ⁵⁵ are bonded as the 1-position.

(5-6-iv)
As the ionic hydrophilic group, a sulfo group or a carboxy group is preferable, and a carboxy group is more preferable.

The compounds represented by the formulas (5) and (5-1) to the formula (5-6) have a maximum absorption wavelength (λ _max ) of an absorption spectrum measured using water as a solvent of 550 nm to 700 nm. Is more preferable, and it is especially preferable that it is 580 nm-650 nm. Moreover, it is preferable that the compound represented by Formula (5) and Formula (5-1)-Formula (5-6) has an at least 3 or more ionic hydrophilic group. More preferably, it has 3-6 ionic hydrophilic groups, and still more preferably 4-5 ionic hydrophilic groups.

  Specific examples of the compound represented by the formula (5) are shown below, but the compound represented by the formula (5) is not limited to the following examples.

  The compounds represented by Formula (5) and Formula (5-1) to Formula (5-6) can be synthesized according to, for example, the methods described in Patent Documents 3 to 8, or the method.

In the formula (6), ^{A 6} group, and the aryl group in ^{D 6} groups phenyl is preferably. The arylene group in the B ⁶ group and the C ⁶ group includes an arylene group having 6 to 30 carbon atoms, preferably 6 to 10 carbon atoms. Specific examples thereof include phenylene and naphthylene, with phenylene being preferred and paraphenylene being more preferred. The A ⁶ group, the D ⁶ group, the B ⁶ group, and the C ⁶ group can each have 1 to 3, preferably 1 or 2, groups selected from the substituent group 1. The compound represented by the formula (6) is usually 1 to 8, preferably 1 to 7, more preferably 1 to 6, and further preferably 1 to 5 ionic hydrophilic per molecule. Has a sex group.

In the formula (6), examples of the substituent of the A ⁶ group, the B ⁶ group, the C ⁶ group, and the D ⁶ group include, among the substituent groups 1, an alkyl group; a halogen atom; a cyano group; a hydroxy group; A group selected from the group consisting of a group; a carboxy group; an amino group; an alkoxy group; an acylamino group; an alkylamino group; an alkylthio group; a carbamoyl group; a sulfamoyl group; preferable. In addition, an alkyl group which may be substituted with a group selected from the group consisting of a hydroxy group, a carbamoyl group, and an ionic hydrophilic group; a halogen atom; a cyano group; a hydroxy group; a nitro group; a carboxy group; An alkoxy group optionally substituted with a group selected from the group consisting of a hydroxy group, a carbamoyl group, and an ionic hydrophilic group; an acylamino group; a group selected from the group consisting of a hydroxy group, a carbamoyl group, and an ionic hydrophilic group An alkylamino group which may be substituted with a group selected from the above: an alkylthio group optionally substituted with a group selected from the group consisting of a hydroxy group, a carbamoyl group and an ionic hydrophilic group; a carbamoyl group; a sulfamoyl group; Substituted with a group selected from the group consisting of a hydroxy group, a carbamoyl group, and an ionic hydrophilic group. Optionally have a sulfonyl group; an acyl group; and, an ionic hydrophilic group; more preferably a group selected from the group consisting of. Of these, the substituents for the A ⁶ group and the D ⁶ group are more preferably a group selected from a halogen atom and an ionic hydrophilic group. Further, the substituent of the B ⁶ group and the C ⁶ group is selected from the group consisting of an unsubstituted alkyl group, a halogen atom, an alkoxy group optionally substituted with an ionic hydrophilic group, and an ionic hydrophilic group. More preferred is a group.

  A particularly preferred combination as the compound represented by the formula (6) includes the following (6-i) and (6-ii).

(6-i)
The A ⁶ group and the D ⁶ group are phenyl groups having an ionic hydrophilic group, and further have a halogen atom or an unsubstituted alkoxy group. The B ⁶ group and the C ⁶ group are a phenyl group having an alkoxy group substituted with a halogen atom and an ionic hydrophilic group, and R ⁶¹ is a carbonyl group. The positions of the substituents of the A ⁶ group and the D ⁶ group are the substituents of the B ⁶ group and the C ⁶ group which are the 3rd and 4th positions with the substitution position of the azo group in the formula (6) as the 1st position. In the formula (6), the substitution position of the nitrogen atom is the 1-position, the 2-position, and the 5-position (preferably the alkoxy group substituted with the ionic hydrophilic group is the 2-position and the halogen atom is the 5-position) is there.

(6-ii)
The A ⁶ group is a phenyl group having an ionic hydrophilic group, and the D ⁶ group is a phenyl group or a naphthyl group having an ionic hydrophilic group. The B ⁶ group is a paraphenylene group having an ionic hydrophilic group, and the C ⁶ group may have a group selected from the group consisting of an unsubstituted alkyl group, an unsubstituted alkoxy group, and an ionic hydrophilic group. Good phenyl group. R ⁶¹ is a group represented by the formula (9), and R ⁹¹ is an alkylamino group substituted with an ionic hydrophilic group. The position of the substituent of the A ⁶ group is the 3rd or 4th position, with the substitution position of the azo group in the formula (6) as the 1st position. When the D ⁶ group is a phenyl group, the position of the substituent of the D ⁶ group is the 3rd position or the 4th position with the substitution position of the azo group in the formula (6) as the 1st position. When the D ⁶ group is a naphthyl group, the substitution position of the azo group in the formula (6) is the 2-position, and the substitution position of the D ⁶ group is the 4-position and the 8-position, or the 6-position and the 8-position. is there. The position of the substituent of the B ⁶ group is the 2nd position with the nitrogen atom substitution position in the formula (6) as the 1st position. The position of the substituent of the C ⁶ group is the 2nd position or the 3rd position with the substitution position of the nitrogen atom in the formula (6) as the 1st position.

Specific examples of the compound represented by the formula (6) are shown below, but the compound represented by the formula (6) is not limited to the following examples.
The abbreviations in Table 26 to Table 33 below have the following meanings.
A ⁶ & D ⁶ : means that the A ⁶ group and the D ⁶ group are the same group.
B ⁶ & C ⁶ : Means that the B ⁶ group and the C ⁶ group are the same group.
Ph: phenyl.
SPO: sulfopropoxy.
PL: Paraphenylene.
Me: methyl.
CPO: Carboxypropoxy.
SEO: sulfoethoxy.
SBO: sulfobutoxy.
SEA: sulfoethylamino.
SMA: sulfomethylamino.
SPA: sulfopropylamino.
Np: naphthyl.

How to read each group in Table 26 to Table 33 is No. 6-1 and no. 6-300 will be briefly described as an example.
No. 6-1:
“3-SO ₃ H-4-F-Ph” is “3-sulfo-4-fluoro-phenyl”. “2- (3-SPO) -5-F-PL” is “2- (3-sulfopropoxy) -5-fluoro-paraphenylene”. That is, no. 6-1 is a group A ^{6 and a} group D ⁶ is a 3-sulfo-4-fluoro-phenyl group, and a group B ^{6 and a} group C ⁶ are 2- (3-sulfopropoxy) -5-fluoro-para. It means a phenylene group and R ⁶¹ is a carbonyl group compound.
No. 6-300:
“3-SO ₃ H-Ph” is “3-sulfo-phenyl”. “2- (3-SPO) -PL” is “2- (3-sulfopropoxy) -paraphenylene”. “4,6,8- (SO ₃ H) ₃ -2-Np” is “4,6,8-trisulfo-2-naphthyl”. That is, no. 6-300 is, ^{A 6} groups 3 sulfo - phenyl group, ^{B 6} group is 2- (3-sulfopropoxy) - paraphenylene group, ^{C 6} group is unsubstituted paraphenylene group, ^{D 6} groups 4, A 6,8-trisulfo-2-naphthyl group, R ⁶¹ is a group represented by the formula (9), and R ⁹¹ is a compound having a sulfoethylamino group.

  The compound represented by the formula (6) can be synthesized, for example, according to the methods described in Patent Documents 9 and 10, or the method.

In the formula (7), the aryl group in the A ⁷¹ group and the A ⁷² group is preferably phenyl. Examples of the arylene group in the B ⁷¹ group, the C ⁷¹ group, the B ⁷² group, and the C ⁷² group include arylene groups having 6 to 30 carbon atoms, preferably 6 to 10 carbon atoms. Specific examples thereof include phenylene and naphthylene, with phenylene being preferred and paraphenylene being more preferred. A ⁷¹ group, B ⁷¹ group, C ⁷¹ group, A ⁷² group, B ⁷² group, C ⁷² group is 1 to 3, preferably 1 or 2 groups selected from the substituent group 1; More preferably, each can have one. The compound represented by the formula (7) usually has 1 to 8, preferably 1 to 7, more preferably 1 to 6 ionic hydrophilic groups in one molecule.

In the formula (7), when R ⁷¹ is the formula (10), the substituents of the A ⁷¹ group, the B ⁷¹ group, the A ⁷² group, and the B ⁷² group are ionic hydrophilic among the substituent group 1 Groups are preferred. As the substituent of the C ⁷¹ group and the C ⁷² group, among the substituent group 1, a group consisting of an alkyl group, a halogen atom, a hydroxy group, an alkoxy group, an acylamino group, an alkylamino group, an arylamino group, and a ureido group A group selected from is preferred. R ⁹¹ is preferably an alkylamino group substituted with an ionic hydrophilic group. In the formula (7), when R ⁷¹ is the formula (10), the C ⁷¹ group and the C ⁷² group are bonded to the nitrogen atom marked with “*” in the formula (10).

A particularly preferred combination as the compound in which R ⁷¹ is represented by formula (10) in formula (7) includes the following (7-i).

(7-i)
The A ⁷¹ group and the A ⁷² group are each independently a phenyl group having an ionic hydrophilic group (preferably a sulfo group). The B ⁷¹ group and the B ⁷² group are each independently phenylene (preferably paraphenylene) having an ionic hydrophilic group (preferably a sulfo group). The C ⁷¹ group and the C ⁷² group are each independently phenylene having an unsubstituted alkyl group (preferably paraphenylene). The position of the substituent of the A ⁷¹ group and the A ⁷² group is the 4th position with the substitution position of the azo group in the formula (7) as the 1st position. The position of the substituent that the B ⁷¹ group and the B ⁷² group have is the third position with the substitution position of the A ⁷¹ group or the azo group to which the A ⁷² group is bonded in the formula (7) as the first position. The position of the substituent of the C ⁷¹ group and the C ⁷² group is the 3rd position with the substitution position of “—NH—” in the formula (7) as the 1st position. R ⁹¹ is preferably a mono- or di-alkylamino group substituted with an ionic hydrophilic group (preferably a group selected from a carboxy group and a sulfo group).

In the formula (7), when R ⁷¹ is the formula (11), the substituents of the A ⁷¹ group, the B ⁷¹ group, the A ⁷² group, and the B ⁷² group include, among the substituent group 1, an alkyl group, a halogen atom, Groups selected from the group consisting of atoms, hydroxy groups, and ionic hydrophilic groups are preferred. As the substituent for the A ⁷¹ group and the A ⁷² group, a group selected from the group consisting of an alkoxy group, a hydroxy group, and an ionic hydrophilic group is more preferable, and an ionic hydrophilic group is more preferable. The number of substituents of the A ⁷¹ group and the A ⁷² group is usually 1 to 5, preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, particularly preferably. Is one. As the substituent for the B ⁷¹ group and the B ⁷² group, a group selected from the group consisting of an alkyl group and an alkoxy group is more preferable, and unsubstituted is more preferable. When the B ⁷¹ group and the B ⁷² group have a substituent, the number is usually 1 to 4, preferably 1 to 3, and more preferably 1 or 2. As the substituent of the C ⁷¹ group and the C ⁷² group, among the substituent group 1, an ionic hydrophilic group is preferable. The number of substituents ^{contained in the} C ⁷¹ group and the C ⁷² group is usually 1 to 4, preferably 1 to 3, more preferably 1 or 2, and still more preferably 1. In the formula (7), when R ⁷¹ is the formula (11), the C ⁷¹ group and the C ⁷² group are bonded to the carbon atom marked with “*” in the formula (11). A particularly preferred combination of R ⁷¹ in the formula (7) as the compound represented by the formula (11) includes the following (7-ii) and (7-iii).

(7-ii)
The A ⁷¹ group and the A ⁷² group are each independently a phenyl group having a group selected from the group consisting of an alkoxy group, a hydroxy group, and an ionic hydrophilic group. The substitution position is the 1-position of the substitution position of the azo group, the 3-position, the 4-position, and the 5-position when there are three substituents; the 3-position, and the 4-position when there are two substituents; The 3rd or 4th position is preferred. The B ⁷¹ group and the B ⁷² group are unsubstituted phenylene (preferably paraphenylene); or phenylene (preferably paraphenylene) having a group selected from the group consisting of an alkyl group and an alkoxy group. When it has a substituent, the substitution position is the 2-position when the substitution position of the azo group to which the C ⁷¹ group is bonded is 1-position, the 2-position when the substituent is 2, and the 5-position; The third position is preferred. The C ⁷¹ group and the C ⁷² group are each independently a phenylene group (preferably a paraphenylene group) having an ionic hydrophilic group (preferably a sulfo group). The substitution position is preferably the 2-position with the binding position to R ⁷¹ as the 1-position.

(7-iii)
The A ⁷¹ group and the A ⁷² group are each independently a phenyl group having one ionic hydrophilic group (preferably a sulfo group). The substitution position is preferably the 4-position with the substitution position of the azo group as the 1-position. The B ⁷¹ group and the B ⁷² group are unsubstituted phenylene (preferably paraphenylene). The C ⁷¹ group and the C ⁷² group are each independently a phenylene group (preferably a paraphenylene group) having one ionic hydrophilic group (preferably a sulfo group). The substitution position is preferably the 2-position with the binding position to R ⁷¹ as the 1-position.

Specific examples of the compound represented by the formula (7) are shown below, but the compound represented by the formula (7) is not limited to the following examples.
The abbreviations in Table 34 and Table 35 below have the following meanings.
In R ⁷¹ , “10” means a group represented by the formula (10), and “11” means a group represented by the formula (11).
A ⁷¹ & A ⁷² : It means that the A ⁷¹ group and the A ⁷² group are the same group.
B ⁷¹ & B ⁷² : Means that the B ⁷¹ group and the B ⁷² group are the same group.
C ⁷¹ & C ⁷² : means that the C ⁷¹ group and the C ⁷² group are the same group.
Ph: phenyl.
PL: Paraphenylene.
Me: methyl.
Et: ethyl.
ⁿ Pr: n-propyl.
SEA: sulfoethylamino.
_(CP) 2 A :( di - carboxypropyl) amino.
CEA: carboxyethylamino.
CPeA: Carboxypentylamino.
SMA: sulfomethylamino.
_(SM) 2 A :( di - sulfomethyl) amino.
(SE) ₂ A: (Di-sulfoethyl) amino.
CMA: Carboxymethylamino.
(CM) ₂ A: (Di-carboxymethyl) amino.
(CE) ₂ A: (Di-carboxyethyl) amino.
SPA: sulfopropylamino.
_(SP) 2 A :( di - sulfopropyl) amino.
OMe: Methoxy.
OH: hydroxy.

How to read each group in Table 34 and Table 35 is No. 7-1 and No. 7-44 will be briefly described as an example.
No. 7-1:
“4-SO ₃ H-Ph” is “4-sulfo-phenyl”. “3-SO ₃ H-PL” is “3-sulfo-paraphenylene”. “3-Me-PL” is “3-methyl-paraphenylene”. “SEA” is sulfoethylamino. That is, no. ^{7-1, A 71} group, and ^{A 72} groups 4-sulfophenyl - a phenyl ^{group, B 71} group, and ^{B 72} groups 3 sulfo - paraphenylene a ^{group, C 71} group, and ^{C 72} groups Is a 3-methyl-paraphenylene group, R ⁷¹ is a group represented by the formula (10), and R ⁹¹ is a sulfoethylamino group.
No. 7-44;
“3-CO ₂ H-4-OMe-5-SO ₃ H-Ph” is “3-carboxy-4-methoxy-5-sulfophenyl”. “2,5- (Me) ₂ -PL” is “2,5-dimethyl-paraphenylene”. “2-SO ₃ H-PL” is “2-sulfo-paraphenylene”. That is, no. 7-44 ^{is, A 71} group, and ^{A 72} radicals is 3-carboxy-4-methoxy-5-sulfophenyl ^{group, B 71} group, and ^{B 72} groups 2,5-dimethyl - be paraphenylene group , C ⁷¹ group, and C ⁷² group are 2-sulfo-paraphenylene groups, and R ⁷¹ is a compound represented by the formula (11).

In the formula (8), the aryl group in ^eight, and B ⁸ groups A, phenyl, naphthyl, anthracenyl, and the respective groups such phenanthrenyl. These groups can further have a substituent. Moreover, when it has two or more substituents, the substituents couple | bond together and a condensed ring can be formed. The condensed ring can further have a substituent. Examples of the substituent that the aryl group and the condensed ring may have include an azo group, a halogen atom, a carboxy group, a carbamoyl group, a sulfo group, a sulfamoyl group, a hydroxy group, a mercapto group, an amino group, a cyano group, and a phospho group. Group, phosphino group, phosphinyloxy group, phosphinylamino group, nitro group, silyl group, acyl group, alkyl group (preferably halogen atom, hydroxy group, carboxy group, carbamoyl group, sulfo group, and sulfamoyl group) A C1-C6 alkyl group optionally substituted with one or more substituents selected from: an alkoxy group (preferably a halogen atom, a hydroxy group, a carboxy group, a carbamoyl group, a sulfo group, and a sulfamoyl group). C1-C optionally substituted with one or more selected substituents An alkoxy group), a sulfoalkyl group (preferably a C1-C6 sulfo which may be substituted with one or more substituents selected from a halogen atom, a hydroxy group, a carboxy group, a carbamoyl group, a sulfo group, and a sulfamoyl group. Alkyl group), an alkylthio group (preferably a C1-C6 alkylthio optionally substituted by one or more substituents selected from a halogen atom, a hydroxy group, a carboxy group, a carbamoyl group, a sulfo group, and a sulfamoyl group) Group), an alkylamino group (preferably a C1-C6 alkylamino optionally substituted with one or more substituents selected from a halogen atom, a hydroxy group, a carboxy group, a carbamoyl group, a sulfo group, and a sulfamoyl group) Group), or acylamino group, aryloxy group, hete Ring group, a heterocyclic oxy group, an arylthio group, a heterocyclic thio group, an arylamino group, heterocyclic amino group, an arylsulfonyl group, can be exemplified heterocyclic sulfonyl group, etc., but is not limited thereto. The heterocyclic groups in the A ⁸ group and the B ⁸ group include thiophene, furan, pyrrole, thiazole, oxazole, pyrazole, imidazole, isothiazole, isoxazole, thiadiazole, oxadiazole, triazole, pyridine, pyridazine, pyrimidine, and Examples of each group include pyrazine. These groups can further have a substituent. Moreover, when it has two or more substituents, the substituents couple | bond together and a condensed ring can be formed. The condensed ring can further have a substituent. Examples of the substituent that the heterocyclic ring and the condensed ring may have include an azo group, a halogen atom, an alkyl group (including a cycloalkyl group), an alkenyl group (including a cycloalkenyl group), an alkynyl group, an aryl group, a hetero group Ring group, cyano group, hydroxyl group, nitro group, carboxyl group and salts thereof, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group Amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, aryl Thio group, heterocyclic thio group, sulfamoyl group, sulfo group and its salt, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group Imide group, phosphino group, phosphono group and salts thereof, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, quaternary ammonium group and the like.

In the formula (9), as the substituent in R ^91, an alkylamino group, or arylamino group. These groups are preferably substituted with ionic hydrophilic groups. These groups have the same meaning as the substituent group 1 described above. R ⁹¹ is more preferably a mono- or di-alkylamino group substituted with an ionic hydrophilic group, or a phenylamino group substituted with an ionic hydrophilic group. The number of substitutions of ionic hydrophilic groups is one for one alkyl group when an alkylamino group; and usually one to three for one phenyl group when a phenylamino group, preferably One or two. Among these, a mono- or di-alkylamino group substituted with an ionic hydrophilic group (preferably a group selected from a carboxy group and a sulfo group) is particularly preferable. At this time, the alkyl moiety is linear or branched, and is preferably linear. Moreover, the carbon number is 1-6, Preferably it is 1-4.

  Examples of the colorant (B) include C.I. I. Known dyes having numbers can also be used. Among such dyes, direct dyes (CI direct) and acid dyes (CI acid) are preferable, and direct dyes are more preferable. Specific examples of such dyes include C.I. I. Yellow dyes such as direct yellow 34, 50, 58, 86, 132, 142, 161, 173, and acid yellow 17, 23; I. Orange dyes such as direct orange 17, 26, 29, 39, 49; I. Examples thereof include red dyes such as direct red 62, 75, 79, 80, 84, 89, 225, 226, and 227. Of these, yellow dyes are preferred.

  The salt of the compound represented by the formula (1), the colorant (A) and the colorant (B) is a salt with an inorganic or organic cation. Among them, examples of the salt with an inorganic cation include alkali metal salts, alkaline earth metal salts, and ammonium salts. Preferred inorganic salts are lithium, sodium, potassium salts, and ammonium salts. Examples of the salt with an organic cation include, but are not limited to, a salt with a quaternary ammonium ion represented by the following formula (1-82). Moreover, the compound represented by Formula (1) can also be made into the mixture of the free acid, its tautomer, and those various salts. For example, a mixture of a sodium salt and an ammonium salt; a mixture of a free acid and a sodium salt; a mixture of a lithium salt, a sodium salt, and an ammonium salt; Depending on the type of salt, the physical properties such as solubility may differ, and if necessary, select the type of salt as appropriate; or if multiple salts are included, change the ratio to It can also be a physical property.

In formula (1-82), Z ⁸²¹ , Z ⁸²² , Z ⁸²³ , and Z ⁸²⁴ are each independently selected from the group consisting of a hydrogen atom, an unsubstituted alkyl group, a hydroxyalkyl group, and a hydroxyalkoxyalkyl group. And at least one is a group other than a hydrogen atom. Preferable specific examples of the alkyl groups of Z ^{821 to} Z ⁸²⁴ in the above formula (1-82) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl and the like. . Preferable specific examples of the hydroxyalkyl group include hydroxy (C1-C4) alkyl groups such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like. Is mentioned. Specific examples of the hydroxyalkoxyalkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl and the like. And a hydroxy (C1-C4) alkoxy (C1-C4) alkyl group. In these, a hydroxyethoxy (C1-C4) alkyl group is preferable.

  The ink may contain an ink preparation agent as a component other than the above, if necessary. Examples of the ink preparation agent include water-soluble organic solvents, preservatives, antifungal agents, pH adjusters, chelating reagents, rust inhibitors, water-soluble ultraviolet absorbers, antioxidants, and surfactants.

  Examples of the water-soluble organic solvent include C1 such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, 1,2-hexanediol, 1,6-hexanediol, and trimethylolpropane. -C6 alkanol; carboxylic acid amides such as N, N-dimethylformamide and N, N-dimethylacetamide; lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone and N-methylpyrrolidin-2-one; Cyclic ureas such as 1,3-dimethylimidazolidin-2-one and 1,3-dimethylhexahydropyrimido-2-one; acetone, 2-methyl-2-hydroxypentan-4-one, and ethylene carbonate Ketones or keto alcohols such as tetrahydrofuran; And cyclic ethers such as dioxane; ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, Mono-, oligo- having C2-C6 alkylene units such as triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol having a molecular weight of 400, 800, 1540 or higher, polypropylene glycol, thiodiglycol or dithiodiglycol And poly-alkylene glycols or thioglycols; polyols (triols) such as glycerin, diglycerin, hexane-1,2,6-triol; γ-butyrolactone; Examples thereof include dimethyl sulfoxide.

  Examples of preservatives include, for example, organic sulfur, organic nitrogen sulfur, organic halogen, haloaryl sulfone, iodopropargyl, haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzothiazole , Isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone, benzyl Examples thereof include bromoacetate compounds and inorganic salt compounds. In addition, proxel series such as trade names Proxel GXL (S) and Proxel XL-2 (S) manufactured by Arch Chemical Co., are preferably mentioned.

  Specific examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one, and salts thereof. .

  As the pH adjuster, any substance can be used as long as it can control the pH of the ink within a range of about 5 to 11 without adversely affecting the prepared ink. Specific examples thereof include, for example, alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (ammonia water) Alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate and potassium carbonate; alkali metal salts of organic acids such as potassium acetate; inorganic bases such as sodium silicate and disodium phosphate.

  Specific examples of the chelating reagent include, for example, disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracil diacetate.

  Specific examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  Examples of water-soluble ultraviolet absorbers include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

  As examples of the antioxidant, for example, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocyclic rings. It is done.

  Examples of the surfactant include known surfactants such as anion, cation, nonion, amphoteric, silicone-based and fluorine-based. Of these, surfactants selected from nonions and silicones are preferred, and silicones are more preferred. Examples of anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, polyoxyethylene alkyl ether sulfates, N-acyl amino acids or salts thereof, N-acyl methyl taurate, Alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, Examples thereof include alkylaryl sulfonates, diethylsulfosuccinates, diethylhexylsulfosuccinates, dioctylsulfosuccinates and the like.

  Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

  Nonionic surfactants include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl Acetylene glycol (alcohol) series such as lu-1-hexyn-3-ol; trade name Surfynol 104, 105, 82, 465, Olphine STG, etc. manufactured by Nissin Chemical; Polyglycol ether series (for example, SIGMA-ALDRICH) Manufactured by Tergitol 15-S-7, etc.).

  Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and imidazoline derivatives. Can be mentioned.

  Examples of silicone surfactants include polyether-modified siloxane and polyether-modified polydimethylsiloxane. For example, Dynol 960 and Dinol 980 manufactured by Air Products, Silface SAG001, Silface SAG002, Silface SAG003, Silface SAG005, Silface SAG503A, Silface SAG008, and Sylface SAG009 manufactured by Nissin Chemical Co., Ltd. , Silface SAG010, BYK-345, BYK-347, BYK-348, BYK-349, BYK-3455 and the like manufactured by Big Chemie. Of these, polyether-modified siloxanes known from BYK series manufactured by BYK Chemie are preferred.

  Examples of the fluorosurfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group as a side chain. And polyoxyalkylene ether polymer compounds. As the fluorosurfactant, various types of products can be easily purchased from, for example, DuPont, Omniva, DIC, and Big Chemie.

  The ink can be obtained by mixing and stirring the components described above in an arbitrary order. The obtained ink can be subjected to microfiltration with a membrane filter or the like as necessary. The pore diameter of the filter for performing microfiltration is usually 1 μm to 0.1 μm, preferably 0.8 μm to 0.1 μm.

  The ink can be used for various applications such as writing, printing, information recording, and textile printing. Among these, it is particularly preferable to use for ink jet recording.

  The ink jet recording method is a recording method in which image formation is performed by ejecting ink droplets in accordance with a recording signal and attaching them to a recording medium. There are no particular restrictions on the ink nozzles or the like of the ink jet printer that ejects ink, and the physical properties of the ink can be appropriately adjusted according to the purpose.

  The ink does not depend on the recording system of the ink jet printer, and any system can be used. Examples thereof include various systems such as charge control, drop-on-demand (pressure pulse), acoustic ink jet, and thermal ink jet.

  The recording medium means a substance that can be colored by the ink. Examples thereof include paper, film, fiber and cloth (cellulose, nylon, wool, etc.), leather, base material for color filter, and the like. Among the recording media, those in which an ink receiving layer is provided on a substrate such as paper, synthetic paper, or film are preferable. The ink-receiving layer is formed by, for example, impregnating or coating a base material with a cationic polymer; porous white inorganic substances capable of absorbing pigments in ink, such as porous silica, alumina sol, and special ceramics; It is provided by a method such as coating on the surface of a substrate together with a hydrophilic polymer such as; A recording medium provided with such an ink receiving layer is usually called ink jet exclusive paper (film) / glossy paper (film). Specific examples include Canon Inc., trade name: Professional Photo Paper, Super Photo Paper, or Matt Photo Paper; Seiko Epson Corporation, trade name: Photo Paper (Glossy), PM Matt Paper, Crispia; Japan Hewlett-Packard Co. Made by company, product name Advanced Photo Paper, Premium Plus Photo Paper, Premium Glossy Film or Photo Paper. Also, plain paper such as PPC paper having no ink receiving layer can be used.

  When recording on a recording medium by the inkjet recording method, for example, a container (referred to as an ink tank or the like) containing the ink is loaded at a predetermined position of the inkjet printer, and recording is performed on the recording medium by the recording method. The ink jet recording method can perform full color recording as an ink set of a plurality of inks selected from the color inks. At that time, a container containing ink of each color is loaded at a predetermined position of the ink jet printer in the same manner as described above, and is recorded on the recording medium by the recording method described above.

  About all the said contents, the combination of preferable things is more preferable, The combination of more preferable things is still more preferable. The same applies to combinations of preferable and more preferable ones, and combinations of more preferable and more preferable ones.

  The ink preferably contains the compound represented by the formula (1) and the colorant (B), and contains the compound represented by the formula (1), the colorant (B), and the colorant (A). More preferably.

When printing using the ink, when adjusting the hue of the ink in order to express a more neutral black color in the printed matter, it is difficult to define it more generally than you like. The a * value, which is the value to be expressed, is in the range of -8 to 8, the b * value is in the range of -15 to 5, and C * that can be calculated from the a * value and the b * value by the following formula (1). By adjusting the value to be 11 or less, generally good black expression is possible.
C * = √ (a *) ² + (b *) ² Formula (1)

  The ink of the present invention is a water-based ink substantially containing water, and any of recording media having an ink receiving layer such as ink jet dedicated paper and general-purpose plain paper having no ink receiving layer can be used. High-quality image formation can be performed. In addition, this ink has no storage, solid property change, color change, etc. after long-term storage, and has good storage stability. An image recorded with the ink of the present invention is particularly excellent in ozone gas resistance, has high printing density, excellent bronzing properties, low color rendering, low saturation, and a high-quality black hue. Excellent fastness such as light resistance, moisture resistance and water resistance. Further, by using in combination with inks containing magenta, cyan and yellow pigments, full-color ink jet recording with various fastnesses and excellent storage stability is possible.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by a following example. In addition, each synthesis reaction and the like were performed under stirring unless otherwise specified.

[Synthesis Example]: Synthesis of a compound represented by the formula (1).
(Process 1)
18.4 parts of cyanuric chloride and trade name Leocol TD-50 (0.1 part) were added to 200 parts of ice water, and the mixture was stirred at 10 ° C. or lower for 30 minutes. Next, 31.7 parts of 2,5-disulfoaniline (use a commercial product with a purity of 88.4%) was added, and the pH was adjusted to 2.8 to 3.0 with a 10% aqueous sodium hydroxide solution at 0 to 10 ° C. for 2 hours. The reaction was carried out at 25-30 ° C. for 1 hour while adjusting the pH to 2.8-3.0. To the obtained liquid, 16.9 parts of 4-chloro-3-nitroaniline was added, and the reaction was performed at 40 to 45 ° C. for 2 hours while adjusting the pH to 5.0 to 5.5 with a 10% aqueous sodium hydroxide solution. To the obtained liquid, 18.8 parts of 2-aminoethanesulfonic acid was added, and the reaction was performed at 70 to 80 ° C. for 3 hours while adjusting the pH to 7.0 to 7.5 with a 10% aqueous sodium hydroxide solution. At this time, the liquid volume was 600 parts. 120 parts of sodium chloride was added to this liquid and stirred for 30 minutes, and then the precipitated solid was filtered to obtain 193 parts of a wet cake containing a compound represented by the following formula (1-83).

(Process 2)
193 parts of a wet cake containing the formula (1-83) obtained in Step 1 was dissolved in 90 parts of N-methyl-2-pyrrolidone, and then 19.1 parts of sodium 3-mercaptopropanesulfonate and 15 parts of potassium carbonate. 2 parts were added. After the addition, the mixture was heated to 100 to 110 ° C. and reacted at the same temperature for 2 hours. The resulting liquid was cooled to 60 ° C. After adding 150 parts of water to this solution, 35% hydrochloric acid was further added to adjust the pH to 1.0 to 1.5. The liquid volume at this time was 550 parts. After adding 110 parts of sodium chloride to this liquid and stirring for 30 minutes, the precipitated solid was collected by filtration to obtain 204 parts of a wet cake containing a compound represented by the following formula (1-84).

(Process 3)
To 150 parts of water, 204 parts of a wet cake of the compound represented by the formula (1-84) obtained in (Step 2), 5 parts of activated carbon, and 0.6 part of anhydrous iron (III) chloride are added, and 60 parts are added. After heating to ° C., 11.3 parts of 80% hydrazine hydrate was added dropwise over about 30 minutes. The obtained liquid was heated to 90 ° C. and reacted at the same temperature for 2 hours. The obtained liquid was cooled to 40 ° C., insoluble matters were removed by filtration, and the filtrate was cooled to room temperature. 50% sulfuric acid was added to the obtained liquid to adjust the pH to 1.0 to 1.5. The liquid volume at this time was 625 parts. After adding 125 parts of sodium chloride to this liquid and stirring for 30 minutes, the precipitated solid was collected by filtration to obtain 98 parts of a wet cake containing a compound represented by the following formula (1-85).

(Process 4)
After adding 12.2 parts of sodium 2-amino-5-nitrobenzenesulfonate to 50 parts of water, an aqueous solution was obtained at pH 4.0 to 5.0 by adding a 25% aqueous sodium hydroxide solution. After adding 18.3 parts of 35% hydrochloric acid, 10.5 parts of 40% aqueous sodium nitrite solution was added and allowed to react for about 30 minutes. To this, 1.5 parts of sulfamic acid was added and stirred for 5 minutes to obtain a diazo reaction liquid. On the other hand, 11.0 parts of a compound of the following formula (1-86) obtained by the method described in International Publication No. 2012/081640 is added to 100 parts of water, and pH 4.0 is added by adding a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as 5.0. This aqueous solution was dropped into the diazo reaction solution over about 5 minutes. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 4.0 to 6.0 by adding a 15% aqueous sodium carbonate solution, and then sodium chloride was added. The precipitated solid was collected by filtration to obtain 103.8 parts of a wet cake containing a compound represented by the following formula (1-87).

(Process 5)
After adding the entire amount of the wet cake of the compound represented by the formula (1-87) obtained in (Step 4) to 80 parts of water, the aqueous solution was adjusted to pH 6.0 to 7.0 by adding a 25% aqueous sodium hydroxide solution. Got. After adding 16.5 parts of 35% hydrochloric acid to the obtained aqueous solution, 10.6 parts of 40% sodium nitrite aqueous solution was added and allowed to react for about 30 minutes. 7.5 parts of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid. On the other hand, after adding 64.7 parts of the wet cake of the compound represented by the formula (1-85) obtained in (Step 3) to 100 parts of water, pH 4.0 to 4.0 by adding a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as 5.0. This aqueous solution was dropped into the diazo reaction solution over about 5 minutes. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 3.5 by adding a 15% aqueous sodium carbonate solution. Sodium chloride was added to the obtained liquid, and the precipitated solid was collected by filtration to obtain 104 parts of a wet cake containing a compound represented by the following formula (1-88).

(Step 6)
A solution was prepared by adding 52 parts of a wet cake of the compound represented by the formula (1-88) obtained in (Step 5) to 100 parts of water and stirring. After adding 7.8 parts of 35% hydrochloric acid to the obtained solution, 2.8 parts of 40% aqueous sodium nitrite solution was added and stirred for about 30 minutes. The sulfamic acid 0.8 part was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid. On the other hand, 3.7 parts of a compound of the following formula (1-89) obtained by the method described in JP-A-2004-083492 is added to 80 parts of water, and pH 6.0 is adjusted by adding a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as 7.0. This aqueous solution was dropped into the diazo reaction solution over about 5 minutes. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 4.5 by adding a 15% aqueous sodium carbonate solution. A 25% aqueous sodium hydroxide solution was added to the obtained liquid to adjust the pH to 7.0 to 7.5. The solid which precipitated by adding sodium chloride to the obtained liquid was separated by filtration, and 29.5 parts of a wet cake containing a compound represented by the following formula (1-90) was obtained.

(Step 7)
A solution was prepared by adding 29.5 parts of a wet cake of the compound represented by the formula (1-90) obtained in (Step 6) to 80 parts of water and stirring. After adding 6.3 parts of 35% hydrochloric acid to the obtained solution, 2.3 parts of 40% aqueous sodium nitrite solution was added and stirred for about 30 minutes. 0.5 parts of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid. On the other hand, 4.4 parts of a compound of the following formula (1-91) obtained by the method described in International Publication No. 2012/081640 is added to 80 parts of water, and pH 6.0 is added by adding 5% aqueous sodium hydroxide solution. An aqueous solution was obtained as ˜7.0. The diazo reaction solution was added dropwise to this aqueous solution at 15 to 30 ° C. over about 30 minutes. At this time, a 15% aqueous sodium carbonate solution was added to maintain the pH of the reaction solution at 6.5 to 7.5, and the reaction was further continued for 2 hours while maintaining the same temperature and pH adjustment. The solid which precipitated by adding sodium chloride to the obtained liquid was separated by filtration, and 21.5 parts of wet cake was obtained. The obtained wet cake was dissolved in 40 parts of water, the pH was adjusted to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of methanol was added, and the precipitated solid was collected by filtration. The obtained wet cake was again dissolved in 40 parts of water, and then 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain 12.1 parts of a black powder of a sodium salt (λmax: 597 nm) of a compound represented by the following formula (1-92).

[(A) Preparation of ink]
The components shown in Table 36 and Table 37 below were mixed to form a solution, and then filtered through a 0.45 μm membrane filter to obtain inks of Examples and Comparative Examples. The pH of each ink was adjusted to a range of 8.0 to 9.5.

Abbreviations and the like in Table 36 have the following meanings. The numerical value of each component is “part”.
1-92: Sodium salt of the compound represented by the formula (1-92) obtained in the above synthesis example.
3-17: No. in Table 21 3-17 compounds.
4-1: No. in Table 23 The compound of 4-1.
6-282: No. in Table 33 The compound of 6-282.
7-1: No. in Table 34 7-1 compounds.
7-39: No. in Table 35 The compound of 7-39.
GLY: Glycerin.
NMP: N-methyl-2-pyrrolidone.
IPA: isopropyl alcohol.
BCA: Butyl carbitol.
TAU: Taurine.
EDA: disodium ethylenediaminetetraacetic acid.
SF104: Surfinol 104PG50.
“Aq.NaOH” and “remainder” means that the pH of each solution was adjusted to 8.0 to 9.5 with a 25% aqueous sodium hydroxide solution, and then water was added to make the total amount of the solution 100 parts. Means that.

Abbreviations and the like in Table 37 have the following meanings. The numerical value of each component is “part”.
1-92: Sodium salt of the compound represented by the formula (1-92) obtained in the above synthesis example.
3-17: No. in Table 21 3-17 compounds.
4-1: No. in Table 23 The compound of 4-1.
6-282: No. in Table 33 The compound of 6-282.
7-1: No. in Table 34 7-1 compounds.
7-39: No. in Table 35 The compound of 7-39.
Comparative dye A: a compound of the following formula (A).
GLY: Glycerin.
NMP: N-methyl-2-pyrrolidone.
IPA: isopropyl alcohol.
BCA: Butyl carbitol.
TAU: Taurine.
EDA: disodium ethylenediaminetetraacetic acid.
SF104: Surfinol 104PG50.
“Aq.NaOH” and “remainder” means that the pH of each solution was adjusted to 8.0 to 9.5 with a 25% aqueous sodium hydroxide solution, and then water was added to make the total amount of the solution 100 parts. Means that.

In the above, the compound used as the comparison pigment | dye A is shown as a following formula (A). The formula (A) does not include the group represented by the formula (2) in any of R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ^{110 in} the formula (1).

[(B) Inkjet recording]
Each ink of Examples and Comparative Examples was subjected to inkjet recording on the following glossy paper using an inkjet printer (manufactured by Canon Inc., trade name: PIXUS ip 7230). At the time of recording, an image pattern was formed so that six gradation levels of 100%, 85%, 70%, 55%, 40%, and 25% density were obtained, and a halftone recorded matter was obtained. Using the obtained recorded matter as a test piece, the following test was conducted.
Glossy paper: manufactured by Canon Inc., trade name: Canon photographic paper / platinum grade (PT-201).
Glossy paper: manufactured by Canon Inc., trade name: Canon photo paper / glossy gold (GL-101).

[(C) Color measurement of test piece]
When it was necessary to measure the color of the test piece, a colorimeter manufactured by X-rite, trade name SpectroEye was used. The colorimetric conditions are DIN or ANSI A based on the density standard, a viewing angle of 2 degrees, and a light source D65.

[(D) Ozone resistance test]
Each test piece was installed in an ozone weather meter (model OMS-H, manufactured by Suga Test Instruments Co., Ltd.), and a test was performed in which it was left for 24 hours at an ozone concentration of 10 ppm, a bath temperature of 23 ° C., and a humidity of 50% RH. For each test piece, the printing density (Dc value) before and after the test of the 55% gradation portion was measured to determine the dye residual ratio. The test results are shown in Table 38 below. A larger value of the dye residual ratio (%) means an excellent result.

[(E) Hue evaluation]
The a * value and b * value, which are values representing the hue of the printed material, were respectively printed on the printed materials obtained by inkjet printing using the inks obtained in Examples 6 to 13 and Comparative Examples 1 to 5 according to JIS Z 8729. The chroma C * value that can be calculated from the a * value and the b * value was calculated, and the results are shown in Table 39 below. Moreover, the said ozone resistance test was done using printed matter, and the color difference (DELTA) E value before and behind a test was shown. The color difference ΔE can be calculated from the numerical differences ΔL *, Δa *, Δb * between L *, a *, and b * before and after the test by the following formula (2). Note that a *, b *, C *, and ΔE were each calculated to the second decimal place, and the second decimal place was rounded off to make the first decimal place valid.
ΔE = √ (ΔL *) ² + (Δa) ² + (Δb *) ² Formula (2)

As is apparent from Table 39, in Examples 6 to 13, the a * value is in the range of -8 to 8, the b * value is in the range of -15 to 5, and the C * value is 11 or less. From this, it can be seen that a good black print is obtained. On the other hand, in Comparative Example 5, the b * values were -15.98 and -16.18, and the C * values were 16.36 and 16.21, both of which were outside the above setting range, and a good black print was obtained. It shows that it cannot be obtained. This is because it is not a combination of the present formula (1) and the colorant (B) or a combination of the present formula (1), the colorant (A) and the colorant (B). The combination of the colorant (B) or the combination of the formula (1), the colorant (A) and the colorant (B) indicates that it is necessary to obtain a good black print. Yes.
In Examples 6 to 13, which are a combination of the present formula (1) and the colorant (B), or a combination of the present formula (1), the colorant (A) and the colorant (B), before and after the ozone gas test. The value of ΔE representing the degree of hue change is 5.0 or less, and the combination of the present formula (1) and the colorant (B), or the present formula (1) and the colorant (A) In Comparative Examples 1 to 4 other than the combination of the colorant (B), the value of ΔE exceeds 5.0. The value of ΔE indicates that if the numerical value is small, the rate of change before and after the test is small, and the ozone gas resistance is excellent. In Table 39 above, Comparative Example 4 is 4.3 and 5.0 or less in printing on PT-201, but 5.5 and exceeding 5.0 in printing on GL-101. Therefore, there is dependency on printing paper. On the other hand, it turns out that Examples 6-13 show favorable ozone gas resistance irrespective of printing paper. Therefore, this invention has shown that the aqueous ink excellent in ozone gas resistance can be provided.

  The ink of the present invention is extremely suitable as a black ink for various recordings such as writing utensils, particularly for inkjet recording.

Claims (10)

A compound represented by the following formula (1) or a tautomer thereof, or a salt thereof, and at least one colorant selected from the following colorant (A) and colorant (B) ink.
[In Formula (1),
R ¹¹ represents an alkyl group, an aryl group, or a carboxy group,
R ¹² represents a cyano group, a carbamoyl group, or a carboxy group,
R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a sulfo group,
R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represents an alkylthio group; an alkoxy group; or a group represented by the following formula (2):
R ¹⁸ , R ¹⁹ and R ¹¹⁰ each independently represent a hydrogen atom; a carboxy group; a sulfo group; an alkylcarbonylamino group; a halogen atom; an alkyl group; an alkoxy group; or a group represented by the following formula (2):
R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; an alkylcarbonylamino group; a halogen atom; a cyano group; a nitro group; a sulfamoyl group; an alkyl group; Or represents an alkylsulfonyl group.
Any of the above groups can further have a substituent.
However, at least one of R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ¹¹⁰ is a group represented by the following formula (2).
Moreover, it can have a benzene ring represented by a broken line.
[In Formula (2),
R ¹¹⁶ represents a sulfoanilino group or a sulfonaphthylamino group.
The group represented by R ¹¹⁶ further includes a carboxy group, a phosphate group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkoxy group, an amino group, an alkylamino group, an arylamino group, an alkylcarbonylamino group, a ureido group, One or more substituents selected from the group consisting of an alkyl group, a cyano group, a halogen atom, an alkylsulfonyl group, and an alkylthio group can be included.
R ¹¹⁷ represents an anilino group, a naphthylamino group, an alkylamino group, an arylamino group, an amino group, an alkylthio group, an arylthio group, a phenoxy group, an alkoxy group, or a hydroxy group.
The group represented by R ¹¹⁷ further includes a sulfo group, a carboxy group, a phosphate group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkoxy group, an amino group, an alkylamino group, an arylamino group, an alkylcarbonylamino group, It may have one or more groups selected from the group consisting of a ureido group, an alkyl group, an aryl group, a furyl group, a pyridyl group, a cyano group, a halogen atom, an alkylsulfonyl group, and an alkylthio group.
Further, “*” in the formula (2) represents a bonding position. ].
Colorant (A):
A compound having λmax of 500 nm to 700 nm and a half width of 100 nm to 500 nm.
Colorant (B):
A compound having λmax of 350 nm to 450 nm and a half width of 50 nm to 250 nm. In the formula (1),
R ¹¹ is an alkyl group,
R ¹⁵ is an alkylthio group, an alkoxy group, or a group represented by the formula (2),
The ink according to claim 1, wherein R ¹⁶ and R ¹⁷ are each independently an alkylthio group or a group represented by the formula (2). In the formula (1),
R ¹¹ is an alkyl group,
R ¹² is a cyano group,
R ¹³ and R ¹⁴ are each independently a hydrogen atom, an alkoxy group, or a sulfo group,
R ¹⁵ is an alkoxy group,
R ¹⁶ and R ¹⁷ are each independently an alkylthio group,
R ¹⁸ and R ¹¹⁰ are each independently an alkyl group or an alkylcarbonylamino group,
R ¹⁹ is a group represented by the formula (2),
The ink according to claim 1, wherein R ¹¹¹ , R ¹¹² , R ^113, and R ¹¹⁴ are each independently a hydrogen atom, a sulfo group, or a nitro group. The colorant (A) is at least one colorant selected from the group represented by the following formulas (3) to (5), tautomers thereof, or salts thereof. The ink described in 1.
[In Formula (3),
A ³ group is a carboxy group; a sulfo group; a halogen atom; a cyano group; a nitro group; a sulfamoyl group; an alkyl group; an alkoxy group; and an aryl group having at least one group selected from the group consisting of: And
The B ³ group and the C ³ group are each independently a paraphenylene group having at least one group selected from the group consisting of a carboxy group; a sulfo group; an alkyl group; an alkoxy group; and an alkylthio group;
R ³¹ represents an alkyl group, an aryl group, or a carboxy group,
R ³² represents a cyano group, a carbamoyl group, or a carboxy group,
R ³³ and R ³⁴ each independently represent a hydrogen atom, an alkyl group, a halogen atom, or a sulfo group.
Any of the above groups can further have a substituent. ].
[In Formula (4),
R ⁴¹ , R ⁴² , R ⁴⁵ , R ⁴⁶ and R ⁴⁷ are each independently a hydrogen atom; a halogen atom; a cyano group; a hydroxy group; a carboxy group; a sulfo group; a sulfamoyl group; an N-alkylaminosulfonyl group; Sulfonyl group; alkylcarbonyl group; arylcarbonyl group; ureido group; alkyl group; alkoxy group; alkylcarbonylamino group; arylcarbonylamino group; alkylsulfonylamino group; Represents a group selected from the group consisting of:
R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom; a halogen atom; a cyano group; a carboxy group; a sulfo group; a nitro group; an alkyl group; an alkoxy group; an alkylcarbonylamino group; an alkylsulfonylamino group; Represents at least one group selected from the group consisting of:
n represents 0 or 1, respectively.
Any of the above groups can further have a substituent. ].
[In Formula (5),
A ⁵ group represents an aryl group or a heterocyclic group,
G represents a nitrogen atom or —C (R ⁵⁶ ) ═.
R ⁵⁶ represents a hydrogen atom, a sulfo group, a carboxy group, a carbamoyl group, or a cyano group.
R ⁵¹ , R ⁵⁴ and R ⁵⁵ each independently represents an aryl group,
R ⁵² and R ⁵³ each independently represent a substituent. ] The colorant (B) has at least two ionic hydrophilic groups in one molecule, and is a compound represented by the following formulas (6) to (8) or a tautomer thereof, or a salt thereof: The ink according to claim 1, wherein the ink is at least one colorant selected from the group.
[In Formula (6),
A ⁶ group and D ⁶ group each independently represent an aryl group,
B ⁶ group and C ⁶ group each independently represent an arylene group,
R ⁶¹ represents a group represented by the following formula (9) or a carbonyl group. ]
[In Formula (7),
A ⁷¹ group and A ⁷² group each independently represent an aryl group,
B ⁷¹ group, C ⁷¹ group, B ⁷² group, and C ⁷² group each independently represent an arylene group,
R ⁷¹ represents a group represented by the following formula (10) or formula (11). ]
[In Formula (8),
The A ⁸ group and the B ⁸ group each independently represent an aryl group or a heterocyclic group, but both do not represent an aryl group at the same time. ]
[In Formula (9), R ⁹¹ represents a substituent, and * represents a binding site. ]
[In formula (10), R ⁹¹ represents the same meaning as in formula (9), and * represents a binding site with C ⁷¹ group and C ⁷² group. ]
In formula (11), * represents a bonding site to the ^{C 71} group, and ^{C 72} groups. ]   Furthermore, the ink as described in any one of Claims 1-5 containing a water-soluble organic solvent.   An ink jet recording method for forming an image using the ink according to claim 6.   A recording medium to which the ink according to claim 1 is attached.   An ink jet printer cartridge filled with the ink according to claim 6.   An ink jet printer comprising the ink jet printer cartridge according to claim 9.