JP2013112729A - Ink set - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink set excellent in color reproducibility, moisture resistance and gas resistance, with which an image having an excellent color balance can be recorded.SOLUTION: The ink set includes at least a yellow ink, magenta ink and cyan ink, wherein the yellow ink contains, as a colorant, at least one compound selected from the group consisting of a compound expressed by general formula (y-1) or its salt and an azo compound having a triazine ring and a pyrazole ring. In formula (y-1), Qrepresents a halogen atom; x represents an integer of 2 to 4; and y represents an integer of 1 to 3.

Description

  The present invention relates to an ink set.

  Conventionally, ink compositions have been used to record images on various recording media (for example, paper, plastic, glass, metal, etc.). Such an ink composition contains various components, and particularly contains a colorant (for example, a dye, a pigment, etc.) in order to obtain an image having a desired color.

  An ink composition containing a colorant may be used, for example, in an inkjet recording method. In the ink jet recording method, a droplet of an ink composition is ejected from an ink jet recording head or the like, and the droplet is attached to a recording medium to record an image. In general, as an ink composition used in an ink jet recording method, in addition to a color ink (for example, a yellow ink, a magenta ink, a cyan ink, etc.) capable of recording an image having a hue such as yellow, magenta, and cyan as a colorant, desired Thus, a black ink capable of forming an image having a black hue is used. A combination of two or more of these inks is used as an ink set (see Patent Document 1).

  The ink is required to have performance suitable for the intended use and environment. For example, an image recorded with ink may be damaged by gas (for example, ozone) present in the environment or moisture (humidity) in the environment, and may cause discoloration or fading. Therefore, it is required that an image excellent in gas resistance and moisture resistance can be recorded for each ink. Such image discoloration and fading are often caused by the colorant contained in the ink, and therefore the colorant contained in the ink has been improved.

  However, even if the gas resistance and moisture resistance of the image obtained for each ink are excellent, if these inks are used as an ink set, the hue balance of the image obtained by combining each ink is lost, which is good. A correct image may not be obtained. This is because there are variations in performance such as gas resistance and moisture resistance among inks. If the performance varies between inks, discoloration or fading of only a specific color may progress in an image obtained by combining the inks. Then, the color change of the image is recognized in a shorter time than the image formed by the single ink causes the color change. That is, it is required that each ink is excellent in gas resistance and moisture resistance and that the difference in gas resistance and moisture resistance performance between the inks is small (see Patent Document 2).

  In addition, when two or more types of ink are used as an ink set, it is required that an image obtained by combining each ink can reproduce a desired color satisfactorily.

JP 2001-288392 A JP-A-2005-105135

  However, an image recorded using the ink described in the above-mentioned patent document may have insufficient ink moisture resistance and gas resistance.

  In particular, an image recorded using a plurality of inks using the ink set described in the above patent document may not be excellent in ink moisture resistance and gas resistance, and may not be excellent in color reproducibility. .

  One of the objects according to some embodiments of the present invention is to provide an ink set capable of recording an image excellent in color reproducibility, moisture resistance and gas resistance and excellent in color balance. .

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the ink set according to the present invention is:
An ink set comprising at least yellow ink, magenta ink, and cyan ink,
The yellow ink is selected from the group consisting of a compound represented by the following general formula (y-1) or a salt thereof and a compound represented by the following general formula (y-2) or a salt thereof as a colorant. Containing at least one of
The magenta ink contains, as a colorant, at least one selected from the group consisting of a compound represented by the following general formula (m-1) or a salt thereof,
The cyan ink has, as a colorant, at least one selected from the group consisting of a compound represented by the following general formula (c-1) or a salt thereof, a compound represented by the following general formula (c-2), or And at least one selected from the group consisting of salts thereof.

(In formula (y-1), Q ^Y1 represents a halogen atom; x represents an integer of 2 to 4; y represents an integer of 1 to 3.)

(In formula (y-2), X ^Y21 , X ^Y22 , Y ^Y21 , and Y ^Y22 each independently represent a hydrogen atom or a cyano group, and Z ^Y21 and Z ^Y22 represent a substituent having an aromatic ring. R ^Y21 and R ^Y22 represent an alkyl group, and M ^Y2 represents a metal atom.)

(In the formula (m-1), A ^M1 represents an alkylene group having 1 or 2 carbon atoms, an alkylene group having 1 or 2 carbon atoms containing a phenylene group, or a group represented by the following formula (m-1-1). X ^M1 represents an amino group, a hydroxy group, a chlorine atom, or a phenoxy group substituted with a sulfo group or a carboxy group.)

(In formula (m-1-1), R ^M1 represents a hydrogen atom or an alkyl group.)

(In the formula (c-1),
Rings A ^{C1 to} D ^C1 represented by broken lines each independently represent a benzene ring or a 6-membered nitrogen-containing heteroaromatic ring condensed to a porphyrazine ring, and the average number of nitrogen-containing heteroaromatic rings is 0. .00 to 3.00 and the rest are benzene rings,
E ^C1 represents C2-C12 alkylene;
X ^C1 is a substituent such as sulfo group, carboxy group, phosphate group, sulfamoyl group, carbamoyl group, hydroxy group, C1-C6 alkoxy group, amino group, mono C1-C4 alkylamino group, di-C1-C4 alkylamino. Group, mono C6-C10 arylamino group, di-C6-C10 arylamino group, C1-C3 alkylcarbonylamino group, ureido group, C1-C6 alkyl group, nitro group, cyano group, halogen atom, C1-C6 alkylsulfonyl group And a sulfoanilino group, a carboxyanilino group, a phosphonoanilino group, a sulfonaphthylamino group, a carboxynaphthylamino group, which may have one or two or more substituents selected from the group consisting of C1-C6 alkylthio groups Or a phosphononaphthylamino group,
R ^C1 is a hydrogen atom; a sulfo group; a carboxy group; a phosphate group; a sulfamoyl group; a carbamoyl group; a hydroxy group; a C1-C6 alkoxy group; an amino group; a mono C1-C6 alkylamino group; Diarylamino group; C1-C3 alkylcarbonylamino group; ureido group; C1-C6 alkyl group; nitro group; cyano group; halogen atom; C1-C6 alkylsulfonyl group; or alkylthio group;
The group F ^C1 represents a phenyl group; or a 6-membered nitrogen-containing heteroaromatic group;
a represents an integer of 1 to 6,
b is an average value of 0.00 or more and less than 3.90,
c is an average value of 0.10 or more and less than 4.00,
The sum of b and c is an average value of 1.00 or more and less than 4.00. )

(In Formula (c-2), X ^C21 , X ^C22 , X ^C23 and X ^C24 each independently represent —SO—Z ^C2 or —SO ₂ —Z ^C2 ,
Z ^C2 each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group,
Y ^C21 , Y ^C22 , Y ^C23 , Y ^C24 , Y ^C25 , Y ^C26 , Y ^C27 and Y ^C28 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group. , Heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, Alkoxycarbonylamino group, sulfonamido group, carbamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic ring Thio group, phos Lil group, an acyl group, a carboxyl group or a sulfonic group,
a _{1 to} a ₄ satisfy 4 ≦ a ₁ + a ₂ + a ₃ + a ₄ ≦ 8, and each independently represents an integer of 1 or 2,
M ^C2 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. )

  According to the ink set of Application Example 1, it is possible to record an image having excellent color reproducibility, moisture resistance, and gas resistance and excellent color balance.

[Application Example 2]
In application example 1,
Furthermore, at least one of the first black ink and the second black ink is provided,
The first black ink contains a pigment as a colorant,
The second black ink is represented by the following general formula (b-2) and at least one selected from the group consisting of a compound represented by the following general formula (b-1) or a salt thereof as a colorant. And at least one selected from the group consisting of a compound or a salt thereof.

(In the above formula (b-1), n is 0 or 1,
R ^B11 represents a carboxy group; a C1-C8 alkoxycarbonyl group; a C1-C4 alkyl group; a C1-C4 alkyl group substituted with a C1-C8 alkoxycarbonyl group or a carboxy group; a phenyl group; or a hydroxy group, a sulfo group or a carboxy group Represents a phenyl group substituted with a group,
R ^B12 , R ^B13 and R ^B14 each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group; a mono- or di-C1-C4 alkylamino group substituted with a hydroxy group, a sulfo group or a carboxy group; A C1-C4 alkylcarbonylamino group; a C1-C4 alkylcarbonylamino group substituted with a hydroxy group or a carboxy group; an N′-C1-C4 alkylureido group substituted with a hydroxy group, a sulfo group or a carboxy group; Chlorine atom, C1-C4 A phenylamino group substituted by an alkyl group, a nitro group, a sulfo group or a carboxy group; a benzoylamino group in which the benzene ring is substituted by a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group; or a benzene ring Each represents a chlorine atom, a phenylsulfonylamino group substituted with a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group;
Group A ^B1 is a substituted heterocyclic group represented by the following general formula (b-1-1),
The group B ^B1 is a phenyl group or a substituted phenyl group or naphthyl group or a substituted naphthyl group, and when the group B ^B1 is a substituted phenyl group, a hydroxy group; a sulfo group; a carboxy group; a C1-C4 alkyl group A C1-C4 alkoxy group; a C1-C4 alkylsulfonyl group; a nitro group; an amino group; a mono- or di-C1-C4 alkylamino group; an acetylamino group; and a benzene ring as a chlorine atom, a C1-C4 alkyl group, a nitro group; A benzoylamino group substituted with a sulfo group or a carboxy group; having a substituent selected from the group consisting of, and when the group B ^B1 is a substituted naphthyl group, a hydroxy group; a sulfo group; a C1-C4 alkoxy group; A phenylsulfonyloxy group in which the benzene ring is substituted with a methyl group, a nitro group or a chlorine atom; Having a substituent selected from that group. )

(In the formula (b-1-1), R ^B16 , R ^B17 and R ^B18 each independently represent a hydrogen atom; a chlorine atom; a carboxy group; a sulfo group; a nitro group; a hydroxy group; a carbamoyl group; a sulfamoyl group; C1-C4 alkyl group; C1-C4 alkoxy group; C1-C4 alkoxy group substituted with a hydroxy group, C1-C4 alkoxy group, sulfo group or carboxy group; C1-C4 alkylsulfonyl group; Hydroxy group, sulfo group or carboxy group A C1-C4 alkylsulfonyl group substituted with a group; or a phenylsulfonyl group in which the benzene ring is substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group;

(In the above formula (b-2), R ^B21 , R ^B22 , R ^B23 , R ^B24 , R ^B25 , R ^B26 , R ^B27 and R ^B28 are each independently a hydrogen atom; a halogen atom; a sulfo group; a carboxy group A sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a C1-C4 alkoxy group; a substituent selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group; A C1-C4 alkoxy group substituted with at least one group selected from: a C1-C4 alkylcarbonylamino group; a C1-C4 alkylcarbonylamino group substituted with a carboxy group; a ureido group; a mono C1-C4 alkylureido group; Di-C1-C4 alkylureido group; A mono C1-C4 alkylureido group substituted with at least one group selected from the group consisting of a group and a carboxy group; as a substituent, at least selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group At least one selected from the group consisting of a halogen atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group, a di-C1-C4 alkylureido group substituted with one type of group; a benzoylamino group; A benzoylamino group substituted with one type of group; a benzenesulfonylamino group; or at least one selected from the group consisting of a halogen atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group. A phenylsulfonylamino group substituted with a kind of group;
X ^B2 represents a divalent crosslinking group. )

[Application Example 3]
In application example 1 or application example 2,
Furthermore, the magenta ink may contain at least one selected from the group consisting of a compound represented by the following general formula (m-2) or a salt thereof as a colorant.

(In the above formula (m-2), A ^M2 represents a 5-membered heterocyclic group,
B ^M21 and B ^M22 each represent -CR ^M21 =, -CR ^M22 =, or one of them represents a nitrogen atom, and the other represents -CR ^M21 = or -CR ^M22 =,
R ^M23 and R ^M24 each independently represent a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group, and R ^M23 and R ^M24 may further have a substituent;
G ^M2 , R ^M21 , and R ^M22 each independently represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. An acyl group, a hydroxy group, an alkoxy group, an aryloxy group, a silyloxy group, an acyloxy group, a carbamoyloxy group, a heterocyclic oxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyl group, an aryl group, or a heterocyclic group. Substituted amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl and Riruchio group, an alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio ^{group,, G M2, R M21,} R M22 may be further substituted,
R ^M21 and R ^M23 , or R ^M23 and R ^M24 may combine to form a 5- to 6-membered ring. )

[Application Example 4]
In any one of Application Examples 1 to 3,
The compound represented by the general formula (y-1) may be a compound represented by the following formula (y-11).

[Application Example 5]
In any one of Application Examples 1 to 4,
The compound represented by the general formula (y-2) may be a compound represented by the following general formula (y-21).

(In the above formula (y-21), X ^Y21 , X ^Y22 , Y ^Y21 and Y ^Y22 each independently represent a hydrogen atom or a cyano group, and W ^Y21 , W ^Y22 , W ^Y23 , W ^Y24 , W ^Y25 , W ^Y211 , W ^Y212 , W ^Y213 , W ^Y214 and W ^Y215 each independently represent a hydrogen atom, a carboxyl group or a salt thereof, M ^Y2 represents a metal atom, and t-Bu represents a tertiary butyl group.

[Application Example 6]
In any one of Application Examples 1 to 5,
The compound represented by the general formula (m-1) may be a compound represented by the following general formula (m-11).

（上記式（ｍ−１１）中、Ｍ^Ｍ１は、ＮＨ_４またはＮａを示す。）

(In the formula (m-11), M ^M1 represents NH ₄ or Na.)

[Application Example 7]
In any one of Application Examples 1 to 6,
In the general formula (c-1),
A pyridine ring in which the nitrogen-containing heteroaromatic rings in rings A ^{C1 to} D ^C1 are independently condensed at the 2-position and 3-position, or at the 3-position and 4-position; or a pyrazine ring condensed at the 2-position and 3-position And
E ^C1 is a linear C2-C4 alkylene,
X ^C1 is a substituent such as a sulfo group, a carboxy group, a hydroxy group, a C1-C6 alkoxy group, an amino group, a mono C1-C4 alkylamino group, a diC1-C4 alkylamino group, a C1-C3 alkylcarbonylamino group, A sulfoanilino group which may have 0 to 2 substituents of one or two types selected from the group consisting of a nitro group, a halogen atom, a C1-C6 alkylsulfonyl group and an alkylthio group; A carboxyanilino group optionally having 0 to 2 substituents of one or two types selected from the group consisting of a group, a carboxy group, a hydroxy group, and a sulfamoyl group; a phosphonoanilino group; or Sulfona optionally having 0 to 2 substituents of one or two types selected from sulfo group and hydroxy group A butylamino group;
R ^C1 is a hydrogen atom; a sulfo group; a carboxy group; a C1-C6 alkoxy group; a C1-C6 alkyl group; or a halogen atom;
The group F ^C1 is a phenyl group; or the pyridyl group in which R ^C1 is a hydrogen atom;
a can be an integer of 1 or 2.

[Application Example 8]
In any one of Application Examples 1 to 7,
The compound represented by the general formula (c-2) may be a compound represented by the following general formula (c-21).

(In formula (c-21), Z ^C21 , Z ^C22 , Z ^C23 and Z ^C24 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group, ^C2 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide, provided that at least one of Z ^C21 , Z ^C22 , Z ^C23 and Z ^C24 is an ionic hydrophilic group As a substituent.)

[Application Example 9]
In application example 2,
In the general formula (b-1),
R ^B11 is a carboxy group; a C1-C8 alkoxycarbonyl group; a C1-C4 alkyl group substituted with a C1-C4 alkyl group carboxy group; or a phenyl group;
R ^B12 , R ^B13 and R ^B14 each independently represent a hydrogen atom; a sulfo group; a C1-C4 alkyl group; a C1-C4 alkoxy group; a C1-C4 alkoxy group substituted with a sulfo group or a carboxy group; C1-C4 An alkylcarbonylamino group; or an N′-C1-C4 alkylureido group substituted with a sulfo group or a carboxy group,
In the general formula (b-1-1),
R ^B16 , R ^B17 and R ^B18 are each independently a hydrogen atom; a chlorine atom; a carboxy group; a sulfo group; a nitro group; a C1-C4 alkoxy group; a C1-C4 alkoxy group; or a C1-C4 alkylsulfonyl group. ,
The group B ^B1 in the general formula (b-1) is a phenyl group having a substituent selected from the group consisting of a hydroxy group; a sulfo group; a carboxy group; a C1-C4 alkyl group; a C1-C4 alkoxy group; Can be.

[Application Example 10]
In application example 2,
In the general formula (b-2),
It is, or C1-C4 alkyl group or substituted with C1-C4 alkoxy groups piperazine-1,4-diyl group; the divalent bridging group represented by ^{X B2} is piperazine-1,4-diyl group Can do.

[Application Example 11]
In application example 3,
The compound represented by the general formula (m-2) may be a compound represented by the following general formula (m-22).

(In the formula ^{(m-22), R M25} , R M26, R M27, R M28, R M29, R M210, R M211, R M212, R M213, R M214 are each independently a hydrogen atom, an alkyl group Represents a sulfo group or a salt thereof, and M ^M2 represents a hydrogen atom or an alkali metal atom.)

  Hereinafter, preferred embodiments of the present invention will be described. The embodiment described below describes an example of the present invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications that are implemented within a range that does not change the gist of the present invention.

  In the present invention, “Cv-Cw” (v and w are each an integer) means v to w carbon atoms. For example, C1-C4 alkyl refers to an alkyl group containing 1-4 carbon atoms. Further, “Cv-Cw” may have a linear or branched structure unless otherwise specified.

1. Ink Set An ink set according to an embodiment of the present invention includes at least yellow ink, magenta ink, and cyan ink. Hereinafter, components contained in each ink will be described.

  Each ink constituting the ink set according to the present embodiment (hereinafter also referred to as “each ink according to the present embodiment”) contains a colorant described later. Each of the colorants described below is excellent in moisture resistance and gas resistance, has excellent color reproducibility, and has a small deterioration rate difference due to gas (for example, ozone) and a moisture absorption rate difference between the colorants. . For this reason, the ink set according to the present embodiment is less likely to cause image degradation (discoloration, fading, etc.), and even if the image degradation progresses over time, the difference in the degradation speed of each ink is small. It is possible to record an image that makes it difficult to feel the deterioration of the entire image.

  Hereinafter, components included in each ink according to the present embodiment will be described.

1.1. Yellow Ink The yellow ink according to the present embodiment has, as a colorant, a compound represented by the following general formula (y-1) or a salt thereof (hereinafter also simply referred to as “dye (y-1)”), and the following. It contains at least one selected from the group consisting of a compound represented by the general formula (y-2) or a salt thereof (hereinafter also simply referred to as “dye (y-2)”).

1.1.1. Dye (y-1)
The dye (y-1) is represented by the following formula (y-1) when expressed as a free acid. The dye (y-1) may be ionized in the yellow ink. In that case, at least one of the —SO ₃ H groups of the dye represented by the formula (y-1) is ionized to form —SO _3. ^- may have a further counter ions in this case is not particularly limited. Therefore, the dye (y-1) of this embodiment may be in any form of acid, ion and salt, but when expressed as a free acid, it is represented by the following formula (y-1). Is.

(In formula (y-1), Q ^Y1 represents a halogen atom; x represents an integer of 2 to 4; y represents an integer of 1 to 3.)
The dye (y-1) belongs to a water-soluble yellow pigment. When the dye (y-1) is added to a solvent containing water, at least one of the five —SO ₃ H groups is ionized to become —SO ₃ ^— , which is ionized in the solvent. Can exist. When the dye (y-1) is added to a solvent containing water, all of the five —SO ₃ H groups are ionized to form —SO ₃ ^— and exist in the solvent. It may be.

In the above formula (y-1), Q ^Y1 represents a halogen atom. Examples of the halogen atom include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). Among these, Q ^Y1 is preferably F or Cl, and particularly preferably Cl. In the formula (y-1), two Q ^Y1 are present, but the two Q ^Y1 may be independently different halogen atoms.

  In formula (y-1), x represents an integer of 2 to 4. x can be appropriately selected in consideration of the solubility of the dye (y-1) in water and the like, but from this point of view, x is preferably an integer 3. In the formula (y-1), x appears in two places, but these x may be different integers.

  In formula (y-1), y represents an integer of 1 to 3. y may be appropriately selected in consideration of the solubility of the dye (y-1) in water and the like, and is preferably an integer 2 from such a viewpoint.

The above Q ^Y1 , x, and y can be appropriately designed according to the requirement for solubility in water, for example.

Specific examples of the dye (y-1) are shown in the following table. In the table below, Q ^Y1 , x, and y are synonymous with those described for the above formula (y-1).

As a method of adding the dye (y-1) to the ink, a yellow ink may be obtained by adding the dye (y-1) itself (in the state of a free acid), or represented by the formula (y-1). A yellow ink may be added by adding it as a salt of a compound. In this way, the dye (y-1) can be contained in the ink. In addition, when the dye (y-1) is added as a salt, five —SO ₃ H groups present when the dye (y-1) is represented as a free acid are each independently a lithium salt, a sodium salt, It can be any one of a potassium salt and an ammonium salt.

  When expressed as the free acid of the present embodiment, the compound represented by the formula (y-1) and a salt thereof can be obtained by the following method or the like. For example, in the synthesis reaction of the dye (y-1), the solid precipitated by adding an organic solvent such as acetone or C1-C4 alcohol or adding sodium chloride to the reaction solution after completion of the final step is filtered and separated. By doing, the sodium salt of dye (y-1) etc. can be obtained as a wet cake. Further, after dissolving the obtained sodium salt wet cake in water, an acid such as hydrochloric acid is added to adjust the pH appropriately, and the precipitated solid is separated by filtration to obtain a free acid dye (y-1 ), Or a compound in which a part of the dye (y-1) is a sodium salt.

  Moreover, after dissolving the obtained sodium salt wet cake or its dry solid in water, an ammonium salt such as ammonium chloride is added, and an acid such as hydrochloric acid is added to adjust its pH to, for example, 1 to 3, followed by precipitation. An ammonium salt of the dye (y-1) can be obtained by separating the obtained solid by filtration.

  Moreover, mineral acid (for example, hydrochloric acid, a sulfuric acid, etc.) can be added to the reaction liquid after completion | finish of reaction, and the solid of dye (y-1) can also be obtained directly. In this case, the wet cake of the dye (y-1) is added to the water and stirred, and, for example, potassium hydroxide; lithium hydroxide; ammonia water; or organic quaternary ammonium hydroxide; Thus, a potassium salt, a lithium salt, an ammonium salt, or a quaternary ammonium salt according to each added compound can be obtained.

  Moreover, in the method illustrated above, by limiting the number of moles of hydroxide or the like to be added with respect to the number of moles of the dye (y-1), for example, a mixed salt of a lithium salt and a sodium salt; Sodium salts, mixed salts of ammonium salts, and the like can also be prepared. The salt of the dye (y-1) can change the physical properties such as solubility or the performance of the ink when blended in the ink depending on the type of the salt. From the viewpoint of solubility of the dye (y-1) in water, the dye (y-1) is preferably added as a salt.

  In the synthesis of the dye (y-1), the reaction liquid after completion of the final step can be directly used for ink production. However, after synthesis, the reaction solution or the like may be dried by a method such as spray drying to isolate the dye (y-1) or a salt thereof, and then added to the ink. In addition, when blended in the ink in this way, the reaction solution or isolate contains a smaller amount of an inorganic salt such as a metal chloride such as sodium chloride; sulfate, such as sodium sulfate. It is preferable. For example, the total content of sodium chloride and sodium sulfate is preferably about 1% by mass or less with respect to the total mass of the dye, and the lower limit is preferably 0% by mass, that is, the detection limit or less of the detection device. Examples of a method for obtaining a reaction solution or an isolate having a low inorganic salt content include, for example, a method of separating a salt by a known reverse osmosis membrane; a water-soluble organic solvent such as acetone or C1-C4 alcohol or a water-containing water-soluble organic solvent And a method of purifying or crystallizing by any of these methods, and desalting treatment can be performed by any of these methods.

The content of the dye (y-1) in the yellow ink can be appropriately selected in consideration of the type of dye, the type of solvent component, and the like. However, in the yellow ink of this embodiment, in the total mass of the yellow ink, ions in which at least one of the five —SO ₃ H groups of the dye is ionized to become —SO ₃ ^— are converted into mass, It is preferable to contain 0.1-10 mass%, Preferably it is 0.5-5 mass%. By setting it as the above range, color development on a recording medium or image density is excellent, and clogging can be made difficult to occur.

The ion in which at least one of the five —SO ₃ H groups existing in the formula (y-1) is ionized to become —SO ₃ ^— has a sufficiently high solubility in water. -1) It is difficult to cause precipitation or the like. Therefore, one of the functions of the dye (y-1) in yellow ink is to reduce clogging of the nozzle and the nib. Further, the dye (y-1) is present in the coating film constituting the image in an acid or salt state when the yellow ink is converted into an image or the like and dried. That is, such an image contains the dye (y-1) or a salt thereof. Since the dye (y-1) or a salt thereof has good moisture resistance and gas resistance, as one of the functions of the dye (y-1) in the yellow ink, the light resistance of the image formed by the yellow ink and The gas resistance can be improved. Further, since the dye (y-1) or a salt thereof has good moisture resistance, as one of the functions of the dye (y-1) in the yellow ink, the moisture resistance of an image formed with the yellow ink is improved. Can be mentioned.

1.1.2. Dye (y-2)
The dye (y-2) is represented by the following formula (y-2). The dye (y-2) has properties such as excellent color developability, moisture resistance and gas resistance.

(In formula (y-2), X ^Y21 , X ^Y22 , Y ^Y21 , and Y ^Y22 each independently represent a hydrogen atom or a cyano group, and Z ^Y21 and Z ^Y22 represent a substituent having an aromatic ring. R ^Y21 and R ^Y22 represent an alkyl group, and M ^Y2 represents a metal atom.)

R ^Y21 and R ^Y22 are preferably a C1-C10 alkyl group which may have a straight chain or a branched chain as an alkyl group, and a C1-C5 alkyl group which may have a straight chain or a branched chain. More preferably.

^Examples of the metal atom representing ^MY2 include alkali metals such as lithium, sodium, and potassium.

^Examples of the substituent having an aromatic ring representing Z ^Y21 and Z ^Y22 include an aryl group, an aryl group substituted with a carboxyl group or a salt thereof, and the like.

  In particular, the compound represented by the formula (y-2) is preferably a compound represented by the following formula (y-21) from the viewpoint of further improving ozone resistance.

(In the formula (y-21), X ^Y21 , X ^Y22 , Y ^Y21 and Y ^Y22 each independently represent a hydrogen atom or a cyano group, and W ^Y21 , W ^Y22 , W ^Y23 , W ^Y24 , W ^Y25 , W ^{Y211, W Y212, W Y213,} W Y214 and ^{W Y215} each independently represent a hydrogen atom, a carboxyl group or a salt ^{thereof, M Y2} represents a metal atom, t-Bu represents a tertiary butyl group.)

  The content of the dye (y-2) contained in the yellow ink can be appropriately selected in consideration of the type of the dye, the type of the solvent component, etc., but is 0.1 to 10 with respect to the total mass of the yellow ink. It is preferable to contain 0.0% by weight. By setting it as said range, while being excellent in the color development property or image density on a recording medium, it can make it difficult to produce clogging of a nozzle.

1.2. Magenta Ink The magenta ink according to the exemplary embodiment includes, as a colorant, a compound represented by the following general formula (m-1) or a salt thereof (hereinafter also simply referred to as “dye (m-1)”). Containing at least one selected from.

1.2.1. Dye (m-1)
The dye (m-1) is represented by the following general formula (m-1). By containing the compound represented by the formula (m-1) or a salt thereof, a magenta ink having excellent moisture resistance and gas resistance and balanced characteristics can be provided.

(In the formula (m-1), A ^M1 represents an alkylene group having 1 or 2 carbon atoms, an alkylene group having 1 or 2 carbon atoms containing a phenylene group, or a group represented by the following formula (m-1-1). X ^M1 represents an amino group, a hydroxy group, a chlorine atom, or a phenoxy group substituted with a sulfo group or a carboxy group.)

(In formula (m-1-1), R ^M1 represents a hydrogen atom or an alkyl group.)
In Formula (m-1), A ^M1 is preferably an alkylene group having 1 or 2 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.

In the above formula (m-1), X ^M1 represents an amino group, a hydroxy group, a chlorine atom, or a phenoxy group substituted with a sulfo group or a carboxy group. Among these, a phenoxy group substituted with a sulfo group or a carboxy group is preferable, and a phenoxy group substituted with a carboxy group is more preferable. A phenoxy group substituted with a carboxy group has a good effect of improving moisture resistance, and a phenoxy group substituted with two carboxy groups has a better moisture resistance and is particularly preferable.

  Specific examples of the phenoxy group substituted with a sulfo group or a carboxy group include 4-sulfophenoxy, 2,4-disulfophenoxy, 4-carboxyphenoxy, and 3,5-dicarboxyphenoxy, more preferably 4 -Carboxyphenoxy and 3,5-dicarboxyphenoxy, more preferably 3,5-dicarboxyphenoxy.

  Examples of the salt of the compound represented by the formula (m-1) include ammonium salts and alkali metal salts.

  The content of the dye (m-1) contained in the magenta ink can be appropriately selected in consideration of the kind of the dye, the kind of the solvent component, etc., but is 0.1% by mass with respect to the total mass of the magenta ink. It is preferably 10 to 10% by weight. By setting it as said range, while being excellent in the color development property or image density on a recording medium, it can make it difficult to produce clogging of a nozzle.

1.2.2. Dye (m-2)
In addition to the dye (m-1), the magenta ink according to the present embodiment further includes a compound represented by the following general formula (m-2) or a salt thereof (hereinafter simply “dye (m-2)”). Or at least one selected from the group consisting of: By using the dye (m-1) and the dye (m-2) in combination, it is possible to provide a magenta ink having excellent color developability and moisture resistance and balanced characteristics.

In formula (m-2), A ^M2 represents a 5-membered heterocyclic group. B ^M21 and B ^M22 each represent -CR ^M21 = and -CR ^M22 =, or either one represents a nitrogen atom and the other represents -CR ^M21 = or -CR ^M22 =.

  Examples of the 5-membered heterocyclic group include a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a benzothiazole ring, a benzoxazole ring, and a benzoisothiazole ring. Furthermore, you may have a substituent. Of the heterocyclic rings, a pyrazole ring is preferable.

In said ^RM21 , a hydrogen atom or an alkyl group is preferable, and a hydrogen atom is more preferable. In the above ^RM22 , an aliphatic group is preferable, and a methyl group, an ethyl group, an optionally branched propyl group, or an optionally branched butyl group is more preferable.

R ^M23 and R ^M24 each independently represent a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. R ^M23 and R ^M24 may further have a substituent.

In the above ^RM23 , an aromatic group is preferable, and specific examples include a benzene ring group or a naphthalene ring group. In the above ^RM24 , a heterocyclic group is preferable, and specific examples include a benzothiazole ring group.

G ^M2 , R ^M21 , and R ^M22 each independently represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. An acyl group, a hydroxy group, an alkoxy group, an aryloxy group, a silyloxy group, an acyloxy group, a carbamoyloxy group, a heterocyclic oxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyl group, an aryl group, or a heterocyclic group. Substituted amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl and Riruchio group, an alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group. R ^M23 and R ^M24 may be further substituted. R ^M21 and R ^M23 , or R ^M23 and R ^M24 may combine to form a 5- to 6-membered ring.

  Among the compounds represented by the formula (m-2), a compound represented by the following formula (m-21) is preferable.

In Formula (m-21), R ^M25 , R ^M26 , R ^M27 , R ^M28 , and R ^M29 represent a hydrogen atom, an alkyl group, a sulfo group, or a salt thereof. In Formula (m-21), when R ^M25 and R ^M29 are both alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may have a substituent. Good. X ^M2 represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and Y ^M2 and Z ^M2 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxy group A carbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group is represented. Each group may further have a substituent. When R ^{M25 to} R ^M29 contain a sulfo group, it is in the form of —SO ₃ M. In that case, M is preferably an alkali metal atom, more preferably at least one of Li and Na.

In the above ^XM2 , an aromatic group, an alicyclic group, and a heterocyclic group are particularly preferable. Specific examples include, for example, a benzene ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, and a pyridine. Ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, benzimidazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, oxane ring, sulfolane ring and thiane ring. Among these, a heterocyclic ring is more preferable.

Preferred specific examples of Y ^M2 and Z ^M2 are the same as the preferred specific examples of R ^M23 and R ^M24 in the dye (m-2).

  Among the compounds represented by the formula (m-21), a compound represented by the following formula (m-22) is particularly preferable because it has excellent color developability and ozone resistance.

Wherein ^{(m-22), R M25} , R M26, R M27, R M28, R M29, R M210, R M211, R M212, R M213, R M214 is a hydrogen atom, an alkyl group, a sulfo group or a salt thereof M ^M2 represents a hydrogen atom or an alkali metal atom. When both R ^M25 and R ^M29 are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may further have a substituent, and R ^M210 and R ^{M29 When} both ^M214 are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may further have a substituent.

  When the dye (m-2) is added to the magenta ink, the content thereof is preferably 0.2 to 2.5% by mass with respect to the total weight of the magenta ink, and 0.3% by mass. It is more preferable that it is% -2.0 mass%. By setting it as the said range, the light resistance and ozone resistance of an image can be improved, and the fall of moisture resistance may be suppressed.

  In the magenta ink, when the dye (m-1) and the dye (m-2) are used in combination, the content ratio of the dye (m-1) and the dye (m-2) is 1: 2 to 2. 15: 1 is preferable, and 5: 1 to 13: 1 is preferable. By containing both dyes in such a ratio, moisture resistance and ozone resistance may be satisfied at a high level in some cases.

  The magenta ink may contain magenta dyes other than those described above within a range that does not significantly impair each characteristic such as light resistance for adjusting the color tone.

1.3. Cyan Ink The cyan ink according to the exemplary embodiment includes, as a colorant, a compound represented by the following general formula (c-1) or a salt thereof (hereinafter also simply referred to as “dye (c-1)”). And at least one selected from the group consisting of a compound represented by the following general formula (c-2) or a salt thereof (hereinafter also simply referred to as “dye (c-2)”): , Containing.

  By including the dye (c-1) and the dye (c-2) in the cyan ink, the two dyes act in a complementary manner, and are excellent in ozone resistance and bronze resistance, and also in moisture resistance. Is obtained.

1.3.1. Dye (c-1)
The dye (c-1) is a porphyrazine compound represented by the following general formula (c-1). That is, in this example, tetrabenzoporphyrazine (usually called phthalocyanine) is replaced with nitrogen-containing heteroaromatic rings in excess of four benzo (benzene) rings and not more than three.

In formula (c-1),
Rings A ^{C1 to} D ^C1 represented by broken lines each independently represent a benzene ring or a 6-membered nitrogen-containing heteroaromatic ring condensed to a porphyrazine ring, and the average number of nitrogen-containing heteroaromatic rings is 0. .00 to 3.00 and the rest are benzene rings,
E ^C1 represents C2-C12 alkylene;
X ^C1 is a substituent such as sulfo group, carboxy group, phosphate group, sulfamoyl group, carbamoyl group, hydroxy group, C1-C6 alkoxy group, amino group, mono C1-C4 alkylamino group, di-C1-C4 alkylamino. Group, mono C6-C10 arylamino group, di-C6-C10 arylamino group, C1-C3 alkylcarbonylamino group, ureido group, C1-C6 alkyl group, nitro group, cyano group, halogen atom, C1-C6 alkylsulfonyl group And a sulfoanilino group, a carboxyanilino group, a phosphonoanilino group, a sulfonaphthylamino group, a carboxynaphthylamino group, which may have one or two or more substituents selected from the group consisting of C1-C6 alkylthio groups Or a phosphononaphthylamino group,
R ^C1 is a hydrogen atom; a sulfo group; a carboxy group; a phosphate group; a sulfamoyl group; a carbamoyl group; a hydroxy group; a C1-C6 alkoxy group; an amino group; a mono C1-C6 alkylamino group; Diarylamino group; C1-C3 alkylcarbonylamino group; ureido group; C1-C6 alkyl group; nitro group; cyano group; halogen atom; C1-C6 alkylsulfonyl group; or alkylthio group;
The group F ^C1 represents a phenyl group; or a 6-membered nitrogen-containing heteroaromatic group;
a represents an integer of 1 to 6,
b is an average value of 0.00 or more and less than 3.90,
c is an average value of 0.10 or more and less than 4.00,
The sum of b and c is an average value of 1.00 or more and less than 4.00.

Wherein (c-1), as the nitrogen-containing heteroaromatic ring in (four rings of ring ^{A C1,} B ^{C1, C} C1 and ^{D C1)} ring ^{A C1} to ^{D C1} is represented by a dashed line, for example, pyridine ring , Nitrogen-containing heteroaromatic rings containing 1 or 2 nitrogen atoms such as pyrazine ring, pyrimidine ring and pyridazine ring. Among these, a pyridine ring or a pyrazine ring is preferable, and a pyridine ring is more preferable. As the number of nitrogen-containing heteroaromatic rings increases, ozone resistance improves, but bronzing tends to occur easily, and the number of nitrogen-containing heteroaromatic rings is adjusted appropriately taking into account ozone resistance and bronzing Then, a balanced ratio may be selected. Although the number of nitrogen-containing heteroaromatic rings depends on the type of heterocycle, it cannot be generally stated, but is usually an average value of more than 0.00 to 3.00 or less, preferably 0.20 to 2.00, More preferably, it is the range of 0.50 or more and 1.75 or less, and still more preferably 0.75 or more and 1.50 or less.

The remaining rings A ^{C1 to} D ^C1 are benzene rings, and the benzene rings in the rings A ^{C1 to} D ^C1 are also usually average values of 1.00 or more and less than 4.00, preferably 2.00 or more and 3. 80 or less, more preferably 2.25 or more and 3.50 or less, and still more preferably 2.50 or more and 3.25 or less. The porphyrazine-based compound of the present invention is a mixture of a plurality of compounds, as is apparent from the fact that the number of nitrogen-containing heteroaromatic rings of rings A ^{C1 to} D ^C1 is represented by an average value.

In the present specification, unless otherwise specified, the number of the nitrogen-containing heteroaromatic rings is rounded off to the second digit by rounding off the third digit after the decimal point. However, for example, when the number of nitrogen-containing heteroaromatic rings is 1.375 and the number of benzene rings is 2.625, when both are rounded off, the former is 1.38 and the latter is 2.63, and the total of both is the ring A ^C1 Or the total of ^DC1 exceeds 4.00.

  In such a case, for the sake of convenience, the third decimal place on the nitrogen-containing heteroaromatic ring side is rounded down, and only the benzene ring side is rounded off, so that the former is described as 1.37 and the latter as 2.63. As for b and c in the formula (c-1), as described below, the third decimal place is rounded off to the second digit as a rule. Truncate the third digit and round off only the c side.

In the formula (c-1), the alkylene in E ^C1, linear, include branched or cyclic alkylene, linear or cyclic are preferred, straight-chain is preferable. The range of carbon number is usually C2-C12, preferably C2-C6, more preferably C2-C4, and still more preferably C2-C3. Preferable specific examples are ethylene, propylene, or butylene, more preferably ethylene or propylene, and particularly preferably ethylene.

In the formula (c-1), X ^C1 represents a sulfoanilino group, a carboxyanilino group, a phosphonoanilino group, a sulfonaphthylamino group, a carboxynaphthylamino group, or a phosphononaphthylamino group. The number of substitutions of sulfo, carboxy and phosphono in these anilino group and naphthylamino group are all one, and sulfoanilino group, carboxyanilino group, phosphonoanilino group or sulfonaphthylamino group is preferable, and sulfoanilino group is particularly preferable. .

Wherein the X ^C1 sulfoanilino group, carboxy anilino group, Hosuhonoanirino group, sulfo naphthyl amino - group, carboxy naphthyl amino group or a phosphono naphthyl amino group, as a substituent, a sulfo group; a carboxy group; a phosphate group; a sulfamoyl group; Carbamoyl group; Hydroxy group; C1-C6 alkoxy group; Amino group; Mono C1-C4 alkylamino group; DiC1-C4 alkylamino group; Monoarylamino group; Diarylamino group; C1-C3 alkylcarbonylamino group; A C1-C6 alkyl group; a nitro group; a cyano group; a halogen atom; a C1-C6 alkylsulfonyl group; and a C1-C6 alkylthio group; further having one or more groups selected from the group consisting of: The group of 20 groups from the sulfo group to the C1-C6 alkylthio group mentioned here is hereinafter simply referred to as “group of 20 substituents” in the present specification. The number of substitutions in X ^C1 of a group selected from the group of 20 substituents is usually 0 to 4, preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1. is there. The substitution position of the group selected from the group of 20 substituents is not particularly limited, but the carbon atom in the anilino group and naphthylamino group, that is, on the benzene ring in the former case, on the naphthalene ring in the latter case. Is preferably substituted.

When X ^C1 is a sulfoanilino group, among the group of 20 substituents, sulfo group, carboxy group, hydroxy group, C1-C6 alkoxy group, amino group, mono C1-C4 alkylamino group, di-C1-C4 alkyl group An amino group, a C1-C3 alkylcarbonylamino group, a C1-C6 alkyl group, a nitro group, a halogen atom, a C1-C6 alkylsulfonyl group, and a C1-C6 alkylthio group are preferable, and a sulfo group is particularly preferable.

When X ^C1 is a carboxyanilino group, a sulfo group, a carboxy group, a hydroxy group, and a sulfamoyl group are preferred among the group of 20 substituents.

When X ^C1 is a phosphonoanilino group, the group selected from the group of 20 substituents is preferably absent.

When X ^C1 is a sulfonaphthylamino group, a sulfo group and a hydroxy group are preferred among the group of 20 substituents.

  When X is a carboxynaphthylamino-group or a phosphononaphthylamino-group, it is preferable that the group selected from the group of 20 substituents is not present.

Specific examples of X ^C1 in the formula (c-1) include 2-sulfoanilino, 3-sulfoanilino, 4-sulfoanilino, 2,4-disulfoanilino, 2,5-disulfoanilino, 3,6-disulfo-1-naphthylamino. 5,7-disulfo-2-naphthylamino, 6,8-disulfo-2-naphthylamino, 3,6,8-trisulfo-1-naphthylamino, 4-sulfoanilino, 2,5-disulfoanilino, or 3 , 6,8-Trisulfo-1-naphthylamino is more preferred, and 2,5-disulfoanilino is more preferred.

In the formula (c-1), R ^C1 represents a hydrogen atom, a sulfo group; a carboxy group; a phosphate group; a sulfamoyl group; a carbamoyl group; a hydroxy group; a C1-C6 alkoxy group; Di-C1-C6 alkylamino group; mono-C6-C10 arylamino group; di-C6-C10 arylamino group; C1-C3 alkylcarbonylamino group; ureido group; C1-C6 alkyl group; nitro group; Represents an atom; a C1-C6 alkylsulfonyl group; or an alkylthio group.

In the formula (c-1), the group F ^C1 represents a phenyl group; or a 6-membered nitrogen-containing heteroaromatic group. Examples of the 6-membered nitrogen-containing heteroaromatic group include a nitrogen-containing heteroaromatic group containing one nitrogen atom. A specific example is pyridyl.

  In the 6-membered nitrogen-containing heteroaromatic ring, the position of bonding with the alkylene represented by “a” is not particularly limited, but it is preferable that the bonding is performed with a carbon atom adjacent to the nitrogen atom. That is, when the group F is pyridyl, the substitution position of the nitrogen atom is taken as the 1st position, and 2-pyridyl, 3-pyridyl, 4-pyridyl, and the like, which are bonded at a carbon atom adjacent to the nitrogen atom, Is preferred.

In the formula (c-1), when the group F ^C1 is a phenyl group, among the R, a hydrogen atom, a sulfo group, a carboxy group, a C1-C6 alkoxy group, a C1-C6 alkyl group, and a halogen atom are preferable, and hydrogen An atom, a sulfo group, a carboxy group, a methoxy group, a methyl group, a fluorine atom and a chlorine atom are more preferred, and a hydrogen atom, a sulfo group and a carboxy group are more preferred.

In the formula (c-1), when the group F ^C1 is a 6-membered nitrogen-containing heteroaromatic group, among the R ^C1 , a hydrogen atom or a halogen atom is preferable, and a hydrogen atom is particularly preferable.

In the formula (c-1), the substitution position of R ^C1 in the group F ^C1 is not particularly limited. When the group F ^C1 is a phenyl group, the bonding position with “(CH ₂ ) a” is the 1st position, and the substitution position of R ^C1 is the 2nd, 3rd, or 4th position, and the 4th position is preferred.

When the group F ^C1 is a 6-membered nitrogen-containing heteroaromatic group, preferably pyridyl, the bonding position of “(CH ₂ ) a” and R is based on the nitrogen atom of the pyridine ring as the 1st position, the former being the 2nd position, The latter is a combination of the 3rd, 4th, 5th, or 6th position, and the combination of the former being the 2nd and the latter being the 4th is preferable.

In the formula (c-1), a represents the number of repetitions of “(CH ₂ )”, that is, the length of alkylene, and is usually an integer of 1-6, preferably 1-4, more preferably 1-3, More preferably, it is an integer of 1-2, particularly preferably 1.

The sum of b, c and b and c in the formula (c-1) is an average value. b is 0.00 or more and less than 3.90, c is 0.10 or more and less than 4.00, and the sum of b and c is an average value of 1.00 or more and less than 4.00. At this time, the nitrogen-containing heteroaromatic ring in the rings A ^{C1 to} D ^C1 has an average value exceeding 0.00 and not more than 3.00, and similarly, the benzene ring is not less than 1.00 and less than 4.00.

Preferably, when the nitrogen-containing heteroaromatic ring in rings A ^{C1 to} D ^C1 is 0.20 or more and 2.00 or less, and the benzene ring is 2.00 or more and 3.80 or less, b is 0.00 or more and 3.40 or less. , C is 0.40 or more and 2.00 or less, and the sum of b and c is 2.00 or more and 3.80 or less.

More preferably, when the nitrogen-containing heteroaromatic ring in the rings A ^{C1 to} D ^C1 is 0.50 to 1.75 and the benzene ring is 2.25 to 3.50, b is 0.35 to 3.05. C is 0.45 or more and 1.90 or less, and the sum of b and c is 2.25 or more and 3.50 or less.

More preferably, when the nitrogen-containing heteroaromatic ring in the rings A ^{C1 to} D ^C1 is 0.75 or more and 1.50 or less and the benzene ring is 2.50 or more and 3.25 or less, b is 0.70 or more and 2.75 or less. And c is 0.50 or more and 1.80 or less, and the sum of b and c is 2.50 or more and 3.25 or less. As cb increases, the ozone resistance tends to improve. It tends to occur, and the ratio of b and c may be adjusted as appropriate while considering ozone resistance and bronze resistance, and a balanced ratio may be selected.

The unsubstituted sulfamoyl group and the substituted sulfamoyl group, each of which represents the number of substitutions represented by b and c, are groups substituted on the benzene ring when the rings A ^{C1 to} D ^C1 are benzene rings. In the case where the rings A ^{C1 to} D ^C1 are 6-membered nitrogen-containing heteroaromatic rings, they are not substituted.

  In this specification, b, c, and the sum of b and c are all rounded off to the second digit after the third decimal day.

In the rings A ^{C1 to} D ^C1 , E ^C1 , X ^C1 , R ^C1 , groups F ^C1 , a, b and c, porphyrazine compounds in which preferable ones are combined are more preferable, and porphy in which more preferable ones are combined. Razine compounds are more preferred. The same applies to preferable ones, combinations of preferable ones and more preferable ones, and the like.

The porphyrazine-based compound of the present invention represented by the formula (c-1) can also form a salt by utilizing sulfo, carboxy, phosphono and the like in the molecule. When forming a salt, the counter cation is an inorganic metal, ammonia (NH ₃₎ or preferably formed each cation and salts of organic bases.

  Inorganic metals include alkali metals and alkaline earth metals. Examples of the alkali metal include lithium, sodium, potassium and the like. Examples of the alkaline earth metal include calcium and magnesium.

  Examples of the organic base include organic amines, for example, C1-C3 alkylamines such as methylamine and ethylamine, mono-, di- or tri-C1-C4 alkanols such as monoethanolamine, diethanolamine and triethanolamine. Examples include amines.

  Of the above-mentioned salts using a counter cation, preferred are alkali metal salts such as sodium, potassium and lithium; monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and the like Salts of mono-, di- or tri-C1-C4 alkanolamine, and ammonium salts, but are not limited thereto.

  Further, the salt of the porphyrazine-based compound of the present invention may change the physical properties such as solubility or the performance of the ink when used as an ink, particularly the performance related to fastness, depending on the type of the salt. . For this reason, it is also preferable to select the type of salt according to the performance of the target ink.

As the porphyrazine-based compound represented by the formula (c-1) or a salt thereof, particularly preferable compounds are compounds having the following combinations (a) to (f).
(A) The nitrogen-containing heteroaromatic rings in rings A ^{C1 to} D ^C1 are each independently a pyridine ring condensed at the 2-position and 3-position, or at the 3-position and 4-position; or at the 2-position and 3-position A fused pyrazine ring is preferred.
(B) E ^C1 is preferably linear C2-C4 alkylene.
(C) X ^C1 is a sulfo group, carboxy group, hydroxy group, C1-C6 alkoxy group, amino group, mono C1-C4 alkylamino group, di-C1-C4 alkylamino group, C1-C3 alkyl as a substituent. A sulfoanilino group which may have 0 to 2 substituents of one or two types selected from the group consisting of a carbonylamino group, a nitro group, a halogen atom, a C1-C6 alkylsulfonyl group and an alkylthio group; A carboxyanilino group optionally having 0 to 2 substituents of one or two types selected from the group consisting of a sulfo group, a carboxy group, a hydroxy group, and a sulfamoyl group; a phosphonoanilino group; or As a substituent, it may have one or two kinds of substituents selected from a sulfo group and a hydroxy group. A good sulfonaphthylamino group is preferred.
(D) R ^C1 is preferably a hydrogen atom; a sulfo group; a carboxy group; a C1-C6 alkoxy group; a C1-C6 alkyl group; or a halogen atom.
(E) The group F ^C1 is preferably a phenyl group; or a pyridyl group in which R ^C1 is a hydrogen atom.
(F) As a, 1 or 2 is preferable.

Specific examples of the rings A ^{C1 to} D ^C1 , E ^C1 , X ^C1 , R ^C1 and the group F ^C1 and the numbers of a, b and c in the formula (c-1) are shown in the following table. The following examples are representative examples for specifically explaining the dye (c-1), and the present invention is not limited to the following examples. In addition, when the nitrogen-containing heteroaromatic ring of the rings A ^{C1 to} D ^C1 is a pyridine ring, there are positional isomers of the nitrogen atom as described later, and it is obtained as a mixture of isomers when synthesizing a porphyrazine compound. It is done. These isomers are difficult to identify, and it is also difficult to identify isomers by analysis. For this reason, it is usually used as a mixture. The dye (c-1) includes such a mixture. In the present specification, when a structural formula is used without distinguishing these isomers, a typical structural formula is described for convenience. In addition, about the number of b and c in a table | surface, in order to avoid complexity, the 2nd digit after a decimal point was rounded off, and the one-digit day was described. In the table, “2,3-pyrido” is a pyridine ring fused to a porphyrazine ring at the 2-position and 3-position, “benzo” is a benzene ring fused to a porphyrazine ring, and “2-pyridyl” Means that the bonding position with “(CH ₂ ) a” is the second position, with the nitrogen atom of the pyridine ring being the first position. As for “4-chloro” and the like in R ^C1 , when the group F is a phenyl group, the bonding position with “(CH ₂ ) a” is the 1st position; when the group F ^C1 is pyridyl, the pyridine ring Represents the substitution position of R ^C1 in the case where the nitrogen atom is the 1-position;

  The dye (c-1) can usually be used without blending other pigments, but may be blended with known cyan pigments as long as the effects of the present invention are not impaired. .

  When blended with a known cyan pigment, the pigment blended is C.I. I. Numbered triphenylmethane dyes and phthalocyanine dyes can be used, but phthalocyanine dyes are preferred.

1.3.2. Dye (c-2)
The dye (c-2) is a phthalocyanine compound represented by the following general formula (c-2).

In the formula (c-2), X ^C21 , X ^C22 , X ^C23 and X ^C24 each independently represent —SO—Z ^{C 2} or —SO ₂ —Z ^C ₂ , and —SO ₂ —Z ^{C 2} is particularly preferable. .

Z ^C2 each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group, and particularly represents an alkyl group, an aryl group, or a heterocyclic group, and each further represents a substituent. You may have. Of these, a substituted alkyl group, a substituted aryl group and a substituted heterocyclic group are preferred, a substituted alkyl group and a substituted aryl group are more preferred, and a substituted alkyl group is most preferred.

The alkyl group represented by Z ^C2 is preferably an alkyl group having 1 to 30 carbon atoms. Cycloalkyl group Z ^C2 represents the number of carbon atoms is preferably a cycloalkyl group having 5 to 30. The alkenyl group represented by Z ^C2 is preferably an alkenyl group having 2 to 30 carbon atoms. Aralkyl group Z ^C2 represents the number of carbon atoms is preferably an aralkyl group having 7 to 30. Aryl groups Z ^C2 represents preferably an aryl group having from 6 to 30 carbon atoms.

As the heterocyclic group represented by Z ^C2 , an aromatic heterocyclic group is preferable, and preferred examples thereof are the same as those described above, and pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, Examples include benzothiazole, isothiazole, benzisothiazole, and thiadiazole. These may have a substituent, and examples of the substituent include a substituent when Z ^C2 , Y ^C21 , Y ^C22 , Y ^C23 and Y ^C24 described later can further have a substituent. The same can be mentioned.

Y ^C21 , Y ^C22 , Y ^C23 , Y ^C24 , Y ^C25 , Y ^C26 , Y ^C27 and Y ^C28 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group. , Heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, Alkoxycarbonylamino group, sulfonamido group, carbamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic ring Thio group, phos Lil group, an acyl group, a carboxyl group or a sulfonic group, and each may further have a substituent. Among them, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, an alkoxycarbonyl group, a carboxyl group, and a sulfone group are preferable, and in particular, a hydrogen atom, A halogen atom, a cyano group, a carboxyl group and a sulfone group are preferred, and a hydrogen atom is most preferred.

When Y ^C21 , Y ^C22 , Y ^C23 , Y ^C24 , Y ^C25 , Y ^C26 , Y ^C27 , Y ^C28 and Z ^C2 are groups that can further have a substituent, the hydroxyl group is not particularly limited. , Alkoxy group, sulfamoyl group, sulfonamido group, acylamino group, carbamoyl group, cyano group and ionic hydrophilic group (for example, carboxyl group, sulfone group, quaternary ammonium group, sulfonylsulfamoyl group and acylsulfamoyl group) ) Are preferred, and among them, a hydroxy group, a sulfamoyl group and an ionic hydrophilic group are particularly preferred.

a _{1 to} a ₄ satisfy 4 ≦ a ₁ + a ₂ + a ₃ + a ₄ ≦ 8, preferably 4 ≦ a ₁ + a ₂ + a ₃ + a ₄ ≦ 6, and each independently represents an integer of 1 or 2. Particularly preferred is the case where a ₁ = a ₂ = a ₃ = a ₄ = 1.

M ^C2 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.

Preferred examples of M ^C2 include metal elements, oxides, and halides in addition to hydrogen atoms. Of these, Cu, Ni, Zn, Al and the like are preferable, and Cu is most preferable.

Also, the phthalocyanine compound represented by the formula (c-2) is, L (via a divalent linking group) Pc (phthalocyanine ring) is a dimer ^{(e.g., Pc-M C2 -L-M} C2 -Pc ) Or a trimer, and a plurality of M ^C2 may be the same or different from each other.

The divalent linking group represented by L includes an oxy group (—O—), a thio group (—S—), a carbonyl group (—CO—), a sulfonyl group (—SO ₂ —), an imino group (—NH -), a methylene group _(-CH 2 -), and a group formed by combining these.

At least one of X ^C21 , X ^C22 , X ^C23 , X ^C24 , Y ^C21 , Y ^C22 , Y ^C23 , Y ^C24 , Y ^C25 , Y ^C26 , Y ^C27 and Y ^C28 is an ionic hydrophilic group or an ionic hydrophilic group Group having a functional group as a substituent.

The ionic hydrophilic group as a substituent, a sulfonic group _(-SO ³ - ^X +), a carboxyl group _(-CO ² - ^X +), and quaternary ammonium group ^(-N + RR'R "X ^-) , acylsulfamoyl groups ^{_{(-SO 2 N + X-COR}} ), a sulfonylcarbamoyl group _{^{(-CON + X-SO 2 R}} ), etc. sulfonylsulfamoyl groups ^{_{(-SO 2 N + X-SO}} 2 R) Preferred are a sulfone group, a carboxyl group, and a quaternary ammonium group, and particularly preferred is a sulfone group, and the sulfone group, carboxyl group, acylsulfamoyl group, sulfonylcarbamoyl group, and sulfonylsulfamoyl group are in a salt state. Examples of counter ions that form salts include alkali metal ions (eg, sodium ions, potassium ions, lithium ions). ), Ammonium ions, organic cations (eg, tetramethylguanidinium ions), organic and / or inorganic anions (eg, halogen ions, methanesulfonic acid ions, benzenesulfonic acid ions). X represents a hydrogen atom or a counter ion, and R, R ′, and R ″ each represents a substituent.

  Since the dye (c-2) has at least one ionic hydrophilic group or a group having an ionic hydrophilic group as a substituent in one molecule, the solubility or dispersibility in an aqueous medium is good. It becomes. From such a viewpoint, the dye (c-2) preferably has at least two ionic hydrophilic groups in one molecule, and at least one of the plurality of ionic hydrophilic groups is a sulfone group. Among them, those having at least two sulfone groups in one molecule are most preferable.

The molecular weight of the dye (c-2) is preferably in the range of 750 to 3000, more preferably in the range of 995 to 2500, and particularly preferably in the range of 995 to 2000, of 995 to 1800. The range is most preferable. However, in the formula (c-2), L (via a divalent linking group) Pc (phthalocyanine ring) is a dimer ^{(e.g., Pc-M C2 -L-M} C2 -Pc) or trimer In the case of formation, the preferred molecular weight, for example the particularly preferred molecular weight, is twice (in the case of a dimer) or three times (in the case of a trimer) the particularly preferred molecular weight (range 995 to 1800) described above. . Here, the preferable molecular weight of the dimer or trimer is a value including the linking group L.

Particularly preferred compounds as the phthalocyanine compound represented by the above formula (c-2) are compounds having the following combinations (a) to (f).
(A) With respect to X ^{C21 to} X ^C24 , —SO ₂ —Z ^{C 2} is preferable independently.
(B) With respect to ^ZC2 , each independently preferably a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group, and most preferably a substituted alkyl group.
(C) With respect to Y ^{C21 to} Y ^C28 , a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, and a sulfone group are preferable, and a hydrogen atom is most preferable.
(D) Each of a _{1 to} a ₄ is preferably independently 1 or 2, and particularly preferably a ₁ = a ₂ = a ₃ = a ₄ = 1.
(E) MC ² is preferably Cu, Ni, Zn, or Al, and most preferably Cu.
(F) The molecular weight of the dye (c-2) is preferably in the range of 750 to 2500, more preferably in the range of 995 to 2500, and of these, the range of 995 to 2000 is particularly preferable. Most preferably, it is in the range of ~ 1800.

  As for the preferable combination of substituents of the compound represented by the formula (c-2), a compound in which at least one of various substituents is the above preferable group is preferable, and more various substituents are the above preferable groups. Are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

  Among the compounds represented by the formula (c-2) used in the present invention, a compound represented by the following formula (c-21) (hereinafter also referred to as “dye (c-21)”) is particularly preferable.

In formula (c-21), M ^C2 and Z ^{C21 to} Z ^C24 have the same meanings as M ^C2 and Z ^C2 in formula (c-2), and preferred examples are also the same. However, at least one of Z ^{C21 to} Z ^C24 has an ionic hydrophilic group as a substituent.

Among the above compounds, a compound in which M ^C2 in the formula (c-21) is Cu, and Z ^{C21 to} Z ^C24 having an ionic hydrophilic group as a substituent is a sulfoalkyl group, more preferably a sulfone group. Is a salt, and the compound in which the counter cation forming the salt is a lithium cation is preferred.

  The dye (c-21) includes, for example, a phthalonitrile compound represented by the following formula (c-2-1) and / or a diiminoisoindoline derivative represented by the following formula (c-2-2) and M- ( Y) It is synthesized by reacting a metal derivative represented by d. Specific examples of the metal derivatives include copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, iron chloride, zinc chloride, zinc bromide, iodine Zinc chloride, zinc acetate, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, acetylacetone manganese, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride, tin chloride, etc. Is mentioned.

The dye (c-21) thus obtained is usually R ^C21 (SO ₂ —Z ^C11 ), R ^C22 (SO ₂ —Z ^C22 ), R ^C23 (SO ₂ —Z ^C23 ), R ^C24 (SO ₂ ). -Z ^C24 ) is a mixture of compounds represented by the following formulas (c-21-1) to (c-21-4), which are isomers having different introduction positions.

  Furthermore, when preparing a dye using two or more types of formula (c-2-1) and / or formula (c-2-2) having different substituents, the dye is represented by the formula (c-21). These compounds are dye mixtures with different types and positions of substituents.

  Examples of the colorant used in the cyan ink include compounds having the corresponding structures described in JP-A Nos. 2002-249677, 2003-213167, 2003-213168, and JP-A-2004-2670 (dyes). Particularly preferred are those listed in the table below. The compounds described in the following table can be synthesized by the method described in the above publication. Of course, the starting compound, the dye intermediate and the synthesis method are not limited to these.

  The content of the dye (c-2) in the cyan ink is determined by the type of the dye (c-2), the type of the solvent component, and the like, but is preferably 0.1 to 10% by mass with respect to the total weight of the cyan ink. More preferably, it is the range of 0.5-5 mass%. By setting the content to 0.1% by mass or more, it is possible to ensure color developability or image density on the recording medium. Characteristics can be easily secured.

1.4. Black ink The ink set according to the present embodiment may further include at least one of a first black ink and a second black ink. Hereinafter, components included in each black ink will be described.

1.4.1. First Black Ink The first black ink contains a pigment as a colorant. The pigment of the first black ink is a self-dispersing pigment. Self-dispersing pigments are pigments that can be dispersed and / or dissolved in an aqueous medium without a dispersant. Here, “dispersed and / or dissolved in an aqueous medium without a dispersing agent” means that the surface is stably present in the aqueous medium due to the hydrophilic group on the surface without using a dispersing agent for dispersing the pigment. The state that is.

  When a self-dispersing pigment is used, the amount of dispersant used to disperse the pigment can be reduced, so that foaming of the ink due to the dispersant can be reduced, and an ink with good ejection stability can be easily prepared. In addition, since a significant increase in viscosity due to the dispersant can be suppressed, it is possible to contain more pigment, and the printing density can be sufficiently increased.

First black ink is a self-dispersion pigment having a hydrophilic group on the pigment surface, the hydrophilic _{group, -OM, -COOM, -CO -,} - SO 3 M, -SO 2 M, -SO 2 NH ₂ , -RSO ₂ M, -PO ₃ HM, -PO ₃ M ₂ , -SO ₂ NHCOR, -NH ₃ , and -NR ₃ (wherein M represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium). And R is preferably one or more hydrophilic groups selected from the group consisting of an alkyl group having 1 to 12 carbon atoms or a naphthyl group which may have a substituent.

  Moreover, as a pigment used as the raw material of the self-dispersing pigment of the first black ink, for example, carbon black produced by a known method such as a contact method, a furnace method, or a thermal method can be used. Specific examples of preferred carbon black in the present invention include No. 2300, 900, MCF88, no. 20B, no. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, No2200B (Mitsubishi Chemical Corporation), Color Black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Pretex 35, U, V, 140U, Special Black 6 5, 4A, 4, 250 (above Degussa), Conductex SC, Raven 1255, 5750, 5250, 5000, 3500, 1255, 700 (above Columbia Carbon), Regal 400R, 330R, 660R, Mogul L , Monarch 700, 800, 880, 900, 1000, 1100, 1300, 1400, Elftex 12 (manufactured by Cabot Corporation), and the like. These carbon blacks may be used singly or as a mixture of two or more.

  The self-dispersing pigment contained in the first black ink is produced, for example, by bonding (grafting) the hydrophilic group to the surface of the pigment by subjecting the pigment to physical treatment or chemical treatment. Examples of the physical treatment include vacuum plasma treatment. Examples of the chemical treatment include a wet oxidation method that oxidizes with an oxidizing agent in water, and examples of the oxidizing agent include ozone, hypohalite, persulfate, and the like.

  In the present invention, a black self-dispersed pigment surface-treated by oxidation treatment with hypohalous acid and / or hypohalite, oxidation treatment with ozone, or oxidation treatment with persulfuric acid and / or persulfate, This is preferable in terms of high color development. Commercially available products can also be used as the self-dispersing pigment for the first black ink, and preferred examples include Microjet CW1 (manufactured by Orient Chemical Industry Co., Ltd.).

  The self-dispersing pigment in the first black ink is preferably contained in an amount of 6% by weight or more. When the pigment concentration in the black ink composition is 6% by weight or more, the recorded matter is highly colored.

  The self-dispersing pigment preferably has an average particle size in the range of 50 to 250 nm from the viewpoints of ink storage stability and prevention of nozzle clogging.

1.4.2. Second Black Ink The second black ink is selected from the group consisting of a compound represented by the following general formula (b-1) or a salt thereof (hereinafter also simply referred to as “dye (b-1)”) as a colorant. At least one selected from at least one selected from the group consisting of a compound represented by the following general formula (b-2) or a salt thereof (hereinafter also simply referred to as “dye (b-2)”); Containing.

1.4.2.1. Dye (b-1)
The dye (b-1) is represented by the following general formula (b-1). The dye (b-1) has a property that it is difficult to be decomposed even when it is irradiated with light or exposed to gas (especially ozone) in the atmosphere. Therefore, an image formed using the second black ink is excellent in light resistance and gas resistance, and hardly undergoes discoloration or fading due to the influence of light or air.

  Further, the dye (b-1) has a property of being excellent in moisture resistance. For this reason, it is difficult for image bleeding due to the influence of moisture or the like.

  The content of the dye (b-1) is preferably 1% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 5% by mass or less with respect to the total mass of the second black ink. . When the content of the dye (b-1) is within the above range, the color density of the recorded image can be improved, and the light resistance and gas resistance can be improved.

In the above formula (b-1), n is 0 or 1, and R ^B11 is substituted with a carboxy group; a C1-C8 alkoxycarbonyl group; a C1-C4 alkyl group; a C1-C8 alkoxycarbonyl group or a carboxy group. A C1-C4 alkyl group; a phenyl group; or a phenyl group substituted with a hydroxy group, a sulfo group or a carboxy group.

R ^B12 , R ^B13 and R ^B14 each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; Group, C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group, C1-C4 alkoxy group substituted by sulfo group or carboxy group; mono- or di-C1-C4 alkylamino substituted by hydroxy group, sulfo group or carboxy group C1-C4 alkylcarbonylamino group; C1-C4 alkylcarbonylamino group substituted with a hydroxy group or a carboxy group; N′-C1-C4 alkylureido group substituted with a hydroxy group, a sulfo group or a carboxy group; benzene Ring is chlorine atom, C1 A phenylamino group substituted by a C4 alkyl group, a nitro group, a sulfo group or a carboxy group; a benzoylamino group in which the benzene ring is substituted by a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group; or benzene And a phenylsulfonylamino group in which the ring is substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group.

The group A ^B1 is a substituted heterocyclic group represented by the following general formula (b-1-1).

In the general formula (b-1-1), R ^B16 , R ^B17 and R ^B18 each independently represent a hydrogen atom; a chlorine atom; a carboxy group; a sulfo group; a nitro group; a hydroxy group; a carbamoyl group; C1-C4 alkyl group; C1-C4 alkoxy group; C1-C4 alkoxy group substituted with a hydroxy group, C1-C4 alkoxy group, sulfo group or carboxy group; C1-C4 alkylsulfonyl group; Hydroxy group, sulfo group or carboxy group A C1-C4 alkylsulfonyl group substituted with a group; or a phenylsulfonyl group in which the benzene ring is substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group, respectively.

The group B ^B1 is a phenyl group, a substituted phenyl group, a naphthyl group, or a substituted naphthyl group. In the case where the group B ^B1 is a substituted phenyl group, a hydroxy group; a sulfo group; a carboxy group; a C1-C4 alkyl group; a C1-C4 alkoxy group; a C1-C4 alkylsulfonyl group; a nitro group; an amino group; A substituent selected from the group consisting of: a C1-C4 alkylamino group; an acetylamino group; and a benzoylamino group in which the benzene ring is substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group; Have. On the other hand, when the group B ^B1 is a substituted naphthyl group, from the group consisting of a hydroxy group; a sulfo group; a C1-C4 alkoxy group; and a phenylsulfonyloxy group in which the benzene ring is substituted with a methyl group, a nitro group, or a chlorine atom; With selected substituents.

  The dye (b-1) is a compound having a tautomer. Examples of the tautomers include compounds such as the following general formulas (b-1-2) to (b-1-4), and these tautomers are also the dyes (b-1) according to this embodiment. Can be used as

N, R ^B11 , R ^B12 , R ^B13 , R ^B14 , group A ^B1 and group B ^B1 in the above general formulas (b-1-2) to (b-1-4) are those in formula (b-1). Means the same.

Among them, R ^B11 in formula (b-1) is preferably a carboxy group; a C1-C4 alkoxycarbonyl group; an unsubstituted C1-C4 alkyl group; a carboxy group-substituted C1-C4 alkyl group; or an unsubstituted phenyl group. Specific examples of preferable R ^B11 in formula (b-1) include methyl, ethyl, tert-butyl, carboxymethyl, 3-carboxypropyl, carboxy, and phenyl, and more preferably methyl, carboxymethyl, carboxy, and phenyl. More preferably methyl or carboxy.

R ^{B12 to} R ^B14 in formula (b-1) are each a hydrogen atom; a sulfo group; a carboxy group; a C1-C4 alkyl group; a C1-C4 alkoxy group; or a sulfo group-substituted N′-C1-C4. Alkoxy groups are preferred. Specific examples of preferable R ^{B12 to} R ^B14 in the general formula (b-1) are a hydrogen atom, sulfo, methyl, methoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, and more preferably hydrogen. Atomic, sulfo, methyl, methoxy, 3-sulfopropoxy.

In a preferable combination of R ^{B12 to} R ^B14 in the general formula (b-1), R ^B12 is 3-sulfopropoxy or 4-sulfobutoxy, R ^B13 is a hydrogen atom, and R ^B14 is methyl.

R ^{B16 to} R ^B18 in the general formula (b-1-1) are each a hydrogen atom; a chlorine atom; a carboxy group; a sulfo group; a nitro group; a C1-C4 alkyl group; a C1-C4 alkoxy group; A C4 alkylsulfonyl group is preferred. Specific examples of preferable R ^{B16 to} R ^B18 in the general formula (b-1-1) are a hydrogen atom, a chlorine atom, carboxy, sulfo, nitro, methyl, methoxy, and methylsulfonyl, and more preferably a hydrogen atom, sulfo , Methoxy. In addition, at least one of R ^{B16 to} R ^B18 is preferably a hydrogen atom, and at least one is preferably a substituent other than a hydrogen atom.

A preferable combination of R ^B16 , R ^B17 and R ^{B18 in} the general formula (b-1-1) is a hydrogen atom, methoxy and sulfo, or one is sulfo and the other two are hydrogen atoms. When one is sulfo and the other two are hydrogen atoms, the substitution position of sulfo is more preferably the 6-position of the benzothiazole ring.

In the general formula (b-1), the group B ^B1 is a phenyl group or a substituted phenyl group, and when the group B ^B1 is a substituted phenyl group, a hydroxy group; a sulfo group; a carboxy group; a C1-C4 alkyl group; C1-C4 alkoxy group; amino group; mono or di C1-C4 alkylamino group; acetylamino group; benzoylamino group in which the benzene ring is substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group Having a substituent selected from the group consisting of:

In the case where the group B ^B1 in the general formula (b-1) is a phenyl group having a substituent, and the substituent is a C1-C4 alkoxy group, the alkoxy group includes preferable ones. It may be the same as when R ^{B12 to} R ^{B14 in} 1) are an unsubstituted C1-C4 alkoxy group.

When the group B ^B1 in the general formula (b-1) is a mono- or di-C1-C4 alkylamino group-substituted phenyl group, the mono- or di-C1-C4 alkylamino group, including preferred ones, is represented by the general formula (b- This may be the same as in the case where R ^{B12 to} R ^{B14 in} 1) are an unsubstituted mono or di C1-C4 alkylamino group.

  In general formula (b-1), n is preferably 1.

Among the above, the group B ^B1 in the general formula (b-1) is preferably a substituted phenyl group, and the substituent is a hydroxy group; a sulfo group; a carboxy group; a C1-C4 alkyl group; a C1-C4 alkoxy group. Is preferred. Specific examples of preferred substituents when the group B ^B1 in the general formula (b-1) is a substituted phenyl group are hydroxy, sulfo, carboxy, methyl, methoxy, and more preferably sulfo, carboxy.

Specific examples of the preferable group B ^B1 in the general formula (b-1) include 4-sulfophenyl, 2,4-disulfophenyl, 4-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methylphenyl, 5- Sulfo-3-carboxy-2-hydroxyphenyl and 4-methoxyphenyl, more preferably 4-sulfophenyl, 4-carboxyphenyl, and 3,5-dicarboxyphenyl.

The compound which combined the preferable thing described about the substituent of general formula (b-1) and (b-1-1)-(b-1-4) is more preferable, The compound which combined more preferable things is More preferred. The same applies to the case where more preferable ones are combined. As described above, n, R ^{B11 to} R ^B14 , group A ^B1 and group B ^B1 in general formulas (b-1-2) to (b-1-4) are the same as those in general formula (b-1). Shows the same meaning as.

  The salt of the compound represented by the general formula (b-1) is an inorganic or organic cation salt. Specific examples of the inorganic salt include alkali metal salts, alkaline earth metal salts, and ammonium salts. Among these, preferable inorganic salts are lithium, sodium, potassium salts and ammonium salts.

  Moreover, a mixture may be sufficient as the free acid of the dye (b-1) which concerns on this embodiment, its tautomer, and those various salts. For example, a mixture of a sodium salt of dye (b-1) and an ammonium salt of dye (b-1), a mixture of a free acid of dye (b-1) and a sodium salt of dye (b-1), Any combination of lithium salt of dye, sodium salt of dye (b-1) and ammonium salt of dye (b-1) may be used. Depending on the type of salt, the physical properties such as solubility may differ, so it is possible to select the type of salt as necessary or change the ratio when multiple salts are included. A mixture having physical properties suitable for the above can be obtained.

  Although it does not specifically limit as a suitable specific example of dye (b-1), The compound etc. which are represented with the structural formula shown to the following table | surface are mentioned. In each table, functional groups such as sulfo groups and carboxy groups are described in the form of free acids for convenience.

  The dye (b-1) can be synthesized, for example, by the following method. In addition, the structural formula of the compound in each process shall be represented in the form of a free acid for convenience.

  First, the compound represented by the following general formula (b-1-5) is diazotized by a conventional method, and this is coupled with a compound represented by the following general formula (b-1-6) by a conventional method. A compound represented by the general formula (b-1-7) is obtained. Next, after diazotizing the obtained compound of the general formula (b-1-7) by a conventional method, this and a compound represented by the following general formula (b-1-8) are coupled by a conventional method. To obtain a compound represented by the following general formula (b-1-9). And after diazotizing the compound of the obtained general formula (b-1-9) by a conventional method, this and the compound represented by the following general formula (b-1-10) are coupled by a conventional method. By this, the dye (b-1) which concerns on this embodiment represented by general formula (b-1) can be obtained. In addition, the compound represented by general formula (b-1-10) can purchase a commercial item as a product, or is compoundable by a well-known method.

In general formula (b-1-5), group A ^B1 represents the same meaning as in formula (b-1). In general formula (b-1-6), R ^B12 , R ^B13 and R ^B14 represent the same meaning as in formula (b-1). In general formula (b-1-7), groups A ^B1 , R ^B12 , R ^B13 and R ^B14 represent the same meaning as in formula (b-1). In general formula (b-1-8), n represents the same meaning as in formula (b-1). In general formula (b-1-9), R ^B12 , R ^B13 and R ^B14 represent the same meaning as in formula (b-1). In general formula (b-1-10), R ^B11 and group B ^B1 represent the same meaning as in formula (b-1).

1.4.2.2. Dye (b-2)
The dye (b-2) is represented by the following formula (b-2). The dye (b-2) can be used as a dye for color correction of the dye (b-1). Therefore, by adjusting the content of the dye (b-1) and the dye (b-2) in the second black ink and the content ratio of these dyes, the image formed using the second black ink The hue can be easily brought close to an achromatic color. That is, the hue of the image recorded using the second black ink can be made to exhibit excellent black color by visual observation due to the complementary action of the dye (b-1) and the dye (b-2). In this specification, excellent black means that the a ^* value of the image is in the range of −3 to 3, and the b ^* value is −3 to 3. The a ^* value and the b ^* value are defined by the CIE (International Commission on Illumination) as an L ^* a ^* b ^* color system.

  In addition, the dye (b-2) is contained in the ink together with the dye (b-1), whereby an image having excellent color developability can be obtained. In particular, even when an image is recorded with a high duty value using the second black ink containing the dye (b-1) and the dye (b-2), the bronze phenomenon hardly occurs. The bronze phenomenon is a phenomenon that is likely to occur when an image is recorded with a high duty value, and the color developability and hue are impaired by showing a hue different from the original hue or showing a metallic luster. It is a phenomenon.

The “duty value” is “duty (%) = actual ejection dot number / (vertical resolution × horizontal resolution) × 100 (where“ actual ejection dot number ”is the actual ejection dot number per unit area). , “Vertical resolution” and “Horizontal resolution are resolutions per unit area.”) ”.

  In the second black ink, the ratio (MB / MA) of the content [MA (mass%)] of the dye (b-1) and the content [MB (mass%)] of the dye (b-2) is 0.2 or more and 1 or less, and preferably 0.2 or more and 0.7 or less. When the content ratio of the dye (b-1) and the dye (b-2) is within the above range, an image exhibiting a good black color (close to an achromatic color) can be obtained or recorded It is possible to improve the color density and improve light resistance and gas resistance.

In the general formula (b-2), R ^B21 , R ^B22 , R ^B23 , R ^B24 , R ^B25 , R ^B26 , R ^B27 and R ^B28 are each independently a hydrogen atom; a halogen atom; a sulfo group; a carboxy group A sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a C1-C4 alkoxy group; a substituent selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group; A C1-C4 alkoxy group substituted with at least one group selected from: a C1-C4 alkylcarbonylamino group; a C1-C4 alkylcarbonylamino group substituted with a carboxy group; a ureido group; a mono C1-C4 alkylureido group; Di-C1-C4 alkylureido group; A mono C1-C4 alkylureido group substituted with at least one group selected from the group consisting of a fo group and a carboxy group; the substituent is selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group A di-C1-C4 alkylureido group substituted with at least one group; a benzoylamino group; and a benzene ring selected from the group consisting of a halogen atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group A benzoylamino group substituted with at least one group; a benzenesulfonylamino group; or at least a benzene ring selected from the group consisting of a halogen atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group A phenylsulfonylamino group substituted with one type of group;

X ^B2 represents a divalent crosslinking group.

Among the above, as R ^B21 to R ^B28 , a hydrogen atom; a halogen atom; a C1-C4 alkyl group; a C1-C4 alkoxy group; a Cl-C4 alkoxy group substituted with a sulfo group or a carboxy group; An amino group; Among these, a hydrogen atom, a chlorine atom, methyl, ethyl, t-butyl, 2-carboxyethoxy, 3-carboxypropoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy; more preferred are a hydrogen atom, Methyl and 3-sulfopropoxy are particularly preferred.

In the general formula (b-2), R ^B21 to R ^B28 are preferably a C1-C4 alkoxy group in which at least one is substituted with a sulfo group. R ^B21 to R ^B24 are each independently a C1-C4 alkoxy group substituted with a hydrogen atom, a C1-C4 alkyl group, or a sulfo group, and at least one of R ^B21 to R ^B24 is a sulfo group More preferably, it is a substituted C1-C4 alkoxy group, and R ^B25 to R ^B28 are each independently a hydrogen atom or a C1-C4 alkyl group. More preferably, at least one of R ^B21 and R ^B22 is a sulfopropoxy group, at least one of R ^B23 and R ^B24 is a sulfopropoxy group, and R ^B25 to R ^B28 are C1-C4 alkyl groups.

The substitution position of the R ^B21 R ^B28 is not particularly limited, in each of the benzene rings to which they are substituted, position 1 the substitution position of the nitrogen atom attached to the triazine ring, a 4-position to the substitution position of the azo group, R ^B21 To R ^B24 are preferably substituted at the 2-position, and R ^B25 to R ^B28 are preferably substituted at the 5-position.

In the general formula (b-2), as the crosslinking group represented by X ^B2, to the extent that the compound represented by general formula (b-2) exhibits a solubility in water, in particular as long as the divalent Not limited. Here, the solubility of the compound represented by the general formula (b-2) in water is usually 5 g or more, preferably 10 g of the compound represented by the general formula (b-2) with respect to 1 liter of water. As mentioned above, it is good to melt | dissolve, respectively. Specific examples thereof include a divalent atom (preferably a divalent heteroatom) such as a nitrogen atom, an oxygen atom or a sulfur atom; an alkylenediamino group, an alkylenedioxy group or an alkylenedithio group each of C1-C8; N , N′-hydrazinediyl group; an aminoalkoxyalkylamino group in which two alkylamino groups are substituted on an oxygen atom; and the end of an alkylene oxide chain containing one or more ether bonds such as an aminoalkoxyalkoxyalkylamino group In which one amino group and one alkylamino group are substituted; The divalent bridging group representing ^XB2 is a group selected from the group consisting of a hydroxy group, a carboxy group and an alkoxy group as a carbon atom substituent; and, as a nitrogen atom substituent, an alkyl moiety is a hydroxy group Or an alkyl group which may be substituted with a carboxy group;

Among the ^above, a divalent piperazin-1,4-diyl group as a cross-linking group represented by ^{X B2;} group consisting of piperazine-1,4-diyl group substituted by C1-C4 alkyl group or C1-C4 alkoxy group Is preferably selected from the group consisting of piperazine-1,4-diyl groups, and more preferably.

  In the general formula (b-2), the substitution positions of the four sulfo groups whose substitution positions are not specified are not particularly limited. The sulfo group substituted on the benzene ring having one azo bond may be substituted at the 2, 3 or 4 position, preferably at the 4 position, with the substitution position of the azo bond as the 1 position.

  The second dye represented by the general formula (b-2) is preferably a compound represented by the following general formula (b-21), and is a compound represented by the following general formula (b-22). It is more preferable.

In the general formula (b-21), R ^{B21 to} R ^B28 and X ^B2 represent the same meaning as in the formula (b-2).

In the general formula (b-22), R ^{B21 to} R ^B28 and X ^B2 represent the same meaning as in the formula (b-2).

Substitution positions of R ^{B21 to} R ^B28 in general formulas (b-2), (b-21) and (b-22), R ^{B21 to} R ^B28 in general formula (b-2), and general formula (b-2) ) And a substitution position of sulfo in which the substitution position in general formula (b-21) is not specified, a compound in which preferable ones are combined is more preferable, and a combination of more preferable ones is more preferable. The same applies to preferable combinations, preferable combinations and more preferable combinations.

  The salt of the compound represented by the general formula (b-2) can be an inorganic or organic cation salt. Inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. Among these, preferred inorganic salts are alkali metal salts such as lithium, sodium and potassium, and ammonium salts.

  Moreover, a mixture may be sufficient as the free acid of dye (b-2) which concerns on this embodiment, and those various salts. For example, a mixture of a sodium salt of dye (b-2) and an ammonium salt of dye (b-2), a mixture of a free acid of dye (b-2) and a sodium salt of dye (b-2), dye ( Any combination of a lithium salt of b-2), a sodium salt of dye (b-2) and an ammonium salt of dye (b-2) may be used. 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 change the ratio when multiple salts are included. A mixture having excellent physical properties can be obtained.

  Although it does not specifically limit as a suitable specific example of dye (b-2), The compound etc. which are represented with the structural formula shown to the following table | surface are mentioned. In each table, functional groups such as a sulfo group and a carboxy group are described in the form of a free acid for convenience.

  Among the compounds shown in the above table, the second black ink is compound No. A compound of the following formula (b-23) represented by 1 or a salt thereof can be preferably used.

1.4.2.3. Other Coloring Agent The second black ink may further contain a coloring agent other than the dye (b-1) and the dye (b-2). Although it does not specifically limit as coloring materials other than dye (b-1) and dye (b-2), For example, the compound (henceforth "dye (b-3)" represented by the following general formula (b-3) Also called).

  The dye (b-3) can further easily adjust the hue of the second black ink. Specifically, when the second black ink contains the dye (b-3), the complement of the dye (b-1), the dye (b-2) and the dye (b-3) contained in the ink. This makes it easier to bring the hue of the formed image closer to an achromatic color.

  When the second black ink contains the dye (b-3), the content [MA (mass%)] of the dye (b-1) and the content [MC (mass%) of the dye (b-3) ] (MC / MA) is preferably 0.5 or more and 1.5 or less, and more preferably 0.7 or more and 1.3 or less. When the content ratio of the dye (b-1) and the dye (b-3) is within the above range, an image exhibiting a good black color (close to an achromatic color) can be obtained more easily, The color reproducibility of the recorded image can be improved and the light resistance can be improved.

In the general formula (b-3), R ^B31 represents a halogen atom; a hydrogen atom; SO ₃ M; or COOM. R ^B32 and R ^B33 each independently represent a hydrogen atom; SO ₃ M; or COOM. ^{Further, M B3} each independently represents at least one of Li and Na. However, in General Formula (b-3), R ^B32 and R ^B33 are not all hydrogen atoms.

  Examples of the compound represented by the general formula (b-3) include a compound represented by the following general formula (b-31), a compound represented by the following general formula (b-32), and the following general formula ( and a compound represented by b-33). These compounds represented by the general formulas (b-31) to (b-33) may be used alone or in combination of two or more. The compound represented by (b-31) is preferably used alone.

In formula (b-31), M ^B3 each independently represents at least one of Li and Na.

In formula (b-32), M ^B3 independently represents at least one of Li and Na.

In formula (b-33), M ^B3 independently represents at least one of Li and Na.

1.5. Other components contained in each ink Each ink described above may contain other components other than the colorant. Hereinafter, components that can be added to each ink will be described.

1.5.1. Water Each ink according to this embodiment may contain water. The water is preferably water from which ionic impurities such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water or ultrapure water are removed as much as possible.

1.5.2. Resin Each ink according to the present embodiment may contain a resin. As the ink dries, the resin fuses the resin components and the resin component and the coloring component together to fix the colorant to the recording medium, thereby improving the fixability of the image portion of the recorded matter. Therefore, in each ink according to the present embodiment, it is preferable that the resin is contained in the ink containing the pigment as the colorant.

  These resins are preferably one or more selected from the group consisting of acrylic resins, methacrylic resins, styrene resins, urethane resins, acrylamide resins, and epoxy resins. These resins may be used as homopolymers or as copolymers.

  In the present invention, a resin having a single particle structure can be used. On the other hand, in the present invention, it is also possible to use a resin having a core / shell structure including a core portion and a shell portion surrounding the core portion. In the present invention, the “core / shell structure” means “a form in which two or more polymers having different compositions are present in phase separation in the particles”. Therefore, the shell portion may not only cover the core portion completely, but may cover a portion of the core portion. Further, a part of the shell polymer may form a domain or the like in the core particle. Further, it may have a multilayer structure of three or more layers including one or more layers having different compositions between the core portion and the shell portion.

  The resin used in the present invention can be obtained by known emulsion polymerization. That is, it can be obtained by emulsion polymerization of an unsaturated vinyl monomer (unsaturated vinyl monomer) in water in the presence of a polymerization catalyst and an emulsifier.

  As unsaturated vinyl monomers, acrylic acid ester monomers, methacrylic acid ester monomers, aromatic vinyl monomers, vinyl ester monomers, vinyl, which are generally used in emulsion polymerization Cyanide monomers, halogenated monomers, olefin monomers, diene monomers and the like can be mentioned.

  Further, specific examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate. Acrylic esters such as octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, glycidyl acrylate; methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl Methacrylate, 2-ethyl Methacrylic esters such as hexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate; and vinyl esters such as vinyl acetate; vinyl such as acrylonitrile, methacrylonitrile Cyanogen compounds; halogenated monomers such as vinylidene chloride and vinyl chloride; aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole and vinylnaphthalene Olefins such as ethylene and propylene, dienes such as butadiene and chloroprene, vinyl ether, vinyl ketone, vinyl pyrrolidone Vinyl monomers such as; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid; acrylamides such as acrylamide and N, N′-dimethylacrylamide; 2-hydroxyethyl acrylate, 2 -Hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and hydroxyl group-containing monomers such as 2-hydroxypropyl methacrylate.

  Moreover, the polymerization initiator, the emulsifier, and the molecular weight modifier used in the emulsion polymerization can be used according to a conventional method.

  From the viewpoints of long-term storage stability and ejection stability of the ink, the resin preferably has a particle size in the range of 5 to 400 nm, more preferably in the range of 50 to 200 nm.

  The addition amount of these resins may be appropriately determined in consideration of fixability and the like, but each ink composition preferably contains 2% by weight or more in terms of solid content.

  You may add to each ink which concerns on this embodiment what became the emulsion state which resin disperse | distributed in the solvent.

1.5.3. Surfactant Each ink according to the present embodiment can contain a surfactant. Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. Surfactant may be used individually by 1 type, and may be used in mixture of 2 or more types.

  Among these, nonionic surfactants can improve the permeability and fixability of the ink to the recording medium, and the shape of the ink droplets deposited on the recording medium by the ink jet recording method is close to a perfect circle. Can be preferably used.

  Among nonionic surfactants, acetylene glycol surfactants are more preferably used because they are excellent in ability to maintain surface tension and interfacial tension appropriately and have almost no foaming property. be able to. Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3, And 5-dimethyl-1-hexyn-3-ol and 2,4-dimethyl-5-hexyn-3-ol. Commercially available acetylene glycol surfactants can also be used, such as Surfinol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA (all are trade names, manufactured by Air Products and Chemicals Inc.), Olphin B, Y, P, A, STG, SPC , E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), acetylenol E00, E00P, E40, E100 (all trade names, Kawaken Fine Chemical Co., Ltd.).

1.5.4. Penetration Accelerator Each ink according to the present embodiment can contain a penetration enhancer. The penetration enhancer has a function of further improving the wettability of the ink with respect to the recording medium and applying it uniformly. As a result, it is possible to further reduce the density unevenness and bleeding of the ink of the formed image, and to further improve the color density of the image. A penetration enhancer may be used individually by 1 type, and may be used in mixture of 2 or more types.

  Examples of the penetration enhancer include glycol ethers. Glycol ethers are particularly excellent in effect as penetration enhancers. Examples of glycol ethers include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol. Examples include propyl ether and dipropylene glycol monobutyl ether. Among these, triethylene glycol monobutyl ether can be preferably used from the viewpoint of excellent compatibility with components contained in the ink composition according to the present embodiment.

1.5.5. Humectant Each ink according to the present embodiment can contain a humectant. Examples of the humectant include 1,2-alkanediols, polyhydric alcohols, pyrrolidone derivatives, ureas, and the like. A moisturizer may be used individually by 1 type, and may be used in mixture of 2 or more types.

  Since 1,2-alkanediols have an excellent effect of increasing the wettability of the ink to the recording medium and uniformly wetting it, an excellent image can be formed on the recording medium.

  Examples of 1,2-alkanediols include 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, and the like. .

  Polyhydric alcohols can be preferably used from the viewpoint that when ink is used in an ink jet recording apparatus, drying and solidification of the ink on the nozzle surface of the head can be suppressed to reduce clogging, ejection failure, and the like. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, and trimethylol. Examples include propane.

  The pyrrolidone derivative can be preferably used from the viewpoint of suppressing clogging and ejection failure by suppressing drying and solidification of the ink on the nozzle surface of the head. Examples of pyrrolidone derivatives include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-butyl-2-pyrrolidone, and 5-methyl-2-pyrrolidone. Etc.

  Ureas can be preferably used from the viewpoint that when the ink composition is used in an ink jet recording apparatus, clogging or ejection failure can be reduced by suppressing drying and solidification of the ink on the nozzle surface of the head. Examples of ureas include urea, thiourea, ethylene urea, 1,3-dimethylimidazolidinone and the like.

1.5.6. pH adjuster Each ink according to the present embodiment may contain a pH adjuster. The pH adjuster can easily adjust the pH value of the ink composition. A pH adjuster may be used individually by 1 type, and may be used in mixture of 2 or more types.

  Examples of pH adjusters include inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid), inorganic bases (for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia), organic bases (triethanolamine, diethanolamine, mono Ethanolamine, tri-iso-propanolamine), organic acids (for example, adipic acid, citric acid, succinic acid, 2-naphthoic acid, etc.) and the like.

1.5.7. Other Components Each ink according to the present embodiment can further contain a preservative / fungicide, a rust inhibitor, a chelating agent, and the like. If each ink according to the present embodiment contains these compounds, the characteristics may be further improved.

1.6. Physical Properties When the ink set according to this embodiment is used in an ink jet recording apparatus, the viscosity of each ink at 20 ° C. is preferably 2 mPa · s or more and 10 mPa · s or less, preferably 3 mPa · s or more and 6 mPa · s or less. It is more preferable. If the viscosity at 20 ° C. is within the above range, the ink can be suitably used for an ink jet recording apparatus because it can be discharged in an appropriate amount from the nozzle and can further reduce the occurrence of flight bending or scattering. The viscosity of the ink can be measured by keeping the temperature of the ink at 20 ° C. using a vibration viscometer VM-100AL (manufactured by Yamaichi Electronics Co., Ltd.).

  The pH at 20 ° C. of each ink according to the present embodiment is preferably 7 or more and 9 or less.

2. Inkjet Recording Method The inkjet recording method according to the present embodiment includes a step of ejecting each ink droplet. The ink jet recording method according to this embodiment can be performed using a conventionally known ink jet recording apparatus.

  An ink jet recording method using an ink jet recording apparatus can be performed, for example, as follows. Specifically, an image can be formed by ejecting ink as droplets onto a recording medium and attaching the ink droplets to the recording medium. Any of the conventionally known methods can be used as the inkjet ejection method, and in particular, a method of ejecting droplets using the vibration of a piezoelectric element (using an inkjet head that forms ink droplets by mechanical deformation of an electrostrictive element). In the recording method, excellent image recording can be performed.

  Although it does not specifically limit as a recording medium, For example, paper, cardboard, a textile product, leather, a sheet | seat or film, a plastics, glass, ceramics, a metal etc. are mentioned.

3. EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

3.1. Dye ink 3.1.1. Dyes used The dyes used in Examples and Comparative Examples are shown below.

(1) Synthesis | combination of dye (y-11) Dye (y-11) is compoundable by a conventional method, and it synthesize | combined as follows in this embodiment. The dye (y-11) is an example of the dye (y-1).

  First, 20.8 parts of 5-amino-2-chlorobenzenesulfonic acid was dissolved in 200 parts of water while adjusting the pH to 6 with sodium hydroxide, and then 7.2 parts of sodium nitrite was added. This solution was added dropwise to 20 parts of 5% hydrochloric acid at 0 to 10 ° C. over 30 minutes, followed by stirring at 10 ° C. or lower for 1 hour to carry out a diazotization reaction to prepare a diazo reaction solution.

  On the other hand, 26.6 parts of 2- (sulfopropoxy) -5-chloroaniline were dissolved in 130 parts of water while adjusting the pH to 7 with sodium hydroxide, and 10.4 parts of sodium bisulfite and 8.6 parts of 35 Using methyl formalin, a methyl-ω-sulfonic acid derivative was obtained by a conventional method. The obtained methyl-ω-sulfonic acid derivative was added to the previously prepared diazo reaction solution, and the mixture was stirred at 0 to 15 ° C. and pH 2 to 24 for 24 hours. The reaction solution was adjusted to pH 11 with sodium hydroxide, stirred at 80 to 95 ° C. for 5 hours while maintaining the same pH, further salted out by adding 100 parts of sodium chloride, and the precipitated solid was separated by filtration. 100 parts of an azo compound represented by the formula (y-1-1) was obtained as a wet cake.

  Product name: Leocol (registered trademark) TD90 (surfactant) 0.10 part was added to 250 parts of ice water and stirred vigorously, and 3.6 parts of cyanuric chloride was added thereto, and 0-5 Stir at 30 ° C. for 30 minutes to obtain a suspension. Subsequently, 100 parts of a wet cake of the compound represented by the above formula (y-1-1) was dissolved in 200 parts of water, and the above suspension was dropped into this solution over 30 minutes. After completion of dropping, the mixture was stirred at pH 6-8 and 25-45 ° C. for 6 hours. To the obtained liquid, 37.5 parts of taurine was added and stirred at pH 7-9 and 75-90 ° C. for 4 hours. After cooling the obtained reaction liquid to 20-25 degreeC, 800 parts of acetone was added to this reaction liquid, and it stirred at 20-25 degreeC for 1 hour. The precipitated solid was separated by filtration to obtain 50.0 parts of a wet cake. The wet cake was dried with a hot air dryer at 80 ° C. to obtain 13.5 parts of a sodium salt (λmax: 408 nm) of a compound represented by the following formula (y-11). The dye represented by the formula (y-11) thus obtained is referred to as a dye (y-11).

(2) Synthesis of Dye (y-22) Dye (y-22) was synthesized by a conventional method. The dye (y-22) is an example of the dye (y-2).

(3) Synthesis of Dye (m-11) Dye (m-11) was synthesized by a conventional method. The dye (m-11) is an example of the dye (m-1).

(In formula (m-11), M ^M1 represents NH ₄ or Na.)

(4) Synthesis of Dye (m-23) Dye (m-23) was synthesized by a conventional method. The dye (m-23) is an example of the dye (m-2).

(5) Synthesis of Dye (c-11) Dye (c-11) can be synthesized by a conventional method, and in this embodiment, synthesized according to the following steps 1 to 4. The dye (c-11) is an example of the dye (c-1).

  The dye (c-11) synthesized as follows is a mixture containing isomers and the like as described in the dye (c-1). Unless otherwise specified, the substitution positions of the unsubstituted and substituted sulfamoyl groups in the dye (c-11) are a mixture of those substituted at the α-position and β-position of the porphyrazine ring.

(Process 1)
Synthesis of a compound in which 1.20 of the rings A ^{C1 to} D ^{C1 in} the following formula (c-1-1) is a pyridine ring condensed at the 2-position and 3-position, and the remaining 2.80 is a benzene ring.

  To 375 parts of sulfolane, 31.11 parts of phthalic anhydride, 15.04 parts of quinolinic acid, 108 parts of urea, 10.1 parts of copper (II) chloride and 1.5 parts of ammonium molybdate are added, and the temperature is raised to 200 ° C. And reacted at the same temperature for 5 hours. After completion of the reaction, the reaction mixture was cooled to 65 ° C., 50 parts of DMF (N, N-dimethylformamide) was added, and the precipitated solid was separated by filtration. The obtained solid was washed with 50 parts of DMF to obtain 75.1 parts of a wet cake. The obtained wet cake was added to 450 parts of DMF, heated to 110 ° C., and reacted at the same temperature for 1 hour. The precipitated solid was separated by filtration and washed with 200 parts of water to obtain a wet cake. The obtained wet cake was added to 450 parts of 5% hydrochloric acid, heated to 60 ° C., and stirred at the same temperature for 1 hour. The precipitated solid was separated by filtration and washed with 200 parts of water to obtain a wet cake. The obtained wet cake was added to 450 parts of 5% aqueous ammonia, stirred at 60 ° C. for 1 hour, the precipitated solid was separated by filtration and washed with 200 parts of water to obtain 78.6 parts of a wet cake. The obtained wet cake was dried at 80 ° C. to obtain 24.9 parts of the target compound as a blue solid.

(Process 2)
Among the rings A ^{C1 to} D ^{C1 in} the following formula (c-1-2), 1.20 is a pyridine ring condensed at the 2-position and 3-position, the remaining 2.80 is a benzene ring, and n is 2.80. Synthesis of certain compounds.

  After gradually adding 5.8 parts of the compound of formula (c-1-1) obtained in (Step 1) to 46.2 parts of chlorosulfonic acid at room temperature so as not to exceed 60 ° C., 140 ° C. For 4 hours. The obtained reaction solution was cooled to 70 ° C., 17.9 parts of thionyl chloride was added dropwise over 30 minutes, and the mixture was further reacted at 70 ° C. for 3 hours. The reaction solution was cooled to 30 ° C. or lower, slowly poured into 800 parts of ice water, the precipitated solid was separated by filtration, and washed with 200 parts of cold water to obtain 38.2 parts of the target compound wet cake.

(Process 3)
Synthesis of organic amine represented by the following formula (c-1-3).

  18.4 parts of cyanuric chloride and trade name Leocol TD-90 (0.05 parts) were added to 100 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 having a purity of 88.4%) was added, and the pH was adjusted to 2.0 to 3.0 with a 10% aqueous sodium hydroxide solution at 0 to 10 ° C. for 2 hours. Reaction was performed at 25-30 degreeC for 1 hour. Next, 10.9 parts of benzylamine was added to the reaction solution, and the reaction was carried out at 25 to 30 ° C. for 1 hour and at 30 to 40 ° C. for 1 hour while adjusting the pH to 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution. A reaction solution containing a condensate was obtained.

  The reaction solution containing the secondary condensate obtained as described above was gradually added to an aqueous solution obtained by adding 60.1 parts of ethylenediamine to 120 parts of ice and stirred at room temperature for 1 hour. To this solution, 150 parts of ice and 200 parts of concentrated hydrochloric acid were added to adjust the pH to 1.0. At this time, the liquid volume was 700 parts. To this reaction solution, 140 parts of sodium chloride was added and stirred overnight to precipitate a solid. The precipitated solid was separated by filtration to obtain 70.0 parts of a wet cake. The obtained wet cake was added to 280 parts of water and dissolved with 10% aqueous sodium hydroxide solution to pH 9.0. At this time, the liquid volume was 360 parts. This solution was diluted with concentrated hydrochloric acid to pHl. The mixture was adjusted to 0, 70 parts of sodium chloride was added, and the mixture was stirred overnight to precipitate a solid. The precipitated solid was separated by filtration to obtain 60.3 parts of a wet cake. The obtained wet cake was added to a mixed solvent of 255 parts of methanol and 45 parts of water and stirred at 50 ° C. for 1 hour, and then the precipitated solid was separated by filtration to obtain 50.3 parts of a wet cake. The obtained wet cake was dried to obtain 15.3 parts of a white powder of the organic amine represented by the target formula (c-1-3).

(Process 4)
A compound represented by the following formula (c-11) [a pyridine ring in which 1.20 of the rings A ^{C1 to} D ^{C1 in} the following formula (c-11) is condensed at the 2-position and 3-position, and the remaining 2.80 Synthesis of a dye having a benzene ring (dye (c-11)).

  38.2 parts of the wet cake obtained in (Step 2) was added to 200 parts of ice water and suspended by stirring at 5 ° C. or lower. After 10 minutes, while maintaining 10 ° C. or lower, 3.7 parts of the organic amine of the formula (c-1-3) obtained in (Step 3) was mixed with 1.5 parts of 28% aqueous ammonia and 40 parts of water. The solution dissolved in was added to the suspension and reacted with 28% aqueous ammonia while maintaining pH 9.0. While maintaining the same pH, the temperature was raised to 20 ° C., and the reaction was further continued overnight at the same temperature.

  The liquid volume at this time was 300 parts. The temperature of the reaction solution was raised to 50 ° C., 60 parts of sodium chloride was added, and the mixture was stirred for 30 minutes, adjusted to pH 5.0 with concentrated hydrochloric acid, the precipitated solid was separated by filtration, and washed with 100 parts of a 20% sodium chloride aqueous solution. As a result, 24.2 parts of a wet cake were obtained. The obtained wet cake was added to 200 parts of water, and adjusted to pH 9.0 with 25% sodium hydroxide aqueous solution to obtain a solution. The liquid volume at this time was 250 parts. The temperature of the solution was raised to 50 ° C., 50 parts of sodium chloride was added and stirred for 30 minutes, adjusted to pH 4.0 with concentrated hydrochloric acid, the precipitated solid was separated by filtration, and washed with 100 parts of a 20% aqueous sodium chloride solution. , 22.3 parts of a wet cake were obtained. The obtained wet cake was added to a mixed solution of 160 parts of isopropyl alcohol and 40 parts of water and stirred at 50 ° C. for 1 hour, and then the precipitated solid was separated by filtration to obtain 14.4 parts of a wet cake. The obtained wet cake was dried to obtain 10.8 parts of a free acid of the porphyrazine compound of the present invention (dye (c-11)) represented by the above formula (c-11) as a blue powder.

(6) Dye (c-21)
The dye (c-21) can be synthesized by a conventional method, and was synthesized according to the method described in “1.3.2. Dye (c-2)” in this embodiment. The dye (c-21) is an example of the dye (c-2).

(7) Dye (b-11)
The dye (b-11) can be synthesized by a conventional method, and in this embodiment, the dye (b-11) is represented by the formula (b-11) according to the method described in “1.4.2.2. Dye (b-1)”. ) Is synthesized into a lithium salt by a conventional method. Dye (b-11) is an example of dye (b-1).

(8) Dye (b-23)
The dye (b-23) can be synthesized by a conventional method. In this embodiment, the dye (b-23) was synthesized by Steps 1 and 2 described later.

(Process 1)
To 200 parts of water, 35.7 parts of a monoazo compound represented by the following formula (b-2-1) was added, and 7.2 parts of sodium nitrite was added to adjust the pH to 6 with sodium hydroxide to obtain a solution. . This solution was dropped into an aqueous solution obtained by diluting 31.3 parts of 35% hydrochloric acid with 200 parts of water over 30 minutes while maintaining the temperature at 0 to 10 ° C., followed by stirring at 20 ° C. or lower for 1 hour to carry out a diazotization reaction. went. To the obtained reaction solution, 0.4 part of sulfamic acid was added and stirred for 5 minutes to obtain a final diazo reaction solution.

  On the other hand, 24.0 parts of a compound represented by the following formula (b-2-2) and 25% aqueous sodium hydroxide solution are added to 300 parts of water at 40 to 50 ° C. to adjust the pH to 5 to 6, thereby obtaining an aqueous solution. It was. While maintaining this aqueous solution at 15 to 25 ° C., the above diazo reaction solution was added dropwise over 30 minutes. During the dropping, the pH was maintained at 5 to 6 by adding an aqueous sodium carbonate solution. Subsequently, after stirring at 15-25 degreeC and pH 5-6 for 2 hours, it adjusted to pH0-1 by adding 35% hydrochloric acid. The resulting liquid was stirred for 2 hours while being heated to 65 ° C., then cooled to 25 ° C., and the precipitate was collected by filtration to obtain a wet solution containing a compound represented by the following formula (b-2-3). 130 parts of cake were obtained.

(Process 2)
65 parts of the wet cake obtained in Step 1 above was added to 250 parts of water to make a solution by adding a 25% aqueous sodium hydroxide solution. The pH of the solution was 7-8. To this solution, 0.1 part of Leocol TD-90 (manufactured by Lion Corporation, surfactant) was added, and then 3.8 parts of cyanuric chloride was added at 15 to 25 ° C. Next, it stirred at 15-25 degreeC, maintaining at pH 5-6 by addition of sodium carbonate aqueous solution for 2 hours. Next, this reaction liquid was heated to 60 to 65 ° C. and stirred for 5 hours while maintaining the pH at 6 to 7 by adding an aqueous sodium carbonate solution.

  Next, 0.89 parts of piperazine was added, heated to 90 to 95 ° C., and stirred for 16 hours while maintaining the pH at 8 to 9 by adding an aqueous sodium carbonate solution. The obtained reaction liquid was cooled to 25 ° C., sodium chloride was added, and the precipitated solid was collected by filtration to obtain a wet cake. 400 parts of water was added to this wet cake to prepare a solution. 50 parts of methanol and 800 parts of 2-propanol were added to this solution, and the precipitated solid was collected by filtration and dried to obtain a sodium salt of a compound represented by the following formula (b-23). This was converted into a lithium salt by a conventional method and used as the dye (b-23).

(9) Dye (b-31)
The dye (b-31) was synthesized by a conventional method. The dye (b-31) is a lithium salt of a compound represented by the following formula (b-31), and is an example of the dye (b-3).

(10) Other dyes The dyes used in Examples and Comparative Examples other than the above are as follows.
-Dye (y-3): C.I. I. Direct Yellow 132 (DY132)
-Dye (m-3): C.I. I. Direct Red 227 (DR227)
-Dye (c-3): C.I. I. Direct Blue 199 (DB199)
-Dye (b-4): C.I. I. Direct Black 195 (BK195)

3.1.2. Preparation of dye ink Each component was mixed and stirred at the blending amounts shown in Table 17 and Table 18, and pressure filtration was performed with a membrane filter having a pore size of 1.0 μm to obtain a dye ink. In addition, the unit described in Table 17 and Table 18 is mass%. The dye ink refers to an ink containing any of the dyes described above.

3.2. Pigment ink 3.2.1. Preparation of Pigment Dispersion Liquid 20 g of commercially available carbon black S170 (manufactured by Degussa) was mixed with 500 g of water and dispersed with a home mixer for 5 minutes. The obtained liquid was put into a 3 liter glass container equipped with a stirrer, and an ozone-containing gas having an ozone concentration of 8% by weight was introduced at 500 mL / min while stirring with a stirrer. At this time, the ozone generator generated ozone using an electrolytic generation type ozonizer manufactured by Permerex Electrode. The obtained dispersion stock solution is filtered through glass fiber filter paper GA-100 (manufactured by Advantech Toyo Co., Ltd.), and further concentrated while adjusting to pH 9 by adding 0.1N potassium hydroxide solution until the pigment concentration becomes 20% by weight. And a black pigment dispersion was prepared.

3.2.2. Preparation of Pigment Ink Each component was mixed and stirred at the blending amounts shown in Table 18, and pressure filtration was performed with a membrane filter having a pore size of 1.0 μm to obtain a pigment ink. The pigment ink refers to an ink containing the pigment.

  The resin emulsion contained in the pigment ink was manufactured as follows. A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 900 g of ion-exchanged water and 1 g of sodium lauryl sulfate, and the temperature was raised to 70 ° C. while purging with nitrogen under stirring. Maintaining the internal temperature at 70 ° C., adding 4 g of potassium persulfate as a polymerization initiator, dissolving, and previously stirring 450 g of ion exchange water, 3 g of sodium lauryl sulfate, 20 g of acrylamide, 365 g of styrene, 545 g of butyl acrylate, and 30 g of methacrylic acid The emulsion prepared by adding below was continuously dropped into the reaction solution over 4 hours. After completion of dropping, aging was performed for 3 hours. The obtained resin emulsion was cooled to room temperature, and then ion-exchanged water and an aqueous sodium hydroxide solution were added to adjust the solid content to 40% by weight and pH 8. The glass transition temperature of the resin in the obtained aqueous emulsion was −6 ° C.

Moreover, what was described with the brand name among the components described in Table 17 and Table 18 is as follows.
・ Orphine E1010 (trade name, manufactured by Nissin Chemical Industry Co., Ltd., acetylene glycol surfactant)
Surfynol 104PG50 (trade name, manufactured by Air Products and Chemicals, Inc., acetylene glycol surfactant)

3.3. Evaluation Test In the evaluation test, the above inks were combined to obtain ink sets according to Examples and Comparative Examples. Table 19 shows combinations of inks in the ink sets according to Examples and Comparative Examples.

3.3.1. Ozone resistance (1) Evaluation of ozone resistance in a single color The ink set obtained as described above is mounted on an ink jet printer (trade name “EP-803”, manufactured by Seiko Epson Corporation), and a recording medium (photograph) A solid pattern image was recorded for each color on paper (gloss), model number “KA420PSK” (manufactured by Seiko Epson Corporation), and an evaluation sample was obtained. The solid pattern image was recorded by adjusting the duty so that the obtained image had an OD (Optical Density) of 1.0.

  The obtained evaluation sample is installed in an ozone weather meter OMS-L type (trade name, manufactured by Suga Test Instruments Co., Ltd.), and is subjected to ozone for a predetermined time under conditions of a temperature of 23 ° C., a humidity of 50% RH, and an ozone concentration of 5 ppm. An exposure test was conducted.

  Then, the OD value before and after ozone exposure of the image recorded on the sample was measured using a colorimeter (trade name “Xrite i1”, manufactured by Xrite). The OD value was measured using a D50 light source, a viewing angle of 2 °, Red for cyan, Green for magenta, and Blue for yellow, and no filter for black.

  In addition, evaluation of ozone resistance was performed by calculating | requiring the optical density residual rate (Relic Optical Density: ROD) of the image of each evaluation sample after an exposure test from the obtained measured value (OD value). The calculation method of ROD is “ROD (%) = (Dn / Do) × 100 (where Dn is the OD value of the image after the end of the exposure test and Do is the OD value of the image before the start of the exposure test)”. .

The evaluation criteria are as follows.
Evaluation A: ROD does not decrease to 70% by 80 hours.
Evaluation B: ROD decreases to 70% over 60 hours and 80 hours or less.
Evaluation C: ROD decreases to 70% over 40 hours and 60 hours or less.
Evaluation D: ROD decreases to 70% within 40 hours.

(2) Evaluation of ozone resistance as an ink set Based on the evaluation results of ozone resistance in a single color, the ozone resistance as an ink set was evaluated based on the following evaluation criteria.
Evaluation A: The ozone resistance evaluation results are all A for three colors (four colors when black is included).
Evaluation B: The ozone resistance evaluation result is one or more of three colors (four colors when black is included), and B rank ink exists.
Evaluation C: The ozone resistance evaluation result is one or more of three colors (four colors when black is included), and C rank ink is present.
Evaluation D: The ink resistance evaluation result is one or more of three colors (four colors when black is included) and D rank ink exists.

3.3.2. Color Balance The difference in ROD change (color balance) between each color of the evaluation samples generated by the above ozone resistance evaluation test was evaluated for each ink set according to the following criteria.
Evaluation A: The difference (ROD difference) between the maximum value and the minimum value of ROD of each color is less than 15 points by 80 hours after the start of the test.
Evaluation B: The ROD difference exceeds 15 points within 60 to 80 hours after the start of the test.
Evaluation C: ROD difference exceeds 15 points within 40 to 60 hours after the start of the test.
Evaluation D: The ROD difference exceeds 15 points within 40 hours after the start of the test.

3.3.3. Humidity resistance (1) Evaluation of moisture resistance in a single color Using the above inkjet printer EP-803, the color of each ink, Cyan, Magenta, Yellow, Black (however, black is included only when the ink set includes black ink) And white characters (solid images of each color formed with white characters) are printed on a recording medium (photo paper (glossy), model number “KA420PSK”, manufactured by Seiko Epson Corporation). It was dried for 24 hours in a 50 ° C. and 50% RH environment. Subsequently, these were left still in an environment of 35 ° C. and 85% RH not exposed to light. After standing in this environment for 4 days, the degree of bleeding of letters and white letters was visually observed and evaluated according to the following criteria.
Evaluation A: No oozing of the colorant is observed.
Evaluation B: The bleeding out of the colorant is hardly observed.
Evaluation C: The bleeding of the colorant is observed, and the outline of the character is broken.
Evaluation D: The bleeding out of the colorant is observed, the character is thick, and the whole white character is dyed with the color of the colorant.

(2) Evaluation of moisture resistance as ink set Based on the evaluation results of moisture resistance with a single color, the moisture resistance as an ink set was evaluated based on the following evaluation criteria.
Evaluation A: The evaluation results of moisture resistance are all A for three colors (four colors when black is included).
Evaluation B: The evaluation result of the moisture resistance is one or more of three colors (four colors when black is included), and B rank ink exists.
Evaluation C: The evaluation result of the moisture resistance is one or more of three colors (four colors when black is included), and C rank ink is present.
Evaluation D: The D-rank ink is present in one or more of three colors (four colors when black is included) as a result of evaluating moisture resistance.

3.3.4. Color reproducibility (production of reference color chart image)
The ink set of Example 2 (yellow, magenta, cyan) or the ink set of Example 5 (yellow, magenta, cyan, black) described in JP-A-2005-105135 is mounted on the inkjet printer EP-803. . The printer EP-803 is set to “photo paper setting”, “clean”, “no color correction”, and “Bi-D” on a recording medium (photo paper (glossy), model number “KA420PSK”, manufactured by Seiko Epson Corporation). A color chart image was printed. In this way, a three-color reference color chart created using three colors of ink (yellow, magenta, cyan) and a black reference color chart image created using black ink were obtained.

The obtained reference color chart image was measured with a colorimeter (trade name “Xrite i1”, manufactured by Xrite), and L ^* value, a ^* value, and b ^* value were measured. From these values, the value (gamut value) of L ^* a ^* b ^* color reproduction range volume was calculated. The value calculated by this was used as the reference value.

The L ^* a ^* b ^* color reproduction range volume value (gamut value) is obtained by dividing the L ^* axis in the color space of the L ^* a ^* b ^* color system by 10 and dividing the a ^{* at} each divided L ^* value ^. After obtaining the b ^* space region (a ^* value and b ^* value), it is calculated by calculating the a ^* b ^* space region of all L ^* values.

(Preparation of evaluation sample)
Next, the ink sets of Examples and Comparative Examples were mounted on the inkjet printer EP-803. And it printed on the conditions similar to preparation of a reference | standard color chart image, and produced the evaluation sample in which the color chart image was printed. The obtained evaluation sample was subjected to color measurement under the same conditions as those of the reference color chart image of three colors and black, and the gamut value of the evaluation sample was calculated.

  In the ink sets of Examples and Comparative Examples, when an ink set composed of three colors of ink was used, a comparison was made with a three-color reference color chart image produced using three colors of ink. . In addition, in the ink sets of the example and the comparative example, when an ink set composed of four colors of ink was used, 3 produced using three colors (yellow, magenta, cyan) of the four colors of ink. A comparison was made between a color reference color chart and a black reference color chart image produced using black ink.

(Evaluation of color reproducibility)
The color reproducibility was evaluated by comparing the gamut values of the three color and black reference color chart images with the gamut values of the evaluation samples. The standard evaluation is as follows.
Evaluation A: The gamut value exceeds 110% with respect to the reference ink set.
Evaluation B: The gamut value is more than 105% and less than 110% with respect to the reference ink set.
Evaluation C: The gamut value is more than 100% and less than 105% with respect to the reference ink set.
Evaluation D: The gamut value is less than 100% with respect to the reference ink set.

3.4. Evaluation Results Table 20 shows the evaluation results of the above ozone resistance and color balance, and Table 21 shows the evaluation results of moisture resistance and color reproducibility.

  As shown in the evaluation test results, each ink used in the ink set according to the example was excellent in ozone resistance and moisture resistance. In addition, the ink set according to the example was excellent in ozone resistance, color balance, moisture resistance, and color reproducibility as the ink set.

  On the other hand, as shown in the evaluation test results, the ink set according to the comparative example has characteristics of each ink (ozone resistance, moisture resistance) and characteristics as an ink set (ozone resistance, color balance, humidity resistance, color reproducibility). There was a tendency for at least one of these to decrease.

  The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (11)

An ink set comprising at least yellow ink, magenta ink, and cyan ink,
The yellow ink is selected from the group consisting of a compound represented by the following general formula (y-1) or a salt thereof and a compound represented by the following general formula (y-2) or a salt thereof as a colorant. Containing at least one of
The magenta ink contains, as a colorant, at least one selected from the group consisting of a compound represented by the following general formula (m-1) or a salt thereof,
The cyan ink has, as a colorant, at least one selected from the group consisting of a compound represented by the following general formula (c-1) or a salt thereof, a compound represented by the following general formula (c-2), or An ink set comprising: at least one selected from the group consisting of salts thereof.

(In formula (y-1), Q ^Y1 represents a halogen atom; x represents an integer of 2 to 4; y represents an integer of 1 to 3.)

(In formula (y-2), X ^Y21 , X ^Y22 , Y ^Y21 , and Y ^Y22 each independently represent a hydrogen atom or a cyano group, and Z ^Y21 and Z ^Y22 represent a substituent having an aromatic ring. R ^Y21 and R ^Y22 represent an alkyl group, and M ^Y2 represents a metal atom.)

(In the formula (m-1), A ^M1 represents an alkylene group having 1 or 2 carbon atoms, an alkylene group having 1 or 2 carbon atoms containing a phenylene group, or a group represented by the following formula (m-1-1). X ^M1 represents an amino group, a hydroxy group, a chlorine atom, or a phenoxy group substituted with a sulfo group or a carboxy group.)

(In formula (m-1-1), R ^M1 represents a hydrogen atom or an alkyl group.)

(In the formula (c-1),
Rings A ^{C1 to} D ^C1 represented by broken lines each independently represent a benzene ring or a 6-membered nitrogen-containing heteroaromatic ring condensed to a porphyrazine ring, and the average number of nitrogen-containing heteroaromatic rings is 0. .00 to 3.00 and the rest are benzene rings,
E ^C1 represents C2-C12 alkylene;
X ^C1 is a substituent such as sulfo group, carboxy group, phosphate group, sulfamoyl group, carbamoyl group, hydroxy group, C1-C6 alkoxy group, amino group, mono C1-C4 alkylamino group, di-C1-C4 alkylamino. Group, mono C6-C10 arylamino group, di-C6-C10 arylamino group, C1-C3 alkylcarbonylamino group, ureido group, C1-C6 alkyl group, nitro group, cyano group, halogen atom, C1-C6 alkylsulfonyl group And a sulfoanilino group, a carboxyanilino group, a phosphonoanilino group, a sulfonaphthylamino group, a carboxynaphthylamino group, which may have one or two or more substituents selected from the group consisting of C1-C6 alkylthio groups Or a phosphononaphthylamino group,
R ^C1 is a hydrogen atom; a sulfo group; a carboxy group; a phosphate group; a sulfamoyl group; a carbamoyl group; a hydroxy group; a C1-C6 alkoxy group; an amino group; a mono C1-C6 alkylamino group; Diarylamino group; C1-C3 alkylcarbonylamino group; ureido group; C1-C6 alkyl group; nitro group; cyano group; halogen atom; C1-C6 alkylsulfonyl group; or alkylthio group;
The group F ^C1 represents a phenyl group; or a 6-membered nitrogen-containing heteroaromatic group;
a represents an integer of 1 to 6,
b is an average value of 0.00 or more and less than 3.90,
c is an average value of 0.10 or more and less than 4.00,
The sum of b and c is an average value of 1.00 or more and less than 4.00. )

(In Formula (c-2), X ^C21 , X ^C22 , X ^C23 and X ^C24 each independently represent —SO—Z ^C2 or —SO ₂ —Z ^C2 ,
Z ^C2 each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group,
Y ^C21 , Y ^C22 , Y ^C23 , Y ^C24 , Y ^C25 , Y ^C26 , Y ^C27 and Y ^C28 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group. , Heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, Alkoxycarbonylamino group, sulfonamido group, carbamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic ring Thio group, phos Lil group, an acyl group, a carboxyl group or a sulfonic group,
a _{1 to} a ₄ satisfy 4 ≦ a ₁ + a ₂ + a ₃ + a ₄ ≦ 8, and each independently represents an integer of 1 or 2,
M ^C2 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. ) In claim 1,
Furthermore, at least one of the first black ink and the second black ink is provided,
The first black ink contains a pigment as a colorant,
The second black ink is represented by the following general formula (b-2) and at least one selected from the group consisting of a compound represented by the following general formula (b-1) or a salt thereof as a colorant. An ink set comprising: at least one selected from the group consisting of a compound or a salt thereof.

(In the above formula (b-1), n is 0 or 1,
R ^B11 represents a carboxy group; a C1-C8 alkoxycarbonyl group; a C1-C4 alkyl group; a C1-C4 alkyl group substituted with a C1-C8 alkoxycarbonyl group or a carboxy group; a phenyl group; or a hydroxy group, a sulfo group or a carboxy group Represents a phenyl group substituted with a group,
R ^B12 , R ^B13 and R ^B14 each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group; a mono- or di-C1-C4 alkylamino group substituted with a hydroxy group, a sulfo group or a carboxy group; A C1-C4 alkylcarbonylamino group; a C1-C4 alkylcarbonylamino group substituted with a hydroxy group or a carboxy group; an N′-C1-C4 alkylureido group substituted with a hydroxy group, a sulfo group or a carboxy group; Chlorine atom, C1-C4 A phenylamino group substituted by an alkyl group, a nitro group, a sulfo group or a carboxy group; a benzoylamino group in which the benzene ring is substituted by a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group; or a benzene ring Each represents a chlorine atom, a phenylsulfonylamino group substituted with a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group;
Group A ^B1 is a substituted heterocyclic group represented by the following general formula (b-1-1),
The group B ^B1 is a phenyl group or a substituted phenyl group or naphthyl group or a substituted naphthyl group, and when the group B ^B1 is a substituted phenyl group, a hydroxy group; a sulfo group; a carboxy group; a C1-C4 alkyl group A C1-C4 alkoxy group; a C1-C4 alkylsulfonyl group; a nitro group; an amino group; a mono- or di-C1-C4 alkylamino group; an acetylamino group; and a benzene ring as a chlorine atom, a C1-C4 alkyl group, a nitro group; A benzoylamino group substituted with a sulfo group or a carboxy group; having a substituent selected from the group consisting of, and when the group B ^B1 is a substituted naphthyl group, a hydroxy group; a sulfo group; a C1-C4 alkoxy group; A phenylsulfonyloxy group in which the benzene ring is substituted with a methyl group, a nitro group or a chlorine atom; Having a substituent selected from that group. )

(In the formula (b-1-1), R ^B16 , R ^B17 and R ^B18 each independently represent a hydrogen atom; a chlorine atom; a carboxy group; a sulfo group; a nitro group; a hydroxy group; a carbamoyl group; a sulfamoyl group; C1-C4 alkyl group; C1-C4 alkoxy group; C1-C4 alkoxy group substituted with a hydroxy group, C1-C4 alkoxy group, sulfo group or carboxy group; C1-C4 alkylsulfonyl group; Hydroxy group, sulfo group or carboxy group A C1-C4 alkylsulfonyl group substituted with a group; or a phenylsulfonyl group in which the benzene ring is substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group;

(In the above formula (b-2), R ^B21 , R ^B22 , R ^B23 , R ^B24 , R ^B25 , R ^B26 , R ^B27 and R ^B28 are each independently a hydrogen atom; a halogen atom; a sulfo group; a carboxy group A sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a C1-C4 alkoxy group; a substituent selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group; A C1-C4 alkoxy group substituted with at least one group selected from: a C1-C4 alkylcarbonylamino group; a C1-C4 alkylcarbonylamino group substituted with a carboxy group; a ureido group; a mono C1-C4 alkylureido group; Di-C1-C4 alkylureido group; A mono C1-C4 alkylureido group substituted with at least one group selected from the group consisting of a group and a carboxy group; as a substituent, at least selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group At least one selected from the group consisting of a halogen atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group, a di-C1-C4 alkylureido group substituted with one type of group; a benzoylamino group; A benzoylamino group substituted with one type of group; a benzenesulfonylamino group; or at least one selected from the group consisting of a halogen atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group. A phenylsulfonylamino group substituted with a kind of group;
X ^B2 represents a divalent crosslinking group. ) In claim 1 or claim 2,
Furthermore, the magenta ink contains at least one selected from the group consisting of a compound represented by the following general formula (m-2) or a salt thereof as a colorant.

(In the above formula (m-2), A ^M2 represents a 5-membered heterocyclic group,
B ^M21 and B ^M22 each represent -CR ^M21 =, -CR ^M22 =, or one of them represents a nitrogen atom, and the other represents -CR ^M21 = or -CR ^M22 =,
R ^M23 and R ^M24 each independently represent a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group, and R ^M23 and R ^M24 may further have a substituent;
G ^M2 , R ^M21 , and R ^M22 each independently represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. An acyl group, a hydroxy group, an alkoxy group, an aryloxy group, a silyloxy group, an acyloxy group, a carbamoyloxy group, a heterocyclic oxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyl group, an aryl group, or a heterocyclic group. Substituted amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl and Riruchio group, an alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio ^{group,, G M2, R M21,} R M22 may be further substituted,
R ^M21 and R ^M23 , or R ^M23 and R ^M24 may combine to form a 5- to 6-membered ring. ) In any one of Claims 1 thru | or 3,
An ink set, wherein the compound represented by the general formula (y-1) is a compound represented by the following formula (y-11).

In any one of Claims 1 thru | or 4,
An ink set, wherein the compound represented by the general formula (y-2) is a compound represented by the following general formula (y-21).

(In the above formula (y-21), X ^Y21 , X ^Y22 , Y ^Y21 and Y ^Y22 each independently represent a hydrogen atom or a cyano group, and W ^Y21 , W ^Y22 , W ^Y23 , W ^Y24 , W ^Y25 , W ^Y211 , W ^Y212 , W ^Y213 , W ^Y214 and W ^Y215 each independently represent a hydrogen atom, a carboxyl group or a salt thereof, M ^Y2 represents a metal atom, and t-Bu represents a tertiary butyl group. In any one of Claims 1 thru | or 5,
An ink set, wherein the compound represented by the general formula (m-1) is a compound represented by the following general formula (m-11).

(In the formula (m-11), M ^M1 represents NH ₄ or Na.) In any one of Claims 1 thru | or 6,
In the general formula (c-1),
A pyridine ring in which the nitrogen-containing heteroaromatic rings in rings A ^{C1 to} D ^C1 are independently condensed at the 2-position and 3-position, or at the 3-position and 4-position; or a pyrazine ring condensed at the 2-position and 3-position And
E ^C1 is a linear C2-C4 alkylene,
X ^C1 is a substituent such as a sulfo group, a carboxy group, a hydroxy group, a C1-C6 alkoxy group, an amino group, a mono C1-C4 alkylamino group, a diC1-C4 alkylamino group, a C1-C3 alkylcarbonylamino group, A sulfoanilino group which may have 0 to 2 substituents of one or two types selected from the group consisting of a nitro group, a halogen atom, a C1-C6 alkylsulfonyl group and an alkylthio group; A carboxyanilino group optionally having 0 to 2 substituents of one or two types selected from the group consisting of a group, a carboxy group, a hydroxy group, and a sulfamoyl group; a phosphonoanilino group; or Sulfona optionally having 0 to 2 substituents of one or two types selected from sulfo group and hydroxy group A butylamino group;
R ^C1 is a hydrogen atom; a sulfo group; a carboxy group; a C1-C6 alkoxy group; a C1-C6 alkyl group; or a halogen atom;
The group F ^C1 is a phenyl group; or the pyridyl group in which R ^C1 is a hydrogen atom;
An ink set in which a is an integer of 1 or 2. In any one of Claims 1 thru | or 7,
An ink set, wherein the compound represented by the general formula (c-2) is a compound represented by the following general formula (c-21).

(In formula (c-21), Z ^C21 , Z ^C22 , Z ^C23 and Z ^C24 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group, ^C2 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide, provided that at least one of Z ^C21 , Z ^C22 , Z ^C23 and Z ^C24 is an ionic hydrophilic group As a substituent.) In claim 2,
In the general formula (b-1),
R ^B11 is a carboxy group; a C1-C8 alkoxycarbonyl group; a C1-C4 alkyl group substituted with a C1-C4 alkyl group carboxy group; or a phenyl group;
R ^B12 , R ^B13 and R ^B14 each independently represent a hydrogen atom; a sulfo group; a C1-C4 alkyl group; a C1-C4 alkoxy group; a C1-C4 alkoxy group substituted with a sulfo group or a carboxy group; C1-C4 An alkylcarbonylamino group; or an N′-C1-C4 alkylureido group substituted with a sulfo group or a carboxy group,
In the general formula (b-1-1),
R ^B16 , R ^B17 and R ^B18 are each independently a hydrogen atom; a chlorine atom; a carboxy group; a sulfo group; a nitro group; a C1-C4 alkoxy group; a C1-C4 alkoxy group; or a C1-C4 alkylsulfonyl group. ,
The group B ^B1 in the general formula (b-1) is a phenyl group having a substituent selected from the group consisting of a hydroxy group; a sulfo group; a carboxy group; a C1-C4 alkyl group; a C1-C4 alkoxy group; Is the ink set. In claim 2,
In the general formula (b-2),
Divalent bridging group represented by ^{X B2} is piperazine-1,4-diyl group; or C1-C4 alkyl group or C1-C4 piperazine-1,4-diyl group substituted with an alkoxy group, Ink set. In claim 3,
The ink set, wherein the compound represented by the general formula (m-2) is a compound represented by the following general formula (m-22).

(In the formula ^{(m-22), R M25} , R M26, R M27, R M28, R M29, R M210, R M211, R M212, R M213, R M214 are each independently a hydrogen atom, an alkyl group Represents a sulfo group or a salt thereof, and M ^M2 represents a hydrogen atom or an alkali metal atom.)