WO2015147113A1

WO2015147113A1 - Coloring composition, ink for inkjet recording, inkjet recording method, inkjet printer cartridge, and inkjet-recorded matter

Info

Publication number: WO2015147113A1
Application number: PCT/JP2015/059266
Authority: WO
Inventors: 和史古川; 祐太朗法月; 立石　桂一
Original assignee: 富士フイルム株式会社
Priority date: 2014-03-28
Filing date: 2015-03-25
Publication date: 2015-10-01
Also published as: JP6182663B2; JPWO2015147113A1

Abstract

　The purpose of the present invention is to provide a coloring composition with which the occurrence of bronzing can be minimized, and which has exceptional light resistance and ozone resistance; an ink for inkjet recording that employs the coloring composition; an inkjet recording method that employs the ink for inkjet recording; an inkjet printer cartridge; and inkjet-recorded matter. Provided are: a coloring composition containing a compound represented by general formula (Q) and a compound represented by general formula (1) which are disclosed in the description, the ratio of the content of the compound represented by general formula (1) to the content of the compound represented by general formula (Q), expressed on a mass basis, being 0.02-0.25; an ink for inkjet recording that employs the coloring composition; an inkjet recording method that employs the ink for inkjet recording; an inkjet printer cartridge; and inkjet-recorded matter.

Description

Coloring composition, ink for ink jet recording, ink jet recording method, ink jet printer cartridge, and ink jet recorded matter

The present invention relates to a colored composition, an ink for ink jet recording, an ink jet recording method, an ink jet printer cartridge, and an ink jet recorded matter.

The ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording.
Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. There are a method for ejecting droplets, a method for generating bubbles in ink by discharging heat, a method for discharging droplets, a method using ultrasonic waves, and a method for attracting and discharging droplets by electrostatic force. As the ink for ink jet recording, water-based ink, oil-based ink, or solid (melted type) ink is used.

Patent Documents 1 and 2 disclose a coloring composition having a disazo dye and a phthalocyanine dye, and describe that an image having excellent fastness can be provided.

Japanese Unexamined Patent Publication No. 2004-225004 Japanese Unexamined Patent Publication No. 2005-146244

The colored compositions described in Patent Documents 1 and 2 exhibit excellent performance as described above, but there is room for further performance improvement regarding the suppression of bronze gloss generation. When bronze gloss occurs, the color balance of the entire image becomes non-uniform and the image quality deteriorates, making it difficult to obtain a good image. Moreover, as a coloring composition, it is calculated | required that light resistance and ozone resistance are favorable with suppression of bronze glossiness.

An object of the present invention is to provide a coloring composition that can suppress the occurrence of bronze gloss and is excellent in light resistance and ozone resistance. Another object of the present invention is to provide an ink for ink jet recording containing the coloring composition, an ink jet recording method using the ink for ink jet recording, an ink cartridge, and an ink jet recorded matter.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above object can be achieved by the coloring composition shown below. The mechanism of action is unknown, but is presumed as follows.
First, the coloring composition of the present invention contains a compound represented by the general formula (Q) (disazo dye) and a compound represented by the general formula (1) (phthalocyanine dye) at a specific mass ratio. . As a result, the association of the dyes was controlled, and it was considered that the occurrence of bronze gloss could be suppressed while maintaining excellent ozone gas fastness.
That is, the above problem can be solved by the following means.

[1]
It contains a compound represented by the following general formula (Q) and a compound represented by the following general formula (1), and is represented by the general formula (1) with respect to the content of the compound represented by the general formula (Q). A coloring composition having a content ratio of 0.02 to 0.25 on a mass basis.
General formula (Q)

In general formula (Q), A represents an aryl group or a heterocyclic group. G represents a nitrogen atom or —CZ═. When G represents —CZ═, Z represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. R ₁₀₁ , R ₁₀₂ and R ₁₀₇ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl Group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, Acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, An alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfo group is represented. R ₁₀₃ to R ₁₀₆ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group Or a sulfamoyl group.
However, R ₁₀₃ and R ₁₀₄ are not both hydrogen atoms. In addition, any of A and R ₁₀₁ to R ₁₀₇ may have a substituent.
However, the compound represented by the general formula (Q) has at least one ionic hydrophilic group in the molecule.

In general formula (1),
R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, hetero group Ring group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonyl Amino group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imido group, hetero Ring thio group, phosphoryl group, a It represents a group or an ionic hydrophilic group. These groups may further have a substituent.
Z ₁ , Z ₂ , Z ₃ and Z ₄ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted Alternatively, it represents an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent.
l, m, n, p, q ₁ , q ₂ , q ₃ and q ₄ each independently represent 1 or 2;
M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
[2]
The colored composition according to [1], wherein the compound represented by the general formula (Q) is a compound represented by the following general formula (3-1) or the following general formula (3-2).

In general formula (3-1), R ₁₁₁ , R ₁₁₂ , R ₁₁₃ and R ₁₁₄ each independently represent a hydrogen atom or a substituent. X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a hydrogen atom or a substituent. M represents a hydrogen atom or a counter cation each independently. G represents a nitrogen atom or —CZ═. When G represents —CZ═, Z represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.

In general formula (3-2), R ₂₀₃ represents a substituent. X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a hydrogen atom or a substituent. M represents a hydrogen atom or a counter cation each independently. G represents a nitrogen atom or —CZ═. When G represents —CZ═, Z represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.
[3]
The coloring composition according to [2], wherein the compound represented by the general formula (Q) is a compound represented by the general formula (3-2).
[4]
In the general formula (1), Z ₁ , Z ₂ , Z ₃ and Z ₄ are each independently groups represented by the following general formula (3) or the following general formula (4) [1] to [3] The coloring composition of any one of these.

In general formulas (3) and (4), L represents an alkylene group having 1 to 12 carbon atoms, M ³ represents a hydrogen atom or a counter cation, and R ₂₀ represents an alkyl group having 1 to 6 carbon atoms. * Represents a binding site.
[5]
The colored composition according to any one of [1] to [4], wherein the general formula (1) is at least one of a compound represented by the following (1A) and a compound represented by (1B).

[6]
[1] to [5] The content of the compound represented by the general formula (1) is 0.05 to 0.15 in mass ratio with respect to the content of the compound represented by the general formula (Q). ] The coloring composition of any one of these.
[7]
The colored composition according to any one of [1] to [6], wherein the phthalocyanine dye contained in the colored composition is only the compound represented by the general formula (1).
[8]
[1] An ink for ink-jet recording using the colored composition according to any one of [7].
[9]
The inkjet recording method using the ink for inkjet recording as described in [8].
[10]
An ink jet printer cartridge filled with the ink for ink jet recording according to [8].
[11]
An ink jet recorded matter in which a colored image is formed on a recording material using the ink for ink jet recording described in [8].

According to the present invention, it is possible to provide a coloring composition that can suppress the occurrence of bronze gloss and is excellent in light resistance and ozone resistance. In addition, an inkjet recording ink containing the coloring composition, an inkjet recording method using the inkjet recording ink, an ink cartridge, and an inkjet recorded product can be provided.

The present invention is described in detail below.
First, the substituent group A, the substituent group B, and the substituent group C in the present invention are defined.

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

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

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

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

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

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

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

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

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

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

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

The heterocyclic oxy group is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, such as a 1-phenyltetrazol-5-oxy group and a 2-tetrahydropyranyloxy group.

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

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

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

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

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

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

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

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

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

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

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

The arylthio group is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as a phenylthio group, a p-chlorophenylthio group, and an m-methoxyphenylthio group.

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

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

The alkyl or arylsulfinyl group is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group or an ethylsulfinyl group. , Phenylsulfinyl group, p-methylphenylsulfinyl group and the like.

The alkyl or arylsulfonyl group is preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as a methylsulfonyl group or an ethylsulfonyl group. , Phenylsulfonyl group, p-methylphenylsulfonyl group and the like.

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

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

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

The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, or an N, N-di-n-octyl group. A carbamoyl group, an N- (methylsulfonyl) carbamoyl group, and the like can be given.

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

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

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

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

The phosphinyloxy group is preferably a substituted or unsubstituted phosphinyloxy group having 0 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group.

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

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

Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group. Particularly preferred are a sulfo group and a carboxyl group. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. Examples of counter cations that form a salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic. Cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) are included, and lithium salt, sodium salt, potassium salt, and ammonium salt are preferable, and lithium salt, sodium salt, or lithium salt is a main component. The mixed salt is more preferable, and a lithium salt or a mixed salt containing a lithium salt as a main component is most preferable.

(Substituent group B)
Straight or branched alkyl group having 1 to 12 carbon atoms, straight or branched aralkyl group having 7 to 18 carbon atoms, straight or branched alkenyl group having 2 to 12 carbon atoms, straight chain having 2 to 12 carbon atoms Or a branched alkynyl group, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl) , T-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), halogen atom (eg, chlorine atom, bromine atom), aryl group (eg, phenyl, 4-t- Butylphenyl, 2,4-di-t-amylphenyl), heterocyclic groups (eg imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thiol) Nyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group (eg methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy), aryloxy Groups (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenyloxy, acylamino groups (for example, acetamide, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide), alkylamino groups (eg methylamino, butylamino, diethylamino, methylbutylamino), arylamino groups (eg phenylamino, 2-chloroanilino) Ureido groups (eg phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino groups (eg N, N-dipropylsulfamoylamino), alkylthio groups (eg methylthio, octylthio, 2- Phenoxyethylthio), arylthio groups (eg phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino groups (eg methoxycarbonylamino), alkylsulfonylamino groups and aryls Sulfonylamino group (eg, methylsulfonylamino, phenylsulfonylamino, p-toluenesulfonylamino), carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl group (eg For example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), alkylsulfonyl group (for example, methylsulfonyl, octylsulfonyl), arylsulfonyl group (for example, phenylsulfonyl, p- Toluenesulfonyl), alkyloxycarbonyl groups (eg methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy groups (eg 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo groups (eg phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenyl) Rucarbamoyloxy), silyloxy groups (eg trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino groups (eg phenoxycarbonylamino), imide groups (eg N-succinimide, N-phthalimide), heterocyclic thio groups ( For example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), a sulfinyl group (for example, 3-phenoxypropylsulfinyl), a phosphonyl group (for example, , Phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl groups (eg, phenoxycarbonyl), acyl groups (eg, acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (caps Bokishiru group, a sulfo group). These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group B described above.

(Substituent group C)
Halogen atom (for example, chlorine atom, bromine atom); linear or branched alkyl group having 1 to 12 carbon atoms, aralkyl group having 7 to 18 carbon atoms, alkenyl group having 2 to 12 carbon atoms, 2 to 2 carbon atoms 12 linear or branched alkynyl groups, a cycloalkyl group having 3 to 12 carbon atoms which may have a side chain, a cycloalkenyl group having 3 to 12 carbon atoms which may have a side chain ( Specific examples of the above group include, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl): aryl group (for example, phenyl, 4-t- Butylphenyl, 2,4-di-t-amylphenyl); heterocyclic groups (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyridyl) An alkyloxy group (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy); an aryloxy group (eg, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3 -Nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl); acylamino groups (eg acetamide, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide); alkylamino groups (eg Anilino group (eg, phenylamino, 2-chloroanilino; ureido group (eg, phenylureido, methylureido, N, N-dibutylureido)); Moylamino group (eg, N, N-dipropylsulfamoylamino); alkylthio group (eg, methylthio, octylthio, 2-phenoxyethylthio); arylthio group (eg, phenylthio, 2-butoxy-5-t-octylphenylthio) , 2-carboxyphenylthio); alkyloxycarbonylamino groups (eg methoxycarbonylamino); sulfonamido groups (eg methanesulfonamide, benzenesulfonamide, p-toluenesulfonamido, octadecane); carbamoyl groups (eg N -Ethylcarbamoyl, N, N-dibutylcarbamoyl); sulfamoyl groups (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-diethylsulfamoyl); sulfonyl groups (eg, Tansulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl); alkyloxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl); heterocyclic oxy group (eg, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy) An azo group (eg, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo); an acyloxy group (eg, acetoxy); a carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy); silyloxy groups (for example, trimethylsilyloxy, dibutylmethylsilyloxy); aryloxycarbonylamino groups (for example, phenoxycarbonyl) Amino); imide group (eg, N-succinimide, N-phthalimi); heterocyclic thio group (eg, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio) , 2-pyridylthio); sulfinyl group (eg 3-phenoxypropylsulfinyl); phosphonyl group (eg phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl); aryloxycarbonyl group (eg phenoxycarbonyl); acyl group (For example, acetyl, 3-phenylpropanoyl, benzoyl); ionic hydrophilic groups (for example, carboxyl group, sulfo group, and quaternary ammonium group); other cyano group, hydroxyl group, nitro group, amino group.

[Compound represented by formula (Q)]
The compound represented by the following general formula (Q) will be described.
General formula (Q)

In the general formula (Q), when G represents —CZ═, Z represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.
As Z, acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, aryl Sulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy group, halogenated aryloxy group, halogenated alkylamino group, A halogenated alkylthio group, an aryl group substituted with another electron-withdrawing group having a σp value of 0.20 or more, a nitro group, a heterocyclic group (preferably a pyridyl group), a halogen atom, or a selenocyanate group. . Z is preferably a cyano group, a pyridyl group, a methylsulfonyl group, a phenylsulfonyl group, a methoxycarbonyl group, a carbamoyl group or a nitro group, more preferably a cyano group.

In general formula (Q), R ₁₀₁ , R ₁₀₂ and R ₁₀₇ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group or a carbamoyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryl Oxycarbonyloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonyla Mino group, nitro group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfinyl group, arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group, or sulfo group To express. These groups may have a substituent, and examples of the substituent include a substituent selected from the above substituent group A. Halogen, alkyl group, cyano group, hydroxyl group, alkoxy group, ionic hydrophilic Sexual groups are preferred.
When R ₁₀₁ , R ₁₀₂ or R ₁₀₇ represents a halogen atom, the halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom.

When R ₁₀₁ , R ₁₀₂ or R ₁₀₇ represents an alkyl group, an alkenyl group or an alkynyl group, it may be linear, branched or cyclic. The alkyl group, alkenyl group or alkynyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclohexyl group. Groups are preferred. As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferable, an alkenyl group having 2 to 6 carbon atoms is more preferable, and specifically, a vinyl group or an allyl group is preferable. Alkynyl is more preferably an alkynyl group having 2 to 4 carbon atoms.

When R ₁₀₁ , R ₁₀₂ or R ₁₀₇ represents an aryl group, the aryl group is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, and further a phenyl group or a naphthyl group. Preferred is a phenyl group.
In the case where R ₁₀₁ , R ₁₀₂ or R ₁₀₇ represents a heterocyclic group, the heterocyclic group is preferably an aromatic heterocyclic group, and a 5-membered or 6-membered aromatic heterocyclic ring having a nitrogen atom, a sulfur atom or an oxygen atom. Groups are more preferred. As the heterocyclic group, if the substitution position is not limited, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine A ring etc. are mentioned preferably. The 5-membered or 6-membered aromatic heterocyclic group may further have a condensed ring structure, and for example, a benzothiazole ring is preferable.

Preferred range of each group when R ₁₀₁ , R ₁₀₂ or R ₁₀₇ represents an alkoxycarbonyl group, alkoxy group, alkoxycarbonyloxy group, alkoxycarbonylamino group, alkylsulfonylamino group, alkylthio group, alkylsulfonyl group or alkylsulfinyl group As for, the part of the alkyl group contained in each group becomes a preferable range when R ₁₀₁ , R ₁₀₂ or R ₁₀₇ represents an alkyl group.
Each of when R ₁₀₁ , R ₁₀₂ or R ₁₀₇ represents an aryloxycarbonyl group, aryloxy group, aryloxycarbonyloxy group, aryloxycarbonylamino group, arylthio group, arylsulfonylamino group, arylsulfonyl group or arylsulfinyl group The preferred range of the group is that the portion of the aryl group contained in each group is a preferred range when R ₁₀₁ , R ₁₀₂ or R ₁₀₇ represents an aryl group.
As a preferred range of each group when R ₁₀₁ , R ₁₀₂ or R ₁₀₇ represents a heterocyclic oxycarbonyl group, a heterocyclic oxy group, a heterocyclic sulfonylamino group, a heterocyclic thio group, a heterocyclic sulfonyl group or a heterocyclic sulfinyl group Is a preferable range in the case where the above-mentioned R ₁₀₁ , R ₁₀₂ or R ₁₀₇ represents a heterocyclic group.

As a preferred range of each group when R ₁₀₁ , R ₁₀₂ or R ₁₀₇ represents an acyl group, an acyloxy group or an acylamino group, the alkyl group or aryl group part contained in each group is the above R ₁₀₁ , R ₁₀₂ or R _This is a preferable range when ₁₀₇ is an alkyl group or an aryl group.

From the viewpoint of ozone gas fastness, at least one of R ₁₀₁ and R ₁₀₂ is a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, or an alkylsulfonyl group. And a cyano group is more preferable.

In general formula (Q), R ₁₀₃ to R ₁₀₆ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, An alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group is represented. These groups may have a substituent, and examples of the substituent include a substituent selected from the above substituent group A, a halogen atom (preferably a chlorine atom), an ionic hydrophilic group, and an alkyl group. , A hydroxyl group and an alkoxy group are preferable.
When R ₁₀₃ to R ₁₀₆ represent an alkyl group, an alkenyl group or an alkynyl group, they may be linear, branched or cyclic. The alkyl group, alkenyl group or alkynyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms. Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, or A 2-ethylhexyl group is preferable, a methyl group, an ethyl group, or an n-propyl group is more preferable, and an ethyl group is still more preferable. As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferable, an alkenyl group having 2 to 6 carbon atoms is more preferable, and specifically, a vinyl group or an allyl group is preferable. Alkynyl is more preferably an alkynyl group having 2 to 4 carbon atoms.
When R ₁₀₃ to R ₁₀₆ represent an aryl group, the aryl group includes an aryl group having 6 to 20 carbon atoms, preferably an aryl group having 6 to 12 carbon atoms, specifically, a phenyl group or a naphthyl group. Preferably, a phenyl group is more preferable.
Examples of the heterocyclic group in the case where R ₁₀₃ to R ₁₀₆ represent a heterocyclic group include the same as those in the case where R ₁₀₂ is a heterocyclic group.
_Examples of the acyl group when R ₁₀₃ to R ₁₀₆ represent an acyl group include an acyl group having 2 to 10 carbon atoms, preferably an acetyl group, a propionyl group, and a butyryl group, and more preferably an acetyl group.
A preferred range of each group when R ₁₀₃ to R ₁₀₆ represent an alkoxycarbonyl group or an alkylsulfonyl group is a preferred range when the portion of the alkyl group contained in each group is the above-mentioned R ₁₀₃ to R ₁₀₆ is an alkyl group. It has become.
A preferred range of each group when R ₁₀₃ to R ₁₀₆ represent an aryloxycarbonyl group or an arylsulfonyl group is preferable when the portion of the aryl group contained in each group is the above R ₁₀₃ to R ₁₀₆ is an aryl group. It became a range.
From the viewpoints of solubility in water and fastness to ozone gas, R ₁₀₃ to R ₁₀₆ are each independently preferably a hydrogen atom, an alkyl group, an aryl group, or an acyl group, more preferably a hydrogen atom, an alkyl group, or an aryl group, A hydrogen atom or an aryl group is more preferable.
It is particularly preferred that one of R ₁₀₃ and R ₁₀₄ represents a hydrogen atom and the other represents an alkyl group or an aryl group, and one of R ₁₀₅ and R ₁₀₆ represents a hydrogen atom and the other represents an alkyl group or an aryl group.
Most preferably, one of R ₁₀₃ and R ₁₀₄ represents a hydrogen atom and the other represents an aryl group, and one of R ₁₀₅ and R ₁₀₆ represents a hydrogen atom and the other represents an aryl group.
When R ₁₀₃ to R ₁₀₆ represent an alkyl group or an aryl group, it is particularly preferable to have an ionic hydrophilic group. The ionic hydrophilic group is preferably a sulfo group or a carboxyl group, more preferably a sulfo group, and a sulfo group. More preferred is a lithium salt (—SO ₃ Li), a sodium salt of a sulfo group (—SO ₃ Na), or a potassium salt of a sulfo group (—SO ₃ K), and a lithium salt of a sulfo group (—SO ₃ Li) Particularly preferred.

In general formula (Q), A represents an aryl group or a heterocyclic group.
The aryl group when A represents an aryl group includes an aryl group having 6 to 20 carbon atoms, preferably an aryl group having 6 to 12 carbon atoms, and specifically, a phenyl group or a naphthyl group is preferable.
When A represents a heterocyclic group, the heterocyclic group is preferably an aromatic heterocyclic group, more preferably a 5- or 6-membered aromatic heterocyclic group having a nitrogen atom, a sulfur atom or an oxygen atom, and a nitrogen atom. Or the 5-membered or 6-membered aromatic heterocyclic group which has a sulfur atom is still more preferable. Examples of the heterocyclic group include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring. Preferably mentioned. The 5-membered or 6-membered aromatic heterocyclic group may further have a condensed ring structure, and for example, a benzothiazole ring is preferable.
From the viewpoint of storage stability in water, A preferably represents an aryl group.

The aryl group or heterocyclic group represented by A may have a substituent.
Examples of the substituent that A may have include a substituent selected from the above-mentioned substituent group A, and an ionic hydrophilic group or an electron-withdrawing group having a Hammett's σp value of 0.3 or more is preferable. , A halogen atom (preferably a chlorine atom), a cyano group, a nitro group, —SO ₃ M or —CO ₂ M (M represents a hydrogen atom or a counter cation) is more preferable. Examples of the counter cation include ammonium ion, alkali metal ion (for example, lithium ion, sodium ion, potassium ion) and organic cation (for example, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). M preferably represents a hydrogen atom or a counter cation, more preferably represents an alkali metal ion or an ammonium ion, further preferably represents an alkali metal ion, and particularly preferably represents a lithium ion, a potassium ion or a sodium ion. Most preferably, it represents lithium ions.
Specific examples of electron withdrawing groups having Hammett's σp value of 0.3 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group Diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, Halogenated alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, aryl group substituted with other electron-withdrawing group having σp value of 0.3 or more, nitro group, heterocyclic group , Halogen atom, azo group, or selenium Examples include a cyanate group. A cyano group, a methylsulfonyl group, a phenylsulfonyl group, a methoxycarbonyl group, a carbamoyl group, and a nitro group are preferable, and a cyano group, a methylsulfonyl group, a sulfamoyl group, and a nitro group are more preferable. If the σp value is an electron withdrawing group in this range, the hue of the azo compound can be adjusted, light fastness and ozone gas fastness can be improved, and an effect can be obtained in that it is used as a water-soluble dye for inkjet recording black ink. Can do. The upper limit of Hammett's substituent constant σp value is preferably an electron withdrawing group of 1.0 or less.

Preferred examples of A are shown below, but are not limited thereto. In the following specific examples, * represents a bonding position. M represents a hydrogen atom or a counter cation.

From the viewpoint of ozone gas fastness, R ₁₀₇ is preferably an alkyl group or an aryl group, more preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.

From the viewpoint of light fastness, R ₁₀₇ is preferably a group represented by the following general formula (7-1).
Formula (7-1)

In the general formula (7-1), R ₇₁ represents a substituent. * Represents a bonding position.

R ₇₁ in the general formula (7-1) represents a substituent. Examples of the substituent represented by R ₇₁ include a substituent selected from the above substituent group B, and from the viewpoint of light fastness, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group Are preferably a heterocyclic group, or a substituted or unsubstituted amino group, more preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted amino group. The alkyl group is preferably an alkyl group having 1 to 7 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, a methyl group, an ethyl group, or n-propyl. Group, isopropyl group, t-butyl group and 2-ethylpentyl group are more preferred, methyl group, ethyl group and n-propyl group are more preferred, and methyl group and ethyl group are particularly preferred. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 8 carbon atoms, still more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. As the heterocyclic group, a thiophene ring and a pyridine ring are preferable. The amino group is preferably an amino group substituted with a substituted or unsubstituted alkyl group, an amino group substituted with a substituted or unsubstituted aryl group, and further an alkyl group having 1 to 6 carbon atoms substituted with a hydroxyl group. A substituted amino group and an amino group substituted with a phenyl group substituted with a hydroxyl group are more preferred.
When the alkyl group, aryl group, heterocyclic group, or amino group has a substituent, examples of the substituent include a monovalent substituent, such as an ionic hydrophilic group, an arylamino group, an alkylamino group, and a halogen atom. An ionic hydrophilic group is more preferable, and —SO ₃ M or —CO ₂ M (M represents a hydrogen atom or a counter cation, and specific examples and preferable ranges thereof are the same as those described above).
R ₇₁ is particularly preferably an alkyl group having —CO ₂ M as a substituent, or a phenyl group having —CO ₂ M as a substituent at least in the ortho position.
Preferred specific examples of R ₇₁ are shown below, but are not limited thereto. In the following specific examples, * represents a bonding position. M represents a hydrogen atom or a counter cation.

From the viewpoint of light fastness, R ₁₀₇ is preferably a group represented by the following general formula (7-2).
Formula (7-2)

In general formula (7-2), R ₇₂ represents a substituent. * Represents a bonding position.

R ₇₂ in the general formula (7-2) has the same meaning as R ₇₁ in the general formula (7-1), and specific examples and preferred ranges thereof are also the same.

From the viewpoint of light fastness, R ₁₀₇ is preferably a group represented by the following general formula (7-3).
General formula (7-3)

In general formula (7-3), R ₇₃ represents a substituent. * Represents a bonding position.

R ₇₃ in the general formula (7-3) represents a substituent. Examples of the substituent represented by R ₇₃ include a substituent selected from the above substituent group B, and include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or An unsubstituted alkylsulfonyl group or a substituted or unsubstituted arylsulfonyl group is preferred, and from the viewpoint of light fastness, a substituted or unsubstituted heterocyclic group, or an alkyl or arylsulfonyl group is more preferred, and a substituted or unsubstituted arylsulfonyl group is preferred. Heterocyclic groups are more preferred. As the heterocyclic group, a triazine ring group is preferable.
When the alkyl group, aryl group, heterocyclic group, alkylsulfonyl group, or arylsulfonyl group has a substituent, examples of the substituent include a monovalent substituent, an ionic hydrophilic group, a hydroxyl group, and an amino group. An arylamino group, an alkylamino group, an alkyl group, and an alkylthio group are preferable, and these may be further substituted with a hydroxyl group or an ionic hydrophilic group. The ionic hydrophilic group is preferably —SO ₃ M or —CO ₂ M (M represents a hydrogen atom or a counter cation, and specific examples and preferred ranges are the same as those described above).
Preferred specific examples of R ₇₃ are shown below, but are not limited thereto. In the following specific examples, * represents a bonding position. M represents a hydrogen atom or a counter cation.

From the viewpoint of light fastness, R ₁₀₇ is preferably a group represented by the following general formula (7-4).
General formula (7-4)

In the general formula (7-4), R ₇₄ represents a substituent. * Represents a bonding position.

R ₇₄ in the general formula (7-4) has the same meaning as R ₇₃ in the general formula (7-3), and specific examples and preferred ranges thereof are also the same.

From the viewpoint of light fastness, R ₁₀₇ is preferably a group represented by the following general formula (7-5).
General formula (7-5)

In the general formula (7-5), R ₇₅ represents a substituent. * Represents a bonding position.

R ₇₅ in the general formula (7-5) represents a substituent. The substituent R ₇₅ represents, and a substituted group selected from the substituent group B, and the viewpoint of light fastness, a nitro group, a hydroxyl group, a halogen atom, an alkyl group, an ionic hydrophilic group, an amino group A substituted or unsubstituted alkoxy group or an alkylthio group, preferably a nitro group, a hydroxyl group, a chlorine atom, a methyl group, an ionic hydrophilic group, an amino group, an ionic hydrophilic group, or an unsubstituted carbon number 1-3 alkoxy groups and methylthio groups are preferred. The ionic hydrophilic group is preferably —SO ₃ M or —CO ₂ M (M represents a hydrogen atom or a counter cation, and specific examples and preferred ranges are the same as those described above).
Preferred examples of R ₇₅ include a nitro group, a hydroxyl group, a chlorine atom, a methyl group, —SO ₃ Na, —SO ₃ Li, —SO ₃ K, an amino group, a methoxy group, and a propyloxy group substituted with a sulfo group. , A methylthio group.

From the viewpoint of light fastness, R ₁₀₇ is preferably a group represented by the following general formula (7-6).
General formula (7-6)

In the general formula (7-6), R ₇₆ represents a substituent. * Represents a bonding position.

R ₇₆ in the general formula (7-6) has the same meaning as R ₇₅ in the general formula (7-5), and specific examples and preferred ranges thereof are also the same.

From the viewpoint of light fastness, R ₁₀₇ is preferably a naphthyl group. When R ₁₀₇ is a naphthyl group, it is more preferably a 2-naphthyl group or a 3-naphthyl group, and further preferably a 2-naphthyl group. That is, R ₁₀₇ is preferably represented by the following formula (7-7).
Formula (7-7)

In formula (7-7), * represents a bonding position.

The compound represented by the general formula (1) has at least one ionic hydrophilic group in the molecule, and preferably has three or more ionic hydrophilic groups, more preferably an ionic hydrophilic group. 3 to 6, more preferably 4 to 5 ionic hydrophilic groups. As a result, the water-solubility and aqueous solution storage stability of the compound represented by the general formula (1) are improved, satisfying the required performance as a water-soluble dye for inkjet recording black ink at a high level, and further used as an inkjet recording ink. There is an effect that it is possible to further improve the image quality of the ink-jet printed material.

An aqueous solution and a water-soluble ink composition using the compound represented by the general formula (1) as a coloring matter (coloring agent) include a composition containing a coloring material such as a dye or a pigment and a dispersant (such as a solvent) thereof. Meaning that it can be suitably used for image formation.

In the compound represented by the general formula (1), the maximum absorption wavelength (λ _max ) of an absorption spectrum measured using water as a solvent is preferably 550 nm to 700 nm, more preferably 550 nm to 650 nm, and further 570 nm to 650 nm. It is particularly preferred that

The compound represented by the general formula (Q) is preferably a compound represented by the following general formula (3-1).

G in the general formula (3-1) has the same meaning as G in the general formula (Q), and specific examples and preferred ranges thereof are also the same.

M represents a hydrogen atom or a counter cation. Examples of the counter cation include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic cation (eg, tetramethylammonium ion, tetramethylguanidinium). Ion, tetramethylphosphonium). As counter cations other than lithium ions, potassium ions and sodium ions are preferable, and sodium ions are more preferable.

The salt formed is preferably a lithium salt, a sodium salt, a potassium salt, or an ammonium salt, more preferably a lithium salt or a mixed salt mainly composed of a lithium salt, and most preferably a lithium salt.

_Examples of the substituent represented by R ₁₁₁ , R ₁₁₂ , R ₁₁₃ , and R _{114 in the} general formula (3-1) can include, independently of each other, substituent group B, a substituted or unsubstituted alkyl group, It is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and an alkyl group substituted with an ionic hydrophilic group (an alkyl group having 1 to 10 carbon atoms includes a methyl group, an ethyl group, Group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, or t-butyl group is preferable, and methyl group, ethyl group, or n-propyl group is more preferable. n-propyl group is more preferred) or an aryl group substituted with an ionic hydrophilic group (an aryl group having 6 to 20 carbon atoms is preferred, and a phenyl group and a naphthyl group are preferred, and a phenyl group is more preferred). It is more preferable.

In the general formula (3-1), X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a hydrogen atom or a monovalent substituent. As the substituent when X ₁ , X ₂ , X ₃ , X ₄ and X ₅ represent a substituent, the substituent group A can be exemplified.
X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each independently a hydrogen atom, an ionic hydrophilic group, a cyano group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a nitro group. Preferably a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a hydrogen atom, an ionic hydrophilic group, a cyano group, a methanesulfonyl group, a phenylsulfonyl group , A nitro group, a methoxycarbonyl group, and a carbamoyl group, more preferably a hydrogen atom, an ionic hydrophilic group, or a cyano group.

In general formula (3-1), X ₂ and X ₄ are preferably each independently a hydrogen atom or an ionic hydrophilic group. X ₁ , X ₃ , and X ₅ are each independently preferably either a hydrogen atom or substituent group A, and at least one of X ₁ , X _3, and X ₅ has a Hammett σp value It preferably represents an electron withdrawing group of 0.3 or more. The upper limit of Hammett's substituent constant σp value is an electron withdrawing group of 1.0 or less.
If at least one of X ₁ , X ₃ , and X ₅ is an electron-withdrawing group having a σp value in this range, the hue of the azo compound can be adjusted, light fastness, and ozone gas fastness can be improved. An effect can be acquired by using as a water-soluble dye for black ink.

Specific examples of the electron withdrawing group having a σp value of 0.3 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diaryl Phosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated Alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, aryl group substituted with other electron-withdrawing group having σp value of 0.3 or more, nitro group, heterocyclic group, halogen Atoms, azo groups, or selenocyanes Group. A cyano group, a methylsulfonyl group, a phenylsulfonyl group, a methoxycarbonyl group, a carbamoyl group, and a nitro group are preferable, and a cyano group, a methylsulfonyl group, and a nitro group are more preferable.

From the viewpoints of hue, coloring power, and water-soluble storage stability, among the above, at least one of X ₂ and X ₄ is preferably an ionic hydrophilic group, and X _1, X ₃ , and X ₅ Is preferably a hydrogen atom or an electron-withdrawing group having a Hammett's σp value of 0.3 or more, X _1, X ₃ and X ₅ are hydrogen atoms, and X ₂ and X ₄ are ionic More preferably, it is a hydrophilic group. As the ionic hydrophilic group, —SO ₃ M or —CO ₂ M (M represents a hydrogen atom or a monovalent counter cation) is preferable, —CO ₂ M is more preferable, and —CO ₂ Li is particularly preferable. .

The compound represented by the general formula (Q) or (3-1) is preferably a compound represented by the following general formula (4-1).

In general formula (4-1), R ₁₁₁ , R ₁₁₂ , R ₁₁₃ and R ₁₁₄ each independently represent a hydrogen atom or a substituent. X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a hydrogen atom or a substituent. M represents each independently a hydrogen atom or a counter cation.

R ₁₁₁ , R ₁₁₂ , R ₁₁₃ , R ₁₁₄ , X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and M in the general formula (4-1) are each independently the above general formula (3-1) R ₁₁₁ , R ₁₁₂ , R ₁₁₃ , R ₁₁₄ , X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and M are the same, and specific examples and preferred ranges are also the same.

The reason why this structure is preferable is that the ring containing G in the general formula (Q) is not a nitrogen-containing 5-membered hetero ring but a thiophene ring, so that the image fastness of the printed matter is preserved (for example, ozone gas fastness, Light fastness), discoloration (color change), and fading (decoloring) can be improved at a higher level, and the suitability as a gray to black ink is improved, which requires a small change in discoloration.

The compound represented by the general formula (Q), (3-1) or (4-1) is preferably a compound represented by the following general formula (5-1).

In general formula (5-1), each M independently represents a hydrogen atom or a counter cation, and when M represents a counter cation, it is preferably a lithium ion, a sodium ion, a potassium ion, or an ammonium ion.

The compound represented by the general formula (Q) is preferably a compound represented by the following general formula (3-2).

In general formula (3-2), R ₂₀₃ represents a substituent. X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a hydrogen atom or a substituent. M represents a hydrogen atom or a counter cation. G represents a nitrogen atom or —CZ═. When G represents —CZ═, Z represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.

_Examples of the substituent represented by R ₂₀₃ in the general formula (3-2) include the substituent group B, and include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted hetero group. It is preferably a cyclic group, more preferably an alkyl group substituted with an ionic hydrophilic group, or an aryl group, and particularly preferably an alkyl group substituted with an ionic hydrophilic group.
In the alkyl group substituted with the ionic hydrophilic group, the alkyl group is preferably a methyl group, an ethyl group, or an n-propyl group, and particularly preferably an ethyl group. As the ionic hydrophilic group, —SO ₃ M or —CO ₂ M (M represents a hydrogen atom or a counter cation) is preferable, —CO ₂ M is more preferable, and —CO ₂ Li is particularly preferable.

M in the general formula (3-2) has the same meaning as M in the general formula (3-1), and specific examples and preferred ranges thereof are also the same.

In the general formula (3-2), X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a hydrogen atom or a substituent. X _1, _X _2, examples of the substituent when X 3, _{X 4} and _{X 5} represents a substituent can be exemplified substituent group A.
X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each independently a hydrogen atom, an ionic hydrophilic group, a cyano group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a nitro group. Preferably a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a hydrogen atom, an ionic hydrophilic group, a cyano group, a methanesulfonyl group, a phenylsulfonyl group , A nitro group, a methoxycarbonyl group, and a carbamoyl group, a hydrogen atom, an ionic hydrophilic group (-SO ₃ M or —CO ₂ M is preferable, —CO ₂ M is more preferable, —CO ₂ Li Is particularly preferred), or a cyano group is particularly preferred.

In general formula (3-2), X ₂ and X ₄ are preferably each independently a hydrogen atom or an ionic hydrophilic group. X ₁ , X ₃ , and X ₅ are preferably each independently a hydrogen atom or substituent group A, and at least one of X ₁ , X _3, and X ₅ has a Hammett's σp value of 0 It is preferable to represent 3 or more electron withdrawing groups. The upper limit of Hammett's substituent constant σp value is an electron withdrawing group of 1.0 or less.
If at least one of X ₁ , X ₃ , and X ₅ is an electron-withdrawing group having a σp value in this range, the hue of the azo compound can be adjusted, light fastness, and ozone gas fastness can be improved. An effect can be acquired by using as a water-soluble dye for black ink.

From the viewpoints of hue, coloring power, and water-soluble storage stability, among the above, at least one of X ₂ and X ₄ is preferably an ionic hydrophilic group, and X _1, X ₃ , and X ₅ Is preferably a hydrogen atom or an electron-withdrawing group having a Hammett's σp value of 0.3 or more, X ₁ , X ₃ , and X ₅ are hydrogen atoms, and X ₂ and X ₄ are ionic More preferably, it is a hydrophilic group. As the ionic hydrophilic group, —SO ₃ M or —CO ₂ M (M represents a hydrogen atom or a counter cation) is preferable, —CO ₂ M is more preferable, and —CO ₂ Li is particularly preferable.

The compound represented by the general formula (Q) or (3-2) is preferably a compound represented by the following general formula (4-2).

In general formula (4-2), R ₂₀₃ represents a substituent. X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ each independently represent a hydrogen atom or a substituent. M represents a hydrogen atom or a counter cation each independently.

R ₂₀₃ , X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and M in the general formula (4-2) are respectively R ₂₀₃ , X ₁ , X ₂ , X in the general formula (3-2). ₃ , X ₄ , X ₅ and M have the same meaning, and specific examples and preferred ranges are also the same.

The compound represented by the general formula (Q), (3-2) or (4-2) is preferably a compound represented by the following general formula (5-2).

M independently represents a hydrogen atom or a counter cation, and when M represents a counter cation, it preferably represents a lithium ion, a sodium ion, a potassium ion, or an ammonium ion.

M in the general formula (5-2) has the same meaning as M in the general formula (3-2), and specific examples and preferred ranges are also the same.

The compounds of the general formula (Q), (3-1), (3-2), (4-1), (4-2), (5-1), or (5-2) Although a specific example is shown, this invention is not limited to these. In the following structural formula, M represents a hydrogen atom or a counter cation, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

(Synthesis method)
The compound represented by the general formula (Q) can be synthesized by a coupling reaction between a diazo component and a coupler, and these are described in JP-A-2003-306623, JP-A-2005-139427, and the like. This is described in Japanese Unexamined Patent Publication No. 2012-177073.

[Phthalocyanine dye represented by formula (1)]
Next, the phthalocyanine dye represented by the general formula (1) will be described in detail.

In general formula (1),
R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl 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, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group , Heterocyclic thio group, phosphoryl Group, an acyl group or an ionic hydrophilic group. These groups may further have a substituent.
Z ₁ , Z ₂ , Z ₃ and Z ₄ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent.
l, m, n, p, q ₁ , q ₂ , q ₃ and q ₄ each independently represent 1 or 2.
M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.

In general formula (1), R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or an alkenyl. Group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl 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, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryl Oxycarbonylamino group, imide group, heterocycle It represents an OH group, a phosphoryl group, an acyl group or an ionic hydrophilic group. These groups may further have a substituent. Examples of the substituent include the substituents described in the above substituent group C.

Examples of the halogen atom represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ include a fluorine atom, a chlorine atom and a bromine atom.

The alkyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkyl group having a substituent and an unsubstituted alkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom and an ionic hydrophilic group. Examples of the alkyl group include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.

The cycloalkyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The alkenyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkenyl group having a substituent and an unsubstituted alkenyl group. As the alkenyl group, an alkenyl group having 2 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include a vinyl group and an allyl group.

The aralkyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

The aryl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryl group having a substituent and an unsubstituted aryl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

The heterocyclic group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic group include a 2-pyridyl group, a 2-thienyl group and a 2-furyl group.

The alkylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkylamino group having a substituent and an unsubstituted alkylamino group. The alkylamino group is preferably an alkylamino group having 1 to 6 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.

The alkoxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkoxy group having a substituent and an unsubstituted alkoxy group. The alkoxy group excluding the substituent is preferably an alkoxy group having 1 to 12 carbon atoms. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

The aryloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

The amide group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an amide group having a substituent and an unsubstituted amide group. The amide group is preferably an amide group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the amide group include an acetamide group, a propionamide group, a benzamide group, and a 3,5-disulfobenzamide group.

The arylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 12 carbon atoms when a substituent is removed. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.

The ureido group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

The sulfamoylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. A group is included. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino group.

The alkylthio group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkylthio group having a substituent and an unsubstituted alkylthio group. The alkylthio group is preferably an alkylthio group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group include a methylthio group and an ethylthio group.

The arylthio group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an arylthio group having a substituent and an unsubstituted arylthio group. The arylthio group is preferably an arylthio group having 6 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an alkyl group and an ionic hydrophilic group. Examples of the arylthio group include a phenylthio group and a p-tolylthio group.

The alkoxycarbonylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. It is. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

The sulfonamide group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a sulfonamide group having a substituent and an unsubstituted sulfonamide group. The sulfonamide group is preferably a sulfonamide group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonamide group include methanesulfonamide, benzenesulfonamide, and 3-carboxybenzenesulfonamide.

The carbamoyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

The sulfamoyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group and an aryl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group, a di- (2-hydroxyethyl) sulfamoyl group, and a phenylsulfamoyl group.

The alkoxycarbonyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

The heterocyclic oxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R _{15 includes} a heterocyclic oxy group having a substituent and an unsubstituted heterocyclic oxy group. It is. The heterocyclic oxy group is preferably a heterocyclic oxy group having a 5-membered or 6-membered heterocyclic ring. Examples of the substituent include a hydroxyl group and an ionic hydrophilic group. Examples of the heterocyclic oxy group include a 2-tetrahydropyranyloxy group.

The azo group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an azo group having a substituent and an unsubstituted azo group. Examples of the azo group include a p-nitrophenylazo group.

The acyloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an acyloxy group having a substituent and an unsubstituted acyloxy group. The acyloxy group is preferably an acyloxy group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

The carbamoyloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

The silyloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a silyloxy group having a substituent and an unsubstituted silyloxy group. Examples of the substituent include an alkyl group. Examples of the silyloxy group include a trimethylsilyloxy group.

The aryloxycarbonyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. It is. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

The aryloxycarbonylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino A group is included. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

The imide group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an imide group having a substituent and an unsubstituted imide group. Examples of the imide group include an N-phthalimide group and an N-succinimide group.

The heterocyclic thio group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R _{15 includes} a heterocyclic thio group having a substituent and an unsubstituted heterocyclic thio group. It is. The heterocyclic thio group preferably has a 5-membered or 6-membered heterocyclic ring. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic thio group include a 2-pyridylthio group.

The phosphoryl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a phosphoryl group having a substituent and an unsubstituted phosphoryl group. Examples of the phosphoryl group include a phenoxyphosphoryl group and a phenylphosphoryl group.

The acyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

The ionic hydrophilic group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a sulfo group, a carboxyl group, a quaternary ammonium group, and the like. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.

R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido, among others Group, sulfonamido group, carbamoyl group, sulfamoyl group and alkoxycarbonyl group are preferable, hydrogen atom, halogen atom and cyano group are particularly preferable, and hydrogen atom is most preferable.

In general formula (1), Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, It represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent. Examples of the substituent include the substituents described in the above substituent group C.

The alkyl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent group, a hydroxyl group, an alkoxy group, a cyano group, an alkylamino group (RNH-, RR'N-), a carbamoyl group (-CONHR), a sulfamoyl group _{_{(-SO 2 NHR, -SO 2 NRR}} ') Sulfonylamino group (—NHSO ₂ R), —SONHR group, —SONRR ′ group, halogen atom and ionic hydrophilic group. (Note that R and R ′ represent an alkyl group and a phenyl group, and these may further have a substituent. Examples of the substituent include an alkylamino group, a hydroxyl group, and an ionic hydrophilic group. R and R ′ may form a ring by a chemical bond.) Examples of the alkyl group include methyl, ethyl, butyl, n-propyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trimethyl. Included are fluoromethyl, 3-sulfopropyl and 4-sulfobutyl.

The cycloalkyl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The alkenyl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes an alkenyl group having a substituent and an unsubstituted alkenyl group. As the alkenyl group, an alkenyl group having 2 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include a vinyl group and an allyl group.

The aralkyl group represented by Z ₁ , Z ₂ , Z ₃ and Z ₄ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

The aryl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes an aryl group having a substituent and an unsubstituted aryl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms when the substituent is removed. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl, m-sulfophenyl. Examples of the substituent include an alkyl group (R—), an alkoxy group (RO—), an alkylamino group (RNH—, RR′N—), a carbamoyl group (—CONHR), a sulfamoyl group (—SO ₂ NHR), A sulfonylamino group (—NHSO ₂ R), a halogen atom, and an ionic hydrophilic group are included (note that R and R ′ represent an alkyl group and a phenyl group, and these may also have an ionic hydrophilic group. Good).

The heterocyclic group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group, and may form a condensed ring with another ring. Good. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. The heterocyclic group may form a condensed ring with another ring. Examples of the heterocyclic group include, but are not limited to, the substitution position of the heterocyclic ring. Oxazole, benzoxazole, thiadiazole, oxadiazole, pyrrole, benzopyrrole, indole, isoxazole, benzoisoxazole, thiophene, benzothiophene, furan, benzofuran, pyridine, quinoline, isoquinoline, pyridazine, pyrimidine, pyrazine, cinnoline, phthalazine, Quinazoline, quinoxaline, triazine and the like are included. Examples of the substituent include an alkyl group (R—), an aryl group (R—), an alkoxy group (RO—), an alkylamino group (RNH—, RR′N—), a carbamoyl group (—CONHR), and a sulfamoyl group. (—SO ₂ NHR), a sulfonylamino group (—NHSO ₂ R), a sulfonyl group (—SO ₂ R), an acylamino group (—NHCOR), a halogen atom, and an ionic hydrophilic group are included (note that R, R above) 'Represents an alkyl group or an aryl group, and these may have an ionic hydrophilic group or a substituent having an ionic hydrophilic group).

Z ₁ , Z ₂ , Z ₃ and Z ₄ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted alkyl group or a substituted aryl group. A substituted heterocyclic group is more preferred, and a substituted alkyl group is still more preferred.

At least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent. Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.

Z ₁ , Z ₂ , Z ₃ and Z ₄ are preferably each independently a group represented by the following general formula (3) or (4).

In the general formulas (3) and (4), L represents an alkylene group having 1 to 12 carbon atoms, M ³ represents a hydrogen atom or a counter cation, and R ₂₀ represents an alkyl group having 1 to 6 carbon atoms. * Represents a bond.

L in the general formulas (3) and (4) represents an alkylene group having 1 to 12 carbon atoms, preferably represents an alkylene group having 1 to 8 carbon atoms, and represents an alkylene group having 1 to 6 carbon atoms. Is more preferable, and an alkylene group having 1 to 3 carbon atoms is more preferable.
M ³ in the general formula (3) represents a hydrogen atom or a counter cation. When M ³ is a hydrogen atom, it is in the form of a free acid, and when M ³ is a counter cation, it is in the form of a salt. Examples of counter cations that form salts include monovalent counter cations, and alkali metal ions, ammonium ions, organic cations, and the like are preferable. Examples of the organic cation include tetramethylammonium ion, tetramethylguanidinium ion, and tetramethylphosphonium. The counter cation is preferably an alkali metal ion, more preferably a lithium ion, a sodium ion, or a potassium ion.
R ₂₀ in the general formula (4) represents an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

In the general formula (1), l, m, n and p each independently represent 1 or 2. That is, 4 ≦ l + m + n + p ≦ 8 is satisfied. Preferably, 4 ≦ l + m + n + p ≦ 6 is satisfied, and most preferably, each is 1 (1 = m = n = p = 1).

In general formula (1), q ₁ , q ₂ , q ₃ and q ₄ each independently represent 1 or 2. In particular, q ₁ = q ₂ = q ₃ = q ₄ = 2 is preferable.

In General Formula (1), M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.

What is preferable as M ₁ is a metal element other than a hydrogen atom, such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru. Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and the like. Of these, Cu, Ni, Zn, Al and the like are particularly preferable, and Cu is most preferable. Preferred examples of the metal oxide include VO and GeO. Moreover, as a metal hydroxide, Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _2, etc. are mentioned preferably. Furthermore, as the metal _{_{halide, AlCl, SiCl 2, VCl,}} VCl 2, VOCl, FeCl, GaCl, ZrCl , and the like.

[Synthesis of phthalocyanine dyes]
Examples of the phthalocyanine derivatives used in the present invention include “Phthalocyanine—Chemistry and Function” (P. 1 to 62) published by K. Shirai and Kobayashi, Inc. C. Leznoff-A. B. P. Lever co-authored, published by VCH, “Phthalogicanes-Properties and Applications” (P. 1 to 54), etc., can be synthesized by combining quoted or similar methods.
The compound represented by the general formula (1) can be synthesized with reference to the description of [0057] to [0074] of Japanese Patent Application Laid-Open No. 2005-307189.

The phthalocyanine dye represented by the general formula (1) of the present invention is an α-substituted type (at least one of the 1st and 4th positions of the phthalocyanine ring, at least one of the 5th and 8th positions, and at least one of the 9th and 12th positions). , -S (O) q ₁ -Z ₁ , -S (O) q ₂ -Z ₂ , -S (O) q ₃ -Z ₃ , -S (O) q It hits the phthalocyanine compound) having a specific substituent represented by ₄ -Z _4. In the present invention, it is important for good fastness to have at least one of —SO—Z and —SO ₂ —Z (Z is synonymous with Z ₁ to Z ₄ ) in the α-position.

Specific examples of the phthalocyanine dye represented by the general formula (1) are shown below using the following general formula (IV), but the phthalocyanine dye used in the present invention is not limited to the following examples.

(Example of phthalocyanine dye represented by formula (1))

(Coloring composition)
The colored composition of the present invention contains a compound represented by the general formula (Q) (disazo dye) and a compound represented by the general formula (1) (α-substituted phthalocyanine dye) at a specific mass ratio. By containing both in a coloring composition with appropriate content, generation | occurrence | production of bronze gloss can be suppressed and the image excellent in light resistance and ozone resistance can be obtained.
In the colored composition of the present invention, the ratio of the content of the compound represented by the general formula (1) to the content of the compound represented by the general formula (Q) (compound represented by the general formula (1) / The content of the compound represented by the general formula (Q) is 0.02 to 0.25, preferably 0.05 to 0.15 on a mass basis.
When the mass ratio of the compound represented by the general formula (1) to the compound represented by the general formula (Q) is 0.02 or more, an effect of suppressing bronze gloss can be obtained. On the other hand, if the mass ratio of the compound represented by the general formula (1) to the compound represented by the general formula (Q) is 0.25 or less, the association is not solved and good ozone fastness is maintained. be able to. Moreover, by including both in the said range, observation light dependence was able to be improved as an unexpected effect. Even when the β-substituted phthalocyanine dye is added in the above range in the colored composition, it is not possible to suppress the occurrence of bronze gloss, and it is not possible to obtain ozone fastness and other effects. The colored composition of the present invention preferably contains no β-substituted phthalocyanine dye. That is, the phthalocyanine dye contained in the coloring composition is preferably only the compound represented by the general formula (1) (α-substituted phthalocyanine dye).
In the present invention, at least one of the 1-position and the 4-position of the phthalocyanine ring, at least one of the 5-position and the 8-position, at least one of the 9-position and the 12-position, and at least one of the 13-position and the 16-position have a substituent. Phthalocyanine having the above-mentioned specific substituent in at least one of 2-position and 3-position, at least one of 6-position and 7-position, at least one of 10-position and 11-position, and at least one of 14-position and 15-position (β-position) The compound is referred to as β-substitution type.

The content of the disazo dye represented by the general formula (Q) in the coloring composition is preferably 0.2 to 20% by mass, more preferably 0.5 to 10% by mass, and 1.0 to 8.0%. Mass% is particularly preferred.
The coloring composition of the present invention preferably contains 0.2 to 20% by mass of the total dye, more preferably 0.5 to 10% by mass, and particularly preferably 1.0 to 8.0% by mass. contains.

The coloring composition of the present invention can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for ink jet recording. The coloring composition of the present invention is represented by a compound represented by the general formula (Q) (disazo dye) and a general formula (1) using a lipophilic medium or an aqueous medium as a medium. It can be prepared by dissolving and / or dispersing a compound (α-type phthalocyanine dye). Preferably, an aqueous medium is used.

The coloring composition of the present invention may contain other additives as necessary within a range that does not impair the effects of the present invention. Examples of other additives include additives that can be used in ink jet recording inks described later.

[Ink for inkjet recording]
Next, the ink for inkjet recording of the present invention will be described.
The colored composition of the present invention can be suitably used as an ink for inkjet recording.
The ink for ink jet recording dissolves and / or dissolves the compound represented by the general formula (Q) (disazo dye) and the compound represented by the general formula (1) (α-type phthalocyanine dye) in an oleophilic medium or an aqueous medium. It can be produced by dispersing. The ink for inkjet recording is preferably an ink using an aqueous medium.
The ink for ink jet recording can contain other additives as required within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are directly added to the ink liquid in the case of water-soluble ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.

The ink for ink jet recording of the present invention preferably has a viscosity of 30 mPa · s or less. The surface tension is preferably 25 mN / m or more and 70 mN / m or less. Viscosity and surface tension are various additives such as viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, UV absorbers, antioxidants, antifading agents, antifungal agents, and rust inhibitors. It can be adjusted by adding a dispersant and a surfactant.

The ink for ink jet recording of the present invention can be used for ink for ink jet recording of various colors, but is preferably used for ink for ink jet recording of black color.

The ink composition of the present invention can be used for recording methods such as printing, copying, marking, writing, drawing, stamping and the like, and is particularly suitable for use in an ink jet recording method.

[Inkjet recording method]
The present invention also relates to an inkjet recording method for forming an image using the colored composition or the inkjet recording ink of the present invention.

[Inkjet printer cartridge and inkjet recording]
The ink cartridge for ink jet recording of the present invention is filled with the ink for ink jet recording of the present invention described above. Further, the ink-jet recorded matter of the present invention is obtained by forming a colored image on a recording material using the above-described ink for ink-jet recording of the present invention.

Hereinafter, a recording paper and a recording film used for ink jet printing using the ink of the present invention will be described.
The support in recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMPMP, CGP, and waste paper pulp such as DIP. Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there. In addition to these supports, either synthetic paper or plastic film sheets may be used. The thickness of the support is preferably 10 to 250 μm and the basis weight is preferably 10 to 250 g / m ² .

Polymer latex may be added to the constituent layers (including the backcoat layer) of the inkjet recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer latex is described in JP-A Nos. 62-245258, 62-136648, and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.

The ink of the present invention is not limited to an ink jet recording system, and is a known system, for example, a charge control system that discharges ink using electrostatic attraction, a drop-on-demand system (pressure) that uses the vibration pressure of a piezo element. Pulse method), acoustic ink jet method that converts electrical signal into acoustic beam and irradiates ink and uses ink to discharge ink, and thermal ink jet that heats ink to form bubbles and uses generated pressure Used for systems. Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Synthesis of Compound Represented by General Formula (Q)>
Compounds (Q1) to (Q17) are prepared by a coupling reaction between a diazo component and a coupler by the method described in JP-A No. 2003-306623, JP-A No. 2005-139427 and JP-A No. 2012-177073. Synthesized.

<Synthesis of Compound Represented by General Formula (1)>
Shirai-Kobayashi, published by IPC Co., Ltd. “Phthalocyanine: Chemistry and Function” (P.1-62), C.I. C. Leznoff-A. B. P. In collaboration with Lever, published by VCH, “Phthalocyanines-Properties and Applications” (P. 1 to 54), Japanese Patent Application Publication No. 2005-307189, [0057] to [0074] and the like, the following phthalocyanine dyes (1A), (1B), (2A) to (2D), and DB-86 were synthesized. In the following structural formula, Me represents a methyl group.

[Preparation of ink for inkjet recording]
[Example 1]
An ink for ink jet recording (sample No. 1) having the composition shown below was prepared.

Composition of ink for inkjet recording (sample No. 1) Disazo dye (Q1): 3.5% by mass
-Phthalocyanine dye 1B: mass ratio to disazo dye 0.11
・ Diethylene glycol: 2.0% by mass
・ Glycerin: 12.0% by mass
Diethylene glycol monobutyl ether: 23.0% by mass
・ 2-Pyrrolidone: 8.0% by mass
・ Triethanolamine: 1.8% by mass
Benzotriazole: 0.006% by mass
・ Surfinol TG: 0.9% by mass
・ PROXEL XL2: 0.2% by mass
・ Water: Remaining amount

Except for changing the type and amount of dye as shown in Tables 9 and 10 below, Sample No. Ink compositions (Sample Nos. 2 to 63) were prepared in the same manner as in Preparation 1.

Next, a printed material was prepared by the method described below, and the obtained printed material was evaluated for image quality (bronze gloss).

[Bronze gloss evaluation]
Inkjet printer Stylus Color 880 (trade name) (trade name, manufactured by Seiko Epson Corporation) was used, ink jet recording ink (Sample Nos. 1 to 63) was filled in the ink cartridge, and an ink jet recording medium (photographic paper <glossy) >), Solid printing was performed so that the applied amount was 0.23 to 0.34 mg per square centimeter, and the resulting printed matter was measured with a gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.). Was used (measurement angle 60 degrees), and the glossiness was determined. Printing was performed at 20 ° C. and a relative humidity of 40%. Using the obtained glossiness and the increased value calculated based on the following formula as a criterion for determining the degree of occurrence of bronze phenomenon, the determination was made based on the following criterion.
Increase value = Glossiness (printed material)-Glossiness (recording medium)
[Criteria]
Evaluation A: Less than 15 Evaluation B: 15 or more and less than 35 Evaluation C: 35 or more The obtained results are shown in Tables 9 and 10 as “bronze gloss”.

(Light resistance evaluation)
Using a weather meter (manufactured by Atlas Co., Ltd.), an image (a monochromatic image pattern with density changed stepwise created using a printer and paper for bronze gloss evaluation. Reflected image density measured by a reflection densitometer is 0.7. Xenon light (100,000 lux) was irradiated for 14 days. The OD value of each color recorded on each printed matter was measured using a reflection densitometer (X-Rite 310TR, manufactured by X-Rite Co., Ltd.) after a certain period of time from the start of irradiation. The reflection density was measured at three points of 0.7, 1.0, and 1.8.
From the obtained results, the residual optical density (ROD) was determined using the following formula: ROD (%) = (D / D ₀ ) × 100. (In the formula, D represents the OD value after the exposure test, and D ₀ represents the OD value before the exposure test.)
Further, based on the results of the above test, the light resistance of each color recorded on the recorded matter was ranked A to C using the following criteria.
[Criteria]
Evaluation A: ROD 14 days after the start of the test is 85% or more at any concentration.
Evaluation B: ROD 14 days after the start of the test is such that the concentration at any one point is less than 85%.
Evaluation C: The ROD after 14 days from the start of the test has a concentration of any two or three points of less than 85%.
In this test, a recorded matter with little decrease in ROD even when exposed to light for a long time is excellent. The obtained results are shown in Tables 9 and 10.

[Ozone resistance evaluation]
Under the condition that the ozone gas concentration was set to 5 ppm (25 ° C., relative humidity 60%), the recorded material (printed material prepared under the same conditions as the light resistance evaluation) was exposed to ozone gas for 14 days. The ozone gas concentration was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS. The OD value of each color recorded on each printed matter was measured using a reflection densitometer (X-Rite 310TR, manufactured by X-Rite Co., Ltd.) after a certain period from the start of exposure. The reflection density was measured at three points of 0.7, 1.0, and 1.8.
From the obtained results, the optical density residual ratio (ROD) was determined using the following formula: ROD (%) = (D / D ₀ ) × 100. (In the formula, D represents the OD value after the exposure test, and D ₀ represents the OD value before the exposure test.)

Further, based on the results of the above test, the ozone resistance of each color recorded on the recorded matter was ranked A to C using the following criteria.
[Criteria]
Evaluation A: ROD after 7 days from the start of the test is 85% or more at any concentration.
Evaluation B: The ROD after 7 days from the start of the test is such that the concentration at any one point is less than 85%.
Evaluation C: The ROD after 7 days from the start of the test is such that the concentration at any two or three points is less than 85%.

In this test, the recorded material with little decrease in ROD is excellent even when exposed to ozone for a long time. The obtained results are shown in Tables 9 and 10 as “ozone resistance”.

Furthermore, a printed material was prepared by the method shown below, and the obtained printed material was evaluated for observation light source dependency.

[Evaluation of observation light source dependency]
Inkjet printer Stylus Color 880 (trademark) (trade name, manufactured by Seiko Epson Corporation) and inkjet recording ink (Sample Nos. 1 to 63) are used, respectively, and an inkjet recording medium (photographic paper crispier <high gloss > (Trade name, manufactured by Seiko Epson Corporation)) was printed with black solids so that a shot amount of 0.23 to 0.34 mg per square centimeter was obtained. The reflection spectrum of the obtained printed matter was measured with a spectral absorption measuring instrument (Shimadzu Corporation, UV-2400). The reflection spectrum R (λ) was measured from 380 nm to 780 nm in increments of 5 nm.
The following 15 light sources were used as observation light sources.
D50, A, D65, F1, F2, F3, F4, F5, F6, F7, F8, F9, F10, F11, F12
These light source spectra P (λ) are obtained from Table T. of “Technical Report Colorimetry 3rd Edition (CIE 15: 2004)”. 1. And Table T6.1. The described spectrum was used as the emission spectrum.
Color matching function (CIE 1986) of X, Y, Z color specification

Table T. of “Technical Report Colorimetry 3rd Edition (CIE 15: 2004)”. 5. The described one was used.
The tristimulus values X, Y, and Z of the printed material were calculated according to the following formula.

The tristimulus values Xn, Yn, Zn at the white point of the light source are defined below.

According to the following formula, the reflection spectrum of each pigment and the colorimetric values L *, a * and b * in the CIE LAB space for the light source were calculated.

However, the function f used in the above formula is defined as follows.

The color difference ΔE between hue 1 (L1 *, a1 *, b1 *) and hue 2 (L2 *, a2 *, b2 *) is defined as follows, and the color difference between each light source with respect to the standard light source D50 is defined as The maximum value of these color differences was calculated as ΔEmax.
^{^{ΔE = ((L1 * -L2 *}} ) 2 + (a1 * -a2 *) 2 + (b1 * -b2 *) 2) 1/2

(Criteria)
A: ΔEmax <5
B: 5 ≦ ΔEmax <10
C: 10 ≦ ΔEmax

Sample No. which is an example of the present invention. 1 to 6, 9 to 11, 14, 16 to 22, 40, 41, 43 to 47, 49 to 51 are suppressed in the occurrence of bronze gloss, have excellent light resistance and ozone resistance, and further depend on the observation light source. It was low and excellent.
Sample No. Nos. 7, 8, 12, 13, 15, 23, 24, 25, 28, 37, 42, 48, 52 to 54 and 60 contain no α-type phthalocyanine dye or are in a mass ratio to the disazo dye. Therefore, the effect of suppressing the generation of bronze could not be obtained. Sample No. Nos. 26, 27, 29 to 36, 38, 39, 55 to 59, and 61 to 63 have a phthalocyanine dye added to the disazo dye in a mass ratio exceeding 0.25. The evaluation result of the property was poor.
About the sample described as "impossible evaluation", since the correct colorimetric value was not able to be obtained because bronze gloss occurred, it was set as "not evaluation".

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on March 28, 2014 (Japanese Patent Application No. 2014-070536), the contents of which are incorporated herein by reference.

Claims

It contains a compound represented by the following general formula (Q) and a compound represented by the following general formula (1), and is represented by the general formula (1) with respect to the content of the compound represented by the general formula (Q). A coloring composition having a content ratio of 0.02 to 0.25 on a mass basis.
General formula (Q)

In general formula (Q), A represents an aryl group or a heterocyclic group. G represents a nitrogen atom or —CZ═. When G represents —CZ═, Z represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. R 101 , R 102 and R 107 are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl Group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, Acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, An alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfo group is represented. R 103 to R 106 are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group Or a sulfamoyl group.
However, R 103 and R 104 are not both hydrogen atoms. In addition, any of A and R 101 to R 107 may have a substituent.
However, the compound represented by the general formula (Q) has at least one ionic hydrophilic group in the molecule.

In general formula (1),
R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, hetero group Ring group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonyl Amino group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imido group, hetero Ring thio group, phosphoryl group, a It represents a group or an ionic hydrophilic group. These groups may further have a substituent.
Z 1 , Z 2 , Z 3 and Z 4 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted Alternatively, it represents an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. However, at least one of Z 1 , Z 2 , Z 3 , and Z 4 has an ionic hydrophilic group as a substituent.
l, m, n, p, q 1 , q 2 , q 3 and q 4 each independently represent 1 or 2;
M 1 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
The colored composition according to claim 1, wherein the compound represented by the general formula (Q) is a compound represented by the following general formula (3-1) or the following general formula (3-2).

In general formula (3-1), R 111 , R 112 , R 113 and R 114 each independently represent a hydrogen atom or a substituent. X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a substituent. M represents a hydrogen atom or a counter cation. G represents a nitrogen atom or —CZ═. When G represents —CZ═, Z represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.

In general formula (3-2), R 203 represents a substituent. X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a substituent. M represents a hydrogen atom or a counter cation. G represents a nitrogen atom or —CZ═. When G represents —CZ═, Z represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.
The colored composition according to claim 2, wherein the compound represented by the general formula (Q) is a compound represented by the general formula (3-2).
In the general formula (1), Z 1 , Z 2 , Z 3 and Z 4 are each independently a group represented by the following general formula (3) or the following general formula (4). The coloring composition of Claim 1.

In general formulas (3) and (4), L represents an alkylene group having 1 to 12 carbon atoms, M 3 represents a hydrogen atom or a counter cation, and R 20 represents an alkyl group having 1 to 6 carbon atoms. * Represents a binding site.
The colored composition according to any one of claims 1 to 4, wherein the general formula (1) is at least one of a compound represented by the following (1A) and a compound represented by (1B).
The content of the compound represented by the general formula (1) is 0.05 to 0.15 in terms of mass ratio with respect to the content of the compound represented by the general formula (Q). The coloring composition of any one of Claims.
The colored composition according to any one of claims 1 to 6, wherein the phthalocyanine dye contained in the colored composition is only the compound represented by the general formula (1).
An ink for inkjet recording using the colored composition according to any one of claims 1 to 7.
An ink jet recording method using the ink for ink jet recording according to claim 8.
An ink jet printer cartridge filled with the ink for ink jet recording according to claim 8.
An ink jet recorded matter in which a colored image is formed on a recording material using the ink for ink jet recording according to claim 8.