WO2016042977A1

WO2016042977A1 - Ink composition, inkjet printing ink, inkjet printing method, and azo compound

Info

Publication number: WO2016042977A1
Application number: PCT/JP2015/073619
Authority: WO
Inventors: 慎也林; 隆史飯泉; 立石　桂一
Original assignee: 富士フイルム株式会社
Priority date: 2014-09-16
Filing date: 2015-08-21
Publication date: 2016-03-24

Abstract

The present invention provides an ink composition with high ozone resistance, particularly, initial stage ozone resistance, little discoloration and excellent light stability, an inkjet printing ink, an inkjet printing method and an azo compound by means of an ink composition containing a water-soluble dye represented by general formula (1), an inkjet printing ink, an inkjet printing method and an azo compound represented by general formula (1) in the Specification.

Description

Ink composition, ink for ink jet recording, ink jet recording method, and azo compound

The present invention relates to an ink composition, an ink for ink jet recording, an ink jet recording method, and an azo compound.

Ink jet recording methods are rapidly spreading and further developed because of low material costs, 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 of discharging bubbles, a method of generating bubbles in the ink by heat and discharging droplets, a method of using ultrasonic waves, and a method of sucking 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.

In particular, disazo dyes, trisazo dyes, tetrakisazo dyes and the like have been studied as dyes for black ink having excellent ozone resistance (see Patent Documents 1 to 3).

Patent Document 4 discloses an ink jet recording method in which an ozone fading preventing agent is contained in a recording medium from the viewpoint of preventing fading due to ozone.

Japanese Unexamined Patent Publication No. 2012-2111293 European Patent Application No. 2712894 International Publication No. 2012/081640 Japanese Unexamined Patent Publication No. 2005-014223

Although the performance of ink for ink jet recording has been improved by research so far, higher level of fastness to light and ozone than the dyes described in

Patent Documents

1 and 2 has been demanded. The dye described in Patent Document 3 has a problem of causing a color change. In the method of adding an ozone fading inhibitor to the recording medium as described in Patent Document 4, there is a problem that the type of the fading preventing agent is limited depending on the performance required for the recording medium.

The present invention is an ink composition capable of forming an image excellent in ozone resistance (particularly initial ozone resistance), small in color change, and excellent in light resistance, an ink for ink jet recording, an ink jet recording method, And an azo compound.

The present inventors have found that the above problem can be solved by using a specific disazo dye in which a group capable of reacting with ozone is bonded to a chromophore through a linking group.
That is, the present invention relates to the following matters.

[1]
An ink composition containing a water-soluble dye represented by the following general formula (1).
General formula (1)

In general formula (1),
A represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group.
G represents a nitrogen atom or —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group.
L ₁ represents a linking group selected from the following group L ₁ .

In the formula, * represents a bond with a phenyl group, and ** represents a bond with L ₂ . R ₄ represents a hydrogen atom or a substituent.
L ₂ represents a linking group.
n represents 0, 1 or 2.
L ₃ represents an ozone fading preventing group.
R ₃ represents a hydrogen atom or a substituent. R ₃ may form a ring with L ₂ or L ₃ .
m represents 1 or 2.
Each M independently represents a hydrogen atom or a monovalent counter cation.
[2]
Represents a group in which the L ₃ is selected from the group L ₃ in the following ink composition according to [1].

In the formula, R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom or a substituent. k represents an integer of 0 to 3. p represents an integer of 1 to 6.
[3]
The ink composition according to [1] or [2], wherein L ₁ in the water-soluble dye represented by the general formula (1) represents a linking group selected from the following group L ₁ ′.

In the formula, * represents a connecting position with a phenyl group, and ** represents a connecting position with L ₂ . R ₄ represents a hydrogen atom or a substituent.
[4]
The ink composition according to any one of [1] to [3], wherein L ₃ in the water-soluble dye represented by the general formula (1) represents a group selected from the following group L ₃ ′.

In the formula, R ₅ and R ₆ each independently represent a hydrogen atom or a substituent. k represents an integer of 0 to 3. p represents an integer of 1 to 6.
[5]
The ink composition according to any one of [1] to [4], wherein the water-soluble dye represented by the general formula (1) is a water-soluble dye represented by the following general formula (2).
General formula (2)

In general formula (2),
X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent.
_G in formula (2) _{_{in, L 1, L 2, n}} , L 3, R 3, m, and M is _G in formula _{(1), L 1, L} 2, n, L 3, R ₃ Synonymous with m and M.
[6]
The water-soluble dye represented by the general formula (1) or (2) is a water-soluble dye represented by the following general formula (3), any one of [1] to [5] Ink composition.
General formula (3)

In the general formula (3), G, L ₁ , L ₂ , n, L ₃ , R ₃ , m, and M are G, L ₁ , L ₂ , n, L ₃ , R in the general formula (1). ₃ Synonymous with m and M.
[7]
[1] to [6] An inkjet recording ink comprising the ink composition according to any one of [6].
[8]
An ink jet recording method using the ink for ink jet recording according to [7].
[9]
A compound represented by the following general formula (1).
General formula (1)

In the formula, * represents a bond with a phenyl group, and ** represents a bond with L ₂ . R ₄ represents a hydrogen atom or a substituent.
L ₂ represents a linking group.
n represents 0, 1 or 2.
L ₃ represents an ozone fading preventing group.
R ₃ represents a hydrogen atom or a substituent. R ₃ may form a ring with L ₂ or L ₃ .
m represents 1 or 2.
Each M independently represents a hydrogen atom or a monovalent counter cation.

According to the present invention, an ink composition, ink jet recording ink, and ink jet recording that can form an image having excellent ozone resistance (particularly, initial ozone resistance), small color change, and excellent light resistance. Methods and azo compounds can be provided.

It is the figure which showed the spectrum before and behind the test at the time of evaluating ozone resistance about the printed matter using the ink for inkjet recording containing a comparative example compound (2). 1 is a ¹ H NMR chart of Compound (1) -1 of the present invention.

The present invention is described in detail below.
First, in the present invention, the substituent group A ′, the substituent group J, the ionic hydrophilic group, and Hammett's substituent constant σp value are defined.

(Substituent group A ′)
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, N-diethylsulfamoyl, N-phenylsulfamoyl), a sulfonyl group (eg, methylsulfonyl, octylsulfonyl, phenylsulfonyl, p -Toluenesulfonyl), sulfonamide groups (eg methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecane), alkyloxycarbonyl groups (eg methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy groups (eg 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), 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), a silyloxy group (eg trimethylsilyloxy, dibutylmethylsilyloxy), an aryloxycarbonylamino group (eg phenoxy) Carbonylamino), imide group (eg, N-succinimide, N-phthalimide), heterocyclic thio group (eg, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6- Thio, 2-pyridylthio), sulfinyl groups (eg 3-phenoxypropylsulfinyl), phosphonyl groups (eg phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl groups (eg phenoxyphosphonyl) Alkoxycarbonyl), acyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl), an ionic hydrophilic group (carboxyl group, a sulfo group, and quaternary ammonium groups). These substituents may be further substituted, and examples of the further substituent include groups selected from the substituent group A ′ described above.

(Substituent group J)
For example, 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 , Carbamoyloxy 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, aryloxycarboni Examples include groups, alkoxycarbonyl groups, carbamoyl groups, aryl or heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, silyl groups, and ionic hydrophilic groups. . These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group J described above.

More specifically, 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. Specifically, the alkyl group is preferably 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. Group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group and the like, and the cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as a cyclohexyl group, A cyclopentyl group, 4-n-dodecylcyclohexyl group and the like. The bicycloalkyl group is preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a bicycloalkane having 5 to 30 carbon atoms. Monovalent groups from which one hydrogen atom has been removed, for example, bicyclo [1,2,2] heptan-2-yl group, bicycl [2,2,2] octan-3-yl group.

Examples of the aralkyl group include a substituted or unsubstituted aralkyl group, and the substituted or unsubstituted aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms. 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. Specifically, the alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group, and the like. Is preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as 2-cyclopentene-1 -Yl group, 2-cyclohexen-1-yl group and the like. As the bicycloalkenyl group, a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, That is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond, for example, bicyclo [2 2,1] hept-2-en-1-yl group, a bicyclo [2,2,2] oct-2-en-4-yl group and the like.

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

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, an ethylsulfinyl group, phenyl. Examples thereof include a sulfinyl group and a p-methylphenylsulfinyl group.

The alkyl or arylsulfonyl group is preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, or a phenyl group. Examples thereof include a sulfonyl group and a p-methylphenylsulfonyl group.

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.

(Ionic hydrophilic group)
A sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, a quaternary ammonium group and the like can be mentioned. 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. Cation (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) is included, lithium salt, sodium salt, potassium salt, ammonium salt is preferable, lithium salt or mixed salt containing lithium salt as a main component Are more preferred, and lithium salts are most preferred.

The counter cation (monovalent counter cation) of the ionic hydrophilic group contained in the compound represented by the general formula (1) of the present invention preferably contains lithium ions as a main component. The counter cations may not be all lithium ions, but the lithium ion concentration in each of the ink compositions is preferably 50% by mass or more, more preferably based on the total counter cations in each ink composition. Is 75% by mass or more, more preferably 80% by mass, and particularly preferably 95% by mass or more.
Under such conditions, the ink composition contains hydrogen ions, alkali metal ions (for example, sodium ions and potassium ions), alkaline earth metal ions (for example, magnesium ions and calcium ions), 4 A quaternary ammonium ion, a quaternary phosphonium ion, a sulfonium ion, or the like can be included as a counter cation.

Regarding the types and ratios of the counter cation of the colorant, the Chemical Society of Japan “New Experimental Chemistry Course 9 Analytical Chemistry” (1977 Maruzen) and the Chemical Society of Japan “4th edition Experimental Chemistry Course 15 Analysis” (1991 Maruzen) ) Describes various theories about analysis methods and elements, so that analysis methods can be selected, analyzed and quantified by referring to them. In particular, it is easy to determine by an analysis method such as ion chromatography, atomic absorption method, inductively coupled plasma emission spectrometry (ICP).
As a method for obtaining the colorant of the present invention in which the counter cation contains lithium ions, any method may be used. For example, (1) a method of converting a counter cation from another cation to lithium ions using an ion exchange resin, (2) a method of acid precipitation or salting out from a system containing lithium ions, and (3) a counter cation of lithium ions A method of forming a colorant using a raw material and a synthetic intermediate, and (4) a method of introducing an ionic hydrophilic group by functional group conversion of each colorant using a reactive agent whose counter cation is a lithium ion (5) A compound in which the counter cation of the ionic hydrophilic group in the colorant is a silver ion is synthesized, and this is reacted with a lithium halide solution to remove the precipitated silver halide. The method of making it.

The ionic hydrophilic group in each colorant may be any as long as it is an ionic dissociation group. Preferred ionic hydrophilic groups include a sulfo group (may be a salt), a carboxyl group (may be a salt), a hydroxyl group (may be a salt), a phosphono group (may be a salt), a quaternary ammonium group, and an acylsulfamoyl group. (May be a salt), a sulfonylcarbamoyl group (may be a salt), a sulfonylsulfamoyl group (may be a salt), and the like.
A sulfo group, a carboxyl group, or a hydroxyl group (including salts thereof) is preferable. When the ionic hydrophilic group is a salt, a preferable counter cation is lithium or a mixed salt of an alkali metal (for example, sodium, potassium), ammonium, and an organic cation (for example, pyridinium, tetramethylammonium, guanidinium) based on lithium. Among them, lithium or an alkali metal mixed salt containing lithium as a main component is preferable, and a lithium salt of a sulfo group and a lithium salt of a carboxy group are particularly preferable.

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

In the present invention, when the compound is a salt, the salt is dissociated into ions in the ink, but it is expressed as “contains a salt” for convenience.

Next, groups and substituents in the present application will be described.

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

In the present specification, an aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The aliphatic group may have a branch and may form a ring. The number of carbon atoms in the aliphatic group is preferably 1-20, and more preferably 1-16. The aryl part of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, particularly preferably phenyl. Examples of aliphatic groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl, cyclohexyl groups, benzyl groups, 2-phenethyl Groups, vinyl groups, and allyl groups.

In the present specification, the monovalent aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably phenyl or naphthyl, particularly preferably phenyl. The number of carbon atoms in the monovalent aromatic group is preferably 6 to 20, and more preferably 6 to 16. Examples of the monovalent aromatic group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl. The divalent aromatic group is a divalent version of these monovalent aromatic groups. Examples thereof include phenylene, p-tolylene, p-methoxyphenylene, o-chlorophenylene, and m- (3 -Sulfopropylamino) phenylene, naphthylene and the like.

The heterocyclic group includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. The heterocyclic group is preferably a 5- or 6-membered heterocyclic group, and N, O, and S can be exemplified as the hetero atom of the heterocyclic ring. Examples of the substituent include aliphatic groups, halogen atoms, alkyl and arylsulfonyl groups, acyl groups, acylamino groups, sulfamoyl groups, carbamoyl groups, ionic hydrophilic groups, and the like. Examples of the heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group and 2-furyl group. The divalent heterocyclic group is a group that has become a bond by removing a hydrogen atom from the monovalent heterocyclic ring.

The carbamoyl group 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 alkoxycarbonyl group includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

The aryloxycarbonyl group includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

The heterocyclic oxycarbonyl group includes a heterocyclic oxycarbonyl group having a substituent and an unsubstituted heterocyclic oxycarbonyl group. The heterocyclic oxycarbonyl group is preferably a heterocyclic oxycarbonyl group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic oxycarbonyl group include a 2-pyridyloxycarbonyl group. The acyl group includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

The alkoxy group includes an alkoxy group having a substituent and an unsubstituted alkoxy group. The alkoxy group is preferably an alkoxy group having 1 to 20 carbon atoms. Examples of the substituent include an alkoxy group, a hydroxy 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 includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include phenoxy group, p-methoxyphenoxy group and o-methoxyphenoxy group.

The heterocyclic oxy group includes a substituted heterocyclic oxy group and an unsubstituted heterocyclic oxy group. The heterocyclic oxy group is preferably a heterocyclic oxy group having 2 to 20 carbon atoms. Examples of the substituent include an alkyl group, an alkoxy group, and an ionic hydrophilic group. Examples of the heterocyclic oxy group include a 3-pyridyloxy group and a 3-thienyloxy group.

The silyloxy group is preferably a silyloxy group substituted with an aliphatic group or aromatic group having 1 to 20 carbon atoms. Examples of the silyloxy group include trimethylsilyloxy and diphenylmethylsilyloxy.

The acyloxy group includes an acyloxy group having a substituent and an unsubstituted acyloxy group. The acyloxy group is preferably an acyloxy group having 1 to 20 carbon atoms. 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 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 alkoxycarbonyloxy group includes an alkoxycarbonyloxy group having a substituent and an unsubstituted alkoxycarbonyloxy group. The alkoxycarbonyloxy group is preferably an alkoxycarbonyloxy group having 2 to 20 carbon atoms. Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group and an isopropoxycarbonyloxy group.

The aryloxycarbonyloxy group includes an aryloxycarbonyloxy group having a substituent and an unsubstituted aryloxycarbonyloxy group. The aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having 7 to 20 carbon atoms. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group.

The amino group includes an amino group substituted with an alkyl group, an aryl group or a heterocyclic group, and the alkyl group, the aryl group and the heterocyclic group may further have a substituent. The alkylamino group is preferably an alkylamino group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group. The arylamino group includes an arylamino group having a substituent, an unsubstituted arylamino group, and an anilino group. The arylamino group is preferably an arylamino group having 6 to 20 carbon atoms. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include a phenylamino group and a 2-chlorophenylamino group.
The heterocyclic amino group includes a heterocyclic amino group having a substituent and an unsubstituted heterocyclic amino group. The heterocyclic amino group is preferably a heterocyclic amino group having 2 to 20 carbon atoms. Examples of the substituent include an alkyl group, a halogen atom, and an ionic hydrophilic group.

The acylamino group includes an acylamino group having a substituent and an unsubstituted acylamino group. The acylamino group is preferably an acylamino group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-disulfobenzoylamino group.

The ureido group includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 20 carbon atoms. 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 includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino group.

The alkoxycarbonylamino group includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

The aryloxycarbonylamino group includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

The alkyl and arylsulfonylamino groups include substituted alkyl and arylsulfonylamino groups, and unsubstituted alkyl and arylsulfonylamino groups. The sulfonylamino group is preferably a sulfonylamino group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of these sulfonylamino groups include a methylsulfonylamino group, an N-phenyl-methylsulfonylamino group, a phenylsulfonylamino group, and a 3-carboxyphenylsulfonylamino group.

The heterocyclic sulfonylamino group includes a heterocyclic sulfonylamino group having a substituent and an unsubstituted heterocyclic sulfonylamino group. The heterocyclic sulfonylamino group is preferably a heterocyclic sulfonylamino group having 1 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfonylamino group include a 2-thiophenesulfonylamino group and a 3-pyridinesulfonylamino group.

The heterocyclic sulfonyl group includes a heterocyclic sulfonyl group having a substituent and an unsubstituted heterocyclic sulfonyl group. The heterocyclic sulfonyl group is preferably a heterocyclic sulfonyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfonyl group include a 2-thiophenesulfonyl group and a 3-pyridinesulfonyl group.

The heterocyclic sulfinyl group includes a heterocyclic sulfinyl group having a substituent and an unsubstituted heterocyclic sulfinyl group. The heterocyclic sulfinyl group is preferably a heterocyclic sulfinyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfinyl group include a 4-pyridinesulfinyl group.

Alkyl, aryl and heterocyclic thio groups include substituted alkyl, aryl and heterocyclic thio groups and unsubstituted alkyl, aryl and heterocyclic thio groups. Alkyl, aryl and heterocyclic thio groups are preferably those having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkyl, aryl and heterocyclic thio groups include a methylthio group, a phenylthio group, and a 2-pyridylthio group.

The alkyl and arylsulfonyl groups include substituted alkyl and arylsulfonyl groups, unsubstituted alkyl and arylsulfonyl groups. Examples of the alkyl and arylsulfonyl groups include a methylsulfonyl group and a phenylsulfonyl group, respectively.

The alkyl and arylsulfinyl groups include substituted alkyl and arylsulfinyl groups, unsubstituted alkyl and arylsulfinyl groups. Examples of the alkyl and arylsulfinyl groups include a methylsulfinyl group and a phenylsulfinyl group, respectively.

The sulfamoyl group includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

Further, the substituent in the present invention may be any group that can be substituted. For example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, a hetero group Ring oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, hetero Ring sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryl Oxycarbonylamino group, hetero Oxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxy group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group, sulfo group Famoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group, ionic hydrophilic group (for example, carboxyl group, sulfo group, Phosphono group and quaternary ammonium group). These substituents may be further substituted, and examples of the further substituent include groups selected from the substituents described above.

The ink composition of the present invention will be described below.
The ink composition of the present invention contains a water-soluble dye represented by the following general formula (1).

When the ink composition contains the water-soluble dye represented by the general formula (1), the ink composition has high ozone resistance, particularly ozone resistance at the initial stage, small color change, and excellent light resistance. Things are provided. The following mechanism can be considered as this reason.
As the reaction of ozone, 1,3-dipolar addition reaction, electrophilic reaction and the like are known. For example, the reaction with olefin is known to react as shown in the following scheme 1. Further, it reacts with electron donating compounds such as sulfide and amine to form, for example, sulfoxide and amine oxide.

For example, in the following compound described in International Publication No. 2012/081640 (Comparative Example Compound (2)), sulfide capable of reacting with ozone is directly bonded to the chromophore. When the ozone fastness of this compound was evaluated, a color change occurred as an initial stage (see FIG. 1. X-rite 310TR (manufactured by X-Rite) was used for spectrum measurement). Thus, when a group capable of reacting with ozone is directly bonded to the chromophore, the chromophore is easily affected when reacting with ozone, which may cause discoloration remarkably.

As a result of intensive studies, the groups that can react with ozone do not bind directly to the chromophore, but are bonded via a linking group, making the chromophore less susceptible and causing an initial color change. The inventors have found that it effectively works as a chromophore substitution group for ozone, and completed the present invention.
The water-soluble dye represented by the general formula (1) is specifically shown below.

[Water-soluble dye represented by the general formula (1)]
The azo dye used in the ink composition of the present invention is represented by the general formula (1). The azo dye (black dye) represented by the general formula (1) (hereinafter sometimes referred to as “azo compound represented by the general formula (1)”) will be described below.

General formula (1):

In the formula, * represents a bond with a phenyl group, and ** represents a bond with L ₂ . R ₄ represents a hydrogen atom or a substituent.

L ₂ represents a linking group.
n represents 0, 1 or 2.
L ₃ represents an ozone fading preventing group.
R ₃ represents a hydrogen atom or a substituent. R ₃ may form a ring with L ₂ or L ₃ .
m represents 1 or 2.
Each M independently represents a hydrogen atom or a monovalent counter cation.

A in the general formula (1) represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group. The aryl group includes a substituted or unsubstituted aryl group. More specifically, an aryl group having substituent group J can be mentioned.
The aryl group represented by A is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group. Examples of the substituent include the groups described in the above-mentioned Substituent Group J, and the ionic hydrophilic group or the Hammett's σp value is preferably 0.3 or more.

The nitrogen-containing heterocyclic group represented by A includes a substituted or unsubstituted nitrogen-containing heterocyclic group. The heterocyclic group represented by A is preferably a monovalent group obtained by removing one hydrogen atom from a 5-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and has 2 to 4 carbon atoms. The 5-membered aromatic heterocyclic group is more preferable. Examples of the substituent include the groups described in the above-mentioned Substituent group J. Examples of the nitrogen-containing 5-membered heterocyclic group include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a thiazole ring, an isothiazole ring, and a thiadiazole ring.

A is preferably an aryl group having a substituent, more preferably an ionic hydrophilic group or an aryl group having a Hammett σp value of 0.2 or more, and an ionic hydrophilic group. More preferably, the naphthyl group has an electron withdrawing group having a group or Hammett's σp value of 0.2 or more, and an ionic hydrophilic group and an electron withdrawing group having a Hammett's σp value of 0.2 or more. Most preferably, it is a naphthyl group.

G in the general formula (1) represents a nitrogen atom or —C (R ₂ ) ═. R ₂ represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group. When the carbamoyl group has a substituent, the substituent is an alkyl group (methyl group, ethyl group), An aryl group (phenyl group) can be mentioned.

G is preferably —C (R ₂ ) ═. R ₂ is preferably a carbamoyl group (—CONH ₂ group) or a cyano group, and more preferably a cyano group.

In General Formula (1), L ₁ represents a linking group selected from the following group L ₁ .

Examples of the substituent represented by R ₄ include the substituent group A ′, which is preferably an unsubstituted alkyl group having 1 to 6 carbon atoms or an acyl group having 2 to 6 carbon atoms, such as a methyl group, an ethyl group, -It is more preferably a carboxyethyl group or an acetyl group.
R ₄ is preferably a hydrogen atom.

L ₁ is more preferably a linking group selected from the following group L ₁ ′.

In the formula, * represents a connecting position with a phenyl group, and ** represents a connecting position with L ₂ . R ₄ represents a hydrogen atom or a substituent.
R ₄ has the same meaning as R ₄ shown in the above-mentioned group L ₁ , and preferred examples are also the same.

In general formula (1), L ₂ represents a linking group. n represents 0, 1 or 2.
The linking group represented by L ₂ is an alkylene group, an arylene group, a heterocyclic residue, —CO—, —SO ₂ —, —NR ₁₁ — (R ₁₁ represents a hydrogen atom, an alkyl group, or an aryl group), — O— and a divalent or trivalent group obtained by combining these linking groups are preferable. Furthermore, these may have a substituent such as an alkyl group, an aryl group, an alkoxy group, an amino group, an acyl group, an acylamino group, a halogen atom, a hydroxyl group, a carboxyl group, a sulfamoyl group, a carbamoyl group, and a sulfonamide group. .
L ₂ is more preferably an alkylene group, an arylene group, —CO—, —NH—, —O—, or a divalent group obtained by combining these linking groups.

In the general formula (1), L ₃ represents an ozone fading preventing group.
In the present application, the ozone fading preventing group is a group capable of reacting with ozone, and effectively acts as a substitution group for the chromophore in the general formula (1), thereby bringing about an effect of suppressing color change in the initial stage. The ozone fading preventing group is not particularly limited as long as it is a group capable of reacting with ozone, and specific examples include thioether, unsaturated double bond, N-alkyl group, aldehyde group, hydrazine and the like.

L ₃ preferably represents a group selected from the following group L ₃ .

In the formula, R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom or a substituent. k represents an integer of 0 to 3. p represents an integer of 1 to 6.
In addition,

May be cis or trans.

Examples of the substituent represented by R ₅ , R ₆ , R ₇ , R ₈ and R ₉ include a substituent group A ′, and a substituted or unsubstituted alkyl group, acyl group, aryl group or ionic hydrophilicity It is preferably a group.
R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are preferably a hydrogen atom, a methyl group, an ethyl group, an aryl group or an ionic hydrophilic group.
k represents an integer of 0 to 3, and preferably represents an integer of 0 to 2.
p represents an integer of 1 to 6, and preferably represents an integer of 1 to 4.

L ₃ is more preferably a group selected from the following group L ₃ ′.

In the formula, R ₅ and R ₆ each independently represent a hydrogen atom or a substituent. k represents an integer of 0 to 3. p represents an integer of 1 to 6.
_R _5, R 6, k and p have the same meanings as _{_R 5,} _R _6, k and p shown in the group _{L 3,} and preferred examples are also the same.

In general formula (1), R ₃ represents a hydrogen atom or a substituent. R ₃ may form a ring with L ₂ .
Examples of the substituent represented by R ₃ include substituent group J. The substituent represented by R ₃ may be further repeatedly substituted with a substituent listed in the substituent group J.
The substituent represented by R ₃ is preferably an alkyl group, aryl group, alkylthio group, mercapto group, hydroxyl group, alkyloxy group, cycloalkyl group, or ionic hydrophilic group.
R ₃ is preferably a hydrogen atom, an alkyl group, an aryl group, or an ionic hydrophilic group.

As the ionic hydrophilic group in the general formula (1), —SO ₃ M ₁ or —CO ₂ M ₁ is preferable, —SO ₃ M ₁ is more preferable, and —SO ₃ Li is particularly preferable.

M ₁ and M in the general formula (1) each independently represent a hydrogen atom or a monovalent counter cation. Examples of monovalent counter cations include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions) and organic cations (eg, tetramethylammonium ions, tetramethylguanidinium ions, tetramethylphosphonium). Can be mentioned. As counter cations other than lithium ions, potassium ions and sodium ions are preferable, and sodium ions are more preferable.

As a salt to be formed, a lithium salt, a sodium salt, a potassium salt, or an ammonium salt is preferable, a lithium salt or a mixed salt containing a lithium salt as a main component is more preferable, and a lithium salt is most preferable.
When the azo compound represented by the general formula (1) is a mixed salt, it is a mixed salt of a lithium salt and a sodium salt from the viewpoints of solubility in water, aqueous solution viscosity, surface tension, and storage stability of a high concentration aqueous solution. It is preferable that a part of a plurality of M represents a lithium ion and the remaining M represents a sodium ion. A mode in which all M in (1) is mixed with a dye representing a sodium ion may be used.
When M is a mixed salt of a lithium salt and a sodium salt, the molar ratio of lithium salt to sodium salt (Li: Na) is preferably 99: 1 to 25:75, particularly 99: 1 to 50:50. 99: 1 to 55:45 is more preferable, and 99: 1 to 65:35 is most preferable among them. Within this range, the solubility and dissolution rate in water are good, the viscosity and surface tension of the high-concentration aqueous solution can be easily adjusted, and the storage stability of the high-concentration aqueous solution tends to be excellent. In particular, the prescription design of the constituent requirements of the ink composition of the water-soluble ink for ink jet becomes easy, and an excellent raw material (high concentration aqueous solution, ink composition) that satisfies the required performance of the water-soluble ink for ink jet at a high level can be provided. Play.
The ratio of cations of the mixed salt can be measured by ion chromatography analysis.

The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).
General formula (2):

In general formula (2),
X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent.
_G in formula (2) _{_{in, L 1, L 2, n}} , L 3, R 3, m, and M is _G in formula _{(1), L 1, L} 2, n, L 3, R ₃ Synonymous with m and M.

In the general formula (2), X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent. As the substituent in the case where X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ represent a substituent, the above-mentioned substituent J can be mentioned.
X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are each independently a hydrogen atom, halogen atom, ionic hydrophilic group, cyano group, substituted or unsubstituted alkylsulfonyl group, substituted or It is preferably an unsubstituted arylsulfonyl group, nitro group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, hydrogen atom, chlorine atom, ionic hydrophilicity Group, cyano group, methanesulfonyl group, phenylsulfonyl group, nitro group, methoxycarbonyl group, and carbamoyl group are more preferable, and a hydrogen atom, ionic hydrophilic group, cyano group, or nitro group is particularly preferable. .
In the general formula (2), X ₁ , X ₃ , X ₅ and X ₇ are each independently preferably either a hydrogen atom or a substituent group J. Furthermore, X ₂ , X ₄ and X ₆ At least one of these preferably represents an electron-withdrawing group having a Hammett's σp value of 0.3 or more.
If at least one of X ₂ , X ₄ , and X ₆ 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.

X ₂ , X ₄ and X ₆ are each independently a hydrogen atom, halogen atom, ionic hydrophilic group, cyano group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, nitro group, substituted Or an unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a hydrogen atom, a chlorine atom, an ionic hydrophilic group, a cyano group, a methanesulfonyl group, a phenylsulfonyl A group, a nitro group, a methoxycarbonyl group, and a carbamoyl group are more preferable, and a hydrogen atom, an ionic hydrophilic group, a cyano group, or a nitro group is particularly preferable.

Furthermore, it is preferable that at least one of X ₂ , X ₄ , and X ₆ represents an electron-withdrawing group having a Hammett's σp value of 0.2 or more. More preferably, it is an electron withdrawing group of 0 or less, X ₂ and X ₆ are ionic hydroxyl groups, and X ₄ represents an electron withdrawing group having a Hammett σp value of 0.2 or more.

Specific examples of the electron withdrawing group having a σp value of 0.2 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, halogen atom, aryl group substituted with other electron-withdrawing group having σp value of 0.3 or more, nitro group, heterocyclic ring Group, halogen atom, azo group, or Includes a selenocyanate group. A cyano group, a methylsulfonyl group, a phenylsulfonyl group, a methoxycarbonyl group, a chlorine atom, a carbamoyl group, and a nitro group are preferable, and a cyano group, a chlorine atom, a methylsulfonyl group, and a nitro group are more preferable.

From the viewpoint of hue, coloring power, and water-soluble storage stability, among the above, at least one of X ₂ , X ₄ , and X ₆ is preferably an ionic hydrophilic group, and X ₂ , X ₄ , and it is preferable that at least one of X ₆ is σp value of Hammett's 0.2 or more electron-withdrawing group, X ₃ is σp value of Hammett's a 0.2 or more electron-withdrawing group More preferably, X ₂ and X ₆ are ionic hydrophilic groups. As the ionic hydrophilic group, —SO ₃ M ₁ or —CO ₂ M ₁ (M ₁ represents a hydrogen atom or a monovalent counter cation) is preferable, —SO ₃ M ₁ is more preferable, —SO ₃ Li is particularly preferred.

Examples of G, L ₁ , L ₂ , L ₃ , R ₃ and M in the general formula (2) are each independently G, L ₁ , L ₂ , L ₃ , R _{3 in the} general formula (1). And examples of M, and preferable examples are also the same.

The compound represented by the general formula (1) or (2) is more preferably a compound represented by the following general formula (3).
General formula (3):

In the general formula (3), G, L ₁ , L ₂ , n, L ₃ , R ₃ , m, and M are G, L ₁ , L ₂ , n, L ₃ , R in the general formula (1). ₃ Synonymous with m and M.

Examples of G, L ₁ , L ₂ , L ₃ , R ₃ and M in the general formula (3) are each independently G, L ₁ , L ₂ , L ₃ , R _{3 in the} general formula (1). And examples of M, and preferable examples are also the same.

The azo compound represented by the general formula (3) is capable of adjusting the hue, improving light fastness and ozone gas fastness, and can obtain a high effect in terms of use as a water-soluble dye for inkjet recording black ink.

Specific examples of the azo compound represented by the general formula (1) are shown below, but the azo compound used in the present invention is not limited to the following examples.
In the chemical structural formulas of the following specific examples, those in which double bond portions (olefin-corresponding portions) cross each other represent E-form or a mixture of geometric isomers of E-form and Z-form.
In the exemplified compounds, M is not particularly limited, but represents a hydrogen atom, a lithium ion, a sodium ion, a potassium ion, a quaternary ammonium salt, or a mixture thereof.

The present invention also relates to an azo compound represented by the above general formula (1), general formula (2), or general formula (3), and an aqueous solution using the azo compound of the present invention as a coloring matter (colorant) and The water-soluble ink composition means a composition containing a coloring material such as a dye or a pigment and a dispersant (such as a solvent) thereof, and can be particularly suitably used for image formation.

(Ink composition)
The ink composition of the present invention (also referred to as the ink of the present invention) contains the water-soluble dye represented by the general formula (1) in an aqueous medium, and is preferably dissolved in the aqueous medium. By using the water-soluble dye represented by the general formula (1), an ink composition having high ozone resistance, particularly ozone resistance at an initial stage, small color change, and excellent light resistance is provided. . The ink composition of the present invention can be preferably used as a black ink.
The content of the water-soluble dye represented by the general formula (1) in the ink composition is preferably 0.1 to 10% by mass, more preferably 0.1% by mass with respect to the total mass of the ink composition. 7 to 6.0% by mass. By setting it within this range, the light resistance, ozone resistance, and water resistance of the image to be formed are improved, the color tone is excellent, and better ink jet characteristics tend to be obtained.
The ink composition of the present invention is preferably used as an ink for ink jet recording. That is, the present invention also relates to an ink jet recording ink containing the ink composition of the present invention. The content of the water-soluble dye represented by the general formula (1) in the ink for inkjet recording is the same as the content in the ink composition.

In addition to the water-soluble dye represented by the general formula (1), the ink composition of the present invention (preferably an ink for ink jet recording) is used in combination with other dyes in order to adjust the color tone and balance the performance. May be. For the purpose of obtaining a full-color image, an ink containing another dye may be used in combination with the ink for ink jet recording of the present invention. Examples of dyes that can be used in combination include the following.

As yellow dyes, for example, phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components; for example, open-chain active methylene compounds as coupling components Azomethine dyes; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dye species such as quinophthalone dyes, nitro-nitroso dyes And dyes, acridine dyes, acridinone dyes and the like. These dyes may be those that exhibit yellow only after a part of the chromophore is dissociated, in which case the counter cation may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, and may further be a polymer cation having them in a partial structure.

Examples of magenta dyes include aryl or heteryl azo dyes having phenols, naphthols, and anilines as coupling components; azomethine dyes having pyrazolones and pyrazolotriazoles as coupling components; for example, arylidene dyes, styryl dyes, merocyanine Dyes, methine dyes such as oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc. Examples thereof include ring dyes. These dyes may exhibit magenta only after part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, and may further be a polymer cation having them in a partial structure.

Examples of cyan dyes include azomethine dyes such as indoaniline dyes and indophenol dyes; polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; phthalocyanine Dyes; anthraquinone dyes; for example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components, and indigo / thioindigo dyes. These dyes may exhibit cyan only after a part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, and may further be a polymer cation having them in a partial structure.
Also, black dyes such as polyazo dyes can be used.

Examples of water-soluble dyes include direct dyes, acid dyes, food dyes, basic dyes, and reactive dyes. Preferred examples include C.I. I.

Direct Red

2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 21, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, C.I. I. Direct violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101, C.I. I. Direct yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 86, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 132, 142, 144, 161, 163, C.I. I.

Direct Blue

1, 10, 15, 22, 25, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108, 109, 151, 156, 158, 159, 160, 168, 189, 192, 193, 194, 199, 200, 201, 202, 203, 207, 211, 213, 214, 218, 225, 229, 236, 237, 244, 248, 249, 251, 252, 264, 270, 280, 288, 289, 291, C.I. I. Direct Black 9, 17, 19, 22, 32, 51, 56, 62, 69, 77, 80, 91, 94, 97, 108, 112, 113, 114, 117, 118, 121, 122, 125, 132, 146, 154, 166, 168, 173, 199, C.I. I. Acid Red 35, 42, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 151, 154, 158, 249, 254, 257, 261, 263, 266, 289, 299, 301, 305, 336, 337, 361, 396, 397, C.I. I. Acid Violet 5, 34, 43, 47, 48, 90, 103, 126, C.I. I. Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195, 196, 197, 199, 218, 219, 222, 227, C.I. I. Acid Blue 9, 25, 40, 41, 62, 72, 76, 78, 80, 82, 92, 106, 112, 113, 120, 127: 1, 129, 138, 143, 175, 181, 205, 207, 220, 221, 230, 232, 247, 258, 260, 264, 271, 277, 278, 279, 280, 288, 290, 326, C.I. I. Acid Black 7, 24, 29, 48, 52: 1, 172, C.I. I.

Reactive Red

3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55, C.I. I.

Reactive violet

1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34, C.I. I. Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, C.I. I.

Reactive Blue

2, 3, 5, 8, 10, 13, 14, 15, 17, 18, 19, 21, 25, 26, 27, 28, 29, 38, C.I. I.

Reactive Black

4, 5, 8, 14, 21, 23, 26, 31, 32, 34, C.I. I.

Basic Red

12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46, C.I. I.

Basic violet

1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48, C.I. I. Basic yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40, C.I. I.

Basic Blue

1, 3, 5, 7, 9, 22, 26, 41, 45, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71, C.I. I. Basic black 8, etc. are mentioned.

Further, pigments can be used in combination with the ink composition of the present invention.
As the pigment used in the present technology, commercially available pigments and known pigments described in various documents can be used. Regarding the literature, the Color Index (Edited by The Society of Dyers and Colorists), “Revised New Handbook of Pigments” edited by the Japan Pigment Technology Association (published in 1989), “Latest Pigment Applied Technology” published by CMC (published in 1986), “Printing Ink Technology” CMC Publishing (1984), W. Herbst, K.M. Hunger co-authored, Industrial Organic Pigments (VCH Verlagsgesellschaft, published in 1993). Specifically, for organic pigments, azo pigments (azo lake pigments, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, indigo pigments, quinacridone Pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments), dyed lake pigments (acid or basic dye lake pigments), azine pigments, etc. C.I. of yellow pigment I. Pigment Yellow 34, 37, 42, 53, and other red pigments such as C.I. I. Pigment Red 101, 108, etc., blue pigments such as C.I. I. Pigment Blue 27, 29, 17: 1, etc. I. Pigment Black 7, magnetite, and other white pigments such as C.I. I.

Pigment White

4, 6, 18, 21 and the like.

As a pigment having a preferable color tone for image formation, a phthalocyanine pigment, an anthraquinone-based indanthrone pigment (for example, CI Pigment Blue 60), and a dyed lake pigment-based triarylcarbonium pigment are preferable for a blue or cyan pigment. In particular, phthalocyanine pigments (preferred examples include copper pigments such as CI Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, monochloro or low chlorinated copper) Among the phthalocyanines and aluminium phthalocyanines, the pigments described in European Patent No. 860475, the metal-free phthalocyanine which is CI Pigment Blue 16, and the phthalocyanines whose central metals are Zn, Ni and Ti are preferable, among which CI Pigment is preferable. Blue 15: 3, 15: 4 and aluminum phthalocyanine) are most preferred.

For red to purple pigments, azo pigments (preferred examples include

CI Pigment Red

3, 5, 11, 22, 38, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 52: 1, 53: 1, 57: 1, 63: 2, 144, 146, and 184). I. Pigment Red 57: 1, 146, 184), quinacridone pigments (preferred examples include CI Pigment Red 122, 192, 202, 207, 209, CI Pigment Violet 19, 42. Among them, CI Pigment Red 122 is preferable, and dyed lake pigment type triarylcarbonium pigments (preferred examples are xanthene CI Pigment Red 81: 1, CI Pigment Violet). 1, 2, 3, 27, 39), dioxazine pigments (eg, CI Pigment Violet 23, 37), diketopyrrolopyrrole pigments (eg, CI Pigment Red 254), perylene Pigments (eg C I.Pigment Violet 29), anthraquinone pigments (e.g., C.I. Pigment Violet 5: 1, the 31, the 33), thioindigo (e.g. C.I. Pigment Red 38, the 88) is preferably used.

Examples of yellow pigments include azo pigments (preferred examples include monoazo pigment-based

CI Pigment Yellow

1, 3, 74, 98, disazo pigment-based

CI Pigment Yellow

12, 13, 14, 16, 17, 83. , Azo-based CI Pigment Yellow 93, 94, 95, 128, 155, benzimidazolone-based CI Pigment Yellow 120, 151, 154, 156, 180, etc., among which benzidine is preferable. Compounds that do not use compounds as raw materials), isoindoline / isoindolinone pigments (preferred examples include CI Pigment Yellow 109, 110, 137, and 139), quinophthalone pigments (preferred examples include CI Pigment). Yell Etc. w 138), such as flavanthrone pigments (e.g., C.I. Pigment Yellow 24) are preferably used.

Preferred examples of the black pigment include inorganic pigments (preferably carbon black and magnetite as examples) and aniline black.
In addition, an orange pigment (C.I. Pigment Orange 13, 16, etc.) or a green pigment (C.I. Pigment Green 7, etc.) may be used.

The pigment that can be used in the present technology may be the aforementioned bare pigment or a surface-treated pigment. Surface treatment methods include resin or wax surface coating, surfactant deposition, reactive substances (eg radicals derived from silane coupling agents, epoxy compounds, polyisocyanates, diazonium salts, etc.) pigments A method of bonding to the surface is conceivable and is described in the following documents and patents.
(1) Properties and applications of metal soap (Sachishobo)
(2) Printing ink printing (CMC Publishing 1984)
(3) Latest pigment application technology (CMC Publishing 1986)
(4) US Pat. Nos. 5,554,739 and 5,571,311 (5) JP-A Nos. 9-151342, 10-140065, 10-292143, and 11-166145 In particular, Self-dispersing pigments prepared by allowing a diazonium salt described in US Patent 4) to act on carbon black and encapsulated pigments prepared by the method described in Japanese Patent (5) above are used in inks. In particular, the dispersion stability can be obtained without using an extra dispersant.

In the present invention, the pigment may be further dispersed using a dispersant. Various known dispersants can be used in accordance with the pigment to be used, for example, a surfactant-type low-molecular dispersant or a polymer-type dispersant. Examples of the dispersant include those described in JP-A-3-69949, European Patent 549486 and the like. In addition, when a dispersant is used, a pigment derivative called a synergist may be added to promote adsorption of the dispersant to the pigment.
The particle size of the pigment that can be used in the present technology is preferably in the range of 0.01 to 10 μm after dispersion, and more preferably 0.05 to 1 μm.
As a method for dispersing the pigment, a known dispersion technique used in ink production or toner production can be used. Examples of the dispersing machine include vertical or horizontal agitator mills, attritors, colloid mills, ball mills, three roll mills, pearl mills, super mills, impellers, dispersers, KD mills, dynatrons, and pressure kneaders. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

[Ink pH]
The ink composition of the present invention preferably has a pH of 7.0 or more and 10.0 or less from the viewpoints of storage stability and ejection properties of the ink composition.

[Surfactant]
Next, the surfactant that can be contained in the ink composition of the present invention (preferably ink for inkjet recording) will be described.
Examples of the surfactant used in the present invention include anionic surfactants such as fatty acid salts, higher alcohol ester salts, alkylbenzene sulfonate salts, sulfosuccinic acid ester salts, higher alcohol phosphoric acid ester salts, aliphatic amine salts, 4 Nonionic surfactants such as cationic surfactants such as quaternary ammonium salts, ethylene oxide adducts of higher alcohols, ethylene oxide adducts of alkylphenols, polyhydric alcohol fatty acid esters, acetylene glycol and its ethylene oxide adducts And amphoteric surfactants such as amino acid type and betaine type, fluorine-based compounds, and silicon-based compounds. These may be used alone or in combination of two or more.

By adding a surfactant to the ink composition of the present invention and adjusting the liquid physical properties of the ink such as surface tension, the ink ejection stability is improved, the water resistance of the image is improved, and the printed ink bleeds. It is possible to have an excellent effect in prevention and the like. Further, two or more kinds of the above surfactants may be used in combination.
The ink composition used in the present invention preferably contains 0.005 to 5% by mass of a surfactant, more preferably 0.005 to 3% by mass. When the content of the surfactant in the ink composition is in the range of 0.005 to 5% by mass, the discharge stability does not deteriorate, the occurrence of bleeding at the time of color mixing, the deterioration of print quality such as the generation of whiskers does not occur, At the time of ejection, it is possible to suppress printing defects due to adhesion of ink to the periphery of the nozzle.

The ink composition of the present invention is prepared by dissolving the above dye in an aqueous medium, adding a specific amount of a surfactant as required, and further dissolving and / or dispersing other additives as necessary. can do. The “aqueous medium” in the present invention means a mixture of water or a mixture of water and a small amount of a water-miscible organic solvent with additives such as wetting agents and stabilizers added as necessary.

When preparing the ink liquid of the present invention, in the case of water-soluble ink, it is preferable to first dissolve in water. Thereafter, various solvents and additives are added, dissolved and mixed to obtain a uniform ink solution.
As the dissolution method at this time, various methods such as dissolution by stirring, dissolution by ultrasonic irradiation, and dissolution by shaking can be used. Of these, the stirring method is particularly preferably used. In the case of stirring, various methods such as fluidized stirring known in the art and stirring using shearing force using an inverted agitator or dissolver can be used. On the other hand, a stirring method using a shearing force with the bottom surface of the container, such as a magnetic stirrer, can also be preferably used.

With respect to the preparation method of the water-based inkjet ink, JP-A-5-148436, JP-A-5-295212, JP-A-7-97541, JP-A-7-82515, JP-A-7-118857, JP-A-2002-020657, Details are described in each publication of Japanese Utility Model Publication No. 2002-060663, and can also be used for the preparation of the ink for inkjet recording of the present invention.

The ink composition of the present invention comprises a water-soluble dye represented by the general formula (1) in an aqueous medium. The aqueous medium may contain a water-miscible organic solvent, and the water-miscible organic solvent contained in the aqueous medium has a solubility at 25 ° C. of the dye used of 10 (g / 100 g solvent) or less. Is preferred. Here, the solubility means the mass of a solute that can be dissolved at a certain temperature in 100 g of the solvent, and the unit is “g / 100 g solvent”.
The solubility of the dye of the present invention varies somewhat depending on its structure. For the ink of the present invention, a water-miscible organic solvent having a solubility of 10 (g / 100 g solvent) or less is appropriately selected depending on the dye type. It is preferable.
The solubility of the dye of the present invention at 25 ° C. is more preferably 8 (g / 100 g solvent) or less, and still more preferably 5 (g / 100 g solvent) or less.
Moreover, it is preferable that the said water-miscible organic solvent is a mixture which consists of 2 or more types by which at least 1 type contains alcohol and / or its derivative (s). The addition amount of the water-miscible organic solvent is preferably 1 to 60% by mass, more preferably 5 to 50% by mass. By setting this value, the ink stability, ejection stability, and drying property tend to be good.

Examples of the water-miscible organic solvent include the following. A water-miscible organic solvent suitable for the present invention can be selected from the following.
Alcohol (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (eg, ethylene glycol, diethylene glycol, thiol) Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,5-pentanediol, 1, 2-hexanediol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetri Thiodiglycol), glycol derivatives (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl Ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethyl Glycol monoisobutyl ether, propylene glycol monopropyl ether,

Ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amines (eg ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N -Ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide) Dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, - vinyl-2-pyrrolidone, 2-oxazolidone, ethylene urea (2-imidazolidinone), 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone, diacetone alcohol). Two or more kinds of the water-miscible organic solvents may be used in combination.

When the other dye used in the present invention is an oil-soluble dye, it can be prepared by dissolving the oil-soluble dye in a high-boiling organic solvent and emulsifying and dispersing it in an aqueous medium.
The high-boiling organic solvent used has a boiling point of 150 ° C. or higher, preferably 170 ° C. or higher. The high boiling point organic solvent can be used in an amount of 0.01 to 3 times, preferably 0.01 to 1.0 times the mass ratio of the oil-soluble dye.
These high boiling point organic solvents may be used alone or in a mixture of several kinds.

In the present invention, the oil-soluble dye and the high-boiling organic solvent are emulsified and dispersed in an aqueous medium. In the emulsification dispersion, a low boiling organic solvent can be used depending on the case from the viewpoint of emulsification. The low boiling point organic solvent is an organic solvent having a boiling point of about 30 ° C. or higher and 150 ° C. or lower at normal pressure.

The emulsification dispersion is used to disperse an oil phase in which a dye is dissolved in a mixed solvent of a high-boiling organic solvent and, optionally, a low-boiling organic solvent, in an aqueous phase mainly composed of water to form fine oil droplets in the oil phase. Done. Under the present circumstances, additives, such as surfactant, a wetting agent, a dye stabilizer, an emulsion stabilizer, etc. which were mentioned above can be added to either or both of a water phase and an oil phase as needed. As an emulsification method, a method of adding an oil phase to an aqueous phase is common, but a so-called phase inversion emulsification method in which an aqueous phase is dropped into an oil phase can also be preferably used.

In the present invention, in addition to the above compounds, when used as an inkjet recording ink, a drying inhibitor for preventing clogging due to drying at the ink jetting port, a penetration accelerator for penetrating the ink with paper, Additives such as UV absorbers, antioxidants, viscosity modifiers, surface tension modifiers, dispersants, dispersion stabilizers, rust inhibitors, antiseptics, antifungal agents, pH adjusters, antifoaming agents, chelating agents, etc. An appropriate amount can be used by appropriately selecting.

The drying inhibitor used in the present invention is preferably a water-soluble organic solvent having a vapor pressure lower than that of water.
Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said anti-drying agent may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

Examples of penetration enhancers used in the present invention include alcohols such as ethanol, isopropanol, butanol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surface activity. An agent or the like can also be used. If these are contained in the ink in an amount of 10 to 30% by mass, they are sufficiently effective, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding or paper loss (print-through).

Examples of the ultraviolet absorber used for improving the storability of the image in the present invention include JP-A Nos. 58-185677, 61-190537, JP-A-2-782, and JP-A-5-97075. Benzotriazole compounds described in JP-A-9-34057, etc., benzophenone compounds described in JP-A-46-2784, JP-A-5-194443, US Pat. No. 3,214,463, etc. -30492, 56-21141, and cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, and JP-A-8-239368. Triazine compounds described in JP-A-10-182621, JP-A-8-501291, etc., Research Disclosure Turbocharger over No. A compound described in No. 24239, a compound that emits fluorescence by absorbing ultraviolet rays typified by a stilbene series or a benzoxazole series, a so-called fluorescent whitening agent can also be used.

As the antioxidant used for improving the storability of the image in the present invention, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in Japanese Patent No. 15162 and the compounds represented by the general formulas and compound examples of the representative compounds described on pages 127 to 137 of JP-A-62-215272 can be used.

Examples of the rust inhibitor used in the present invention include acidic zinc sulfate, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol nitrate, dicyclohexylammonium nitrite and the like. These are preferably used in an amount of 0.02 to 5.00% by mass in the ink.

The pH adjusting agent used in the present invention can be suitably used in terms of pH adjustment, imparting dispersion stability, etc., and the pH of the ink at 25 ° C. is adjusted to 8-11. When the pH is less than 8, the solubility of the dye is lowered and the nozzle is easily clogged, and when it exceeds 11, the water resistance is deteriorated. As a pH adjuster, an organic base, an inorganic alkali, etc. are mentioned as a basic thing, An organic acid, an inorganic acid, etc. are mentioned as an acidic thing.
Examples of the organic base include triethanolamine, diethanolamine, N-methyldiethanolamine, and dimethylethanolamine. Examples of the inorganic alkali include alkali metal hydroxides (for example, sodium hydroxide, lithium hydroxide, and potassium hydroxide), carbonates (for example, sodium carbonate, sodium hydrogen carbonate, and the like), ammonium, and the like. Examples of the organic acid include acetic acid, propionic acid, trifluoroacetic acid, and alkylsulfonic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid.

The surface tension of the ink used in the present invention is preferably 20 to 50 mN / m or less at 25 ° C., and more preferably 20 to 40 mN / m or less. By setting this value, the ejection stability and the printing quality tend to be good, and it becomes easy to prevent printing defects due to the adhesion of ink to the peripheral portion of the nozzle during ejection.

The viscosity of the ink used in the present invention is preferably 30 mPa · s or less. Furthermore, since it is more preferable to adjust to 20 mPa * s or less, a viscosity modifier may be used in order to adjust a viscosity. Examples of the viscosity modifier include water-soluble polymers such as celluloses and polyvinyl alcohol, and nonionic surfactants. For more details, see Chapter 9 of “Viscosity Adjustment Technology” (Technical Information Association, 1999) and “Chemicals for Inkjet Printers (98 Supplement)-Material Development Trends and Perspective Survey” (CMC, 1997) 162- Page 174.

Furthermore, in the present invention, a polymer fine particle dispersion may be used. Details thereof are described in JP-A No. 2002-264490.
In the present invention, the above-mentioned cation, anion, and nonionic surfactants are used as a dispersant and a dispersion stabilizer, and fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like are used as necessary. be able to.

<Recording medium>
The ink of the present invention is a known recording material, that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153898, JP-A-10-217473, JP-A-10-235995, JP-A-10-337947, and JP-A-10-217597 10-337947, etc., can be used to form an image on dedicated paper for inkjet, film, electrophotographic co-paper, fabric, glass, metal, ceramics, and the like.

The recording paper and recording film used for inkjet printing using the ink of the present invention will be described below. The support for recording paper and recording film consists of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP, 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 those manufactured by various devices such as long net paper machines and circular net paper machines can be used. It is. 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 . The support may be provided with an ink receiving layer and a backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar. In the present invention, as the support, paper and plastic film laminated on both sides with polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine blue, neodymium oxide) to the polyolefin.

The ink receiving layer provided on the support contains a pigment and an aqueous binder. As the pigment, a white pigment is good, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include inorganic white pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins, and melamine resins. The white pigment contained in the ink receiving layer is preferably a porous inorganic pigment, and synthetic amorphous silica having a large pore area is particularly suitable. As the synthetic amorphous silica, either anhydrous silicic acid obtained by a dry production method (gas phase method) or hydrous silicic acid obtained by a wet production method can be used, but it is particularly desirable to use hydrous silicic acid. Two or more of these pigments may be used in combination.

Specific examples of the recording paper containing the pigment in the image receiving layer include JP-A-10-81064, JP-A-10-119423, JP-A-10-157277, JP-A-10-217601, and JP-A-10-348409. No. 2001-138621, 2000-43401, 2000-2111235, 2000-309157, 2001-96897, 2001-138627, JP-A-11-91242, 8-2087, Those disclosed in JP-A-8-2090, JP-A-8-2091, JP-A-8-2093, JP-A-8-174992, JP-A-11-192777, JP-A-2001-301314 and the like can be used.

Examples of the aqueous binder contained in the ink receiving layer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. Water-dispersible polymers such as water-soluble polymers, styrene butadiene latexes, and acrylic emulsions. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and resistance to peeling of the ink receiving layer.
The ink receiving layer can contain a mordant, a water resistance agent, a light resistance improver, an ozone resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used.
As for the polymer mordant, JP-A-48-28325, JP-A-54-74430, JP-A-54-124726, JP-A-55-22766, JP-A-55-142339, JP-A-60-23850, JP-A-60-23851, 60-23852, 60-23835, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122942, 60- No. 235134, JP-A-1-161236, U.S. Pat.Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386, 4,193,800, 4,283,853, 4,282,305, It is described in each specification of the same No. 4450224. An image receiving material containing a polymer mordant described in JP-A-1-161236, pages 212 to 215 is particularly preferred. When the polymer mordant described in the publication is used, an image with excellent image quality is obtained and the light resistance of the image is improved.

The water-proofing agent is effective for making the image water-resistant. As these water-proofing agents, cationic resins are particularly desirable. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, and cationic polyacrylamide. The content of these cationic resins is preferably 1 to 15% by mass, particularly 3 to 10% by mass, based on the total solid content of the ink receiving layer.

Examples of the light resistance improver and gas resistance improver include phenol compounds, hindered phenol compounds, thioether compounds, thiourea compounds, thiocyanate compounds, amine compounds, hindered amine compounds, TEMPO compounds, hydrazine compounds, hydrazide compounds, amidine compounds, Vinyl group-containing compounds, ester compounds, amide compounds, ether compounds, alcohol compounds, sulfinic acid compounds, saccharides, water-soluble reducing compounds, organic acids, inorganic acids, hydroxy group-containing organic acids, benzotriazole compounds, benzophenone compounds, triazine compounds , Heterocyclic compounds, water-soluble metal salts, organometallic compounds, metal complexes, and the like.
Specific examples of these compounds include JP-A-10-182621, JP-A-2001-260519, JP-A-2000-260519, JP-B-4-34953, JP-B-4-34513, and JP-B-4-34512. , JP-A-11-170686, JP-A-60-67190, JP-A-7-276808, JP-A-2000-94829, JP-T 8-512258, JP-A-11-321090, etc. Is mentioned.

The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. Surfactants are described in JP-A Nos. 62-173463 and 62-183457.
An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (eg, fluorine oil), and a solid fluorine compound resin (eg, tetrafluoroethylene resin). The organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-2994 and JP-A-62-135826.

As the hardener, materials described in JP-A-1-161236, page 222, JP-A-9-263036, JP-A-10-119423, JP-A-2001-310547, and the like can be used.

Examples of other additives added to the ink receiving layer include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusters, matting agents, and hardening agents. . The ink receiving layer may be one layer or two layers.

Recording paper and recording film can be provided with a backcoat layer, and examples of components that can be added to this layer include white pigments, aqueous binders, and other components. Examples of white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. White inorganic pigments such as diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide, Examples thereof include organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin, and melamine resin.

As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.

Polymer latex may be added to the constituent layers (including the back 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, 62-1316648, 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 back layer.

<Inkjet recording method>
The present invention also relates to an ink jet recording method using the ink for ink jet recording according to the present invention.
The ink of the present invention is not limited to the ink jet recording system, and is a known system such as a charge control system that ejects ink using electrostatic attraction, a drop-on-demand system (pressure pulse system) that uses the vibration pressure of a piezo element. ), An acoustic ink jet method that converts an electrical signal into an acoustic beam, irradiates the ink and uses ink to eject the ink, and a thermal ink jet method that heats the ink to form bubbles and uses the generated pressure. Used.
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.
A preferred combination of a recording material and a recording method is an inkjet recording in which an image receiving material having an image receiving layer containing white inorganic pigment particles on a support is ejected with ink droplets according to a recording signal, and an image is recorded on the image receiving material. Is the method.

The ink for ink jet recording of the present invention can also be used for purposes other than ink jet recording. For example, it can be used for display image materials, image forming materials for interior decoration materials, and image forming materials for outdoor decoration materials.

Display image materials include posters, wallpaper, small decorative items (such as figurines and dolls), commercial flyers, wrapping paper, wrapping materials, paper bags, plastic bags, packaging materials, signs, transportation (automobiles, buses, trains, etc.) ) Refers to various things such as images drawn and attached to the side, clothes with logos, and so on. When the dye of the present invention is used as a material for forming a display image, the image includes all patterns of dyes that can be recognized by humans, such as abstract designs, characters, and geometric patterns, in addition to images in a narrow sense.

Interior decoration materials refer to various items such as wallpaper, decorative accessories (such as figurines and dolls), lighting fixtures, furniture components, floor and ceiling design components. When the dye of the present invention is used as an image forming material, the image includes all patterns of dyes that can be recognized by humans such as abstract designs, characters, and geometric patterns in addition to images in a narrow sense.

«Outdoor decoration materials include various materials such as wall materials, roofing materials, signboards, gardening materials, outdoor decoration accessories (such as figurines and dolls), and outdoor lighting fixtures. When the dye of the present invention is used as an image forming material, the image includes not only images in a narrow sense but also all patterns of dyes that can be recognized by humans, such as abstract designs, characters, and geometric patterns.

In the above applications, examples of media on which a pattern is formed include various materials such as paper, fiber, cloth (including non-woven fabric), plastic, metal, and ceramics. As the dyeing form, the dye can be fixed in the form of mordanting, printing, or a reactive dye having a reactive group introduced. Among these, it is preferable that the mordanting is performed.

<Other inks>
In order to form a full-color image or the like, the ink of the present invention can be used in combination with an ink having a color tone different from that of the ink of the present invention. The ink of the present invention is preferably used together with at least one kind of ink selected from, for example, black ink, cyan ink, magenta ink, yellow ink, red ink, green ink, and blue ink. Further, a so-called light ink having substantially the same color tone as these inks can be used in combination. The water-soluble dye of these inks or light inks may be a known dye or a newly synthesized water-soluble dye.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples.

(Synthesis Example 1)
Compound (1) -1 used in the present invention can be derived from, for example, the following synthetic route.
A synthesis scheme of compound (1) -1 (M: Li / Na≈90 / 10 (mol / mol)) is shown below.

(1-1) Synthesis of Compound (A) -2:
Compound (A) -1 was synthesized by the method described in International Publication No. 2012/127758. Compound (A) -1 (5.0 g) was dissolved in acetone (75 mL), and ice-cooled to adjust the internal temperature to 10 ° C. or lower. The maleic anhydride 2.23g was added here, and it stirred for 30 minutes, Then, it stirred at room temperature for 1 hour. The precipitated crystals were filtered and washed with acetone to obtain 6.5 g of Compound (A) -2. The NMR measurement results of the obtained compound (A) -2 are as follows. ¹ H NMR (400 MHz in DMSO-d6; δ ppm; J Hz) 6.32 (1H, d), 6.49 (1H, d), 6.49 (1H, s), 7.26 (2H, s) 7.51 (2H, d), 7.68 (2H, d), 10.49 (1H, s)

(1-2) Synthesis of Compound (A) -4:
Compound (A) -3 was synthesized by the method described in WO2010 / 041065. 3.67 g of compound (A) -3 was suspended in 73 g of water, and 50% aqueous NaOH solution was added to adjust the pH to 8. The mixture was ice-cooled, 4.2 mL of hydrochloric acid was added at 5 ° C. or lower, and the mixture was stirred at the same temperature for 30 minutes. At the same temperature, 2.54 mL of 30% aqueous sodium nitrite solution was added dropwise and stirred for 1 hour, then 0.1 g of urea was added and stirred for 5 minutes to obtain a diazonium salt solution.
Separately, 3 g of compound (A) -2 was suspended in 60 mL of methanol, and 3 g of lithium acetate was added. The internal temperature was adjusted to 10 ° C. or lower by cooling with ice, and the above diazonium salt solution was added thereto so that the internal temperature was 10 ° C. or lower. At that time, lithium acetate was appropriately added so that the pH was 5 or more. After adding the diazonium salt solution, the mixture was warmed to room temperature, stirred at the same temperature for 1 hour, and then hydrochloric acid was added until the pH was 1 or less. The precipitated solid was filtered, rinsed with 2N hydrochloric acid, rinsed with 10 mL of water, and dried at 50 ° C. for 12 hours to obtain 5.8 g of Compound (A) -4.

(1-3) Synthesis of compound (1) -1:
4.8 g of the obtained compound (A) -4 and 4.5 g of compound (A) -5 were suspended in 120 g of water, and the temperature was raised to an internal temperature of 35 ° C. 1.4 g of isoamyl nitrite was added dropwise over 30 minutes. The temperature was raised and the mixture was stirred at 40 ° C. for 1 hour. After completion of the reaction, the pH is adjusted to 8 to 8.5 using a 4N aqueous lithium hydroxide solution, further lithium chloride is added, the precipitated solid is filtered, washed with isopropanol, and compound (1) -1 3.5 g was obtained. The measured ¹ H NMR ( ¹ H NMR (400 MHz in DMSO-d6; δ ppm; J Hz)) of Compound (1) -1 is shown in FIG.
As a result of LC-MS, a peak corresponding to compound (1) -1 was detected. When the UV spectrum when 20 mg of the powder was dissolved in 1000 mL of water was measured, the maximum absorption wavelength was 625 nm.

(Synthesis Example 2)
A synthesis scheme of compound (1) -2 (M: Li / Na≈90 / 10 (mol / mol)) is shown below.

(2-1) Synthesis of compound (A) -7:
Compound (A) -6 was synthesized by the method described in International Publication No. 2012/127758. Compound (A) -6 (5.0 g) was dissolved in acetone (75 mL), and the mixture was cooled with ice to bring the internal temperature to 10 ° C. or lower. The maleic anhydride 2.23g was added here, and it stirred for 30 minutes, Then, it stirred at room temperature for 1 hour. The precipitated crystals were filtered and washed with acetone to obtain 6.5 g of Compound (A) -7. The NMR measurement results of the obtained compound (A) -7 are as follows. ¹ H NMR (400 MHz in DMSO-d6; δ ppm; J Hz) 6.32 (1H, d), 6.48 (1H, d), 6.92 (1H, s), 7.04 (2H, s) , 7.62 (2H, d), 7.75 (2H, d), 10.45 (1H, s)

(2-2) Synthesis of Compound (A) -8:
Compound (A) -3 (3.81 g) was suspended in water (76 g), and 50% aqueous NaOH solution was added to adjust the pH to 8. The mixture was ice-cooled, 4.2 mL of hydrochloric acid was added at 5 ° C. or lower, and the mixture was stirred at the same temperature for 30 minutes. At the same temperature, 2.63 mL of 30% aqueous sodium nitrite solution was added dropwise and stirred for 1 hour, then 0.1 g of urea was added and stirred for 5 minutes to obtain a diazonium salt solution.
Separately, 2.9 g of compound (A) -7 was suspended in 60 mL of methanol, and 5 g of lithium acetate was added. The internal temperature was adjusted to 10 ° C. or lower by cooling with ice, and the above diazonium salt solution was added thereto so that the internal temperature was 10 ° C. or lower. At that time, lithium acetate was appropriately added so that the pH was 5 or more. After adding the diazonium salt solution, the mixture was warmed to room temperature, stirred at the same temperature for 1 hour, and then hydrochloric acid was added until the pH was 1 or less. The precipitated solid was filtered, rinsed with 2N hydrochloric acid, rinsed with 10 mL of water, and dried at 50 ° C. for 12 hours to obtain 5.5 g of Compound (A) -8.

(2-3) Synthesis of Compound (1) -2:
4 g of the obtained compound (A) -8 and 4.3 g of compound (A) -5 were suspended in 120 g of water, and the internal temperature was raised to 35 ° C. 1.4 g of isoamyl nitrite was added dropwise over 30 minutes. The temperature was raised and the mixture was stirred at 40 ° C. for 1 hour. After completion of the reaction, the pH is adjusted to 8 to 8.5 using a 4N aqueous lithium hydroxide solution, further lithium chloride is added, the precipitated solid is filtered, washed with isopropanol, and compound (1) -2.8 g were obtained.
As a result of LC-MS, a peak corresponding to compound (1) -2 was detected. When the UV spectrum when 20 mg of the powder was dissolved in 1000 mL of water was measured, the maximum absorption wavelength was 627 nm.

(Synthesis Example 3)
A synthesis scheme of compound (1) -3 (M: Li / Na≈80 / 20 (mol / mol)) is shown below.

(3-1) Synthesis of Compound (A) -9:
10.0 g of compound (A) -1 was dissolved in 100 mL of dimethylacetylamide, and ice-cooled to bring the internal temperature to −5 ° C. or lower. To this, 4.2 g of chloroacetic chloride was slowly added and stirred at −10 ° C. for 30 minutes, and then 600 mL of water was added. The precipitated crystals were filtered and washed with acetone to obtain 10.8 g of Compound (A) -9. The NMR measurement results of the obtained compound (A) -9 are as follows. ¹ H NMR (400 MHz in DMSO-d6; δ ppm; J Hz) 4.27 (2H, s), 6.49 (1H, s), 7.30 (2H, s), 7.51 (2H, d) , 7.64 (2H, d), 10.41 (1H, s)

(3-2) Synthesis of compound (A) -10:
5 g of compound (A) -9 was dissolved in 50 mL of dimethyl sulfoxide and stirred at room temperature. The thiophenol 2.8g was dripped here, and also sodium hydrogencarbonate 2.16g was added, and it heated up so that internal temperature might be 50 degreeC. After stirring at the same temperature for 1.5 hours, 150 mL of water was added and stirred at room temperature for 30 minutes. The precipitated solid was filtered and thoroughly washed with water to obtain 7.7 g of a thiophenol salt of compound (A) -10. The NMR measurement result of the obtained compound (A) -10 is as follows. ¹ H NMR (400 MHz in DMSO-d6; δ ppm; J Hz) 3.88 (2H, s), 6.47 (1H, s), 7.21-7.52 (14H, m), 7.61 ( 2H, d), 10.31 (1H, s)

(3-3) Synthesis of Compound (A) -11:
Compound (A) -3 3.22g was suspended in water 76g, 50% NaOH aqueous solution was added, and it was made pH 8, and was dissolved. The mixture was ice-cooled, 3.6 mL of hydrochloric acid was added at 5 ° C. or lower, and the mixture was stirred at the same temperature for 30 minutes. At the same temperature, 6.7 mL of a 10% aqueous sodium nitrite solution was dropped and stirred for 1 hour, and then 0.1 g of urea was added and stirred for 5 minutes to obtain a diazonium salt solution. Separately, 4 g of compound (A) -10 was suspended in 120 mL of methanol and 12 mL of dimethyl sulfoxide, and 4 g of lithium acetate was added. The internal temperature was adjusted to 10 ° C. or lower by cooling with ice, and the above diazonium salt solution was added thereto so that the internal temperature was 10 ° C. or lower. At that time, lithium acetate was appropriately added so that the pH was 5 or more. After adding the diazonium salt solution, the mixture was warmed to room temperature, stirred at the same temperature for 1 hour, and then hydrochloric acid was added until the pH was 1 or less. The precipitated solid was filtered, rinsed with 2N hydrochloric acid, rinsed with 100 mL of ethyl acetate, and dried at 50 ° C. for 12 hours to obtain 4.5 g of Compound (A) -11.

(3-4) Synthesis of compound (1) -3:
4 g of the obtained compound (A) -11 and 4.3 g of compound (A) -5 were suspended in 120 g of water, and the internal temperature was raised to 35 ° C. 1.4 g of isoamyl nitrite was added dropwise over 30 minutes. The temperature was raised and the mixture was stirred at 40 ° C. for 1 hour. After completion of the reaction, the pH is adjusted to 8 to 8.5 using a 4N aqueous lithium hydroxide solution, further lithium chloride is added, the precipitated solid is filtered, washed with isopropanol, and compound (1) -3 1.9 g was obtained.
As a result of LC-MS, a peak corresponding to compound (1) -3 was detected. When the UV spectrum when 20 mg of the powder was dissolved in 1000 mL of water was measured, the maximum absorption wavelength was 621 nm.

(Synthesis Example 4)
A synthesis scheme of compound (1) -5 (M: Li / Na≈70 / 30 (mol / mol)) is shown below.

(4-1) Synthesis of compound (A) -12:
Compound (A) -1 (10 g) was dissolved in dimethylacetamide (100 mL), and ice-cooled to adjust the internal temperature to −5 ° C. Cyanuric chloride (10.5 g) was added in portions so that the internal temperature was 0 ° C. or lower. The mixture was stirred at an internal temperature of 0 ° C. or lower for 3 hours, 100 mL of water was added, and the precipitated solid was filtered and thoroughly washed with water to obtain 14.5 g of Compound (A) -12.

(4-2) Synthesis of Compound (A) -13:
5 g of compound (A) -12 was dissolved in 50 mL of dimethyl sulfoxide, and 6.2 g of sodium 3-mercaptopropanesulfonate was added thereto at room temperature. After adding 4.8 g of potassium carbonate, the internal temperature was raised to 55 ° C. and stirred for 1 hour. After cooling to room temperature, the precipitated solid was filtered off, and 300 mL of isopropanol was added to the obtained filtrate. The precipitated solid was filtered, thoroughly washed with isopropanol, and dried at 40 ° C. to obtain 6.8 g of Compound (A) -13. The NMR measurement result of the obtained compound (A) -13 is as follows. ¹ H NMR (400 MHz in DMSO-d6; δ ppm; J Hz) 1.96-2.00 (4H, m), 2.49-2.58 (4H, m), 3.18-3.22 (4H M), 6.51 (1H, s), 7.20 (2H, s), 7.52 (2H, d), 7.70 (2H, d), 10.25 (1H, s)

(4-3) Synthesis of Compound (A) -14:
3.67 g of compound (A) -3 was suspended in 73 g of water, and 50% aqueous NaOH solution was added to adjust the pH to 8. The mixture was ice-cooled, 4.2 mL of hydrochloric acid was added at 5 ° C. or lower, and the mixture was stirred at the same temperature for 30 minutes. At the same temperature, 2.54 mL of 30% aqueous sodium nitrite solution was added dropwise and stirred for 1 hour, then 0.1 g of urea was added and stirred for 5 minutes to obtain a diazonium salt solution.
Separately, 6.5 g of compound (A) -13 was dissolved in 100 mL of water and cooled with ice to lower the internal temperature to 10 ° C. or below, and the above-described diazonium salt solution was added thereto so that the internal temperature was 10 ° C. or lower. . After adding the diazonium salt solution, the mixture was warmed to room temperature and stirred at the same temperature for 1 hour, and then 600 mL of isopropanol was added. The precipitated solid was filtered, rinsed with isopropanol, and dried at 50 ° C. for 12 hours to obtain 7.1 g of Compound (A) -14.

(4-4) Synthesis of compound (1) -5:
4 g of the obtained compound (A) -14 and 4 g of compound (A) -5 were dissolved in 120 g of water, and the internal temperature was raised to 35 ° C. 1.4 g of isoamyl nitrite was added dropwise over 30 minutes. The temperature was raised and the mixture was stirred at 40 ° C. for 1 hour. After completion of the reaction, the pH was adjusted to 8 to 8.5 using 4N lithium hydroxide aqueous solution, 600 mL of isopropanol was added, the supernatant was removed by decantation, and dissolved in 100 mL of water. Lithium chloride was added, and the precipitated solid was filtered and washed with isopropanol to obtain 2.8 g of Compound (1) -5.
As a result of LC-MS, a peak corresponding to compound (1) -5 was detected. When the UV spectrum when 20 mg of the powder was dissolved in 1000 mL of water was measured, the maximum absorption wavelength was 630 nm.

(Synthesis Example 5)
A synthesis scheme of compound (1) -6 (M: Li) is shown below.

(5-1) Synthesis of Compound (A) -15:
Dissolve 2.9 g of compound (A) -9 in 90 mL of dimethylacetamide, add 5.5 g of 3,6-dithia-1,8-octanediol, add 2.8 g of potassium carbonate, and heat to 50 ° C. Stir for 3 hours. After cooling to room temperature, a dimethylacetamide solution of (A) -15 was obtained.

(5-2) Synthesis of Compound (A) -16:
3.67 g of compound (A) -3 was suspended in 73 g of water, and 50% aqueous NaOH solution was added to adjust the pH to 8. The mixture was ice-cooled, 4.2 mL of hydrochloric acid was added at 5 ° C. or lower, and the mixture was stirred at the same temperature for 30 minutes. At the same temperature, 2.54 mL of 30% aqueous sodium nitrite solution was added dropwise and stirred for 1 hour, then 0.1 g of urea was added and stirred for 5 minutes to obtain a diazonium salt solution.
The above dimethylacetamide solution of (A) -15 was ice-cooled to an internal temperature of 10 ° C. or lower, and the above diazonium salt solution was added thereto so that the internal temperature was 10 ° C. or lower. After adding the diazonium salt solution, the mixture was warmed to room temperature, stirred at the same temperature for 1 hour, and then hydrochloric acid was added until the pH was 1 or less. The precipitated solid was filtered, rinsed with 2N hydrochloric acid, rinsed with 100 mL of ethyl acetate, and dried at 50 ° C. for 12 hours to obtain 5.6 g of Compound (A) -16.

(5-3) Synthesis of Compound (1) -6:
4 g of the obtained compound (A) -16 and 4 g of compound (A) -5 were dissolved in 120 g of water, and the internal temperature was raised to 35 ° C. 1.5 g of isoamyl nitrite was added dropwise over 30 minutes. The temperature was raised and the mixture was stirred at 40 ° C. for 1 hour. After completion of the reaction, the pH is adjusted to 8 to 8.5 using a 4N aqueous lithium hydroxide solution, further lithium chloride is added, the precipitated solid is filtered, washed with isopropanol, and compound (1) -6 2.4 g was obtained.
As a result of LC-MS, a peak corresponding to compound (1) -6 was detected. When the UV spectrum when 20 mg of the powder was dissolved in 1000 mL of water was measured, the maximum absorption wavelength was 625 nm.

(Synthesis Example 6)
A synthesis scheme of compound (1) -16 (M: Li / Na≈95 / 5 (mol / mol)) is shown below.

(6-1) Synthesis of Compound (A) -20:
16.5 g of 4′-nitroacetophenone was dissolved in 83 mL of dimethylacetamide, 22.4 g of allyl alcohol and 13.9 g of potassium carbonate were added, and the mixture was stirred at 70 ° C. for 5 hours. 200 mL of water was added, and the precipitated solid was filtered to obtain 14.2 g of a crude compound (A) -18. 14.2 g of the obtained compound (A) -18 was dissolved in 70 mL of isopropanol, 6.0 g of ammonia acetate, 5.5 g of acetic acid and 6.4 g of malononitrile were added, and the mixture was stirred at 80 ° C. for 4 hours. After cooling to room temperature, the precipitated solid was filtered and washed with 20 mL of isopropanol to obtain 11.3 g of a crude product of compound (A) -19.
11.3 g of the obtained compound (A) -19 was suspended in 50 mL of isopropanol, 1.6 g of sulfur was added, 2.6 g of triethylamine was added, the internal temperature was raised to 80 ° C., and the same temperature was maintained for 8 hours. Stir. The mixture was cooled to an internal temperature of 10 ° C. and stirred at the same temperature for 1 hour. The precipitated solid was filtered and washed with 50 mL of isopropanol. The obtained solid was purified by silica gel chromatography (hexane: ethyl acetate = 2: 1) to obtain 5.5 g of compound (A) -20.

(6-2) Synthesis of Compound (A) -21:
Compound (A) -3 (3.81 g) was suspended in water (76 g), and 50% aqueous NaOH solution was added to adjust the pH to 8. The mixture was ice-cooled, 4.2 mL of hydrochloric acid was added at 5 ° C. or lower, and the mixture was stirred at the same temperature for 30 minutes. At the same temperature, 2.63 mL of a 30% aqueous sodium nitrite solution was added dropwise and stirred for 1 hour, and then 0.1 g of urea was added and stirred for 5 minutes to obtain a diazonium salt solution.
Separately, 2.6 g of compound (A) -20 was suspended in 60 mL of methanol, and 4 g of lithium acetate was added. The internal temperature was adjusted to 10 ° C. or lower by cooling with ice, and the above diazonium salt solution was added thereto so that the internal temperature was 10 ° C. or lower. At that time, lithium acetate was appropriately added so that the pH was 5 or more. After adding the diazonium salt solution, the mixture was warmed to room temperature, stirred at the same temperature for 1 hour, and then hydrochloric acid was added until the pH was 1 or less. The precipitated solid was filtered, rinsed with 2N hydrochloric acid, rinsed with 10 mL of water, and dried at 50 ° C. for 12 hours to obtain 3.3 g of Compound (A) -21.

(6-3) Synthesis of compound (1) -16:
The obtained compound (A) -21 3.3 g and compound (A) -5 3.7 g were suspended in water 90 g, and the internal temperature was raised to 35 ° C. 1.4 g of isoamyl nitrite was added dropwise over 30 minutes. The temperature was raised and the mixture was stirred at 40 ° C. for 1 hour. After completion of the reaction, the pH is adjusted to 8 to 8.5 using a 4N aqueous lithium hydroxide solution, further lithium chloride is added, the precipitated solid is filtered, washed with isopropanol, and compound (1) -16 1.1 g was obtained.
As a result of LC-MS, a peak corresponding to compound (1) -16 was detected. When the UV spectrum when 20 mg of the powder was dissolved in 1000 mL of water was measured, the maximum absorption wavelength was 615 nm.

(Synthesis Example 7)
Synthesis of compound (2) -1:
In the synthesis of compound (1) -1, compound (2) -1 was synthesized in the same manner using monoamino 3-amino-1,5-naphthalenedisulfonate instead of compound (A) -3.
As a result of LC-MS, a peak corresponding to compound (2) -1 was detected. When the UV spectrum when 20 mg of the powder was dissolved in 1000 mL of water was measured, the maximum absorption wavelength was 610 nm.

(Synthesis Example 8)
Synthesis of compound (2) -3:
Compound (2) -3 was synthesized in the same manner by using monosodium 7-aminonaphthalene-1,3,5-trisulfonate instead of compound (A) -3 in the synthesis of compound (1) -3. .
As a result of LC-MS, a peak corresponding to compound (2) -3 was detected. When the UV spectrum when 20 mg of the powder was dissolved in 1000 mL of water was measured, the maximum absorption wavelength was 618 nm.

(Synthesis Example 9)
Synthesis of compound (3) -1:
Compound (3) -1 was synthesized in the same manner by using 2-aminobenzonitrile instead of compound (A) -3 in the synthesis of compound (1) -1.
As a result of LC-MS, a peak corresponding to compound (3) -1 was detected. When the UV spectrum when 20 mg of the powder was dissolved in 1000 mL of water was measured, the maximum absorption wavelength was 598 nm.

(Synthesis Example 10)
A synthesis scheme of Comparative Example (1) -1 is shown below.

In the synthesis of Compound (1) -1, synthesis was carried out in the same manner using Compound (A) -22 described in EP-A-2721894 instead of Compound (A) -2, and Comparative Example (1) -1 was obtained.
As a result of LC-MS, a peak corresponding to Comparative Example (1) -1 was detected. When the UV spectrum when 20 mg of the powder was dissolved in 1000 mL of water was measured, the maximum absorption wavelength was 627 nm.

(Synthesis Example 11)
A synthesis scheme of Comparative Example (1) -2 is shown below.

5 g of compound (A) -1 was suspended in 75 mL of acetonitrile, and the internal temperature was cooled to 5 ° C. To this, 4.1 g of 3-phenylpropionyl chloride was added dropwise so that the internal temperature was 10 ° C. or lower. 1.9 g of pyridine was added dropwise so that the internal temperature was 10 ° C. or lower, and the mixture was stirred at an internal temperature of 5 ° C. for 2 hours. The reaction solution was poured into 200 mL of water, and the precipitated solid was filtered and thoroughly washed with water to obtain 8.5 g of Compound (A) -24. The NMR measurement result of the obtained compound (A) -24 is as follows. ¹ H NMR (400 MHz in DMSO-d6; δ ppm; J Hz) 2.64 (2H, t), 2.92 (2H, t), 6.45 (1H, s), 7.16-7.31 ( 5H, m), 7.47 (2H, d), 7.62 (2H, d), 10.01 (1H, s)

In the synthesis of compound (1) -3, synthesis was carried out in the same manner using compound (A) -24 instead of compound (A) -10, to obtain Comparative Example (1) -2.
As a result of LC-MS, a peak corresponding to Comparative Example (1) -2 was detected. When the UV spectrum when 20 mg of the powder was dissolved in 1000 mL of water was measured, the maximum absorption wavelength was 615 nm.

The compounds used as comparative examples in the present application are shown below. In the following comparative example compounds, M is not particularly limited, but represents a hydrogen atom, a lithium ion, a sodium ion, a potassium ion, a quaternary ammonium salt, or a mixture thereof.

[Example 1]
Based on the following composition, each component was stirred at room temperature for 30 minutes, and then the obtained solution was filtered using a membrane filter having an opening of 1.0 μm to obtain an ink composition. In addition, the numerical value of each component indicates the mass% of each component when the mass of the ink composition is 100%, and the “remaining” indicating the amount of water is an amount that is 100% in total with the components other than water. Indicates.

(Ink composition)
Water-soluble dye of general formula (1): Compound (1) -1: 6%
・ Glycerin: 8%
・ Ethylene glycol: 3%
・ Diethylene glycol: 5%
・ 2-pyrrolidone: 5%
・ Ethyleneurea: 2%
・ Orphine E1010 (acetylene, manufactured by Nissin Chemical Industry Co., Ltd.): 1%
・ Ultra pure water: the rest

[Examples 2 to 18 and Comparative Examples 1 to 6]
Ink compositions of Examples 2 to 18 and Comparative Examples 1 to 6 were prepared in the same manner as the preparation of the ink composition of Example 1, except that the dyes were changed as shown in Table 1 below.

(Image recording and evaluation)
The above ink composition is loaded into a black ink cartridge of a Canon ink jet printer (trade name: PIXUS iP8600), and an OD of about 1.0 is obtained for Fujifilm's ink jet paper “paint” photo finish. The printed matter was created as follows. OD was measured with X-rite 310TR (manufactured by X-Rite). The following evaluation was performed about the obtained printed matter.

(1) Ozone resistance For ozone resistance, after measuring the concentration Ci immediately after printing, leave the sample in a box where the ozone gas concentration is set to 5 ppm for 72 hours. The concentration Cf was measured with rite310TR (manufactured by X-Rite), and the residual ratio = Cf / Ci × 100 was determined and evaluated. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
The residual ratio was evaluated as A when the residual ratio was 80% or more, B as less than 80% and 70% or more as C, and C as less than 70%.

(2) Initial ozone resistance In the above-mentioned ozone resistance test, the residual ratio after standing for 12 hours was evaluated as A for 95% or more, B for 90% to less than 95%, and C for less than 90%.

(3) Color change In the above-mentioned initial ozone resistance test, A was evaluated when the hue did not change visually, and B was evaluated when the color change was confirmed visually.

(4) Light resistance Light resistance was obtained by irradiating images with xenon light (95,000 lux) for 6 days using a weather meter manufactured by Atlas. The OD before and after the test was measured with X-rite 310TR (manufactured by X-Rite Co., Ltd.), and the residual ratio was determined and evaluated.
The residual ratio was evaluated as A when the residual ratio was 80% or more, B as less than 80% and 70% or more as C, and C as less than 70%.

From the above results, it can be seen that by using the water-soluble dye of the present invention, it is possible to form an image having excellent ozone resistance, particularly ozone resistance at the initial stage, small color change, and excellent light resistance. It was.

The ink composition, ink for ink jet recording, ink jet recording method, and azo compound of the present invention form an image having excellent ozone resistance (particularly, initial ozone resistance), small color change, and excellent light resistance. can do.

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 September 16, 2014 (Japanese Patent Application No. 2014-188247), the contents of which are incorporated herein by reference.

Claims

An ink composition containing a water-soluble dye represented by the following general formula (1).
General formula (1)

In general formula (1),
A represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group.
G represents a nitrogen atom or —C (R 2 ) ═. R 2 represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group.
L 1 represents a linking group selected from the following group L 1 .

In the formula, * represents a bond with a phenyl group, and ** represents a bond with L 2 . R 4 represents a hydrogen atom or a substituent.
L 2 represents a linking group.
n represents 0, 1 or 2.
L 3 represents an ozone fading preventing group.
R 3 represents a hydrogen atom or a substituent. R 3 may form a ring with L 2 or L 3 .
m represents 1 or 2.
Each M independently represents a hydrogen atom or a monovalent counter cation.
The ink composition according to claim 1, wherein L 3 represents a group selected from the following group L 3 .

In the formula, R 5 , R 6 , R 7 , R 8 , and R 9 each independently represent a hydrogen atom or a substituent. k represents an integer of 0 to 3. p represents an integer of 1 to 6.
The ink composition according to claim 1, wherein L 1 in the water-soluble dye represented by the general formula (1) represents a linking group selected from the following group L 1 ′.

In the formula, * represents a connecting position with a phenyl group, and ** represents a connecting position with L 2 . R 4 represents a hydrogen atom or a substituent.
The ink composition according to any one of claims 1 to 3, wherein L 3 in the water-soluble dye represented by the general formula (1) represents a group selected from the following group L 3 '.

In the formula, R 5 and R 6 each independently represent a hydrogen atom or a substituent. k represents an integer of 0 to 3. p represents an integer of 1 to 6.
The ink composition according to any one of claims 1 to 4, wherein the water-soluble dye represented by the general formula (1) is a water-soluble dye represented by the following general formula (2).
General formula (2)

In general formula (2),
X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and X 7 each independently represent a hydrogen atom or a monovalent substituent.
G in formula (2) in, L 1, L 2, n , L 3, R 3, m, and M is G in formula (1), L 1, L 2, n , L 3, R 3 Synonymous with m and M.
The ink according to any one of claims 1 to 5, wherein the water-soluble dye represented by the general formula (1) or the general formula (2) is a water-soluble dye represented by the following general formula (3). Composition.
General formula (3)

In the general formula (3), G, L 1 , L 2 , n, L 3 , R 3 , m, and M are G, L 1 , L 2 , n, L 3 , R in the general formula (1). 3 Synonymous with m and M.
An ink for ink-jet recording containing the ink composition according to any one of claims 1 to 6.
An ink jet recording method using the ink for ink jet recording according to claim 7.
A compound represented by the following general formula (1).
General formula (1)

In general formula (1),
A represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group.
G represents a nitrogen atom or —C (R 2 ) ═. R 2 represents a hydrogen atom, a sulfo group, a carboxy group, a substituted or unsubstituted carbamoyl group, or a cyano group.
L 1 represents a linking group selected from the following group L 1 .

In the formula, * represents a bond with a phenyl group, and ** represents a bond with L 2 . R 4 represents a hydrogen atom or a substituent.
L 2 represents a linking group.
n represents 0, 1 or 2.
L 3 represents an ozone fading preventing group.
R 3 represents a hydrogen atom or a substituent. R 3 may form a ring with L 2 or L 3 .
m represents 1 or 2.
Each M independently represents a hydrogen atom or a monovalent counter cation.