JP6247971B2 - COMPOUND, COLORING COMPOSITION, INKJET RECORDING INK, INKJET RECORDING METHOD, INKJET PRINTER CARTRIDGE, AND INKJET RECORDED MATERIAL - Google Patents

Description

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

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

  Patent Document 1 describes that an azo compound having a specific structure has an excellent hue as a black ink, can suppress the occurrence of bronze gloss, and can provide an image excellent in light resistance and ozone resistance. .

JP 2012-177073 A

  The azo compound described in Patent Document 1 exhibits excellent performance as described above, but there is room for further performance improvement regarding the storage stability of the ink containing this azo compound.

  An object of the present invention is to provide a compound that can form an image excellent in light resistance and ozone resistance and capable of forming an image with suppressed bronze gloss and having excellent storage stability. . Another object of the present invention is to provide a coloring composition containing the compound, an ink for ink jet recording, an ink jet recording method using the ink for ink jet recording, an ink jet printer cartridge, and an ink jet recorded matter.

一般式（１）中、Ｒは無置換のアルキル基を表す。
＜２＞
Ｒがメチル基である＜１＞に記載の化合物。
＜３＞
＜１＞又は＜２＞に記載の化合物を含有する着色組成物。
＜４＞
＜１＞又は＜２＞に記載の化合物を含有するインクジェット記録用インク。
＜５＞
＜４＞に記載のインクジェット記録用インクを用いるインクジェット記録方法。
＜６＞
＜４＞に記載のインクジェット記録用インクを充填したインクジェットプリンタカートリッジ。
＜７＞
＜４＞に記載のインクジェット記録用インクを用いて、被記録材に着色画像を形成したインクジェット記録物。
本発明は、上記＜１＞〜＜７＞に係る発明であるが、以下、それ以外の事項についても参考のため記載している。 The above-described problems of the present invention can be solved by the following means.
<1>
A compound represented by the following general formula (1).
General formula (1)

In general formula (1), R represents an unsubstituted alkyl group .
<2>
The compound according to <1>, wherein R is a methyl group.
< 3 >
The coloring composition containing the compound as described in <1> or <2> .
< 4 >
An ink for inkjet recording containing the compound according to <1> or <2> .
< 5 >
An ink jet recording method using the ink for ink jet recording according to < 4 >.
< 6 >
< 4 > An ink jet printer cartridge filled with the ink for ink jet recording described in < 4 >.
< 7 >
< 4 > An ink jet recording product in which a colored image is formed on a recording material using the ink for ink jet recording described in < 4 >.
The present invention is the invention according to the above <1> to < 7 >, but other matters are described below for reference.

[1]
A compound represented by the following general formula (1).
General formula (1)

In general formula (1), R represents a substituted or unsubstituted alkyl group or a halogen atom. 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. R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a substituent. M represents a hydrogen atom or a counter cation each independently.
[2]
The compound according to [1], wherein R is an alkyl group having 1 to 10 carbon atoms or a halogen atom.
[3]
R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydrogen atom,
The compound according to [1] or [2], which is an alkyl group substituted with a halogen atom, a hydroxyl group or an ionic hydrophilic group, or an aryl group substituted with a halogen atom, a hydroxyl group or an ionic hydrophilic group.
[4]
G is -C _(R 2) = represents a compound according to any one of _{which R 2} represents cyano group [1] to [3].
[5]
The compound according to any one of [1] to [4], wherein M represents a lithium ion, a potassium ion, or a sodium ion.
[6]
A coloring composition containing the compound according to any one of [1] to [5].
[7]
[1] An ink for ink jet recording containing the compound according to any one of [5].
[8]
An ink jet recording method using the ink for ink jet recording according to [7].
[9]
An ink jet printer cartridge filled with the ink for ink jet recording according to [7].
[10]
An ink-jet recorded matter in which a colored image is formed on a recording material using the ink for ink-jet recording described in [7].

  ADVANTAGE OF THE INVENTION According to this invention, the compound which can form the image which is excellent in light resistance and ozone resistance, can suppress the bronze glossiness, and can prepare the ink which is excellent in storage stability can be provided. . Moreover, the coloring composition containing this compound, the inkjet recording ink, the inkjet recording method using the inkjet recording ink, an inkjet printer cartridge, and an inkjet recorded matter can be provided.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group. Particularly preferred are a sulfo group and a carboxyl group. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. Examples of counter cations that form a salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic. 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.

(Substituent group B)
C1-C12 linear or branched alkyl group, C7-C18 linear or branched aralkyl group, C2-C12 linear or branched alkenyl group, C2-C12 linear Or a branched alkynyl group, a C3-C12 cycloalkyl group, a C3-C12 cycloalkenyl group (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl) , T-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), halogen atom (for example, chlorine atom, bromine atom), aryl group (for example, phenyl, 4-t- Butylphenyl, 2,4-di-t-amylphenyl), heterocyclic groups (eg imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thiol) Nyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group (for example, 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 group (for example, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, 2- Phenoxyethylthio), arylthio groups (eg phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino groups (eg methoxycarbonylamino), alkylsulfonylamino groups and aryls A sulfonylamino group (eg, methylsulfonylamino, phenylsulfonylamino, p-toluenesulfonylamino), a carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), a sulfamoyl group (eg, For example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), alkylsulfonyl group (for example, methylsulfonyl, octylsulfonyl), arylsulfonyl group (for example, phenylsulfonyl, p- Toluenesulfonyl), alkyloxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenyl) Rucarbamoyloxy), silyloxy groups (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino groups (eg, phenoxycarbonylamino), imide groups (eg, N-succinimide, N-phthalimide), heterocyclic thio groups ( For example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (for example, 3-phenoxypropylsulfinyl), phosphonyl group (for example, , Phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl groups (eg, phenoxycarbonyl), acyl groups (eg, acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (caps Bokishiru group, a sulfo group). These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group B described above.

[Compound represented by the general formula (1)]
The compound represented by the following general formula (1) will be described.
General formula (1)

In general formula (1), R represents a substituted or unsubstituted alkyl group or a halogen atom. 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. R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a substituent. M represents a hydrogen atom or a counter cation each independently.

  The compound represented by the general formula (1) has a cyano group in the ortho position with respect to the azo group of the phenyl group bonded to the azo group, and a substituted or unsubstituted alkyl group or halogen atom in the para position. It is considered that an ink having excellent storage stability can be obtained. The details of this mechanism of action are not clear, but it is considered that a hydrophobic substituted or unsubstituted alkyl group or halogen atom at the para position makes it difficult for nucleophiles such as hydrophilic water to approach.

In general formula (1), R represents a substituted or unsubstituted alkyl group or a halogen atom.
R is preferably an alkyl group having 1 to 10 carbon atoms or a halogen atom.
When R represents a substituted or unsubstituted alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is preferable. Further preferred. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group are preferable, and a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group are preferable. A butyl group is more preferable, and a methyl group is still more preferable. The alkyl group may have a substituent, and the substituent in the case of having a substituent includes a substituent selected from the above-mentioned substituent group A, and includes an amino group and an alkylamino group (preferably having 1 carbon atom). An alkylamino group having 12 to 12 carbon atoms, more preferably an alkylamino group having 1 to 6 carbon atoms, more preferably a dimethylamino group or a diethylamino group, and an arylamino group (preferably an arylamino group having 6 to 20 carbon atoms). More preferably an arylamino group having 6 to 10 carbon atoms, further preferably a phenylamino group and a cyanophenylamino group, a hydroxyl group and an alkoxy group (preferably an alkoxy group having 1 to 12 carbon atoms). Yes, more preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an ethoxy group or a methoxy group), an arylthio group ( Preferably, it is a C6-C20 arylthio group, More preferably, it is a C6-C10 arylthio group, A phenylthio group and an ethylbenzenethio group are still more preferable.) An alkylthio group (preferably C1-C20) More preferably an alkylthio group having 1 to 10 carbon atoms, more preferably a methylthio group and an ethylthio group), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 10 carbon atoms, and more Preferably it is a C1-C6 alkylsulfonyl group, and a methanesulfonyl group and an ethanesulfonyl group are still more preferable.
When R represents a halogen atom, preferred are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is more preferred.

In the general formula (1), 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. When the carbamoyl group has a substituent, the substituent is an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or ethyl group). Group) and an aryl group (preferably an aryl group having 6 to 8 carbon atoms, more preferably a phenyl group). R ₂ is preferably a carboxy group, a substituted or unsubstituted carbamoyl group or a cyano group, and more preferably a cyano group.
G preferably represents a nitrogen atom or —C (CN) ═, and more preferably —C (CN) ═.

In general formula (1), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a substituent. It is preferable that one of R ₁₁ and R ₁₂ represents a hydrogen atom and the other represents a substituent. It is preferable that one of R ₁₃ and R ₁₄ represents a hydrogen atom and the other represents a substituent.
Preferred examples of R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ include a hydrogen atom or a substituent selected from the above substituent group B. A hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl Group, or a substituted or unsubstituted heterocyclic group, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, a hydrogen atom, a halogen atom, a hydroxyl group More preferably an alkyl group substituted by a group or an ionic hydrophilic group, or an aryl group substituted by a halogen atom, a hydroxyl group or an ionic hydrophilic group, and a hydrogen atom, a hydroxyl group or an ionic hydrophilic group is substituted. Alkyl group or aryl group substituted by hydroxyl group or ionic hydrophilic group Particularly preferably in a hydrogen atom, it is most preferred ionic hydrophilic group group substituted, or an ionic hydrophilic group is an aryl group substituted. Examples of the alkyl group include an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a t-butyl group. Preferably, a methyl group, an ethyl group, or an n-propyl group is more preferable, and an ethyl group is still more preferable. Examples of the aryl group include an aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable. The ionic hydrophilic group is preferably a sulfo group, a carboxyl group or a hydroxy group, more preferably a sulfo group, a lithium salt of a sulfo group (—SO ₃ Li), a sodium salt of a sulfo group (—SO ₃ Na), or sulfo Group potassium salt (—SO ₃ K) is more preferred, and a lithium salt of sulfo group (—SO ₃ Li) is particularly preferred.

Specific examples where R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ represent substituents are shown below, but the present invention is not limited thereto. * Represents a bonding position.

In general formula (1), M represents a hydrogen atom or a counter cation each independently. Examples of the counter cation include ammonium ion, alkali metal ion (for example, lithium ion, sodium ion, potassium ion) and organic cation (for example, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium).
M preferably represents a counter cation, more preferably represents an alkali metal ion or ammonium ion, more preferably represents an alkali metal ion, particularly preferably represents a lithium ion, potassium ion or sodium ion, and lithium ion Most preferably, is represented.

  Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto. In the following structural formulas, Me represents a methyl group.

(Synthesis method)
The compound represented by the general formula (1) can be synthesized by a coupling reaction between a diazo component and a coupler, and for these, JP 2012-177073 A, JP 2003-306623 A, and There exists description in Unexamined-Japanese-Patent No. 2005-139427 etc.

[Aqueous solution]
The compound represented by the general formula (1) can be made into an aqueous solution by dissolving water in a main solvent.
The aqueous solution containing the compound (pigment) represented by the general formula (1) is prepared by dissolving in an aqueous medium when the dye is water-soluble, and lipophilic when the dye is oil-soluble. It is preferable to prepare by dissolving and / or dispersing in a medium and / or an aqueous medium. The aqueous medium is a solvent mainly containing water, and optionally contains an organic solvent such as a water-miscible organic solvent. This organic solvent may have a function as a viscosity reducing agent. The lipophilic medium is mainly composed of an organic solvent.
In the aqueous solution, the main solvent is water, preferably the water content in the total solvent is 50% by mass to 100% by mass, more preferably the water content in the total solvent is 60% by mass to 100% by mass. It is. The aqueous solution may contain a water-miscible organic solvent and a lipophilic medium in addition to water.

In the aqueous solution, the compound represented by the general formula (1) is dissolved or dispersed in the solvent, preferably dissolved. In the aqueous solution, the content of the compound represented by the general formula (1) is preferably 1% by mass to 25% by mass, more preferably 2% by mass to 20% by mass with respect to the total mass of the aqueous solution. More preferably, it is 2 mass%-15 mass%. By setting the content in the above range, there is an effect that the storage stability of the aqueous solution is good and the preparation of the water-soluble ink for inkjet is easy.
The aqueous solution preferably has a pH of 7.0 to 9.0 at 25 ° C., more preferably 7.5 to 8.5. By adjusting the pH to the above range, there are the effects that high solution stability of the azo compound in the aqueous solution can be imparted and the preparation of the water-soluble ink for inkjet is easy.
The aqueous solution may be referred to as “ink stock solution”.
The use of the aqueous solution is not particularly limited, but is preferably used for inkjet.

〔Preservative〕
In the aqueous solution, generation of insoluble matter due to decay may be a problem. In order to prevent this, a preservative can be added to the aqueous solution.
Various preservatives that can be used in the present invention can be used.
Examples of the preservative include inorganic preservatives (such as silver ion-containing substances) and salts containing heavy metal ions. Organic preservatives include quaternary ammonium salts (tetrabutylammonium chloride, cetylpyridinium chloride, benzyltrimethylammonium chloride, etc.), phenol derivatives (phenol, cresol, butylphenol, xylenol, bisphenol, etc.), phenoxyether derivatives (phenoxyethanol) Etc.), heterocyclic compounds (benzotriazole, proxel, 1,2-benzisothiazolin-3-one, etc.), acid amides, carbamic acid, carbamates, amidine / guanidine, pyridines (sodium pyridinethione- 1-oxide, etc.), diazines, triazines, pyrrole / imidazoles, oxazoles / oxazines, thiazoles / thiadiazines, thioureas, thiosemicarbazides , Dithiocarbamates, sulfides, sulfoxides, sulfones, sulfamides, antibiotics (penicillin, tetracycline, etc.), sodium dehydroacetate, sodium benzoate, ethyl p-hydroxybenzoate, and salts thereof Can be used. In addition, as the antiseptic, those described in the antibacterial and microscopic handbook (Technical Hall: 1986), the antibacterial and antifungal encyclopedia (edited by the Japanese Society for Antibacterial and Antifungal Society), etc. can be used.
As a preservative, a phenol derivative and a heterocyclic compound are preferable, a heterocyclic compound is more preferable, and a heterocyclic compound (Proxel XL-II: manufactured by Fuji Film Imaging Colorant Co., Ltd.) is further preferable.
Preservatives can be added singly or in combination of two or more. Various preservatives such as oil-soluble structures and water-soluble structures can be used, but water-soluble preservatives are preferred.
Among these, it is preferable that at least one preservative is a heterocyclic compound. In the present invention, when two or more kinds of preservatives are used in combination, the effects of the present invention can be exhibited even better. For example, the combination of a heterocyclic compound and an antibiotic, the combination of a heterocyclic compound and a phenol derivative, etc. are mentioned preferably. The content ratio in the case of combining two kinds of preservatives is not particularly limited, but a range of preservative A / preservative B = 0.01 to 100 (mass ratio) is preferable.
Although the addition amount of the preservative to the aqueous solution can be used within a wide range, it is preferably 0.001 to 10% by mass, more preferably 0.1 to 5% by mass. By setting the content of the preservative within the above range, there is an effect of suppressing the growth of bacteria in the aqueous solution.

  The aqueous solution can further contain a pH adjuster.

  Further, the aqueous solution may be adjusted to a more preferable hue by using another colorant together with the compound represented by the general formula (1). Any dye can be used as the dye to be used in combination.

(Coloring composition)
The coloring composition of this invention contains the compound represented by the said General formula (1).

0.2-20 mass% is preferable, as for content in the coloring composition of the compound represented by General formula (1), 0.5-10 mass% is more preferable, 1.0-8.0 mass % Is particularly preferred.
The colored composition of the present invention preferably contains 0.2 to 20% by mass of the total dye, more preferably 0.5 to 10% by mass, and particularly preferably 1.0 to 8.0% by mass. contains.

In the colored composition of the present invention, the pH of the colored composition at 25 ° C. is preferably adjusted to 7.0 to 10.0 with a pH adjuster, and the pH is adjusted to 7.5 to 9.5. More preferably. When the pH is 7.0 or more, the solubility of the dye is improved and the nozzle can be prevented from being clogged. Moreover, if pH is 10.0 or less, there exists a tendency for the long-term storage stability of an ink to be excellent.
As a pH adjuster used for a coloring composition, lithium hydrogencarbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate are preferable, and lithium hydrogencarbonate and sodium hydrogencarbonate are more preferable.
The use of the coloring composition of the present invention is not particularly limited, and is an ink composition for printing such as inkjet, an ink sheet in a thermal recording material, a color toner for electrophotography, an LCD, a display such as PDP, and the like. Although it can be preferably used for the preparation of a color filter used in an image pickup device such as a CCD and a dyeing solution for dyeing various fibers, an ink composition for inkjet recording is particularly preferable.
The said aqueous solution can be used for the manufacturing method of a coloring composition.
The coloring composition is preferably black ink, but should not be limited to black ink, and can include ink of any color by mixing with other dyes or pigments.
The manufacturing method of a coloring composition includes the process (henceforth a liquid preparation process) which produces the desired ink composition of the said viscosity range at least using aqueous solution.
The liquid preparation step is a step of preparing the aqueous solution obtained as described above into an ink composition having a specific viscosity and desired use, and may be a final product or an intermediate product. It may be. This preparation step includes at least a step of diluting the aqueous solution with a medium, preferably an aqueous medium. The aqueous solution containing the oil-soluble dye is not particularly limited in the medium used in this dilution step, but is preferably prepared as an aqueous ink composition by being emulsified and dispersed in an aqueous medium. This medium may contain various components of a necessary concentration, or these components may be added separately to the aqueous solution, or both of them may be combined.
Since the colored composition produced according to the present invention is produced using an aqueous solution having a high dye concentration, the solubility of the dye is improved as compared with the colored composition produced by a normal method, and thus the ejection stability is improved. improves.

When producing an aqueous solution, it is preferable to add the process (filtering process) which removes the dust which is solid content by filtration. A filtration filter is used for this operation, and a filter having an effective diameter of 1 μm or less, preferably 0.3 μm or less is used as the filtration filter at this time. Various materials can be used as the filter material, but in the case of an aqueous solution of a water-soluble dye, it is preferable to use a filter prepared for an aqueous solvent. Among them, it is particularly preferable to use a jacket type filter made of a polymer material that is difficult to generate dust. As a filtration method, the jacket may be passed by liquid feeding, and either pressure filtration or vacuum filtration can be used.
In this invention, the viscosity reducing agent may be used and the said filtration process can be performed without resistance.

  Various methods such as dissolution by stirring, dissolution by ultrasonic irradiation, and dissolution by shaking can be used as a method for dissolving the dye and other components in the step of preparing the aqueous solution and the preparation step. Of these, the stirring method is particularly preferably used. When agitation is performed, various methods such as known fluidization agitation and agitation 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.

Next, the dye used for the aqueous solution and coloring composition of this invention is demonstrated. The dye is not particularly limited, but the half-value width (Wλ, _1/2 ) in an absorption spectrum of a diluted solution having a λmax of 500 nm to 700 nm and an absorbance normalized to 1.0 is 100 nm or more, preferably 120 nm. It is preferable to include at least one azo compound represented by the general formula (1) which is not less than 500 nm and more preferably not less than 120 nm and not more than 350 nm.

The compound represented by the general formula (1) alone has a high image quality “(good) black” = black that does not depend on the observation light source and the color tone of B, G, or R is difficult to be emphasized. If feasible, this dye can be used alone as a raw material for an aqueous solution or ink composition, but it is usually used in combination with a dye that covers a region where the absorption of this dye is low. It is common. Usually, in the case of an ink composition using an azo compound represented by the general formula (1), it is preferably used in combination with another dye having a main absorption (λmax of 350 nm to 500 nm) in the yellow region. Further, it is also possible to prepare an ink composition in combination with other dyes.
Other dyes can be used in the aqueous solution, but are preferably mixed and used in preparation of the ink composition from the viewpoint of storage stability.

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

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

  In 100% by mass of the inkjet recording ink of the present invention, the compound represented by the general formula (1) is preferably contained in an amount of 0.2% by mass or more and 10% by mass or less, and preferably 1% by mass or more and 6% by mass or less. Is more preferable. In addition, in the inkjet recording ink of the present invention, other dyes may be used in combination with the compound represented by the general formula (1). When using 2 or more types of pigment | dyes together, it is preferable that the sum total of content of a pigment | dye is the said range.

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

  The ink for inkjet recording of the present invention can be used not only for forming a single color image but also for forming a full color image. In particular, it is preferably used for black ink-jet recording ink.

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

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

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

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

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

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

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the following examples, “%” and “parts” represent “% by mass” and “parts by mass” unless otherwise specified, and the molecular weight indicates the mass average molecular weight.
In addition, Example 2 and Examples-15-18, 23-26 shall be read as Reference Example 2, Reference Examples-15-18, 23-26, respectively.

(Synthesis of BLACK-1)
A synthesis scheme is shown below.

Synthesis of intermediate (c-1):
Water (31 mL) was added to 2.9 g of 2-amino-5-methylbenzonitrile (a-1), and the mixture was stirred at room temperature. After dropwise addition of 5.1 mL of 12M aqueous hydrochloric acid, the reaction mixture was cooled to an internal temperature of 0 ° C. While maintaining the internal temperature at 0-4 ° C, a 25% aqueous solution of 1.6 g of sodium nitrite was added dropwise, and the mixture was stirred at an internal temperature of 0-5 ° C for 1 hour. Thereafter, 0.4 g of sulfamic acid was added and stirred for 10 minutes to obtain a diazonium salt solution. Separately from the diazonium salt solution, 75 ml of water was added to the intermediate (b-1) (synthesized by the method described in JP2012-177073) and cooled to an internal temperature of 2 ° C. It was added dropwise at a temperature of 2-5 ° C. over 5 minutes. After raising the internal temperature to room temperature, after stirring for 1.5 hours, 500 ml of isopropanol was added dropwise, and the precipitated crystals were filtered. It dried at 40 degreeC for 12 hours, and obtained 15.5g of c-1.
¹ H NMR: δ = 10.65 (brs, 1H), 10.32 (brs, 1H), 10.09 (brs, 1H), 8.92 (d, 2H), 8.18 (s, 1H), 8.06 (brs, 1H), 7.85 ( brs, 1H), 7.79 (s, 1H), 7.70 (d, 2H), 7.53 (d, 1H), 7.48 (d, 1H), 7.42 (d, 1H), 7.31 (d, 1H), 3.68 (t , 2H), 2.80 (t, 2H), 2.37 (s, 3H), 400 MHz in DMSO-d6

Synthesis of (BLACK-1):
6.0 g of the above obtained (c-1) and 3.5 g of the intermediate (d-1) (synthesized by the method described in JP2012-177073) are completely dissolved in 180 mL of water, and hydrochloric acid is added dropwise. The pH was adjusted to 0.9. After setting the internal temperature to 40 ° C., 0.8 g of isoamyl nitrite was added dropwise, and the mixture was stirred at the same temperature for 30 minutes. Thereafter, 1.2 g of isoamyl nitrite was further added dropwise and stirred at an internal temperature of 40 ° C. for 3 hours. Lithium hydroxide was added to the reaction solution to adjust the pH to 8.0, and then 500 mL of isopropanol was added dropwise over 30 minutes. The slurry-like reaction liquid was filtered and washed with 200 mL of isopropanol to obtain crude (BLACK-1). The crude product was dissolved by adding 40 mL of water, passed through a Li-type cation exchange resin, and then adjusted to pH 8.0 with a lithium hydroxide solution. After removing dust with a membrane filter to remove insoluble matters, the solution was concentrated with an evaporator to obtain 3.4 g of BLACK-1.
Λmax of the solution spectrum was 691 nm in DMF (dimethylformamide), 608 nm in water, ESI-mass spectrum measurement showed a molecular weight of 1282.10, and ion chromatography confirmed that the counter cation of sulfonic acid was lithium.
¹ H NMR: δ = 10.35 (s, 1H), 9.80 (brs, 1H), 9.67 (brs, 1H), 9.00 (brs, 1H), 8.74 (brs, 1H), 8.10 (d, 1H), 8.02 ( d, 1H), 7.88 (d, 1H), 7.83 (d, 2H), 7.82 (d, 1H), 7.78 (d, 2H), 7.69 (d, 2H), 7.64 (d, 2H), 7.59 (d , 2H), 7.49 (d, 2H), 7.19 (d, 1H), 7.10 (s, 1H), 3.76 (t, 2H), 2.77 (t, 2H), 2.69 (s, 3H), 2.37 (s, 3H), 400 MHz in DMSO-d6

(Synthesis of BLACK-2)
A synthesis scheme is shown below.

Synthesis of intermediate (c-2):
50 mL of water was added to 5.3 g of 2-amino-5-chlorobenzonitrile (a-2), and the mixture was stirred at room temperature. After 9.4 mL of 12M hydrochloric acid was added dropwise, the reaction solution was cooled to an internal temperature of 0 ° C. While maintaining the internal temperature at 0-4 ° C, a 25% aqueous solution of 2.5 g of sodium nitrite was added dropwise, and the mixture was stirred at an internal temperature of 0-5 ° C for 1 hour. Thereafter, 0.6 g of sulfamic acid was added and stirred for 10 minutes to obtain a diazonium salt solution. Separately from the diazonium salt solution, 90 mL of water is added to the intermediate (b-1) (synthesized by the method described in JP2012-177073), and the mixture is cooled to an internal temperature of 2 ° C. It was added dropwise at a temperature of 2-5 ° C. over 5 minutes. After raising the internal temperature to room temperature, after stirring for 1.5 hours, 500 ml of isopropanol was added dropwise, and the precipitated crystals were filtered. It dried at 40 degreeC for 12 hours, and 25.2g of c-2 was obtained.
It was confirmed that the molecular weight was 831.02 by ESI-mass spectrum measurement.

Synthesis of (BLACK-2):
After cooling a mixed solvent of 50 ml of acetic acid and 15 ml of concentrated sulfuric acid to 0 ° C., 40% nitrosylsulfuric acid (1.7 g) was added dropwise, and the above was obtained while maintaining the internal temperature at 0-4 ° C. (c-2) 4.2 g was added in portions and stirred for 1 hour. Thereafter, 92 mg of sulfamic acid was added and stirred for 10 minutes to obtain a diazonium salt solution. Separately from the diazonium salt solution, 25 ml of water and 200 ml of methanol are added to the intermediate (d-1) (synthesized by the method described in JP2012-177073) and cooled to an internal temperature of 2 ° C., and then the prepared diazonium salt is prepared. The solution was added dropwise at an internal temperature of 2-5 ° C. over 5 minutes. Lithium hydroxide was added to the reaction solution to adjust the pH to 8.0, and 6500 mL of isopropanol was added dropwise over 30 minutes. The slurry-like reaction liquid was filtered and washed with 200 mL of isopropanol to obtain crude (BLACK-2). The crude product was dissolved by adding 50 mL of water, passed through a Li-type cation exchange resin, and then adjusted to pH 7.0 with a lithium hydroxide solution. After removing dust with a membrane filter to remove insoluble matters, the membrane was concentrated with an evaporator to obtain 3.2 g of BLACK-2.
Λmax of the solution spectrum was 707 nm in DMF, 613 nm in water, the molecular weight was 1302.05 by ESI-mass spectrum measurement, and it was confirmed by ion chromatography that the counter cation of sulfonic acid was lithium.
¹ H NMR: δ = 10.40 (s, 1H), 9.75 (brs, 1H), 9.62 (brs, 1H), 8.69 (brs, 1H), 8.63 (brs, 1H), 8.25 (d, 1H), 8.10 ( d, 1H), 8.01 (d, 1H), 7.94 (d, 1H), 7.86 (d, 2H), 7.81 (d, 2H), 7.68 (d, 2H), 7.62 (d, 2H), 7.59 (d , 2H), 7.48 (d, 2H), 7.18 (d, 1H), 7.08 (d, 1H), 3.71 (t, 2H), 2.75 (t, 2H), 2.75 (s, 3H), 400 MHz in DMSO -d6

[Preparation of aqueous solution]
The aqueous solution containing the coloring compound is herein referred to as “ink stock solution”. In addition, pH was adjusted to 8.1-8.3 using 4 mol / L lithium hydroxide aqueous solution for aqueous solution.

[Example 1]
After dissolving 100 g of the dye compound (BLACK-1) in 900 g of ultrapure water while stirring at room temperature, 0.1 g was added as a solid content of an antiseptic (Proxel XL-II: manufactured by Fuji Film Imaging Colorant). Using a 4 mol / L lithium hydroxide aqueous solution, the pH was adjusted to 8.2, and then unnecessary substances were filtered using a 0.2 μm membrane filter to obtain an ink stock solution-1.

[Example 2]
Except that (BLACK-2) was used instead of the dye compound (BLACK-1), the same operation as in Example 1 was performed to obtain an ink stock solution-2.

[Comparative Example 1]
A comparative ink stock solution-01 was obtained in the same manner as in Example 1 except that the following comparative compound 1 was used instead of the dye compound (BLACK-1).
Comparative compound 1

[Test method for storage stability of ink stock solution]
Regarding the change in pH value, based on the pH value immediately after preparation of the ink stock solution (liquid temperature 25 ° C.) and the pH value (liquid temperature 25 ° C.) after forced thermal aging test (stored at 60 ° C. for 14 days) The level was set as follows.
A: Difference in pH value before and after forced thermal aging test is less than 0.3 B: Difference in pH value before and after forced thermal aging test is 0.3 or more and less than 0.5 C: pH value before and after forced thermal aging test The difference in pH is 0.5 or more and less than 0.7 D: The difference in pH value before and after the forced thermal aging test is 0.7 or more

Regarding the ABS value change, the ABS (absorbance) value and forced thermal aging after dilution of the ink stock solution immediately after the ink stock solution preparation with ultrapure water so that the mass of the dye compound with respect to the total mass of the ink stock solution becomes 1/5000. After the test (stored at 60 ° C. for 14 days), the ink stock solution is as follows based on the ABS value after dilution with ultrapure water so that the mass of the dye compound relative to the total mass of the ink stock solution is 1/5000. It was set.
A: Difference in ABS value before and after forced thermal aging test is less than 0.05 B: Difference in ABS value before and after forced thermal aging test is 0.05 or more and less than 0.10 C: ABS value before and after forced thermal aging test Difference: 0.10 or more and less than 0.15 D: ABS value difference before and after forced thermal aging test is 0.15 or more The results are shown in Table 1 below.

[Examples 11 to 26, Comparative Examples 11 to 12]
[Preparation of ink for inkjet recording]
Based on the composition shown in Table 2 below, each inkjet recording ink was prepared. In the same manner as in Example 1, an ink stock solution containing a dye compound and a preservative was prepared, diluted by adding the remaining components, stirred for 30 minutes at room temperature, and then using a 4 mol / L lithium hydroxide aqueous solution. Then, the pH was adjusted to 8.2, and the obtained solution was filtered using a membrane filter having an aperture of 1.0 μm to obtain each ink for ink jet recording. In Table 2, the numerical value of each component indicates the mass% of each component when the mass of the ink for inkjet recording is 100%, and the “residue” indicating the amount of water is combined with the components other than water. The amount is 100% in total.
Inkjet recording inks B-01 to B-18 were thus prepared.

[Storage stability test method of ink for inkjet recording]
Regarding pH value change, based on the pH value (liquid temperature 25 ° C.) immediately after ink preparation for ink jet recording and the pH value (liquid temperature 25 ° C.) after forced thermal aging test (60 ° C. for 14 days), The following levels were set.
A: Difference in pH value before and after forced thermal aging test is less than 0.3 B: Difference in pH value before and after forced thermal aging test is 0.3 or more and less than 0.5 C: pH value before and after forced thermal aging test The difference in pH is 0.5 or more and less than 0.7 D: The difference in pH value before and after the forced thermal aging test is 0.7 or more

Regarding the ABS value change, the ABS (absorbance) of the inkjet recording ink immediately after the ink preparation for inkjet recording was diluted with ultrapure water so that the mass of the coloring compound relative to the total mass of the inkjet recording ink was 1/5000. ) Value and forced thermal aging test (at 60 ° C. for 14 days) ABS value after diluting the ink for inkjet recording with ultrapure water so that the mass of the dye compound relative to the total mass of the ink for inkjet recording becomes 1/5000 Based on this, the following levels were set.
A: Difference in ABS value before and after forced thermal aging test is less than 0.05 B: Difference in ABS value before and after forced thermal aging test is 0.05 or more and less than 0.10 C: ABS value before and after forced thermal aging test Difference: 0.10 or more and less than 0.15 D: ABS value difference before and after forced thermal aging test is 0.15 or more

  As the ink jet printer, Stylus Color 880 (trade name) (trade name, manufactured by Seiko Epson Corporation) was used, and an ink jet recording medium {photographic paper <gloss> (trade name, manufactured by Seiko Epson Corporation)} was used. Monochrome with ink cartridges filled with ink jet recording ink, loaded into an ink jet printer, and the density changed stepwise so that the OD value measured with a reflection densitometer (X-Rite 310TR) is 0.7 to 1.8. An image pattern was printed, and image fastness (light resistance and ozone gas resistance) and image quality (bronze gloss) were evaluated.

[Bronze gloss evaluation]
The presence or absence of bronze gloss was evaluated by visually observing the image immediately after recording for 24 hours and then visually observing it. The case where bronze gloss was not confirmed at all was designated as A, the case where a slight bronze phenomenon was confirmed as B, and the case where bronze gloss was clearly confirmed as C.
The obtained results are shown in Table 3 as “image quality bronze”.

[Ozone resistance test method]
An ink jet recording medium printed under conditions where the ozone gas concentration was set to 5 ppm (25 ° C .; 60% RH) was exposed to ozone gas for 7 days. The ozone gas concentration was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS. The OD value recorded on each printed matter was measured using a reflection densitometer (X-Rite 310TR) at every elapse of a certain period from the start of exposure. The reflection density was measured at three points where the OD values before the exposure test were 0.7, 1.0, and 1.8.
From the results obtained, the following formula:
ROD (%) = (D / D ₀ ) × 100
Was used to determine the residual optical density (ROD). In the formula, D represents the OD value after the exposure test, and D ₀ represents the OD value before the exposure test.
Further, based on the results of the above test, the ozone resistances recorded on the ink jet recording medium were ranked A to D using the following criteria.
[Criteria]
Evaluation A: ROD after 7 days from the start of the test is 85% or more at any concentration.
Evaluation B: The ROD after 7 days from the start of the test is such that the concentration at any one point is less than 85%.
Evaluation C: The ROD after 7 days from the start of the test is such that the concentration at any two points is less than 85%.
Evaluation D: ROD after 7 days from the start of the test is less than 85% at all concentrations.
In this test, a recorded material with little decrease in ROD is excellent even when exposed to ozone for a long time. The obtained results are shown in Table 3 as “ozone gas fastness”.

[Light resistance test method]
A weather meter (manufactured by Atlas) was used to irradiate the printed inkjet recording medium with xenon light (100,000 lux) for 14 days. The OD value recorded on each printed matter was measured using a reflection densitometer (X-Rite 310TR) at every elapse of a certain period from the start of irradiation. The reflection density was measured at three points where the OD values before the exposure test were 0.7, 1.0, and 1.8.
From the results obtained, the following formula:
ROD (%) = (D / D ₀ ) × 100
Was used to determine the residual optical density (ROD). In the formula, D represents the OD value after the exposure test, and D ₀ represents the OD value before the exposure test.
Furthermore, based on the results of the above test, the light resistance recorded on the ink jet recording medium was ranked A to D using the following criteria.
[Criteria]
Evaluation A: ROD 14 days after the start of the test is 85% or more at any concentration.
Evaluation B: ROD 14 days after the start of the test is such that the concentration at any one point is less than 85%.
Evaluation C: The ROD after 14 days from the start of the test is such that the concentration at any two points is less than 85%.
Evaluation D: ROD 14 days after the start of the test is less than 85% at all concentrations.
In this test, a recorded matter with little decrease in ROD even when exposed to light for a long time is excellent. The obtained results are shown in Table 1-3.

Claims (7)

A compound represented by the following general formula (1).
General formula (1)

In general formula (1), R represents an unsubstituted alkyl group . The compound according to claim 1, wherein R is a methyl group. The coloring composition containing the compound of Claim 1 or 2 . Jet recording ink containing a compound according to claim 1 or 2. An ink jet recording method using the ink for ink jet recording according to claim 4 . An ink jet printer cartridge filled with the ink for ink jet recording according to claim 4 . An ink-jet recorded matter in which a colored image is formed on a recording material using the ink for ink-jet recording according to claim 4 .