JP2002129072A - Ink for ink-jet recording and method for recording image using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink for ink-jet recording, which is good in hue and capable of forming an image having good light-resistance, and provide a method for recording the image. SOLUTION: The ink for ink-jet recording comprises a compound represented by general formula (1). In the formula, Ar is an aryl or heterocyclic group; R1 to R3 are each hydrogen or halogen atom, -CN, -NH2, -NO2, -OH, -CO2H, -SO3H, quaternary ammonium group, -CO2M1/n, -SO3M1/n, alkyl group, alkenyl group, alkynyl group, aryl group, acyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkylphosphoryl group, arylphosphoryl group or substituted amino group; M is a metal atom; and (n) is a integer of 1 or 4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ink jet recording ink and an image recording method using the same.

[0002]

2. Description of the Related Art Ink jet recording systems have rapidly spread and are further developed due to low material costs, high-speed recording, low noise during recording, and easy color recording. It is a recording method that is going on. Ink jet recording methods include a method in which pressure is applied by a piezo element to eject droplets, a method in which bubbles are generated in ink by heat to eject droplets, and a method in which droplets are sucked and ejected by electrostatic force. There are water-based inks, oil-based inks, and solid (melt-type) inks as inkjet inks.

JP-A-4-359967 and JP-A-4-35967
JP-A-359968 discloses a dye for the purpose of achieving both hue and light fastness, but its performance as a water-based ink is not sufficient, and further improvement in hue is particularly desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ink jet recording ink and an image recording method capable of forming an image having good hue and good light fastness.

[0005]

The above objects can be attained by providing the following ink for ink jet recording and an image recording method. (1) An inkjet recording ink containing a compound represented by the following general formula (I).

[0006]

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In the formula, Ar represents an aryl group or a heterocyclic group. R ^{1 to} R ³ each represent a hydrogen atom, a halogen,
_{-CN, -NH 2, -NO 2,} -OH, -CO 2 H, -S
O ₃ H, quaternary ammonium group, —CO ₂ M _{1 / n} , —SO ₃ M
_{1 / n} , alkyl group, alkenyl group, alkynyl group, aryl group, acyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, Represents an alkylsulfonyl group, an arylsulfonyl group, an alkylphosphoryl group, an arylphosphoryl group, or a substituted amino group. M represents a metal atom, and n represents an integer of 1 to 4. (2) The group represented by Ar- in the general formula (I) is
The inkjet recording ink according to the above (1), which is a group represented by the following general formula (II).

[0008]

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In the formula, R ⁴ and R ⁵ represent a hydrogen atom, an alkyl group or an aryl group. R ^{6 to} R ⁹ are the same as R in claim 1;
^{1 ~R 3} as synonymous. (3) The group represented by Ar- in the general formula (I) is
The ink for inkjet recording according to the above (1), which is a group represented by the following general formula (III).

[0010]

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In the formula, R ^{10 to} R ¹² represent a hydrogen atom, an alkyl group or an aryl group. R ¹³ represents a hydrogen atom, a halogen, an alkyl group, an alkoxy group, an aryl group, or an aryloxy group. X represents O or S. (4) The group represented by Ar- in the general formula (I) is
The ink for inkjet recording according to the above (1), which is a group represented by the following general formula (IV).

[0012]

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In the formula, R ¹⁴ represents a hydrogen atom, an alkyl group or an aryl group. R ¹⁵ and R ¹⁶ represent a hydrogen atom, a halogen, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or an aryl group. Y represents O or S. (5) An inkjet recording ink containing a compound represented by the following general formula (V).

[0014]

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In the formula, Ar 'has the same meaning as Ar in the first aspect.
You. R¹⁷And R¹⁸Is R in claim 1 ¹~ R^ThreeSynonymous with
You. R¹⁹Is a hydrogen atom, an alkyl group, an aryl group, or
Represents an acyl group. Z represents an oxygen atom or a sulfur atom. (6) The method according to any one of (1) to (5).
Provide energy to the ink for inkjet recording.
Discharging the ink droplets onto a recording medium,
Recording an image composed of the ink on the upper surface.
Image recording method.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. As mentioned above, such as sharpening the absorption of the dye,
In order to improve the hue, it is preferable that the structure is biased toward either the azo structure or the hydrazone structure, or a structure that does not cause tautomerization, but the present inventors have a dissociative group. As a result of studying a technique for fixing the azo dye to the hydrazone structure, the present inventors have found that the hydrazone dye of the present invention represented by the general formula (I) tends to isomerize to the azo structure, and completed the present invention. The hydrazone dye of the present invention gives cyan coloring excellent in hue such as sharp absorption of the dye.

The hydrazone dye of the present invention is represented by the above general formula (I). In the formula, Ar represents an aryl group or a heterocyclic group. R ¹ to R ³ are each a hydrogen atom, a _{halogen, -CN, -NH 2, -NO 2} , -OH, -
CO ₂ H, —SO ₃ H, quaternary ammonium group, —CO ₂ M
_{1 / n, -SO 3 M 1} / n, alkyl group, alkenyl group, alkynyl group, an aryl group, an acyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkoxy group, an aryloxy Represents an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylphosphoryl group, an arylphosphoryl group, or a substituted amino group. M represents a metal atom, and n represents an integer of 1 to 4. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom and a chlorine atom are more preferable.

Ar in the general formula (I) represents an aryl group or a heterocyclic group, which may be further substituted. Examples of the aryl group include a phenyl group and a naphthyl group, and further include a halogen, a cyano group, a nitro group, CO ₂ H, CO ₂ Na, CO ₂ K, SO ₃ H, SO ₃ N
a, SO ₃ K, an amino group, an alkoxy group, an acylamino group, an amide group, and the like may be substituted. The following are preferred as the aryl group.

[0019]

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[0020]

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In addition, Ar may be a divalent group. In this case, the hydrazone dye of the present invention has two hydrazone rings. Preferred divalent Ar includes the following.

[0022]

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As the heterocyclic group, 2-pyridyl, 3-
Examples include pyridyl, 4-pyridyl, thienyl, 3-thiophenyl, 2-thiazolyl, 5-thiazolyl, benzothiazolyl, diazolyl, triazolyl, benzodiazolyl, benzoxazolyl, 2-furanyl, and benzothiophenyl. The following are preferred as the heterocyclic group.

[0024]

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The above R¹~ R^ThreeIs a further substituent
May be replaced by R¹~ R ^ThreeOf the substituents of
An aryl group further includes an alkyl group, an alkoxy group,
Oxy group, halogen atom, nitro group, cyano group,
Substituted carbamoyl group, substituted sulfamoyl group, substituted amino
Group, substituted oxycarbomoyl group, substituted oxysulfonyl
Group, alkylthio group, arylthio group, alkylsulfo
Nil group, arylsulfonyl group, aryl group, hydroxy
Group, acyl group, acyloxy group, substituted sulfonyloxy
Si group, substituted aminocarbonyloxy group, substituted phosphoryl
Oxy group, -CO_TwoH, -SO_ThreeH, quaternary ammonium
Group, -CO_TwoM_{1 / n}, -SO_ThreeM_{1 / n}(M and n are defined above.
The same as the general formula, and specific examples of the quaternary ammonium group include:
R below¹~ R^ThreeQuaternary ammonium which is a substituent in
The same as those shown as specific examples of the
You may.

The aryl group has 6 to 6 carbon atoms.
30 aryl groups are preferred, for example a phenyl group, 2
-Methylphenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 2-ethoxyphenyl group, 2-propoxyphenyl group, 2-isopropoxyphenyl group, 2-
Butoxyphenyl group, 2- (2-ethylhexyloxy) phenyl group, 2-octyloxyphenyl group, 2-
Undecyloxyphenyl group, 2-trifluoromethylphenyl group, 2- (2-ethylhexyloxy) -5-
Chlorophenyl group, 2,2′-hexyloxy-3,5
-Dichlorophenyl group, 3- (2,4-di-t-pentylphenoxyethoxy) phenyl group, 2- (dibutylaminocarbonylethoxy) phenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,4 ,
6-trimethylphenyl group, 3-chlorophenyl group, 3
-Nitrophenyl group, 3-cyanophenyl group, 3-trifluoromethylphenyl group, 3-methoxyphenyl group,
3-ethoxyphenyl group, 3-butoxyphenyl group, 3
-(2'-ethylhexyloxy) phenyl group, 3,4
-A cyclophenyl group, a 3,5-dichlorophenyl group,
3,4-dimethoxyphenyl group, 3,5-dibutoxyphenyl group, 3-octyloxyphenyl group, 3- (dibutylaminocarbonylmethoxy) phenyl group, 3- (di-2-ethylhexylaminocarbonylmethoxy) phenyl group, 3-dodecyloxyphenyl group, 4-chlorophenyl group, 4-cyanophenyl group, 4-nitrophenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-isopropoxyphenyl group , 4-butoxyphenyl group, 4- (2-
Ethylhexyloxy) phenyl group, 4-isopentyloxyphenyl group, 4- (octadecyloxy) phenyl group, 4-benzylphenyl group, 4-aminosulfonylphenyl group, 4-N, N-dibutylsulfonylphenyl group, 4-ethoxy Carbonylphenyl group, 4- (2-ethylhexyloxycarbonyl) phenyl group, 4-t-
Octylphenyl group, 4-fluorophenyl group, 3-acetylphenyl group, 2-acetylaminophenyl group,
2,4-di-t-pentylphenyl group, 4- (2-ethylhexyloxy) carbonylphenyl group, 4-methylthiophenyl group, 4- (4-chlorophenylthio) phenyl group, besides hydroxyphenyl group, phenylsulfonyl Examples include a phenyl group, a phenylsulfonyloxyphenyl group, a phenylcarbonyloxyphenyl group, a dimethylaminocarbonyloxyphenyl group, a butylcarbonyloxyphenyl group, and the like. In addition, groups represented by the following formulas may be mentioned.

[0027]

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Among the substituents of R ^{1 to} R ³ , the alkyl group may be linear or branched, and may have an unsaturated bond. Further, these alkyl groups may be substituted with an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryl group, a hydroxy group, a halogen atom, or the like. The aryl group further includes an alkyl group, an alkoxy group, a nitro group, a cyano group, a hydroxy group or a halogen atom, —CO ₂ H, —S
O ₃ H, quaternary ammonium group, —CO ₂ M _{1 / n} , —SO ₃ M
_{1 / n} (the definitions of M and n are the same as those in the above general formula, and specific examples of the quaternary ammonium group are those shown as specific examples of the quaternary ammonium group which is a substituent in R ^{1 to} R ³ described below. And the like). As the alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, trifluoromethyl group, ethyl group, butyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, Octadecyl, propyl, isopropyl, isobutyl, sec-butyl, t-butyl, pentyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, isopentyl, heptyl, nonyl, undecyl, propenyl Group, heptadecenyl group, t-octyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, 2-
An ethylhexyloxycarbonylmethyl group, a 1- (ethoxycarbonyl) ethyl group, a 2 ′, 4′-diisopentylphenyloxymethyl group, a 2 ′, 4′-di-t-butylphenyloxymethyl group, an ethoxycarbonylethyl group, 2-ethylhexyloxycarbonylethyl group, butyldecyloxycarbonylethyl group, dibutylaminocarbonylmethyl group, dibenzylaminocarbonylethyl group, ethyloxycarbonylpropyl group, 2-ethylhexyloxycarbonylpropyl group, 2,4-di-t
-Amylphenyloxypropyl group, 1- (2 ′, 4 ′)
-Di-t-amylphenyloxy) propyl group, 2,4
-Di-t-butylphenyloxypropyl group, acetylaminoethyl group, N, N-dihexylaminocarbonylethyl group, 2,4-di-t-amyloxyethyloxycarbonylpropyl group, isostearyloxycarbonylpropyl, 1- (2,4-di-t-pentylphenyloxy) propyl group, 2,4-di-t-pentylphenyloxyethyloxycarbonylpropyl group, naphthyloxyethyloxycarbonylethyl group, N-methyl-
N- phenylethyl oxycarbonyl ethyl, methanesulfonylamino propyl _{group, - (CH 2) m CO} 2 H,
_{- (CH 2) m CO 2} Na, - (CH 2) m CO 2 K, - (C
_{H 2) m SO 3 H,} - (CH 2) m SO 3 Na, - (CH 2) m
SO ₃ K (m represents an integer of 1 to 4) and the like.

Of the substituents R ^{1 to} R ³ , the alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, for example, a vinyl group, —CH ＝ CH—Ph (cinamyl group) and the like. , An alkynyl group having 2 to 2 carbon atoms
10 alkynyl groups are preferred, for example an ethynyl group,
Examples include a 2-methyl-ethynyl group and a 2-phenyl-ethynyl group.

Among the substituents of R ^{1 to} R ³ , the acyl group is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl, propanoyl, butanoyl, hexanoyl, octanoyl, 2-octanoyl, Examples include an ethylhexanoyl group, a decanoyl group, a dodecanoyl group, an octadecanoyl group, a 2-cyanopropanoyl group, and a 1,1-dimethylpropanoyl group. Other examples of the acyl group include those shown below.

[0031]

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Among the substituents of R ^{1 to} R ³ , the substituted carbamoyl group includes carbamoyl, N-alkylcarbamoyl, N-arylcarbamoyl, N, N-dialkylcarbamoyl, N, N-diarylcarbamoyl , N-alkyl-N-arylcarbamoyl groups and the like. Examples of the substituted carbamoyl group include C1 to C1
30 substituted carbamoyl groups are preferred, for example, N-methylcarbamoyl group, N-ethylcarbamoyl group, N-
A propylcarbamoyl group, an N-butylcarbamoyl group,
N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-2-ethylhexylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenyl Carbamoyl group, N-2-chlorophenylcarbamoyl group, N-2-
Methoxyphenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyloxy) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3- Cyanophenylcarbamoyl group, N-4-methoxycarbamoyl group, N-4- (2 ′
-Ethylhexyloxy) phenylcarbamoyl group, N
-4-cyanophenylcarbamoyl group, N-methyl-N
-Phenylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like. Examples of the substituted carbamoyl group further include those shown below.

[0033]

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Among the substituents of R ^{1 to} R ³ , the alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl,
Butoxycarbonyl group, hexyloxycarbonyl group,
2-ethylhexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenyloxyethyloxycarbonyl group, phenyloxypropyloxycarbonyl group, 2,4-di-t-amylphenyloxyethylcarbonyl group , 2,6-di -t- butyl-4-methyl cyclohexyloxy carbonyl group, isostearyl oxycarbonyl _{group, -CO 2 - (CH 2)} m CO 2 H, -CO 2
_{- (CH 2) m CO 2} Na, -CO 2 - (CH 2) m CO
_{2 K, -CO 2 - (CH} 2) m SO 3 H, -CO 2 - (C
_{H 2) m SO 3 Na,} -CO 2 -. (CH 2) m SO 3 K (m denotes an integer of 1 to 4), and the like.

Among the substituents of R ^{1 to} R ^3, the aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 30 carbon atoms, for example, 2-methylphenyloxycarbonyl group, 2-chlorophenyloxycarbonyl Group, 2,6-dimethylphenyloxycarbonyl group, 2,4,6-trimethylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group,
2-butoxyphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 2,2-ethylhexylphenyloxycarbonyl group, 3- (2-ethylhexyloxy) phenyloxycarbonyl group, 4-fluoro Examples include a phenyloxycarbonyl group, a 4-chlorophenyloxycarbonyl group, a 4-cyanophenyloxycarbonyl group, a 4-butoxyphenyloxycarbonyl group, and the like. The following are further examples of the aryloxycarbonyl group.

[0036]

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Among the substituents of R ^{1 to} R ³ , the acyloxy group is preferably an acyloxy group having 2 to 20 carbon atoms, for example, acetyloxy, propanoyloxy, butanoyloxy, pentanoyloxy. Group, trifluoromethylcarbonyloxy group, octanoyloxy group, decanoyloxy group, undecanoyloxy group, octadecanoyloxy group and the like. The following are further examples of the acyloxy group.

[0038]

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Of the substituents R ^{1 to} R ³ , the alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, Isobutoxy, sec-butoxy, t-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, dodecyloxy, octadecyloxy , Ethoxycarbonylmethyloxy group, 2-ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group , - octylaminocarbonyl methyloxy group, N- methyl -N- benzylaminocarbonyl methyl group, a benzyl group, a cyano methyl _{group, -O- (CH 2) m CO} 2 H, -O- (CH 2) m
_{CO 2 Na, -O- (CH 2} ) m CO 2 K, -O- (C
_{H 2) m SO 3 H,} -O- (CH 2) m SO 3 Na, -O-
(CH ₂ ) _m SO ₃ K (m represents an integer of 1 to 4)
And the like.

Among the substituents of R ^{1 to} R ^3, the aryloxy group is preferably an aryloxy group having 6 to 30 carbon atoms, for example, phenyloxy group, 1-naphthyloxy group and 2-naphthyloxy group. Group, 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3
-Chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-
(2-ethylhexyloxy) phenyloxy group, 3-
Examples include a nitrophenyloxy group, a 4-fluorophenyloxy group, a 4-cyanophenyloxy group, a 4-butoxyphenyloxy group, a 4- (2-ethylhexyloxy) phenyloxy group, and a 4-octadecylphenyloxy group.

R¹~ R^ThreeOf the substituents, alkylthio
As the group, an alkylthio group having 1 to 30 carbon atoms is preferable.
For example, methylthio, ethylthio, propyl
Luthio, isopropylthio, butylthio, isobu
Tylthio group, sec-butylthio group, t-butylthio
Group, pentylthio group, isopentylthio group, hexylchi
O group, heptylthio group, octylthio group, 2-ethyl
Xylthio, decylthio, dodecylthio, octa
Decylthio group, ethoxycarbonylmethylthio group, 2-
Ethylhexyloxycarbonylmethylthio group, amino
Carbonylmethylthio group, N, N-dibutylaminocarb
Bonylmethyl group, N-methylaminocarbonylmethylthio
O group, N-ethylaminocarbonylmethylthio group, N-
Octylaminocarbonylmethylthio group, N-methyl-
N-benzylaminocarbonylmethylthio group, benzyl
Thio group, cyanomethylthio group, -S- (CH_Two)_mCO_Two
H, -S- (CH_Two)_mCO_TwoNa, -S- (CH_Two)_mC
O_TwoK, -S- (CH_Two)_mSO _ThreeH, -S- (CH_Two)_mS
O_ThreeNa, -S- (CH_Two)_mSO_ThreeK (m is 1 to 4
Indicates an integer. ) And the like.

Among the substituents of R ^{1 to} R ³ , the arylthio group is preferably an arylthio group having 6 to 30 carbon atoms, such as phenylthio, 1-naphthylthio, 2-naphthylthio, and 2-chlorophenylthio. Group,
2-methylphenylthio, 2-methoxyphenylthio, 2-butoxyphenylthio, 3-chlorophenylthio, 3-trifluoromethylphenylthio, 3-
Cyanophenylthio, 3- (2-ethylhexyloxy) phenylthio, 3-nitrophenylthio, 4-
A fluoriphenylthio group, a 4-cyanophenylthio group,
Examples thereof include a 4-butoxyphenylthio group, a 4- (2-ethylhexyloxy) phenylthio group, and a 4-octadecylphenylthio group.

Among the substituents of R ^{1 to} R ³ , the substituted sulfamoyl group includes sulfamoyl, N-alkylsulfamoyl, N-arylsulfamoyl, N, N-
It includes a dialkylsulfamoyl group, an N, N-diarylsulfamoyl group, and an N-alkyl-N-arylsulfamoyl group.

Among the substituents of R ^{1 to} R ³ , the substituted sulfamoyl group is preferably a substituted sulfamoyl group having 0 to 30 carbon atoms, for example, an N-methylsulfamoyl group, an N-ethylsulfamoyl group , N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfamoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2-methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group,
N-2-methoxyphenylsulfamoyl group, N-2-
Isopropoxyphenylsulfamoyl group, N-2-
(2-ethylhexyloxy) phenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3
-Nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxysulfamoyl group, N-4- (2'-ethylhexyloxy) phenylsulfamoyl group, N-4- Cyanophenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group, N , N-di (2-ethylhexyl) sulfamoyl group and the like.

Among the substituents of R ^{1 to} R ³ , the alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, for example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, Examples thereof include a butylsulfonyl group, a hexylsulfonyl group, a cyclohexylsulfonyl group, an octylsulfonyl group, a 2-ethylhexylsulfonyl group, a decanoylsulfonyl group, a dodecanoylsulfonyl group, an octadecanoylsulfonyl group, and a cyanomethylsulfonyl group.

Among the substituents of R ^{1 to} R ³ , the arylsulfonyl group is preferably an arylsulfonyl group having 6 to 30 carbon atoms, for example, a phenylsulfonyl group,
1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethyl Phenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-
A (2-ethylhexyloxy) phenylsulfonyl group,
3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4
-Butoxyphenylsulfonyl group, 4- (2-ethylhexyloxy) phenylsulfonyl group, 4-octadecylphenylsulfonyl group and the like.

Among the substituents of R ^{1 to} R ³ , the alkyl phosphoryl group is preferably an alkyl phosphoryl group having 2 to 40 carbon atoms, for example, a methyl phosphoryl group, an ethyl phosphoryl group, a propyl phosphoryl group, and an isopropyl phosphoryl group. Butyl phosphoryl group, isobutyl phosphoryl group, sec-butyl phosphoryl group, t-butyl phosphoryl group, pentyl phosphoryl group, isopentyl phosphoryl group, hexyl phosphoryl group, heptyl phosphoryl group, octyl phosphoryl group, 2-ethylhexyl phosphoryl group, decyl phosphoryl Group, dodecyl phosphoryl group,
Octadecylphosphoryl group, ethoxycarbonylmethylphosphoryl group, 2-ethylhexyloxycarbonylmethylphosphoryl group, aminocarbonylmethylphosphoryl group, N, N-dibutylaminocarbonylmethylphosphoryl group, N-methylaminocarbonylmethylphosphoryl group, N-ethylaminocarbonyl Methylphosphoryl group,
N-octylaminocarbonylmethylphosphoryl group, benzylphosphoryl group and the like.

Among the substituents of R ^{1 to} R ³ , the aryl phosphoryl group is preferably an aryl phosphoryl group having 12 to 50 carbon atoms, for example, a phenyl phosphoryl group, a 1-naphthyl phosphoryl group, and a 2-naphthyl phosphoryl group. A 2-chlorophenyl phosphoryl group, a 2-methylphenyl phosphoryl group, a 2-methoxyphenyl phosphoryl group, a 2-butoxyphenyl phosphoryl group, a 3-chlorophenyl phosphoryl group, a 3-trifluoromethylphenyl phosphoryl group, a 3-cyanophenyl phosphoryl group, 3-
(2-ethylhexyloxy) phenyl phosphoryl group,
3-nitrophenyl phosphoryl group, 4-fluorophenyl phosphoryl group, 4-cyanophenyl phosphoryl group,
-Butoxyphenylphosphoryl group, 4- (2-ethylhexyloxy) phenylphosphoryl group, 4-octadecylphenylphosphoryl group and the like.

Among the substituents of R ^{1 to} R ³ , the substituted amino group includes amino, N-alkylamino, N-arylamino, N-acylamino, N-sulfonylamino, N, N- Dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group,
And N-disulfonylamino group. As the substituted amino group, a substituted amino group having 0 to 50 carbon atoms is preferable. For example, an N-methylamino group, an N-ethylamino group, an N-propylamino group, an N-isopropylamino group, an N-tertbutylamino group N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyloxy)
Phenylamino group, N-3-chlorophenylamino group,
N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-4-methoxyamino group, N-4-
(2′-ethylhexyloxy) phenylamino group, N
-4-cyanophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N, N
-Diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N
A-(di-2-ethylhexylcarbonyl) amino group,
N, N- (dimethylsulfonyl) amino group, N, N-
(Diethylsulfonyl) amino group, N, N- (dibutylsulfonyl) amino group, N, N- (2-ethylhexylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group and the like. Further, examples of the substituted amino group include the following.

[0050]

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[0051]

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R¹~ R^ThreeAs a quaternary ammonium group
Is tetramethylammonium, tetraethylammonium
, Benzyltrimethylammonium, dodecyltri
Methylammonium is preferred and the counter anion is Cl^-,
Br^-, I^-, ClO_Four ^-, BF_Four ^-, PF₆ ^-, HSO_Four ^-, C
₆H_Five(Phenyl) -SO_Three ^-Are preferred. And M
Li, Na, K, Mg, Ca, Ba, Al, Zn,
Ni, Cu, Fe and the like are preferable. The above general formula
R of two compounds represented by (I)¹~ R^ThreeAny one of
Has a structure in which two groups are linked via a divalent linking group
A hydrazone dye containing two dye structures
Is also possible.

In the general formula (II), R ⁴ and R ⁵ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ⁴ and R ⁵ may be the same or different. As the substituent,
Alkoxy group, alkoxycarbonyl group, alkylsulfonyl group, substituted amino group, substituted amide group, aryl group,
Examples include, but are not limited to, an aryloxy group.

The alkyl group has 1 to 18 carbon atoms.
Are preferred, for example, a methyl group, a trifluoromethyl group, an ethyl group, a propyl group, an isopropyl group,
Butyl group, sec-butyl group, t-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group,
Cyclohexyl group, octyl group, t-octyl group, 2-
Ethylhexyl, nonyl, octadecyl, benzyl, 4-methoxybenzyl, tolphenylmethyl, ethoxycarbonylmethyl, butoxycarbonylmethyl, 2-ethylhexyloxycarbonylmethyl, 2 ', 4'-diisopentyl Phenyloxymethyl group, 2 ′, 4′-di-t-butylphenyloxymethyl group, dibenzylaminocarbonylmethyl group, 2,4-di-t-amylphenyloxypropyl group, ethoxycarbonylpropyl group, 1- ( 2 ′, 4′-di-t-amylphenyloxy) propyl group, acetylaminoethyl group, 2- (N, N-dimethylamino) ethyl group, 2-
(N, N-diethylamino) propyl group, methanesulfonylaminopropyl group, acetylaminoethyl group, 2-
(N, N-dimethylamino) ethyl group, 2- (N, N-
A diethylamino) propyl group is preferred.

The aryl group has 6 carbon atoms.
~ 30 aryl groups are preferable, for example, a phenyl group,
2-methylphenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 2-butoxyphenyl group, 2- (2
-Ethylhexyloxy) phenyl group, 2-octyloxyphenyl group, 3- (2,4-di-t-pentylphenoxyethoxy) phenyl group, 4-chlorophenyl group,
2,5-dichlorophenyl group, 2,4,6-trimethylphenyl group, 3-chlorophenyl group, 3-methylphenyl group, 3-methoxyphenyl group, 3-butoxyphenyl group, 3-cyanophenyl group, 3- (2 -Ethylhexyloxy) phenyl group, 3,4-dichlorophenyl group,
3,5-dichlorophenyl group, 3,4-dimethoxyphenyl group, 3- (dibutylaminocarbonylmethoxy) phenyl group, 4-cyanophenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-butoxyphenyl group, 4- (2-ethylhexyloxy) phenyl group, 4
-Benzylphenyl group, 4-aminosulfonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4- (2-ethylhexylcarbonyl) phenyl group, 4-fluorophenyl group, 3- Acetylphenyl group, 2-acetylaminophenyl group, 4- (4-chlorophenylthio) phenyl group, 4- (4-methylphenyl) thio-2,5-butoxyphenyl group, 4- (N-benzyl-N-methyl Amino) -2-dodecyloxycarbonylphenyl group, and the like, but are not particularly limited thereto. Further, these groups further include an alkyloxy group, an alkylthio group, a substituted phenyl group, a cyano group, a substituted amino group,
It may be substituted by a halogen atom, a heterocyclic group or the like.

In the general formula (III), R^Ten, R¹¹, R
¹²Is a hydrogen atom, a substituted or unsubstituted alkyl
Represents a group or a substituted or unsubstituted aryl group.
R^Ten, R ¹¹, R¹²Can be the same or different
Is also good. As the substituent, an alkyl group, an alkoxy group,
Alkylthio, aryl, aryloxy, ant
Thiol group, acyl group, alkoxycarbonyl group,
Bamoyl group, carboamide group, sulfonyl group, sulfa
Moyl group, sulfonamide group, ureide group, halogen source
And an amino group, a heterocyclic group and the like.

The alkyl group may have 1 to 18 carbon atoms.
Are preferred, for example, a methyl group, a trifluoromethyl group, an ethyl group, a propyl group, an isopropyl group,
Butyl group, sec-butyl group, t-butyl group, ventil group, isopentyl group, cyclopentyl group, hexyl group,
Cyclohexyl group, octyl group, t-octyl group, 2-
Ethylhexyl, nonyl, octadecyl, benzyl, 4-methoxybenzyl, triphenylmethyl, ethoxycarbonylmethyl, butoxycarbonylmethyl, 2-ethylhexyloxycarbonylmethyl, 2 ', 4'-diisopentyl Phenyloxymethyl group, 2 ′, 4′-di-t-butylphenyloxymethyl group, dibenzylaminocarbonylmethyl group, 2,4-di-t-amylphenyloxypropyl group, ethoxycarbonylpropyl group, 1- ( 2 ′, 4′-di-t-amylphenyloxy) propyl group, acetylaminoethyl group, 2- (N, N-dimethylamino) ethyl group, 2-
(N, N-diethylamino) propyl group, methanesulfonylaminopropyl group, acetylaminoethyl group, 2-
(N, N-dimethylamino) ethyl group, 2- (N, N-
Diethylamino) propyl group, 1-methyl-2- (4-
(Methoxyphenoxy) ethyl group, di-n-butylaminocarbonylmethyl group, di-n-octylaminocarbonylmethyl group and the like are preferable.

The aryl group has 6 carbon atoms.
~ 30 aryl groups are preferable, for example, a phenyl group,
2-methylphenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 2-butoxyphenyl group, 2- (2
-Ethylhexyloxy) phenyl group, 2-octyloxyphenyl group, 3- (2,4-di-t-pentylphenoxyethoxy) phenyl group, 4-chlorophenyl group,
2,5-dichlorophenyl group, 2,4,6-trimethylphenyl group, 3-chlorophenyl group, 3-methylphenyl group, 3-methoxyphenyl group, 3-butoxyphenyl group, 3-cyanophenyl group, 3- (2 -Ethylhexyloxy) phenyl group, 3,4-dichlorophenyl group,
3,5-dichlorophenyl group, 3,4-dimethoxyphenyl group, 3- (dibutylaminocarbonylmethoxy) phenyl group, 4-cyanophenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-butoxyphenyl group, 4- (2-ethylhexyloxy) phenyl group, 4
-Benzylphenyl group, 4-aminosulfonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4- (2-ethylhexylcarbonyl) phenyl group, 4-fluorophenyl group, 3- Acetylphenyl group, 2-acetylaminophenyl group, 4- (4-chlorophenylthio) phenyl group, 4- (4-methylphenyl) thio-2,5-butoxyphenyl group, 4- (N-benzyl-N-methyl Amino) -2-dodecyloxycarbonylphenyl group, and the like, but are not particularly limited thereto.
Further, these groups may be further substituted by an alkyloxy group, an alkylthio group, a substituted phenyl group, a cyano group, a substituted amino group, a halogen atom, a heterocyclic group and the like.

In the general formula (III), R¹³Alkyl in
Group and aryl group are the same^TenOr R¹²A
The same as the alkyl group and the aryl group. Also the general formula
In (III), R¹³Is an alkoxy group, R¹³Is
-OR²⁰And R²⁰Is R ^TenOr R¹²A
Same as the alkyl group. It also has the general formula (III)
And R¹³Is an aryloxy group, R¹³Is -OR^{twenty one}so
Yes, R^{twenty one}Is R^TenOr R¹²And the aryl group in
Is the same. Also, R¹³Represents a halogen atom,
Chloro and fluoro groups are preferred.

In the general formula (IV), the alkyl group and the aryl group for R ¹⁴ are the same as the alkyl group and the aryl group for R ¹⁰ to R ¹² . Further, in the general formula (IV), the halogen, alkyl group, aryl group, alkoxy group and aryloxy group in R ¹⁵ and R ¹⁶ are the same as R ¹³ described above. In the general formula (IV), R
The alkylthio groups at ¹⁵ and R ¹⁶ are each -S-
R ²² and —SR ²³ , wherein R ²² and R ²³ are
¹⁰ to be the same as the alkyl group in R ^12. Further, in the general formula (IV), the arylthio groups for R ¹⁵ and R ¹⁶ are —S—R ²⁴ and —S—R ²⁵ , respectively.
R ²⁴ and R ²⁵ are the same as the above-mentioned aryl groups for R ¹⁰ to R ¹² . Further, the alkyl group, aryl group and acyl group in R ¹⁹ of the general formula (V) are the same as those described above for R ¹ to R ³
And the same as the alkyl group, aryl group, and acyl group.

The hydrazone dye of the present invention has an oil solubility
Water solubility, pigment structure, and the like can be controlled by appropriately introducing a substituent.

Tables 1 to 21 show specific examples of the Ar portion of the hydrazone dye represented by formula (I) of the present invention, and Tables 22 to 28 show specific examples of the coupler portion. Specific examples of the Ar, Ar and coupler moieties are not limited to these. The Ar portion is indicated by Arabic numerals, and the coupler portion is indicated by Arabic numerals with parentheses. [Ar part]

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

[Table 5]

[0068]

[Table 6]

[0069]

[Table 7]

[0070]

[Table 8]

[0071]

[Table 9]

[0072]

[Table 10]

[0073]

[Table 11]

[0074]

[Table 12]

[0075]

[Table 13]

[0076]

[Table 14]

[0077]

[Table 15]

[0078]

[Table 16]

[0079]

[Table 17]

[0080]

[Table 18]

[0081]

[Table 19]

[0082]

[Table 20]

[0083]

[Table 21]

Specific examples of the coupler portion of the dye of the present invention are described below.

[0085]

[Table 22]

[0086]

[Table 23]

[0087]

[Table 24]

[0088]

[Table 25]

[0089]

[Table 26]

[0090]

[Table 27]

[0091]

[Table 28]

The compounds represented by the general formulas (I) and (V) of the present invention have the following properties:
Water-soluble group (-SO ₃ H, 4 quaternary ammonium groups, -CO ₂ M
_{1 / n,} preferably has at least one -SO ₃ M 1 _{/ n),} it is preferred to have particularly two or more. In the ink for inkjet recording of the present invention, the compounds represented by the general formula (I) and the general formula (V)
It is preferably contained in an amount of 0.2 to 10% by weight,
More preferably, the content is 5% by weight.

The ink jet recording ink of the present invention comprises
The compound represented by the general formula (I) and the general formula (V) can be prepared by dissolving or dispersing in a mixed solvent mainly composed of water and a water-soluble organic solvent. As a water-soluble organic solvent that can be used as a liquid medium of the aqueous ink,
For example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-
Alcohols such as butanol, t-butanol, pentanol, hexanol, cyclohexanol, and benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Polyhydric alcohols such as polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether , Propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, glycol derivatives such as ethylene glycol monophenyl ether; ethanolamine, diethanolamine, triethanolamine, N
Amines such as -methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine and tetramethylpropylenediamine; formamide, N, N-dimethylformamide, N, N-dimethyl Acetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-
Polar solvents such as methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, and acetone. The water-soluble organic solvent together with water,
Two or more kinds may be used in combination.

In a mixed solvent of water and the water-soluble organic solvent,
The compounds represented by the general formulas (I) and (V) may be dissolved or dispersed in the mixed solvent. When the compound is dispersed in a mixed solvent, various dispersers (for example, a ball mill, a sand mill,
Attritor, roll mill, agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer,
Pearl mill, jet mill, ang mill, etc.)
Preferably, the compound is finely divided. After dissolving the dye in the organic solvent, the dye can be used by dispersing it in the above-mentioned mixed solvent using an appropriate dispersant or surfactant.
With respect to the method for preparing the aqueous ink, see JP-A-5-14843.
6, No. 5-295121, No. 7-97541, No. 7-82515, No. 7-118584, and the like.

The ink for ink jet recording of the present invention may contain a dye other than the compounds represented by the general formulas (I) and (V) for the purpose of adjusting the hue and the like. Further, the ink of the present invention may optionally include
Various additives may be added. As the additive,
Viscosity adjusters, surface tension adjusters, resistivity adjusters, film adjusters, ultraviolet absorbers, antioxidants, anti-fading agents, fungicides,
Rust inhibitors, dispersants, surfactants and the like can be mentioned. Also,
When the ink for inkjet recording of the present invention is in the form of a water-based ink or an oil-based ink, its viscosity is set to 40 cp.
It is preferable to adjust below, and the surface tension is
It is preferable to adjust to 20 dyn / cm to 100 dyn / cm.

The formulas (I) and (V)
The compound represented by formula (1) can be used as an ink for inkjet recording in the form of an oil-based ink. in this case,
It can be prepared by dissolving or dispersing the compound represented by the general formula (1) in a liquid medium containing an organic solvent as a main component. Examples of the organic solvent used in the liquid medium include alcohols such as ethanol, pentanol, heptanol, octanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, and anis alcohol; Ethyl ether,
Ethylene glycol monophenyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diethyl Glycol derivatives such as acetate, ethylene glycol monoethyl ether acetate, propylene glycol diacetate;

Ketones such as benzyl methyl ketone, diacetone alcohol and cyclohexanone; ethers such as butyl phenyl ether, benzyl ethyl ether and hexyl ether; ethyl acetate, amyl acetate, benzyl acetate, phenyl ethyl acetate, phenyl ethyl acetate, phenoxy ethyl acetate;
Ethyl phenylacetate, benzyl propionate, ethyl benzoate, butyl benzoate, ethyl laurate, butyl laurate, isopropyl myristate, isopropyl palmitate, triethyl phosphate, tributyl phosphate, diethyl phthalate, dibutyl phthalate, malonic acid Diethyl, dipropyl malonate, diethyl diethylmalonate,
Diethyl succinate, dibutyl succinate, diethyl glutarate, diethyl adipate, dibutyl adipate, di (2-methoxyethyl) adipate, diethyl sebacate, diethyl maleate, dibutyl maleate, dioctyl maleate, diethyl fumarate, Esters such as dioctyl fumarate and 3-hexenyl cinnamate; hydrocarbon solvents such as petroleum ether, petroleum benzyl, tetralin, delican, 1-amylbenzene, dimethylnaphthalene; acetonitrile, formamide, N, N-dimethylformamide, N , N-dimethylacetamide, dimethylsulfoxide, sulfolane, propylene carbonate, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, and a polar solvent such as N, N-diethyldodecaneamide. These solvents may be used alone or as a mixture of two or more.

The compound represented by the general formula (1) may be dissolved in the organic solvent, or may be dispersed together with a suitable dispersant. For the method of preparing the oil-based ink, see JP-A-3-231975 and JP-T-5-50888.
Reference can be made to the method described in Japanese Patent Publication No.

The formulas (I) and (V)
The compound represented by the formula (1) can be used as an ink for inkjet recording in the form of a solid ink. in this case,
The compound represented by the general formula (1) is prepared by dissolving or dispersing it in a phase change solvent that is in a solid state at room temperature and is melted by an energy provided when ink is ejected to be in a liquid state. be able to. Examples of the phase change solvent include beeswax, carnauba wax, rice wax, wood wax, jojoba oil, whale wax, candelilla wax, lanolin, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, petrolactam Natural wax such as polyethylene wax, chlorinated hydrocarbon, palmitic acid,
Organic acids such as stearyl acid, behenic acid, tiglic acid, 2-acetonaphthobehenic acid, 12-hydroxystearic acid, dihydroxystearic acid; dodecanol, tetradecanol, hexadecanol, eicosanol, docosanol, tetracosanol, hexacosa Octanol, octacosanol, dodecenol, myricyl alcohol, tetracenol, hexadecenol, eicosenol, docosenol, pinene glycol, hinokiol, butynediol, nonanediol, isophthalyl alcohol,
Alcohols such as mesicerin, hexanediol, decanediol, tetradecanediol, hexadecanediol, docosandiol, tetracosandiol, tvneol, phenylglycerin, eicosandiol, octanediol, phenylpropylene glycol;

Phenols such as bisphenol A and p-α-cumylphenol; organic acid esters of the above organic acids such as glycerin, ethylene glycol and diethylene glycol; cholesterol stearate, cholesterol palmitate, cholesterol myristate, cholesterol behenate; Cholesterol fatty acid esters such as cholesterol laurate and cholesterol melicate; saccharose stearate, saccharose palmitate, saccharose behenate, saccharose laurate, saccharose melinate, lactose stearate, lactose palmitate, lactose behenate, lactose laurate, melisin Sugar fatty acid esters such as acid lactose; benzoylacetone, diacetbenzene, benzophenone, Kosanon, heptacosanone,
Ketones such as heptatriacontanone, hentriacontanone, stearone, laurone; oleamide;
Lauric amide, stearic amide, ricinoleamide, palmitic amide, tetrahydrofuran amide, erucamide, myristic amide, 12-hydroxystearic amide, N-stearyl erucamide, N-oleyl stearamide, N , N-ethylenebislauric acid amide, N, N-ethylenebisstearic acid amide, N, N-ethylenebisbehenic acid amide, N, N-xylylenebisstearic acid amide,
N-butylenebisstearic acid amide, N, N-dioleyladipamide, N, N-dioleylsebacic amide, N, N-distearylsebacic amide,
N-distearyl terephthalamide, phenacetin,
Amides such as toluamide and acetamide; sulfonamides such as p-toluenesulfonamide, ethylbenzenesulfonamide and butylbenzenesulfonamide;
Is mentioned.

The phase change temperature of the phase change solvent from solid to liquid is preferably from 60 to 200 ° C., and from 80 to 15 ° C.
More preferably, it is 0 ° C. The solid ink may be prepared by dissolving the compound represented by the general formula (I) and the general formula (V) in the phase change solvent that has been melted by heating, or may be prepared by dissolving a suitable dispersant. It may be prepared by dispersing or dissolving together with a binder or a binder. For the method of preparing the solid ink, see JP-A-5-186723,
Reference can be made to the method described in JP-A-70490.

The ink-jet recording ink of the present invention comprises:
When the energy is applied, the liquid droplets are ejected to a recording medium, land on the recording medium, and form an image on the recording medium. The ink jet recording ink of the present invention may be applied to any type of ink jet printer. For example, it may be used for any of a continuous type and an on-demand type inkjet printer. Further, there is no limitation on the type of the ink jet head, and the ink jet head can be preferably used for a printer having a head of any type such as a bubble jet (registered trademark) type, a thermal jet type, or a type using ultrasonic waves.

Also, for example, a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue and different densities, and a method of using colorless and transparent inks. It can be used for many new types of inkjet recording type printers such as the type used. In particular, when the ink is used as a printer ink for forming an image close to a photograph by ejecting a large amount of ink having a high print speed and a low density, the improvement effect is remarkably exhibited.

The recording medium used in the image recording method of the present invention includes plain paper, coated paper, plastic film and the like. It is preferable to use coated paper as the recording medium because the image quality and image storage durability are improved.

In the image recording method of the present invention, a recording paper containing a mordant may be used as a recording medium.
In particular, it is preferable to use a recording paper containing an immobilized polymer mordant. Examples of the polymer mordant include JP-A-48-28325, JP-A-54-74430, and JP-A-54-74430.
-124726, 55-22766, 55-1
No. 42339, No. 55-23850, No. 60-238
No. 51, No. 60-23852, No. 60-23853
No. 60-57836, No. 60-60643, No. 60-118834, No. 60-60643, No. 60
-118834, 60-122940, 60-
No. 122941, No. 60-122942, No. 60-2
No. 35134, JP-A-1-161236, U.S. Pat. Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690 and 4,115,124. Nos. 4,124,386, 4,193,800, 4,273,853, 4,282,305, and 4,450,224. . In particular, JP-A-1-161236
No. 2, pages 212 to 215, it is preferable to use a recording paper containing a polymer mordant. When an image is formed using a recording paper containing the polymer mordant, an image with excellent image quality is obtained and the light fastness of the image is improved.

In the image recording method of the present invention, a recording paper containing an inorganic pigment can be used as a recording medium. The type of the inorganic pigment is not particularly limited,
Any inorganic pigment can be used. For example, silica pigment, alumina pigment, titanium dioxide pigment, zinc oxide pigment, zirconium oxide pigment, mica-like iron oxide, lead white, lead oxide pigment, cobalt oxide pigment, strontium chromate, molybdenum pigment, smectite, magnesium oxide pigment, oxide Examples thereof include calcium pigments, calcium carbonate pigments, mullite, and the like, and one kind or two or more kinds can be used.

In the image recording method of the present invention, a recording paper containing various hydrophilic binders can be used as a recording medium. As the hydrophilic binder, any compound including gelatin or a derivative thereof, polyvinyl alcohol or a derivative thereof, polyalkylene oxide or a derivative thereof, and other superabsorbent polymers can be used. For example, those described in JP-A-1-161236, pp. 215 to 222, can be used. In the image recording method of the present invention, it is preferable to use a recording paper containing a matting agent as the recording material. As the matting agent, conventionally known matting agents can be used.
What is described on page 263-264 of 61236 can be used. In the image recording method of the present invention, recording paper hardened with a hardener can be used. There are no particular restrictions on the type of hardener, and known hardeners, for example, those described on page 222 of JP-A-1-161236 can be used.

In the constituent layers of the recording medium, various surfactants can be used for the purpose of improving coating properties, improving releasability, improving slipperiness, preventing static charge, and the like. Specific examples of the surfactant are described in JP-A-62-173463 and JP-A-62-1.
No. 83457 and the like. Further, an organic fluoro compound may be included for the above purpose. Representative examples of the organic fluoro compound include JP-B-57-9053.
Nos. 8-17, JP-A-61-20994, 62-
Examples thereof include fluorine surfactants described in each publication such as No. 135826, and hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as ethylene tetrafluoride resin.

The constituent layers (including the back layer) of the recording medium may contain various polymer latexes for the purpose of improving film physical properties such as dimensional stability, curl prevention, adhesion prevention, and film crack prevention. Can be. Specifically, JP-A Nos. 62-245258 and 62-131648,
Any of the polymer latexes described in each gazette such as JP-A-62-10066 can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or less) is used for the mordant layer, the mordant layer can be prevented from cracking and curl can be improved. An anti-curl effect is obtained. In the image recording method of the present invention, a constituent layer may contain an anti-fading agent. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.
As an example, JP-A-1-161236, page 225-
What is described on page 247 can be used.

The recording medium may contain a fluorescent whitening agent. In particular, it is preferable that a fluorescent whitening agent is incorporated in the recording medium, or it is contained in ink or the like and supplied from the outside to the recording medium. In the present invention, the support of the recording medium is not particularly limited, but is a polyolefin (for example, polyethylene, polystyrene,
Paper laminated with a homopolymer such as polyethylene terephthalate or polybutene, or a copolymer of any combination thereof, or a plastic support (provided that a white pigment such as titanium oxide or zinc oxide, cobalt blue or ultramarine, It is preferable to add a coloring dye such as neodymium).

[0111]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. The dye compound in the present invention is represented by A
This is shown as a combination of an r portion and a coupler portion represented by the following formula. For example, exemplary compound 2- (1) is Ar
A portion (diazo portion) represented by 2 in Table 1 above;
This means that the coupler portion is a combination of those shown in Table 22 (1). That is, the dye compound represented by 2- (1) has the following structure.

[0112]

Embedded image

[0113]

Embedded image <Example 1> An ink A having the following composition was prepared. [Ink A] Dye (exemplified compound 109- (32)) 4 parts by mass (compound represented by the above general formula (I)) diethylene glycol 9 parts by mass tetraethylene glycol monobutyl ether 9 parts by mass glycerin 7 parts by mass diethanolamine 1 part by mass Water 70 parts by mass The above-mentioned components were stirred for 1 hour while heating at 30 to 40 ° C., and then subjected to pressure filtration using a micro filter having an average pore diameter of 0.8 μm and a diameter of 47 mm to obtain a desired ink A.

Using the prepared ink A, an ink jet printer PM-700C (manufactured by Seiko Epson Co., Ltd.) was used to print on Fuji Photo Film ink-jet paper and super photo grade (photo glossy paper) to obtain an image sample.

The hue and light fastness were evaluated using the obtained image samples. The evaluation results are shown in Table 29 below. Evaluation of Hue The hue of the image part was visually evaluated. -Light resistance evaluation The image samples were irradiated with xenon light (85,000 lux) for 3 days using an "Atlas CI 65 weather meter", and the image densities before and after xenon irradiation were measured with a reflection densitometer ("X-Rite"). 310TR ”)
The dye remaining rate was calculated. The higher the residual dye ratio, the higher the light fastness. The reflection density before irradiation is 1, 1.5,
The evaluation was made at three points of 2.0, and when the residual ratio of the dye was 80% or more at any concentration, it was evaluated as Δ, when 50 to 80%, Δ, and other cases, as ×.

<Examples 2 to 7> Inks were produced in the same manner as in Example 1 except that the dyes (Exemplary Compound 109- (32)) used in Example 1 were replaced with the dyes shown in Table 29 below. Then, in the same manner as in Example 1, the hue and the light resistance were evaluated. The evaluation results are shown in Table 29 below.

Example 8 An ink was produced in the same manner as in Example 1 except that the dye (Example Compound 109- (32), 4 parts by mass) used in Example 1 was changed to the following dye. Dye (Exemplified Compound 270- (32)) 1.3 parts by mass Dye (compound represented by Structural Formula 1) 1.3 parts by mass Dye (compound represented by Structural Formula 2) 1.4 parts by mass Preparation The hue and light fastness of the ink thus obtained were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 29 below.

[0118]

Embedded image

Example 9 Example 1 was repeated except that the compound represented by the structural formula 1 of Example 8 was replaced with the dye 109- (32).
The hue and light resistance were evaluated in the same manner as described above. The evaluation results are shown in Table 29 below.

[0120]

[Table 29]

[0121]

According to the present invention, it is possible to provide an ink jet recording ink and an image recording method capable of forming an image having good hue and light fastness.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Sachiko Shinshiro 200-Onakazato, Fujinomiya-shi, Shizuoka Fuji Photo Film Co., Ltd. F-term (reference) 2C056 EA13 FC01 FC02 2H086 BA01 BA53 BA56 BA57 4J039 BA29 BC05 BC12 BC16 BC19 BC20 BC29 BC31 BC33 BC36 BC44 BC45 BC47 BC50 BC51 BC52 BC53 BC54 BC55 BC56 BC65 BC66 BC67 BC72 BC73 BC75 BC76 BC77 BC79 BE02 EA35 GA24

Claims (6)

[Claims] 1. An ink jet recording ink containing a compound represented by the following general formula (I). Embedded image In the formula, Ar represents an aryl group or a heterocyclic group. R ¹
To R ³ are each a hydrogen atom, a halogen, -CN, -N
H ₂ , —NO ₂ , —OH, —CO ₂ H, —SO ₃ H, quaternary ammonium group, —CO ₂ M _{1 / n} , —SO ₃ M _{1 / n} , alkyl group, alkenyl group, alkynyl group, Aryl group, acyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkylphosphoryl group, aryl Represents a phosphoryl group or a substituted amino group. M represents a metal atom, and n represents an integer of 1 to 4. 2. The ink for inkjet recording according to claim 1, wherein the group represented by Ar— in the general formula (I) is a group represented by the following general formula (II). Embedded image In the formula, R ⁴ and R ⁵ represent a hydrogen atom, an alkyl group, or an aryl group. R ^{6 to} R ⁹ have the same meanings as R ^{1 to} R ^{3 in} claim 1. 3. The ink jet recording ink according to claim 1, wherein the group represented by Ar— in the general formula (I) is a group represented by the following general formula (III). Embedded image In the formula, R ^{10 to} R ¹² represent a hydrogen atom, an alkyl group, or an aryl group. R ¹³ represents a hydrogen atom, a halogen, an alkyl group, an alkoxy group, an aryl group, or an aryloxy group. X represents O or S. 4. The ink for inkjet recording according to claim 1, wherein the group represented by Ar— in the general formula (I) is a group represented by the following general formula (IV). Embedded image In the formula, R ¹⁴ represents a hydrogen atom, an alkyl group or an aryl group. R ¹⁵ and R ¹⁶ represent a hydrogen atom, a halogen, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or an aryl group. Y is O
Or represents S. 5. A compound represented by the following general formula (V)
Includes ink for inkjet recording. Embedded imageIn the formula, Ar ′ has the same meaning as Ar in claim 1. R¹⁷And
And R¹⁸Is R in claim 1 ¹~ R^ThreeIs synonymous with R¹⁹Is hydrogen
Represents an atom, alkyl, aryl, or acyl group
You. Z represents an oxygen atom or a sulfur atom. 6. The method according to claim 1, wherein energy is supplied to the ink jet recording ink according to any one of claims 1 to 5, wherein the ink droplets are ejected onto a recording medium, and the ink is formed on the recording medium. An image recording method for recording an image.