JPH09111163A - Ink jet recording liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an ink jet recording liq. which can ensure lightfastness of a color image, an improvement in color tone for color reproduction, particularly for magenta as a main object color, and use for a long period of time by incorporating a particular dye. SOLUTION: A dye represented by the formula [wherein X represents an NR3 R4 group (wherein R3 and R4 represent each an alkyl, an alkenyl, an aryl, an aralkyl, or a cycloalkyl) or an OH group; Y1 and Y2 represent CR (wherein R represents H, an alkyl, or an acylamino), or an N atom; Z represents a group of atoms capable of forming a nitrogen-contg. heterocyclic ring which may be substd. with at least one group selected from among an alkyl, a cycloalkyl, cyano, an alkoxy, an aryl, an aryloxy, an aralkyl, an alkylsulfinyl, an acylamino, sulfonylamino, ureido, an alkylthio, an alkoxycarbonyl, carbamoyl, an acyl, amino, an alkylsulfonyl, and sulfamoyl; R1 represents H, a halogen, an alkyl, a cycloalkyl or the like; and R2 represents an alkyl, a cycloalkyl or the like] is dissolved in a solvent or dispersed in a solvent system to prepare the objective ink jet recording liq.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording liquid containing a specific dye. In particular, the present invention relates to an inkjet recording liquid having excellent color tone and color image fastness.

[0002]

2. Description of the Related Art An ink jet recording system is a system in which a droplet is pressure-discharged by electro-mechanical conversion of a piezo element, a system in which bubbles are generated by electro-thermal conversion to discharge a pressure drop, and a droplet is discharged by electrostatic force. It is roughly classified into a method of sucking and discharging.

[0003] Ink-jet inks are suitable for the recording system used, for example, selected from the above, have a high recorded image density and good color tone, and have light resistance, heat resistance and water resistance. Excellent color image fastness, such as color stability, fast fixing to the recording medium, does not bleed after recording, excellent storage stability as ink, no problem with safety such as toxicity and flammability, inexpensive Is required.

[0004] From such a viewpoint, various recording liquids for ink jet have been proposed and studied, but the recording liquids that simultaneously satisfy many requirements are extremely limited.

In color image recording using yellow, magenta, cyan, and black, for example, C.I. I. A conventionally known C.I. described in the index. I. Dyes and pigments having a number have been widely studied. Particularly in the magenta ink, C.I. I. Xanthenes such as Acid Red 52, C.I. I. It is known to use an azo-based water-soluble dye such as Direct Red 20, but the former has a problem in fastness such as light resistance, and the latter has a color reproduction that lacks the sharpness of magenta tones. It had a problem of spectral absorption characteristics regarding the property.

To solve this problem, Japanese Patent Laid-Open No. 3-23
In 1975, a recording method aimed at achieving both color tone and light fastness is shown, but when used as an aqueous ink, it lacks sufficient water solubility, and there is a problem with sufficient storability as a dye. It was difficult to guarantee long-term use.

[0007]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an ink jet recording liquid having excellent light fastness of a color image and excellent color tone for good color reproducibility, particularly magenta ink jet recording. To provide the liquid. Still another object of the present invention is to provide a water-based inkjet recording liquid that can ensure long-term use in addition to achieving both light resistance and color tone.

[0008]

The above objects of the present invention have been achieved by the following constitutions as a result of intensive studies by the present inventors.

1. An ink jet recording liquid containing a dye represented by the following general formula (1).

[0010]

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In the formula, X is an NR ₃ R ₄ group (R ₃ and R ₄ may be the same or different. R ₃ is an optionally substituted alkyl group, alkenyl group, aryl group, It represents an aralkyl group or a cycloalkyl group, and R ₄ has the same meaning as R ₃ .

R ₃ may be bonded to R ₄ to form a ring together with the nitrogen atom, or may be bonded to R ₁ to form a ring) or an OH group. Y ₁ and Y ₂ are CR
(R represents a hydrogen atom, an alkyl group or an acylamino group) or a nitrogen atom, and at least one of Y ₁ and Y ₂ is a nitrogen atom.

Z is an alkyl group, a cycloalkyl group, a cyano group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an alkylsulfinyl group, an acylamino group or a sulfonyl which may have a 5- or 6-membered substituent. Represents an atom group forming a nitrogen-containing heterocycle which may be substituted with at least one of an amino group, a ureido group, an alkylthio group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, an amino group, an alkylsulfonyl group, and a sulfamoyl group. The heterocycle may form a condensed ring with another ring.

R ₁ is a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, a cycloalkyl group, a cyano group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an alkylsulfinyl group, an acylamino group. Group, sulfonylamino group, ureido group, alkylthio group, alkoxycarbonyl group, carbamoyl group, acyl group, amino group, alkylsulfonyl group, sulfamoyl group, and each R ₂ may have a substituent. Alkyl group, cycloalkyl group, cyano group, alkoxy group, aryl group, aryloxy group, aralkyl group, alkylsulfinyl group, acylamino group, sulfonylamino group, ureido group, alkylthio group, alkoxycarbonyl group, carbamoyl group, acyl group, Amino group, alk It represents a rusulfonyl group or a sulfamoyl group. Furthermore, at least one of the substituents on the ring represented by R ₂ and Z has a Hammett σp value of
It is a substituent of -0.05 or more and 1.0 or less.

2. An ink jet recording liquid containing a dye represented by the following general formula (2).

[0016]

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In the formula, X ₁ is an NR ₃₁ R ₄₁ group (R ₃₁ and R ₄₁ may be the same or different. R ₃₁ is an optionally substituted alkyl group, alkenyl group or aryl group. represents an aralkyl group, a cycloalkyl group or a hydrogen atom, R ₄₁ has the same meaning as R ₃₁ .R ₃₁ may form a ring together with a nitrogen atom bonded together with R _41, also R ₁₁
May form a ring) or an OH group.

Y ₁₁ and Y ₁₂ are each CR ₁ (R ₁ is a hydrogen atom,
An acylamino group or R ₃₁ ) or a nitrogen atom, and at least one of Y ₁₁ and Y ₁₂ is a nitrogen atom. Z ₁ represents a group of atoms forming a nitrogen-containing heterocycle which may have a 5- or 6-membered substituent, and this heterocycle may form a condensed ring with another ring.

R ₁₁ represents a hydrogen atom, a halogen atom or a monovalent substituent, and R ₁₂ represents a monovalent substituent. Furthermore, at least one of the substituents on the ring represented by R ₁₂ and Z ₁ has a Hammett σp value of −0.05 or more 1.
It is a substituent of 0 or less.

The present invention will be described in detail below.

Hereinafter, the compound represented by the general formula (1) of the present invention will be described in detail.

X is an NR ₃ R ₄ group (R ₃ and R ₄ may be the same or different. R ₃ is an optionally substituted alkyl group (eg, methyl group, ethyl group, propyl group). ), An alkenyl group (for example, an allyl group), an aryl group (for example, a phenyl group), an aralkyl group (for example, a benzyl group), and a cycloalkyl group (for example, a cyclohexyl group and a cyclopentyl group), and R ₄ has the same meaning as R ₃ . R ₃
Represents an OH group, which may be bonded to R ₄ to form a ring together with a nitrogen atom, or may be bonded to R ₁ to form a ring), or is preferably an OH group, and preferably R ₃ and R ₄ are Both are NR ₃ R ₄ groups which are substituted or unsubstituted lower alkyl groups.

Examples of the substituent include a hydroxy group, an alkoxy group, a cyano group, an alkylsulfonylamino group and a halogen atom. R ₃ and R ₄ or R ₃ and R ₁ may be bonded to each other to form a 5- or 6-membered ring.

R ₁ is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom), or an alkyl group which may have a substituent, a cycloalkyl group, a cyano group, an alkoxy group, an aryl group, an aryloxy group, Aralkyl group,
Alkylsulfinyl group, acylamino group, sulfonylamino group, ureido group, alkylthio group, alkoxycarbonyl group, carbamoyl group, acyl group, amino group,
It represents at least one of an alkylsulfonyl group and a sulfamoyl group, but is preferably an alkyl group or an alkoxy group.

R ₂ is an alkyl group which may have a substituent, a cycloalkyl group, a cyano group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an alkylsulfinyl group, an acylamino group, a sulfonylamino group and a ureido group. Represents a group, an alkylthio group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, an amino group, an alkylsulfonyl group, and a sulfamoyl group.

Further, at least one of the substituents on the ring represented by R ₂ and Z has a Hammett σp value of −0.
05 or more and 1.0 or less, and examples of such a substituent include an aryl group (eg, phenyl group), a halogen-substituted alkyl group (eg, trifluoromethyl group, trichloromethyl group, tetrafluoroethyl group), cyano Group, alkylsulfonyl group (eg methanesulfonyl group), alkylsulfinyl group (eg methanesulfinyl group), sulfamoyl group (eg diethylsulfamoyl group), carbamoyl group (eg diethylcarbamoyl group), alkoxycarbonyl group (eg methoxycarbonyl group) ) And the like.

Y ₁ and Y ₂ each represent CR (R represents a hydrogen atom, an alkyl group or an acylamino group) or a nitrogen atom, and at least one of Y ₁ and Y ₂ is a nitrogen atom.

Z is an alkyl group, a cycloalkyl group, a cyano group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an alkylsulfinyl group, an acylamino group or a sulfonyl which may have a 5- or 6-membered substituent. A group of atoms forming a nitrogen-containing heterocycle which may be substituted with at least one of an amino group, a ureido group, an alkylthio group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, an amino group, an alkylsulfonyl group and a sulfamoyl group. This heterocycle may form a condensed ring with another ring.

Next, the dye represented by the general formula (2) will be described in detail.

X ₁ is an NR ₃₁ R ₄₁ group (R ₃₁ and R ₄₁ may be the same or different. R ₃₁ is an optionally substituted alkyl group (eg, methyl group, ethyl group, propyl group). Group), alkenyl group (eg allyl group), aryl group (eg phenyl group), aralkyl group (eg benzyl group), cycloalkyl group (eg cyclohexyl group,
A cyclopentyl group) or a hydrogen atom, and R ₄₁ is R ₃₁
Is synonymous with

R ₃₁ may be bonded to R ₄₁ to form a ring together with a nitrogen atom, or may be bonded to R ₁₁ to form a ring) or an OH group, preferably R ₃₁ and R ₄₁ are NR ₃₁ R ₄₁ in which both are a substituted or unsubstituted lower alkyl group.

Examples of the substituent include a hydroxy group, an alkoxy group, a cyano group, an alkylsulfonylamino group,
And a halogen atom. R ₃₁ and R ₄₁ or R ₃₁ and R ₁₁ may be bonded to each other to form a 5- or 6-membered ring.

R ₁₁ represents a hydrogen atom, a halogen atom (for example, a fluorine atom or a chlorine atom) or a monovalent substituent,
As the valent substituent, an alkyl group which may have a substituent, a cycloalkyl group, a cyano group, an alkoxy group,
Aryl group, aryloxy group, aralkyl group, acylamino group, sulfonylamino group, ureido group, alkylthio group, alkoxycarbonyl group, carbamoyl group,
An acyl group, an amino group, a sulfonyl group, a sulfamoyl group, an alkylsulfinyl group and the like can be mentioned, but an alkyl group or an alkoxy group is preferable.

R ₁₂ represents a monovalent substituent, and examples thereof include an alkyl group which may have a substituent, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an acylamino group and a sulfonyl group. Amino group,
Examples thereof include a ureido group, an alkylthio group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, an amino group, an alkylsulfonyl group, and a sulfamoyl group.

Further, at least one of the substituents on the ring represented by R ₁₂ and Z ₁ has a Hammett σp value of −0.
05 or more and 1.0 or less, and examples of such a substituent include an aryl group (eg, phenyl group), a halogen-substituted alkyl group (eg, trifluoromethyl group, trichloromethyl group, tetrafluoroethyl group), cyano Group, alkylsulfonyl group (eg methanesulfonyl group), alkylsulfinyl group (eg methanesulfinyl group), sulfamoyl group (eg diethylsulfamoyl group), carbamoyl group (eg diethylcarbamoyl group), alkoxycarbonyl group (eg methoxycarbonyl group) ) And the like.

Y ₁₁ and Y ₁₂ are each CR ₁ (R ₁ is a hydrogen atom,
An acylamino group or R ₃₁ ) or a nitrogen atom, and at least one of Y ₁₁ and Y ₁₂ is a nitrogen atom. Z ₁ represents a group of atoms forming a nitrogen-containing heterocycle which may have a 5- or 6-membered substituent, and this heterocycle may form a condensed ring with another ring.

The dye represented by the general formula (2) is particularly preferably a dye represented by the following general formula (3) or (4).

[0038]

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[0039]

[Chemical 6]

In the general formula (3) or (4),
R ₁₁ , R ₁₂ , X ₁ , Y ₁₁ , and Y ₁₂ have the same meanings as defined in the general formula (2), and R ₅ is an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, It represents an aralkyl group, an acylamino group, a sulfonylamino group, a ureido group, an alkylthio group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, an amino group, a cyano group, an alkylsulfonyl group, a sulfamoyl group and an alkylsulfinyl group. At least one of R ₁₂ and R ₅ is a substituent having a Hammett σp value of −0.05 or more and 1.0 or less.

The value of Hammett's σp in the present invention is the value in the area of chemistry, Supplement No. 122 (Kakueido 198.3.1).
The publications on pages 85 to 121 can be referred to.

Specific compound examples of the dye of the present invention are shown below, but the present invention is not limited thereto.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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Specific methods for synthesizing the above-mentioned dyes include Chem. Ber. , 85, 1012 (195
2). Am. Chem. Soc. , 74, 3828
(1952) and the like and JP-A-6-8063.
No. 8, No. 5-239367, etc. can be referred to.

The ink jet recording liquid containing the dye of the present invention can use various solvent systems such as an aqueous solvent, an oil solvent and a solid (phase change) solvent, and the effect of the present invention is particularly exhibited in the aqueous solvent. .

As the aqueous solvent, water (for example, ion-exchanged water is preferable) and a water-soluble organic solvent are generally used.

Examples of the water-soluble organic solvent include alcohols (eg, methanol, ethanol, propanol,
Isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc., and polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene) Propylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, diethylene glycol Monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc. ), Amines (for example,
Ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylene Diamines), amides (for example,
Formamide, N, N-dimethylformamide, N, N
-Dimethylacetamide, etc.), heterocycles (for example, 2-
Pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc., sulfoxides (eg, dimethyl sulfoxide), sulfones (eg,
Sulfolane), urea, acetonitrile, acetone and the like.

The aqueous solvent as described above can be used as it is if the dye of the present invention is soluble in the solvent system. On the other hand, if the solid is insoluble as it is,
Dyes are made into fine particles using various dispersing machines (for example, ball mill, sand mill, attritor, roll mill, agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, jet mill, ong mill, etc.) or are soluble. After dissolving the dye in the organic solvent, the dye can be dispersed in the solvent system together with the polymer dispersant and the surfactant. Furthermore, in the case of a liquid or semi-molten substance which is insoluble as it is, it can be dissolved as it is or in a soluble organic solvent, and can be dispersed in the solvent system together with a polymer dispersant and a surfactant.

Specific methods for preparing an aqueous solvent used for such an ink jet recording liquid are described, for example, in JP-A-5-148436, 5-295312 and 7-.
97541, 7-82515, 7-11858.
The method described in No. 4 etc. can be referred to.

The oil-based solvent used in the present invention is an organic solvent.

Examples of the solvent of the oil-based solvent include alcohols (for example, pentanol, heptanol, octanol, phenylethyl alcohol, phenylpropyl alcohol, and fluorinated alcohol) in addition to those exemplified as the water-soluble organic solvent in the above water-based solvent. Furyl alcohol, anil alcohol, etc.), esters (ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol diacetate, ethyl acetate, amyl acetate, benzyl acetate, phenyl ethyl acetate,
Phenoxyethyl acetate, ethyl phenylacetate, benzyl propionate, ethyl benzoate, butyl benzoate, butyl laurate, isopropyl myristate, triethyl phosphate, tributyl phosphate, diethyl phthalate, dibutyl phthalate, diethyl malonate, malonic acid Dipropyl,
Diethyl diethyl malonate, diethyl succinate, dibutyl succinate, diethyl glutarate, diethyl adipate, dipropyl adipate, dibutyl adipate, di (2-methoxyethyl) adipate, diethyl sebacate, diethyl maleate, dibutyl maleate. , Dioctyl maleate, diethyl fumarate, dioctyl fumarate, -3-hexenyl cinnamate, etc., ethers (eg, butylphenyl ether, benzyl ethyl ether, hexyl ether, etc.), ketones (eg, benzyl methyl ketone, Benzylacetone, diacetone alcohol, cyclohexanone, etc.), hydrocarbons (for example, petroleum ether, petroleum benzyl, tetralin, decalin, tertiary amylbenzene, dimethylnaphthalene, etc.),
Amides (for example, N, N-diethyldodecane amide etc.) are mentioned.

The oil-based solvent as described above can be used by dissolving the dye of the present invention as it is, or can be used by dispersing or dissolving it together with a resinous dispersant or a binder.

A specific method for preparing an oil-based solvent used in such an ink jet recording liquid is described in JP-A-3-2.
The method described in No. 31975 and Japanese Patent Publication No. 5-508883 can be referred to.

The solid (phase change) solvent used in the present invention is a phase change solvent which is solid at room temperature as a solvent and which is in a liquid state when it is heated and jetted from the ink jet recording liquid.

Examples of such a phase change solvent include natural waxes (eg, beeswax, carnauba wax, rice wax, wood wax, jojoba oil, spermaceti wax, candelilla wax, lanolin, montan wax, ozokerite, ceresin, paraffin). Wax, microcrystalline wax, petrolactam, etc.), polyethylene wax derivative, chlorinated hydrocarbon, organic acid (eg palmitic acid,
Stearic acid, behenic acid, tiglic acid, 2-acetonaphthone behenic acid, 12-hydroxystearic acid, dihydroxystearic acid and the like, and organic acid esters (for example, alcohols such as glycerin, diethylene glycol and ethylene glycol of the above organic acids) Esters, etc.), alcohols (eg, dodecanol, tetradecanol,
Hexadecanol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, dodecenol, myricyl alcohol, tetracenol, hexadecenol, eicosenol, docosenol, pinene glycol, hinokiol, butynediol, nonanediol, isophthalyl alcohol, mesicerine, Terephthalyl alcohol, hexanediol,
Decanediol, dodecanediol, tetradecanediol, hexadecanediol, docosandiol, tetracosanediol, tvneol, phenylglycerin, eicosandiol, octanediol, phenylpropylene glycol, bisphenol A, para-alpha cumyl phenol, etc.), ketone (For example, benzoylacetone, diacetbenzene, benzophenone, tricosanone, heptacosanone, heptatriacontanone, hentriacontanone, heptatriacontanone, stearone, lauron, dianisole, etc.), amide (for example,
Oleic acid amide, lauric acid amide, stearic acid amide, ricinoleic acid amide, palmitic acid amide, tetrahydrofuranic acid amide, erucic acid amide, myristic acid amide, 12-hydroxystearic acid amide, N-
Stearyl erucamide, N-oleyl stearamide, N, N'-ethylenebislauric amide,
N, N'-ethylenebisstearic acid amide, N, N '
-Ethylenebisoleic acid amide, N, N'-methylenebisstearic acid amide, N, N'-ethylenebisbehenic acid amide, N, N'-xylylenebisstearic acid amide, N, N'-butylenebisstearic acid Amide,
N, N'-dioleyl adipamide, N, N'-distearyl adipamide, N, N'-dioleyl sebacamide, N, N'-cystearyl sebacamide, N, N'-diamide Stearyl terephthalamide,
N, N'-distearylisophthalamide, phenacetin, toluamide, acetamide, oleic acid dimer /
Reaction products of dimer acids such as ethylenediamine / stearic acid (1: 2: 2 molar ratio) with diamines and fatty acids, such as tetraamides; sulfonamides (eg, paratoluenesulfonamide, ethylbenzenesulfonamide;
Butylbenzenesulfonamide, etc.), silicones (for example, silicone SH6018 (Toray Silicone), silicone KR215, 216, 220 (Shin-Etsu Silicone), etc.), coumarones (for example, Escron G-90)
(Nippon Steel Chemical Co., Ltd.), cholesterol fatty acid esters (eg, cholesterol stearate, cholesterol palmitate, cholesterol myristate, cholesterol behenate, cholesterol laurate, cholesterol melissate), saccharide fatty acid esters (saccharose stearate, palmitin) Acid saccharose, saccharose behenate, saccharose laurate, saccharose melinate, lactose stearate, lactose palmitate, lactose myristate, lactose behenate, lactose laurate, lactose melinate, and the like.

The phase change temperature in the solid-liquid phase change of the solid (phase change) solvent is preferably 60 to 200 ° C, more preferably 80 to 150 ° C.

The solid (phase change) solvent as described above can be used by dissolving the dye of the present invention in a heated solvent in a molten state as it is, or by dispersing it with a resinous dispersant or a binder. It can also be dissolved and used.

Specific methods for preparing such phase change solvents are described in JP-A-5-186723 and JP-A-7-70490.
The method described in the publication can be referred to.

The ink jet recording liquid of the present invention in which the dye of the present invention is dissolved by using the above-mentioned water-based, oil-based or solid (phase change) solvent has a viscosity of 40 cp during flight.
s or less, and more preferably 30 cps or less.

Further, the ink jet recording liquid of the present invention has a surface tension of 20 dyn / cm to 1 during flight.
00 dyn / cm is preferable, and 30 to 80 dyn / cm
Is more preferable.

The dye of the present invention is preferably used in the range of 0.1 to 25% by weight of the ink jet recording liquid, more preferably 0.5 to 10% by weight.

The resin type dispersant used in the present invention is preferably a high molecular weight compound having a molecular weight of 1,000 to 1,000,000. It is preferably contained at 50% by weight.

The ink jet recording liquid of the present invention has ejection stability, compatibility with print heads and ink cartridges,
Depending on the purpose of improving storage stability, image storability, and other various properties, a viscosity adjusting agent, a surface tension adjusting agent, a resistivity adjusting agent,
A film-forming agent, a dispersant, a surfactant, an ultraviolet absorber, an antioxidant, an anti-fading agent, an antibacterial agent, an anticorrosive agent and the like can also be added.

The ink jet recording liquid of the present invention is not particularly limited with respect to the recording system used, but can be preferably used as an ink jet recording liquid for an on-demand type ink jet printer. The on-demand type system includes an electro-mechanical conversion system (for example,
Single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc., electric-heat conversion method (for example, thermal inkjet type, bubble jet type, etc.), electrostatic suction method (for example, , Electric field control type, slit jet type, etc., discharge type (for example, spark jet type, etc.) can be given as specific examples.

[0071]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 An ink jet printer MJ-5000C was prepared by using each ink composition having the composition shown in Table 1, Table 2 and Table 3.
(Seiko Epson Corporation, electrical-mechanical conversion method)
In this way, a sample recorded on the special paper for inkjet Super Fine special paper MJSP1 (manufactured by Seiko Epson Corporation) was obtained.

Copolymer A in Table 3 is Acryloi
d DM-55 (made by Rohm and Haas, acrylic copolymer), copolymer B is Elvax 40-W.
(Epoxy / vinyl acetate copolymer manufactured by Dupont)
Represents

The results of evaluation of light resistance, color tone and storability using this sample are shown in Table 1, Table 2 and Table 3.

The unit of the amount of each compound in Table 1, Table 2 and Table 3 is% by weight in the ink.

Light resistance: 2 with a xenon fade meter
The reduction rate of the reflection spectrum density at the maximum absorption wavelength in the visible region from the unexposed sample of the sample after 4 hours of irradiation.

Light resistance (%) = (maximum absorption wavelength concentration of explosive sample / maximum absorption wavelength concentration of unexposed sample) × 100 Color tone: A reflection spectrum at an interval of 10 nm in the 390 to 730 nm region of the sample was measured, and this was measured by CI.
A * and b * were calculated based on the EL * a * b * color space system. The color tone preferable for magenta is defined as follows.

Preferable a *: 76 or more, preferable b *: −30 or more and 0 or less O: A region where both a * and b * are preferable Δ: A region where only one of a * and b * is preferable X: Either a * or b * Storability outside the preferable range: The ink was stored in a closed glass container at 80 ° C. for 1 week and then recorded in the same manner, and the presence or absence of jetting abnormality in continuous jetting for 500 hours and the above-mentioned color tone were evaluated. The preferred storability was defined as follows.

◯: There is no abnormality in continuous ejection, and the change in color tone from unstored ink is ± 10 or less for both a * and b *. X: At least one of continuous ejection abnormality or change in color tone is a * or b *. When 10 or more are recognized

[0080]

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[0081]

[Table 1]

[0082]

[Table 2]

[0083]

[Table 3]

As is clear from the above results, the present invention is superior to the comparison in all aspects of light resistance, color tone and storability.

As a recording medium, a special glossy film MJSP is used instead of the superfine special paper MJSP1.
4 (manufactured by Seiko Epson Corp.) gave similar good results.

Furthermore, the ink of the present invention can be used without problems even in the continuous discharge test of the printer.
High reliability was confirmed for the mechanical conversion method.

Example 2 Using each ink composition having the composition shown in Tables 4 and 5, an inkjet printer BJC-600J (manufactured by Canon Inc., electro-thermal conversion system) was used to produce a dedicated inkjet color paper BJ paper. A sample recorded on (LC-101) A4 (Canon) was obtained. Using this sample, light resistance, color tone and storage stability were evaluated. The results are shown in Tables 4 and 5. The unit of the amount of each compound in Tables 4 and 5 is% by weight in the ink. The definition of the evaluation item is the same as that in the first embodiment.

[0088]

[Table 4]

[0089]

[Table 5]

As is clear from the above results, the present invention is superior to the comparison in all aspects of light resistance, color tone and storability.

Further, in the printer system of the present invention, no abnormality of the head due to thermal deterioration of the ink was confirmed, and it was confirmed that the system has compatibility with the electric-heat conversion system.

[0092]

The ink jet recording liquid according to the present invention is
Excellent in light resistance of color image and excellent color tone for good color reproducibility. Especially suitable for magenta color as a main target. Water-based inkjet recording liquid ensures both light resistance and color tone and long-term use is guaranteed. can do.

Continuation of the front page (72) Inventor Daisuke Ishibashi 1 Konica Stock Company, Sakura-cho, Hino-shi, Tokyo In-house (72) Inventor Yamato Komamura 1 Konica Stock-company, Sakura-cho, Hino-shi, Tokyo In-house (72) Katsutoshi Kato Konica Stock Company, 1st Sakura-cho, Hino-shi, Tokyo (72) Inventor Tatsuo Tanaka Konica Stock Company, 1st Sakura-cho, Hino-shi, Tokyo

Claims (2)

[Claims] 1. An inkjet recording liquid containing a dye represented by the following general formula (1). Embedded image [In the formula, X is an NR ₃ R ₄ group (R ₃ and R ₄ may be the same or different. R ₃ is an optionally substituted alkyl group, alkenyl group, aryl group or aralkyl group. ,
It represents a cycloalkyl group, and R ₄ has the same meaning as R ₃ . R ₃
Represents a ring which may be bonded to R ₄ to form a ring together with a nitrogen atom, or may be bonded to R ₁ to form a ring) or an OH group. Y ₁ and Y ₂ each represent CR (R represents a hydrogen atom, an alkyl group or an acylamino group) or a nitrogen atom, and at least one of Y ₁ and Y ₂ is a nitrogen atom. Z represents a 5- or 6-membered alkyl group, cycloalkyl group, cyano group, alkoxy group, aryl group, aryloxy group, aralkyl group, alkylsulfinyl group, acylamino group, sulfonylamino group, A group of atoms forming a nitrogen-containing heterocycle which may be substituted with at least one of a ureido group, an alkylthio group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, an amino group, an alkylsulfonyl group, and a sulfamoyl group. The ring may form a condensed ring with another ring. R ₁ is a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, a cycloalkyl group, a cyano group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an alkylsulfinyl group, an acylamino group, a sulfonyl group. At least one of an amino group, a ureido group, an alkylthio group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, an amino group, an alkylsulfonyl group and a sulfamoyl group, R ₂ is an alkyl group which may have a substituent, Cycloalkyl group, cyano group, alkoxy group, aryl group, aryloxy group, aralkyl group, alkylsulfinyl group, acylamino group, sulfonylamino group, ureido group, alkylthio group, alkoxycarbonyl group, carbamoyl group, acyl group, amino group, Alkyl sulfonyl And a sulfamoyl group. Further, at least one of the substituents on the ring represented by R ₂ and Z has a Hammett σp value of
It is a substituent of -0.05 or more and 1.0 or less. ] 2. An inkjet recording liquid containing a dye represented by the following general formula (2). Embedded image [In the formula, X ₁ is an NR ₃₁ R ₄₁ group (R ₃₁ and R ₄₁ may be the same or different. R ₃₁ is an optionally substituted alkyl group, alkenyl group, aryl group or aralkyl. group, a cycloalkyl group or a hydrogen atom, R ₄₁ is .R ₃₁ is synonymous with R ₃₁ may form a ring together with a nitrogen atom bonded together with R _41, also coupled with R ₁₁ rings May be formed) or represents an OH group. Y ₁₁ , Y ₁₂
Are each CR ₁ (R ₁ is a hydrogen atom, an acylamino group or R
₃₁ ) or a nitrogen atom, and at least one of Y ₁₁ and Y ₁₂ is a nitrogen atom. Z ₁ represents a group of atoms forming a nitrogen-containing heterocycle which may have a 5- or 6-membered substituent, and this heterocycle may form a condensed ring with another ring. R ₁₁ represents a hydrogen atom, a halogen atom or a monovalent substituent, and R ₁₂ represents a monovalent substituent. Furthermore, at least one of the substituents on the ring represented by R ₁₂ and Z ₁ has a Hammett σp value of −0.05 or more 1.
It is a substituent of 0 or less. ]