JPH09241553A - Ink jet recording liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink jet recording liquid excellent in the light resistance of a color image, excellent in the color tone for good color reproduction, and excellent in the light resistance and the color tone of magenta color by incorpo rating a specified bye. SOLUTION: This ink jet recording liquid is obtained by incorporating a dye represented by formula I (e.g. one having formula II). In formula I, R represents an alkyl, an alkenyl, an aralkyl, or a carboxylalkyl; X1 to X10 each represent H, an alkyl, an alkenyl, acylamino, an alkylsulfonyl, an aralkyl, a hydroxyalkyl, acyl, amino, cyano, hydroxy, sulfo, or carboxyl; Y1 and Y2 each represent sulfor or a halogen; Z represents sulfo, carboxyl, sulfamoyl, carbamoyl, an alkoxycarbonyl, or a halogen; (l) and (m) are each 0, 1, or 2; (n) is 1, 2, 3, 4, or 5; and An<-> represents a counter anion, provided that if there is a counter anion in the molecule An<-> is not required.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an inkjet recording liquid containing a specific dye.

[0002]

2. Description of the Related Art Ink jet recording is a method of ejecting minute ink droplets to record characters or images on a recording medium. This recording method enables recording on various recording media, easy colorization, and recent inkjet printer cost reduction, downsizing, high fineness, and high speed, The demand is expanding dramatically.

In this ink jet recording method,
Known are a continuous method in which ink is continuously ejected and the necessary droplets are attached to a recording medium by controlling the charge applied to the droplets, and an on-demand method in which only the necessary droplets are ejected. There is. Further, the on-demand method is a method in which a droplet is pressure-discharged by electro-mechanical conversion of a piezo element, a method in which a bubble is generated by electric-heat conversion to eject a pressure drop, and a method in which a droplet is sucked and discharged by an electrostatic force. Etc.

In the ink jet recording liquid for ink jet, for example, it is suitable for a recording method selected from the above, has a high recorded image density and has a good color tone, and has a color image such as light resistance, heat resistance and water resistance. Excellent fastness, fast fixing to the recording medium, no bleeding after recording, excellent ink storage stability,
It is required that there is no problem in safety such as toxicity and flammability and that it is inexpensive.

From these viewpoints, various ink jet recording liquids for ink jet have been proposed and studied, but the recording liquids satisfying many of the above requirements at the same time are extremely limited.

In color image recording using yellow, magenta, cyan and black, for example, C.I. I. (Color Index), the conventionally known C.I. I. No. Dyes and pigments having the above have been widely studied. Particularly in the ink jet recording liquid for magenta, C.I. I. Xanthene-based, such as Acid Red 52,
C. I. It is known to use water-soluble azo dyes such as Direct Red 20, but the former has a problem in fastness such as light resistance, and the latter has spectral absorption related to color reproducibility such as lack of saturation. It had a characteristic problem.

To solve this problem, JP-A-59-1
33273, 59-147065, 59-15.
5089, 60-190478, 60-199.
Although phenylxanthene dyes substituted with an anilino group are described in JP-A No. 079, JP-A-5-295312 and the like, they have drawbacks that absorption at a short wavelength is not preferable as a hue and light resistance is insufficient. .

[0008]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an ink jet recording liquid having excellent light resistance of a color image and excellent color tone for good color reproducibility, and particularly excellent in light resistance and color tone of magenta color. An object is to provide an inkjet recording liquid.

[0009]

The object of the present invention is achieved by the following constitution.

[0010] 1. An ink jet recording liquid containing a dye represented by the following general formula I.

[0011]

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In the formula, R is an alkyl group, an alkenyl group,
Represents an aralkyl group or a carboxyalkyl group, X ₁
To X ₁₀ represent a hydrogen atom, an alkyl group, an alkenyl group, an acylamino group, an alkylsulfonyl group, an aralkyl group, a hydroxyalkyl group, an acyl group, an amino group, a cyano group, a hydroxy group, a sulfo group or a carboxyl group. Y
₁ and Y ₂ represent a sulfo group and a halogen atom, respectively. Z
Represents a sulfo group, a carboxyl group, a sulfamoyl group, a carbamoyl group or an alkoxycarbonyl group, and a halogen atom. l and m represent an integer of 01 or 2, and n represents an integer of 1, 2, 3, 4 or 5. An ⁻ represents a counter anion. However, when a counter anion exists in the molecule, An ⁻ is not necessary.

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

[0014]

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In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a carboxyalkyl group or a sulfoalkyl group, and at least one of R _{1 and} R ₂ is a sulfoalkyl group. Represent X ₁ ~
X ₁₀ represents a hydrogen atom, an alkyl group, an alkenyl group, an acylamino group, an alkylsulfonyl group, an aralkyl group, a hydroxyalkyl group, an acyl group, an amino group, a cyano group, a hydroxy group, a sulfo group or a carboxyl group. Y ₁
And Y ₂ each represent a sulfo group or a halogen atom. Z
Represents a sulfo group, a carboxyl group, a sulfamoyl group, a carbamoyl group or an alkoxycarbonyl group, and a halogen atom. l and m represent an integer of 0, 1 or 2, and n represents an integer of 1, 2, 3, 4 or 5. An ⁻ represents a counter anion. However, when a counter anion exists in the molecule, An ⁻ is not necessary.

3. An inkjet recording liquid comprising a dye represented by the following general formula III.

[0017]

[Chemical 6]

In the formula, R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a carboxyalkyl group or a sulfoalkyl group. X ₁₁ ~ X ₂₀
Is a hydrogen atom, alkyl group, alkenyl group, acylamino group, alkylsulfonyl group, aralkyl group, hydroxyalkyl group, acyl group, amino group, cyano group, hydroxy group, sulfo group, carboxyl group, alkylsulfonamide group or arylsulfonamide. Represents a group, and X ₁₁ ~
At least one of X ₂₀ is an alkylsulfonamide group or an arylsulfonamide group. Y ₁ and Y
₂ represents a sulfo group and a halogen atom, respectively. Z represents a sulfo group, a carboxyl group, a sulfamoyl group, a carbamoyl group or an alkoxycarbonyl group, and a halogen atom. l and m represent an integer of 0, 1 or 2, and n is 1,
Represents an integer of 2, 3, 4 or 5. An ⁻ represents a counter anion. However, when a counter anion exists in the molecule, An
^- is assumed to be unnecessary.

The present invention will be described in more detail below.

First, the dye represented by formula I will be described.

In the general formula I, R is an alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group). Group, octyl group, 2-ethylhexyl group,
Nonyl group, decyl group, 2-butylhexyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, and other linear, branched, or cyclic alkyl groups), alkenyl groups (eg, allyl group, 2-butenyl group, etc.) ), An aralkyl group (eg, benzyl group, phenethyl group, etc.) or a carboxyalkyl group (eg, carboxyethyl group, carboxypropyl group, etc.). R is preferably an alkyl group. X _{1 to} X ₁₀ are hydrogen atoms, alkyl groups (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group), alkenyl groups (eg, allyl group, 2-butenyl group, etc.) , An acylamino group (eg, acetylamino group, propionylamino group, butyrylamino group, pivalylamino group, octanoylamino group, benzoylamino group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, octyl Sulfonyl group etc.), aralkyl group (eg benzyl group, phenethyl group etc.), hydroxyalkyl (eg hydroxymethyl group, hydroxyethyl group etc.), acyl group (acetyl group, propionyl group, butyryl group, isobutyryl group, pivalyl group) , Octanoyl group, etc.) Amino group, a cyano group,
It represents a hydroxy group, a sulfo group or a carboxyl group.

A preferable group of X _{1 to} X ₁₀ is an alkyl group,
Sulfo group and carboxyl group, more preferable groups are
This is the case where both X ₁ and X ₆ have an alkyl group and at least one sulfo group or a carboxyl group at another position. Y ₁ and Y ₂ each represent a sulfo group or a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.). A preferred group for Y ₁ and Y ₂ is a sulfo group.

Z is a sulfo group, a carboxyl group, a sulfamoyl group (methylaminosulfonyl group, ethylsaminosulfonyl group, propylaminosulfonyl group, octylaminosulfonyl group, etc.), a carbamoyl group (methylaminocarbonyl group, ethylaminocarbonyl group, (Propylaminocarbonyl group, octylaminocarbonyl group, etc.)
Or an alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group,
Isobutoxycarbonyl group, etc.) and a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.).

A preferred group for Z is a sulfo group or a carboxyl group. A more preferable group is a sulfo group. l
And m represent an integer of 0, 1 or 2, and a preferred integer of l and m is 0. n represents an integer of 1, 2, 3, 4 or 5, and a preferable integer of n is 1 or 2. A more preferable integer is 1.

[0025] An ^- represents a counter anion. As the counter anion, a halide ion (eg, chloride, bromide, etc.), a sulfate ion, an organic sulfonate ion (eg, alkyl sulfonate having 1 to 20 carbon atoms, benzene sulfonate, etc.), a fatty acid ion (aliphatic having 1 to 20 carbon atoms) Carboxylate, etc.), benzoate ion, oxalate ion, perchlorate ion, tetrafluoroborate ion or hexafluorophosphate ion.

However, when the molecule has a counter anion as a substituent (for example, when Z is a sulfo group or a carboxyl group), An ^- is not necessary. It is more preferable that the counter anion is present as a substituent in the molecule (that is, if An ⁻ is unnecessary).

Specific compound examples of the dye represented by the general formula I (also referred to as the dye I of the present invention) are shown below, but the present invention is not limited thereto.

[0028]

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[0029]

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[0030]

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[0031]

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Next, the dye represented by formula II will be described.

In the general formula II, R ₁ and R ₂ are each a hydrogen atom, an alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group,
Pentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group,
2-ethylhexyl group, nonyl group, decyl group, 2-butylhexyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and other linear, branched, cyclic alkyl groups, etc.), alkenyl groups (eg, allyl group, 2-butenyl group etc.), aralkyl group (eg benzyl group, phenethyl group etc.) or carboxyalkyl group (eg carboxyethyl group, carboxypropyl group etc.), or sulfoalkyl group (sulfomethyl group, sulfoethyl group,
Sulfopropyl group, sulfobutyl group, etc.), and at least one of R _{1 and} R ₂ represents a sulfoalkyl group.

Preferred atoms and groups for R ₁ and R ₂ are as follows: when one is a sulfoalkyl group and the other is an alkyl group, when one is a sulfoalkyl group and the other is a hydrogen atom, or when R ₁ and R ₂ are the same. This is the case when both are sulfoalkyl groups.

X _{1 to} X ₁₀ are hydrogen atoms, alkyl groups (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group), alkenyl groups (eg, allyl group, 2-butenyl group). Groups), acylamino groups (eg, acetylamino group, propionylamino group, butyrylamino group, pivalylamino group, octanoylamino group, benzoylamino group, etc.), alkylsulfonyl groups (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group) Group, octylsulfonyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), hydroxyalkyl (eg, hydroxymethyl group, hydroxyethyl group, etc.), acyl group (acetyl group, propionyl group, butyryl group, isobutyryl group) , Pivalyl group, octanoy Group), amino group, cyano group,
It represents a hydroxy group, a sulfo group or a carboxyl group.

A preferable group of X _{1 to} X ₁₀ is an alkyl group,
Sulfo group and carboxyl group, more preferable groups are
This is the case where both X ₁ and X ₆ have an alkyl group.

Y ₁ and Y ₂ each represent a sulfo group or a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.). A preferred group for Y ₁ and Y ₂ is a sulfo group.

Z is a sulfo group, a carboxyl group, a sulfamoyl group (methylaminosulfonyl group, ethylsaminosulfonyl group, propylaminosulfonyl group, octylaminosulfonyl group, etc.), a carbamoyl group (methylaminocarbonyl group, ethylaminocarbonyl group, (Propylaminocarbonyl group, octylaminocarbonyl group, etc.)
Or an alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group,
Isobutoxycarbonyl group, etc.) and a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.).

The preferred group of Z is a sulfo group or a carboxyl group. A more preferable group is a sulfo group. 1 and m represent an integer of 0, 1 or 2, and a preferred integer of 1 and m is 0. n represents an integer of 1, 2, 3, 4 or 5, and a preferable integer of n is 1 or 2. A more preferable integer is 1.

[0040] An ^- represents a counter anion. As the counter anion, a halide ion (eg, chloride ion, bromide ion, etc.), a sulfate ion, an organic sulfonate ion (eg, alkyl sulfonate having 1 to 20 carbon atoms, benzene sulfonate, etc.), a fatty acid ion (having 1 to 20 carbon atoms) Aliphatic carboxylate), benzoate ion, oxalate ion, perchlorate ion, tetrafluoroborate ion or hexafluorophosphate ion.

However, when the molecule has a counter anion as a substituent (for example, when Z is a sulfo group or a carboxyl group), An ⁻ is not required. It is more preferable that the counter anion is present as a substituent in the molecule (that is, if An ⁻ is unnecessary).

Specific examples of the dye represented by the general formula II (also referred to as the dye II 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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Next, the dye represented by formula III will be described.

In the general formula III, R ₃ and R ₄ are each a hydrogen atom, an alkyl group (eg, methyl group, ethyl group,
Propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, neopentyl group, cyclopentyl group,
Hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 2-
Butylhexyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, and other linear, branched, or cyclic alkyl groups), alkenyl groups (eg, allyl group, 2-
Butenyl group), aralkyl group (eg, benzyl group,
Phenethyl group) or carboxyalkyl group (eg, carboxyethyl group, carboxypropyl group, etc.),
Alternatively, it represents a sulfoalkyl group (a sulfomethyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, or the like).
Preferable atoms and groups of R ₃ and R ₄ are such that when one is a sulfoalkyl group and the other is an alkyl group, when one is an alkyl group and the other is a hydrogen atom, both R ₃ and R ₄ are hydrogen atoms. At some time, or when both R ₃ and R ₄ are alkyl groups.

X _{11 to} X ₂₀ are hydrogen atoms, alkyl groups (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group), alkenyl groups (eg, allyl group, 2-butenyl). Groups), acylamino groups (eg, acetylamino group, propionylamino group, butyrylamino group, pivalylamino group, octanoylamino group, benzoylamino group, etc.), alkylsulfonyl groups (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group) Group, octylsulfonyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), hydroxyalkyl (eg, hydroxymethyl group, hydroxyethyl group, etc.), acyl group (acetyl group, propionyl group, butyryl group, isobutyryl group) , Pivalyl group, octanoy Group, etc.), amino group, cyano group,
It represents a hydroxy group, a sulfo group, a carboxyl group, an alkyl sulfonamide group or an aryl sulfonamide group, and at least one of X _{11 to} X ₂₀ is an alkyl sulfonamide group or an aryl sulfonamide group. X ₁₁
Preferably the to X _20, at least one of X _11, X _16, if having an alkyl sulfonamide group, and having an alkyl group in X _11, X _16, an alkyl sulfonamide group in X ₁₄ or X _19, If you have.

Y ₁ and Y ₂ each represent a sulfo group or a halogen atom (eg, fluorine atom, chlorine atom, bromine atom). A preferred group for Y ₁ and Y ₂ is a sulfo group.

Z is a sulfo group, a carboxyl group, a sulfamoyl group (a methylaminosulfonyl group, an ethylsaminosulfonyl group, a propylaminosulfonyl group, an octylaminosulfonyl group, etc.), a carbamoyl group (a methylaminocarbonyl group, an ethylaminocarbonyl group, (Propylaminocarbonyl group, octylaminocarbonyl group, etc.)
Or an alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group,
Isobutoxycarbonyl group, etc.) and a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.). A preferred group for Z is a sulfo group or a carboxyl group. A more preferable group is a sulfo group. 1 and m represent an integer of 0, 1 or 2, and a preferred integer of 1 and m is 0. n represents an integer of 1, 2, 3, 4 or 5, and a preferable integer of n is 1 or 2. A more preferable integer is 1.

[0052] An ^- represents a counter anion. As the counter anion, a halide ion (eg, chloride, bromide, etc.), a sulfate ion, an organic sulfonate ion (eg, alkyl sulfonate having 1 to 20 carbon atoms, benzene sulfonate, etc.), a fatty acid ion (aliphatic having 1 to 20 carbon atoms) Carboxylate, etc.), benzoate ion, oxalate ion, perchlorate ion, tetrafluoroborate ion or hexafluorophosphate ion.

However, when a counter anion is present as a substituent in the molecule (for example, when Z is a sulfo group or a carboxyl group), An ^- is not required. It is more preferable that the counter anion is present as a substituent in the molecule (that is, if An ⁻ is unnecessary).

Specific compound examples of the dye represented by the general formula III (also referred to as the dye III of the present invention) are shown below, but the present invention is not limited thereto.

[0055]

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[0056]

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[0057]

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[0058]

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General formula I, general formula II and general formula II of the present invention
The inkjet recording liquid containing the dye represented by I (hereinafter, also referred to as the dye of the present invention) can use various solvent systems such as water-based ink, oil-based ink, and solid (phase change) ink. Aqueous ink is particularly preferably used as a solvent system.

The water-based ink solvent is, in addition to the dye of the present invention,
Water and water-soluble organic solvents are generally used as solvents. Examples of water-soluble organic solvents include alcohols (eg, methanol, ethanol, propanol, i-propanol,
Butanol, i-butanol, sec-butanol, t
-Butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ethers (eg ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl 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 Cole monophenyl ether, etc., amines (eg ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine) , Polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, 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 can be mentioned.

In the aqueous ink solvent as described above, the dye of the present invention can be used as it is if it is soluble in the solvent system. On the other hand, when it is a solid that is insoluble as it is, the dye is dispersed in 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.). It can be used as fine particles, or the dye can be dissolved in a soluble organic solvent and then dispersed in the solvent system together with a polymer dispersant and a surfactant. Furthermore,
When it is a liquid or a semi-molten substance which is insoluble as it is, it can be dispersed in the solvent system as it is or by dissolving it in a soluble organic solvent together with a polymer dispersant and a surfactant.

Specific methods for preparing such an aqueous ink solvent are described in, for example, JP-A-5-148436 and JP-A-5-148436.
295312, 7-97541, 7-8251.
No. 5, No. 7-118584, etc. can be referred to.

The oil-based ink solvent uses an organic solvent as a solvent in addition to the dye of the present invention. Examples of the solvent for the oil-based ink include alcohols (for example, pentanol, heptanol, octanol, phenylethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, and anyl) in addition to those exemplified as the water-soluble organic solvent in the above water-based ink solvent. 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, phenylethyl acetate, phenoxyethyl acetate, phenylethyl acetate, propione Acid benzyl, ethyl benzoate, butyl benzoate, butyl laurate, myristic acid-i-
Propyl, triethyl phosphate, tributyl phosphate, diethyl phthalate, dibutyl phthalate, diethyl malonate, dipropyl malonate, diethyl diethyl malonate, diethyl succinate, dibutyl succinate, diethyl glutarate, diethyl adipate, dipropyl adipate, adipine Dibutyl acid, di (2-methoxyethyl adipate), diethyl sebacate, diethyl maleate, dibutyl maleate, dioctyl maleate, diethyl fumarate, dioctyl fumarate, -3-hexenyl cinnamate, ethers (for example, Butyl phenyl ether, benzyl ethyl ether, hexyl ether, etc.), ketones (eg, benzyl methyl ketone, benzyl acetone, diacetone alcohol, cyclohexanone, etc.), hydrocarbons (eg, petroleum ether, petroleum ether) Jill, tetralin, decalin, t
-Amylbenzene, dimethylnaphthalene, etc.), amides (eg, N, N-diethyldodecane amide) and the like.

In the oil-based ink solvent as described above, the dye of the present invention can be dissolved and used as it is,
Further, a resinous dispersant or a binder may be used in combination for dispersion or dissolution. For specific methods for preparing such oil-based ink solvents, the methods described in JP-A-3-231975, JP-A-5-508883 and the like can be referred to.

As the solid (phase change) ink solvent, in addition to the ink jet recording liquid of the present invention, a solvent which is solid at room temperature and which is a liquid state melted at the time of jetting the ink jet recording liquid is used. Examples of such phase change solvents 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 derivatives, chlorinated hydrocarbons, organic acids (eg palmitic acid, stearic acid, behenic acid, tiglic acid, 2
-Acetonaphthone behenic acid, 12-hydroxystearic acid, dihydroxystearic acid, etc., organic acid esters (for example, esters of the above organic acids with alcohols such as glycerin, diethylene glycol, ethylene glycol, etc.), alcohols (for example, dodecanol, tetradeca) Nole, hexadecanol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, dodecenol, myricyl alcohol, tetracenol, hexadecenol, eicosenol, docosenol, pinene glycol, hinokiol, butynediol, nonanediol, isophthalyl alcohol, Mesicillin, terephthalyl alcohol, hexanediol, decanediol, dodecanediol, tetradecanediol, hexadecanediene Alcohol, docosane diol, tetracosan diol, terpineol, phenylglycerin, eicosane diol, octane diol, phenyl propylene glycol, bisphenol A, para-alpha cumyl phenol, etc., ketones (for example, benzoylacetone, diacetobenzene, benzophenone, Tricosanone, heptacosanone, heptatriacontanone, hentriacontanone, stearone, laurone, dianisole, etc., amides (eg oleic acid amide, lauric acid amide, stearic acid amide, ricinoleic acid amide, palmitic acid amide, tetrahydrofuranic acid amide, eruca) Acid amide, myristic acid amide, 12-hydroxystearic acid amide, N-stearyl erucic acid amide, N
Oleyl stearamide, N, N'-ethylenebislauric acid amide, N, N'-ethylenebisstearic acid amide, N, N'-ethylenebisoleic acid amide, N, N'-methylenebisstearic acid amide; N,
N'-ethylenebisbehenamide, N, N'-xylylenebisstearic acid amide, N, N'-butylenebisstearic acid amide, N, N'-dioleyladipamide, N, N'-distearyl Adipic amide,
N, N'-dioleyl sebacic acid amide, N, N'-distearyl sebacic acid amide, N, N'-distearyl isophthalic acid amide, phenacetin, toluamide, acetamide, oleic acid dimer / ethylenediamine / stearic acid ( (A molar ratio of 1: 2: 2) such as a reaction product of a dimer acid, a diamine and a fatty acid such as tetraamide), a sulfonamide (for example, paratoluenesulfonamide, ethylbenzenesulfonamide, butylbenzenesulfonamide, etc.), a silicone (For example, silicone SH6018
(Toray Silicone), Silicone KR215,216,
220 (Shin-Etsu Silicone) and the like, and coumarones (for example,
Escuron G-90 (Nippon Steel Chemicals, etc.), cholesterol fatty acid ester (eg, cholesterol stearate, cholesterol palmitate, cholesterol myristate, cholesterol behenate, cholesterol laurate, cholesterol melicinate), saccharide fatty acid ester (stearic acid) Saccharose, saccharose palmitate, saccharose behenate, saccharose laurate, saccharose melicinate, lactose stearate, lactose palmitate, lactose myristate, lactose behenate, lactose laurate, lactose melicate and the like).

The phase change temperature of the solid-liquid phase change of the solid ink solvent is preferably 60 ° C. or higher, and 80
It is more preferable that the temperature is 150 ° C.

In the solid ink solvent as described above, the dye of the present invention can be used as it is by dissolving it in a heated solvent in a molten state, or can be dispersed or dissolved in combination with a resinous dispersant or a binder. Can also be used.

Specific methods for preparing such solid ink solvents are described in JP-A-5-186723 and JP-A-7-704.
The method described in No. 90, etc. can be referred to.

The above-mentioned water-based, oil-based, and solid ink solvents each have a flying viscosity of preferably 40 cps or less, more preferably 30 cps or less.

The surface tension of the ink jet recording liquid of the present invention during flight is preferably 20 dyn / cm or more, more preferably 30 to 80 dyn / cm.

In the ink jet recording liquid of the present invention,
The dyes represented by the general formula I, the general formula II and the general formula III of the present invention are preferably used in the range of 0.1 to 25% by weight based on the total amount of the inkjet recording liquid, and 0.5 to 10% by weight. It is more preferably in the range of%.

In the ink jet recording liquid of the present invention, a viscosity adjusting agent and a surface tension adjusting agent are used depending on the purposes of improving ejection stability, compatibility with print heads and ink cartridges, storage stability, image storability, and various other properties. An agent, a specific resistance adjusting agent, a film forming agent, a dispersant, a surfactant, an ultraviolet absorber, an antioxidant, an anti-fading agent, a mildew proofing agent, an anticorrosive agent and the like can also be added.

The ink jet recording liquid of the present invention is not particularly limited as to the recording method used, but it can be preferably used as an ink for an on-demand ink jet printer. Examples of the on-demand type method include an electro-mechanical conversion method (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.), and an electric-heat conversion method (for example, a thermal inkjet type). , Bubble jet type, etc., electrostatic attraction type (eg electric field control type, slit jet type etc.), discharge type (eg spark jet type) etc. can be mentioned as specific examples.

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EXAMPLES The present invention will be described more specifically with reference to examples, but the present invention is not limited to the embodiments in the examples.

Example 1 Each ink composition having the composition shown in Table 1 was used to record on an ink jet dedicated coated paper by an ink jet printer MJ-5000C (manufactured by Seiko Epson Corporation, electro-mechanical conversion system). A magenta image sample was obtained. Table 1 shows the results of evaluation of light resistance and color tone defined as follows using this sample.

Light resistance: PDA-65 (manufactured by Konica Corporation)
Of the sample after 24 hours of exposure with a xenon fade meter calculated from the measurement of the reflection density by the green light of the image, light resistance (%) = (green light reflection density of the exposed sample / (Green light reflection density of unexposed sample) × 100 Color tone: blue using PDA-65 (manufactured by Konica Corporation)
The reflection densities of green and red lights were measured, and the relative blue light reflection densities and relative red light reflection densities when the reflection densities of green light were normalized to 1 were calculated and evaluated according to the following criteria. It shows a magenta image of good color tone with little improper absorption in the wavelength range of red light.

◯: When relative blue light reflection density is less than 0.25 and relative red light reflection density is less than 0.10 Δb: When relative blue light reflection density is 0.25 or more and relative red light reflection density is less than 0.10. Δr: When the relative blue light reflection density is less than 0.25 and the relative red light reflection density is 0.10 or more ×: When the relative blue light reflection density is 0.25 or more and the relative red light reflection density is 0.10.

The unit of the amount of each compound in Table 1 is% by weight based on the total ink jet recording liquid. The structures of Comparative-1, Comparative-2 and Surfactant-1 shown in the table are shown below.

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Embedded image

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[Table 1]

As is clear from the results shown in Table 1, the ink jet recording liquid of the present invention is superior in light resistance to the case where the comparative ink jet recording liquid is used, and the blue light and the red light with respect to the reflection density in the green light region are obtained. It can be seen that the color tone is good with less improper absorption in the light region.

Further, it can be used without any problem in the continuous ejection test of the printer, and the high reliability of the electro-mechanical conversion system of the ink jet recording liquid of the present invention was confirmed.

Example 2 Using each ink composition having the composition shown in Table 2, a sample recorded on glossy paper for exclusive use for inkjet by an inkjet printer BJC-600J (manufactured by Canon Inc., electric-heat conversion system) was used. Obtained. The results of evaluation of light resistance and color tone using this sample in the same manner as in Example 1 are shown in Table 2.

The unit of the amount of each compound in Table 2 is% by weight with respect to the total ink jet recording liquid, and the definition of the compounds of Comparative-1 and Comparative-2 and the evaluation items are the same as in Example 1. .

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[Table 2]

As is clear from the results shown in Table 2, the ink jet recording liquid of the present invention is superior in light resistance to the case where the comparative ink jet recording liquid is used, and the blue light and the red light with respect to the reflection density in the green light region. It can be seen that the color tone is good with less improper absorption in the light region.

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

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INDUSTRIAL APPLICABILITY As has been demonstrated in the above examples, the ink jet recording liquid of the present invention has excellent light resistance of color images and excellent color tone for good color reproducibility. It has an excellent effect on color tone.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hitoshi Morimoto, Konica Stock Company, Hino City, Tokyo 1 Konica Stock Company (72) Inventor, Daisuke Ishibashi 1, Sakura City, Hino City, Tokyo Konica Stock Company, in-house

Claims (3)

[Claims] 1. An ink jet recording liquid containing a dye represented by the following general formula I. Embedded image [In the formula, R represents an alkyl group, an alkenyl group, an aralkyl group or a carboxyalkyl group, and X _{1 to} X ₁₀ represent a hydrogen atom, an alkyl group, an alkenyl group, an acylamino group,
It represents an alkylsulfonyl group, aralkyl group, hydroxyalkyl group, acyl group, amino group, cyano group, hydroxy group, sulfo group or carboxyl group. Y ₁ and Y ₂ represent a sulfo group and a halogen atom, respectively. Z represents a sulfo group, a carboxyl group, a sulfamoyl group, a carbamoyl group or an alkoxycarbonyl group, and a halogen atom. l and m represent an integer of 0, 1 or 2, and n is 1,
Represents an integer of 2, 3, 4 or 5. An ⁻ represents a counter anion. However, when a counter anion exists in the molecule, An
^- is assumed to be unnecessary. ] 2. An ink jet recording liquid containing a dye represented by the following general formula II. Embedded image [In the formula, R ₁ and R ₂ are each a hydrogen atom, an alkyl group,
Alkenyl group, aralkyl group, carboxyalkyl group,
Alternatively, it represents a sulfoalkyl group, and at least one of R _{1 and} R ₂ represents a sulfoalkyl group. X _{1 to} X ₁₀ are hydrogen atoms, alkyl groups, alkenyl groups, acylamino groups, alkylsulfonyl groups, aralkyl groups, hydroxyalkyl groups, acyl groups, amino groups, cyano groups, hydroxy groups,
Represents a sulfo group or a carboxyl group. Y ₁ and Y
₂ represents a sulfo group and a halogen atom, respectively. Z represents a sulfo group, a carboxyl group, a sulfamoyl group, a carbamoyl group or an alkoxycarbonyl group, and a halogen atom. l and m represent an integer of 0, 1 or 2, and n is 1,
Represents an integer of 2, 3, 4 or 5. An ⁻ represents a counter anion. However, when a counter anion exists in the molecule, An
^- is assumed to be unnecessary. ] 3. An ink jet recording liquid containing a dye represented by the following general formula III. Embedded image [In the formula, R ₃ and R ₄ are each a hydrogen atom, an alkyl group,
Alkenyl group, aralkyl group, carboxyalkyl group,
Alternatively, it represents a sulfoalkyl group. X _{11 to} X ₂₀ are hydrogen atom, alkyl group, alkenyl group, acylamino group, alkylsulfonyl group, aralkyl group, hydroxyalkyl group, acyl group, amino group, cyano group, hydroxy group, sulfo group, carboxyl group, alkylsulfonamide Represents a group or an arylsulfonamide group, and at least one of X _{11 to} X ₂₀ is an alkylsulfonamide group or an arylsulfonamide group. Y ₁ and Y ₂ represent a sulfo group and a halogen atom, respectively. Z represents a sulfo group, a carboxyl group, a sulfamoyl group, a carbamoyl group or an alkoxycarbonyl group, and a halogen atom. l and m represent an integer of 0, 1 or 2, and n is 1, 2, 3, 4 or 5
Represents an integer. An ⁻ represents a counter anion. However, when a counter anion exists in the molecule, An ⁻ is not necessary. ]