JPH0959552A - Ink-jet recording solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink-jet recording solution containing a coloring matter having a specific structure, excellent light resistance of color image, color tone for improving color reproducibility and shelf stability when made into an aqueous ink, especially providing a clear magenta recorded image. SOLUTION: This ink-Jet recording solution contains 0.5-10wt.% of a coloring matter of the formula (R1 and R2 are each H, an aliphatic group, etc.; R3 is a halogen, an alkyl, etc.; (n) is 0-3; R4 is an aliphatic group, an aromatic group, etc.; R5 is H, an acyl, etc.; with the proviso that at least one substituent group of R3 to R5 is one acting as an ionic hydrophilic group at pH8 to pH13) based on the ink-jet recording solution. An aqueous solvent is preferable as a solvent system used for the objective recording solution. The recording solution has <=30cps viscosity during flying and 30-80dyne/cm surface tension during flying. When a resin type dispersant is used, a polymer compound having 1,000-1,000,000 molecular weight is preferable and the content of the polymer compound is preferably 0.1-50wt.% in the ink-jet recording solution.

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 Conventionally, an ink jet system is a system in which droplets are ejected under pressure by electro-mechanical conversion of a piezo element.
The method is roughly classified into a method in which bubbles are generated by electric-heat conversion to eject droplets by pressure, a method in which droplets are sucked and ejected by electrostatic force, and the like.

[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. On the other hand, when it is used as an inkjet recording liquid, it has a drawback that the dye image is likely to bleed as the recording liquid solvent permeates into the recording medium and the dot shape becomes non-uniform.

[0007]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an ink jet recording liquid excellent in light fastness of a color image and excellent in color tone for good color reproducibility, particularly a magenta recording liquid as a main object. To provide. 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. Another object of the present invention is to provide an ink jet recording liquid exhibiting a uniform dot shape in addition to achieving both light resistance and color tone.

[0008]

As a result of intensive studies conducted by the present inventors, the above object of the present invention was found to be achieved by the following constitution of the present invention.

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

[0010]

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In the formula, R ₁ and R ₂ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ₃ is a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or an acylamino group. , Sulfonylamino group, ureido group, urethane group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, amino group, sulfo group,
Represents a carboxyl group, n represents an integer of 0 to 3, R ₄
Is an aliphatic group, aromatic group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, sulfonylamino group, ureido group, urethane group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group group, an acyl group, an amino group, R ₅ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, an acyl group. However, at least one substituent selected from R ₃ , R ₄ and R ₅ has a group which acts as an ionic hydrophilic group in the alkaline region of pH 8 to 13.

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

[0013]

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In the formula, R ₁ and R ₂ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ₆ is a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or an acylamino group. , Sulfonylamino group, ureido group, urethane group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, amino group, m
Represents an integer of 0 to 3, R ₇ is an aliphatic group, an aromatic group,
Heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, sulfonylamino group, ureido group, urethane group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, amino group , R ₈ is an aliphatic group,
It represents an aromatic group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, or an acyl group. However, when R ₇ and R ₈ both represent an aliphatic group, R ₇ and R ₈ represent an aliphatic group having 2 or more carbon atoms, and when R ₇ is an aromatic group and R ₈ is an aliphatic group, R ₈
Represents an aliphatic group having 2 or more carbon atoms.

3. An inkjet recording liquid containing a dye represented by the following general formula (3).

[0016]

[Chemical 6]

In the formula, R ₁ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ₆ represents a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acylamino group or a sulfonylamino group. Group, ureido group, urethane group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, amino group, m represents an integer of 0 to 3, and R ₉ is aliphatic Group, aromatic group, heterocyclic group,
Represents an alkoxy group or an amino group, L represents an alkylene group, Y represents a carbonyl group, a sulfonyl group, an oxalyl group,
Represents a phosphoryl group, R ₁₀ is an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an alkoxycarbonyl group, It represents a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group or an amino group, and R ₁₁ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group or an acyl group.

4. The inkjet recording liquid according to 1 is a water-based inkjet recording liquid containing 10% by weight to 99.9% by weight of water, and the dye represented by the general formula (1) is an aqueous inkjet recording liquid. An inkjet recording liquid which is present in the liquid.

5. The inkjet recording liquid according to 2 above is an aqueous inkjet recording liquid containing 10% by weight to 99.8% by weight of water in the recording liquid, and the dye of the general formula (2) is contained in the aqueous inkjet recording liquid. An ink jet recording liquid which is present as a dispersion in the ink.

6. The inkjet recording liquid according to 2 or 5 above has a molecular weight of 1,000 to 1,000,0 in the recording liquid.
An ink jet recording liquid containing 0.1 to 50% by weight of the polymer compound No. 00.

7. The inkjet recording liquid according to 3 above is an aqueous inkjet recording liquid containing 10% by weight to 99.8% by weight of water in the recording liquid, and the dye of the general formula (3) is in an aqueous inkjet recording liquid. An ink jet recording liquid which is present as a dispersion in the ink.

8. The inkjet recording liquid according to 3 or 7 above has a molecular weight of 1,000 to 1,000,0 in the recording liquid.
An ink jet recording liquid containing 0.1 to 50% by weight of the polymer compound No. 00.

Hereinafter, the present invention will be described in detail.

First, the dye represented by the general formula (1) will be described in detail.

R ₁ and R ₂ are hydrogen atoms or aliphatic groups (for example,
An atom selected from an alkyl group having 1 to 20 carbon atoms, an allyl group, a propargyl group, etc.), an aromatic group (for example, a phenyl group, a naphthyl group, etc.), and a heterocyclic group (for example, a nitrogen atom, an oxygen atom or a sulfur atom). A 5- or 6-membered heterocyclic group, etc., which has a ring in R ₁ and R ₂ together with a nitrogen atom (for example, any combination of atoms selected from a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom or a sulfur atom). A 5- or 6-membered ring, etc.) may be formed. These groups may be further substituted with an appropriate substituent, and examples of the substituent include an aliphatic group (for example, an alkyl group having 1 to 20 carbon atoms), an aromatic group (for example, a phenyl group, naphthyl). Group), a heterocyclic group (for example, a 5- or 6-membered heterocyclic group having an atom selected from a nitrogen atom, an oxygen atom, or a sulfur atom), an alkoxy group (for example, an alkoxy group having 1 to 25 carbon atoms). , An aryloxy group (eg, a phenoxy group, a naphthyloxy group, etc.), an acylamino group (eg, an alkanoylamino group having 1 to 25 carbon atoms, a benzoylamino group, etc.), an acyloxy group (eg, a carbon number of 1 to 1)
25 alkanoyloxy group, benzoyloxy group, etc.), acyl group (eg, alkanoyl group having 1 to 25 carbon atoms, benzoyl group, etc.), carbamoyl group (eg, alkylcarbamoyl group having 1 to 25 carbon atoms, phenylcarbamoyl group, etc.) ), Alkoxycarbonyl group (for example, alkoxycarbonyl having 1 to 25 carbon atoms), sulfonylamino group (for example, alkanesulfonylamino group having 1 to 25 carbon atoms, benzenesulfonylamino group, etc.), sulfamoyl group (for example, carbon number) 1-25 alkylsulfamoyl group, phenylsulfamoyl group, etc.), hydroxyl group, sulfonyl group (for example, alkanesulfonyl group having 1-25 carbon atoms, benzenesulfonyl group, etc.), alkylthio group (for example, 1 carbon atom) ~ 25 alkylthio groups, etc.), arylthio groups ( Example, phenylthio group, etc.),
Ureido group (for example, alkylureido group having 1 to 25 carbon atoms, phenylureido group, etc.), urethane group (for example,
An alkyl urethane group having 1 to 25 carbon atoms), a cyano group,
Sulfo group, carboxyl group, nitro group, amino group (for example, alkylamino group having 1 to 25 carbon atoms, 2 to 5 carbon atoms)
0 dialkylamino group, anilino group, carbon number 7 to 31
N-alkylanilino group, unsubstituted amino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.)
And the like. R ₁ and R ₂ are preferably aliphatic or aromatic groups, and more preferably substituted or unsubstituted aliphatic groups.

R ₃ is a halogen atom (eg, chlorine atom,
Bromine atom, etc.), alkyl group (for example, straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms), alkoxy group (for example, straight chain, branched or cyclic alkoxy group having 1 to 25 carbon atoms) , An aryl group (eg, phenyl group, naphthyl group, etc.), an aryloxy group (eg, phenoxy group, etc.),
Acylamino group (for example, alkanoylamino group having 1 to 25 carbon atoms, benzoylamino group, etc.), sulfonylamino group (for example, alkanesulfonylamino group having 1 to 25 carbon atoms, benzenesulfonylamino group, etc.), ureido group (for example, An alkylureido group having 1 to 25 carbon atoms, a phenylureido group, etc., a urethane group (for example, 1 to carbon atoms)
25 alkyl urethane group, etc.), alkylthio group (for example, alkylthio group having 1 to 25 carbon atoms), arylthio group (for example, phenylthio group, etc.), alkoxycarbonyl group (for example, alkoxycarbonyl group having 1 to 25 carbon atoms, etc.) ), A carbamoyl group (eg, an alkylcarbamoyl group having 1 to 25 carbon atoms, a phenylcarbamoyl group, etc.), a sulfamoyl group (eg, an alkylsulfamoyl group having 1 to 25 carbon atoms, a phenylsulfamoyl group, etc.), a sulfonyl group (For example, an alkanesulfonyl group having 1 to 25 carbon atoms, a benzenesulfonyl group, etc.), an acyl group (for example, an alkanoyl group having 1 to 25 carbon atoms, a benzoyl group, etc.), an amino group (for example, an alkyl group having 1 to 25 carbon atoms). Amino group, dialkylamino group having 2 to 50 carbon atoms, anilino group, 7 to 3 carbon atoms Of N- alkyl anilino group), a sulfo group, a carboxyl group. R ₃ is preferably an alkyl group, an acylamino group or a sulfonylamino group, more preferably a lower alkyl group or a lower alkanoylamino group.

R ₄ is an aliphatic group (for example, having 1 to 20 carbon atoms).
Linear, branched, cyclic alkyl groups, etc.), aromatic groups (eg phenyl groups etc.), heterocyclic groups (eg pyridyl,
Furyl, thienyl, pyrrolyl, etc.), alkoxy groups (alkoxy groups having 1 to 20 carbon atoms), aryloxy groups (eg, phenoxy, etc.), alkylthio groups (eg, alkylthio groups having 1 to 20 carbon atoms), arylthio groups (Eg, phenylthio group, etc.), acylamino group (eg,
An alkanoylamino group having 1 to 20 carbon atoms, a benzoylamino group, and the like, a sulfonylamino group (for example, 1 to 1 carbon atoms)
20 alkanesulfonylamino group, benzenesulfonylamino group and the like), ureido group (for example, having 1 to 20 carbon atoms)
Alkylureide, phenylureido, etc.), urethane group (for example, alkyl urethane group having 1 to 20 carbon atoms), alkoxycarbonyl group (for example, 1 to 2 carbon atoms)
0 alkoxycarbonyl group, etc.), carbamoyl group (eg, C1-20 alkylcarbamoyl group, arylcarbamoyl group, etc.), sulfamoyl group (eg,
An alkylsulfamoyl group having 1 to 20 carbon atoms, a phenylsulfamoyl group, etc.), a sulfonyl group (for example, an alkanesulfonyl group having 1 to 20 carbon atoms, a benzenesulfonyl group, etc.), an acyl group (for example, 1 to carbon atoms) 20 alkanoyl group, benzoyl group, etc.), amino group (for example, alkylamino group having 1 to 20 carbon atoms, dialkylamino group having 2 to 40 carbon atoms, piperidino group, piperazino group, morpholino group, pyrrolidino group, anilino group, N having 7 to 26 carbon atoms
-Alkylanilino group, unsubstituted amino group, etc.).
R ₄ is preferably an aliphatic group or an aromatic group.

R ₅ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group,
It represents an acyl group, and examples of each substituent include an aliphatic group of R ₄ , an aromatic group, a heterocyclic group, an alkoxycarbonyl group,
Examples thereof include the groups described above for the carbamoyl group and the acyl group. R ₅ is preferably an aliphatic group or an aromatic group.

The above R ₃ , R ₄ and R ₅ groups may be further substituted with appropriate substituents, and examples of preferable substituents include R ₁ and R ₂ which may be substituted. Examples include those mentioned above.

In the compound represented by the general formula (1),
At least one substituent selected from R ₃ , R ₄ and R ₅ has a group that acts as an ionic hydrophilic group in the alkaline region of pH 8 to 13, and examples of such an ionic hydrophilic group include: Sulfonic acid, carboxylic acid,
Hydroxamic acid, aromatic hydroxyl group (eg, phenol, naphthol, etc.), heteroaromatic hydroxyl group (eg, hydroxypyridine, pyrazole, hydroxytriazine, etc.), sulfonamide group, active methylene group (eg, malonate ester, Malonamide, malononitrile β-keto acid derivative, etc.), oxamide group, mercapto group, quaternary ammonium group and the like. Among these, more preferable ionic hydrophilic groups are carboxylic acids and sulfonic acids, and those having at least one carboxylic acid group are most preferable. When the ionic hydrophilic group is an aqueous inkjet recording liquid containing 10% by weight to 99.9% by weight of water in the inkjet recording liquid, it provides reliability (storability) for long-term use. Especially important.

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

R ₁ and R ₂ represent the same groups as R ₁ and R ₂ in the dye represented by the general formula (1). R ₆ is a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group,
It represents a sulfamoyl group, a sulfonyl group, an acyl group or an amino group, and preferable examples of these substituents include those mentioned above for the similar substituents of R _{3 in} the dye represented by the general formula (1). .

R ₆ is preferably an alkyl group, an acylamino group or a sulfonylamino group, more preferably a lower alkyl group or a lower alkanoylamino group.

R ₇ is an aliphatic group, an aromatic group, a heterocyclic group,
Alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, sulfonylamino group,
It represents an ureido group, a urethane group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, and an amino group. Preferred examples of these substituents include R _{4 in the} dye represented by the general formula (1). The substituents mentioned above include those mentioned above. R ₇ is preferably an aliphatic group or an aromatic group.

R ₈ is an aliphatic group, an aromatic group, a heterocyclic group,
It represents an alkoxycarbonyl group, a carbamoyl group, or an acyl group, and preferable examples of these substituents include those mentioned above for the similar substituents of R _{4 in} the dye represented by the general formula (1). R ₈ is preferably an aliphatic group or an aromatic group.

The above R ₆ , R ₇ and R ₈ groups may be further substituted with a suitable substituent, and examples of preferable substituents include R ₁ in the dye represented by the general formula (1), Examples of the group which may be substituted on R ₂ include those mentioned above. In the dye represented by the general formula (2), R ₇ ,
When both R ₈ represent an aliphatic group, R ₇ and R ₈ have 2 carbon atoms.
The above-mentioned aliphatic groups are represented, and particularly preferable is a dye in which one of R ₇ and R ₈ is an aliphatic group having 2 or more carbon atoms and the other aliphatic group is an aliphatic group having 4 or more carbon atoms.

In the dye represented by the general formula (2), R
_{When 7} is an aromatic group and R ₈ is an aliphatic group, R ₈ represents an aliphatic group having 2 or more carbon atoms.

The carbon number specific range of the above-mentioned substituent is particularly important for obtaining a uniform dot shape on the recording medium when used as an ink jet recording liquid.

Next, the dye represented by formula (3) will be described in detail.

[0040] R ₁ represents R ₁ group having the same meaning as in the dye represented by the general formula (1).

[0041] R ₆ represents a R ₆ group having the same meaning as in the dye represented by the general formula (2).

R ₉ is an aliphatic group, an aromatic group, a heterocyclic group,
It represents an alkoxy group or an amino group, and examples of preferable substituents include the groups described above for the groups similar to R _{4 in the} dye represented by the general formula (1).

L represents an alkylene group, and the alkylene group is particularly preferably an ethylene or propylene group.

Y represents a carbonyl group, a sulfonyl group, an oxalyl group or a phosphoryl group, and a carbonyl group or a sulfonyl group is particularly preferable.

-L in the dye represented by the general formula (3)
The —NH—Y—R ₉ group is particularly important in that it provides dyes with even more improved color and lightfastness.

R ₁₀ is an aliphatic group, an aromatic group, a heterocyclic group,
Alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, sulfonylamino group,
It represents an ureido group, a urethane group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, and an amino group. Preferred examples of these substituents include R _{4 in} the dye represented by the general formula (1). The thing etc. which were mentioned above about a substituent are mentioned. R ₁₀ is preferably an aliphatic group or an aromatic group.

R ₁₁ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group,
It represents an acyl group, and preferable examples of these substituents include those mentioned above for the similar substituents of R ₄ in the dye of the general formula (1). R ₁₁ is preferably an aliphatic group or an aromatic group.

The above L, R ₉ , R ₁₀ and R ₁₁ groups may be further substituted with a suitable substituent, and preferable examples of the substituent include R in the dye represented by the general formula (1).
Examples of the groups that may be substituted for R ₁ and R ₂ include those mentioned above.

The general formulas (1), (2), and
Specific compound examples of the dye represented by (3) are shown below, but the invention is not limited thereto.

[0050]

[Chemical 7]

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

[Chemical 12]

[0056]

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The ink jet recording liquid containing the dye represented by the general formula (1) of the present invention can use various solvent systems such as an aqueous solvent, an oil solvent and a solid (phase change) solvent. Can be used particularly preferably as a solvent system.

The ink jet recording liquid containing the dyes represented by the general formulas (2) and (3) of the present invention may use various solvent systems such as an aqueous solvent, an oil solvent and a solid (phase change) solvent. However, an aqueous solvent can be particularly preferably used as the solvent system. . As the aqueous solvent, water (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 by dissolving the dye of the present invention as it is if it 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 in, for example, 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, full-type 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 may be used by dissolving the dye of the present invention as it is, or may be used by dispersing or dissolving it in combination 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 melted at the time of jetting of the ink jet recording liquid by heating.

Examples of such phase change solvents include natural waxes (eg, beeswax, carnauba wax, rice wax, wood wax, jojoba oil, whale 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 a phase change solvent are described in JP-A-5-186723 and JP-A-7-70490.
The method described in the publication can be referred to.

In the case of an aqueous ink jet recording liquid, the water content is 10 to 99.9% by weight in the case of the dye of the general formula (1).
Is preferable, and in the case of the general formulas (2) and (3), 10 to 99.
8% by weight is preferred.

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 at flight of 40 cp.
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 when it is flying.
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.

Particularly in the case of an ink jet recording liquid of an aqueous solvent, in the form containing the dyes of the general formulas (2) and (3) of the present invention, it is preferable to contain the above-mentioned polymer compound, and particularly the carboxyl group in the molecule. It is preferable to contain a polymer compound having a group or a sulfo group.

Examples of the polymer compound having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid,
Itaconic acid, maleic acid, fumaric acid monomers, those copolymerized with these monomers and other vinyl monomers (for example, the unsaturated acids or their esters, amide derivatives, styrene, vinylnaphthalene, etc.), etc. Is mentioned.

As the polymer compound having a sulfo group,
Preferred examples include copolymers of styrene sulfonic acid and other vinyl monomers as described above, and condensation products of naphthalene sulfonic acids or benzene sulfonic acids with formalin.

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 as to the recording system used, but it can be preferably used as an ink jet recording liquid for an on-demand 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.

[0081]

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-50 was prepared by using each ink jet recording liquid having the composition shown in Table 1, Table 2 and Table 3.
00C (manufactured by Seiko Epson Corp., electro-mechanical conversion method) to obtain a sample recorded on a dedicated paper for inkjet Super Fine dedicated paper MJSP1 (manufactured by Seiko Epson). Copolymer A in Table 3 is Ac
ryloid DM-55 (Rohm and Haa
s company, acrylic copolymer), copolymer B is Elvax
40-W (manufactured by Dupont, ethylene / vinyl acetate copolymer).

The results of evaluation of light resistance, color tone, storability and dot shape using this sample are shown in Tables 1, 2 and 3. The unit of the amount of each compound in Table 1, Table 2 and Table 3 is% by weight in the ink jet recording liquid.

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 non-explosion 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 measured as C
A * and b * were calculated based on the IE L * 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 * Preservability outside the preferable range: The ink jet recording liquid was stored in a closed glass container at 80 ° C. for 1 week and then recorded similarly, and the presence or absence of ejection abnormality in continuous ejection for 500 hours and the evaluation of the color tone were evaluated. The preferred storability was defined as follows.

◯: No abnormalities in continuous ejection and color tone change from unstored ink is less than ± 10 for both a * and b * ×: At least one of continuous ejection abnormality or color tone change is a * or b * 10 or more recognized is the dot shape: calculated each inkjet recording liquid defined below average value of the dot shape factor of (C _a) and coefficient of variation is the ratio of the standard error _{(S) (S / C a} ). The closer the variation coefficient is to 0, the more uniform the dot shape. No. 1
The sample was evaluated by the following definition using the relative coefficient of variation when the coefficient of variation in the sample was normalized to 1.

C = (L _C / L _D ) × 100 C: Dot shape factor L _C : Circumferential length of circle having the same area as the dot L _D : Circular length of dot

[0089]

[Equation 1]

S: standard error of shape coefficient C _i : i-th dot shape coefficient C _A : average value of measured dot shape coefficients N: number of measurements (30) ◯: relative variation coefficient of less than 0.9 Δ : Relative coefficient of variation of 0.9 or more and less than 1 x: Relative coefficient of variation of 1 or more

[0091]

Embedded image

[0092]

[Table 1]

[0093]

[Table 2]

[0094]

[Table 3]

As is clear from the above results, the ink jet recording liquid of the present invention is superior in light resistance, color tone, storability and dot shape as compared with the case of using the comparative ink jet recording liquid.

As a recording medium, a special glossy film MJSP is used instead of the superfine special paper MJSP1.
Even when 4 (manufactured by Seiko Epson Corp.) was used, the ink jet recording liquid of the present invention gave similar good results.

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

Example 2 Ink jet printer BJC-600J was prepared by using each ink jet recording liquid having the composition shown in Tables 4 and 5.
(Canon, electric-heat conversion method), inkjet dedicated paper color BJ paper (LC-101)
A sample recorded on A4 (Canon) was obtained. Using this sample, light resistance, color tone, storability and dot shape were evaluated. The results are shown in Tables 4 and 5. still,
The unit of the amount of each compound in Tables 4 and 5 is% by weight in the ink jet recording liquid. The definition of the evaluation item and the evaluation standard are the same as in the first embodiment.

[0099]

[Table 4]

[0100]

[Table 5]

As is clear from the above results, the ink jet recording liquid of the present invention was able to obtain the same effects as in Example 1.

Further, in the printer system described above, the ink jet recording liquid of the present invention was confirmed to have compatibility with the electro-thermal conversion system without any abnormality of the head due to thermal deterioration.

[0103]

As shown in the above examples, by using the ink jet recording liquid and the recording method of the present invention, a clear magenta recorded image excellent in light resistance, color tone, storability and dot shape can be obtained. .

Front page continued (72) Inventor Daisuke Ishibashi 1st Sakura-cho, Hino City, Tokyo Konica Stock Company In-house

Claims (8)

[Claims] 1. An ink jet recording liquid containing a dye represented by the following general formula (1). Embedded image [Wherein R ₁ and R ₂ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ₃ represents a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acylamino group or a sulfonyl group. Represents an amino group, a ureido group, a urethane group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, an amino group, a sulfo group, and a carboxyl group, and n represents an integer of 0 to 3. R ₄ is an aliphatic group,
Aromatic group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, sulfonylamino group, ureido group, urethane group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, Represents an amino group, R ₅
Represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, or an acyl group.
However, at least 1 selected from R ₃ , R ₄ and R ₅
One substituent has a group which acts as an ionic hydrophilic group in the alkaline region of pH 8 to 13. ] 2. An ink jet recording liquid containing a dye represented by the following general formula (2). Embedded image [In the formula, R ₁ and R ₂ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ₆ is a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acylamino group or a sulfonyl group. Amino group, ureido group, urethane group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, amino group, m represents an integer of 0 to 3, and R ₇ represents Aliphatic group, aromatic group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, sulfonylamino group, ureido group, urethane group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group represents an acyl group, an amino group, R ₈ is an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy Carbonyl group, a carbamoyl group, an acyl group. However, when both R ₇ and R ₈ represent an aliphatic group, R ₇ and R ₈ represent an aliphatic group having 2 or more carbon atoms, and R ₇
Is an aromatic group and R ₈ is an aliphatic group, R ₈ represents an aliphatic group having 2 or more carbon atoms. ] 3. An inkjet recording liquid containing a dye represented by the following general formula (3). Embedded image [In the formula, R ₁ represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and R ₆ represents a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acylamino group, a sulfonylamino group, Ureido group, urethane group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, amino group, m represents an integer of 0 to 3, R ₉ represents an aliphatic group, An aromatic group, a heterocyclic group, an alkoxy group, an amino group is represented, L is an alkylene group, Y is a carbonyl group, a sulfonyl group, an oxalyl group, a phosphoryl group, R ₁₀ is an aliphatic group, an aromatic group, A heterocyclic group,
Alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, sulfonylamino group,
A ureido group, a urethane group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, and an amino group, and R ₁₁ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxycarbonyl group, or carbamoyl. Represents a group and an acyl group. ] 4. The ink jet recording liquid according to claim 1 is an aqueous ink jet recording liquid containing 10% by weight to 99.9% by weight of water in the recording liquid, and is represented by the general formula (1). An ink jet recording liquid, wherein a dye to be present is present in an aqueous ink jet recording liquid. 5. The ink jet recording liquid according to claim 2, which is an aqueous ink jet recording liquid containing 10% by weight to 99.8% by weight of water in the recording liquid, and the dye of the general formula (2). Is present in the water-based inkjet recording liquid as a dispersion. 6. The ink jet recording liquid according to claim 2 or 5, wherein the recording liquid has a molecular weight of 1,000 to 1,000,0.
An ink jet recording liquid containing 0.1 to 50% by weight of the polymer compound No. 00. 7. The ink jet recording liquid according to claim 3, which is an aqueous ink jet recording liquid containing 10% by weight to 99.8% by weight of water in the recording liquid, and the dye of the general formula (3). Is present in the water-based inkjet recording liquid as a dispersion. 8. The ink jet recording liquid according to claim 3 or 7, wherein the recording liquid has a molecular weight of 1,000 to 1,000,0.
An ink jet recording liquid containing 0.1 to 50% by weight of the polymer compound No. 00.