JPH11279469A - Water-based ink composition and colored form - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject magenta-colored ink composition highly safe to both the environment and humans, having hue and color clearness suitable for affording a wide range of formula colors, capable of giving printed matters of high light resistance and water fastness with high color value. SOLUTION: This ink composition contains, as color component, a compound (salt) of formula I [D is a water-soluble color residue; X is a sulfo group or carboxy; Y is a (substituted) amino, (substituted) hydroxy or chlorine atom]. It is recommended that the above color component is obtained, for example, by subjecting the corresponding diazo component and a coupling component to ordinary diazotization and alkali coupling process to form a color component which, in turn, is subjected to primary reaction with a cyanuric acid halide under cooling in a weakly acidic condition followed by secondary reaction of the reaction product with a diaminobenzene at room to higher temperatures in an approximately neutral condition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous ink composition and a colored material used for recording, fiber coloring and the like.

[0002]

2. Description of the Related Art Among various color recording methods, various types of ink ejection methods have been developed for a recording method using an ink jet printer, which is one of the representative methods. The recording material is adhered to various recording materials (paper, film, cloth, etc.) to perform recording. This recording method is quiet because there is no generation of sound because the recording head does not contact the recording material, and it has been rapidly spreading in recent years because of its features of miniaturization, high speed, and easy colorization. Significant growth is expected in the future. Among them, when an image or character information on a color display of a computer is recorded in color by an ink jet printer, it is generally expressed by subtractive color mixture using four inks of yellow, magenta, cyan and black. In order to reproduce an additive color image by R, G, B of a CRT display or the like as faithfully as possible with a subtractive color image, the hue of the dye used and its sharpness are important. Stable and
Further, it is required that the density of the printed image is high and that it is excellent in fastness such as water resistance and light resistance. In the future, when used for exhibitions such as advertisements in order to expand the field of use, it will be more likely to be exposed to light (electric lights, fluorescent lights, sunlight, etc.)
In particular, an ink composition having light resistance is required. Various methods have been proposed to satisfy these requirements (for example, JP-A-7-90211 and JP-A-8-7
No. 3791).

[0003]

Among the pigments used in inks for ink jet color printers, magenta is
A hue and sharpness suitable for obtaining a wide range of compound colors have low light fastness and / or water fastness levels, while light fastness and / or
Alternatively, those having a high level of water resistance have a problem in that they are inadequate for providing a wide range of colors in terms of hue and lack sharpness. Further, when a dye having a low color value is used, the dye concentration in the ink must be increased, and the stability of the ink is reduced accordingly. Further, it is important that the dye used in the ink has high safety. The present invention is used for color recording including ink-jet printing, has a hue and sharpness suitable for obtaining a wide range of compound colors, and the light resistance of the recorded matter thereby, the water fastness is strong,
It is an object of the present invention to provide a water-based ink having high color value and high safety to humans and the environment, particularly a water-based ink of magenta color.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have accomplished the present invention. That is, the present invention provides (1) a dye component represented by the following formula (1):

[0005]

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Wherein D represents a water-soluble dye residue;
Represents a sulfonic acid group or a carboxyl group, and Y represents a substituted or unsubstituted amino group, a substituted or unsubstituted hydroxyl group or a chlorine atom. Aqueous ink composition comprising a compound represented by the following formula) or a salt thereof,
(2) the aqueous ink composition of (1), wherein the dye residue of D is an azo dye residue, (3) the aqueous ink composition of (2), wherein the hue of the azo dye residue is magenta; (4) The residue of the azo dye having a magenta color is represented by the following formula (4)

[0007]

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Wherein A represents a benzene skeleton or a naphthalene skeleton. (3) The aqueous ink composition of (3), and (5) a magenta azo dye residue represented by the following formula (2):

[0009]

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(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, Hydrogen atom, hydroxyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, substituted or unsubstituted amino group, nitro group, sulfonic acid ester group, alkylsulfonyl group having 1 to 9 carbon atoms, carbon number (3) represents an arylsulfonyl group, a carboxyl group or a carboxylic acid ester group, a sulfonic acid group, or a cyano group.
(6) The azo dye residue having a magenta color is represented by the following formula (3)

[0011]

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(Wherein, R ₅ and R ₆ each independently represent a sulfonic acid group, a carboxyl group, or a hydrogen atom, and n represents 0 or 1).
(7) Y is a substituted or unsubstituted anilino group, a substituted or unsubstituted benzylamino group,
An amino group, a carboxyl group as a substituent, a hydroxyl group, an alkylamino group which may have one or two alkoxy groups having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms having 1 to 2 carbon atoms.
Optionally having a dialkylamino group, a morpholino group, an allylamino group, a diallylamino group, a cyclohexylamino group, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a substituted or unsubstituted phenoxy group, a benzyloxy group,
Represented by a cyclohexyloxy group or a chlorine atom (1)
The aqueous ink composition according to any one of (1) to (6),
(8) The aqueous ink composition according to any one of (1) to (7), wherein X is a sulfonic acid group and located adjacent to the amino group, (9) any of (1) to (8) Or 1
(10) The colored body of (9), which has been colored by a printer.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous ink composition of the present invention contains a compound represented by the above formula (1) or a salt thereof as a dye component. In the above formula (1), D is a water-soluble dye residue, X is a sulfonic acid group or a carboxyl group, Y is a substituted or unsubstituted amino group, a substituted or unsubstituted hydroxyl group or a chlorine atom. In particular, the present invention is characterized in that in formula (1), two amino groups and benzene having a sulfonic acid group or a carboxyl group as X are bonded via one amino group to the triazine ring. The substitution position of the amino group and X is such that the amino group bonded to the triazine ring is 1
Position, the other amino group is in the 3- or 4-position, X
Is the 4- or 5-position if the other amino group is 3-position,
When the other amino group is in the 4-position, the 3-position is preferred.

The water-soluble dye residue of D is not particularly limited as long as it is a water-soluble dye residue, but an azo water-soluble dye residue is preferable, and a magenta azo water-soluble dye residue is particularly preferable. preferable. Examples of the magenta azo water-soluble dye residue include groups having a benzene azo naphthalene skeleton or a naphthalene azo naphthalene skeleton represented by the above formula (4). In the above formula (4), the sulfonic acid group whose substitution position is not specified is preferably bonded to the amino group at the 3- or 4-position.

The magenta azo water-soluble dye residue having a benzene azo naphthalene skeleton includes, for example, a dye residue represented by the above formula (2), and a magenta azo water-soluble dye having a naphthalene azo naphthalene skeleton. Examples of the sex dye residue include a dye residue represented by the above formula (3). In the dye residues of formulas (2) and (3), the sulfonic acid group in the naphthalene nucleus on the right is 3
-, 6-position or 4-, 6-position.

In the formula (2), R ₁ , R ₂ , R ₃ and R
₄ is each independently a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a hydrogen atom, a hydroxyl group, a substituted or unsubstituted carbamoyl group, A substituted sulfamoyl group,
Substituted or unsubstituted amino group, nitro group, sulfonate group, alkylsulfonyl group having 1 to 9 carbon atoms,
It is an arylsulfonyl group having 6 to 15 carbon atoms, a carboxyl group, a carboxylic acid ester group, a sulfonic acid group or a cyano group.

Examples of the substituted or unsubstituted alkyl group having 1 to 9 carbon atoms for R ₁ , R ₂ , R ₃ and R ₄ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. , Isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, trifluoromethyl group, dimethylaminomethyl group, hydroxyethyl group and the like. Examples of the halogen atom include a chlorine atom and a bromine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an isopropoxy group, and an n-butoxy group. Examples of the substituted or unsubstituted carbamoyl group include a carbamoyl group, an N, N-dimethylcarbamoyl group, an N-ethylcarbamoyl group, and a phenylcarbamoyl group. As a substituted or unsubstituted sulfamoyl group,
For example, sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl, N-
A benzylsulfamoyl group;

The substituted or unsubstituted amino group includes
Examples include an amino group, an N-methylamino group, an N, N-dimethylamino group, an acetylamino group, a carbamoylamino group and the like. Examples of the sulfonic acid ester group include an ethoxysulfonyl group, a phenoxysulfonyl group,
A benzyloxysulfonyl group; Carbon number 1
Examples of the alkylsulfonyl group of No. 9 to 9 include a methylsulfonyl group, a hydroxyethylsulfonyl group, a benzylsulfonyl group and the like. Examples of the arylsulfonyl group having 6 to 15 carbon atoms include a phenylsulfonyl group and a 4-butylphenylsulfonyl group.
Examples of the carboxylate group include an alkoxycarbonyl group having 1 to 5 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group.

[0019] Among R ₁ is a carboxyl group, a sulfonic acid group, a cyano group or a carbamoyl group, R _2,
More preferably, both R ₃ and R ₄ are hydrogen atoms.

In the formula (3), R ₅ and R ₆ each independently represent a sulfonic acid group, a carboxyl group or a hydrogen atom, and n represents 0 or 1. The substitution position of the azo group is 1-position or 2-position. Preferred combinations of R ₅ and R _6, when n is 0, for example, R ₆ is a sulfonic acid group at R ₅ is a hydrogen atom, substitution position is 5- or 6-position of the R _6, also R ₅
And R ₆ are both sulfonic acid groups, the substitution position of R ₅ is 6-position, and the substitution position of R ₆ is 8-position. When n is 1, the substitution position is, for example, the 1-, 3-, or 4-position, both R ₅ and R ₆ are hydrogen atoms, R ₅ is a hydrogen atom and R ₆
Is a sulfonic acid group, and the substitution position of R ₆ is 5-position, 6-position or 8
R ₅ is a hydrogen atom and R ₆ is a carboxy group, and the substitution position is the 6-position.

In the formula (1), Y represents a substituted or unsubstituted amino group, a substituted or unsubstituted hydroxyl group or a chlorine atom. As a substituted or unsubstituted amino group,
For example, a substituted or unsubstituted anilino group, a substituted or unsubstituted benzylamino group, an amino group, a carboxyl group, a hydroxyl group, or an alkylamino optionally having 1 or 2 alkoxy groups having 1 to 4 carbon atoms as a substituent Group, carbon number 1
And a dialkylamino group which may have 1 to 2 alkoxy groups, a morpholino group, an allylamino group, a diallylamino group, and a cyclohexylamino group.
Examples of the substituted or unsubstituted hydroxyl group include a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a substituted or unsubstituted phenoxy group, a benzyloxy group, and a cyclohexyloxy group.

The substituted or unsubstituted anilino group includes, for example, anilino group, 4-butylanilino group, 4-octylanilino group, 2-carboxyanilino group, 3,5
-Dicarboxyanilino group, 4-hydroxy-3-carboxyanilino group and the like. Examples of the substituted or unsubstituted benzylamino group include a benzylamino group, a 4-methylbenzylamino group, a 4-chlorobenzylamino group, and a 4-carboxybenzylamino group. Carboxyl group, hydroxyl group, carbon number 1 as a substituent
Examples of the alkylamino group or dialkylamino group which may have 1 to 2 alkoxy groups include a dimethylamino group, an ethylamino group, an n-butylamino group, an octylamino group, a carboxymethylamino group, (Carboxymethyl) amino group, 1,2-dicarboxypropylamino group, 2-hydroxyethylamino group, di (2-hydroxyethyl) amino group, 2-hydroxypropylamino group and the like.

The alkoxy group having 1 to 4 carbon atoms includes, for example, methoxy group, ethoxy group, isopropoxy group, n-
Butoxy group and the like. Examples of the substituted or unsubstituted phenoxy group include a phenoxy group, a 4-carboxyphenoxy group, a 3-methylphenoxy group, and a 4-sulfophenoxy group.

Wherein Y is a hydroxyl group, a chlorine atom, a morpholino group, a 2-hydroxyethylamino group, an anilino group,
A benzylamino group is preferred, and a hydroxyl group is particularly preferred.

Of the dye components used in the present invention, preferred are, for example, those of the following formulas (5) and (6). As a preferable combination of each substituent, for example, in the formula (5), R ₁ is a carboxyl group, a sulfonic group, a cyano group or a carbamoyl group;
R ₂ , R ₃ and R ₄ are all hydrogen atoms, Y is a hydroxyl group, a chlorine atom, a morpholino group, a 2-hydroxyethylamino group, an anilino group or a benzylamino group, and the amino group on the benzene ring is 3 or At the 4-position, X is a sulfonic acid group or a carboxyl group at the 3-position, or a sulfonic acid group or carboxyl group at the 4- or 5-position, and especially R ₁ is a carboxyl group, and R ₂ , R ₃ and R ₄ are any of Is also a hydrogen atom, Y is a hydroxyl group, the amino group on the benzene ring is at position 4,
X is more preferably a sulfonic acid group at the 3-position.

In the formula (6), A is 1-naphthylamine-5-sulfonic acid, 2-naphthylamine-6-sulfonic acid, 2-naphthylamine-6,8-disulfonic acid,
1-naphthylamine-4-sulfonic acid, 1-naphthylamine-3,6-disulfonic acid, 2-naphthylamine-1
-Sulfonic acid, 2-naphthylamine-1,5-disulfonic acid, 2-naphthylamine-1,6-disulfonic acid, 2
-Naphthylamine-4,8-disulfonic acid, 2-naphthylamine-3,6-disulfonic acid, 6-carboxy-2
-Naphthylamine-1-sulfonic acid, wherein Y is a hydroxyl group, a chlorine atom, a morpholino group, a 2-hydroxyethylamino group, an anilino group or a benzylamino group, and the amino group on the benzene ring is at the 3- or 4-position, and X is A sulfonic acid group or a carboxyl group at the 3-position, or a sulfonic acid group or a carboxyl group at the 4- or 5-position, in particular, A is 2-naphthylamine-1-sulfonic acid, Y is a hydroxyl group, and an amino group on the benzene ring Is more preferably a sulfonic acid group at the 4-position and X at the 3-position.

Next, specific examples of the dye component represented by the formula (1) used in the present invention are shown in Tables 1, 2 and 3. still,
The substituent and the substitution position in each table mean the substituent and the substitution position of the dye component of the chemical formula described before each table.

[0028]

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[0029]

[Table 1] Table 1 No. Position of R ₁ R ₂ R ₃ R ₄ NH2 X and its position Y 1 -COOH HHH 4- 3-SO3H -Cl 2 -COOH HHH 4- 3-SO3H -OH 3 -COOH HHH 4- 3-SO3H -NHCH2COOH 4 -COOH HHH 4- 3-SO3H Benzylamino 5-COOH HHH 4- 3-SO3H Phenoxy 6 -COOH HHH 3- 4-SO3H -Cl 7 -COOH HHH 3- 4-SO3H -OH 8 -COOH HHH 3- 4-SO3H Allylamino 9 -COOH HHH 4- 3-COOH Anilino 10 -COOH HHH 4- 3-COOH -Cl 11 -COOH HHH 4- 3-COOH -OH 12 -COOH HHH 4- 3- COOH -N (C2H5) 2 13 -COOH HHH 3- 4-COOH -Cl

14-COOH HHH 3- 4-COOH -OH 15 -COOH HHH 3- 5-COOH morpholino 16 -SO3H H -CH3 H 4- 3-SO3H -OH 17 -SO3H H -CH3 H 4- 3-COOH 4-methylanilino 18 -SO3H H -CH3 H 4- 3-COOH -OCH3 19 H -COOH H -COOH 4- 3-SO3H -OH 20 H -COOH H -COOH 3- 4-SO3H diallylamino 21 -COOH HH- COOH 3- 4-SO3H -OH 22 -SO3H H -CH3 -Cl 4- 3-SO3H Anilino 23 -SO3C2H5 HHH 4- 3-SO3H -NHC2H4OH 24 -CONH2 HHH 4- 3-SO3H -OC3H7 25 -COOCH3 HHH 4- 3-SO3H 2-carboxyanilino 26 -CN HHH 4- 3-SO3H 2-carboxyanilino

27-Cl HH -CF3 4- 3-SO3H Cyclohexylamino 28H-NHCOCH3 HH 3- 4-SO3H -OH 29 -OH HH -SO2NH2 3- 4-SO3H Cyclophenoxy 30 -OCH3 HH -SO2NHC2H5 3-4 -SO3H -OC4H9 31 -SO2CH3 HHH 3- 4-SO3H -NH (CH3) 3-N (CH3) 2 32 -SO3H HHH 3- 4-SO3H 4-n-octylanilino 33 -CF3 HHH 4- 3-COOH 4-n-octylanilino 34 -CF3 HHH 3- 4-SO3H 4-hydroxy-3-carboxyanilino 35 -COOH HHH 3- 4-SO3H 4-sulfophenoxy 36 -SO3H H -Cl -COOH 4- 3-SO3H 4-carboxyphenoxy 37 -SO3H H -CH3 H 4- 3-COOH benzylamino Comparative Example * -COOH HHH None 2-COOH -OH * Dye No. described in JP-A-8-73791. 1

[0032]

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[0033]

[Table 2] Table 2 No. A Position of NH ₂ X and its position Y 38 1-sulfo-2-naphthyl 4-3-SO3H ethylamino 39 1-sulfo-2-naphthyl 4-3-SO3H-OH 40 1-sulfo-2-naphthyl 3- 4-SO3H-N (CH2COOH) 2 41 1-sulfo-2-naphthyl 4-3-COOH alinino 42 1-sulfo-2-naphthyl 4-3-COOH-Cl 43 1,5-disulfo-2-naphthyl 4- 3-COOH allylamino 44 1,5-disulfo-2-naphthyl 3- 4-COOH-OH 45 1,6-disulfo-2-naphthyl 3-4-SO3H 4-butylanilino 46 4,8-disulfo-2-naphthyl 3 -4-SO3H diallylamino 47 6-sulfo-2-naphthyl 3- 4-SO3H-OH 48 1-sulfo-6-carboxy-2-naphthyl 3- 4-COOH-OH 49 3,6-disulfo-1-naphthyl 3- 4-COOH anilino 50 4-sulfo-1-naphthyl 4- 3-SO3H-OH

[0034]

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[0035]

Table 3 Table 3 No. Position of R ₁ R ₂ R ₃ R ₄ NH ₂ X and its position Y 51 -COOH HHH 4- 3-SO3H -OH 52 -COOH HHH 3- 4-SO3H Anilino 53 -SO3H HHH 4- 3-COOH -OH 54 -SO3H HHH 3- 4-COOH benzylamino

The dye component of the formula (1) used in the present invention comprises:
For example, it is manufactured as follows. That is, a dye component corresponding to a dye residue is produced by a usual diazotization and alkali coupling method using a corresponding diazo component and a coupling component. This dye component is combined with a cyanuric halide under cooling (0 to 10 ° C.) under mildly acidic conditions (pH 4 to 6).
The next reaction. Next, diaminobenzenes were added to the reaction mixture from room temperature while heating (30 to 40 ° C.) at around neutrality (p
H6 to 7) By performing a secondary reaction, a dye component of the formula (1) in which Y is halogen is obtained.

The dye component of the formula (1) in which Y is other than halogen is prepared by adding sodium hydroxide, alcohol and various amines corresponding to Y to the dye component of the formula (1) in which Y is a halogen under heating (70 to 90). ° C) It is obtained by carrying out a tertiary reaction with alkali (pH 9 or more).

Further, after a primary reaction of a coupling component with a cyanuric halide, a diazo component may be coupled, followed by a secondary reaction and a tertiary reaction. The reaction may be performed after the secondary reaction or after the tertiary reaction instead of after the subsequent reaction.

The dye component used in the present invention may be a salt. The salt is a salt at a sulfonic acid group or a carboxyl group, for example, a sodium salt, a potassium salt,
Examples thereof include alkali metal salts such as lithium salts, ammonium salts, and ammonium salts including substituted ammonium. Examples of ammonium salts including substituted ammonium include mono-, di-, tri- or quaternary substituted or unsubstituted alkyl ammonium or mono-, di-,
Tri- or quaternary substituted or unsubstituted alkanol ammoniums are mentioned. For example, monomethylamine,
Monoethylamine, dibutylamine, monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, tetramethylammonium chloride, tetraethylammonium chloride, etc. Salt. A part of the sulfonic acid group and / or the carboxyl group may be in the form of a salt.

The dye component used in the present invention preferably has a low content of inorganic substances such as metal cation chlorides and sulfates, and the standard of the content is, for example, about 1% or less. In order to produce a pigment containing less inorganic substance, desalting may be performed by a usual method using, for example, a reverse osmosis membrane.

The ink used in the present invention is obtained by dissolving the above-mentioned dye component in water and / or a water-soluble organic solvent. Examples of the water-soluble organic solvent include C1-C4 alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, and tert-butanol, N, N-dimethylformamide, and N, N-dimethylacetamide. Lactams such as carboxylic acid amides, ε-caprolactam, N-methylpyrrolidin-2-one and rings such as 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimid-2-one Formula ureas, acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentane-4
Ketones or keto alcohols such as -one, ethers such as tetrahydrofuran and dioxane, for example, ethylene glycol, 1,2-propylene glycol or 1,3-propylene glycol, 1,2-butylene glycol or 1,4-butylene glycol, C such as 6-hexylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol, etc.
Mono-, oligo- or polyalkylene glycols having 2 to C6 alkylene units or polyols such as thioglycol, glycerin, hexane-1,2,6-triol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or C1-C4 alkyl ethers of polyhydric alcohols such as diethylene glycol monoethyl ether or triethylene glycol monomethyl ether or triethylene glycol monoethyl ether, γ
-Butyrolactone or dimethyl sulfoxide. Two or more of these organic solvents may be used in combination.

As water-soluble organic solvents which are miscible with water and are advantageous, N-methylpyrrolidin-2-one, mono-, di- or trialkylene glycols having C2-C6 alkylene units, preferably mono-, di- or triethylene glycol , Dipropylene glycol, dimethyl sulfoxide and the like, in particular, N-methylpyrrolidin-2-one,
The use of diethylene glycol, dimethylsulfoxide is preferred.

The ink used in the present invention can be obtained by dissolving a pigment having a low content of an inorganic substance in water and / or a water-soluble organic solvent together with an ink preparation as required. The pH of the composition is preferably between pH 8 and 1.
About 1 is good.

The pigment component in the ink used in the present invention is preferably 0.1 to 20% by weight, more preferably 0.1 to 20% by weight.
-10% by weight, more preferably about 0.5-8% by weight. Further, the ink may contain a water-soluble organic solvent, preferably about 0 to 30% by weight, and an ink preparation, preferably about 0 to 5% by weight.

Examples of the ink preparation agent include an antiseptic / antifungal agent, a pH adjusting agent, a chelating reagent, a rust inhibitor, a water-soluble ultraviolet absorber, a water-soluble polymer compound, a dye dissolving agent, a surfactant and the like. Examples of preservatives and fungicides include sodium acetate anhydrous, sodium sorbate, 2-pyridinethiol-
Examples thereof include sodium 1-oxide, sodium benzoate, and sodium pentachlorophenol.

As the pH adjuster, the pH of the ink is adjusted to, for example, about 8 to 11 without adversely affecting the ink to be prepared.
Any substance can be used as long as it can be controlled in the range of, for example, diethanolamine, alkanolamine such as triethanolamine, lithium hydroxide,
Examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonium hydroxide, and alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate.

Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate,
Sodium hydroxyethylethylenediaminetriacetate,
And sodium diethylenetriaminepentaacetate and sodium uracildiacetate. Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like. Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamine, polyimine and the like. Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone and sulfonated benzotriazole. Examples of the dye dissolving agent include ε-caprolactam, ethylene carbonate, and urea. Examples of the surfactant include known surfactants such as an anionic surfactant, a cationic surfactant, and a nonionic surfactant.

There are no particular restrictions on the coloration of the aqueous ink composition of the present invention, and examples thereof include paper, fibers and cloths (cellulose, nylon, wool, etc.), leather, base materials for color filters, and the like. . Examples of the coloring method include, for example, dip dyeing, printing, printing methods such as screen printing, and a method using an ink jet printer, and a method using an ink jet printer is preferable.

The aqueous ink composition which may contain the coloring matter represented by the formula (1) or another coloring matter is prepared by printing, copying, marking, writing, drafting, stamping, or recording.
Particularly suitable for use in ink jet printing. This gives high quality prints with remarkably high concentrations and good resistance to water, sunlight and rubbing.

The aqueous ink composition according to the present invention does not cause separation of a precipitate during storage, and further, does not cause clogging of a jet nozzle when the aqueous ink composition of the present invention is used in ink jet printing. When the aqueous ink composition of the present invention is used in an inkjet printing machine under constant recirculation for a relatively long period of time or intermittently with an intermediate shutdown of the inkjet printing machine, the aqueous ink composition of the present invention is physically No change in properties occurs.

[0051]

The present invention will be described in more detail with reference to Synthesis Examples and Examples. In the text, “part” and “%” are based on weight unless otherwise specified.

Synthesis Example 1 Preparation of Compound 1 2-aminobenzoic acid is diazotized by a conventional method, and coupled to 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid (H acid) under neutral to alkaline conditions. The mixture was filtered, dried and dried to produce a monoazo compound.
The obtained monoazo compound was dissolved in water in an amount of 93.4 parts as a free acid to prepare a solution having a pH of 9.2 and 1,000 parts. Cyanuric chloride, 37.8 parts, was dissolved in 250 parts of acetone and poured into 250 parts of ice water with stirring to form a fine suspension. The aqueous solution of the monoazo compound was added dropwise thereto over 2 hours while maintaining the temperature at 0 to 5 ° C. During this period, the pH was maintained at 4 to 6 by adding an aqueous solution of sodium carbonate.
After completion of the dropwise addition, stirring was continued for about 3 hours while maintaining the same conditions to complete the primary condensation. Then, 37.6 parts of 1,4-diaminobenzene-2-sulfonic acid was added to 400 parts of water at pH.
The solution dissolved in 8 was added, and then the secondary condensation was continued at 30 to 40 ° C. for about 3 hours while maintaining the pH at 6 to 7 by adding a sodium carbonate solution to complete the reaction. To the reaction mixture was added sodium chloride in an amount equivalent to 5% of the liquid volume, salted out and filtered.
Drying under reduced pressure at 0 ° C. yielded 129.4 parts of No. One compound (.lambda.max in water at 546 nm) was obtained.

Also, the H acid is first condensed with cyanuric chloride,
The primary condensate is also coupled with a diazonium salt of 2-aminobenzoic acid and then subjected to secondary condensation with 1,4-diaminobenzene-2-sulfonic acid to form N.
o. One compound is obtained.

Synthesis Example 2 Production of Compound No. 2 38.3 parts of compound 1 (as free acid) in water 20
The suspension was dissolved in 0 part by adding 16 parts of sodium hydroxide and hydrolyzed at 80 to 85 ° C for 2 hours. afterwards,
Hydrochloric acid was added to neutralize the solution to a pH of about 9, and sodium chloride (20% with respect to the solution) was added, salted out, filtered and dried. 33.8 parts of compound 2 (λmax in water is 543 nm) were obtained.

Synthesis Example 3 Production of Compound No. 4 38.3 parts (as the free acid) of compound 1 are suspended in 250 parts of water, benzylamine 7.0 is added, and
The temperature was raised to ８５85 ° C., and tertiary condensation was carried out at the same temperature for 2 hours while maintaining the pH at 9 to 9.5 by adding a sodium carbonate solution. After completion of the condensation, 5% sodium chloride solution was added, salting out, filtration and drying were performed. Compound 4 (λmax in water
Was 544 nm).

After the primary condensation of H acid with cyanuric chloride,
After secondary condensation with 1,4-diaminobenzene-2-sulfonic acid, coupling of the diazonium salt of 2-aminobenzoic acid and then tertiary condensation with benzylamine, or after primary condensation of cyanuric chloride and H acid No. 1,4-diaminobenzene-2-sulfonic acid, followed by tertiary condensation with benzylamine and coupling with a diazonium salt of 2-aminobenzoic acid. Compound 4 is obtained.

Synthesis Example 4 Production of Compound No. 6 The same amount of 1,4-diaminobenzene-2-sulfonic acid was used in place of the 1,4-diaminobenzene-2-sulfonic acid used in preparing the compound of Example 1.
When the second condensation was carried out using 3-diaminobenzene-4-sulfonic acid, Compound 6 (λmax in water is 544
nm).

Synthesis Example 5 Production of Compound No. 42 The same procedure was repeated using 2-aminonaphthalene-1-sulfonic acid (tobias acid) in place of the 2-aminobenzoic acid used to produce the compound of No. 1; 4
Compound 2 was obtained (.lambda.max in water was 559 nm).

Example 1 (A) Preparation of Ink A liquid having the following composition was prepared and filtered with a 0.45 μm membrane filter to obtain an aqueous ink composition for each ink jet. Composition Pigment component (compound of No. 2, 4, 7 or 9) 3.0 parts (use a desalted one) Water 67.0 parts Ethylene glycol 5.0 parts Glycerin 5.0 parts N-methylpyrrolidone 7.0 parts Urea 10.0 parts IPA 3.0 parts

(B) Inkjet printing Inkjet printer (trade name: ENCAD NO.
VAJET III), plain paper (Canon Printer Paper A4 (TLB5A4S), special paper A (C
color BJ PaperLC101 (manufactured by Canon)
And special paper B (coated paper for color image jet ST)
Ink jet recording was performed on three types of paper of X73A4 (made by Sharp).

(C) Sunlight fastness test of recorded image The recorded image was irradiated for 20 hours using a carbon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.). Judgment class is JIS
It was determined according to the blue scale rating specified in L-0841. (D) Waterfastness test of recorded image A test piece was placed in a beaker of water with gentle stirring.
After soaking for a minute and drying, the extent of the compound falling off before the test treatment is visually determined. ○ There are few drops. △ About half drop off. × Many drops.

Comparative Example As a dye, the dye No. described in JP-A-8-73791 was used in place of the dye component used in the present invention. Ink jet recording was performed on three types of paper in the same manner as in the above example except that the compound of Formula 1 (the structural formula is shown in Table 1) was used, and (C)
And (D). The evaluation results are shown in Table 4.

[0063]

Table 4 Table 4 Compound No. Sunlight fastness (grade) Waterfastness Plain paper Dedicated paper A Dedicated paper B Plain paper Dedicated paper A Dedicated paper B No. 24 3 4 △ ○ ○ No. 4 3-4 24 △ ○ ○ No. No. 7424 △ ○ ○ No. 9 3-4 24 ○ ○ ○ Comparative example 3-4 24 × ○ ○

From Table 4, it can be seen that the aqueous ink composition containing the dye of the present invention is superior to known similar dyes in terms of water fastness, and has the same or higher fastness to sunlight.

[0065]

The ink composition of the present invention has a hue and clarity suitable for obtaining a wide range of compound colors, thereby has a high water resistance and fastness to sunlight of the recorded matter, a high color value, and a high quality for humans. It is highly valuable as a water-based ink composition for recording, such as for inkjet recording and writing implements, which has high environmental safety.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 251/70 C09B 29/30 C09B 29/30 62/028 C 62/028 62/04 Z 62/04 B41J 3/04 101Y

Claims (10)

[Claims] 1. A dye component represented by the following formula (1): (In the formula, D represents a water-soluble dye residue, X represents a sulfonic acid group or a carboxyl group, and Y represents a substituted or unsubstituted amino group, a substituted or unsubstituted hydroxyl group or a chlorine atom.) A water-based ink composition comprising a compound or a salt thereof. 2. The aqueous ink composition according to claim 1, wherein the water-soluble dye residue of D is an azo dye residue. 3. The aqueous ink composition according to claim 2, wherein the hue of the residue of the azo dye is magenta. 4. The residue of an azo dye having a magenta color is represented by the following formula (4): 4. The aqueous ink composition according to claim 3, wherein A represents a benzene skeleton or a naphthalene skeleton. 5. The residue of an azo dye having a magenta color is represented by the following formula (2): (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms;
An alkoxy group having 1 to 4 carbon atoms, a halogen atom, a hydrogen atom, a hydroxyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted amino group, a nitro group, and a sulfonic ester group A C1-C9 alkylsulfonyl group, a C6-C15 arylsulfonyl group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid group or a cyano group. 4. The aqueous ink composition according to claim 3, which is a group represented by the formula: 6. The residue of an azo dye having a magenta color is represented by the following formula (3). 4. The aqueous ink composition according to claim 3, wherein R ₅ and R ₆ each independently represent a sulfonic acid group, a carboxyl group, or a hydrogen atom, and n represents 0 or 1. . 7. In Y, the substituted or unsubstituted amino group is a substituted or unsubstituted anilino group, a substituted or unsubstituted benzylamino group, an amino group, a carboxyl group, a hydroxyl group, a C1 to C4 1 alkoxy group
Alkylamino group optionally having 1 to 2 carbon atoms
4 is a dialkylamino group, a morpholino group, an allylamino group, a diallylamino group, or a cyclohexylamino group which may have 1 to 2 alkoxy groups, wherein the substituted or unsubstituted hydroxyl group is a hydroxyl group, and has 1 to 4 carbon atoms. The aqueous ink composition according to any one of claims 1 to 6, which is an alkoxy group, a substituted or unsubstituted phenoxy group, a benzyloxy group, a cyclohexyloxy group, or a chlorine atom. 8. The aqueous ink composition according to claim 1, wherein X is a sulfonic acid group and is located at a position adjacent to the amino group. 9. A colored body colored with the aqueous ink composition according to claim 1. 10. The printer according to claim 9, wherein the coloring is performed by a printer.
Colored body.