JP2001288389A - Ink for inkjet and method for inkjet printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink for inkjet capable of forming an image having an excellent cyan color and excellent in preservability, and able to reduce clogging at a discharge opening. SOLUTION: The ink for inkjet contains at least one kind selected from dyes expressed by the following formulae (1) and (2). The ink for inkjet preferably contains a water-soluble organic solvent, a surfactant, and/or urea or a urea derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Ink jet recording methods are inexpensive in material cost, capable of high-speed recording, have low noise during recording, and are easy to perform color recording.
It is rapidly spreading and developing. Ink jet recording methods include a method in which pressure is applied by a piezo element to eject droplets, a method in which bubbles are generated in ink by heat to eject droplets, and a method in which droplets are sucked and ejected by electrostatic force. . Further, as the ink-jet ink, a water-based ink, an oil-based ink, or a solid (melt-type) ink is used.

[0003] Dyes used in ink-jet inks have high solubility in solvents, high density recording is possible, good hue, light, heat,
It is required that they have excellent robustness to air, water and chemicals, have no toxicity, have high purity, and be available at low cost. The ink is required to have good fixability to the image receiving material, not to bleed easily, excellent storage stability, and not to cause clogging at the discharge port.

[0004] Various dyes and pigments have already been proposed and actually used for ink jet. However, at present, a dye satisfying all requirements has not been found yet. Japanese Patent Application Laid-Open No. 9-11 / 1994 describes cyan ink.
An example of a triphenylmethane dye described in JP-A-613 is known. However, in the case of an inkjet ink using the dye, nozzle clogging is liable to occur, image storability after printing is poor, and color tone is poor. Has a drawback such as a change in

[0005]

SUMMARY OF THE INVENTION The present invention relates to an ink-jet ink and an ink-jet recording method having a good cyan color, capable of forming an image having excellent storability, and capable of reducing clogging at a discharge port. The purpose is to provide.

[0006]

Means for solving the above problems are as follows. That is, <1> an inkjet ink containing at least one dye selected from dyes represented by the following general formulas (1) and (2).

General formula (1)

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In the general formula (1), R ¹ and R ² each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, and R ¹ and R ² are bonded to each other to form 5 It may form a six-membered or six-membered ring. R
³ represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a cyano group or a nitro group. A represents a carbon atom or a nitrogen atom, and B ¹ represents a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, a sulfamoyl group, a carbamoyl group or an alkoxycarbonyl group. X ¹ is a hydrogen atom, a halogen atom, an alkyl group,
It represents an alkoxy group, an -NHCOR ⁴ or OCOR ^5,
R ⁴ and R ⁵ each represent an alkyl group or an aryl group. Y represents an alkyl group or an aralkyl group, and Z represents a hydrogen atom, an alkyl group or an aryl group. W ¹ represents a counter anion, n1 represents the number of 0 or more necessary to match the number of positive charges and the number of negative charges in the general formula (I).
General formula (2)

Embedded imageIn the general formula (2), R¹¹And R¹²Is a hydrogen atom,
Kill group, cycloalkyl group, aralkyl group or aryl
R¹¹And R¹²And bond to each other to form a nitrogen atom
Both may form a 5- or 6-membered ring. R¹³Is hydrogen
Atom, halogen atom, lower alkyl group, lower alkoxy
Represents a group, a cyano group or a nitro group. B ¹¹Is a sulphone
Acid groups or salts thereof, carboxylic acid groups or salts thereof,
Rufamoyl group, carbamoyl group or alkoxycar
Represents a bonyl group;¹²~ B^FifteenAre hydrogen and sulfo, respectively.
Acid groups or salts thereof, carboxylic acid groups or salts thereof,
Sulfamoyl group, carbamoyl group or alkoxyca
Represents a rubonyl group. X^TwoRepresents a hydrogen atom, a halogen atom,
Alkyl group, alkoxy group, -NHCOR¹⁴Or -OC
OR^FifteenAnd R¹⁴And R^FifteenIs an alkyl group or
Represents an aryl group. R¹⁶And R¹⁷Is an aryl group
Or a heterocyclic residue;¹⁶And R¹⁷Is linked to heterocycle
May be formed. W^TwoRepresents a counter anion, and n2 represents
The number of positive charges and the number of negative charges in the general formula (I) are matched.
Represents a number of 0 or more required for.

<2><1> containing a water-soluble organic solvent
2. The ink for inkjet described in 1. above. <3> The inkjet ink according to <1> or <2>, which contains a surfactant. <4> The inkjet ink according to any one of <1> to <3>, containing urea or a urea derivative. <5> An inkjet recording method using the inkjet ink according to any one of <1> to <4>.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (Inkjet Ink) The inkjet ink of the present invention contains at least one dye selected from the dyes represented by the general formulas (1) and (2). Features.

-Dye represented by the general formula (1)-In the general formula (1), R ¹ and R ² each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. The group may have a substituent. Examples of the alkyl group include a linear or branched alkyl group having 1 to 6 carbon atoms, and more specifically,
Examples include a carboxymethyl group and a 2-sulfoethyl group. Examples of the cycloalkyl group include a cyclohexyl group and a cyclopentyl group. Examples of the aralkyl group include a benzyl group and a p-methoxybenzyl group. As the aryl group,
For example, m-carboxyphenyl group, o-sulfophenyl group, 2,5-disulfophenyl group, 3-chloro-
And a 6-sulfophenyl group. R ¹ and R ² may be the same or different. R ¹ and R ² may combine with each other to form a 5- or 6-membered ring together with the nitrogen atom. Examples of the 5- or 6-membered ring include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

When the alkyl group, cycloalkyl group, aralkyl group and aryl group have a substituent, examples of the substituent include an alkyl group having 1 to 4 carbon atoms and 1 to 4 carbon atoms.
, A halogen atom (a chlorine atom, a bromine atom, etc.), a sulfo group, a carboxy group and the like.

In the general formula (1), R ³ is a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom), a lower alkyl group (an alkyl group having 1 to 4 carbon atoms), a lower alkoxy group (a carbon atom having 1 to 4 carbon atoms). 1-4), a cyano group or a nitro group.

In the general formula (1), A represents a carbon atom or a nitrogen atom. In the general formula (1), B ¹ represents a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof,
Represents a sulfamoyl group, a carbamoyl group or an alkoxycarbonyl group.

In the general formula (1), X ¹ represents a hydrogen atom, a halogen atom (for example, a chlorine atom or a bromine atom), an alkyl group (for example, an alkyl group having 1 to 4 carbon atoms), or an alkoxy group (for example, An alkoxy group having 1 to 4 carbon atoms), -NH
Represents COR ⁴ or —OCOR ⁵ , wherein R ⁴ and R ⁵ are each an alkyl group (eg, an alkyl group having 1 to 4 carbon atoms) or an aryl group (eg, a phenyl group, an o-tolyl group, etc.)
Represents

In the above general formula (1), Y represents an alkyl group (for example, methyl group, ethyl group, n-butyl group, sulfopropyl group, etc.) or an aralkyl group (for example, benzyl group, o-sulfobenzyl group) Etc.). In the general formula (1), Z represents a hydrogen atom, an alkyl group (for example, an alkyl group having 1 to 4 carbon atoms) or an aryl group (for example, a phenyl group, an o-tolyl group, and the like).

In the general formula (1), W ¹ represents a counter anion. Although the number of charges of the counter anion is not particularly limited, 0 to 1 is preferable. As the counter anion,
Halide ion (for example, chloride ion, bromine ion, etc.), sulfate ion, organic sulfonate ion (for example, aliphatic sulfonate ion having 1 to 12 carbon atoms, benzene sulfonate ion, trifluoromethane sulfonate, etc.) , Fatty acid ions (for example, having 1 to 1 carbon atoms)
2, aliphatic carboxylate ion, trifluoromethane carboxylate and the like), benzoate ion, oxalate ion, tetrafluoroborate ion, hexafluorophosphate ion and the like. The general formula (1)
In the formula, n1 represents a number of 0 or more necessary for matching the number of positive charges and the number of negative charges in the general formula (1). When the dye represented by the general formula (1) has an anionic group represented by a sulfo group or a carboxyl group in the molecule, n
1 = 0, and the counter anion W ¹ may not be needed.

-Dye represented by the general formula (2)-In the general formula (2), R¹¹And R¹²Is a hydrogen atom,
Alkyl, cycloalkyl, aralkyl or ant
And these groups may have a substituent.
No. Examples of the alkyl group include those having 1 to 6 carbon atoms.
A straight-chain or branched alkyl group is mentioned, and more specifically,
Examples include a carboxymethyl group and a 2-sulfoethyl group.
It is. Examples of the cycloalkyl group include, for example, cyclo
Examples include a hexyl group and a cyclopentyl group. Said a
Examples of the aralkyl group include a benzyl group and p-methoxy.
And a cibenzyl group. As the aryl group
Is, for example, m-carboxyphenyl group, o-sulfo
Phenyl group, 2,5-disulfophenyl group, 3-chloro
Ro-6-sulfophenyl group and the like. R¹¹And R
¹²May be the same or different, and R¹¹And R¹²And each other
To form a 5- or 6-membered ring with the nitrogen atom
May be. As the 5- or 6-membered ring,
For example, a pyrrolidine ring, a piperidine ring, a morpholine ring, etc.
No.

When the alkyl group, cycloalkyl group, aralkyl group and aryl group have a substituent, examples of the substituent include an alkyl group having 1 to 4 carbon atoms and 1 to 4 carbon atoms.
, A halogen atom (a chlorine atom, a bromine atom, etc.), a sulfo group, a carboxy group and the like.

In the general formula (2), R ¹³ represents a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom), a lower alkyl group (an alkyl group having 1 to 4 carbon atoms), and a lower alkoxy group (a carbon atom having 1 to 4 carbon atoms). 1-4), a cyano group or a nitro group.

In the general formula (2), B ¹¹ represents a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, a sulfamoyl group, a carbamoyl group or an alkoxycarbonyl group, B ^{12 to} B ¹⁵ each represent a hydrogen atom, Represents a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, a sulfamoyl group, a carbamoyl group or an alkoxycarbonyl group.

In the general formula (2), X^TwoIs a hydrogen atom,
Logen atom (for example, chlorine atom, bromine atom, etc.),
Group (alkyl group having 1 to 4 carbon atoms), alkoxy group (eg,
For example, an alkoxy group having 1 to 4 carbon atoms), -NHCOR^Four
Or -OCOR^FiveRepresents R ¹⁴And R^FifteenAre each
A kill group (for example, an alkyl group having 1 to 4 carbon atoms) or
Reel group (for example, phenyl group, o-tolyl group, etc.)
You.

The general formulas R ¹⁶ and R ¹⁷ each represent an aryl group or a heterocyclic residue. The aryl group may have a substituent, and examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom such as a chlorine atom and a bromine atom. The heterocyclic residue is a heterocyclic residue having at least one heteroatom selected from an oxygen atom, a nitrogen atom and a sulfur atom, and is a condensed ring formed by condensing two or more rings even if it is a single ring. Is also good. Examples of the heterocyclic residue include a 2- or 3-furyl group, a 2- or 3-pyrrolyl group, a 2- or 3-
And a thienyl group. R ¹⁶ and R ¹⁷ may be linked to form a heterocyclic ring. Examples of the heterocyclic ring include carbazole and phenoxazine.

In the general formula (2), W ² represents a counter anion. Although the number of charges of the counter anion is not particularly limited, 0 to 1 is preferable. As the counter anion,
Halide ion (for example, chloride ion, bromine ion, etc.), sulfate ion, organic sulfonate ion (for example, aliphatic sulfonate ion having 1 to 12 carbon atoms, benzene sulfonate ion, trifluoromethane sulfonate, etc.) , Fatty acid ions (for example, having 1 to 1 carbon atoms)
12 aliphatic carboxylate ion, trifluoromethane carboxylate, etc.), benzoate ion, oxalate ion, tetrafluoroborate ion and hexafluorophosphate ion. In the general formula (2), n2
Represents a number of 0 or more necessary for matching the number of positive charges and the number of negative charges in the general formula (2). When the dye represented by the general formula (2) has an anionic group represented by a sulfo group or a carboxyl group in the molecule, n2 = 0, and the counter anion W ² may not be required. is there.

Specific examples (exemplary compounds (11) to (20)) of the dye represented by formula (1) are shown below.
The dye used in the present invention is not limited to these.

[0026]

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[0027]

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[0028]

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Specific examples (exemplary compounds (21) to (25)) of the dye represented by formula (2) are shown below.
The dye used in the present invention is not limited to these.

[0030]

Embedded image

The synthesis examples of the dyes represented by the general formulas (1) and (2) are described below.

Synthesis Example 1 (Synthesis of Exemplified Compound (11)) 7- (1-Ethyl-2-methylindol-3-yl)
-7- (3-ethoxy-diethylaminophen-4-yl) -5,7-dihydro [3,4-b] pyrazin-5
20 g of ON is dissolved in 20 ml of chloroform, and 15 ml of concentrated hydrochloric acid is added dropwise under cooling. Next, 50 ml of isopropanol is added with stirring, and the deposited precipitate is isolated, washed with isopropanol and dried. 7 g of Exemplified Compound (11) is obtained.

Synthesis Example 2 (Synthesis of Exemplified Compound (21)) When 30 g of 3-diphenylamino-6- (N-methyl-N-phenyl) aminofluoran (3) was reacted in the same manner as in Synthesis Example 1, 12 g of Exemplified Compound (21) is obtained.

Starting materials for the dye represented by the general formula (1) are described in JP-A-51-16807 and JP-A-57-212092.
And JP-A-63-113446. The starting material of the dye represented by the general formula (2) can be synthesized by the method described in JP-A-56-77189.

The inkjet ink of the present invention contains at least one of the dyes represented by the general formula (1) and / or the general formula (2) in an amount of 0.1% based on the total mass of the ink.
The content is preferably from 20 to 20% by mass, more preferably from 0.5 to 10% by mass. When the dyes represented by the general formulas (1) and (2) are used as a mixture, they can be used in any ratio, and the sum of the contents of the respective dyes is preferably within the above range.

The ink-jet ink of the present invention is preferably obtained by dispersing or dissolving at least one selected from the dyes represented by the general formulas (1) and (2) in an aqueous medium. The aqueous medium only needs to contain at least water, specifically, water, or
A mixture obtained by adding various additives to a mixture of water and a water-miscible organic solvent, if necessary, is preferably mentioned. In the present invention, the water used for the aqueous medium is preferably deionized water.

The ink-jet ink of the present invention preferably contains a water-soluble organic solvent. As the water-soluble organic solvent that can be used in the present invention, a water-soluble organic solvent having a lower vapor pressure than water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin And lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, and triethylene glycol monoethyl (or butyl) ether. , 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethylmorpholine and other heterocycles, sulfolane, dimethylsulfoxy , Sulfur-containing compounds such as 3-sulfolene, diacetone alcohol, diethanolamine, polyfunctional compounds such as triethanolamine are used.

The water-soluble organic solvent is preferably a water-soluble organic solvent having a lower vapor pressure than water. Among them, polyhydric alcohols such as glycerin, 1,1,1-trimethylolpropane, ethylene glycol, diethylene glycol and triethylene glycol; lower alkyl ethers of polyhydric alcohols such as diethylene glycol monobutyl ether and triethylene glycol monobutyl ether;
-Pyrrolidone, N-methyl-2-pyrrolidone, 1,3-
Heterocycles such as dimethyl-2-imidazolidinone; sulfur-containing compounds such as sulfolane, dimethylsulfoxide and 3-sulfolene; polyfunctional compounds such as diethanolamine and triethanolamine; preferred are glycerin, diethylene glycol and triethylene glycol monobutyl ether. , 2-pyrrolidone and triethanolamine are more preferred.

The ink-jet ink of the present invention preferably contains each of the water-soluble organic solvents in an amount of 0.1 to 20% by mass, more preferably 0.5 to 15% by mass. Further, the inkjet ink of the present invention includes:
The above water-soluble organic solvents may be used alone or in combination of two or more.

The ink-jet ink of the present invention preferably contains a surfactant. Examples of the surfactant that can be used in the present invention include fatty acid salts, higher alcohol ester salts, alkylbenzene sulfonate salts, sulfosuccinate ester salts, higher alcohol phosphate ester salts and the like; anionic amine salts; Cationic surfactants such as quaternary ammonium salts; Nonionic surfactants such as ethylene oxide adducts of higher alcohols, ethylene oxide adducts of alkyl phenols, ethylene oxide adducts of polyhydric alcohol fatty acid esters, and ethylene oxide adducts of acetylene glycol An amphoteric surfactant such as an amino acid type or a betaine type; Sodium dodecylbenzenesulfonate, lauryl sulfonate, sodium dioctyl sulfosuccinate, and those having an addition mole number of the ethylene oxide adduct of preferably in the range of 4 to 20,
For example, “Surfinol 440”, “Surfinol 465”, and “Surfinol 485” (all manufactured by Air Products and Chemicals) correspond thereto and can be preferably used in the present invention.

The amount of the surfactant is not limited, but is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total mass of the ink. These can be used alone or in combination of two or more.

The ink-jet ink of the present invention preferably contains urea or a urea derivative. Examples of the urea and urea derivatives include urea and alkyl ureas (for example, methyl urea, ethyl urea, N, N′-diethyl urea, ethylene urea, N, N′-dihydroxyethyl urea). As the urea or urea derivative that can be used in the present invention, urea, methyl urea, ethyl urea,
N, N'-diethyl urea, ethylene urea, N, N'-dihydroxyethyl urea are preferred, and urea is particularly preferred. The added amount of urea or a urea derivative is preferably 0.01 to 20% by mass based on the total mass of the ink.
More preferably, it is 0.1 to 10% by mass.

The ink-jet ink according to the present invention includes: prevention of clogging due to drying operation at the ink ejection port; ejection stability; compatibility with print heads and ink cartridges; storage stability; In order to further improve various performances such as image quality and image storability, anti-drying agents, penetration enhancers, ultraviolet absorbers, antioxidants, viscosity adjusters, surface tension adjusters, dispersants, dispersion stabilizers, fungicides Agent, rust inhibitor, p
Additives such as an H adjuster, an antifoaming agent and a chelating agent can be appropriately selected and used in an appropriate amount.

Examples of the penetration enhancer that can be used in the present invention include ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether,
Alcohols such as 5-pentanediol, sodium lauryl sulfate, sodium dioctyl sulfosuccinate,
The anionic surfactant of sodium oleate, the nonionic surfactant, and the like can be used. These have sufficient effects when contained in the ink in an amount of 0.1 to 20% by mass, and are more preferably used in a range of 1 to 10% by mass which does not cause printing bleeding or paper-through (print-through).

The ultraviolet absorber which can be used in the present invention to improve the image storability is described in JP-A-58-18.
Nos. 5677, 61-90537, JP-A-2-782, 5-97075, 9-
Benzotriazole compounds described in JP-A-34057, JP-A-46-2784, JP-A-5-19
No. 4483, U.S. Pat. No. 3,214,463, and the like.
Nos. 0492 and 56-21141,
0-88106, cinnamic acid-based compounds, and the like;
JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, and JP-A-10-182621
Compounds disclosed in Japanese Unexamined Patent Application Publication No. Hei 8-501291, Research Disclosure N
o. No. 24239, stilbene compounds,
A compound that absorbs ultraviolet light and emits fluorescence, typically a benzoxazole-based compound, that is, a so-called fluorescent whitening agent, can also be used.

Examples of the antioxidant that can be used in the present invention to improve the storability of an image include various organic and metal complex antifading agents. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles, and the like. Complexes and zinc complexes. More specifically, Research Disclosure No. No. 17643, Sections VII I through J; 15162; 1871
No. 6, page 650, left column. No. 36544, page 527; No. 307105, page 872; The compounds described in the patent cited in US Pat.
No. 5,272, pages 127 to 137, and the compounds represented by the general formulas and compound examples of the compounds can be used.

The fungicides which can be used in the present invention include sodium dehydroacetate, 2-phenoxyethanol, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate,
2-benzisothiazolin-3-one (for example, trade name "Proxel XL2") and salts thereof.
These are preferably contained in the ink at 0.02 to 1.00% by mass.

Examples of the pH adjuster which can be used in the present invention include hydroxides of alkali metals such as lithium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and sodium hydrogen carbonate, potassium acetate, sodium silicate and phosphoric acid. Examples include inorganic bases such as disodium and organic bases such as N-methyldiethanolamine and triethanolamine. In order to improve the storage stability of the ink, the pH is preferably from 6 to 10. More preferably, it is 7-10.

Examples of the surface tension modifier which can be used in the present invention include the above-mentioned nonionic, cationic or anionic surfactants. The surface tension of the inkjet ink of the present invention is preferably 25 to 70 mN / m with or without the use of the surface conditioner.
Further, it is preferably 25 to 60 mN / m.

The viscosity of the inkjet ink of the present invention is preferably 30 mPa · s or less. It is more preferable to adjust the pressure to 20 mPa · s or less.

In the ink-jet ink of the present invention, the above-mentioned cations and anions are used as dispersants and dispersion stabilizers.
Nonionic surfactants, fluorine-based as defoamers,
A chelating agent typified by a silicone compound or EDTA, a rust preventive typified by benzotriazole and its derivatives, and the like can be used as needed.

(Ink Jet Recording Method) The ink jet recording method of the present invention is characterized in that recording is performed using the ink for ink jet of the present invention. Examples of the recording material used in the inkjet recording method of the present invention include plain paper and resin-coated paper. For example, JP-A-8
Nos. 169172 and 8-27693, 2
JP-A-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238873, JP-A-10-153889, and JP-A-10-21
No. 7473, No. 10-235995, No. 10
-337947, 10-217597,
Ink jet paper described in JP-A-10-337947 can be used. Further, an image can be recorded on a film, electrophotographic common paper, cloth, glass, metal, ceramic, or the like.

As the recording material, those having a structure in which an ink receiving layer is provided on a support can be used. The support may be any of pulp, synthetic paper, and plastic film sheet, and paper and plastic film laminated on both sides with polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. Can be It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine, neodymium oxide) to the polyolefin.

The ink receiving layer provided on the support contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Inorganic white pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, zinc carbonate, styrene pigment, acrylic pigment, urea resin,
Organic pigments such as melamine resin and the like can be mentioned. As the white pigment contained in the ink receiving layer, a porous inorganic pigment is preferable, and in particular, synthetic amorphous silica having a large pore area is preferable.

Examples of the aqueous binder contained in the ink receiving layer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide. Water-soluble polymers such as derivatives, and water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion are exemplified. These aqueous binders can be used alone or in combination of two or more. In the present invention,
Among them, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peel resistance of the ink receiving layer.

The ink receiving layer may contain a mordant, a water-proofing agent, a lightfastness improving agent, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is
It is preferably immobilized. For this purpose, a polymer mordant is preferably used. The polymer mordant is described in JP-A-48-28325 and JP-A-54-74.
No. 430, No. 54-124726, No. 55-2276
No. 6, No. 55-142339, No. 60-23850
No. 60-23851, No. 60-23852, No. 60-23853, No. 60-57836, No. 60-
No. 60643, No. 60-118834, No. 60-12
No. 2940, No. 60-122941, No. 60-122
Nos. 942 and 60-235134, JP-A-1-161
236, U.S. Pat. Nos. 2,484,430 and 25.
No. 48564, No. 3148061, No. 3309690
Nos. 4,115,124, 4,124,386, 41
No. 93800, No. 4273853, No. 4282305
And No. 4,450,224. An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A-1-161236 is particularly preferred.

The water-proofing agent is effective for making the image water-resistant. As such a water-proofing agent, a cationic resin is particularly desirable. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethylene imine,
Examples thereof include polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable.

Examples of the light resistance improver include zinc sulfate, zinc oxide, hinderamine antioxidants, benzophenone, and benzotriazole ultraviolet absorbers.

Other additives to be added to the ink receiving layer include pigment dispersants, thickeners, defoamers, dyes, fluorescent brighteners, preservatives, pH adjusters, matting agents, hardeners, etc. Is mentioned. The ink receiving layer may be a single layer or two layers.

A back coat layer can be provided on the recording material, and a polymer latex may be added to the constituent layers (including the back layer). The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curl prevention, adhesion prevention, and film crack prevention. For polymer latex, see JP-A-62-245258.
Nos. 62-131648 and 62-110066
There is a description in each gazette of the issue. Low glass transition temperature (40
Addition of a polymer latex (below 0 ° C.) to the mordant-containing layer can prevent the layer from cracking and curling.
Also, even if a polymer latex having a high glass transition temperature is added to the back layer, curling can be prevented.

In the ink-jet recording method of the present invention, there is no limitation on the ink-jet recording method, and a known method, for example, a charge control method for discharging ink by using electrostatic attraction, a drop-on method using a vibration pressure of a piezoelectric element. A demand method (pressure pulse method), an acoustic ink jet method in which an electric signal is converted into an acoustic beam to irradiate ink to discharge ink using radiation pressure, and a pressure generated by heating ink to form bubbles and using the generated pressure For example, a thermal ink jet (bubble jet (registered trademark)) method or the like can be used.

The ink of the present invention can also be used for full-color printing using yellow, magenta, and cyan inks. The ink jet recording method uses a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving the image quality by using a plurality of inks having substantially the same hue and different densities, or a colorless transparent ink. The method is included.

[0064]

EXAMPLES The present invention will be described in detail with reference to the following examples, but embodiments of the present invention are not limited thereto. In the following description, “parts” are based on mass. <Examples 1 to 8 and Comparative Examples 1 to 3> After mixing and dissolving the following components, respectively, a membrane filter having a pore size of 0.2 μm (trade name: Astropore CASL 20 2.
5 CMD, manufactured by Fuji Photo Film Co., Ltd.) to prepare inks of Examples 1 to 8 and Comparative Examples 1 to 3.

-Ink of Example 1 Exemplified compound (11) 3.0 parts Glycerin 5.0 parts Diethylene glycol 3.0 parts 2-Pyrrolidone 1.5 parts Deionized water 87.5 parts

-Ink of Example 2 Exemplified compound (11) 0.8 parts Glycerin 3.0 parts Diethylene glycol 2.0 parts 2-Pyrrolidone 1.5 parts Deionized water 92.7 parts

Ink of Example 3 Exemplified Compound (21) 2.8 parts Glycerin 5.0 parts Diethylene glycol 2.0 parts Diethylene glycol monobutyl ether 2.0 parts Deionized water 88.2 parts

-Ink of Example 4 Exemplified Compound (21) 0.7 parts Glycerin 3.0 parts Diethylene glycol 2.0 parts Surfynol 465 1.0 parts Deionized water 93.3 parts

Ink of Example 5 Exemplified Compound (12) 3.0 parts Glycerin 4.0 parts Ethylene glycol 2.0 parts Urea 1.2 parts Deionized water 89.8 parts

Ink of Example 6 Exemplified Compound (11) 1.5 parts Exemplified Compound (21) 1.5 parts Glycerin 5.0 parts Diethylene glycol 2.0 parts Surfynol 465 1.0 parts Deionized water 89.0 Department

-Ink of Example 7 Exemplified Compound (12) 0.4 parts Exemplified Compound (24) 0.4 parts Glycerin 4.0 parts Diethylene glycol 2.0 parts Surfynol 465 1.0 parts Deionized water 92.2 Department

Ink of Example 8 Exemplified Compound (11) 3.2 parts Glycerin 5.0 parts Diethylene glycol 2.0 parts Surfynol 465 0.5 parts 1,2-Benzisothiazolin-3-one 0.1 parts Benzo Triazole 0.1 parts Deionized water 89.1 parts

The ink of Comparative Example 1 I. Acid Blue 1 3.0 parts Glycerin 5.0 parts Ethylene glycol monomethyl ether 3.0 parts Deionized water 89.0 parts

The ink of Comparative Example 2 I. Acid Blue 1 0.8 parts Glycerin 3.0 parts Diethylene glycol 2.0 parts 2-Pyrrolidone 1.5 parts Deionized water 92.7 parts

The ink of Comparative Example 3 I. Acid Blue 9 3.0 parts Glycerin 5.0 parts Diethylene glycol 3.0 parts 2-Pyrrolidone 1.5 parts Deionized water 87.5 parts

<Evaluation Test> Examples 1 to 8 obtained above.
Using each of the inks of Comparative Examples 1 to 3, printing was performed by an inkjet printer PM-770C (Seiko Epson Corporation), and (1) clogging property and (2) image storability were evaluated according to the following criteria. The results are shown in Table 1. The following four papers were used for evaluation. (A) Xerox P paper (Fuji Xerox Co., Ltd.) (B) High-grade paper (Fuji Photo Film Co., Ltd.) (C) Photo glossy paper EX (Fuji Photo Film Co., Ltd.) (D) PM photo paper ( Seiko Epson Corporation)

Evaluation Method and Evaluation Criteria (1) Clogging The printer was filled with ink, and after printing alphanumeric characters for 10 minutes continuously, printing was stopped, and after leaving for 2 weeks, nozzle clogging recovery operation Was evaluated, and the number of times of the operation was used to evaluate whether character blur and chipping disappeared. ：: Normal printing is possible with 5 or less recovery operations △: Normal printing is possible with 6 to 10 recovery operations ×: Normal printing is possible with 11 or more recovery operations (2) Image storability Obtained above Using the inks of Examples 1 to 8 and Comparative Examples 1 to 3, solid-printed samples are produced by an inkjet printer PM-770C (Seiko Epson Corporation). The density Ci immediately after printing is set to X-write 3
After the measurement at 10, the sample was irradiated with xenon light (85,000 lux) for 3 days using a weather meter manufactured by Atlas Co., and the density Cf was measured again to determine the residual dye ratio (Cf / Ci) ×
100 was sought. A, 70% if the residual pigment ratio is 70% or more
Less than 40% or more was B, and 40% or less was C. Table 1 shows the evaluation results of (1) clogging property and (2) image storability.

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[Table 1]

As is evident from the results shown in Table 1, the inks of Examples 1 to 8 had no clogging at the nozzle tip, and had stable printing performance and reliability. Examples 1 to 8
The ink of Example 1 was excellent in image storability as compared with the ink of the comparative example, both when printing on plain paper and when printing on paper dedicated to inkjet. Furthermore, when printing was performed on paper having a so-called photographic quality, in which a silica porous layer was provided on the image receiving layer, compared to printing with the ink of the comparative example,
Further improvement in image storability was observed. Further, even in the case of an ink having a low dye concentration called a photo ink, the image storability did not decrease as compared with the case where the ink of the comparative example was used.

[0080]

As described above, according to the present invention, an image having a good cyan color and excellent in storability can be formed.
In addition, it is possible to provide an ink jet recording apparatus and an ink jet recording method capable of reducing clogging at a discharge port.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2C056 EA11 EA13 FC02 2H086 BA52 BA53 BA56 BA59 4H056 BA02 BB05 BB15 BC01 BD01 BF28F BF29F CA01 CA04 CC02 CC08 CE02 CE03 DD07 4J039 BC09 BC10 BC13 BC14 BC15 BC54 BC37 BC51 BC49 BC50 BC64 BC68 BC75 BC79 BE02 BE06 BE12 BE22 EA16 EA35 EA41 EA46 FA01 FA02 FA03 FA06 GA24

Claims (5)

[Claims] 1. The following general formula (1) and the following general formula
At least one dye selected from the dyes represented by (2)
Ink-jet ink characterized by containing a pigment
H. General formula (1)(In the general formula (1), R¹And R^TwoIs a hydrogen atom,
Kill group, cycloalkyl group, aralkyl group or aryl
R¹And R^TwoAnd bond to each other to form a nitrogen atom and
In addition, a 5- or 6-membered ring may be formed. R^ThreeIs hydrogen field
, Halogen atom, lower alkyl group, lower alkoxy
Represents a group, a cyano group or a nitro group. A is a carbon atom or
Represents a nitrogen atom;¹Is a sulfonic acid group or
Salts, carboxylic acid groups or salts thereof, sulfamoyl groups,
Represents a carbamoyl group or an alkoxycarbonyl group.
X¹Is hydrogen atom, halogen atom, alkyl group, alkoxy
Group, -NHCOR^FourOr OCOR^FiveAnd R^FourAnd
And R^FiveRepresents an alkyl group or an aryl group, respectively. Y is
Represents an alkyl group or an aralkyl group, Z is a hydrogen atom,
Represents an alkyl group or an aryl group. W¹Is the counter anion
Where n1 is the number of positive charges and the negative charge in the general formula (I).
Represents a number greater than or equal to 0 required to match the numbers. ) General formula (2)(In the general formula (2), R¹¹And R¹²Is a hydrogen atom,
Alkyl, cycloalkyl, aralkyl or ant
A group represented by R¹¹And R¹²Are bonded to each other to form a nitrogen atom
May form a 5- or 6-membered ring together. R¹³Is water
Element atom, halogen atom, lower alkyl group, lower alkoxy
Represents a cyano group, a cyano group or a nitro group. B ¹¹Is a sulfo
Acid groups or salts thereof, carboxylic acid groups or salts thereof,
Sulfamoyl group, carbamoyl group or alkoxyca
Represents a rubonyl group;¹²~ B^FifteenAre hydrogen and sulf
Sulfonic acid groups or salts thereof, carboxylic acid groups or
Salt, sulfamoyl group, carbamoyl group or alkoxy
Represents a cyclocarbonyl group. X^TwoIs a hydrogen atom, a halogen atom
, An alkyl group, an alkoxy group, -NHCOR¹⁴Or
-OCOR^FifteenAnd R¹⁴And R^FifteenIs an alkyl group
Or an aryl group. R¹⁶And R¹⁷Is each ally
R or a heterocyclic residue;¹⁶And R¹⁷And connected
It may form a heterocyclic ring. W^TwoRepresents a counter anion, and n
2 is the same as the number of positive charges and the number of negative charges in the general formula (I).
Represents a number of 0 or more necessary for ) 2. The inkjet ink according to claim 1, further comprising a water-soluble organic solvent. 3. The method according to claim 1, which comprises a surfactant.
3. The ink for inkjet according to item 1. 4. The ink-jet ink according to claim 1, which contains urea or a urea derivative. 5. An ink-jet recording method using the ink-jet ink according to any one of claims 1 to 4.