JP2002121444A - Ink for ink-jet recording and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink for ink-jet recording having excellent color reproduction, light resistance and abrasion resistance and provide a method for forming an image. SOLUTION: The ink for ink-jet recording contains a dispersion of an amorphous metal chelate pigment. The image-forming method comprises the use of the ink.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet ink and an image forming method, and more particularly to an ink jet ink excellent in color reproducibility, light fastness and scratch resistance.

[0002]

2. Description of the Related Art An ink jet recording method is capable of recording a high-definition image with a relatively simple apparatus, and is rapidly developing in various fields. Ink recorded by an ink jet printer can be classified into an aqueous type and an oil type based on a difference in a main solvent composition. Oil-based inks have the advantage of good water resistance of recorded images, but they have problems such as the odor of volatile solvents, bleeding, and safety, and many of the printers currently sold are environmentally friendly. ,
Water-based ink is used for safety reasons.

[0003] In terms of coloring materials, inks using dyes and inks using pigments can be classified. Inks using dyes generally have excellent color reproducibility, but have poor light fastness. These inks had excellent light fastness, but tended to have poor color reproducibility. Further, in the ink in which the pigment is dispersed, it is difficult to sufficiently reduce the dispersion particle size, which may cause clogging of the nozzles of the printer head, poor storage stability of the ink, and poor scratch resistance after printing. There was a problem.

As one of means for improving the light fastness of a dye, a method of coordinating with a metal to form a metal chelate compound is known. For example, JP-A-10-36728 and JP-A-10-204351. JP-A-10-25157
No. 2, JP-A-10-259331, JP-A-10-259331
JP-A-61015 discloses an ink using a metal chelate dye. However, all of the dyes described therein are compounds having a water-soluble group, and the inks are of a uniform solution type. The light resistance was poor, and bleeding occurred, and the image storability was not sufficient.

[0005]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide an ink jet ink having excellent color reproducibility, light fastness and scratch resistance. A second object of the present invention is to provide an image forming method which is excellent in color reproducibility, light fastness and scratch resistance.

[0006]

The above objects of the present invention are as follows: (1) An ink jet ink containing a dispersion of an amorphous metal chelate dye. (2) The inkjet ink according to (1), wherein the amorphous metal chelate dye is dispersed in a solvent system in which the solubility of the dye is 1% or less. (3) The above (1) or (2), wherein the amorphous metal chelate dye has two or more ligands.
3. The ink for inkjet according to item 1. (4) The amorphous metal chelate dye is nickel,
The inkjet ink according to any one of the above (1) to (3), which is a copper, chromium, cobalt, zinc, aluminum or iron compound. (5) The amorphous metal chelate dye is nickel,
The inkjet ink according to any one of the above (1) to (4), which is a copper, chromium, cobalt or zinc compound. (6) The inkjet ink as described in any one of (1) to (5) above, wherein the dispersed amorphous metal chelate dye has an average particle size of 0.01 to 0.5 μm. (7) The inkjet ink according to any one of the above (1) to (6), which contains 1 to 65% of a water-soluble organic solvent. (8) An image forming method using an ink containing a dispersion of an amorphous metal chelate dye. (9) In an inkjet recording method using at least yellow, magenta, and cyan inks, at least one
An image forming method, comprising using an ink containing a dispersion of an amorphous metal chelate dye in two inks. Achieved by

Hereinafter, the present invention will be described in detail. In the present invention, a chelate dye refers to a compound in which a dye is coordinated to a metal ion at bidentate or more, but may have another ligand. In the present invention, a ligand refers to an atomic group capable of coordinating to a metal ion, and may or may not have a charge. In the present invention, the amorphous state is a solid state and does not have a specific crystal shape.
It has features such as not showing a clear diffraction pattern in line diffraction. The average particle size can be measured by, for example, a laser diffraction method, a laser scattering method, a dynamic laser scattering method, and the like. In the present invention, the Zetasizer 1000 (manufactured by Malvern) based on the dynamic laser scattering method is used. Measured using If the particle size of the dispersed particles is too large, clogging of the nozzles in the printer head is likely to occur or the ink liquid tends to settle.On the other hand, if the particle size is too small, aggregation tends to occur and the dispersion stability deteriorates. The average particle size of the dispersed particles is preferably in the range of 0.01 to 0.5 μm.

The solvent for the ink-jet ink of the present invention may be any solvent, but it is preferable to use water or a mixed solvent of water and a water-soluble solvent. As the water-soluble organic solvent used in the present invention, alcohols (for example,
Methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tert-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc., polyhydric alcohol ethers (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 Bruno ethyl ether, triethylene glycol monobutyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether), amines (e.g., ethanolamine, diethanolamine, triethanolamine, N-
Methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine,
Pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocycles (eg, 2-pyrrolidone, N-methyl-2- Pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-
Imidazolidinone), sulfoxides (eg, dimethyl sulfoxide), sulfones (eg, sulfolane), urea, acetonitrile, acetone and the like.

A specific method for preparing the ink-jet ink of the present invention is described in, for example, JP-A-5-14843.
No. 6, No. 6-29612, No. 7-9754
No. 1, No. 7-82615, No. 7-11858
Reference can be made to the method described in Japanese Patent Publication No. 4 and the like. The viscosity of the above-described inkjet ink at the temperature at the time of flight is preferably 20 mPa · s or less,
More preferably, it is not less than mPa · s and not more than 15 mPa · s. The inkjet ink of the present invention preferably has a surface tension at the time of flight of 15 mN / m or more, more preferably 20 mN / m or more and 80 mN / m or less. In the ink-jet ink of the present invention, a viscosity adjusting agent, a surface tension adjusting agent, a viscosity adjusting agent, Resistance adjuster, film forming agent, dispersant, surfactant,
UV absorbers, antioxidants, anti-fading agents, sunscreen agents, rust preventives and the like can also be added.

[0010] The ink-jet ink of the present invention may contain a surfactant, if necessary. Surfactants preferably used in the inkjet ink of the present invention include anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, and fatty acid salts, polyoxyethylene alkyl ethers, and polyoxyethylene alkyl allyl. Examples include nonionic surfactants such as ethers, acetylene glycols, and polyoxyethylene / polyoxypropylene block copolymers, and cationic surfactants such as quaternary ammonium salts. In particular, an anionic surfactant and a nonionic surfactant can be preferably used. A dispersant can be used for dispersing the dye. Preferred dispersants for the present invention include, for example, formalin condensate of creosote oil sodium sulfonate (eg, Demol C),
Sodium cresol sulfonate and 2-naphthol-6
-Formalin condensate of sodium sulfonate, formalin condensate of sodium cresol sulfonate, formalin condensate of sodium phenol sulfonate, formalin condensate of sodium β-naphthol sulfonate, formalin condensate of β-sodium naphthalene sulfonate (for example, Demol N), lignin sulfonate (for example, Vanirex RN) and the like. Examples of the polymer dispersant include copolymers of acrylic acid monomers, styrene monomers, α, β-ethylenic unsaturated carboxylic acid aliphatic alcohol ester monomers, maleic acid monomers, and fumaric acid monomers. No. For example, styrene / acrylic acid copolymer, styrene / acrylic acid / acrylic acid ester copolymer, styrene / methacrylic acid copolymer, styrene / methacrylic acid / acrylic acid ester copolymer, styrene / maleic acid copolymer, Styrene / maleic acid / acrylic ester copolymers, polyvinyl alcohol and the like are preferred. The ink-jet ink of the present invention is not particularly limited with respect to the recording method to be used, and can be preferably used as a recording liquid for continuous-type and on-demand type ink-jet printers. On-demand systems include electro-mechanical conversion systems (eg, single cavity,
Double-cavity type, bender type, piston type, shared mode type, shared wall type, etc.), electric-heat conversion method (eg, thermal ink jet type, bubble jet (registered trademark) type, etc.), electrostatic suction method (eg, Specific examples include an electric field control type, a slit jet type, and the like, and a discharge method (for example, a spark jet type).

The amorphous metal chelate dye which can be used in the present invention includes a compound represented by the following general formula (1) which is amorphous. General formula (1) M (Dye) ₁ (A) _{m In} general formula (1), M represents a metal ion, and Dye
Represents a dye capable of coordinating with a metal. A represents a ligand other than a dye, 1 represents 1 to 3, and m represents 0, 1, 2, or 3. When m is 0, 1 represents 2 or 3, in which case D
ye may be the same or different. Examples of the metal ion represented by M include metals belonging to Groups I to VIII of the periodic table, for example, Al, Co, Cr, Cu, Fe, M
n, Mo, Ni, Sn, Ti, Pt, Pd, Zr and Z
n ions. Ni, from the color tone, various durability
Particularly preferred are ions of Cu, Cr, Co, Zn, and Fe. More preferably, it is Ni ion. As the dye capable of coordinating with the metal represented by Dye, dyes having various dye structures are used, and conjugated methine dyes, azomethine dyes, and dyes having a coordination group in the azo dye skeleton are preferable. In particular, the following general formulas (2) to
The dye represented by (7) is preferred.

[0012]

Embedded image In the general formulas (2) to (7), X is a group that forms a dye via a conjugated system, and has an atomic group that can coordinate to a monodentate to tridentate metal ion. Examples of the atomic group capable of coordinating with a metal ion include N, S, O bonded to an aromatic ring.
There is a substituent having an atom or a heterocyclic ring.

Examples of the substituent having N, S and O atoms include primary, secondary and tertiary amines (for example, amino group, methylamino group, dimethylamino group, diethylamino group, etc.), Examples thereof include a mercapto group, a thioether group, a hydroxy group, a carboxy group, a carbonyl group, and a sulfo group. Examples of the heterocycle include a pyridine ring, a pyrimidine ring, a furan ring, a thiophene ring, a thiazole ring, an imidazole ring, a 3H-pyrrole ring, an oxazole ring, a 3H-pyrrolidine ring, an oxazolidine ring, an imidazolidine ring, and a thiazolidine ring. 3H-indole ring,
Benzoxazole ring, benzimidazole ring, benzthiazole ring, quinoline ring, isoquinoline ring, indolenine ring, barbitur ring, thiobarbitur ring, rhodanine ring, hydantoin ring, pyrazolidinedione ring, pyridinedione ring, pyrazolone ring, And pyrazolotriazole rings. Y represents an atomic group forming a 5- or 6-membered aromatic carbocyclic or heterocyclic ring. Specific examples of the aromatic carbocycle or heterocycle include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, a furan ring, a thiophene ring, a thiazole ring, an imidazole ring, a naphthalene ring, a 3H-pyrrole ring, an oxazole ring, and 3H. -Pyrrolidine ring, oxazolidine ring, imidazolidine ring, thiazolidine ring, 3H-indole ring, benzoxazole ring, benzimidazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, indolenine ring, barbitur ring, thiobarbitur ring, Examples include a rhodanine ring, a hydantoin ring, a pyrazolidinedione ring, and a pyridinedione ring.

These rings may further form a condensed ring with another carbon ring (for example, a benzene ring) or a heterocyclic ring (for example, a pyridine ring). Further, these rings may further have a substituent, as these substituents, for example,
Examples include an alkyl group, an aryl group, an acyl group, an amino group, a nitro group, a cyano group, an acylamino group, an alkoxy group, a hydroxy group, an alkoxycarbonyl group, and a halogen atom. Further, these groups may be further substituted. Y may further have a coordinable group.
The ligand other than the dye represented by A may be an anion or a neutral molecule. Examples of the anion include a halide ion, a hydroxy ion, and a nitrate ion.
Inorganic anions such as cyano ion, thiocyanate ion, peroxo ion, azide ion, carbonate ion, sulfate ion, tetrafluoroboron ion, acetic acid, oxalic acid, maleic acid, succinic acid, acetylacetone, salicylaldehyde, glycine, ethylenediamine diacetic acid, Ethylenediaminetetraacetic acid, benzoic acid, p-toluenesulfonic acid, phenol, phthalic acid, picolinic acid, thiophenol, anion of dithiolbenzene and the anion of a derivative thereof, and neutral molecules such as ammonia, water, Triphenylphosphine, 1,3
-Propanediamine, 2,2'-bipyridine, 1,10
- phenanthroline, glycinamide, diethylenetriamine, 2,2 ', 2 "-. Terpyridyl, triethylenetetramine, etc. ethylenediamine general formula (2) ~ (4), R 1, R 2, R 3 is a hydrogen atom , A halogen atom or a monovalent substituent;
Or 2 is represented. Hereinafter, specific examples of the dye capable of coordinating with the metal represented by Dye will be described, but the present invention is not limited thereto.

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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The following are specific examples of ligands other than the dye represented by A, but the present invention is not limited thereto.

[0023]

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[0024]

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[0025]

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[0026]

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The following are specific examples of the chelate dye used in the present invention, but the present invention is not limited thereto. Illustration number chelate dye composition Y-1 Ni (D-7 ) 1 (A-27) 2 Y-2 Ni (D-7) 1 (A-31) 2 Y-3 Ni (D-7) 1 (A- _{32) 2 Y-4 Ni (} D-8) 1 (A-32) 2 Y-5 Ni (D-8) 1 (A-22) 1 Y-6 Ni (D-8) 1 (A-29) _{2 Y-7 Ni (D-} 1) 2 (A-21) 1 Y-8 Ni (D-3) 2 (A-17) 1 Y-9 Cu (D-7) 1 (A-19) 1 Y _{-10 Cu (D-7) 1} (A-31) 2 Y-11 Co (D-8) 1 (A-27) 2 M-1 Ni (D-26) 1 (A-32) 2 M-2 _{Ni (D-25) 1 (} A-29) 2 M-3 Ni (D-27) 1 (A-31) 2 M-4 Ni (D-20) 2 (A-13) 1 M-5 Ni ( _{D-22) 2 (A-} 24) 1 M-6 Ni (D-30) 1 (A-32) 2 M-7 Ni (D-31) 2 (A-8) 1 M-8 Ni ( _{-32) 1 (A-19)} 1 M-9 Ni (D-32) 1 (A-27) 2 M-10 Ni (D-33) 1 (A-22) 1 M-11 Ni (D-34 ) ₁ (A-15) ₁ M-12 Cr (D-35) ₁ (A-20) ₁ M-13 Cu (D-26) ₁ (A-31) ₂ M-14 Ni (D-30) ₁ (A-18) ₁ M-15 Ni (D-27) ₁ (A-22) ₁ M-16 Ni (D-25) ₁ (A-8) ₂ M-17 Co (D-28) ₁ (A -19) ₁ C-1 Ni (D-51) ₁ (A-18) ₁ C-2 Ni (D-50) ₂ (A-30) ₂ C-3 Ni (D-54) ₂ (A-19) ) ₁ C-4 Ni (D-55) ₁ (A-32) ₂ C-5 Ni (D-38) ₁ (A-53) ₁ C-6 Ni (D-41) ₂ C-7 Cu (D _{-51) 1 (A-49)} 1 C-8 Ni (D-49) 2 (A-52) 1 C-9 Cu (D-51) 1 (A- _{5) 2 C-10 Ni (} D-53) 2 (A-38) 1

The above-mentioned chelate dye composition is represented by the general formula (1) M (Dye) ₁ (A) _m M: metal atom Dye: an exemplary compound number of a dye capable of coordinating with a metal l: the number of Dye A : Exemplified compound number of ligand other than dye m: Number of A Based on the notation, when the ionizable group in each molecule dissociates to form an ionic bond with a metal, examples of each element It shall show a structure from which a proton has been removed from the compound. The chelated black dye can be obtained by appropriately mixing a chelate dye such as yellow, magenta, and cyan.

[0029]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

[Synthesis of Metal Chelate Dye] Synthesis of Exemplified Compound M-1 D-26 and metal compound Ni (A-32) ₂ were stirred at a ratio of 1: 1 in acetone at room temperature for 3 hours, and then the solvent was added. Was distilled off under reduced pressure to obtain Exemplified Compound M-1. X of the obtained M-1
A line structure analysis was performed, but no clear diffraction pattern was obtained. Example 1 (Dispersion liquid 1) Exemplified compound M-1 20 parts Joncryl 70 (manufactured by Johnson Polymer) 10 parts Nonipol 700 (Sanyo Kasei) 10 parts Glycerin 10 parts Ethylene glycol 20 parts Ion-exchanged water 30 parts Zeta LMZ-2 filled with 0.3% zirconia beads at 90% by volume
(Ashizawa), and coarse particles were removed by centrifugation to obtain a dispersion having an average particle diameter of 140 nm. [Ink Preparation] Using the above dispersion liquid 1, an ink liquid having the following composition was prepared. (Ink 1) (Invention) Dispersion 1 20 parts Ethylene glycol 8 parts Glycerin 3 parts Nonipol 700 0.3 parts Proxel GX-L 0.2 parts Ion-exchanged water 65 parts

(Ink 2) (Comparative) Water-soluble chelate dye M 3 parts Ethylene glycol 15 parts Glycerin 7 parts Ion-exchanged water 75 parts

(Ink 3) (Comparative) Pigment Pigment Red 122 3 parts Ethylene glycol 22 parts Glycerin 3 parts Nonipol 700 0.4 parts Proxel GX-L 0.2 parts Ion-exchanged water 72 parts

(Ink 4) (Comparison) Water-soluble dye C.I. I. Acid Red 289 3 parts Ethylene glycol 22 parts Glycerin 3 parts Deionized water 72 parts

<< Evaluation of Ink >><ColorReproducibility> The prepared ink was subjected to MJ-80 manufactured by Epson Corporation.
Printing was performed on Konica PhotoJet Paper QP using a 0C printer, and the following three levels were evaluated based on the saturation at a density of 1.0. ：: C ^* ≧ 70 Δ: 65 ≦ C ^* <70 ×: C ^* <65 C ^* = (a ^{* 2} + b ^{* 2} ) ^1/2 <light resistance> Remaining rate after irradiation with a 70000 lux xenon fade meter for 120 hours Was measured and evaluated in three steps based on the following criteria. ：: 80% or more △: 50% to 80% ×: 50% or less <Scratch resistance> Solid printing of 15 cm x 24 cm was performed with the above printer, and after sufficient drying, flatness was maintained so that the image would be on the surface. An instrument in which a 2 kg load was applied to a plate (3 cm square) attached to a disinfected gauze and attached to a disinfected gauze was applied to the image surface, and the image surface was mechanically rubbed 100 times. The dye remaining rate (%) was determined from the reflection densities (average values at three points) of the image before and after rubbing, and evaluated on a three-point scale. ：: 95% or more Δ: 90% to 95% ×: 90% or less Table 1 shows the obtained results.

[0035]

[Table 1]

[0036]

According to the ink-jet ink of the present invention, an image having high chroma, good light fastness and good scratch resistance can be obtained.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 2C056 EA13 FC02 2H086 BA52 BA55 BA60 4H056 CA01 CC02 CC08 CE02 CE03 DD06 FA01 4J039 BC59 BE01 BE12 BE22 CA06 EA35 EA36 EA42 EA47 GA24

Claims (9)

[Claims] 1. An ink-jet ink comprising a dispersion of an amorphous metal chelate dye. 2. The ink-jet ink according to claim 1, wherein the amorphous metal chelate dye is dispersed in a solvent system having a solubility of the dye of 1% or less. 3. The ink-jet ink according to claim 1, wherein the amorphous metal chelate dye has two or more ligands. 4. The ink-jet ink according to claim 1, wherein the amorphous metal chelate dye is a nickel, copper, chromium, cobalt, zinc, aluminum or iron compound. 5. The ink-jet ink according to claim 1, wherein the amorphous metal chelate dye is a nickel, copper, chromium, cobalt or zinc compound. 6. The inkjet ink according to claim 1, wherein the dispersed amorphous metal chelate dye has an average particle size of 0.01 to 0.5 μm. 7. The ink-jet ink according to claim 1, comprising 1 to 65% of a water-soluble organic solvent. 8. An image forming method using an ink containing a dispersion of an amorphous metal chelate dye. 9. An image forming method using at least a yellow, magenta, and cyan ink, wherein an ink containing a dispersion of an amorphous metal chelate dye is used as at least one ink.