JP2000169778A - Ink for ink jet and ink jet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make formable an image good in hue and excellent in fastness and fixability on an image receiving material by incorporating a basic polymer having a side chain containing an amino group or the like into a water-base ink for ink jet containing a dyestuff and an aqueous medium. SOLUTION: In an aqueous medium comprising water or water and at least two water-miscible organic solvents, 0.1-30 wt % of a dyestuff and 0.1-50 wt.%, preferably 0.1-20 wt.%, of a basic polymer having a wt. average mol.wt. of 1,000-100,000, preferably 5,000-50,000, comprising a recurring unit of the formula and having a side chain containing a tertiary amino group, a quaternary ammonium group or a nitrogen-containing heterocyclic group so that the amount of the tertiary amino group, the quaternary ammonium group or the nitrogen- containing heterocyclic group is 0.1-10 mol% relative to 1 mole of the dyestuff are blended. In the formula, R is H or methyl; L is a divalent linking group selected among a single bond, -CO-, -O-, alkylene and arylene; Am is a tertiary amino, organic ammonium or nitrogen-containing heterocyclic group.

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 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, an aqueous 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 has excellent fastness to air, water and chemicals, has good fixability to image receiving materials and does not easily spread, has excellent storage stability as ink, has no toxicity, and has high purity. It is required to be available at low cost. The above requirements are not only required when using not only an image receiving material designed exclusively for inkjet (for example, paper dedicated to inkjet) but also a commercially available image receiving material (for example, high quality paper for copying or recycled paper). . An important feature of the ink jet recording method is that an image can be recorded without using a dedicated image receiving material. Therefore, even if it is an ink-jet ink that can record a clear image on a dedicated image-receiving material, if the ink-jet image recording material on the market can record only an unclear image, the ink will have a low evaluation. Therefore, the hue is good for various kinds of image receiving materials,
A general-purpose inkjet ink capable of recording an image having excellent fastness and fixability has been demanded.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a general-purpose ink-jet ink capable of recording an image having a good hue and having excellent fastness and fixability on various kinds of image-receiving materials. is there. Another object of the present invention is to provide a general-purpose ink jet recording method capable of recording an image having good hue and excellent in fastness and fixability on various kinds of image receiving materials.

[0005]

The object of the present invention has been attained by the following ink-jet inks (1) to (8) and the ink-jet recording method (9). (1) An aqueous ink-jet ink containing a dye and an aqueous medium, further containing a basic polymer, wherein the basic polymer has a side chain containing a tertiary amino group, a quaternary ammonium group or a nitrogen-containing heterocyclic group. An ink-jet ink characterized by the following. (2) The inkjet ink according to (1), wherein the basic polymer contains a repeating unit represented by the following formula (I):

[0006]

Embedded image

Wherein R is a hydrogen atom or methyl; L is a single bond or a divalent linking group selected from —CO—, —O—, an alkylene group, an arylene group and a combination thereof. And Am is a tertiary amino group, a quaternary ammonium group or a nitrogen-containing heterocyclic group]. (3) The basic polymer has a nitrogen-containing heterocyclic group (1)
3. The ink for inkjet according to item 1. (4) The nitrogen-containing heterocyclic group is 1-imidazolyl (3)
3. The ink for inkjet according to item 1. (5) The inkjet ink according to (1), wherein the basic polymer has a weight average molecular weight (Mw) of 1,000 to 100,000. (6) The ink jet ink according to (1), wherein the basic polymer is contained in an amount ranging from 0.1 to 50% by weight. (7) The inkjet ink according to (1), which has a viscosity of 50 cp or less at 25 ° C. (8) The inkjet ink according to (1), wherein the dye is an azomethine dye or an azo dye. (9) An ink jet recording method for recording an image on an image receiving material by ejecting the ink for ink jet described in (1) to (8) above in the form of droplets.

[0008]

The present inventor has succeeded in obtaining a general-purpose ink-jet ink by adding a basic polymer known as an additive of an image-receiving material to the ink-jet ink. The basic polymer added to the image receiving material functions as a mordant (see JP-A-10-2175).
No. 97). In the ink jet recording method, since ink droplets are ejected from a nozzle, the ink jet ink is required to have a low viscosity. for that reason,
Adding polymers to inkjet inks
Little was considered. However, the present inventor has studied in detail that even if a basic polymer that functions as a mordant is added to the inkjet ink, the inkjet recording method, particularly the ejection of ink droplets from the nozzles, is unexpectedly adversely affected. I was not able to admit. For the above reasons, according to the present invention, images having good hue, excellent in fastness and excellent in fixability can be recorded on various types of image receiving materials.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The ink-jet ink of the present invention is characterized by containing a basic polymer. The basic polymer has a side chain containing a tertiary amino group, a quaternary ammonium group or a nitrogen-containing heterocyclic group.

[0010] tertiary amino groups are defined by -NR _2.
R is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group or a substituted aryl group. Alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl are preferred, alkyl, substituted alkyl, alkenyl or substituted alkenyl are more preferred, alkyl or substituted alkyl is more preferred, Alkyl groups are most preferred. Two Rs may be different from each other.

The alkyl group preferably has a chain structure rather than a cyclic structure. The chain alkyl group may have a branch. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 12,
Most preferably, it is 1 to 10. The alkyl part of the substituted alkyl group is the same as the above-mentioned alkyl group. Examples of the substituent of the substituted alkyl group include hydroxyl, cyano and aryl groups. The alkenyl group preferably has a chain structure rather than a cyclic structure. The chain alkenyl group may have a branch. The alkenyl group preferably has 2 to 20 carbon atoms, more preferably has 2 to 15 carbon atoms, further preferably has 2 to 12 carbon atoms, and most preferably has 2 to 10 carbon atoms. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group. Examples of the substituent of the substituted alkenyl group are the same as the examples of the substituent of the substituted alkyl group. The alkynyl group preferably has a chain structure rather than a cyclic structure. The chain alkynyl group may have a branch. The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms,
It is more preferably from 2 to 12, and most preferably from 2 to 10. The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. Examples of the substituent of the substituted alkynyl group are the same as the examples of the substituent of the substituted alkyl group.

A quaternary ammonium group is defined by -N ⁺ R ₃ . R represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group,
It is a substituted alkynyl group, an aryl group or a substituted aryl group. Alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, alkynyl groups, substituted alkynyl groups, aryl groups or substituted aryl groups are preferred, and alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, alkynyl groups or substituted alkynyl groups are preferred. Is more preferable, an alkyl group, a substituted alkyl group, an alkenyl group or a substituted alkenyl group is further preferable, an alkyl group or a substituted alkyl group is still more preferable, and an alkyl group is most preferable. The three Rs may be different from each other.
The definitions and examples of the alkyl group, the substituted alkyl group, the alkenyl group, the substituted alkenyl group, the alkynyl group and the substituted alkynyl group are the same as the definition and the examples of R of the tertiary amino group. The quaternary ammonium group may have an anion as a counter ion. Examples of the anion include a halide ion and a sulfonate ion.

The heterocyclic ring of the nitrogen-containing heterocyclic group is preferably a 5- or 6-membered ring, more preferably a 5-membered ring. The heterocyclic ring may contain a heteroatom other than a nitrogen atom (eg, an oxygen atom, a sulfur atom). However, a heterocyclic ring having only a nitrogen atom as a hetero atom is preferable. Unsaturated heterocycles are preferred over saturated heterocycles, and unsaturated heterocycles having the most double bonds are particularly preferred. The number of nitrogen atoms contained in the 5- or 6-membered heterocyclic ring is 1 or 2
It is preferred that The most preferred nitrogen-containing heterocyclic ring is an imidazole ring, and the most preferred nitrogen-containing heterocyclic group is 1
-Imidazolyl. The nitrogen atom contained in the heterocycle is
It may be in the state of ammonium ion. The nitrogen atom in an ammonium ion state may have an anion as a counter ion. Examples of the anion include a halide ion and a sulfonate ion.

The basic polymer preferably contains a repeating unit represented by the following formula (I).

[0015]

Embedded image

In the formula (I), R is a hydrogen atom or methyl. In the formula (I), L is a single bond or a divalent linking group selected from —CO—, —O—, an alkylene group, an arylene group, and a combination thereof. Examples of the divalent linking group by the combination include -arylene group-alkylene group- and -CO-O-alkylene group- (bonded to the main chain on the left side, and bonded to Am on the right side). In the formula (I), Am is a tertiary amino group,
It is a quaternary ammonium group or a nitrogen-containing heterocyclic group. The definitions and examples of the tertiary amino group, quaternary ammonium group and nitrogen-containing heterocyclic group are as described above. Hereinafter, examples of the repeating unit represented by the formula (I) are shown.

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

As the basic polymer, a homopolymer comprising only the repeating unit represented by the formula (I) can be used. Further, a copolymer obtained by combining two or more kinds of the repeating units represented by the formula (I) may be used. Further, a copolymer comprising a repeating unit represented by the formula (I) and another repeating unit may be used. However,
The copolymer preferably contains at least 20 mol%, more preferably at least 40 mol%, and more preferably at least 50 mol% of the repeating unit represented by the formula (I). Is more preferred, and most preferably at least 60 mol%. The following shows examples of other repeating units.

[0022]

Embedded image

The following are specific examples of the basic polymer.
The number of the repeating unit means mol%.

[0024] A-1 :-( I-1) 100 - A-2 :-( I-2) 100 - A-3 :-( I-2) 90 - (II-1) 10 - A-4: _{- (I-3) 100 -} A-5 :-( I-4) 100 - A-6 :-( I-3) 50 - (I-5) 50 - A-7 :-( I-3) 50 _{- (II-2) 50 -} A-8 :-( I-3) 75 - (II-3) 25 - A-9 :-( I-3) 60 - (I-5) 30 - (II-3 ) ₁₀
- A-10 :-( I-3 ) 60 - (II-4) 40 - A-11 :-( I-4) 80 - (II-5) 15 - (II-1)
_{5 - A-12 :-( I-} 6) 100 - A-13 :-( I-7) 100 - A-14 :-( I-3) 90 - (I-7) 10 - A-15: - (II-6) _50- (I-8) _25- (I-9)
_{25 - A-16 :-( II-} 5) 50 - (I-3) 35 - (I-10)
₁₅ -A-17:-(I-11) ₁₀₀ -A-18:-(I-12) ₁₀₀ -A-19:-(I-13) ₁₀₀ -A-20:-(I-14) _47.5- (II-5) _47.5- (II-
1) ₅ -A-21:-(I-15) _47.5- (II-5) _47.5- (II-)
_{1) 5 - A-22 :-(} I-16) 95 - (II-1) 5 - A-23 :-( I-3) 70 - (I-5) 30 - A-24 :-( II- 5) _50- (I-3) _35- (I-10)
₁₅ −

Two or more basic polymers may be used in combination. Preferably, the basic polymer has a weight average molecular weight of 1,000 to 100,000 or less.
More preferably, it has a weight average molecular weight of from 50,000 to 50,000.

The above basic polymers are known as polymer mordants. Polymer mordants having a tertiary imidazole ring are described in U.S. Pat. Nos. 4,282,305, 4,115,124 and 31,48061, and JP-A-60-118834 and JP-A-60-12294.
There is a description in each of the publications. A polymer mordant having a quaternary imidazolium group is disclosed in GB 205610.
No. 1, No. 2093041, No. 1594961, U.S. Pat. Nos. 4,124,386, 4,115,124 and 427
3853 and 4450224 and JP-A-48-28325. A polymer mordant having a quaternary ammonium group is disclosed in US Pat.
Nos. 709,690, 389,088, 395,899
No. 5, No. 5, JP-A-60-57836, and JP-A-60-57836.
No. 0-60643, No. 60-122940, No. 60-
Nos. 122294 and 60-235134. For a polymer mordant having a pyridine ring or a pyridinium group, US Pat. No. 2,548,564,
No. 2484430, No. 3148161, No. 3756
No. 814, each of which is described. For a polymer mordant capable of crosslinking with gelatin, see US Pat. No. 3,625,694.
No. 3,859,096, No. 4,128,538 and British Patent No. 1,277,453. Aqueous sol-type mordants are described in US Pat.
Nos. 7,980,63 and 3,598,995 and JP-A-54-26027, JP-A-54-115228,
It is described in each gazette of JP-A-54-145529. Reactive mordants covalently linked to dyes are described in US Pat.
No. 8976 and JP-A-54-137333. For other polymer mordants,
U.S. Pat. Nos. 2,675,316, 2,882,156 and 3,
No. 271147, No. 3271148, No. 348870
No. 6, No. 3557066, No. 36442482, No. 3
Nos. 709690 and 3788855 and JP-A-50-71332, 53-30328, 52-155528, 53-125 and 53-1.
No. 024.

The ink-jet ink preferably contains the basic polymer in an amount of 0.1 to 50% by weight, more preferably 0.1 to 20% by weight. The amount of the basic functional group (tertiary amino group, quaternary ammonium group or nitrogen-containing heterocyclic group) is 0.1 to 10 per mole of the dye.
It is preferably used in a molar amount, more preferably 1 to 50 mol. The inkjet ink containing a basic polymer preferably has a viscosity of 50 cp or less at 25 ° C.
More preferably, it has a viscosity of p or less.

The ink-jet ink further contains a dye. The basic polymer of the present invention is particularly effective when the dye is an azomethine dye or an azo dye. Azomethine dyes are dyes having a basic structure consisting of a heterocyclic ring = N-aromatic ring. An azo dye is a dye having a basic structure consisting of a heterocyclic ring or an aromatic ring (preferably a heterocyclic ring) -N = N-aromatic ring.

Preferred azomethine dyes are represented by the following formulas (III) and (IV).

[0030]

Embedded image

In the formulas (III) and (IV), R ¹ and R ³ each independently represent a hydrogen atom, a halogen atom,
Alkyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group,
Cyano group, amide group, sulfonamide group, ureido group,
An alkoxycarbonylamino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, an amino or an alkylamino group. The benzene ring contained in each of the above groups includes a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a cyano, an amide group, a sulfonamide group, a ureido group, and an alkoxy group. It may have a substituent selected from the group consisting of carbonylamino, alkylthio, arylthio, alkoxycarbonyl, carbamoyl, sulfamoyl, sulfonyl, acyl, amino and alkylamino. In the formulas (III) and (IV), m is 0, 1, 2, 3, or 4. When m is 2 to 4, a plurality of R ³ are
They may be different from each other. In formula (III) and (IV), X, Y and Z are each independently, = N-or = CR ² - it is. R ² represents a hydrogen atom, an alkyl group,
A cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy group or an aryloxy group. X
And both Y and Z are ＣＲCR ² —, then two R ^{2 s} may combine to form a ring.

In the formula (III), M is a hydrogen atom, dissociation
Inorganic base, primary amine, secondary amine or primary
3 amines. In the formula (IV), R^FourAnd R
^FiveIs independently a hydrogen atom, an alkyl group,
An alkyl group, an aralkyl group or an aryl group,
Alternatively, R ^FourAnd R^FiveAnd combine to form a ring. Ma
R^ThreeAnd R^FourOr R^ThreeAnd R^FiveCombine to form a ring
It may be. Azo represented by formulas (III) and (IV)
Methine dyes use strong hydrophilic groups such as sulfo as substituents.
It is preferable to have it. Sulfo is dissociated
Is preferred, and more preferably in a salt state.
Alkali metals are used as counterions for forming salts with sulfo.
Ions are preferred.

Preferred azo dyes are represented by the following formulas (V) and (VI).

[0034]

Embedded image

In the formulas (V) and (VI), R ⁶ , R
⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl, nitro, amino, an alkylamino group, an alkoxy group. Group, aryloxy group, amide group, arylamino group,
Ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group,
Sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group,
Aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphoryl group, acyl group,
Carboxyl or sulfo. R ⁸ and R ⁹ may combine to form an aromatic ring or a hetero ring. In the formulas (V) and (VI), R ¹⁰ is an unsaturated heterocyclic group. The unsaturated hetero ring is preferably a 5- or 6-membered ring, more preferably a 5-membered ring. The unsaturated hetero ring preferably has the most double bonds. As the hetero atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom and a sulfur atom are more preferable. A benzene ring or another hetero ring may be fused to the unsaturated hetero ring.

In the formula (V), M is a hydrogen atom, dissociation
Inorganic base, primary amine, secondary amine or primary
3 amines. In the formula (VI), R^FourAnd R
^FiveIs independently a hydrogen atom, an alkyl group,
An alkyl group, an aralkyl group or an aryl group,
Alternatively, R ^FourAnd R^FiveAnd combine to form a ring. Ma
R^ThreeAnd R^FourOr R^ThreeAnd R^FiveCombine to form a ring
It may be. Azo represented by formulas (V) and (VI)
Dyes have strong hydrophilic groups such as sulfo as substituents.
Is preferred. Sulfo is preferably dissociated
More preferably, it is in a salt state. Sulfo
Alkali metal ions as counter ions that form salts with
Is preferred.

Hereinafter, specific examples of the azomethine dye and the azo dye will be described.

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

Azomethine dyes and azo dyes are described in JP-A-11-158422 and JP-A-11-17218.
There is a description in each gazette of No. 3.

Two or more azomethine dyes or azo dyes may be used in combination. An azomethine dye or an azo dye and another dye may be used in combination. An azomethine dye or an azo dye mainly shows a magenta or cyan hue. In order to obtain a color image, it is preferable to use a dye having a yellow hue in addition to the azomethine dye or the azo dye. The dye having a yellow hue is described in JP-A-10-95942. It is preferable that the dye is contained in the inkjet ink in a range of 0.1 to 30% by weight.

The medium of the aqueous ink is mainly water. A mixture of water and a water-miscible organic solvent may be used. Examples of water-miscible organic solvents include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (Eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol Alcohol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monomethyl ether Ethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine,
N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, sulfolane) , 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2
-Oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone).

In addition to water, two or more water-miscible organic solvents may be used in combination. An aqueous ink can be prepared by dissolving the dye in an aqueous solvent (water or a mixed solvent of water and a water-miscible organic solvent). A dye may be dispersed in an aqueous solvent to prepare an aqueous ink. In the dispersion, it is preferable to use a disperser (eg, a ball mill, a sand mill, an attritor, a roll mill, an agitator mill, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a jet mill, an ang mill) to convert the dye into fine particles. . After dissolving the dye in an organic solvent, the solution may be emulsified in an aqueous solvent. In emulsification, a suitable dispersant (emulsifier) or surfactant can be used. Methods for preparing aqueous inkjet inks are described in JP-A-5-148436, JP-A-5-295512, and JP-A-7-9-9.
No. 7541, No. 7-82515, No. 7-118584
There is a description in each gazette of the issue.

Examples of organic solvents include alcohols (eg, ethanol, pentanol, heptanol, octanol,
Cyclohexanol, benzyl alcohol, phenethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, anis alcohol), glycols (eg,
Ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene Glycol monoethyl ether, ethylene glycol diacetate, ethylene glycol monoethyl ether acetate, propylene glycol diacetate), ketone (eg, benzyl methyl ketone, diacetone alcohol, cyclohexanone), ether (eg, butyl phenyl ether, benzyl ethyl) Ether, dihexyl ether), ester (eg, ethyl acetate Amyl acetate, benzyl acetate, phenylethyl acetate, phenoxyethyl acetate, phenylethyl acetate, benzyl propionate, ethyl benzoate, butyl benzoate, ethyl laurate, butyl laurate, isopropyl myristate, isopropyl palmitate, triethyl phosphate, Tributyl phosphate, diethyl phthalate, dibutyl phthalate, diethyl malonate, dipropyl malonate, diethyl diethyl malonate, diethyl succinate, dibutyl succinate, diethyl glutarate, diethyl adipate, dibutyl adipate, di-2 adipate −
Methoxyethyl, diethyl sebacate, diethyl maleate, dibutyl maleate, dioctyl maleate, diethyl fumarate, dioctyl fumarate, 3-hexenyl cinnamate), hydrocarbon solvents (eg, petroleum ether, petroleum benzyl, tetralin, decalin) , 1-amylbenzene,
Dimethylnaphthalene) and other polar solvents (eg, acetonitrile, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, sulfolane, propylene carbonate, N-
Methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-diethyldodecaneamide). Two or more organic solvents may be used as a mixture.

Various additives can be used in the ink-jet ink as required. Examples of additives include viscosity adjusters, surface tension adjusters, specific resistance adjusters, film adjusters, ultraviolet absorbers, antioxidants, anti-fading agents, fungicides, rust inhibitors, dispersants and surfactants. Agent included. The additives for ink are described in JP-A-10-95942. As for the anti-fading agent and the ultraviolet absorber, JP-A-1-13546 and JP-A-1-159655,
It is described in the respective publications of JP-A-1-171887. The ink for inkjet has a surface tension of 20 to 100 dyn /
cm.

In order to form a full-color image, magenta tone ink, cyan tone ink and yellow tone ink can be used. Further, in order to adjust the color tone, a black color tone ink may be further used. As the inkjet recording paper, it is desirable to use coated paper from the viewpoints of image quality and image storage durability. Also,
An image receiving material containing an inorganic pigment can be used. Examples of inorganic pigments include silica pigments, alumina pigments, titanium dioxide pigments, zinc oxide pigments, zirconium oxide pigments, mica iron oxide, lead white, lead oxide pigments, cobalt oxide pigments, strontium chromate, molybdenum pigments, smectite, Includes magnesium oxide pigments, calcium oxide pigments, calcium carbonate pigments and mullite. Two or more types of inorganic pigments may be used in combination. The image receiving material of the ink jet recording method preferably has a hydrophilic layer containing a hydrophilic binder as an ink receiving layer. It is preferable to use a superabsorbent polymer as the hydrophilic binder. Examples of hydrophilic binders include gelatin, gelatin derivatives, polyvinyl alcohol, polyvinyl alcohol derivatives, polyalkylene oxides and polyalkylene oxide derivatives. The hydrophilic binder is described in JP-A-1-161236, 215-222.
There is a description on the page.

The image receiving material of the ink jet recording method preferably contains a matting agent. Matting agents are described in JP-A-1-161236, pages 263 to 264. The ink receptive layer provided on the image receiving material in the ink jet recording method is preferably cured with a hardener.
The hardener is described in JP-A-1-161236.
It is described on page 22. A surfactant may be added to the constituent layer of the image receiving material in the ink jet recording method. The surfactant functions as a coating aid, a release improver, a slipperiness improver, or an antistatic agent. Surfactants are described in JP-A Nos. 62-173463 and 62-18345.
No. 7 describes each. An organic fluoro compound may be used instead of the surfactant. Preferably, the organic fluoro compound is hydrophobic. Examples of the organic fluoro compound include a fluorinated surfactant, an oily fluorinated compound (eg, fluorinated oil), and a solid fluorinated compound resin (eg, an ethylene tetrafluoride resin). Regarding the organic fluoro compound, Japanese Patent Publication No. 57-9053 (No.
17 column), JP-A-61-20994, 62-135
No. 826 is described in each publication.

A polymer latex may be added to the constituent layers (including the back layer) of the image receiving material. 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-62-2452.
No. 58, No. 62-136648, No. 62-1100
No. 66 describes each of the publications. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to the layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the back layer. An anti-fading agent may be added to the constituent layer of the image receiving material. Anti-fading agents include antioxidants, UV absorbers and metal complexes. The anti-fading agent is described in JP-A-1-16112.
No. 36, pages 225 to 247. A fluorescent whitening agent may be added to the image receiving material. A fluorescent whitening agent can be added to the ink and supplied to the image receiving material from the outside.

As the support of the image receiving material, paper and plastic films laminated on both sides with a polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are particularly preferably used. 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 polyolefin. Ink jet recording methods include a continuous method and an on-demand method. Ink jet head methods include bubble jet method,
There are a thermal jet method and a method using ultrasonic waves. Ink jet recording methods include a method of ejecting a large number of low density inks called photo inks in small volumes,
A method of improving image quality by using a plurality of inks having substantially the same hue and different densities, and a method of using colorless and transparent ink are included. The present invention is particularly effective in an ink jet recording system in which a large amount of ink having a high print speed and a low density is ejected to form an image close to a photograph.

[0071]

EXAMPLES [Comparative Example 1] (Preparation of aqueous inkjet ink)
After stirring for 1 hour while heating at 0 to 40 ° C., the mixture was subjected to pressure filtration using a microfilter having an average pore diameter of 0.8 μm and a diameter of 47 mm to prepare an aqueous inkjet ink.
The viscosity of the ink was 5 cp at 25 ° C.

組成 Ink liquid composition────────ア ゾ The following azo dye (VII) 4 parts by weight Diethylene glycol 9 parts by weight Tetraethylene glycol monobutyl ether 9 parts by weight Parts glycerin 7 parts by weight diethanolamine 1 part by weight water 70 parts by weight ────────────────────────────────────

[0073]

Embedded image

(Image Recording and Evaluation) An ink jet printer (PM-700C,
Images were recorded on photo glossy paper (Super Photo Grade Inkjet Paper, manufactured by Fuji Photo Film Co., Ltd.) and glossy paper dedicated to Super Fine (MJA4S3P, manufactured by Seiko Epson Corp.) using Seiko Epson Corporation. The resulting image was evaluated for hue and light fastness. As for the hue, the sharper the absorption, the more vivid the hue is obtained. Therefore, the reflection spectrum is measured with a spectrophotometer, and the half widths A (80 nm or less) and B (80
-100 nm) and C (impossible).
The light fastness is measured by intermittently irradiating xenon light (85,000 lux) for 3 days to the image receiving material on which an image is recorded using a weather meter (Atlas CI65), and reflecting the image density before and after xenon irradiation. It measured using the densitometer (X-Rite310TR) and evaluated as a dye residual ratio. The case where the dye remaining ratio was 80% or more was evaluated as A, the case where the ratio was 60 to 80% was evaluated as B, and the case where the density was less than 60% at all concentrations was evaluated as C. The results are shown in Table 1.

[Comparative Examples 2 to 5] In the preparation of the aqueous inkjet ink, an azomethine dye (III-5), an azomethine dye (IV-2), and an azo dye (V-6) were used instead of the azo dye (VII). An inkjet ink was prepared in the same manner as in Comparative Example 1, except that the same amount of the azo dye (VI-10) was used. The viscosity of each of the inks was 5 cp at 25 ° C. Using the prepared ink, an image was recorded and evaluated in the same manner as in Comparative Example 1. The results are shown in Table 1.

[Examples 1 to 4] Comparative examples were prepared except that the amount of glycerin used was changed to 3 parts by weight and 10 parts by weight of basic polymer (A-4) was added in the preparation of the aqueous inkjet ink. In the same manner as in Nos. 2 to 6, ink-jet inks were prepared. The viscosity of the ink is 25 ° C
Was 5 cp in each case. In addition, the weight average molecular weight of the basic polymer (A-4) was 15,000. Using the prepared ink, an image was recorded and evaluated in the same manner as in Comparative Example 1. The results are shown in Table 1.

[0077]

Embedded image

[Examples 5 to 8] Comparative examples were prepared except that the amount of glycerin used was changed to 5 parts by weight and 10 parts by weight of basic polymer (A-23) was added in the preparation of the aqueous inkjet ink. In the same manner as in Nos. 2 to 6, ink-jet inks were prepared. The viscosity of the ink is 25
All were 6 cp at ° C. Using the prepared ink, an image was recorded and evaluated in the same manner as in Comparative Example 1. The results are shown in Table 1.

[0079]

Embedded image

[Examples 9 to 12] Comparative examples were prepared except that the amount of glycerin used was changed to 2 parts by weight and 10 parts by weight of basic polymer (A-24) was added in the preparation of the aqueous inkjet ink. In the same manner as in Nos. 2 to 6, ink-jet inks were prepared. The viscosity of the ink is 2
All were 6 cp at 5 ° C. Using the prepared ink, an image was recorded and evaluated in the same manner as in Comparative Example 1.
The results are shown in Table 1.

[0081]

Embedded image

[0082]

[Table 1] Table 1 Glossy paper ink for photo glossy paper Polymer Dye Quercerin Amount Viscosity Hue Fastness Hue Fastness 比較 Comparative Example 1 None VIII 7 parts by weight 5 cp B A-B B-C B-C Comparative Example 2 None III-5 7 parts by weight 5 cp A A-B BC Comparative Example 3 None IV-2 7 parts by weight 5 cp A-B A-B BC Comparative Example 4 None V-6 7 parts by weight 5 cp A A-B BC Comparative Example 5 None VI-10 7 parts by weight 5 cp A-BA A-BCC Example 1 A-4 III-5 3 parts by weight 5 cp AA AA-B Example 2 A-4 IV-2 3 parts by weight 5 cp A-B AA-BA AB Example 3 A-4 V-6 3 parts by weight 5 cp AA AA-B Implementation Example 4 A-4 VI-10 3 Parts by weight 5 cp A-B AA-A-B A-B Example 5 A-23 III-5 5 parts by weight 6 cp A-A AA-B Example 6 A-23 IV-2 5 parts by weight 6 cp A-B A A ＢB AB Example 7 A-23 V-6 5 parts by weight 6 cp AA AA〜B Example 8 A-23 VI-10 5 parts by weight 6 cp A〜BA A B AB ９Example 9 A-24 III-5 2 parts by weight 6 cp A A-ABAB Example 10 A-24 IV-2 2 parts by weight 6 cp A-BA A-B A-BB Example 11 A-24 V-6 2 parts by weight Part 6 cp A A-B AB Example 12 A-24 VI-10 2 parts by weight 6 cp A-B A-B A-B B ─────────────────

As is clear from the results shown in Table 1, when the ink-jet ink according to the present invention was used,
Regardless of the image receiving material used, the obtained image has high fastness and excellent hue. Further, the images obtained using the inks of Examples 1 to 12 had little blur. Further, even when water was applied to the image, the ink was difficult to flow.

[0084]

By using the ink-jet ink according to the present invention, an image excellent in light fastness and hue can be obtained regardless of the image-receiving material used.

Claims (9)

[Claims] An aqueous ink jet ink containing a dye and an aqueous medium, further comprising a basic polymer, wherein the basic polymer has a side chain containing a tertiary amino group, a quaternary ammonium group or a nitrogen-containing heterocyclic group. An ink-jet ink characterized by having: 2. The ink-jet ink according to claim 1, wherein the basic polymer contains a repeating unit represented by the following formula (I): Wherein R is a hydrogen atom or methyl; L is a single bond or a divalent linking group selected from —CO—, —O—, an alkylene group, an arylene group and a combination thereof; Am is a tertiary amino group, a quaternary ammonium group or a nitrogen-containing heterocyclic group]. 3. The ink-jet ink according to claim 1, wherein the basic polymer has a nitrogen-containing heterocyclic group. 4. The ink-jet ink according to claim 3, wherein the nitrogen-containing heterocyclic group is 1-imidazolyl. 5. The basic polymer is 1000 to 1000.
The inkjet ink of claim 1 having a weight average molecular weight of 00. 6. The basic polymer is contained in an amount of 0.1 to 50% by weight.
The inkjet ink according to claim 1, which is contained in an amount in the range of: 7. The ink-jet ink according to claim 1, which has a viscosity of 50 cp or less at 25 ° C. 8. The ink-jet ink according to claim 1, wherein the dye is an azomethine dye or an azo dye. 9. An ink jet recording method for recording an image on an image receiving material by ejecting the ink for ink jet according to claim 1 in the form of droplets.