# Patent

## Title
Water-based ink for ink-jet recording and ink cartridge

## Abstract

A water-based ink for ink-jet recording includes a dye represented by a general formula (1), water, a water-soluble organic solvent, and 0.5% by weight to 4% by weight of a cationic polymer; wherein in the general formula (1): n1 is 1 or 2, each of three Ms is sodium or ammonium and the three Ms may be same or different from one another, and R0 represents a monoalkylamino group substituted by a carboxyl group and having a number of carbon atoms of 1 to 8.

## Background
CROSS REFERENCE TO RELATED APPLICATION
The present application claims priority from Japanese Patent Application No. 2012-008527 filed on Jan. 18, 2012, the disclosure of which is incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a water-based ink for ink-jet recording and an ink cartridge.
2. Description of the Related Art
In general, it is demanded for a water-based ink for ink-jet recording that the hue is satisfactory and the durability or stoutness is excellent against light, heat, and ozone. A water-based ink which uses a specific dye has been suggested as the water-based ink for ink-jet recording in which the hue is satisfactory and the durability or stoutness is excellent. See, for example, Japanese Patent Application Laid-open No. 2011-111611 (corresponding to United States Patent Application Publication No. US 2011/0128333).
However, some types of the specific dye as described above tend to cause the change in the easiness of diffusion into a recording medium depending on change in an environmental condition under which the specific dye is used, as compared with general dyes. For example, the humidity affects the easiness of diffusion of the specific dye into the recording medium. For this reason, in a case that a water-based ink containing the specific dye is used to perform ink jet recording, then there is caused such a problem that the optical density (OD value) is lowered in some cases.
In view of the above, an object of the present teaching is to provide a water-based ink for ink-jet recording which provides a satisfactory hue, which is excellent in the durability or stoutness against light, heat, and ozone, and which makes it possible to suppress the lowering of optical density (OD value) in a high humidity environment.
SUMMARY OF THE INVENTION
According to a first aspect of the present teaching, there is provided a water-based ink for ink-jet recording, containing a dye represented by a general formula (1), water, a water-soluble organic solvent, and 0.5% by weight to 4% by weight of a cationic polymer;




wherein in the general formula (1):
n1 is 1 or 2,
each of three Ms is sodium or ammonium and the three Ms may be same or different from one another, and
R0 represents a monoalkylamino group substituted by a carboxyl group and having a number of carbon atoms of 1 to 8.
According to a second aspect of the present teaching, there is provided an ink cartridge including the water-based ink for ink-jet recording of the first aspect.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a schematic perspective view illustrating an exemplary construction of an ink-jet recording apparatus according to the present teaching.



DESCRIPTION OF THE PREFERRED EMBODIMENTS
An explanation will be made about an embodiment of the water-based ink for ink-jet recording (hereinafter referred to as “water-based ink” or “ink” in some cases) of the present teaching. However, the embodiment described below is described merely exemplarily, and the present teaching is not limited to this.
The water-based ink of the present teaching contains a colorant, water, and a water-soluble organic solvent. The colorant contains the dye represented by the general formula (1).
The dye represented by the general formula (1) may be a compound in which the three Ms are all sodium (sodium salt), may be a compound in which the three Ms are all ammonium (ammonium salt) or may be a compound in which one M or two Ms among the three Ms is/are sodium and the remaining two Ms or remaining one M are/is ammonium. The dye represented by the general formula (1) may be composed of a single compound among the compounds described above, or may be a mixture containing two or more kinds of the compounds described above. The M may be electrolyzed in the water-based ink to be an ion (at least one of Na+ and NH4+).
Specific preferred examples of the dye represented by the general formula (1) may includes compounds represented by dyes (1-A) to (1-E) shown in the following Table 1.










TABLE 1






n1
M
R0







Dye (1-A)
1
Mixture of Na and NH4
—NHCH2COOH


Dye (1-B)
1
Mixture of Na and NH4 
—NH(CH2)5COOH


Dye (1-C)
1
Mixture of Na and NH4 
—NH(CH2)7COOH


Dye (1-D)
2
Mixture of Na and NH4
—NHCH2COOH


Dye (1-E)
2
Mixture of Na and NH4
—NH(CH2)5COOH









The dye represented by the general formula (1) can be produced, for example, by the method disclosed in United States Patent Application Publication No. US 2012/0081453 of which content or disclosure is incorporated herein by reference in its entity as constructing a part of the present specification.
The blending amount of the dye represented by the general formula (1) with respect to the total amount of the water-based ink is not specifically limited. By making the dye represented by the general formula (1) be contained, it is possible to obtain a water-based ink which provides the satisfactory hue and which is excellent in the durability or stoutness against light, heat, and ozone. The blending amount of the dye represented by the general formula (1) with respect to the total amount of the water-based ink is, for example, 0.1% by weight to 10% by weight, preferably 0.5% by weight to 8% by weight, and more preferably 1% by weight to 6% by weight.
The colorant of the water-based ink may further contain, for example, any other dye and any pigment in addition to the dye represented by the general formula (1). Further, the colorant of the water-based ink may contain only the dye represented by the general formula (1). The pigment is not specifically limited, for which it is possible to use, for example, an inorganic pigment, and an organic pigment. In a case that the pigment is used, it is allowable to use a dispersant in combination, or to use a self-dispersible pigment.
It is preferable that the water is ion exchange water or pure water (purified water). The blending amount of water (water ratio) with respect to the total amount of the water-based ink is, for example, 10% by weight to 90% by weight, and preferably 40% by weight to 80% by weight. The water ratio may be, for example, the balance of the other components.
The water-soluble organic solvent is exemplified, for example, by a humectant which prevents the water-based ink from being dried at a tip or forward end portion of a nozzle of an ink jet head and a penetrant which adjusts the drying speed on the recording medium.
The humectant described above is not specifically limited, which includes, for example, lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol; amides such as dimethylformamide and dimethylacetamide; ketones such as acetone; ketoalcohols (ketone alcohols) such as diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyhydric alcohols such as polyalkylene glycol, alkylene glycol, glycerol and trimethylolpropane; 2-pyrrolidone; N-methyl-2-pyrrolidone; and 1,3-dimethyl-2-imidazolidinone. The polyalkylene glycol includes, for example, polyethylene glycol and polypropylene glycol. The alkylene glycol includes, for example, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, thiodiglycol, and hexylene glycol. One type (kind) of the humectant as described above may be used singly, or two or more types (kinds) of the humectants as described above may be used in combination. Among them, it is preferable to use polyhydric alcohol such as alkylene glycol and glycerol.
The blending amount of the humectant with respect to the total amount of the water-based ink is, for example, 0% by weight to 95% by weight, preferably 5% by weight to 80% by weight, and more preferably 5% by weight to 50% by weight.
The penetrant includes, for example, glycol ether. Glycol ether includes, for example, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, diethylene glycol n-hexyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol n-propyl ether, triethylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tripropylene glycol n-propyl ether, and tripropylene glycol n-butyl ether. One type (kind) of the penetrant as described above may be used singly, or two or more types (kinds) of the penetrants as described above may be used in combination.
The blending amount of the penetrant with respect to the total amount of the water-based ink is, for example, 0% by weight to 20% by weight, preferably 0.1% by weight to 15% by weight, and more preferably 0.5% by weight to 10% by weight.
As described above, the water-based ink further contains the cationic polymer. It is estimated that the lowering of the optical density (OD value) in the high humidity environment is suppressed by containing the cationic polymer. In particular, in a case that a glossy paper having silica particles on a surface of the glossy paper is used as the recording medium, it is estimated that the filling effect is exerted by the interaction between the cationic polymer and an ink-receiving layer composed, for example, of the silica particles on the glossy paper, thereby suppressing the change of the easiness of diffusion (migration) of the dye on the glossy paper which is caused depending on the humidity, and the lowering of the optical density (OD value) is consequently suppressed. Further, it is also estimated that the filling effect is exerted by the interaction between cationic portions of the cationic polymer and anionic portions of the dye, that is, an ionic bond. However, the present teaching is not limited to the estimations.
It is preferable that the cationic polymer is at least one compound among a compound represented by following general formula (2), a compound represented by following general formula (3), a compound represented by following general formula (4), and a compound (polyethyleneimine) represented by following general formula (5).




In the general formula (2), m is an integer of 2 to 6, and n is an integer of 20 to 40.
In the general formula (2), it is especially preferable that m is 4. In this case, the compound represented by the general formula (2) is polylysine. Polylysine can be produced by a method described, for example, in Japanese Patent No. 4228498, Japanese Patent Application Laid-open No. 2003-176353, etc. Further, in the general formula (2), it is preferable that n is 25 to 35.
The compound represented by the general formula (2) may include any derivative of the compound represented by the general formula (2). When any isomer, which includes, for example, tautomers and stereoisomers (for example, geometrical isomer, conformational isomer, and stereoisomer), exists in relation to the compound represented by the general formula (2) or the derivative thereof, any one of the isomers can be used for the present teaching. Salts of the compound represented by the general formula (2) and the derivative thereof can be also used for the present teaching in the same manner as described above. The salt may be either an acid addition salt or a base addition salt. The acid, which forms the acid addition salt, may be either an inorganic acid or an organic acid. The base, which forms the base addition salt, may be either an inorganic base or an organic base. The inorganic acid is not specifically limited. However, the inorganic acid is exemplified, for example, by hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, hypofluorous acid, hypochlorous acid, hypobromous acid, hypoiodous acid, fluorous acid, chlorous acid, bromous acid, iodous acid, fluoric acid, chloric acid, bromic acid, iodic acid, perfluoric acid, perchloric acid, perbromic acid, and periodic acid. The organic acid is not specifically limited as well. However, the organic acid is exemplified, for example, by glutamic acid, p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, p-bromobenzenesulfonic acid, carbonic acid, succinic acid, citric acid, benzoic acid, acetic acid, hydroxycarboxylic acid, propionic acid, malonic acid, adipic acid, fumaric acid, and maleic acid. The inorganic base is not specifically limited. However, the inorganic base is exemplified, for example, by ammonium hydroxide, alkali metal hydroxide, alkaline earth metal hydroxide, carbonate, hydrogen carbonate, and sulfate. More specifically, the inorganic base is exemplified, for example, by sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydroxide, calcium carbonate, potassium sulfate, and calcium sulfate. The organic base is not specifically limited as well. However, the organic base is exemplified, for example, by alcoholamine, trialkylamine, tetraalkylammonium, and tris(hydroxymethyl)aminomethane. The alcoholamine is exemplified, for example, by ethanolamine. The trialkylamine is exemplified, for example, by trimethylamine, triethylamine, tripropylamine, tributylamine, and trioctylamine. The tetraalkylammonium is exemplified, for example, by tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, and tetraoctylammonium.
In the general formulas (3) and (4), R11 to R13 are hydrogen atoms or organic groups respectively. The organic group is exemplified, for example, by alkyl group and aryl group. The alkyl group may have either straight chain or branched chain, which is exemplified, for example, by methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, octadecyl group, 1,3-butadienyl group, and 1,3-pentadienyl group. The aryl group is exemplified, for example, by phenyl group, naphthyl group, tolyl group, and vinylphenyl group. The alkyl group and the aryl group may have any substituent. The alkyl group and the aryl group, which have the substituent, are exemplified, for example, by fluoroethyl group, trifluoroethyl group, methoxyethyl group, phenoxyethyl group, hydroxyphenylmethyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, iodophenyl group, fluorophenyl group, hydroxyphenyl group, methoxyphenyl group, cetoxyphenyl group, and cyanophenyl group.
In the general formula (4), X− is an anion. The anion may be any anion. However, the anion is exemplified, for example, by halide ion, sulfonic acid ion, alkylsulfonic acid ion, arylsulfonic acid ion, alkylcarboxylic acid ion, and arylcarboxylic acid ion.
In the general formulas (3) and (4), p is a positive integer, which is, for example, 10 to 400, preferably 15 to 300, and more preferably 20 to 200. The weight average molecular weight of each of the compounds represented by the general formulas (3) and (4) is not specifically limited. However, the weight average molecular weight is, for example, 600 to 20000, preferably 900 to 15000, and more preferably 1200 to 10000.
In the general formula (3), it is especially preferable that R11 and R12 are hydrogen atoms. In this case, the compound represented by the general formula (3) is polyallylamine. In the general formula (4), it is preferable that R11 to R13 are hydrogen atoms, and X− is chloride ion. In this case, the compound represented by the general formula (4) is polyallylamine hydrochloride (allylamine hydrochloride polymer).
In the general formula (5), q is a positive integer, which is, for example, 12 to 500, preferably 20 to 350, and more preferably 28 to 250. Straight chain polyethyleneimine is shown in the general formula (5). However, the cationic polymer may be polyethyleneimine having branched chain structure including primary, secondary, and tertiary amines. The weight average molecular weight of the compound represented by the general formula (5) is not specifically limited. However, the weight average molecular weight of the compound represented by the general formula (5) is, for example, 600 to 20000, preferably 900 to 15000, and more preferably 1200 to 10000.
It is also allowable to use those other than the compound represented by the general formula (2), the compound represented by the general formula (3), the compound represented by the general formula (4), and the compound represented by the general formula (5) as the cationic polymer. Further, it is allowable that the water-based ink does not contain any cationic polymer other than the compound represented by the general formula (2), the compound represented by the general formula (3), the compound represented by the general formula (4), and the compound represented by the general formula (5). The cationic polymer other than the compound represented by the general formula (2), the compound represented by the general formula (3), the compound represented by the general formula (4), and the compound represented by the general formula (5) is exemplified, for example, by polyamine, polyvinylamine, polyvinylpyridine, polyethyleneimine-epichlorohydrin reaction product, polyamide-polyamine resin, polyamide-epichlorohydrin resin, cationic starch, polyvinyl alcohol, polyvinylpyrrolidone, polyamidine, cationic epoxy resin, polyacrylamide, polyacrylic acid ester, polymethacrylic acid ester, polyvinyl formamide, aminoacetalized polyvinyl alcohol, polyvinyl benzyl onium, dicyandiamide-formalin polycondensate, dicyandiamide-diethylenetriamine polycondensate, epichlorohydrin-dimethylamine addition polymer, dimethyldiallylammonium chloride-SO2 copolymer, dimethyldiallylammonium chloride polymer, and derivatives thereof. Further, the cationic polymer other than the compound represented by the general formula (2), the compound represented by the general formula (3), the compound represented by the general formula (4), and the compound represented by the general formula (5) is also exemplified, for example, by a polymer of single monomer or a copolymer of a plurality of types of monomers composed of at least one of water-soluble monomers including, for example, dimethylaminoethyl methacrylate (DM), methacryloxyethyl trimethyl ammonium chloride (DMC), methacryloxyethyl benzyl dimethyl ammonium chloride (DMBC), dimethylaminoethyl acrylate (DA), acryloyloxyethyl trimethyl ammonium chloride (DMQ), acryloyloxyethyl benzyl dimethyl ammonium chloride (DABC), dimethylaminopropyl acrylamide (DMAPAA), and acrylamide propyl trimethyl ammonium chloride (DMAPAAQ).
The cationic polymer may be prepared privately or independently, or any commercially available product may be used for the cationic polymer. The commercially available product is exemplified, for example, by polylysine produced by Chisso Corporation, “PAA (trade name)-01”, “PAA (trade name)-03”, “PAA (trade name)-08” produced by Nitto Boseki Co., Ltd., and polyethyleneimine produced by Junsei Chemical Co., Ltd.
As described above, the blending amount of the cationic polymer with respect to the total amount of the water-based ink is 0.5% by weight to 4% by weight. By making the blending amount of the cationic polymer be within this range, it is possible to obtain a water-based ink which suppresses the lowering of the optical density (OD value) in a high humidity environment and which is excellent in the jetting stability. The blending amount of the cationic polymer is preferably 0.5% by weight to 3% by weight. In a case that the blending amount of the cationic polymer is 0.5% by weight to 3% by weight, in particular, the discharge stability of the ink is excellent.
The weight average molecular weight of the cationic polymer is, for example, not less than 1200. By using the cationic polymer of which weight average molecular weight is not less than 1200, it is possible to obtain, for example, high filling effect exerted by the interaction between the cationic polymer and an ink-receiving layer of a glossy paper. The weight average molecular weight of the cationic polymer is more preferably 1200 to 8000, and is further more preferably 1200 to 5000.
One cationic polymer may be used singly, or two or more cationic polymers may be used in combination.
The water-based ink may further contain conventionally known additives, if necessary. The additive includes, for example, surfactants, pH-adjusting agents, viscosity-adjusting agents, surface tension-adjusting agents, and fungicides. The viscosity-adjusting agent is exemplified, for example, by polyvinyl alcohol, cellulose, and water-soluble resin.
The water-based ink can be prepared, for example, such that the colorant, water, the water-soluble organic solvent, the cationic polymer, and optionally other additive component(s) as necessary are mixed uniformly in accordance with any conventionally known method, and undissolved matters are removed by a filter or the like.
The water-based ink of this embodiment may be used as a water-based magenta ink. However, the present teaching is not limited only to this. The water-based ink of this embodiment can be provided as a water-based ink of which color is different from magenta, by using a colorant different from the dye represented by the general formula (1).
Since the water-based ink of the embodiment contains the dye represented by the general formula (1), the water-based ink has a satisfactory hue and is excellent in the durability or stoutness against light, heat, and ozone. Further, the water-based ink of the embodiment contains the cationic polymer, and the blending amount of the cationic polymer is the above-described predetermined blending amount. Accordingly, the water-based ink of the embodiment is capable of satisfactorily suppressing any lowering of the optical density (OD value) in a high humidity environment and of realizing the jetting stability, at the same time in a suitable manner.
Next, an explanation will be given about an ink cartridge of the present teaching. The ink cartridge of the present teaching is an ink cartridge containing a water-based ink for ink-jet recording, wherein the water-based ink is the water-based ink for ink jet recording of the present teaching. For example, any conventionally known main body (body) of an ink cartridge can be used for the main body of the ink cartridge of the present teaching.
Next, an explanation will be made about an ink jet recording apparatus of the present teaching and an ink-jet recording method using the ink-jet recording apparatus. The recording includes, for example, printing of letters (text), printing of images, printing, etc.
The ink-jet recording apparatus of the present teaching is an ink-jet recording apparatus including an ink accommodating section and an ink discharging mechanism which discharges an ink accommodated in the ink accommodating section, wherein the water-based ink for ink-jet recording of the present teaching is accommodated in the ink accommodating section.
FIG. 1 shows an exemplary construction of an ink-jet recording apparatus of the present teaching. As shown in FIG. 1, an ink-jet recording apparatus 1 includes, as main constitutive elements, four ink cartridges 2, an ink discharging mechanism (ink-jet head) 3, a head unit 4, a carriage 5, a driving unit 6, a platen roller 7, and a purge unit 8.
Each of the four ink cartridges 2 includes one of the four color water-based inks of yellow, magenta, cyan, and black one by one. For example, the water-based magenta ink is the water-based ink for ink-jet recording of the present teaching. General water-based inks may be used for the water-based inks other than the water-based magenta ink. The ink-jet head 3, which is installed on the head unit 4, performs recording on a recording medium P (for example, recording paper (preferably glossy paper, more preferably glossy paper having a void type ink receiving layer)). The four ink cartridges 2 and the head unit 4 are carried on the carriage 5. The driving unit 6 reciprocatively moves the carriage 5 in a linear direction. For example, a conventionally known driving unit can be used as the driving unit 6 (see, for example, Japanese Patent Application Laid-open No. 2008-246821 corresponding to United States Patent Application Publication No. US 2008/0241398). The platen roller 7 extends in the reciprocating direction of the carriage 5, and the platen roller 7 is arranged to face or to be opposite to the ink-jet head 3.
The purge unit 8 sucks any defective ink containing a bubble or the like remaining at the inside of the ink-jet head 3. For example, a conventionally known purge unit can be used as the purge unit 8 (see, for example, Japanese Patent Application Laid-open No. 2008-246821 corresponding to United States Patent Application Publication No. US 2008/0241398).
A wiper member 20 is arranged adjacently to the purge unit 8 at a portion of the purge unit 8 on a side of the platen roller 7. The wiper member 20 is formed to have a spatula-shaped form. The wiper member 20 wipes a nozzle-formed surface of the ink-jet head 3 in accordance with the movement of the carriage 5. With reference to FIG. 1, the cap 18 covers a plurality of nozzles of the ink-jet head 3, which is returned to the reset position when the recording is completed, in order to prevent the water-based inks from being dried.
In the ink-jet recording apparatus 1 of this embodiment, the four ink cartridges 2 are carried on one carriage 5 together with the head unit 4. However, the present teaching is not limited to this. In the ink-jet recording apparatus described above, the respective four ink cartridges 2 may be carried on any carriage distinctly from the head unit 4. Alternatively, the respective four ink cartridges 2 may be arranged and fixed in the ink-jet recording apparatus without being carried on the carriage 5. In the modes as described above, for example, the respective four ink cartridges 2 are connected to the head unit 4 carried on the carriage 5 by tubes or the like, and each of the water-based inks is supplied from one of the respective four ink cartridges 2 to the head unit 4.
The ink-jet recording, which uses the ink-jet recording apparatus 1, is carried out, for example, as follows. At first, a recording paper P is supplied from a paper-feeding cassette (not shown) provided in the ink-jet recording apparatus 1 on a side portion or lower portion thereof. The recording paper P is introduced between the ink-jet head 3 and the platen roller 7. A predetermined recording is performed on the introduced recording paper P with the water-based ink(s) discharged from the ink-jet head 3. By using the water-based ink of the present teaching, it is possible to realize a stable discharge from the ink-jet head 3, and it is possible to obtain a recorded matter which has a satisfactory hue, which is excellent in the durability or stoutness against light, heat, and ozone, and which is suppressed from the lowering of the optical density (OD value) in a high humidity environment. The recording paper P after the recording is discharged from the ink-jet recording apparatus 1. In FIG. 1, the paper-feeding mechanism and paper-discharging mechanism for the recording paper P are omitted.
The apparatus shown in FIG. 1 adopts the serial type ink-jet head. However, the present teaching is not limited to this. The ink-jet recording apparatus may be an apparatus which adopts a line type ink-jet head.
According to the present teaching, there is provided an ink-jet recording method for performing recording by discharging an ink from an ink discharging mechanism, the method including using, as the ink, the water-based ink for ink-jet recording of the present teaching. The ink-jet recording method can be practiced by, for example, using the ink-jet recording apparatus of the present teaching.
EXAMPLES
Next, Examples of the present teaching will be explained together with Comparative Examples. Note that the present teaching is not limited and restricted by Examples and Comparative Examples described below.
Examples 1 to 20 and Comparative Examples 1 to 10
Respective components of a water-based ink composition (Tables 2 to 5) were mixed uniformly. After that, an obtained mixture was filtrated by using a hydrophilic polytetrafluoroethylene (PTFE) type membrane filter (pore size: 0.20 μm) produced by Toyo Roshi Kaisha, Ltd. Accordingly, water-based inks for ink-jet recording of Examples 1-20 and Comparative Examples 1-10 were obtained. In Tables 2-5, dyes (1-A) to (1-E) are compounds which are represented by dyes (1-A) to (1-E) shown in Table 1, respectively.
<Evaluations of Water-Based Ink for Ink jet Recording>
With respect to the water-based inks of Examples 1-20 and Comparative Examples 1-10, (a) optical density (OD value) difference (ΔOD) evaluation, (b) discharge stability evaluation and (c) overall evaluation were performed by the following methods.
(a) Optical Density (OD Value) Difference (ΔOD) Evaluation
An ink jet printer-equipped digital multifunction machine DCP-385C produced by Brother Industries, Ltd. was used to record a magenta patch on “Exclusive paper (photograph glossy paper) (BP-71)” (Glossy paper A) produced by Brother Industries, Ltd. by using the water-based inks of Examples 1-20 and Comparative Examples 1-10. The optical density (OD value) difference (ΔOD) was calculated for the recorded magenta patch in accordance with the following method. Note that regarding Examples 1, 3 and 5 and Comparative Examples 1-3 and 8-10, magenta patches were recorded also on “Photograph paper Crispia <Highly Glossy>” (Glossy paper B) in Comparative Example 2; magenta patches were recorded also on “Photograph paper <Glossy>” (Glossy paper C) produced by Seiko Epson Corp. in Comparative Example 3; magenta patches were recorded also on “Photograph paper Crispia <Highly Glossy>” (Glossy paper B) and on “Photograph paper <Glossy>” (Glossy paper C) in Examples 1, 3 and 5 and Comparative Examples 1 and 8-10; and the optical density (OD value) difference (ΔOD) was calculated also regarding the recording on each of Glossy papers B or/and C, in the same manner as described above.
The magenta patch was recorded in an environment at the ordinary temperature and the ordinary humidity (temperature: 25° C., relative humidity: 50%), and was stored for 24 hours in the same environment as that provided during the recording to obtain an ordinary temperature-ordinary humidity environment sample. Further, the magenta patch was recorded in an environment at a low temperature and a high humidity (temperature: 18° C., relative humidity: 80%), and was stored for 24 hours in the same environment as that provided during the recording to obtain a low temperature-high humidity environment sample. The optical density (OD value) of each of the ordinary temperature-ordinary humidity environment sample and the low temperature-high humidity environment sample was measured by using a spectrophotometer Spectrolino produced by Gretag Macbeth (built-in filter: none (no), white reference: Abs (absolute white), density reference: ANSI T, density filter: automatic). The optical density (OD value) difference (ΔOD) was calculated between the two environments of the ordinary temperature-ordinary humidity and the low temperature-high humidity in accordance with the following expression. The optical density (OD value) difference (ΔOD) was evaluated in accordance with the following evaluation criteria.

ΔOD=|OD1−OD2|

OD1: optical density (OD value) of magenta patch of low temperature-high humidity environment sample; and
OD2: optical density (OD value) of magenta patch of ordinary temperature-ordinary humidity environment sample.
<Evaluation Criterion for Optical Density (OD Value) Difference (ΔOD) Evaluation>
A: optical density (OD value) difference (ΔOD) was less than 0.08;
B: optical density (OD value) difference (ΔOD) was not less than 0.08 and less than 0.12;
C: optical density (OD value) difference (ΔOD) was not less than 0.12.
(b) Evaluation of Jetting Stability
With respect to the water-base ink of each of Examples 1-20 and Comparative Examples 1-10, each of the water-based inks was used to perform continuous recording of million dots (about 300 sheets of paper) on Regular Paper BP60PA produced by Brother Industries, Ltd. using ink jet printer-equipped digital multifunction machine DCP-385C. The results of the continuous recording were evaluated in accordance with the following evaluation criterion. Note that the term “un-discharge (non-discharge)” indicates such a state that the nozzles of the ink-jet head are clogged and the water-based ink is not discharged from the nozzles; and that the term “discharge-bending (discharge-deflection)” indicates such a state that a part of the nozzles of the ink-jet head are clogged, and the water-based ink is not discharged perpendicularly to the recording paper, but is discharged obliquely with respect to the recording paper.
<Evaluation Criterion for Discharge Stability>
A: Neither un-discharge nor discharge-bending occurred at all during the continuous recording.
B: Un-discharge and discharge-bending hardly occurred during the continuous recording.
C: Un-discharge and discharge-bending occurred at many portions or locations on the recording paper during the continuous recording.
(c) Overall Evaluation
With respect to the water-based inks of Examples 1-20 and Comparative Examples 1-10, the overall evaluation was performed in accordance with the following evaluation criterion based on the results of (a) and (b) described above.
<Evaluation Criterion for Overall Evaluation>
G: There was no “C” evaluation in both of the results of (a) and (b).
NG: There was “C” evaluation in any one of (a) and (b).
The water-based ink composition and the evaluation results of the water-based inks of Examples 1-20 are shown in Tables 2 and 3. The water-based ink composition and the evaluation results of the water-based inks of Comparative Examples 1 to 10 are shown in Tables 4 and 5. Note that regarding Comparative Examples 2-4 shown in Table 4, the weight average molecular weight of the cationic polymer shows the weight average molecular weight of polyvinylpyrrolidone that is a non-cationic polymer or the weight average molecular weight of lysine hydrochloride or dimethyl ethyloctyl ammonium ethylsulfate that are a cationic low molecular weight substance, each of which was used in place of the cationic polymer.









TABLE 2









EXAMPLES















EX1
EX2
EX3
EX4
EX5
EX6
EX7



















Water-based Ink Composition
Dye (1-A)
—
—
—
—
—
—
—


(% by weight)
Dye (1-B)
3.5
—
—
—
—
—
—



Dye (1-C)
—
3.5
3.5
—
—
3.5
—



Dye (1-D)
—
—
—
3.5
—
—
3.5



Dye (1-E)
—
—
—
—
3.5
—
—



Glycerol (*1)
23.5
23.5
23.5
23.5
23.5
22.0
22.5



Diethylene glycol
3.0
3.0
3.0
3.0
3.0
3.0
3.0



Dipropylene glycol monopropyl ether
2.0
2.0
2.0
2.0
2.0
2.0
2.0



Olfine (trade name) E1010 (*2)
0.2
0.2
0.2
0.2
0.2
0.2
0.2



Polylysine (*3)
2.5
—
—
—
—
4.0
3.5



PAA (trade name)-3 (*4)
—
—
2.5
—
—
—
—



PAA (trade name)-8 (*5)
—
2.5
—
—
—
—
—



Polyethyleneimine 1800 (*6)
—
—
—
2.5
—
—
—



Polyethyleneimine 1200 (*7)
—
—
—
—
2.5
—
—



Water
balance
balance
balance
balance
balance
balance
balance














Weight average molecular weight of cationic
4000
8000
3000
1800
1200
4000
4000


polymer




















Glossy paper
A
B
C
A
A
B
C
A
A
B
C
A
A


Optical density (OD value) difference (ΔOD)
A
A
A
A
A
A
A
A
A
A
A
A
A


evaluation














Jetting stability evaluation
A
A
A
A
A
B
B




















Overall evaluation
G
G
G
G
G
G
G
G
G
G
G
G
G





(*1): Produced by Kao Corporation, numerical values in the table indicate active ingredient amounts.


(*2): Ethylene oxide (10 mole) adduct of acetylene diol, produced by Nissin Chemical Industry Co., Ltd.


(*3): Produced by Chisso Corporation (weight average molecular weight: 4000), numerical values in the table indicate active ingredient amounts.


(*4): Unneutralized product of polyallylamine (weight average molecular weight: 3000), produced by Nitto Boseki Co., Ltd., active ingredient amount = 20% by weight, numerical values in the table indicate active ingredient amounts.


(*5): Unneutralized product of polyallylamine (weight average molecular weight: 8000), produced by Nitto Boseki Co., Ltd., active ingredient amount = 20% by weight, numerical values in the table indicate active ingredient amounts.


(*6): Produced by Junsei Chemical Co., Ltd. (weight average molecular weight: 1800).


(*7): Produced by Junsei Chemical Co., Ltd. (weight average molecular weight: 1200).















TABLE 3









EXAMPLES

















EX8
EX9
EX10
EX11
EX12
EX13
EX14





Water-based Ink Composition
Dye (1-A)
—
3.5
—
3.5
—
—
—


(% by weight)
Dye (1-B)
—
—
3.5
—
3.5
—
—



Dye (1-C)
—
—
—
—
—
3.5
—



Dye (1-D)
—
—
—
—
—
—
3.5



Dye (1-E)
3.5
—
—
—
—
—
—



Glycerol (*1)
23.0
25.0
25.5
22.0
22.5
23.0
25.0



Diethylene glycol
3.0
3.0
3.0
3.0
3.0
3.0
3.0



Dipropylene glycol monopropyl ether
2.0
2.0
2.0
2.0
2.0
2.0
2.0



Olfine (trade name) E1010 (*2)
0.2
0.2
0.2
0.2
0.2
0.2
0.2



Polylysine (*3)
3.0
1.0
0.5
—
—
—
—



PAA (trade name)-3 (*4)
—
—
—
—
—
—
1.0



PAA (trade name)-8 (*5)
—
—
—
4.0
3.5
3.0
—



Polyethyleneimine 1800 (*6)
—
—
—
—
—
—
—



Polyethyleneimine 1200 (*7)
—
—
—
—
—
—
—



Water
balance
balance
balance
balance
balance
balance
balance














Weight average molecular weight of cationic
4000
4000
4000
8000
8000
8000
3000


polymer


Glossy paper
A
A
A
A
A
A
A


Optical density (OD value) difference (ΔOD)
A
A
A
A
A
A
A


evaluation


Jetting stability evaluation
A
A
A
B
B
A
A


Overall evaluation
G
G
G
G
G
G
G












EXAMPLES
















EX15
EX16
EX17
EX18
EX19
EX20





Water-based Ink Composition
Dye (1-A)
—
3.5
—
—
—
—


(% by weight)
Dye (1-B)
—
—
3.5
—
—
—



Dye (1-C)
—
—
—
3.5
—
—



Dye (1-D)
—
—
—
—
3.5
—



Dye (1-E)
3.5
—
—
—
—
3.5



Glycerol (*1)
25.5
22.0
22.5
23.0
25.0
25.5



Diethylene glycol
3.0
3.0
3.0
3.0
3.0
3.0



Dipropylene glycol monopropyl ether
2.0
2.0
2.0
2.0
2.0
2.0



Olfine (trade name) E1010 (*2)
0.2
0.2
0.2
0.2
0.2
0.2



Polylysine (*3)
—
—
—
—
—
—



PAA (trade name)-3 (*4)
0.5
—
—
—
—
—



PAA (trade name)-8 (*5)
—
—
—
—
—
—



Polyethyleneimine 1800 (*6)
—
4.0
3.5
3.0
—
—



Polyethyleneimine 1200 (*7)
—
—
—
—
1.0
0.5



Water
balance
balance
balance
balance
balance
balance













Weight average molecular weight of cationic
3000
1800
1800
1800
1200
1200


polymer


Glossy paper
A
A
A
A
A
A


Optical density (OD value) difference (ΔOD)
A
A
A
A
A
A


evaluation


Jetting stability evaluation
A
B
B
A
A
A


Overall evaluation
G
G
G
G
G
G





(*1): Produced by Kao Corporation, numerical values in the table indicate active ingredient amounts.


(*2): Ethylene oxide (10 mole) adduct of acetylene diol, produced by Nissin Chemical Industry Co., Ltd.


(*3): Produced by Chisso Corporation (weight average molecular weight: 4000), numerical values in the table indicate active ingredient amounts.


(*4): Unneutralized product of polyallylamine (weight average molecular weight: 3000), produced by Nitto Boseki Co., Ltd., active ingredient amount = 20% by weight, numerical values in the table indicate active ingredient amounts.


(*5): Unneutralized product of polyallylamine (weight average molecular weight: 8000), produced by Nitto Boseki Co., Ltd., active ingredient amount = 20% by weight, numerical values in the table indicate active ingredient amounts.


(*6): Produced by Junsei Chemical Co., Ltd. (weight average molecular weight: 1800).


(*7): Produced by Junsei Chemical Co., Ltd. (weight average molecular weight: 1200).















TABLE 4









COMPARATIVE EXAMPLES














COM. EX1
COM. EX2
COM. EX3
COM. EX4





Water-based Ink Composition
Dye (1-A)
3.5
—
—
—


(% by weight)
Dye (1-B)
—
3.5
—
—



Dye (1-C)
—
—
3.5
—



Dye (1-D)
—
—
—
3.5



Dye (1-E)
—
—
—
—



Glycerol (*1)
26.0
23.5
23.5
23.5



Diethylene glycol
3.0
3.0
3.0
3.0



Dipropylene glycol monopropyl ether
2.0
2.0
2.0
2.0



Olfine (trade name) E1010 (*2)
0.2
0.2
0.2
0.2



Polylysine (*3)
—
—
—
—



PAA (trade name)-3 (*4)
—
—
—
—



PAA (trade name)-8 (*5)
—
—
—
—



Polyethyleneimine 1800 (*6)
—
—
—
—



Polyethyleneimine 1200 (*7)
—
—
—
—



Kollidon 12PF (*8)
—
2.5
—
—



Lysine hydrochloride (*9)
—
—
2.5
—



Dimethyl ethyloctyl ammonium
—
—
—
2.5



ethylsulfate



Water
balance
balance
balance
balance











Weight average molecular weight of cationic polymer
—
3000
146
186















Glossy paper
A
B
C
A
B
A
C
A


Optical density (OD value) difference (ΔOD) evaluation
C
C
C
C
C
C
C
C











Jetting stability evaluation
A
A
A
A















Overall evaluation
NG
NG
NG
NG
NG
NG
NG
NG












COMPARATIVE EXAMPLES















COM. EX5
COM. EX6
COM. EX7







Water-based Ink Composition
Dye (1-A)
—
3.5
—



(% by weight)
Dye (1-B)
—
—
3.5




Dye (1-C)
—
—
—




Dye (1-D)
—
—
—




Dye (1-E)
3.5
—
—




Glycerol (*1)
21.5
21.5
21.5




Diethylene glycol
3.0
3.0
3.0




Dipropylene glycol monopropyl ether
2.0
2.0
2.0




Olfine (trade name) E1010 (*2)
0.2
0.2
0.2




Polylysine (*3)
4.5
—
—




PAA (trade name)-3 (*4)
—
—
—




PAA (trade name)-8 (*5)
—
4.5
—




Polyethyleneimine 1800 (*6)
—
—
4.5




Polyethyleneimine 1200 (*7)
—
—
—




Kollidon 12PF (*8)
—
—
—




Lysine hydrochloride (*9)
—
—
—




Dimethyl ethyloctyl ammonium ethylsulfate
—
—
—




Water
balance
balance
balance












Weight average molecular weight of cationic polymer
4000
8000
1800



Glossy paper
A
A
A



Optical density (OD value) difference (ΔOD) evaluation
A
A
A



Jetting stability evaluation
C
C
C



Overall evaluation
NG
NG
NG







(*1): Produced by Kao Corporation, numerical values in the table indicate active ingredient amounts.



(*2): Ethylene oxide (10 mole) adduct of acetylene diol, produced by Nissin Chemical Industry Co., Ltd.



(*3): Produced by Chisso Corporation (weight average molecular weight: 4000), numerical values in the table indicate active ingredient amounts.



(*4): Unneutralized product of polyallylamine (weight average molecular weight: 3000), produced by Nitto Boseki Co., Ltd., active ingredient amount = 20% by weight, numerical values in the table indicate active ingredient amounts.



(*5): Unneutralized product of polyallylamine (weight average molecular weight: 8000), produced by Nitto Boseki Co., Ltd., active ingredient amount = 20% by weight, numerical values in the table indicate active ingredient amounts.



(*6): Produced by Junsei Chemical Co., Ltd. (weight average molecular weight: 1800).



(*7): Produced by Junsei Chemical Co., Ltd. (weight average molecular weight: 1200).



(*8): Polyvinyl pyrrolidone produced by BASF (weight average molecular weight: 3000).



(*9): Produced by Kyowa Hakko Bio Co., Ltd. (weight average molecular weight: 146).















TABLE 5









COMPARATIVE EXAMPLES











COM. EX8
COM. EX9
COM. EX10















Water-based Ink Composition
Dye (1-A)
—
—
—


(% by weight)
Dye (1-B)
—
—
—



Dye (1-C)
3.5
—
—



Dye (1-D)
—
3.5
—



Dye (1-E)
—
—
3.5



Glycerol (*1)
25.7
25.7
25.7



Diethylene glycol
3.0
3.0
3.0



Dipropylene glycol monopropyl ether
2.0
2.0
2.0



Olfine (trade name) E1010 (*2)
0.2
0.2
0.2



Polylysine (*3)
0.3
—
—



PAA (trade name)-3 (*4)
—
0.3
—



PAA (trade name)-8 (*5)
—
—
—



Polyethyleneimine 1800 (*6)
—
—
—



Polyethyleneimine 1200 (*7)
—
—
0.3



Kollidon 12PF (*8)
—
—
—



Lysine hydrochloride (*9)
—
—
—



Dimethyl ethyloctyl ammonium
—
—
—



ethylsulfate



Water
balance
balance
balance










Weight average molecular weight of cationic polymer
4000
3000
1200
















Glossy paper
A
B
C
A
B
C
A
B
C


Optical density (OD value) difference (ΔOD) evaluation
C
C
C
C
C
C
C
C
C










Jetting stability evaluation
A
A
A
















Overall evaluation
NG
NG
NG
NG
NG
NG
NG
NG
NG





(*1): Produced by Kao Corporation, numerical values in the table indicate active ingredient amounts.


(*2): Ethylene oxide (10 mole) adduct of acetylene diol, produced by Nissin Chemical Industry Co., Ltd.


(*3): Produced by Chisso Corporation (weight average molecular weight: 4000), numerical values in the table indicate active ingredient amounts.


(*4): Unneutralized product of polyallylamine (weight average molecular weight: 3000), produced by Nitto Boseki Co., Ltd., active ingredient amount = 20% by weight, numerical values in the table indicate active ingredient amounts.


(*5): Unneutralized product of polyallylamine (weight average molecular weight: 8000), produced by Nitto Boseki Co., Ltd., active ingredient amount = 20% by weight, numerical values in the table indicate active ingredient amounts.


(*6): Produced by Junsei Chemical Co., Ltd. (weight average molecular weight: 1800).


(*7): Produced by Junsei Chemical Co., Ltd. (weight average molecular weight: 1200).


(*8): Polyvinyl pyrrolidone produced by BASF (weight average molecular weight: 3000).


(*9): Produced by Kyowa Hakko Bio Co., Ltd. (weight average molecular weight: 146).






As shown in Tables 2 and 3, in Examples 1 to 20, the lowering of the optical density (OD value) of the magenta patch in the low temperature-high humidity environment was suppressed and the jetting stability was excellent. In Examples 1-5, 8-10, 13-15 and 18-20 in each of which the blending amount of the cationic polymer was in the range of 0.5% by weight to 3% by weight, the jetting stability was particularly excellent.
On the other hand, as shown in Tables 4 and 5, in Comparative Example 1 in which the cationic polymer was not used, the filling effect was not expressed, and the optical density (OD value) of the magenta patch was lowered in the low temperature-high humidity environment. Also in Comparative Examples 2-4 each of which used polyvinyl pyrrolidone as a non-cationic polymer or lysine hydrochloride or dimethyl ethyloctyl ammonium ethylsulfate as a cationic low molecular weight substance, instead of using the cationic polymer, the filling effect was not expressed, and the optical density (OD value) of the magenta patch was lowered in the low temperature-high humidity environment. Further, in Comparative Examples 5-7 in each of which the blending amount of the cationic polymer was 4.5% by weight, the jetting stability was inferior. Furthermore, in Comparative Examples 8-10 in each of which the blending amount of the cationic polymer was 0.3% by weight, the filling effect was not expressed, and the optical density (OD value) of the magenta patch was lowered in the low temperature-high humidity environment.
As described above, the water-based ink of the present teaching provides the satisfactory hue, and the ink is excellent in the durability or stoutness against light, heat, and ozone, wherein the lowering of the optical density (OD value) in the high humidity environment is suppressed. The way of use of the water-based ink of the present teaching is not specifically limited, and the water-based ink is widely applicable to various types of ink-jet recording.

## Claims

1. A water-based ink for ink jet recording, comprising a dye represented by a general formula (1), water, a water-soluble organic solvent, and 0.5% by weight to 4% by weight of a cationic polymer, wherein
weight average molecular weight of the cationic polymer is not less than 1200, and




in the general formula (1):
n1 is 1 or 2,
each of three Ms is sodium or ammonium and the three Ms may be same or different from one another, and
R0 represents a monoalkylamino group substituted by a carboxyl group and having a number of carbon atoms of 1 to 8.

2. The water-based ink for ink jet recording according to claim 1, wherein 0.5% by weight to 3% by weight of the cationic polymer is contained.

3. The water-based ink for ink jet recording according to claim 1, wherein the cationic polymer is at least one compound selected from a group consisting of a compound represented by a general formula (2), a compound represented by a general formula (3), a compound represented by a general formula (4), and a compound represented by the general formula (5):



in the general formula (2), m is an integer of 2 to 6, and n is an integer of 20 to 40;




in the general formulas (3) and (4), each of R11 to R13 is a hydrogen atom or an organic group;
in the general formula (4), X− is an anion; and




in the general formula (5), q is a positive integer.

4. The water-based ink for ink jet recording according to claim 3, wherein the cationic polymer is at least one compound selected from a group consisting of polylysine, polyallylamine and polyethyleneimine.

5. The water-based ink for ink jet recording according to claim 3, wherein the cationic polymer is polylysine.

6. The water-based ink for ink jet recording according to claim 3, wherein the cationic polymer is polyallylamine.

7. The water-based ink for ink jet recording according to claim 3, wherein the cationic polymer is polyethyleneimine.

8. An ink cartridge comprising the water-based ink for inkjet recording as defined in claim 1.

9. The water-based ink for ink jet recording according to claim 1, wherein the weight average molecular weight of the cationic polymer is 1200 to 5000.

10. The water-based ink for ink jet recording according to claim 1, wherein the cationic polymer is polylysine or polyallylamine, and
the blending amount of the cationic polymer and the weight average molecular weight of the cationic polymer fulfill the following formula (A):


X×Y=1500 to 12000  (A)



in the formula (A):
X: the blending amount of the cationic polymer (% by weight)
Y: the weight average molecular weight of the cationic polymer.