JP2015017187A - Ink for inkjet recording, ink set, and inkjet recording device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink for inkjet recording wherein the dye deposition is inhibited in a green ink as a mixture of cyan dye and yellow dye with high light resistance, and the ink discharge stability and maintainability are improved.SOLUTION: An ink for inkjet recording comprises water, organic solvent, and colorant, wherein the colorant comprises a green ink, and the green ink comprises a predetermined yellow compound, and a predetermined cyan compound.

Description

  The present invention relates to an ink for ink jet recording, an ink set, and an ink jet recording apparatus.

The ink jet recording method is a recording method in which ink droplets are ejected and attached to a recording medium for recording. Since the recording process is simple, it is possible to increase the number of colors at a low cost. This is a recording method that can easily improve the printing quality and can perform high-speed recording without noise. Therefore, in recent years, it has been widely used from home printers to commercial printers.
Since it is widely used, the image quality of the inkjet recording method is continuously improved, and not only the four process colors (cyan, magenta, yellow, black) but also light ink (light cyan, light magenta, gray) And special colors (red, blue, green) have also been used. By increasing the number of colors, it is possible to reduce the graininess of the printed image and expand the color space.

The image quality by the ink jet recording method can satisfy a photographic image from a character image, and in recent years, with the spread of digital cameras and scanners, it has been widely used as a method for outputting a photograph instead of a silver salt photograph. For this reason, in order to compare print output images based on images on a computer display, the user is demanding color development close to that of a display, and color development superior to silver halide photography is demanded. Therefore, ink jet recording apparatuses that require high color development for photographic use have become apparatuses that use inks of a plurality of colors other than process colors.
Business documents such as character images and graphs, Web screen prints, etc. are temporary outputs or are not used for long-term browsing. It is required to be exposed to gases in the indoor environment and not to be inferior in them.
In addition, an ink jet recording method using an ink using a dye as a colorant can be combined with a glossy medium to form a moisture-resistant and transparent image and obtain an image closest to a silver salt photograph. be able to. However, dyes are more likely to cause light fading and gas fading than pigments, and they are greatly affected by these fading due to their increased surface area by fixing to porous glossy media, which have become popular in recent years. Has become an issue.

Various studies have been made on the use of green ink for improving the color gamut of images and the improvement of weather resistance.
For example, in Patent Document 1, C.I. I. Water resistance is improved by using Direct Blue 199 as a cyan dye, and it is described that this cyan dye is developed into a green ink.
In Patent Document 2, durability to light and environmental gas is achieved with an ink set using a copper phthalocyanine compound in which substituents are limited. A specific yellow compound and C.I. I. It is described that a green ink made of Direct Blue 199 is used.
In Patent Document 3, the image fastness and the bronze phenomenon are suppressed by a special color composed of a yellow compound having a specific structure, a magenta dye, and a cyan dye, and the combination of the yellow compound and the cyan compound having a specific structure is used. Green ink is described.

In addition, development technology for highly weather-resistant dyes has been established, but the marketability can be established only for process colors, and only four colors, cyan, magenta, yellow, and black, are available as highly weather-resistant dyes. Have been supplied. When multicoloring is performed to widen the color development area, dyes with different hues such as red, green, and blue are required, but high weather resistance is not performed, and it is attempted to perform multicoloring while maintaining weather resistance It becomes a mixed ink of a weather-resistant dye.
In particular, the green region has a large color difference between a CRT or LCD display and a printed matter, and there is a strong demand for improving the color development of the printed matter. However, at present, green dyes with high weather resistance have not been sufficiently developed, and green inks are obtained as a mixture of cyan dye and yellow dye with high light resistance. However, since cyan dyes with high weather resistance have high crystallinity, when they are mixed with yellow dyes, the dyes are likely to precipitate out of the ink, and the ink crystals dry out from the ink in the ink jet head, ink suction cap, and waste liquid tank. As a result, the viscosity of the ink is increased, so that the ejection stability of the ink jet, the maintenance function of the head, and the waste liquid collecting function are impaired, and the reliability of the ink jet recording apparatus is lowered.

  Therefore, there is no inkjet recording ink that can suppress the precipitation of dye in a green ink as a mixture of a cyan dye and a yellow dye having high light resistance, and can improve the ejection stability and maintainability of the ink. Currently.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention provides an ink for inkjet recording that can suppress the precipitation of dye in a green ink as a mixture of a cyan dye and a yellow dye having a high light resistance, and can improve the ejection stability and maintainability of the ink. For the purpose.

The ink for ink-jet recording of the present invention as a means for solving the above problems comprises water, an organic solvent, and a colorant,
The colorant is a green ink, and the green ink includes a yellow compound containing a compound represented by the following general formula (1) and a salt thereof, and a compound represented by the following general formula (2) and a salt thereof. Contains a cyanide compound.

<General formula (1)>
However, in the general formula (1), R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, and a hydrogen atom. R ₃ and R ₅ each independently represent a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and an alkyl group substituted with these groups. Yes, R ₄ and R ₆ each independently represent a group other than those defined for R ₃ and R ₅ . p and r are each independently an integer of 1 to 5, q and s are each independently an integer of 0 to 4, and p + q ≦ 5 and r + s ≦ 5.

<General formula (2)>
However, in the general formula (2), R is any one of a hydrogen atom, a group represented by the following general formula (2-1), and a group represented by the following structural formula (2-1). t is an integer of 1 to 3, and M is Cu.

<General formula (2-1)>
However, in said general formula (2-1), M is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.

<Structural Formula (2-1)>

  According to the present invention, the above-described problems can be solved and the object can be achieved. In the green ink as a mixture of a cyan dye and a yellow dye having high light resistance, the precipitation of the dye is suppressed, and the ink is discharged. An object of the present invention is to provide an ink for ink jet recording that can improve stability and maintainability.

FIG. 1 is a schematic diagram illustrating an example of an ink cartridge. FIG. 2 is a schematic view including the case of the ink cartridge of FIG. FIG. 3 is a perspective view showing an example of an ink jet recording apparatus. FIG. 4 is a diagram illustrating an example of an ink jet recording apparatus. FIG. 5 is a schematic enlarged view showing an example of an ink jet head of the ink jet recording apparatus.

(Inkjet recording ink)
The ink for inkjet recording of the present invention contains water, an organic solvent, and a colorant, and preferably contains a surfactant, a penetrating agent, and a water-dispersible resin, and further contains other components as necessary. It contains.

<Colorant>
In the present invention, by using a water-soluble dye as the colorant, a vivid hue can be obtained, and an image maintaining the gloss of the recording medium can be obtained.
The colorant contains a green ink, and a yellow dye and a cyan dye are used as the green ink, and both use a dye having high light fastness to improve the color developability and durability of the image. In order to suppress the crystal precipitation of the green ink, the following dyes are used.

  The colorant contains a green ink, and the green ink contains a yellow compound containing a compound represented by the following general formula (1) and a salt thereof, and a compound represented by the following general formula (2) and a salt thereof. Contains a cyanide compound.

<General formula (1)>
However, in the general formula (1), R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, and a hydrogen atom. R ₃ and R ₅ each independently represent a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and an alkyl group substituted with these groups. Yes, R ₄ and R ₆ each independently represent a group other than those defined for R ₃ and R ₅ . p and r are each independently an integer of 1 to 5, q and s are each independently an integer of 0 to 4, and p + q ≦ 5 and r + s ≦ 5.

The yellow dye for green ink contains the compound represented by the general formula (1) or a salt thereof. This dye has excellent color developability and can form a vivid image with a wide color gamut when an image is formed.
As the yellow dye for green ink represented by the general formula (1), for example, a compound represented by the following structural formula is suitable.

<General formula (2)>
However, in the general formula (2), R is any one of a hydrogen atom, a group represented by the following general formula (2-1), and a group represented by the following structural formula (2-1). t is an integer of 1 to 3, and M is Cu.

<General formula (2-1)>
However, in said general formula (2-1), M is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.

<Structural Formula (2-1)>

The cyan dye for green ink contains the compound represented by the general formula (2) or a salt thereof.
Examples of the cyan dye for green ink include those described in paragraphs [0189] to [0231] of JP-A-2007-224274 and paragraphs [0025] to [0063] of JP-A-2009-062515. Can be used.
As the cyan dye for green ink represented by the general formula (2), for example, compounds represented by the following general formula are suitable.

  Further, by using dyes having high weather resistance for cyan, magenta, yellow, and black as process colors, it is possible to improve the color developability and durability of the image. Examples of such highly weather-resistant dyes include the following dyes.

  The highly weatherable yellow dye preferably contains a compound represented by the following general formula (3) and a salt thereof.

<General formula (3)>
In the general formula _{(3), R 1, R} 2, Y 1 and _{Y 2} are each independently a monovalent group, _{X 1} and _{X 2} are each independently, .sigma.p value of Hammett An electron-withdrawing group of 0.20 or more, and Z ₁ and Z ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and M is any one of a hydrogen atom, an alkali metal, ammonium, and organic ammonium.

  Examples of the highly weatherable yellow dye include those described in paragraphs [0016] to [0118] of JP-A-2007-224274 and paragraphs [0063] to [0130] of JP-A-2009-062515. Can be used.

  Examples of the magenta dye include a compound represented by the following general formula (4) and a salt thereof, a compound represented by the following general formula (5) and a salt thereof, and a compound represented by the following general formula (6) and the salt thereof. It is preferable to include at least one selected from salts.

<General formula (4)>
In the general formula (4), R each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, hydroxyalkyl group having 1 to 4 carbon atoms, a cyclohexyl group, or a (H _{(CH 2) m ) n n (CH 2) O} - ( however, m is 1 to 4, n is 1 to 2, o is a mono- or dialkylaminoalkyl group represented by a 1 to 4), Y are each independently , —SO ₃ M, or — (COOM) _n (where n is 1 to 2), and each M is independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium. X is a linking group represented by —NH— (CH ₂ ) _n —NH— (where n is 2 to 6).

  With respect to the compound represented by the general formula (4) and a salt thereof, for example, paragraphs [0168] to [0169] of JP-A-2009-062515, pamphlet of WO2009 / 060654, JP-A-2005-8868. No. publication, etc.

<General formula (5)>
In the general formula (5), _{R 1} is a hydrogen atom or an alkyl group, m is an integer from 1 to 3, _{R 2} is a group represented by the following general formula (5-1) Or a group represented by the following general formula (5-2), and each M is independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.

<General formula (5-1)>
However, in the general formula (5-1), R ₃ is an anilino group having a carboxy group as a substituent, an unsubstituted monoalkyl alkyl group having 1 to 8 carbon atoms, a mono having a sulfo group or a carboxy group as a substituent. The alkylamino group having 1 to 8 carbon atoms, the unsubstituted dialkyl 1 to 6 alkylamino group, or the phenoxy group, and n is 1 or 2.

<General formula (5-2)>
In the general formula (5-2), _{R 4} is an anilino group, 2-sulfoanilino group, 2,5-disulfoanilino group, 2-ethylhexyl amino group, cyclohexylamino group, 4-methoxy-2-sulfoanilino group, It represents a 2-carboxy-5-sulfoanilino group, a 3-carboxy-4-hydroxyanilino group, or an aminobenzimidazole group, and R ₅ represents a hydroxyl group or an amino group.

  As for the compound represented by the general formula (5) and a salt thereof, for example, paragraphs [0152] to [0167] of JP2009-062515A, pamphlet of WO2006 / 075706, JP2003-192930A. No. publication, etc.

<General formula (6)>
However, in said general formula (6), R < ₂ >, R < ₃ >, R < ₄ > and R < ₅ > are each independently an alkyl group, M is each independently a hydrogen atom, an alkali metal, ammonium, or organic Ammonium.

  The compound represented by the general formula (6) and salts thereof are described in, for example, paragraphs [0170] to [0174] of Japanese Patent Application Laid-Open No. 2009-062515, Japanese Patent No. 4783581 and the like.

  The cyan dye preferably includes at least one selected from a compound represented by the following general formula (7) and a salt thereof, and a compound represented by the following general formula (8) and a salt thereof.

<General formula (7)>
However, in said general formula (7), A, B, C, and D are each independently a 6-membered ring having aromaticity, and M is each independently a hydrogen atom, an alkali metal, ammonium, Or it is organic ammonium and E is an alkylene group. X is a sulfo-substituted anilino group, a carboxyl-substituted anilino group, or a phosphono-substituted anilino group, and these substituted anilino groups further include a sulfonic acid group, a carboxyl group, a phosphono group, a sulfamoyl group, a carbamoyl group, a hydroxyl group, an alkoxy group, Selected from the group consisting of amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acetylamino group, ureido group, alkyl group, nitro group, cyano group, halogen, alkylsulfonyl group, and alkylthio group It may have 1 to 4 at least one substituent. Y is a hydroxyl group or an amino group, l, m, and n are 0 ≦ l ≦ 2, 0 ≦ m ≦ 3, 0.1 ≦ n ≦ 3, and l + m + n = 1 to 4.

<General formula (8)>
However, in the general formula (8), R is any one of a hydrogen atom, a group represented by the following general formula (8-1), and a group represented by the following structural formula (8-2). t is an integer of 1 to 3, and M is Cu.

<General formula (8-1)>
However, in said general formula (8-1), M is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.

<Structural Formula (8-2)>

  Regarding at least one selected from the compound represented by the general formula (7) and a salt thereof, and the compound represented by the general formula (8) and a salt thereof, for example, JP-A-2007-224274 Paragraphs [0189] to [0231] and those described in paragraphs [0025] to [0063] of JP-A-2009-062515 can be used.

  Examples of the black dye include paragraphs [0132] to [0189] of JP-A-2007-224274, paragraphs [0189] to [0259] of JP-A-2009-062515, and the like.

In addition to these, the following water-soluble dyes can be added as complementary colors of the respective colors.
Examples of the water-soluble dye include dyes classified in the color index into acid dyes, direct dyes, basic dyes, reactive dyes, and food dyes.

  Examples of the acid dyes and food dyes include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142; C.I. I. Acid Red 1, 8, 13, 14, 18, 26, 27, 35, 37, 42, 52, 82, 87, 89, 92, 97, 106, 111, 114, 115, 134, 186, 249, 254 289; I. Acid Blue 9, 29, 45, 92, 249; I. Acid Black 1, 2, 7, 24, 26, 94; I. Food Yellow 3, 4; I. Food red 7, 9, 14; I. Food black 1, 2, etc. are mentioned.

  Examples of the direct dye include C.I. I. Direct yellow 1, 12, 24, 26, 33, 44, 50, 86, 120, 132, 142, 144; I. Direct Red 1, 4, 9, 13, 17, 20, 28, 31, 39, 80, 81, 83, 89, 225, 227; I. Direct orange 26, 29, 62, 102; I. Direct Blue 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165, 199, 202; I. Direct black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171 and the like.

  Examples of the basic dye include C.I. I. Basic yellow 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 64, 65, 67, 70, 73, 77, 87, 91; C.I. I. Basic Red 2, 12, 13, 14, 15, 18, 22, 23, 24, 27, 29, 35, 36, 38, 39, 46, 49, 51, 52, 54, 59, 68, 69, 70, 73, 78, 82, 102, 104, 109, 112; I. Basic blue 1, 3, 5, 7, 9, 21, 22, 26, 35, 41, 45, 47, 54, 62, 65, 66, 67, 69, 75, 77, 78, 89, 92, 93, 105, 117, 120, 122, 124, 129, 137, 141, 147, 155; I. Basic black 2, 8, etc. are mentioned.

  Examples of the reactive dye include C.I. I. Reactive black 3, 4, 7, 11, 12, 17; I. Reactive Yellow 1, 5, 11, 13, 14, 20, 21, 22, 25, 40, 47, 51, 55, 65, 67; I. Reactive Red 1, 14, 17, 25, 26, 32, 37, 44, 46, 55, 60, 66, 74, 79, 96, 97; I. Reactive blue 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80, 95, and the like.

The content of the dye is preferably 1% by mass to 10% by mass and more preferably 2% by mass to 6% by mass with respect to the ink jet recording ink. When the content is less than 1% by mass, the coloring power is insufficient and color development becomes insufficient. Moreover, light resistance and ozone resistance are deteriorated by making dye a low density | concentration. This means that the dye is in a clustered state with multiple molecules gathered in the vicinity when dried, and when printing at a dilute dye concentration, the cluster is difficult to form after drying, and the dye is dyed as a single molecule, which is an environmental condition. It is estimated that the frequency of exposure increases and the environmental resistance deteriorates.
Since the dye is a water-soluble dye, it is solubilized by ionic dissociation in water as an organic salt. However, there is a limit to solubility, and since the ink contains an organic solvent, the solubility of the dye is often lowered. . When the water in the ink volatilizes, the dye that has been solubilized as a water-soluble component is deposited, resulting in an increase in ink viscosity and nozzle clogging. When the density is further increased, the coloring power per ink drop is increased, and the dot recognizability is increased, so that the graininess of the image tends to be deteriorated.

<Water>
There is no restriction | limiting in particular as said water, According to the objective, it can select suitably, For example, pure water, such as ion-exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water etc. are mentioned. It is done. These may be used individually by 1 type and may use 2 or more types together.

<Organic solvent>
Examples of the organic solvent include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, ethylene carbonate, Etc.
Among these, from the equilibrium water content and the high solubility of the dye, a triol having 4 or less carbon atoms, a triol having 4 or less carbon atoms, polyethylene glycol ether, polyethylene glycols, and 1,3-propanediol are selected. At least one kind of the parent dye organic solvent is preferable, and the content of the parent dye organic solvent is preferably 20% by mass or more, more preferably 30% by mass to 70% by mass with respect to the whole organic solvent.
When the content is less than 20% by mass, the ink moisturizing power is reduced, so that the ink is easily dried, and the precipitation of the dye due to the drying is caused at the head meniscus portion, which may result in ejection failure.

Examples of the triol having 4 or less carbon atoms include 1,2,3-butanetriol, 1,2,4-butanetriol, and glycerin.
Examples of the polyethylene glycol ether of triol having 4 or less carbon atoms include polyoxyethylene glyceryl ether, polyoxyethylene-1,2,3-butanetriol ether, and polyoxyethylene-1,2,4-butanetriol ether. , Etc.
Examples of the polyethylene glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and PEG200.
Among these, glycerin has a very high equilibrium moisture content of 49% by mass in an environment of 23 ° C. and 80%, and it is easy to suppress drying of the ink. This is preferable because it is excellent in securing ejection stability, suppressing the increase in the viscosity of waste ink in the head maintenance device, and preventing waste ink sticking to the maintenance device.

In addition to the solvent excellent in solubility of the dye, other water-soluble solvents can be used as necessary. Examples include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, cyclic ethers, amines, amides, sulfur-containing compounds, propylene carbonate, ethylene carbonate, and other organic solvents. .
Examples of the polyhydric alcohols include 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5- Pentanediol, 2-methyl-2,4-pentanediol, hexylene glycol, 1,6-hexanediol, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, 3-methyl-1,3- Hexanediol, propylpropylene diglycol, and the like.
Examples of the polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monoethyl ether. , Triethylene glycol dimethyl ether, and the like.
Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Examples of the cyclic ethers include epoxies, oxetanes, tetrahydrofurans, tetrahydropyrans, and crown ethers.
Among these, oxetanes and tetrahydrofurans are preferable, and oxetanes are more preferable from the viewpoint of water solubility.
Examples of the amines include monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylmonoethanolamine, N-methyldiethanolamine, N-methylethanolamine, N-phenylethanolamine, and 3-aminopropyldiethylamine. Is mentioned.
Examples of the amide compounds include 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, β-methoxy-N, N-dimethyl. Examples include propionamide and β-butoxy-N, N-dimethylpropionamide. Formamide, N-methylformamide, N, N-dimethylformamide, and N, N-diethylformamide also exist as amide compounds, but they are highly harmful and are not preferred for use. The amide compound has the effect of inhibiting the crystallization of the dye and maintaining the dissolved state of the dye in the solvent, and has the effect of suppressing the crystal precipitation when the ink is dried.
Examples of the sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiodiglycol, and the like.
The total content of the organic solvent in the ink is preferably 10% by mass to 50% by mass, and more preferably 15% by mass to 40% by mass. If the total content is less than 15% by mass, the ejection stability may be lowered, or the dye may be crystallized and fixed by the maintenance device of the ink jet recording apparatus. On the other hand, if it exceeds 50% by mass, the solubility may be inhibited depending on the type of the dye, and the crystallization of the dye may be caused, or the drying on the paper surface is inferior and it takes time to stabilize the color of the glossy paper.

<Surfactant>
Examples of the surfactant include an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, an acetylene glycol surfactant, and a fluorine surfactant. It is preferable to select a surfactant that does not impair the dispersion stability, depending on the combination of the colorant and the organic solvent.

Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, oxalate sulfonate, laurate, and polyoxyethylene alkyl ether sulfate salt.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene polyoxypropylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene And ethylene alkylphenyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamide, and the like.
Examples of the amphoteric surfactant include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine. Specific examples below are preferably used, but are not limited thereto. Examples include lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, dihydroxyethyl lauryl amine oxide, polyoxyethylene coconut oil alkyl dimethyl amine oxide, dimethyl alkyl (coconut) betaine, and dimethyl lauryl betaine.

  Examples of the surfactant include Nikko Chemicals Co., Ltd., Nippon Emulsion Co., Ltd., Nippon Shokubai Co., Ltd., Toho Chemical Co., Ltd., Kao Co., Ltd., Adeka Co., Ltd., Lion Co., Ltd., Aoki Oil Co., Ltd., Sanyo Chemical Industries Co., Ltd. Available from other surfactant manufacturers.

  The acetylene glycol surfactants are 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5. -Acetylene glycols such as dimethyl-1-hexyn-3-ol (for example, Surfynol 104, 82, 465, 485 or TG from Air Products (USA)) can be used, particularly Surfynol 465, 104 and TG indicate good print quality.

Examples of the fluorosurfactant include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, and perfluoroalkylamine oxide. Examples thereof include a compound, a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain, a sulfate ester salt thereof, and a fluorine-based aliphatic polymer ester.
A commercial item can be used as such a fluorine-type surfactant, As this commercial item, for example, Surflon S-111, S-112, S-113, S121, S131, S132, S-141, S -145 (Asahi Glass Co., Ltd.), Fullrad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431, FC-4430 (Sumitomo 3M) , FT-110, 250, 251, 400S (manufactured by Neos), Zonyl FS-62, FSA, FSE, FSJ, FSP, TBS, UR, FSO, FSO-100, FSN N, FSN-100, FS-300, Examples include FSK (manufactured by Dupont), polyfox PF-136A, PF-156A, and PF-151N (manufactured by OMNOVA).

The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. However, those that do not decompose even at high pH are preferable. For example, side chain-modified polydimethylsiloxane, both-end-modified polydimethylsiloxane , One-end-modified polydimethylsiloxane, side-chain both-end-modified polydimethylsiloxane, and the like. A polyether-modified silicone surfactant having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group is an aqueous surfactant. It is particularly preferable because it exhibits good properties as an agent.
As such a surfactant, an appropriately synthesized product or a commercially available product may be used. Such commercially available products can be easily obtained from, for example, Big Chemie, Shin-Etsu Silicone, Toray Dow Corning Silicone, etc.

The polyether-modified silicone surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the polyalkylene oxide structure represented by the following structural formula may be represented by the side chain of Si part of dimethylpolysiloxane. And the like, and the like.
A commercial item can be used as said polyether modified silicone type surfactant, For example, KF-618, KF-642, KF-643 (all are the Shin-Etsu Chemical Co., Ltd. product) etc. are mentioned.

The surfactant is not limited to these, and may be used alone or in combination. Even if it is not easily dissolved by itself in the recording liquid, it can be solubilized by mixing and exist stably.
The content of the surfactant is preferably 0.01% by mass to 5% by mass, and preferably 0.5% by mass to 2% by mass with respect to the ink for inkjet recording, from the viewpoint of exerting a penetrating effect. More preferred.
When the content is less than 0.01% by mass, the added effect is lost. When the content exceeds 5.0% by mass, the permeability to the recording medium is unnecessarily high, and the image density is lowered and the screen is lost. Problems such as the occurrence of.

<Penetration agent>
The penetrant preferably contains at least one polyol having a solubility in water at 20 ° C. of 0.2% by mass or more and less than 5.0% by mass.
Among the polyols, examples of the aliphatic diol include 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, and 2,2-diethyl-1,3. -Propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 5-hexene-1 , 2-diol, 2-ethyl-1,3-hexanediol, and the like. Among these, 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol are preferable.

Other penetrants that can be used in combination are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, and diethylene glycol. Examples thereof include alkyl and aryl ethers of polyhydric alcohols such as monobutyl ether, propylene glycol monobutyl ether and tetraethylene glycol chlorophenyl ether, and lower alcohols such as ethanol.
The content of the penetrant is preferably 0.1% by mass to 4.0% by mass with respect to the ink for inkjet recording. When the content is less than 0.1% by mass, quick-drying cannot be obtained and a blurred image is obtained. On the other hand, if the content exceeds 4.0% by mass, the dispersion stability of the colorant is impaired, the nozzles are easily clogged, and the permeability to the recording medium is unnecessarily high, resulting in an image density. In some cases, problems such as deterioration of the image quality and occurrence of strikethrough may occur.

<Water dispersible resin>
As the water-dispersible resin, those having excellent film-forming properties (image forming properties) and having high water repellency, high water resistance, and high weather resistance have high water resistance and high image density (high color developability). It is useful for image recording, and examples thereof include condensation-type synthetic resins, addition-type synthetic resins, and natural polymer compounds.
The particle size of the water-dispersible resin is related to the viscosity of the dispersion. When the composition is the same, the smaller the particle size, the larger the viscosity at the same solid content. The average particle size of the water-dispersible resin is preferably 50 nm or more so as not to have an excessively high viscosity when converted into an ink. When the particle size is several tens of microns, it becomes larger than the nozzle opening of the ink jet head and cannot be used. It is known that if particles having a large particle diameter exist in the ink even if they are smaller than the nozzle opening, the ejection property is deteriorated. The average particle size is preferably 500 nm or less, and preferably 150 nm or less in order not to impair the ink ejection properties.

The water-dispersible resin has a function of fixing the water-dispersed colorant on the paper surface, and it is desired to form a film at room temperature to improve the fixability of the colorant. For this purpose, the minimum film-forming temperature (MFT) is preferably room temperature or lower, and more preferably 20 ° C. or lower. However, when the glass transition point is −40 ° C. or lower, the resin film becomes more viscous and the printed matter is tacky. Therefore, a water dispersible resin having a glass transition point of −30 ° C. or higher is particularly preferable.
When such a water-dispersible resin is used, it is possible to improve image fixability, water resistance, and gas resistance. However, depending on the recording medium, the glossiness may be changed by forming a resin film. . In addition, since a large amount of addition forms a film when the meniscus of the ink jet head is dried, addition of a resin solid content of 5% by mass or more is not preferable because it causes clogging of the nozzle and changes in glossiness.

<Image preservability improver>
An image preservability improver may be added to the ink for inkjet recording of the present invention.
Examples of the image preservability improver include hindered amine compounds, ultraviolet absorbers, antioxidants, and the like. Since an inkjet recording image is greatly affected by light and gas, it is preferable to add a hindered amine compound, an ultraviolet absorber, and an antioxidant.

-Hinder amine compounds-
As the hindered amine, for example, any of N—CH ₃ type, N—H type, and N—OR type can be used, but N—CH ₃ type and N—OR type are preferable. Some of these hindered amines are miscible with water by mixing with butyl carbitol or butyl cellosolve, but are preferably water-insoluble liquids or powders dispersed therein.
Examples of the water-dispersed hindered amine compound include TINUVIN 123DW manufactured by BASF, Adecanol UC-5225 and Adecanol UC-606 manufactured by ADEKA. Among these, TINUVIN 123DW in which a hindered amine compound is included and dispersed is particularly preferable because it has an effect on stability and ozone resistance when mixed with a dye.
Content of the said hindered amine compound is dependent on the dye density | concentration which should be protected, 1 mass%-10 mass% are preferable with respect to solid content of a dye, and 2 mass%-7 mass% are more preferable.

-UV absorber-
Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, salicylate ultraviolet absorbers, hydroxyphenyltriazine ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, nickel complex ultraviolet absorbers, Examples include inorganic oxide fine particles.
Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. 2, 2 ′, 4, 4′-tetrahydroxybenzophenone, and the like.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, and the like.

  Examples of the salicylate UV absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.

  Examples of the cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3′-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, and butyl-2- And cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

  Examples of the nickel complex ultraviolet absorber include nickel bis (octylphenyl) sulfide, 2,2′-thiobis (4-tert-octylferrate) -n-butylamine nickel (II), 2,2′-thiobis. (4-tert-octylferrate) -2-ethylhexylamine nickel (II), 2,2′-thiobis (4-tert-octylferrate) triethanolamine nickel (II), and the like.

Examples of the inorganic oxide fine particles include zinc oxide fine particles and titanium oxide fine particles, and an average particle size of 50 nm or less is preferable from the viewpoint of transparency.
Among these, a hydroxyphenyl triazine type and a benzotriazole type are preferable, and these aqueous dispersions are preferable when added to the aqueous ink.
Examples of such an aqueous dispersion include TINUVIN 1130, TINUVIN 99DW, TINUVIN 400DW, TINUVIN 477DW manufactured by BASF, and UC-3140 manufactured by ADEKA. Among these, TINUVIN 477DW in which an ultraviolet absorber is included and dispersed in a resin is particularly preferable because of its high effect on ozone resistance.
The content of the ultraviolet absorber in the ink depends on the concentration of the dye to be protected, and is preferably 1% by mass to 10% by mass and more preferably 2% by mass to 7% by mass with respect to the solid content of the dye. preferable.

-Antioxidant-
Examples of the antioxidant include phenolic antioxidants (including hindered phenolic antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.
Examples of the phenolic antioxidant (including hindered phenolic antioxidant) include butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, stearyl-β- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-Butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) ) Propionyloxy] ethyl] 2,4,8,10-tetrixaspiro [5,5] undecane, 1,1,3-to (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Benzene, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, and the like.

  Examples of the amine-based antioxidant include phenyl-β-naphthylamine, α-naphthylamine, N, N′-di-sec-butyl-p-phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine. 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butyl-phenol, butylhydroxyanisole, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), tetrakis [methylene -3 (3,5-di-tert-butyl-4-dihydroxyphenyl) propio Nate] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and the like.

  Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristyl 3,3′-thiodipropionate, and distearyl β. , Β′-thiodipropionate, 2-mercaptobenzimidazole, dilauryl sulfide and the like.

  Examples of the phosphorus antioxidant include triphenyl phosphite, octadecyl phosphite, triisodecyl phosphite, trilauryl trithiophosphite, and trinonylphenyl phosphite.

Since both are poorly water-soluble, it is preferable to add to the ink using a water dispersion. An example of such an aqueous dispersion is ADEKA SDX-2855.
There is no restriction | limiting in particular in content of the said antioxidant, Although it can select suitably according to the objective, 0 mass%-10 mass% are preferable.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected as necessary. Examples include pH adjusters, antiseptic / antifungal agents, chelating reagents, rust preventive agents, oxygen absorbers, and light stabilizers. Can be mentioned.

The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 to 11 without adversely affecting the ink to be prepared, and can be appropriately selected according to the purpose. And alkali metal element hydroxides, ammonium hydroxides, phosphonium hydroxides, alkali metal carbonates, and the like.
If the pH is less than 7 or exceeds 11, the amount of the ink-jet head or ink supply unit that is melted out is large, and problems such as ink degeneration, leakage, and ejection failure may occur.
Examples of the alcohol amines include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, and the like.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
Examples of the ammonium hydroxide include ammonium hydroxide and quaternary ammonium hydroxide.
Examples of the phosphonium hydroxide include quaternary phosphonium hydroxide.
Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

  Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol and the like.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.

  Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

<Method for producing ink for inkjet recording>
The ink for inkjet recording of the present invention is produced by dispersing or dissolving the dye, the organic solvent, the surfactant, the penetrating agent, water and, if necessary, other components in an aqueous medium, and stirring and mixing appropriately. The stirring and mixing can be performed, for example, with a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, or the like, and can be performed with a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like. .

<Ink physical properties>
The physical properties of the ink are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the viscosity and surface tension are preferably in the following ranges.
The viscosity of the ink at 25 ° C. is preferably 2 mPa · s to 20 mPa · s. By setting the ink viscosity at ejection to 3 mPa · s or more, there is an effect that residual vibration during ink ejection is less likely to occur, and vibration after ejection by the drive waveform can be easily suppressed, and the next ejection can be performed in a short time. It becomes suitable for high-speed printing. On the other hand, by suppressing the ink viscosity to 15 mPa · s or less, it becomes easy to stabilize the ejection performance. Since the viscosity changes depending on the use environment, it is preferable that the ink viscosity satisfies the above range within the assumed use range, and the viscosity at 25 ° C. is more preferably 5 mPa · s to 10 mPa · s.
The viscosity can be measured, for example, by adjusting the temperature to each temperature using a viscometer (RE-550L, manufactured by Toki Sangyo Co., Ltd.).

  The static surface tension of the ink is preferably 20 mN / m to 35 mN / m at 25 ° C., more preferably 20 mN / m to 40 mN / m or less. If the static surface tension is in this range, the permeability is high and effective in reducing bleeding, and the drying property on plain paper printing is good. In addition, since dot enlargement occurs on the surface of glossy paper, color development on glossy paper is improved. When the static surface tension exceeds 40 mN / m, the spread of dots is suppressed due to the size of the glossy paper surface layer, and the amount of ink adhering increases to increase the concealment, resulting in an increase in printing cost and drying. The time may be prolonged. On the other hand, when the static surface tension is less than 20 mN / m, the nozzle plate of the ink jet head gets too wet, and wiping spots due to maintenance cause the ink to ooze out around the nozzle holes and cause non-uniform wettability. It will cause bending and non-ejection.

The ink uses a piezoelectric element as pressure generating means for pressurizing the ink in the ink flow path, and deforms a vibration plate that forms the wall surface of the ink flow path to change the volume in the ink flow path to eject ink droplets. A so-called piezo type (refer to Japanese Patent Laid-Open No. 2-51734), or a so-called thermal type that generates bubbles by heating ink in an ink flow path using a heating resistor (Japanese Patent Laid-Open No. 61-59911). In other words, the diaphragm and the electrode that form the wall surface of the ink flow path are arranged opposite to each other, and the diaphragm is deformed by an electrostatic force generated between the vibration plate and the electrode, thereby reducing the volume of the ink flow path. It can be used favorably in a printer equipped with any inkjet head such as an electrostatic type that changes and discharges ink droplets (see Japanese Patent Laid-Open No. 6-71882).
The ink can be used, for example, in a printer having a function of heating a recording medium and the ink at 50 ° C. to 200 ° C. at the time of printing or before and after printing to promote print fixing.

(Ink set)
The ink set of the present invention is not particularly limited in the color of the ink and can be appropriately selected according to the purpose, and yellow, magenta, cyan, black and the like are used. When recording is performed using an ink set in which two or more of these colors are used in combination, a multicolor image can be formed. When recording is performed using an ink set in which all colors are used in combination, a full color image can be formed. it can. Further, by using red, green, blue, gray, light cyan, light magenta, and dark yellow inks other than the process colors, the color gamut of the full color image can be expanded and the graininess of the image can be reduced. Furthermore, since the total amount of secondary color adhesion can be reduced, it is difficult to cause improper absorption of the recording medium, beading and bleeding can be reduced, and hue bending and hue change during drying can be reduced.

The ink set according to the first aspect of the present invention includes the ink for inkjet recording according to the present invention, a yellow ink, a magenta ink, and a cyan ink.
The yellow ink contains a compound represented by the following general formula (3) and a salt thereof.

<General formula (3)>
In the general formula _{(3), R 1, R} 2, Y 1 and _{Y 2} are each independently a monovalent group, _{X 1} and _{X 2} are each independently, .sigma.p value of Hammett An electron-withdrawing group of 0.20 or more, and Z ₁ and Z ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and M is any one of a hydrogen atom, an alkali metal, ammonium, and organic ammonium.

  Examples of the compound represented by the general formula (3) and a salt thereof (high weather resistance yellow dye) include paragraphs [0016] to [0118] of JP-A-2007-224274 and JP-A-2009-062515. Those described in paragraphs [0063] to [0130] of the above.

An ink set according to a second aspect of the present invention includes the ink for inkjet recording of the present invention, a yellow ink, a magenta ink, and a cyan ink.
The magenta ink includes a compound represented by the following general formula (4) and a salt thereof, a compound represented by the following general formula (5) and a salt thereof, and a compound represented by the following general formula (6) and a salt thereof. Including at least one selected from.

<General formula (4)>
In the general formula (4), R each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, hydroxyalkyl group having 1 to 4 carbon atoms, a cyclohexyl group, or a (H _{(CH 2) m ) n n (CH 2) O} - ( however, m is 1 to 4, n is 1 to 2, o is a mono- or dialkylaminoalkyl group represented by a 1 to 4), Y are each independently , —SO ₃ M, or — (COOM) _n (where n is 1 to 2), and each M is independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium. X is a linking group represented by —NH— (CH ₂ ) _n —NH— (where n is 2 to 6).

  With respect to the compound represented by the general formula (4) and a salt thereof, for example, paragraphs [0168] to [0169] of JP-A-2009-062515, pamphlet of WO2009 / 060654, JP-A-2005-8868. No. publication, etc.

<General formula (5)>
In the general formula (5), _{R 1} is a hydrogen atom or an alkyl group, m is an integer from 1 to 3, _{R 2} is a group represented by the following general formula (5-1) Or a group represented by the following general formula (5-2), and each M is independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.

<General formula (5-1)>
However, in the general formula (5-1), R ₃ is an anilino group having a carboxy group as a substituent, an unsubstituted monoalkyl alkyl group having 1 to 8 carbon atoms, a mono having a sulfo group or a carboxy group as a substituent. The alkylamino group having 1 to 8 carbon atoms, the unsubstituted dialkyl 1 to 6 alkylamino group, or the phenoxy group, and n is 1 or 2.

<General formula (5-2)>
In the general formula (5-2), _{R 4} is an anilino group, 2-sulfoanilino group, 2,5-disulfoanilino group, 2-ethylhexyl amino group, cyclohexylamino group, 4-methoxy-2-sulfoanilino group, It represents a 2-carboxy-5-sulfoanilino group, a 3-carboxy-4-hydroxyanilino group, or an aminobenzimidazole group, and R ₅ represents a hydroxyl group or an amino group.

  As for the compound represented by the general formula (5) and a salt thereof, for example, paragraphs [0152] to [0167] of JP2009-062515A, pamphlet of WO2006 / 075706, JP2003-192930A. No. publication, etc.

<General formula (6)>
However, in said general formula (6), R < ₂ >, R < ₃ >, R < ₄ > and R < ₅ > are each independently an alkyl group, M is each independently a hydrogen atom, an alkali metal, ammonium, or organic Ammonium.

  The compound represented by the general formula (6) and salts thereof are described in, for example, paragraphs [0170] to [0174] of Japanese Patent Application Laid-Open No. 2009-062515, Japanese Patent No. 4783581 and the like.

An ink set according to a third aspect of the present invention is an ink set including the ink-jet recording ink of the present invention, a yellow ink, a magenta ink, and a cyan ink,
The cyan ink includes a compound represented by the following general formula (7) and a salt thereof, and at least one selected from a compound represented by the following general formula (8) and a salt thereof.

<General formula (7)>
However, in said general formula (7), A, B, C, and D are each independently a 6-membered ring having aromaticity, and M is each independently a hydrogen atom, an alkali metal, ammonium, Or it is organic ammonium and E is an alkylene group. X is a sulfo-substituted anilino group, a carboxyl-substituted anilino group, or a phosphono-substituted anilino group, and these substituted anilino groups further include a sulfonic acid group, a carboxyl group, a phosphono group, a sulfamoyl group, a carbamoyl group, a hydroxyl group, an alkoxy group, Selected from the group consisting of amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acetylamino group, ureido group, alkyl group, nitro group, cyano group, halogen, alkylsulfonyl group, and alkylthio group It may have 1 to 4 at least one substituent. Y is a hydroxyl group or an amino group, l, m, and n are 0 ≦ l ≦ 2, 0 ≦ m ≦ 3, 0.1 ≦ n ≦ 3, and l + m + n = 1 to 4.

<General formula (8)>
However, in the general formula (8), R is any one of a hydrogen atom, a group represented by the following general formula (8-1), and a group represented by the following structural formula (8-2). t is an integer of 1 to 3, and M is Cu.

<General formula (8-1)>
However, in said general formula (8-1), M is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.

<Structural Formula (8-2)>

  Regarding at least one selected from the compound represented by the general formula (7) and a salt thereof, and the compound represented by the general formula (8) and a salt thereof, for example, JP-A-2007-224274 Paragraphs [0189] to [0231] and those described in paragraphs [0025] to [0063] of JP-A-2009-062515 can be used.

<Ink cartridge>
The ink cartridge used in the present invention contains each ink of the ink jet recording ink or ink set of the present invention in a container, and further includes other members appropriately selected as required.
The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, at least an ink bag formed of an aluminum laminate film, a resin film, or the like Preferred examples include those possessed.

Next, the ink cartridge will be described with reference to FIGS. Here, FIG. 1 is a view showing an example of the ink cartridge of the present invention, and FIG. 2 is a view including a case (exterior) of the ink cartridge 200 of FIG.
As shown in FIG. 1, the ink cartridge 200 is filled into the ink bag 241 from the ink inlet 242 and exhausted, and then the ink inlet 242 is closed by fusion. In use, the needle of the apparatus main body is pierced into the ink discharge port 243 made of a rubber member and supplied to the apparatus.
The ink bag 241 is formed of a packaging member such as a non-permeable aluminum laminate film. As shown in FIG. 2, the ink bag 241 is usually housed in a plastic cartridge case 244 and is detachably attached to various ink jet recording apparatuses.

  The ink cartridge accommodates each ink of the ink for ink jet recording or the ink set of the present invention, and can be used by being detachably attached to various ink jet recording apparatuses, and the ink jet recording apparatus of the present invention to be described later. It is particularly preferable to use it detachably.

(Inkjet recording apparatus and inkjet recording method)
The ink jet recording apparatus of the present invention includes at least ink flying means, and further includes other means appropriately selected as necessary, for example, stimulus generation means and control means.
The ink jet recording method used in the present invention includes at least an ink flying process, and further includes other processes appropriately selected as necessary, for example, a stimulus generation process, a control process, and the like.

  The ink jet recording method of the present invention can be preferably carried out by the ink jet recording apparatus of the present invention, and the ink flying step can be suitably carried out by the ink flying means. Moreover, the said other process can be suitably performed by the said other means.

-Ink flying process and ink flying means-
The ink flying step is a step of forming an image by applying a stimulus to each ink of the ink jet recording ink or ink set of the present invention and causing the ink to fly.
The ink flying means is means for forming an image by applying a stimulus to each ink of the ink jet recording ink or ink set of the present invention and causing the ink to fly. There is no restriction | limiting in particular as this ink flying means, For example, a recording head etc. are mentioned.

  As the recording head, a piezoelectric element is used as a pressure generating means for pressurizing the ink in the ink flow path, and the diaphragm that forms the wall surface of the ink flow path is deformed to change the volume in the ink flow path to eject ink droplets. A so-called piezo type (see Japanese Patent Laid-Open No. 2-51734), or a so-called thermal type that generates bubbles by heating ink in an ink flow path using a heating resistor (Japanese Patent Laid-Open No. 61-61). No. 59911), the diaphragm and the electrode forming the wall surface of the ink flow path are arranged opposite to each other, and the diaphragm is deformed by an electrostatic force generated between the diaphragm and the electrode, whereby the ink flow path inner volume is obtained. This includes any case of an electrostatic type in which ink droplets are ejected by changing the pressure (see Japanese Patent Laid-Open No. 6-71882).

  The stimulus can be generated, for example, by the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose, such as heat (temperature), pressure, vibration, light, etc. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.

  Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, a heating resistor, etc. Examples include a thermal actuator that uses a phase change caused by film boiling of a liquid using an electrothermal transducer such as a body, a shape memory alloy actuator that uses a metal phase change caused by a temperature change, and an electrostatic actuator that uses an electrostatic force.

  The flying mode of the ink jet recording ink is not particularly limited, and varies depending on the type of the stimulus.For example, when the stimulus is “heat”, the ink jet recording ink in the recording head Thermal energy corresponding to a recording signal is applied using, for example, a thermal head, bubbles are generated in the inkjet recording ink by the thermal energy, and the pressure of the bubbles causes the inkjet recording ink to be ejected from the nozzle holes of the recording head. And a method of ejecting and ejecting ink as droplets. Further, when the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in an ink flow path in the recording head, the piezoelectric element bends and the volume of the pressure chamber is increased. And a method of ejecting and ejecting the ink jet recording ink as droplets from the nozzle holes of the recording head.

  The size of the droplets of the inkjet recording ink to be ejected is preferably, for example, 31 pl to 40 pl, and the ejection jet speed is preferably 5 m / s to 20 m / s. The drive frequency is preferably 1 kHz or higher, and the resolution is preferably 300 dpi or higher. The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

There is no restriction | limiting in particular as a material of the ink repellent layer of the nozzle plate in the said recording head, According to the objective, it can select suitably, For example, a silicone type water repellent material, a fluorine type water repellent material, etc. are mentioned. Among these, silicone-based water repellent materials are preferable.
Examples of the silicone-based water repellent material include room temperature-curing liquid silicone resin or elastomer, which is applied to the surface of a substrate and polymerized and cured by being left in the air at room temperature to form an ink repellent film. It is preferable.
The silicone-based water-repellent material is a heat-curable liquid silicone resin or elastomer, and may be applied to the surface of the substrate and cured by heat treatment to form an ink-repellent film.
The silicone-based water repellent material is an ultraviolet curable liquid silicone resin or elastomer, and may be applied to the surface of the substrate and cured by irradiation with ultraviolet rays to form an ink repellant film.
The silicone water repellent material preferably has a viscosity of 1,000 cp (centipoise) or less.

  The silicone resin is a resin having a siloxane bond made of Si and O as a basic skeleton, and is commercially available in various forms such as oil, resin, elastomer, etc. In addition to the ink repellency important in the present invention, it is heat resistant. It has various properties such as properties, releasability, defoaming properties, and tackiness. Silicone resins include room temperature curing, heat curing, ultraviolet curing, and the like, and can be selected according to the production method and usage.

As a method for forming the ink repellent layer containing the silicone resin on the nozzle surface, a method of vacuum-depositing a liquid silicone resin material, a method of forming a silicone oil by plasma polymerization, spin coating, dipping, spray coating Examples thereof include a method of forming by coating and the like, and an electrodeposition method. When forming the ink repellent layer, except for the electrodeposition method, the nozzle holes and the back of the nozzle plate are masked with a photoresist, a water-soluble resin, etc., and after forming the ink repellent layer, the resist is peeled off to remove only the nozzle plate surface. In addition, an ink repellent layer containing a silicone resin can be formed. In this case, care should be taken because a strong alkaline stripping solution will damage the ink repellent layer.
The thickness of the ink repellent layer containing the silicone resin is preferably 0.1 μm to 5.0 μm, and more preferably 0.1 μm to 1.0 μm. When the thickness is less than 0.1 μm, the durability against wiping deteriorates, and the ink repellency may deteriorate during long-term use. When the thickness exceeds 5.0 μm, the ink repellency has a thickness greater than necessary. The manufacturing cost may increase because of the layer.
The surface roughness (Ra) of the ink repellent layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.2 μm or less. By setting the surface roughness Ra to 0.2 μm or less, it is possible to reduce wiping residue during wiping.

Here, one aspect of carrying out the ink jet recording method of the present invention by the ink jet recording apparatus of the present invention will be described with reference to the drawings.
The ink jet recording apparatus shown in FIG. 3 stocks an apparatus main body 101, a paper feed tray 102 for loading paper loaded on the apparatus main body 101, and paper on which an image is recorded (formed) mounted on the apparatus main body 101. A paper discharge tray 103 and an ink cartridge loading unit 104. On the upper surface of the ink cartridge loading unit 104, an operation unit 105 such as operation keys and a display is arranged. The ink cartridge loading unit 104 has a front cover 115 that can be opened and closed for attaching and detaching the ink cartridge 201.

In the apparatus main body 101, as shown in FIGS. 4 and 5, the carriage 133 is slid in the main scanning direction by guide rods 131 and stays 132 which are horizontally mounted on left and right side plates (not shown). It is held movably and moved and scanned in the direction of the arrow in FIG. 9 by a main scanning motor (not shown).
The carriage 133 is provided with a recording head 134 composed of four inkjet recording heads that eject ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). Are arranged in a direction crossing the main scanning direction, and the ink droplet ejection direction is directed downward.

As the ink jet recording head constituting the recording head 134, a piezoelectric actuator such as a piezoelectric element, a thermal actuator that uses a phase change caused by film boiling of a liquid using an electrothermal transducer such as a heating resistor, a metal phase caused by a temperature change A shape memory alloy actuator that uses a change, an electrostatic actuator that uses an electrostatic force, or the like as an energy generating means for ejecting ink can be used.
In addition, the carriage 133 is equipped with a sub tank 135 for each color for supplying ink of each color to the recording head 134. The sub tank 135 is supplied with ink in the ink media set of the present invention from the ink cartridge 201 of the present invention loaded in the ink cartridge loading section 104 via an ink supply tube (not shown).
On the other hand, as a paper feeding unit for feeding the paper 142 stacked on the paper stacking unit (pressure plate) 141 of the paper feeding tray 103, a half-moon roller (feeding) that separates and feeds the paper 142 one by one from the paper stacking unit 141. A separation pad 144 made of a material having a large coefficient of friction is provided facing the paper roller 143) and the paper feed roller 143, and the separation pad 144 is urged toward the paper feed roller 143 side.

  As a transport unit for transporting the paper 142 fed from the paper feed unit below the recording head 134, a transport belt 151 for transporting the paper 142 by electrostatic adsorption and a guide 145 from the paper feed unit. The counter roller 152 for transporting the paper 142 fed via the transport belt 151 with the transport belt 151 and the paper 142 fed substantially vertically upward are changed by approximately 90 ° so as to follow the transport belt 151. A conveying guide 153 and a tip pressure roller 155 urged toward the conveying belt 151 by a pressing member 154, and a charging roller 156 as a charging means for charging the surface of the conveying belt 151. It has been.

  The conveyance belt 151 is an endless belt, is stretched between the conveyance roller 157 and the tension roller 158, and can circulate in the belt conveyance direction. The transport belt 151 includes, for example, a surface layer serving as a sheet adsorption surface formed of a resin material having a thickness of about 40 μm that is not subjected to resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE), and the same surface layer. It has a back layer (medium resistance layer, earth layer) that has been subjected to resistance control with carbon as a material. On the back side of the conveyance belt 151, a guide member 161 is arranged corresponding to a printing area by the recording head 134. Note that, as a paper discharge unit for discharging the paper 142 recorded by the recording head 134, a separation claw 171 for separating the paper 142 from the conveyance belt 151, a paper discharge roller 172, and a paper discharge roller 173 are provided. The paper discharge tray 103 is disposed below the paper discharge roller 172.

  A double-sided paper feeding unit 181 is detachably mounted on the back surface of the apparatus main body 101. The double-sided paper feeding unit 181 takes in the paper 142 returned by the reverse rotation of the transport belt 151, reverses it, and feeds it again between the counter roller 152 and the transport belt 151. A manual paper feed unit 182 is provided on the upper surface of the duplex paper feed unit 181.

In this ink jet recording apparatus, the paper 142 is separated and fed one by one from the paper feed unit, and the paper 142 fed substantially vertically upward is guided by the guide 145 and between the transport belt 151 and the counter roller 152. It is sandwiched and conveyed. Further, the leading end is guided by the conveying guide 153 and pressed against the conveying belt 151 by the leading end pressure roller 155, and the conveying direction is changed by approximately 90 °.
At this time, the conveying belt 151 is charged by the charging roller 156, and the sheet 142 is electrostatically attracted to the conveying belt 151 and conveyed. Therefore, by driving the recording head 134 according to the image signal while moving the carriage 133, ink droplets are ejected onto the stopped paper 142 to record one line, and after the paper 142 is conveyed by a predetermined amount, Record the next line. Upon receiving a recording end signal or a signal that the trailing edge of the sheet 142 has reached the recording area, the recording operation is terminated and the sheet 142 is discharged onto the discharge tray 103.

When a near-end remaining amount of ink in the sub tank 135 is detected, a required amount of ink is supplied from the ink cartridge 201 to the sub tank 135.
In this ink jet recording apparatus, when the ink in the ink cartridge 201 of the present invention is used up, the casing of the ink cartridge 201 can be disassembled and only the ink bag inside can be replaced. Further, the ink cartridge 201 can supply ink stably even when the ink cartridge 201 is placed vertically and has a front loading configuration. Therefore, when the upper portion of the apparatus main body 101 is closed and installed, for example, even when the apparatus main body 101 is stored in a rack or an object is placed on the upper surface of the apparatus main body 101, the ink cartridge 201 is replaced. Can be easily performed.
Here, an example is described in which the present invention is applied to a serial (shuttle type) ink jet recording apparatus that is scanned by a carriage, but the present invention can be similarly applied to a line type ink jet recording apparatus having a line type head.

  Further, the ink jet recording apparatus and the ink jet recording method of the present invention can be applied to various types of recording by the ink jet recording method. For example, the ink jet recording apparatus, the facsimile apparatus, the copying apparatus, the printer / fax / copier multifunction machine, etc. It can be particularly preferably applied.

<Recording medium>
The recording medium is a recording medium having at least one ink-receiving layer on a support, having a lower layer containing silica, polyvinyl alcohol and a crosslinking agent on the support, and alumina or colloidal silica and polyvinyl alcohol. An ink jet recording medium comprising an upper layer that contains substantially no polyvinyl alcohol crosslinking agent.
The upper layer of the recording medium is the recording medium printing surface, and the Beck smoothness of this surface is preferably 300 seconds or more. If the Beck smoothness is 300 seconds or less, it is not preferable because the pixels are spread unevenly, the roundness is liable to be lost, and noise in photographic gradation is likely to occur.
The ink receiving layer of the recording medium has a multilayer structure of two or more layers, and the lower layer contains porous particles such as inorganic oxides with a large specific surface area so that the ink can be absorbed quickly and the colorant can be fixed. It is preferable to do. Specific examples include silica or alumina. Among silicas, synthetic silica having an average primary particle size of 30 nm or less obtained by a vapor phase method and a BET specific surface area of 250 m ² / g or more is an ink absorptivity. And high gloss.
Moreover, as said alumina, (beta) -alumina, (gamma) -alumina etc. can be used, for example.

In addition, the upper layer corresponding to the surface of the recording medium is preferably made of colloidal silica or alumina having a small primary particle diameter and a large secondary particle diameter, and colloidal silica particles treated with an aluminum salt can also be preferably used.
As the binder in the ink receiving layer, a hydrophilic binder that is highly transparent and can obtain higher permeability of the ink solvent is preferably used. In using the hydrophilic binder, it is important that the hydrophilic binder does not swell during the initial permeation of the ink solvent and block the gap, and a hydrophilic binder that does not easily swell near room temperature is preferably used. Particularly preferred hydrophilic binders are fully or partially saponified polyvinyl alcohol or cation-modified polyvinyl alcohol. The lower layer can be formed into a gel-like structure by adding a crosslinking agent such as borax to polyvinyl alcohol, and dried in the gel structure, thereby forming an ink-receiving layer with a large gap and high liquid absorption.
The substrate of the recording medium is not particularly limited, and any of known paper, synthetic paper, resin-coated paper, film, and the like can be used, but a non-ink-absorbing substrate is preferable.
In particular, resin-coated paper used for photographic printing paper is more preferable as a media base material for reproducing photographic image quality.

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

It describes about the dye used in the following Example.
<Dye (Y-I)>

<Dye (CI)>

<Dye (Y-II)>

<Dye (M-I)>

<Dye (M-II)>

<Dye (M-III)>

<Dye (C-II)>
However, l = 0.3, m = 2.3, and n = 1.4.

(Preparation Examples 1 to 30)
<Preparation of ink>
The ink was prepared according to the following procedure according to Tables 1 to 3. In addition, content of each component in Table 1-Table 3 is the mass%.
First, an organic solvent, a surfactant, and water were mixed and stirred for 30 minutes to mix uniformly. An aqueous dye solution was added to the mixed solution, the remaining amount of water was added so that the total amount was 100% by mass, and the mixture was stirred for 30 minutes. Then, pressure filtration was performed with a cellulose acetate membrane filter having a pore diameter of 0.8 μm to remove coarse particles, and each ink was produced.

Details of the components in Tables 1 to 3 are as follows.
* Surfactant (Zonyl FSO-100, polyoxyethylene perfluoroalkyl ether, manufactured by Dupont, 40 mass% active ingredient)
* Emulgen LS-106 (polyoxyalkylene alkyl ether, manufactured by Kao Corporation, 100% by mass of active ingredient)
* UNIOX G450 (polyoxyethylene glyceryl ether, manufactured by NOF Corporation, active ingredient 100% by mass)
* PEG200 (polyethylene glycol, manufactured by Kanto Chemical Co., Inc., 100% by mass of active ingredient)
* Examide M100 (amide solvent, manufactured by Idemitsu Kosan Co., Ltd., active ingredient 100% by mass)
* Proxel LV (manufactured by Arch Chemical Co., Ltd.)

  Next, various characteristics of the produced ink for ink jet recording were evaluated as follows. The results are shown in Table 4.

<Precipitation of dye>
About each produced ink, 2.7g was put into the glass petri dish with a diameter of 26.6 mm, and it was dried for 14 hours in the thermostat with the temperature of 40 degreeC, and 10% of relative humidity. Then, it was left to stand for 20 hours in a desiccator with a temperature of 23 ° C. and a relative humidity of 15%, and the state after being left was observed and evaluated according to the following criteria.
〔Evaluation criteria〕
A: There is no precipitation of dye and it is liquid and fluid.
B: Although a small amount of dye is precipitated, it is liquid and maintains fluidity.
C: There is dye precipitation on the entire surface, and there is no fluidity.

  For the following evaluation, the ink supply path including the print head of the printer (Ricoh Co., Ltd., IPSiO GX e3300) was cleaned by passing pure water, and the liquid was sufficiently passed until the cleaning liquid was not colored. Was extracted from the apparatus as an evaluation printing apparatus. Further, the evaluation ink was stirred for 30 minutes under a reduced pressure condition of 5 Pa to 10 Pa to degas the ink, and the ink was filled into an ink cartridge to obtain an evaluation ink cartridge. This ink cartridge was set in a printing apparatus and filled with ink, and then left overnight and printed on photographic paper Krispia (manufactured by Seiko Epson) in an environment of 23% and 40% RH and evaluated. . The results are shown in Table 4.

<Light resistance evaluation>
A solid color gradation solid image was printed at 1,200 dpi × 1,200 dpi with the evaluation printing apparatus. The output image was dried at 23 ° C. in an environment of 40% RH for 24 hours, and the image density was measured with a reflection densitometer X-Rite 939 to measure the color characteristics of the initial image.
Atlas Xenon Weatherometer Ci35AW with irradiance of 0.35 mW / m ³ (@ 340 nm), B-Si / B-Si filter, black panel temperature 89 ° C, dry bulb temperature 70 ° C, relative humidity 50% RH And irradiation was performed for 24 hours. Thereafter, the image density was measured with a reflection densitometer X-Rite 939 under an environment of 40% RH at 23 ° C., and the color characteristics of the deteriorated image were measured.
The evaluation was performed based on the residual density ratio after the fade of the solid density having a reflection density closest to 1 in the initial image.
In addition, since an appropriate image density cannot be obtained for the green color tone, L ^* value, a ^* value, and b ^* value are obtained for a solid patch having a cyan reflection density closest to 0.7 in the initial image, and the initial value is obtained. Evaluation was performed by obtaining a color difference ΔE from the value.
Color difference ΔE = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² )} ^1/2
〔Evaluation criteria〕
A: Density remaining rate of 85% or more, color difference less than ΔE5 B: Density remaining rate of 80% or more, less than 85%, Color difference ΔE5 or more, less than 10 C: Density remaining rate of 75% or more, less than 80%, Color difference ΔE10 or more, less than 15 D: Density residual ratio is less than 75%, color difference ΔE15 or more

<Ozone resistance evaluation>
A solid color gradation solid image was printed at 1,200 dpi × 1,200 dpi with the evaluation printing apparatus. The output image was dried at 23 ° C. in an environment of 40% RH for 24 hours, and the image density was measured with a reflection densitometer X-Rite 939 to measure the color characteristics of the initial image.
The ozone generation control device OES-10A manufactured by Directec Co., Ltd. was used to expose to an ozone atmosphere at an ozone concentration of 5 ppm, a bath temperature of 40 ° C., a bath humidity of 25% RH, and 24 hours. Thereafter, the image density was measured with a reflection densitometer X-Rite 939 under an environment of 23 ° C. and 40% RH, and the color characteristics of the deteriorated image were measured.
The evaluation was performed based on the residual density ratio after the fade of the solid density having a reflection density closest to 1 in the initial image.
In addition, since an appropriate image density cannot be obtained for the green color tone, L ^* value, a ^* value, and b ^* value are obtained for a solid patch having a cyan reflection density closest to 0.7 in the initial image, and the initial value is obtained. Evaluation was performed by obtaining a color difference ΔE from the value.
Color difference ΔE = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² )} ^1/2
〔Evaluation criteria〕
A: Density remaining rate of 85% or more and color difference less than ΔE3 B: Density remaining rate of 80% or more and less than 85%, Color difference ΔE3 or more and less than 8 C: Density remaining rate of 75% or more and less than 80%, Color difference ΔE8 or more, less than 15 D: Density remaining rate is less than 75%, color difference ΔE15 or more

<Eject recovery after leaving>
After filling the evaluation printing apparatus with ink, it is confirmed from the nozzle check pattern that ink has been ejected from all nozzles, and an initial condition is created. Thereafter, the head was removed from the cap position, and the nozzle surface was exposed, and left at 32 ° C. in a 15% RH environment for 50 hours.
After leaving, the nozzle check pattern printing and cleaning were repeated to evaluate the recoverability.
〔Evaluation criteria〕
A: Recovered so that all nozzles can be discharged with less than 3 cleanings.
B: Recovered so that all nozzles can be discharged after 3 to less than 7 cleanings.
C: It cannot be recovered until all nozzles can be ejected after 7 or more cleanings.

<Maintenance of maintenance function>
Using the head maintenance mechanism of the evaluation printing apparatus, the entire waste liquid tube is filled from the head suction cap, and then left at 32 ° C. in an environment of 15% RH for 48 hours. Thereafter, the evaluation was performed from the state of the suction cap and the state when the ink was added to the cap and the suction operation was performed.
〔Evaluation criteria〕
A: The ink in the suction cap is liquid and can be sucked by the suction operation.
B: Although the ink of the suction cap is a gel-like film, the ink can be sucked by the suction operation.
C: The ink in the suction cap is solid, and the ink cannot be sucked by the suction operation.

From the results of Table 4, as in Example 1, a yellow compound containing the compound represented by the general formula (1) and a salt thereof, and a cyan compound containing the compound represented by the general formula (2) and a salt thereof. The green ink obtained by mixing with is excellent in dye precipitation, light resistance and ozone resistance, and is low in dye precipitation, so it is excellent in ejection recovery after standing and is reliable without impairing the maintenance function. Can be maintained. In contrast, a green ink obtained by mixing a yellow compound containing the compound represented by the general formula (1) and a salt thereof and a cyan compound containing the compound represented by the general formula (2) and a salt thereof. Otherwise, it was found that an ink satisfying all of light resistance, ozone resistance, ejection recovery after standing, and maintenance function maintenance could not be obtained.
In addition, it was found that even if the mixing ratio of the dyes was any way as in Examples 2 to 5, the dyes did not precipitate and the ink was satisfactory.

  From the results of Table 5, as in Examples 6 to 15, the triol having 4 or less carbon atoms, the triol having 4 or less carbon atoms, polyethylene glycol ether, polyethylene glycols, and any parent of 1,3-propanediol Mixing a yellow compound containing the compound represented by the general formula (1) and a salt thereof and a cyan compound containing the compound represented by the general formula (2) and a salt thereof by including the dye organic solvent in the ink It was possible to suppress the precipitation of the dye of the green ink obtained in (1). In particular, as in Examples 6 to 13, by containing 20% by mass or more of the parent dye organic solvent in the total organic solvent, it is possible to effectively suppress the precipitation of the dye, and it is excellent in discharge recoverability after standing and has a maintenance function. Reliability can be maintained without loss.

Next, according to Table 6, each ink set was loaded into the black ink tank, cyan ink tank, magenta ink tank, and yellow ink tank of the printer, and printing was performed with a printer (IPSiO GX e3300, manufactured by Ricoh Co., Ltd.). The hue angle obtained from the colorimetric image at this time is a color defined using a method standardized as a JIS Z8729: 2004 color display method in the CIE (1976) L ^* a ^* b ^* color space ( L ^* a ^* b ^* ) is determined using the color coordinates a ^* b ^* .
JIS The hue angle ^{hab = tan -1 (b * /} a *) as ^{a * ≧ 0, b * ≧} 0 in case if 0 ≦ hab ≦ 90 ^°, if ^{a * <0, b * ≧} 0 90 ° <Hab ≦ 180 °, a ^* ≦ 0, b ^* <0, 180 ° <hab ≦ 270 °, a ^* > 0, b ^* <0, 270 ° <hab <360 °. In the invention, in order to show the difference in bluish color (b ^* ) of reddish colors (a ^* > 0), the hue angle hab = tan ⁻¹ (b ^* / a ^* ) is set as a ^* ≧ 0, b ^* ≧ 0 If 0 ≦ hab ≦ 90 °, a ^* <0, b ^* ≧ 0, 90 ° <hab ≦ 180 °, a ^* <0, b ^* <0, −180 ° <hab <−90 ° , A ^* ≧ 0, b ^* ≦ 0, the hue angle is defined as −90 ° ≦ hab ≦ 0 °.

<Light resistance evaluation>
A single-color gradation solid image was printed at 1,200 dpi × 1,200 dpi using a printer (IPSiO GX e3300, manufactured by Ricoh Co., Ltd.). The output image was dried at 23 ° C. in an environment of 40% RH for 24 hours, and the image density was measured with a reflection densitometer X-Rite 939 to measure the color characteristics of the initial image.
Atlas Xenon Weatherometer Ci35AW with irradiance of 0.35 mW / m ³ (@ 340 nm), B-Si / B-Si filter, black panel temperature 89 ° C, dry bulb temperature 70 ° C, relative humidity 50% RH And irradiation was performed for 24 hours. Thereafter, the image density was measured with a reflection densitometer X-Rite 939 under an environment of 40% RH at 23 ° C., and the color characteristics of the deteriorated image were measured.
The evaluation was performed based on the residual density ratio after the fade of the solid density having a reflection density closest to 1 in the initial image.
In addition, since an appropriate image density cannot be obtained for the green color tone, the colorimetric point showing the maximum saturation is used as the evaluation point at the hue angle of green (150 ≦ θ <180) from all the colorimetric points of the initial image. Evaluation was performed by calculating the L ^* value, a ^* value, and b ^* value after exposure, and the color difference ΔE from the initial value.
Color difference ΔE = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² )} ^1/2
〔Evaluation criteria〕
A: Density remaining rate of 85% or more, color difference less than ΔE5 B: Density remaining rate of 80% or more, less than 85%, Color difference ΔE5 or more, less than 10 C: Density remaining rate of 75% or more, less than 80%, Color difference ΔE10 or more, less than 15 D: Density residual ratio is less than 75%, color difference ΔE15 or more

<Ozone resistance evaluation>
A single-color gradation solid image was printed at 1,200 dpi × 1,200 dpi using a printer (IPSiO GX e3300, manufactured by Ricoh Co., Ltd.). The output image was dried at 23 ° C. in an environment of 40% RH for 24 hours, and the image density was measured with a reflection densitometer X-Rite 939 to measure the color characteristics of the initial image.
The ozone generation control device OES-10A manufactured by Directec Co., Ltd. was used to expose to an ozone atmosphere at an ozone concentration of 5 ppm, a bath temperature of 40 ° C., a bath humidity of 25% RH, and 24 hours. Thereafter, the image density was measured with a reflection densitometer X-Rite 939 under an environment of 23 ° C. and 40% RH, and the color characteristics of the deteriorated image were measured.
The evaluation was performed based on the residual density ratio after the fade of the solid density having a reflection density closest to 1 in the initial image.
In addition, since an appropriate image density cannot be obtained for the green color tone, the colorimetric point showing the maximum saturation is used as the evaluation point at the hue angle of green (150 ≦ θ <180) from all the colorimetric points of the initial image. The L ^* value, a ^* value, and b ^* value after the exposure and the exposure were obtained, and the color difference ΔE from the initial value was obtained for evaluation.
Color difference ΔE = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² )} ^1/2
〔Evaluation criteria〕
A: Density remaining rate of 85% or more, less than color difference ΔE3 B: Density remaining rate of 80% or more, less than 85%, Color difference ΔE3 or more, less than 8 C: Density remaining rate of 75% or more, less than 80%, Color difference ΔE8 or more, less than 15 D: Density remaining rate less than 75%, color difference ΔE15 or more

<Color development evaluation>
A matrix (combined gradation patterns of cyan ink and yellow ink) printed with a printer (Ricoh Co., Ltd., IPSiO GX e3300) is printed at 1,200 dpi × 1,200 dpi, and the secondary colors are combined. A solid image was formed. In addition, in an ink set with green ink, a monochrome single-color gradation solid image was printed at 1,200 dpi × 1,200 dpi. The output image was dried at 23 ° C. in an environment of 40% RH for 24 hours, and the image density was measured with a spectrophotometer X-Rite i1 iSis to measure the color characteristics of the image. Then, the saturation of the colorimetric point showing the maximum saturation was evaluated at the hue angle of green (150 ≦ θ <180) from all the colorimetric points.
〔Evaluation criteria〕
A: 93 or more B: 85 or more and less than 93 C: Less than 85

<Drying evaluation>
A matrix (combined gradation patterns of cyan ink and yellow ink) printed with a printer (Ricoh Co., Ltd., IPSiO GX e3300) is printed at 1,200 dpi × 1,200 dpi, and the secondary colors are combined. A solid image was formed. In addition, in an ink set with green ink, a monochrome single-color gradation solid image was printed at 1,200 dpi × 1,200 dpi. The output image was measured at 23 ° C. in an environment of 40% RH for 10 minutes after printing and 24 hours after printing with a spectrophotometer X-Rite i1 iSis to measure the color characteristics of the image.
Then, from all colorimetric points of the image 24 hours after printing, the color difference after 10 minutes and 24 hours after printing is obtained from the colorimetric value indicating the maximum saturation at the hue angle of green (150 ≦ θ <180). Thus, the evaluation was performed at the value at which the color difference ΔE was maximized.
Color difference ΔE = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² )} ^1/2
〔Evaluation criteria〕
A: Less than 10 B: 10 or more and less than 15 C: 15 or more

<Eject recovery after leaving>
After filling a printer (IPSiO GX e3300, manufactured by Ricoh Co., Ltd.) with ink, it is confirmed from the nozzle check pattern that ink has been ejected from all nozzles, and initial conditions are created. Thereafter, the head was removed from the cap position, and the nozzle surface was exposed, and left at 32 ° C. in a 15% RH environment for 50 hours.
After leaving, the nozzle check pattern printing and cleaning were repeated to evaluate the recoverability.
〔Evaluation criteria〕
A: Recovery so that all nozzles can be ejected with less than 3 cleanings B: Recovery so that all nozzles can be ejected with 3 to less than 7 cleanings C: Recovery until all nozzles can be ejected with 7 or more cleanings Can't

<Maintenance of maintenance function>
An ink is prepared by mixing the ink of the ink set so that the mass ratio is equal, and the entire waste liquid tube is filled from the head suction cap using the head maintenance mechanism of the printer (IPSiO GX e3300, manufactured by Ricoh Co., Ltd.). After that, it is left to stand at 32 ° C. in an environment of 15% RH for 48 hours. Thereafter, the following criteria were evaluated from the state of the suction cap and the state when the ink was added to the cap and the suction operation was performed.
〔Evaluation criteria〕
A: The ink in the suction cap is liquid and can be sucked by the suction operation.
B: Although the ink of the suction cap is a gel-like film, the ink can be sucked by the suction operation.
C: The ink in the suction cap is solid, and the ink cannot be sucked by the suction operation.

From the results of Tables 6 and 7, in the ink sets of Examples 16 to 18, since the ink that suppresses the precipitation of the dye is used for the green ink, it is excellent in discharge recoverability after being left, and the color development and the image drying. The property was good. It has been found that the dry resistance of the maintenance function is improved by using the yellow dye used for the green ink as the yellow ink used in the ink set. Further, when a yellow dye composed of the compound represented by the general formula (3) and a salt thereof was used for the yellow ink, an effect of improving the image coloring property was observed by combining with the green ink.
In addition, as in Comparative Example 6, only the green ink uses an ink that has high weather resistance and suppresses dye precipitation, and other colors are usually weak dye inks, so that light resistance and ozone resistance are maintained. I can't do it.
In addition, it was found that when an ink that does not consider the precipitation of the green ink dye as in Comparative Example 7 was used, even when the ink set was used, the ejection recoverability after being left unsatisfactory and the maintenance function deteriorated. .
In addition, as in Comparative Example 8, if the weather resistance of the green ink is not taken into consideration, it is understood that the light resistance and ozone resistance cannot be maintained as an ink set even if the weather resistance of the other color inks is high. It was.
In addition, as in Comparative Example 9, it was found that if green ink was not used, the color developability and drying properties were inferior, and it was impossible to obtain an image with high color development and good drying properties.

As an aspect of this invention, it is as follows, for example.
<1> It contains water, an organic solvent, and a colorant,
The colorant is a green ink, and the green ink includes a yellow compound containing a compound represented by the following general formula (1) and a salt thereof, and a compound represented by the following general formula (2) and a salt thereof. An ink for inkjet recording, comprising a cyanide compound.
<General formula (1)>
However, in the general formula (1), R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, and a hydrogen atom. R ₃ and R ₅ each independently represent a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and an alkyl group substituted with these groups. Yes, R ₄ and R ₆ each independently represent a group other than those defined for R ₃ and R ₅ . p and r are each independently an integer of 1 to 5, q and s are each independently an integer of 0 to 4, and p + q ≦ 5 and r + s ≦ 5.
<General formula (2)>
However, in the general formula (2), R is any one of a hydrogen atom, a group represented by the following general formula (2-1), and a group represented by the following structural formula (2-1). t is an integer of 1 to 3, and M is Cu.
<General formula (2-1)>
However, in said general formula (2-1), M is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.
<Structural Formula (2-1)>
<2> The organic solvent contains at least one parent dye organic solvent selected from triols having 4 or less carbon atoms, polyethylene glycol ethers of triols having 4 or less carbon atoms, polyethylene glycols, and 1,3-propanediol. The ink for ink-jet recording according to claim 1, wherein the content of the organic solvent for the parent dye is 20% by mass or more of the whole organic solvent.
<3> The inkjet recording ink according to any one of <1> to <2>, wherein the yellow compound contained in the green ink is a compound represented by the following structural formula.
<4> The inkjet recording ink according to any one of <1> to <3>, a yellow ink, a magenta ink, and a cyan ink,
The yellow ink is an ink set including a compound represented by the following general formula (3) and a salt thereof.
<General formula (3)>
In the general formula _{(3), R 1, R} 2, Y 1 and _{Y 2} are each independently a monovalent group, _{X 1} and _{X 2} are each independently, .sigma.p value of Hammett An electron-withdrawing group of 0.20 or more, and Z ₁ and Z ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and M is any one of a hydrogen atom, an alkali metal, ammonium, and organic ammonium.
<5> The inkjet recording ink according to any one of <1> to <3>, a yellow ink, a magenta ink, and a cyan ink,
The magenta ink includes a compound represented by the following general formula (4) and a salt thereof, a compound represented by the following general formula (5) and a salt thereof, and a compound represented by the following general formula (6) and a salt thereof. An ink set comprising at least one selected from the group consisting of:
<General formula (4)>
In the general formula (4), R each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, hydroxyalkyl group having 1 to 4 carbon atoms, a cyclohexyl group, or a (H _{(CH 2) m ) n n (CH 2) O} - ( however, m is 1 to 4, n is 1 to 2, o is a mono- or dialkylaminoalkyl group represented by a 1 to 4), Y are each independently —SO ₃ M or — (COOM) _n (where n is 1 to 2), and M is independently any one of a hydrogen atom, an alkali metal, ammonium, and organic ammonium. X is a linking group represented by —NH— (CH ₂ ) _n —NH— (where n is 2 to 6).
<General formula (5)>
In the general formula (5), _{R 1} is a hydrogen atom or an alkyl group, m is an integer from 1 to 3, _{R 2} is a group represented by the following general formula (5-1) Or a group represented by the following general formula (5-2), and each M is independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.
<General formula (5-1)>
However, in the general formula (5-1), R ₃ is an anilino group having a carboxy group as a substituent, an unsubstituted monoalkyl alkyl group having 1 to 8 carbon atoms, a mono having a sulfo group or a carboxy group as a substituent. The alkylamino group having 1 to 8 carbon atoms, the unsubstituted dialkyl 1 to 6 alkylamino group, or the phenoxy group, and n is 1 or 2.
<General formula (5-2)>
In the general formula (5-2), _{R 4} is an anilino group, 2-sulfoanilino group, 2,5-disulfoanilino group, 2-ethylhexyl amino group, cyclohexylamino group, 4-methoxy-2-sulfoanilino group, It represents a 2-carboxy-5-sulfoanilino group, a 3-carboxy-4-hydroxyanilino group, or an aminobenzimidazole group, and R ₅ represents a hydroxyl group or an amino group.
<General formula (6)>
However, in said general formula (6), R < ₂ >, R < ₃ >, R < ₄ > and R < ₅ > are each independently an alkyl group, M is each independently a hydrogen atom, an alkali metal, ammonium, or organic Ammonium.
<6> The inkjet recording ink according to any one of <1> to <3>, a yellow ink, a magenta ink, and a cyan ink,
The cyan ink includes a compound represented by the following general formula (7) and a salt thereof, and at least one selected from a compound represented by the following general formula (8) and a salt thereof: Is a set.
<General formula (7)>
However, in said general formula (7), A, B, C, and D are each independently a 6-membered ring having aromaticity, and M is each independently a hydrogen atom, an alkali metal, ammonium, Or it is organic ammonium and E is an alkylene group. X is a sulfo-substituted anilino group, a carboxyl-substituted anilino group, or a phosphono-substituted anilino group, and these substituted anilino groups further include a sulfonic acid group, a carboxyl group, a phosphono group, a sulfamoyl group, a carbamoyl group, a hydroxyl group, an alkoxy group, Selected from the group consisting of amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acetylamino group, ureido group, alkyl group, nitro group, cyano group, halogen, alkylsulfonyl group, and alkylthio group It may have 1 to 4 at least one substituent. Y is a hydroxyl group or an amino group, l, m, and n are 0 ≦ l ≦ 2, 0 ≦ m ≦ 3, 0.1 ≦ n ≦ 3, and l + m + n = 1 to 4.
<General formula (8)>
However, in the general formula (8), R is any one of a hydrogen atom, a group represented by the following general formula (8-1), and a group represented by the following structural formula (8-2). t is an integer of 1 to 3, and M is Cu.
<General formula (8-1)>
However, in said general formula (8-1), M is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.
<Structural Formula (8-2)>
<7> An inkjet recording apparatus comprising at least ink flying means for forming a color image by ejecting each ink in the ink set according to any one of <4> to <6> onto a recording medium. is there.

200 Ink cartridge 241 Ink bag 242 Ink inlet 243 Ink outlet 244 Cartridge case

Japanese Patent No. 4055328 JP 2006-199922 A JP 2007-191651 A

Claims (7)

Containing water, organic solvent, and colorant,
The colorant is a green ink, and the green ink includes a yellow compound containing a compound represented by the following general formula (1) and a salt thereof, and a compound represented by the following general formula (2) and a salt thereof. An ink for inkjet recording, comprising a cyanide compound.
<General formula (1)>
However, in the general formula (1), R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, and a hydrogen atom. R ₃ and R ₅ each independently represent a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and an alkyl group substituted with these groups. Yes, R ₄ and R ₆ each independently represent a group other than those defined for R ₃ and R ₅ . p and r are each independently an integer of 1 to 5, q and s are each independently an integer of 0 to 4, and p + q ≦ 5 and r + s ≦ 5.
<General formula (2)>
However, in the general formula (2), R is any one of a hydrogen atom, a group represented by the following general formula (2-1), and a group represented by the following structural formula (2-1). t is an integer of 1 to 3, and M is Cu.
<General formula (2-1)>
However, in said general formula (2-1), M is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.
<Structural Formula (2-1)>
  The organic solvent contains at least one parent dye organic solvent selected from triols having 4 or less carbon atoms, polyethylene glycol ethers of triols having 4 or less carbon atoms, polyethylene glycols, and 1,3-propanediol, The ink for inkjet recording according to claim 1, wherein the content of the organic solvent for the parent dye is 20% by mass or more based on the whole organic solvent. The ink for inkjet recording according to claim 1, wherein the yellow compound contained in the green ink is a compound represented by the following structural formula.
The inkjet recording ink according to any one of claims 1 to 3, a yellow ink, a magenta ink, and a cyan ink,
An ink set, wherein the yellow ink contains a compound represented by the following general formula (3) and a salt thereof.
<General formula (3)>
In the general formula _{(3), R 1, R} 2, Y 1 and _{Y 2} are each independently a monovalent group, _{X 1} and _{X 2} are each independently, .sigma.p value of Hammett An electron-withdrawing group of 0.20 or more, and Z ₁ and Z ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and M is any one of a hydrogen atom, an alkali metal, ammonium, and organic ammonium. The inkjet recording ink according to any one of claims 1 to 3, a yellow ink, a magenta ink, and a cyan ink,
The magenta ink includes a compound represented by the following general formula (4) and a salt thereof, a compound represented by the following general formula (5) and a salt thereof, and a compound represented by the following general formula (6) and a salt thereof. An ink set comprising at least one selected from the group consisting of:
<General formula (4)>
In the general formula (4), R each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, hydroxyalkyl group having 1 to 4 carbon atoms, a cyclohexyl group, or a (H _{(CH 2) m ) n n (CH 2) O} - ( however, m is 1 to 4, n is 1 to 2, o is a mono- or dialkylaminoalkyl group represented by a 1 to 4), Y are each independently —SO ₃ M or — (COOM) _n (where n is 1 to 2), and M is independently any one of a hydrogen atom, an alkali metal, ammonium, and organic ammonium. X is a linking group represented by —NH— (CH ₂ ) _n —NH— (where n is 2 to 6).
<General formula (5)>
In the general formula (5), _{R 1} is a hydrogen atom or an alkyl group, m is an integer from 1 to 3, _{R 2} is a group represented by the following general formula (5-1) Or a group represented by the following general formula (5-2), and each M is independently a hydrogen atom, an alkali metal, ammonium, or organic ammonium.
<General formula (5-1)>
However, in the general formula (5-1), R ₃ is an anilino group having a carboxy group as a substituent, an unsubstituted monoalkyl alkyl group having 1 to 8 carbon atoms, a mono having a sulfo group or a carboxy group as a substituent. The alkylamino group having 1 to 8 carbon atoms, the unsubstituted dialkyl 1 to 6 alkylamino group, or the phenoxy group, and n is 1 or 2.
<General formula (5-2)>
In the general formula (5-2), _{R 4} is an anilino group, 2-sulfoanilino group, 2,5-disulfoanilino group, 2-ethylhexyl amino group, cyclohexylamino group, 4-methoxy-2-sulfoanilino group, It represents a 2-carboxy-5-sulfoanilino group, a 3-carboxy-4-hydroxyanilino group, or an aminobenzimidazole group, and R ₅ represents a hydroxyl group or an amino group.
<General formula (6)>
However, in said general formula (6), R < ₂ >, R < ₃ >, R < ₄ > and R < ₅ > are each independently an alkyl group, M is each independently a hydrogen atom, an alkali metal, ammonium, or organic Ammonium. The inkjet recording ink according to any one of claims 1 to 3, a yellow ink, a magenta ink, and a cyan ink,
The cyan ink includes a compound represented by the following general formula (7) and a salt thereof, and at least one selected from a compound represented by the following general formula (8) and a salt thereof: set.
<General formula (7)>
However, in said general formula (7), A, B, C, and D are each independently a 6-membered ring having aromaticity, and M is each independently a hydrogen atom, an alkali metal, ammonium, Or it is organic ammonium and E is an alkylene group. X is a sulfo-substituted anilino group, a carboxyl-substituted anilino group, or a phosphono-substituted anilino group, and these substituted anilino groups further include a sulfonic acid group, a carboxyl group, a phosphono group, a sulfamoyl group, a carbamoyl group, a hydroxyl group, an alkoxy group, Selected from the group consisting of amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acetylamino group, ureido group, alkyl group, nitro group, cyano group, halogen, alkylsulfonyl group, and alkylthio group It may have 1 to 4 at least one substituent. Y is a hydroxyl group or an amino group, l, m, and n are 0 ≦ l ≦ 2, 0 ≦ m ≦ 3, 0.1 ≦ n ≦ 3, and l + m + n = 1 to 4.
<General formula (8)>
However, in the general formula (8), R is any one of a hydrogen atom, a group represented by the following general formula (8-1), and a group represented by the following structural formula (8-2). t is an integer of 1 to 3, and M is Cu.
<General formula (8-1)>
However, in said general formula (8-1), M is a hydrogen atom, an alkali metal, ammonium, or organic ammonium.
<Structural Formula (8-2)>
  An ink jet recording apparatus comprising at least ink flying means for forming a color image by ejecting each ink in the ink set according to claim 4 onto a recording medium.