WO2005066289A1

WO2005066289A1 - Recording method

Info

Publication number: WO2005066289A1
Application number: PCT/JP2004/019830
Authority: WO
Inventors: Toshiki Taguchi; Takashi Ozawa
Original assignee: Fuji Photo Film Co., Ltd.
Priority date: 2004-01-08
Filing date: 2004-12-28
Publication date: 2005-07-21

Abstract

An ink jet recording method comprises printing, on an image-receiving material, an ink that includes: an anionic dye; and at least one of water and a water-soluble organic solvent, according to an image data to form an image, wherein the anionic dye has three or more hydrogen-bonding functional groups. A recording method comprises ejecting ink drops by using at least two color inks of yellow and magenta each comprising a dye onto a recording material, the recording material comprising a support and an ink-receptive layer provided on the support, according to a recording signal, so as to record an image on the recording material, wherein the percent bleeding of the recorded image is 30% or less.

Description

RECORDING METHOD

Technical Field The present invention relates to an ink jet recording method excellent in image durability, including image stability under high humidity conditions. The present invention relates to a recording ink (preferably an ink for ink jet recording) and a recording method (preferably an ink jet recording method) which can provide an image having an excellent hue and excellent storage properties under severe conditions.

Background Art In recent years, with the spread of computers, ink jet printers have been widely used to print on paper, film, cloth, etc. at offices as well as at home. Examples of ink jet recording method include a method which allows a piezoelectric element to give pressure that causes a droplet to be ejected, si method which comprises heating the ink to generate bubbles, causing a droplet to be ejected, a method involving the use of ultrasonic wave, and a method which uses electrostatic force to suck and discharge a droplet. As inks for these ink jet recording methods there are used aqueous inks, oil-based inks and solid (melt type) inks. Among these inks, aqueous inks are mainly used from the standpoint of producibility, handleability, odor, safety, etc. The dyes to be incorporated in these inks for ink jet recording are required to exhibit a high solubility in solvents, allow a high density recording and have a good hue and an excellent fastness to light, heat, air, water and chemical, a good fixability to recording materials (image-receiving materials), difficulty in running, an excellent preservability, no toxicity and a high purity and be available at a low cost. However, it is extremely difficult to seek dyes meeting these requirements to a high extent. In particular, dyes having a good cyan hue and an excellent weathering resistance have been keenly desired. Various dyes and pigments have been already proposed for ink jet recording and have been actually used. However, no dyes meeting all these requirements have been found yet. Known dyes and pigments provided with color index (C.I.) can difficultly satisfy both the hue and fastness requirements for inks for ink jet recording. To date, fast dyes having a good hue have been studied and excellent dyes have been developed as ink jet recording coloring materials. However, all compounds which are water-soluble dyes have water-soluble groups as substituents. It was found disadvantageous in that when the number of water-soluble groups is increased to enhance the stability ofthe ink, the image thus formed can easily undergo bleeding under high humidity conditions. On the other hand, it is important to remove finely divided bubbles from the ink during the preparation ofthe ink. When the removal of finely divided bubbles from the ink is insufficiently conducted, it is disadvantageous in that the stability of ejection of the ink can be impaired. For example, the ink can clog the ink jet head. It is often practiced to incorporate a surface active agent in the ink for the purpose of adjusting the physical properties ofthe ink and enhancing the capability ofthe ink of penetrating paper. However, the surface active agent is one of factors causing the generation of bubbles. Thus, the removal of bubbles is more important. JP-A-6-24123, JP-A-6-152905 and JP-A-3-33298 describe a recording method in which spreading of dots is prevented when recording is performed to standard paper.

Disclosure of he Invention A first aim ofthe invention is to provide an ink jet recording method which is little subject to image bleeding even under high humidity conditions. It is therefore a second aim ofthe invention to provide a recording method (preferably an ink jet recording method) which exhibits a high ejection stability and can provide a high quality image having an excellent hue and excellent storage properties. It is another aim ofthe invention to provide a recording method (preferably an ink jet recording method) which exhibits a good ejection stability under severe conditions over an extended period of time and can provide an image having high storage properties. The aforementioned first aim ofthe invention is accomplished by the following six constitutions of ink jet recording method. 1) An ink jet recording method comprising printing an ink with an ink on an image-receiving material, according to an image data, so as to form an image, wherein the ink includes: an anionic dye; and at least one of water and a water-soluble organic solvent, and wherein the anionic dye has three or more hydrogen-bonding functional groups. 2) The ink jet recording method as described in Clause (1), wherein a printing surface ofthe image- receiving material contains a compound having four or more hydrogen-bonding functional groups. 3) The ink jet recording method as described in Clause (1) or (2), wherein a printing surface ofthe image-receiving material contains a mordant. 4) The Inkjet recording method as described in any one of Clauses (1) to (3), wherein as the anionic dye there is used at least one compound having an oxidation potential of more positive than 1.0 V. 5) The ink jet recording method as described in any one of Clauses (1) to (4), wherein as the anionic dye there is used at least one of he compounds represented by the following general formulae (1-1) to (1-4): general formula (1-1): (A„-N=N-B„)_n-L wherein An and B each independently represents a heterocyclic group which may be substituted; n represents an integer 1 or 2; and L represents a substituent bonded to An or Bn at arbitrary position, with the proviso that when n is 1, L represents a hydrogen atom or monovalent substituent and when n is 2, L represents a mere bond or divalent connecting group; general formula (1-2):

wherein X₂ι, X₂₂, X₂3 and X₂₄ each independently represents -SO-Z2, -SO2-Z2, -SO2N 21R22, sulfo group, - CONR₂₁R₂₂ or -COOR₂₁ in which Z₂'s each independently represents a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, aralkyl, aryl or heterocyclic group and R₂₁ and R2₂ each independently represents a hydrogen atom or substituted or unsubstituted alkyl, cycloalkyl, alkenyl, aralkyl, aryl or heterocyclic group;

Y₂2, Y₂₃ and Y₂₄ each independently represents a monovalent substituent; a₂ι to a ₄ and b₂ι to b₂₄ represent the number of the substituents X₂ι to X₂₄ and Y₂ι to Y₂₄, respectively; a₂ι to a₂₄ each independently represents a number of from 0 to 4 and at least one of a₂ι to a₂₄ is not zero; b₂i to b₂₄ each independently represents a number of from 0 to 4, with the proviso that when a₂i to a₂₄ and b₂ι to b₂₄ each represent a number of 2 or more, the plurality of X₂ι's to X₂₄'s and Y₂ι's to Y₂₄'s may be the same or different; and M represents a hydrogen atom, metal atom or oxide, hydroxide or halide thereof; general formula (1-3):

wherein A₃₁ represents a 5-membered heterocyclic group; B_3] andB₃₂ each represents =CR₃r or -CR₃₂= or one of B_3] and B₃₂ represents a nitrogen atom and the other represents

R35 and jg each independently represents a hydrogen atom or an aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfbnyl group or sulfamoyl group which may furtlier have substituents; G₃, ₂₁ and R₃₂ each independently represents a hydrogen atom, a halogen atom or an aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including arylamino group and heterocyclic amino group), acylamino group, ureido group, sulfamonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sul&nylamino group, nitro group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfinyl group, arylsulfinyl group; heterocyclic sulfinyl group, sulfamoyl group, sulfo group or heterocyclic thio group which ma be further substituted; R_3Ϊ and R₃₅ or R₃₅ and ₃6 ma be connected to each other to form a 5- or 6-raembered ring; and general formula (1-4):

wherein A41, B₄₁ and Qi each independently represent an aromatic or heterocyclic group which may be substituted, m is 1 or 2, and n is an integer of 0 or more. 6) The ink jet recording method as defined in any one of Clauses (1) to (4), wherein the anionic dye represented by the general formula (1-2) is one represented by the following general formula (1-5): general formula (1-5):

wherein X5₁ to X5₄, Y₅₁ to Y₅8 and Ml have the same meaning as X₂ι to X₂₄, Y₂ι to Y₂₄ and M in the general formula (1-2); and a₅ι to as₄ each independently represent an integer of 1 or 2. The second aim ofthe invention is accomplished by the following constitutions (7) to (16).

(7) A recording method which comprises ejecting ink drops onto a recording material (receiving material) according to a recording signal, the recording material comprising a support and an ink-receptive layer provided on the support, by using at least two color inks comprising a yellow ink and a magenta ink, so as to record an image on the recording material, wherein the percent bleeding ofthe recorded image upon storage ofthe recorded image under high humidity (defined in Clause (8)) is 30% or less.

(8) The recording method as defined in Clause (7), wherein, supposing that an gray image having a 10 mm square and a reflection density of 1.5 (neutral color according to CIE) is prepared using a plurality of color inks according to a neutral gray data outputted to a color printer, the gray image comprising a white line having a width of 0.2 mm extending through the center ofthe 10 mm square, the percent bleeding is represented by the following equation: % Bleeding = (DC - Db)/Da x 100 where Da represents a density ofthe gray image which has been just printed; Db represents a density ofthe white line which has been just printed; and Dc represents a density of the white line which has been allowed to stand at 23°C and 90%RH for 7 days shortly after printing.

(9) The ink jet recording method as defined in Clause (7) or (8), wherein the yellow and magenta inks each further comprise a surface active agent and the surface active agent is a betaine-based surface active agent.

(10) The ink jet recording method as defined in any one of Clauses (7) to (9), wherein the betaine-based surface active agent is represented by the following general formula (2-1): (R)_p-N-[L-(COOM)_q]r - (2-1) wherein R represents a hydrogen atom, alkyl group, aryl group or heterocyclic group; L represents a divalent connecting group; M represents a hydrogen atom, alkaline metal atom, ammonium group, protonated organic amine, protonated nitrogen-containing heterocyclic group or quaternary ammonium ion, with the proviso that if one "COO" of at least one (COOM) group is a counter ion of ammonium ion formed by nitrogen atoms in the molecule represented by the general formula (2-1), corresponding M of the "COO" represents a group which does not exist as a cation; q represents an integer of 1 or more; r represents an integer of 1 or more and 4 or less; and p represents an integer of from 0 to 4, with the proviso that: the sum of p and r is 3 or 4; when the sum of p and r is 4, the nitrogen atom is a protonated ammonium atom (=N⁺=); when q is 2 or more, the plurality of COOM groups may be the same or different; when r is 2 or more, the plurality of [L-(COOM)_q] groups may be the same or different; and when p is 2 or more, the plurality of R's may be the same or different.

(11) The recording method as defined in any one of Clauses (7) to (10), wherein the yellow and magenta inks each further contain a water-miscible organic solvent and the water-miscible organic solvent is selected from the group consisting of triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, tripropylene glycol monomethyl ether and dipropylene glycol monomethyl ether.

(12) The recording method as defined in any one of Clauses (7) to (11), wherein at least one ofthe dyes is a dye having an oxidation potential of more positive than 1.0 V (vs SCE).

(13) The recording method as defined in any one of Clauses (7) to (12), wherein the dye for yellow ink is a yellow dye represented by the following general formula (2-2): (An-N=N-B_π)„-L ... ^' (2-2) wherein A and Bn each independently represents a heterocyclic group which may be substituted; n represents an integer 1 or 2; and L represents a hydrogen atom, mere bond or divalent connecting group, with the proviso that: when n is 1, L represents a hydrogen atom and both An and Bn are a monovalent heterocyclic group; and when n is 2, L represents a mere bond or divalent connecting group, one of A and Bn is a monovalent heterocyclic group and the other is a divalent connecting group, and two A_n's and B_π's each may be the same or different.

(14) The recording method as defined in any one of Clauses (7) to (13), wherein the dye for magenta ink is a magenta dye represented by the following general formula (Ml):

wherein A³¹ represents a 5-membered heterocyclic group; B³¹ and B³² represent =CR^X- and -CR²=, respectively, or one of B³¹ and B³² represents nitrogen atom and the other represents =CR¹- or -CR²=; R⁵ and R⁶ each independently represents a hydrogen atom or substituent; and G³¹, R¹ and R² each independently represents a hydrogen atom or substituent.

(15) The recording method as defined in any one of Clauses (7) to (14), wherein the ink-receptive layer comprises an inorganic white particulate material.

(16) The recording method as defined in any one of Clauses (7) to (15), which is adapted for ink jet recording.

Best Mode For Carrying Out the Invention

[First Embodiment] The first embodiment ofthe invention will be furtlier described hereinafter. The invention discloses a technique of preventing image bleeding. According to the first embodiment ofthe invention, there is provided an ink jet recording method comprising: printing, on an image-receiving material, an ink that includes: an anionic dye; and at least one of water and a water-soluble organic solvent, according to an image data to form an image, wherein the anionic dye has three or more hydrogen-bonding functional groups. There are various ink jet recording methods. As previously mentioned, the ink jet recording method involving the use of an aqueous ink comprising a water-soluble dye dissolved in an aqueous solvent is mainly used both at home and office. The reason for this trend is that the aqueous dye which can be merely dissolved in water to form a uniform solution has a long history and thus can be used with techniques which have been accumulated on various molecular designs. Further, the aqueous ink jet recording method involves the use of an ink free of solid content such as pigment that forms a uniform solution and thus is most suitable for maintenance of desired ejection stability of nozzle, winch is the greatest assignment in ink jet recording. Further, the aqueous solvent has a high safety and a higher handleability than volatile solvent. However, since the aqueous ink jet method involves recording a water-soluble dye on an image- receiving material with a water-soluble solvent left in the ink, image bleeding is observed when the image thus printed is stored under high humidity conditions despite the coexistence of a dye fixing material (e.g., mordant). It was found that this problem becomes remarkable with a dye having a high water solubility. In the invention, a mutual interaction between dye and image-receiving material for dye fixing having a different mechanism from that of ordinary mordant is introduced. In the invention, it was found that the introduction of a bonding group comprising a plurality of hydrogen bonds in combination is effective for this purpose. Hydrogen bond is developed when a hydrogen atom connected to an atom having a high polarity present in an organic functional group forms a false bond while being oriented among polar atoms present in the molecule or foreign molecules. For the details ofthe concept of this hydrogen bond, reference can be made to Motohiro Nishio, "Yuki Kagaku no Tameno Bunshikanryoku Nyumon (Introduction of Intermolecular Force for Organic Chemistry)", Scientific, Kodansha, 2000, pp. 21 - 25. The term "polar atom" as used herein is meant to indicate an atom having a high electronegativity than that of carbon atom as calculated in terms of value proposed by L. Pauling. Examples of such a polar atom include oxygen atom, sulfur atom, selenium atom, nitrogen atom, and phosphorus atom. Examples of functional groups on the part of hydrogen donor capable of developing hydrogen bond include hydroxyl groups (including both alcoholic hydroxyl group and phenolic hydroxyl group), thio groups (including both alkylthio group and arylthio group), carboxyl groups, phosphoric acid groups, phosphone groups, carbonamide groups, sulfonamide groups, alkylcarbonamide groups, arylcarbonamide groups, alkylsulfonamide groups, arylsulfonamide groups, carbamoyl groups, sulfamoyl groups, alkylcarbamoyl groups, arylcarbamoyl groups, alkylsulfamoyl groups, arylsulfamoyl groups, phosphonamide groups, amino groups, heterocyclic groups having N-H bond (e.g., pyrazole group, imidazole group, triazole group, tetrazole group, condensed pyrazole group, condensed imidazole group), and thiocafboxyl groups. On the other hand, as functional groups on the part of hydrogen atom acceptor there may be used groups containing polar atom except hydrogen atom. Examples of these functional groups include ether groups, thioether groups, carbonyl groups, thiocarbonyl groups, amino groups, and nitrogen atom, oxygen atom and sulfur atom contained in heterocyclic group. In the invention, 4 or more, preferably 5 or more, more preferably 8 or more, particularly 10 or more such hydrogen-donating functional groups capable of developing hydrogen bonding properties are contained in one molecule. Particularly preferred examples of hydrogen-bonding functional groups (hydrogen-bonding groups) to be contained in the molecule include amide-based groups (e.g., carbonamide group, sulfonamide group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, carbamoyl group, sulfamoyl group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, phosphonamide group), and heterocyclic groups having N-H bond (e.g., pyrazole group, imidazole group, triazole group, tetrazole group, condensed pyrazole group, condensed imidazole group). In the invention, for the purpose of fixing dye, mordant mutual interaction, too, acts besides the hydrogen-bonding mutual interaction. Referring to the mordant mutual interaction, a compound containing a group having a charge having a sign opposite that ofthe dissociative group of dye is used to cause ionic mutual interaction (coulombic mutual interaction) and hydrophobic mutual interaction in combination, whereby the dye molecule is fixed. This mutual interaction is a technique known in the art of imaging, particularly photography (especially dye diffusion transferring color photographic material) and is widely used in the art of ink jet recording. In general, most dyes have an anionic dissociative group. Thus, cationic compounds are often used on the part of mordant. Examples of cationic compounds include compounds having aminic nitrogen atom (e.g., primary amine, secondary amine, tertiary amine, quaternary ammonium salt, nitrogen-containing heterocyclic compound), and metal salt compounds. It is preferred that the mordant be contained in the coloring material-receiving layer. Preferred examples of inorganic mordants include polyvalent water-soluble metal salts and hydrophobic metal salt compounds. Specific examples ofthe inorganic mordants include salts or complexes of metal selected from the group consisting of magnesium, aluminum, calcium, scandium, titanium, vanadium, manganese, iron, nickel, copper, zinc, gallium, germanium, strontium, yttrium, zircomum, molybdenum, indium, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, hafnium, tungsten and bismuth. Specific examples of these metal salts or complexes include calcium acetate, calcium chloride, calcium formate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, manganese formate dihydrate, manganese ammonium sulfate hexahydrate, cupric chloride, cupric ammonium chloride (II) dihydrate, copper sulfate, cobalt chloride, cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, nickel ammonium sulfate hexahydrate, nickel amide sulfate tetrahydrate, aluminum sulfate, aluminum alum, basic polyaluminum hydroxide, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate, ferrous bromide, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, zinc phenolsulfonate, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, titanium tetrachloride, tetraisopropyl titanate, titanium acetyl acetonate, titanium lactate, zirconium acetyl acetonate, zirconyl oclylate, zirconyl acetate, zirconyl sulfate, zircomum ammonium carbonate, zirconyl stearate, zirconyl oclylate, zirconyl nitrate, zirconium oxychloride, zirconium hydroxychloride, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, magnesium citrate nonahydrate, sodium phosphotungstate, sodium tungsten citrate, dodecatungstophosphoric n-hydrate, dodecatugstosilicic 26-hydrate, molybdenum chloride, dodecamolybdophosphoric n-hydrate, gallium nitrate, germamum nitrate, strontium nitrate, yttrium acetate, yttrium chloride, yttrium nitrate, indium nitrate, lanthanum nitrate, lanthanum chloride, lanthanum acetate, lanthanum benzoate, cerium chloride, cerium sulfate, cerium octylate, praseodymium nitrate, neodymium nitrate, samarium nitrate, europium nitrate, gadolinium nitrate, dysprosium nitrate, erbium nitrate, ytterbium nitrate, hafnium chloride, and bismuth nitrate. Preferred examples ofthe inorganic mordants employable herein include aluminum-containing compounds, titanium-containing compounds, zirconium-containing compounds, and compounds (salts or complexes) of metal belonging to the group IITB ofthe periodic table. In the invention, the amount ofthe aforementioned mordant to be contained in the coloring material- receiving layer is preferably from 0.01 g/m² to 5 g/m², more preferably from 0.1 g/m² to 3 g/m². In the invention, in the case where the aforementioned hydrogen-bonding group is connected to the dye, it can be introduced as a water-soluble moiety ofthe dye molecule, can be introduced via a connecting group or can be separately introduced as a part ofthe molecule. In the case where as the dyes there are used dyes other than the dye ofthe invention in combination of the dye of the invention, the amount ofthe dye ofthe invention to be used is preferably from 20 to 100% by weight, more preferably from 30 to 100% by weight based on the total weight ofthe dyes to be incorporated in the ink. In order to intensify the hydrogen bond, the image-receiving material preferably comprises a compound having a structure having a hydrogen-bonding group that induces hydrogen bond. This compound may be separately added in the form of a special compound or may be previously contained in other materials (either low molecular compound or polymer) which are then incorporated in the image-receiving material. Preferably, this compound is introduced in other polymer materials. It is particularly preferred that such a substituent be introduced in the structure ofthe mordant. The content ofthe polymer, if contained in the mordant, is from 0.01 to 90%, preferably from 0.1 to

70% by mol. The effect ofthe invention is exerted between the dye substituted stereospecifically by a plurality of hydrogen-bonding dissociative groups and the image-receiving material comprising a dye-fixing material having a dye-accepting structure in its molecule. It is further preferred that an image-receiving material comprising an organic amine-based mordant as a mordant be used. Specific examples of these organic amine-based mordants will be given below, but the invention is not limited thereto.

^P~1 - CH₂ ^z-C j H '—80 -f-CH₂ ^-C | H '-20 CH₂NH₂ CO I NH

The dyes to be used in the invention, including those represented by the general formulae (1-1) to (1-4), will be described hereinafter. In the invention, a dye having an oxidation potential of more positive than 1.0 V (more preferably more positive than 1.1 V, particularly more positive than 1.15 V) is preferably used. The use of a dye having an oxidation potential of more positive than 1.0 V makes it possible to obtain an image excellent in durability, particularly ozone resistance. The oxidation potential (Eox) can be easily measured by those skilled in the art. For the details ofthe method for measuring the oxidation potential, reference can be made to P. Delahay, "New Instrumental Methods in Electrochemistry", 1954, Interscience Publishers, A. J. Bard et al, "Electrochemical Methods", 1980, John Wiley & Sons, and Akiya Fujishima, "Denki Kagaku Sokuteiho (Electrochemical Measuring Methods)", 1984, Gihodo Shuppansha. In some detail, the measurement of oxidation potential is carried out by dissolving the test specimen in a solvent such as dimethylformamide and acetonitrile containing a supporting electrolyte such as sodium perchlorate and tetrapropylammonium perchlorate in a concentration of from 1 x 10² to 1 x 10 ^s mol/1, and then measuring the test solution for oxidation potential with respect to SCE (saturated calomel electrode) using cyclic voltammetry. This value may deviate by scores of millivolts due to the effect of difference in potential between solutions or resistivity of test solution. However, the incorporation of a standard specimen (e.g., hydroquinone) makes it possible to assure the reproducibility of potential. In order to unequivocally define potential, the potential (vs SCE) measured in dimethylformamide containing 0.1 mol dm^"3 of tetrapropylammonium perchlorate as a supporting electrolyte (concentration of dye: 0.001 mol dm^"3) is defined as oxidation potential of dye. There are some cases where a water-soluble dye can be difficultly dissolved directly in N,N-dimethyl formamide. In this case, water is used in an amount as small as possible to dissolve the dye. The dye solution is diluted with N,N-dimethylformamide so that the water content is 2% or less, and then measured. The value of oxidation potential Eox indicates the transferability of electrons from the specimen to the electrode. The greater this value is (the more positive the oxidation potential is), the more difficultly can be transferred electrons from the specimen to the electrode, i.e., the more difficultly can be oxidized the specimen. With regard to the structure ofthe compound, the incorporation of electron-withdrawing group causes the oxidation potential to be more positive while the incorporation of electron-donative group causes the oxidation potential to be more negative. Examples of dyes having the aforementioned properties include azo dyes (yellow dye, magenta dye, black dye) and phthalocyanine dyes (cyan dye) having specific properties and structures. These dyes will be described hereinafter. [Yellow dye] The yellow dye to be used in the invention preferably has an oxidation potential of more positive than 1.0 V (vs SCE), more preferably more positive than 1.1 V (vs SCE), particularly more positive than 1.15 V (vs SCE) from the standpoint of fastness, particularly to ozone gas. As such a yellow dye, an azo dye satisfying the aforementioned requirements is particularly preferred. As a dye satisfying these oxidation potential and absorption characteristics there is preferably used one represented by the following general formula (1-1). general formula (1-1): (An-N=N-Bn)„-L In the general formula (1-1), A_n and B_n each independently represent a heterocyclic group which may be substituted. The heterocyclic group is preferably a heterocyclic group formed by a 5-membered or 6- membered ring. The heterocyclic group may have a monocyclic structure or a polycyclic structure formed by the condensation of two or more rings or may be an aromatic heterocyclic group or non-aromatic heterocyclic group. As hetero atoms constituting the aforementioned heterocyclic group there are preferably used nitrogen, oxygen and sulfur atoms. The suffix n represents an integer 1 or 2, preferably 2. L represents a substituent bonded to A_n or Bn at arbitrary position, with the proviso that when n is 1, L represents a hydrogen atom or monovalent substituent and when n is 2, L represents a mere bond or divalent connecting group. Preferred examples ofthe heterocyclic group represented by An in the general formula (1-1) include 5- pyrazolone, pyrazole, triazole, oxazolone, isooxazolone, barbituric acid, pyridone, pyridine, rhodanine, pyrazolinedione, pyrazolopyridone, Meldrum's acid, and condensed heterocyclic group having an aromatic hydrocarbon ring or heterocyclic group condensed to these heterocyclic groups. Preferred among these heterocyclic groups are 5-pyrazolone, 5-aminopyrazole, pyridone, 2,6-diaminopyridine, and pyrazoloazoles. Particularly preferred among these heterocyclic groups are 5-aminopyrazole, 2-hydroxy-6-pyridone, 2,6- diaminopyridine, and pyrazoloazoles. Examples of the heterocyclic group represented by Bn include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthaladine, quinoxaline, pyrrole, indole, furane, benzofurane, thiophene, benzothiophene, pyrazole, imidazole, benzoimidazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, benzothiazole, isothiazole, benzoisothiazole, thiadiazole, benzoisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, and fhiazoline. Preferred among these heterocyclic groups are pyridine, quinoline, thiophene, pyrazole, imidazole, benzoimidazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzoisothiazole, thiadiazole, and benzoisoxazole. More desirable among these heterocyclic groups are quinoline, thiophene, pyrazole, benzoxazole, benzoisoxazole, isothiazole, imidazole, benzothiazole, and thiadiazole. Particularly preferred among these heterocyclic groups are pyrazole, benzoxazole, benzoxazole, imidazole, 1,2,4-thiadiazole, and 1,3,4-thiadiazole. Examples ofthe substituents on A and B_π include halogen atoms, alkyl groups, cycloalkyl groups, aralkyl groups, alkenyl groups, alkinyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, alkoxy groups, aryloxy groups, silyloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, amino groups, acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, sulfamoylamino groups, alkylsulfonylamino groups, arylsulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, alkylsulfinyl groups, arylsulfmyl groups, alkylsulfonyl groups, arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbon)! groups, carbamoyl groups, irnide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, silyl groups, and the following ionic hydrophilic groups. Examples ofthe monovalent substituent represented by L include the aforementioned substituents on A and B , and the following ionic hydrophilic groups. Examples ofthe divalent connecting group represented by L include alkylene group, arylene group, heterocyclic residue, -CO-, -SO_n- (in which n is 0, 1 or 2), -NR- (in which R represents a hydrogen atom, alkyl group or aryl group), -0-, and divalent group comprising these groups in combination. These groups may have substituents exemplified with reference to the substituents on An and B_u or the following ionic hydrophilic groups. The dye ofthe general formula (1-1), if used as a water-soluble dye, preferably has at least one ionic hydrophilic group incorporated therein per molecule. Examples ofthe ionic hydrophilic group include sulfo groups, carboxyl groups, phosphono groups, and quaternary ammonium groups. Preferred among these ionic hydrophilic groups are carboxyl groups, phosphono groups, and sulfo groups. Particularly preferred among these ionic hydrophilic groups are carboxyl groups and sulfo groups. The carboxyl groups, phosphono groups and sulfo groups may be in the form of salt. Examples ofthe counter ion forming the salt include ammonium ion, alkaline metal ion (e.g., lithium ion, sodium ion, potassium ion), and organic cation (e.g., tetramethylammonium ion, tetramethylguanidium ion, tetramethylphosphomum ion). Preferred among these counter ions are alkaline metal salts. Preferred among the dyes represented by the general formula (1-1) are those having An-N=N-Bn moiety corresponding to the general formula (1-A), (1-B) or (1-C). general formula (1-A)

wherein Ri and R₃ each represent a hydrogen atom, cyano group, alkyl group, cycloalkyl group, aralkyl group, alkoxy group, alkylthio group, arylthio group, aryl group or ionic hydrophilic group; R₂ represents a hydrogen atom, alkyl group, cycloalkyl group, aralkyl group, carbamoyl group, acyl group, aryl group or heterocyclic group; and R₄ represents a heterocyclic group, general formula (1-B)

wherein R₅ represents a hydrogen atom, cyano group, alkyl group, cycloalkyl group, aralkyl group, alkoxy group, alkylthio group, arylthio group, aryl group or ionic hydrophilic group; Za represents -N=, -NH- or - C(Rn)=; Zb and Zc each independently represent -N= or -C(Rn) in which Rn represents a hydrogen atom or non-metallic substituent; and Re represents a heterocyclic group, general formula (1-C)

wherein R₇ and R₉ each independently represent a hydrogen atom, cyano group, alkyl group, cycloalkyl group, aralkyl group, aryl group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group or ionic hydrophilic group; Rs represents a hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, cyano group, acylamino group, sulfonylamino group, alkoxycarbonylamino group, ureido group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, amino group, hydroxy group or ionic hydrophilic group; and R_w represents a heterocyclic group. In the general formulae (1-A), (1-B) and (1-C), the alkyl groups represented by Ri, R₂, R₃, R5, R7, Rs and R₉ contain a substituted or unsubstituted alkyl group. These alkyl groups each preferably have from 1 to 20 carbon atoms. Examples ofthe aforementioned substituents include hydroxyl groups, alkoxy groups, cyano groups, halogen atoms, and ionic hydrophilic groups. Examples ofthe alkyl groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifiuoromethyl, 3-sulfopropyl, and 4-sulfobutyl. The cycloalkyl groups represented by Ri, R₂, R3, R5, R?, Rs and R9 include a substituted or unsubstituted cycloalkyl group. These cycloalkyl groups each preferably have from 5 to 12 carbon atoms. Examples ofthe substituents on the cycloalkyl group include ionic hydrophilic groups. Examples ofthe cycloalkyl group include cyclohexyl groups. Examples ofthe aralkyl groups represented by Ri, R₂, R₃, R₅, R₇, Rs and R₉ include substituted and unsubstituted aralkyl groups. These aralkyl groups each preferably have from 7 to 20 carbon atoms. Examples ofthe substituents on the aralkyl group include ionic hydrophilic groups. Examples ofthe aralkyl group include benzyl, and 2-phenethyl. Examples ofthe aryl groups represented by Ri, R₂, R₃, R5, R7, Rs and R₉ include substituted and unsubstituted aryl groups. These aryl groups each preferably have from 6 to 20 carbon atoms. Examples ofthe substituents on the aryl group include alkyl groups, alkoxy groups, halogen atoms, alkylamino groups, and ionic hydrophilic groups. Examples ofthe aryl group include phenyl, p-tollyl, p-methoxyphenyl, o-chlorophenyl, and m-(3 -sulfopropylamino)phenyl. Examples ofthe alkylthio groups represented by Ri, R₂, R₃, R5, R7, Rs and Rg include substituted and unsubstituted alkylthio groups. These alkylthio groups each preferably have from 1 to 20 carbon atoms. Examples ofthe substituents on the alkylthio group include ionic hydrophilic groups. Examples ofthe alkylthio group include methylthio, and ethylthio group. Examples ofthe arylthio groups represented by Ri, R₂, R₃, R5, R₇, Rs and R₉ include substituted and unsubstituted arylthio groups. These arylthio groups each preferably have from 6 to 20 carbon atoms. Examples ofthe substituents on the arylthio group include alkyl groups, and ionic hydrophilic groups. Examples ofthe arylthio group include phenylthio, and p-tolylthio group. The heterocyclic group represented by R₂ preferably is a 5- or 6-membered heterocyclic group which may be further condensed. Preferred examples ofthe hetero atoms constituting the heterocyclic group include nitrogen, sulfur and oxygen atoms. The heterocyclic groups may be aromatic or non-aromatic. These heterocyclic groups may be further substituted. Examples ofthe substituents on the heterocyclic group include those listed with reference to the aryl group described later. Preferred examples ofthe heterocyclic groups include a 6-membered nitrogen-containing aromatic heterocyclic group. Particularly preferred examples of such a 6-membered nitrogen-containing aromatic heterocyclic group include triazine, pyrimidine, and phthaladine. Examples ofthe halogen atom represented by Rg include fluorine atom, chlorine atom, and bromine atom. Examples ofthe alkoxy groups represented by R R₃, R₅ and Rg include substituted and unsubstituted alkoxy groups. These alkoxy groups each preferably have from 1 to 20 alkoxy groups. Examples ofthe substituents include hydroxyl groups, and ionic hydrophilic groups. Examples of the alkoxy groups include methoxy, ethoxy, isopropoxy, methoxyeύioxy, ydroxyethoxy, and 3-carboxypropoxy. Examples ofthe aryloxy group represented by Rg include substituted and unsubstituted aryloxy groups. These aryloxy groups each preferably have from 6 to 20 carbon atoms. Examples ofthe substituents on the aryloxy group include alkoxy groups, and ionic hydrophilic groups. Examples ofthe aryloxy groups include phenoxy, p-mefhoxyphenoxy, and o-methoxyphenoxy. Examples ofthe acylamino group represented by Rg include substituted and unsubstituted acylamino groups. These acylamino groups each preferably have from 2 to 20 carbon atoms. Examples ofthe substituents on the acylamino group include ionic hydrophilic groups. Examples ofthe acylamino group include acetarmde, propionamide, benzamide, and 3,5-disulfobenzamide. Examples ofthe sulfonylamino group represented by Rs include alkylsulfonylamino group, arylsulfonyl group, and heterocyclic sulfonylamino group. The alkyl moiety, aryl moiety and heterocyclic moiety of these sulfonylamino groups may have substituents. Examples ofthe aforementioned substituents include those exemplified with reference to the aryl group. These sulfonylamino groups each preferably have from 1 to 20 carbon atoms. Examples ofthe sulfonylamino group include methylsulfonylamino, and etliylsulfonylamino. Examples ofthe alkoxycarbonylamino group represented by Rs include substituted and unsubstituted alkoxycarbonylamino groups. These alkoxycarbonylamino groups each preferably have from 2 to 20 carbon atoms. Examples ofthe substituents on the alkoxycarbonylamino group include ionic hydrophilic groups. Examples ofthe alkoxycarbonylamino group include ethoxycarbonylamino. Examples ofthe ureido group represented by Rs include substituted and unsubstituted ureido groups. These ureido groups each preferably have from 1 to 20 carbon atoms. Examples ofthe substituents on the ureido group include alkyl groups, and aryl groups. Examples ofthe ureido group include 3-methylureido group, 3,3-dimethylureido group, and 3-phenylureido group. Examples ofthe alkoxycarbonyl groups represented by R₇, Rg and R₉ include substituted and unsubstituted alkoxycarbonyl groups. These alkoxycarbonyl groups each preferably have from 2 to 20 carbon atoms. Examples o the substituents on the alkoxycarbonyl group include ionic hydrophilic groups. Examples of the alkoxycarbonyl group include methoxycarbonyl, and ethoxycarbonyl. Examples ofthe carbamoyl groups represented by R₂, R7, Rs and Rg include substituted and unsubstituted carbamoyl groups. Examples ofthe substituents on the carbamoyl group include alkyl groups. Examples ofthe carbamoyl group include methylcarbamoyl group, and dimethylcarbamoyl group. Examples ofthe sulfamoyl group represented by Rg include substituted and unsubstituted sulfamoyl groups. Examples ofthe substituents on the sulfamoyl group include alkyl groups. Examples ofthe sulfamoyl group include dimetliylsulfamoyl group, and di~(2-hydroxyethyl)sulfamoyl group. Examples ofthe alkylsulfonyl group represented by Rg include alkylsulfonyl group, arylsulfonyl group and heterocyclic sulfonyl group which may further have substituents. Examples of these substituents include ionic hydrophilic groups. Examples of these sulfonyl groups include methylsulfonyl, and phenylsulfonyl. Examples ofthe acyl groups represented by R₂ and Rg include substituted and unsubstituted acyl . groups. These acyl groups each preferably have from 1 to 20 carbon atoms. Examples ofthe substituents on the acyl group include ionic hydrophilic groups. Examples ofthe acyl group include acetyl, and benzoyl. Examples ofthe amino group represented by Rg include substituted and unsubstituted amino groups.

Examples of the substituents on the amino group include alkyl groups, aryl groups, and heterocyclic groups. Examples ofthe amino group include methylamino, diethylamino, anilino, and 2-chloroanilino. The heterocyclic groups represented by R₄, Re and Rι₀ are the same as the heterocyclic groups represented by B_π in the general formula (1-1) which may be substituted. • Preferred examples ofthe heterocyclic groups include those listed with reference to Bn in the general formula (1-1). Even more desirable examples ofthe heterocyclic groups include those listed with reference to Bn in the general formula (1-1). Particularly preferred examples ofthe heterocyclic groups include those listed with reference to B_n in the general formula (1-1). Examples ofthe substituents on the heterocyclic group include ionic hydrophilic groups, C₁-C₁₂ alkyl, aryl and arylthio groups, halogen atoms, cyano groups, sulfamoyl groups, sulfonamide groups, carbamoyl groups, and acylamino groups. These alkyl and aryl groups may further contain substituents. In the general formula (1-B), Za represents -N=, -NH- or -C(R_π)=. Zb and Zc each independently represent -N= or -C(Rn)= in which R_n represents a hydrogen atom or non-metallic substituent Preferred examples ofthe non-metallic substituent represented by R include cyano groups, cycloalkyl groups, aralkyl groups, aryl groups, alkylthio groups, arylthio groups, and ionic hydrophilic groups. These substituents each have the same meamng as those represented by Ri . Preferred examples of these substituents include those listed with reference to Rj. Examples ofthe skeleton ofthe heterocyclic group composed of two 5-membered rings contained in the general formula (1-B) will be given below.

Examples ofthe substituents on the aforementioned substituents which may further have substituents include substituents which may substitute the heterocyclic groups A and B_n in the general formula (1-1). Preferred among the dyes ofthe general formulae (1-A), (1-B) and (1-C) are those represented by the general formula (1-A). Particularly preferred among the dyes ofthe general formula (1-A) is one represented by the following general formula (1-A1). general formula (1-A1):

wherein R²¹ and R²³ each represent a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group or aryl group; R²² represents an aryl group or heterocyclic group; and one of X and Y represents a nitrogen atom and the other represents -CR²⁴ in which R²⁴ represents a hydrogen or halogen atom or a cyano, alkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, alkyloxycarbonyl, carbamoyl, alkoxy, aryl, arylthio, arylsulfonyl, arylsulfinyl, aryloxy or acylamino group. Preferred among these substituents are hydrogen atom, alkyl group, arylthio group, and aryl group. Particularly preferred among these substituents are hydrogen atom, alkylthio group, and aryl group. These substituents each may be further substituted. Preferred examples ofthe dye to be used in the invention include those disclosed in Japanese Patent Application No. 2003-286844, Japanese Patent Application No. 2002-211683, Japanese Patent Application No. 2002-124832, JP-A-2003-128953, and JP-A-2003-41160. Preferred among these dyes are those exemplified below. The dyes employable herein are not limited to these examples. These compounds can be synthesized according to JP-A-2-24191 and JP-A-2001-279145.

The content ofthe yellow dye represented by the general formula (1-1) in the ink is preferably from 0.2 to 20% by weight, more preferably from 0.5 to 15% by weight. [Cyan dye] The phthalocyanine dye which is a cyan dye will be further described hereinafter. The phthalocyanine dye to be used in the invention preferably is excellent in both light-resistance and ozone resistance and has little change of hue and surface conditions (little bronzing and dye precipitation). Referring to light-resistance, it is desired that the ink show a light-resistance of not smaller than 90% as calculated in terms of percent dye remaining in 3 days when exposed to light from a Xenon lamp at Xe: 1.1 W/m (intermittent) through a TAC filter to a site on a PM photographic image-receiving paper produced by EPSON CO., LTD (reflection density after irradiation/initial concentration x 100) where the reflection density OD is 1.0. It is also desired that the ink show a percent dye remaining of not smaller than 85% in 14 days. The measure of change of hue and surface conditions is the amount of Cu ions present as phthalate after the decomposition of phthalocyanine dye. The amount of Cu compounds present on the actual print is preferably predetermined to be 10 mg/m² or less as calculated in terms of Cu ion. Referring to the amount of Cu ions to be eluted from the print, the amount of Cu ions to be eluted with water from a solid image containing Cu compounds in an amount of 20 mg/m² or less as calculated in terms of Cu ion which has been stored in 5 pp ozone atmosphere for 24 hours to undergo ozone fading is preferably 20% or less. All Cu compounds are trapped by the image-receiving material before fading. A phthalocyanine dye having the aforesaid physical properties is obtained by 1) raising the oxidation potential, 2) enhancing the associatiability, 3) introducing an association-accelerating group or strengtliening hydrogen bond during π-π stacking, 4) avoiding the introduction of substituents in α-position, i.e., facilitating stacking, or by other methods. The structural characteristic ofthe phthalocyanine dye to be used in the ink composition is that a phthalocyanine dye the number and position of substituents on which can be predetermined is used while the phthalocyanine dye which has been used in the related art inks is a mixture the number and position of substituents on which cannot be predetermined because it is derived by sulfonation of unsubstituted phthalocyanine. A first structural characteristic is that the phthalocyanine dye ofthe present invention is a phthalocyanine dye obtained without sulfonation of unsubstituted phthalocyanine. A second structural characteristic is introduction of electron-withdrawing group into β-position of benzene rings of phthalocyanine, particularly into all benzene rings. In some detail, those substituted on sulfonyl group (JP-A-2002-249677, JP- A-2003-119415), those substituted on all sulfamoyl groups (JP-A-2002-302623, JP-A-2003-3109), those substituted on heterocyclic sulfamoyl group (JP-A-2002-294097, JP-A-2003-3086), those substituted on heterocyclic sulfonyl group (JP-A-2002-275386, JP-A-2003-3099), those substituted on specific sulfamoyl group (JP-A-2002-256167), those substituted on carbonyl group (3P-A-2003-213153), and those having specific substituents for enhancing solubility and ink stability and preventing bronzing are preferred, and in more detail, those having asymmetric carbon (JP-A-2003-213168), and those in the form of Li salt (JP-A-2003-213167). Further, a first physical characteristic of he phthalocyanine dye ofthe present invention is that it has a high oxidation potential (more positive than 1.0 V). A second physical characteristic ofthe phthalocyanine dye ofthe present invention is that the phthalocyanine dye ofthe present invention has a strong associatiability. Specific examples of such a phthalocyanine dye include those having a specified associatiability of oil-soluble dye (JP-A-2001-342373), and those having a specified associatiability of water-soluble dye (JP-A-2002- 309118). Referring to the relationship between the number and properties (ink absorbance) of associatiable groups, the introduction of associatiable groups makes it more likely that the drop of absorbance can occur and λmax can appear in shorter wavelength range even in a dilute solution. Further, referring to the relationship between the number and properties (reflection density OD on PM920 image-receiving paper produced by EPSON CO., LTD.) of associatiable groups, the more the number of associatiable groups is, the lower is the reflection density OD at the same ion intensity. In other words, it is thought that association proceeds on the image-receiving paper. Referring to the relationship between the number and properties (ozone resistance, light-resistance) of associatiable groups, the more the number of associatiable groups is, the better is ozone resistance. A dye having many associatiable groups tends to have improved light-resistance as well. In order to provide ozone resistance, it is necessary that the benzene rings of phthalocyanine be provided with substituents. Since there is a trade-off relation between reflection density OD and fastness, it is necessary that light-resistance be raised without weakening associatiability. Preferred embodiments of the cyan ink ofthe present invention comprising a phthalocyanine dye having the aforesaid characteristics are as follows.

1) Cyan ink having a percent dye remaining of 90% or more as measured after 3 days of irradiation with xenon light (Xe: 1.1 W/m (intermittent) through TAC filter at the site on an image printed on a PM photographic image-receiving paper produced by EPSON Co., Ltd. where the reflection density OD is 1.0.

2) Cyan ink having a percent dye remaining of 60% or more (preferably 80% oτ more) as measured after 24 hours of storage in 5 ppm atmosphere at the site where printing has been made such that the reflection density is from 0.9 to 1.1 as measured through a status A filter.

3) Cyan ink which allows Cu ions to be eluted with water in an amount of 20% or less based on the total amount of dyes after ozone fading under the conditions of Clause 2.

4) Cyan ink which can penetrate a specific image-receiving paper to a depth of up to 30% of the upper portion of image-receiving layer. As a dye having the aforementioned characteristics there may be used a phthalocyanine dye represented by the aforesaid general formula (1-2). A phtlialocyanine dye has been known as a fast dye but is known to have a poor fastness to ozone gas when used as an ink jet recording dyestuff. In the present invention, it is preferred that an electrophilic group be introduced into the phthalocyanine skeleton to make the oxidation potential more positive than 1.0 V (vs SCE) as previously mentioned. Thus, the introduction of a substituent having a great Hammett's substituent constant σp (a measure of the electiophilicity or electron-donating properties of substituents) such as sulfinyl group, sulfonyl group and sulfamoyl group makes it possible to make the oxidation potential more positive. For the reason of potential adjustment, too, a phthalocyanine dye represented by the aforesaid general formula ( 1 -2) is preferably used. The phthalocyanine dye represented by the aforementioned general formula (1-2) will be further described hereinafter. In the general formula (1-2),

X₂₂, X₂₃ and X₂₄ each independently represent -SO-Z₂, -SO2-Z2, - SO₂NR2₁R22, sulfo group, -CONR21R22 or -CO2R21. Preferred among these substituents are -SO-Z₂, -S0₂-Z₂, - S0₂NR₂ιR₂2, and -CONR21R22, particularly -SO₂-Z2 and -S0₂NR₂ιR22₅ most preferably -S0₂-Z₂. Herein, in the case where any one of a₂ι to a₂ represents an integer of 2 or more,

to X₂₄, if they are plural, may be the same or different and each independently represent any ofthe aforesaid groups. Further, X₂ι, X₂₂, X₂₃ and X₂₄ may be the same substituent or may all be the same but partially different substituents such as -SO₂-Z₂ in which Z₂ is different among X₂ι to X₂₄ or maybe different substituents, e.g., -S0₂-Z₂ and -SO2NR₂1R2₂. The aforesaid groups Z₂ each independently represent substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group and substituted or unsubstituted heterocyclic group. Preferred among these groups are substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group and substituted or unsubstituted heterocyclic group, and particularly preferred among these groups are substituted alkyl group, substituted aryl group and substituted heterocyclic group.O The aforesaid groups R₂ι and R₂₂ each independently represent a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group or substituted or unsubstituted heterocyclic group. Preferred among these groups are hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group or substituted or unsubstituted heterocyclic group, and particularly preferred among these groups are hydrogen atom, substituted alkyl group, substituted aryl group or substituted heterocyclic group. However, it is not preferred that R21 and R₂₂ are a hydrogen atom at the same time. The substituted or unsubstituted alkyl group represented by R₂ι, R₂₂ or Z₂ is preferably a C₁-C₃0 alkyl group. Particularly from the reason of enhancement of dye solubility or ink stability, the alkyl group is preferably branched, and it is particularly preferred that the alkyl group have asymmetric carbons (used in racemate form). Examples ofthe substituents on the alkyl group include those listed with reference to the case where Zα, R₂₁, R₂2, Y21, Y₂₂, Y₂₃ and Y₂₄ are able to have further substituents as described later. Particularly preferred among these substituents are hydroxyl group, ether group, ester group, cyano group, amide group and sulfonamide group because they enhance the association of dyes and hence the fastness thereof. Alternatively, the alkyl group may have a halogen atom or ionic hydrophilic group. The number of carbon atoms in the alkyl group does not include that of carbon atoms in the substituents. This can apply to other groups. The substituted or unsubstituted cycloalkyl group represented by R₂ι, R₂₂ or Z₂ is preferably a C5-C30 cycloalkyl group. Particularly from the reason of enhancement of dye solubility or ink stability, it is particularly preferred that the cycloalkyl group have asymmetric carbons (used in racemate form). Examples of the substituents on the cycloalkyl group include those listed with reference to the case where Z₂, R21, R22, Y21, Y₂₂, Y₂₃ and Y₂₄ are able to have further substituents as described later. Particularly preferred among these substituents are hydroxyl group, ether group, ester group, cyano group, amide group and sulfonamide group because they enhance the association of dyes and hence the fastness thereof. Alternatively, the cycloalkyl group may have a halogen atom or ionic hydrophilic group. The substituted or unsubstituted alkenyl group represented by R₂₁, R₂₂ or Z₂ is preferably a C2-C30 alkenyl group. Particularly from the reason of enhancement of dye solubility or ink stability, the alkenyl group is preferably branched. It is particularly preferred that the alkenyl group have asymmetric carbons (used in racemate form). Examples ofthe substituents on the alkenyl group include those listed with reference to the case where Z₂, R2₁, .₂, Y₂1. Y₂₂, Y₂₃ and Y₂₄ are able to have further substituents as described later. Particularly preferred among these substituents are hydroxyl group, ether group, ester group, cyano group, amide group and sulfonamide group because they enhance the association of dyes and hence the fastness thereof. Alternatively, the alkenyl group may have a halogen atom or ionic hydrophilic group. The substituted or unsubstituted aralkyl group represented by R₂ι, R₂₂ or Z₂ is preferably a C7-C30 aralkyl group. Particularly from the reason of enhancement of dye solubility or ink stability, the aralkyl group is preferably branched. It is particularly preferred that the aralkyl group have asymmetric carbons (used in racemate form). Examples of the substituents on the aralkyl group include those listed with reference to the case where Z₂, R21, R22, Y21, Y22, Y23 and Y₂₄ are able to have further substituents as described later. Particularly preferred among these substituents are hydroxyl group, ether group, ester group, cyano group, amide group and sulfonamide group because they enhance the association of dyes and hence the fastness thereof. Alternatively, the aralkyl group may have a halogen atom or ionic hydrophilic group. The substituted or unsubstituted aryl group represented by R₂ι, R₂₂ or Z is preferably a C6-C30 aryl group. Examples ofthe substituents on the aryl group include those listed with reference to the case where Z₂, R₂₁, R₂₂, Y₂ι, Y₂₂, Y₂₃ and Y₂₄ are able to have further substituents as described later. In particular, en electron- withdrawing group is preferred because it causes the oxidation potential ofthe dye to be higher and thus enhances the fastness thereof. Examples ofthe electron-withdrawing group include those having a positive Hammett's substituent constant σp. Preferred examples ofthe electron-withdrawing group include halogen atom, heterocyclic group, cyano group, carboxyl group, acylamino group, sulfonamide group, sulfamoyl group, carbamoyl group, sulfonyl group, imide group, acyl group, sulfo group, and quaternary ammonium group. Particularly preferred among these electron-withdrawing groups are cyano group, carboxyl group, sulfamoyl group, carbamoyl group, sulfonyl group, imide group, acyl group, sulfo group, and quaternary ammonium group. The heterocyclic group represented by R₂ι, R₂₂ or Z₂ is preferably a 5- or 6-membered heterocyclic group which may be further condensed. The heterocyclic group may be an aromatic heterocyclic group or non- aromatic heterocyclic group. The heterocyclic group represented by R₂ι, R₂₂ or Z will be exemplified in the form of heterocyclic ring with its substitution position omitted, but the substitution position is not limited and, for example, pyridine may have substituents on the 2-, 3- or 4-position. Examples ofthe heterocyclic ring include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthaladine, quinoxaline, pyrrole, indole, furane, benzofurane, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxaole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isooxazole, benzisooxazole, pyrrolidine, piperidine, piperazine, imidazolidine, and thiazoline. In particular, aromatic heterocyclic groups are preferred. Preferred examples ofthe aromatic heterocyclic groups include pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, and thiadiazole. These aromatic heterocyclic groups may have substituents, and examples ofthe substituents on the aromatic heterocyclic group include those listed with reference to the case where Z₂, R_ι, R2₂, Y2₁, Y2₂, Y23 and Y₂₄ are able to have further substituents as described later. Preferred examples ofthe substituents include those listed with reference to the aforementioned aryl group, and even more desirable examples ofthe substituents include those listed with reference to the aforementioned aryl group. Y₂₁, Y.₂, Y23 and Y₂₄ each independently represent a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, acylamino group, arylamino group, ureido group, sulfamoyl group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group, carboxyl group or sulfo group which may further have substituents. Preferred among these groups are hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, carboxyl group and sulfo group, particularly hydrogen atom, halogen atom, cyano group, carboxyl group and sulfo group, most preferably hydrogen atom. In the case where Z₂, R₂ι, R₂₂, Y₂ι, Y₂₂, Y₂₃ and Y₂₄ may further have substituents, they may further have the following substituents. Examples ofthe substituents on Z₂, R₂ι, R₂₂, Y₂ι, Y₂₂, Y23 and Y₂₄ include C₁- ₂ straight-chain or branched alkyl group, C₇-Cι₈ straight-chain or branched aralkyl group, C₂-C₁₂ straight-chain or branched alkenyl group, C₂-Cι₂ straight-chain or branched alkinyl group, C3-C₁₂ straight-chain or branched cycloalkyl group, C₃- C₁₂ straight-chain or branched cycloalkenyl group (These groups each preferably have branches for the reason of dye solubility or ink stability. It is particularly preferred that these groups have asymmetric carbons. Specific examples of these groups include methyl group, ethyl group, propyl group, isopropyl group, sec-butyl group, t- butyl group, 2-ethylhexyl group, 2-methylsulfonylethyl group, 3-phenoxypropyl group, trifluoromethyl group, and cyclopentyl group), halogen atom (e.g., chlorine atom, bromine atom), aryl group (e.g., phenyl group, 4-t- butylphenyl group, 2,4-di-t-amylphenyl group), heterocyclic group (e.g., i idazolyl group, pyrazolyl group, triazolyl group, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group (e.g., methoxy group, ethoxy group, 2-methoxyethoxy group, 2-methanesulfohykefhoxy group), aryloxy group (e.g., phenoxy group, 2- methylphenoxy group, 4-t-butylphenoxy group, 3-nitrophenoxy group, 3-t-butyloxycarbamoylphenoxy group, 3- methoxy carbamoyl group), acylamino group (e.g., acetarmde group, benzamide group, 4-(3-t-butyl-4- hydroxyphenoxy) butanamide group), alkylamino group (e.g., methylamino group, butylamino group, diethylamino group, methylbutylamino group), anilino group (e.g., phenylamino group, 2-chloroanilino group), ureido group (e.g., phenylureido group, metliylureido group, N,N-dibutylureido group), sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino group), alkylthio group (e.g., methylthio group, octylthio group, 2- phenoxyethylthio group), arylthio group (e.g., phenylthio group, 2-butoxy-5-t-octylphenylthio group, 2- carboxyphenylthio group), alkyloxy carbonylamino group (e.g., metlioxycarbonylamino group), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group), carbamoyl group (e.g., N-ethylcarbamoyl group, N,N-dibutylcarbamoyl group), sulfamoyl group (e.g., N-ethylsulfamoyl group, N,N-dipropyl sulfamoyl group, N-phenylsulfamoyl group), sulfonyl group (e.g., methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group), alkyloxycarbonyl group (e.g., methoxycarbonyl group, butyloxycarbonyl group), heterocyclic oxy group (e.g., l-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group), azo group (e.g., phenylazo group, 4-methoxyphenylazo group, 4- pivaloylaminophenylazo group, 2-hydroxy-4-propanoylphenylazo group), acyloxy group (e.g., acetoxy group), carbamoyloxy group (e.g., N-methylcarbamoyloxy group, N-phenylcarbamoyloxy group), silyloxy group (e.g., trimethylsilyloxy group, dibutylmethylsilyloxy group), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group), imide group (e.g., N-succinimide group, N-phthalimide group), heterocyclic thio group (e.g., 2-benzothiazolylthio group, 2,4-di-phenoxy-l,3,5-triazole-6-thio group, 2-pyridylthio group), sulfinyl group (e.g., 3-phenoxypropylsulfinyl group), phosphonyl group (e.g., phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group), aryloxycarbonyl group (e.g., phenoxycarbonyl group), acyl group (e.g., acetyl group, 3-phenylpropanoyl group, benzoyl group), and ionic hydrophilic group (e.g., carboxyl group, sulfo group, phosphono group, quaternary ammonium group). The phthalocyanine dye represented by the general formula (1-2), if it is water-soluble, preferably has an ionic hydrophilic group. Examples ofthe ionic hydrophilic group include sulfo group, carboxyl group, phosphono group, and quaternary ammonium group. Preferred among these ionic hydrophilic groups are carboxyl group, phosphono group, and sulfo group, and particularly preferred among these ionic hydrophilic groups are carboxyl group and sulfo group. The carboxyl group, phosphono group and sulfo group may be used in the form of salt, and examples of the counter ion forming the salt include ammonium ion, alkaline metal ion (e.g., lithium ion, sodium ion, potassium ion), and organic cation (e.g., tetramethylammonium ion, tetramethylguanidium ion, tetramethylphosphonium ion). Preferred among these counter ions are alkaline metal ions, and particularly preferred among these counter ions is lithium ion because it enhances the dye solubility and hence the ink stability. The number of ionic hydrophilic groups is preferably at least 2 per molecule of phthalocyanine-based dye, and it is particularly preferred that there be contained at least two sulfo groups and/or carboxyl groups in the phthalocyanine-based dye. In the general formula (1-2), the suffixes a₂ι to a₂₄ and b₂ι to b₂₄ represent the number ofthe substituents X₂ι to X₂₄ and Y₂ι to Y₂₄, respectively. The suffixes a₂ι to a₂₄ each independently represent an integer of from 0 to 4, with the proviso that the suffixes a₂ι to a₂₄ are not 0 at the same time. The suffixes b₂₁ to b₂ each independently represent an integer of from 0 to 4. When any of a2i to a₂₄ and b₂ι to b₂₄ is an integer of 2 or more, there are a plurality of any of X₂ι 's to X₂₄'s and Y₂ι 's to Y₂4's and they may be the same or different. The suffixes a₂ι and b₂ι satisfy the equation a₂ι + b₂ι = 4. In a particularly preferred combination, a₂ι represents 1 or 2 while b₂ι represents 3 or 2, and in the best combination, a₂ι represents 1 while b₂ι represents 3. The combinations a₂₂ andb₂₂, a₂3 andb₂₃, and a₂4 andb₂₄ are similar to the combination of a₂ι andb₂ι, and preferred examples of the combinations a₂₂ and b₂₂, a₂₃ and b₂₃, and a₂₄ and b₂₄ are also similar to that ofthe combination of a₂ι and b₂ι. M represents a hydrogen atom, metal element or oxide, hydroxide or halide thereof. Preferred examples of M other than hydrogen atom include metal elements such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Ft, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb and Bi. Preferred examples of metal oxide include VO, and GeO. Preferred examples of metal hydroxide include Si(OH)₂, Cr(OH ₂, and Sn(OH) . Examples of metal halide include A1C1, SiCl₂, VC1, VC1₂, VOC1, FeCl, GaCl, and ZrCl. Preferred among these metal elements are Cu, Ni, Zn, and Al, most preferably Cu. In the phthalocyanine dye represented by the general formula (1-2), Pc (phthalocyanine ring) may form a dimer (e.g., Pc-M-L-M-Pc) or trimer with L (divalent connecting group) interposed therebetween, and in this case, M's may be the same or different. Preferred examples ofthe divalent connecting group represented by L include oxy group -0-, thio group -S-, carbonyl group -CO-, sulfonyl group -S0₂-, imino group -NH-, methylene group -CH₂-, and group formed by combining these groups. Referring to preferred combination of substituents on the compound represented by the general formula (1-2), the compound ofthe general formula (1-2) preferably has various substituents at least one of which is one ofthe preferred groups listed above, and more preferably, more ofthe various substituents are the preferred groups listed above, and most preferably, all ofthe various substituents are the preferred groups listed above. Preferred among the phthalocyanine dyes represented by the general formula (1-2) is a phthalocyanine dye having the structure represented by the aforesaid general formula (1-5). The phthalocyanine dye represented by the general formula (1-5) ofthe invention will be described in detail hereinafter. In the aforesaid general formula (1-5), X_5\ to ₅₄ and Y₅₁ to Y₅₈ have the same meaning as X₂₁ to X₂₄ and Y₂ι to Y₂₄ in the general formula (1-2) and preferred examples of X₅₁ to X₅₄ and Y₅₁ to Y5₈ are the same as those in the general formula (1-2). Further, Mi has the same meamng as M in the general formula (1-2) and preferred examples of Mi are the same as those in the general formula (1-2). In the general formula (1-5), a₅ι to a₅₄ each independently represent an integer of 1 or 2, and preferably, the sum of si, a5₂, a₅₃ and a₅₄ is equal to or smaller than 4 and equal to or greater than 6, and it is particularly preferred that asi, as₂, a₅₃ and as₄ each are 1. X₅ι, X₅₂, X₅₃ and X₅₄ may be the same substituent, or X₅ι, X₅₂, X₅₃ and X5₄ each may be a substituent of the same kind but partially different, e.g., -S0₂-Z₂ in which Z₂ differs among X5₁, X_S2, X₅₃ and X₅₄, or X₅ X₅₂, X53 and X5₄ may be different substituents, e.g., -S0₂-Z₂ and -S0₂NR₂ιR₂₂. Particularly preferred examples ofthe combination of substituents among the phthalocyanine dyes represented by the general formula (1-5) will be given below. Preferably, X_5J to X₅₄ each independently represent -SO-Z₂, -S0₂-Z₂, -S0₂NR₂ιR₂₂ or -CONR₂ιR₂₂, particularly -S0₂-Z₂ or -SO2NR21R22, most preferably -S0₂-Z₂. Z₂ S each represent a substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group or substituted or unsubstituted heterocyclic group, and most desirable among these groups are substituted alkyl group, substituted aryl and substituted heterocyclic group. Particularly for the reason of enhancement of dye solubility or ink stability, it is preferred that the substituents have asymmetric carbons (used in racemate form). Further, for the reason of enhancement of association and hence fastness, it is preferred that the substituents have a hydroxyl group, ether group, ester group, cyano group, amide group or sulfonamide group incorporated therein. R₂₁ and ₂₂ each independently represent a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group or substituted or unsubstituted heterocyclic group, particularly a hydrogen atom, substituted alkyl group, substituted aryl group or substituted heterocyclic group. However, it is not preferred that R₂ι and R₂₂ each are a hydrogen atom at the same time. Particularly for the reason of enhancement of dye solubility or ink stability, it is preferred that the substituents have asymmetric carbons (used in racemate form). Further, for the reason of enhancement of association and hence fastness, it is preferred that the substituents have a hydroxyl group, ether group, ester group, cyano group, amide group or sulfonamide group incorporated therein. Y₅ι to Y₅₈ each independently represent a hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, carboxyl group or sulfo group, particularly hydrogen atom, halogen atom, cyano group, carboxyl group or sulfo group, most preferably hydrogen atom. The suffixes asi to as₄ each independently represent 1 or 2, and it is particularly preferred that asi to a_s4 each be 1 at the same time. Mi represents a hydrogen atom, metal element or oxide, hydroxide or halide thereof, particularly Cu, Ni, Zn or Al, most preferably Cu. The phthalocyanine dye represented by the general formula (1-5), if it is water-soluble, preferably has an ionic hydrophilic group. Examples ofthe ionic hydrophilic group include sulfo group, carboxyl group, phosphono group, and quaternary ammonium group. Preferred among these ionic hydrophilic groups are carboxyl group, phosphono group, and sulfo group, and particularly preferred among these ionic hydrophilic groups are carboxyl group and sulfo group. The carboxyl group, phosphono group and sulfo group may be used in the form of salt, and examples ofthe counter ion forming the salt include ammonium ion, alkaline metal ion (e.g., lithium ion, sodium ion, potassium ion), and organic cation (e.g., tetrametlrylammomum ion, tetramethyl guanidium ion, tetramethylphosphomum ion). Preferred among these counter ions are alkaline metal ions, and particularly preferred among these counter ions is lithium ion because it enhances the dye solubility and hence the ink stability. The number of ionic hydrophilic groups is preferably at least 2 per molecule of phthalocyanine-based dye, and it is particularly preferred that there be contained at least two sulfo groups and/or carboxyl groups in the phthalocyanine-based dye. Referring to preferred combination of substituents on the compound represented by the general formula (5), the compound ofthe general formula (1-5) preferably has various substituents at least one of which is one ofthe preferred groups listed above, and more preferably, more ofthe various substituents are the preferred groups listed above, and most preferably, all ofthe various substituents are the preferred groups listed above. Referring to the chemical structure of the phthalocyanine dye represented by the general formula (1-5), it is preferred that at least one electron-withdrawing group such as sulfinyl group, sulfonyl group and sulfamoyl group be incorporated in each of four benzene rings in the phthalocyanine such that σp value ofthe substituents in the entire phthalocyanine skeleton totals not smaller than 1.6. The Hammett's substituent constant σp will be described hereinafter. Hammett's rule is an empirical rule which L. P. Hammett proposed in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, and the validity of this empirical rule has been widely accepted today. Substituent constants required in Hammett's rule are σp value and σm value, and these values are found in many general literatures, and for the details of these values, reference can be made to J. A. Dean, "Lange's Handbook of Chemistry", 12th ed., 1979 (Mc Graw-Hill), and "Kagaku no Ryoiki (Region of Chemistry)", extra edition, No. 122, pp. 96 - 103, 1979 (Nankodo). In the present invention, these substituents are defined or described by Hammett's substituent constant σp, but this does not mean that the known values found in the aforementioned literatures are not limited to certain substituents and it goes without saying that even if the values are unknown in literatures, they contain substituents which may fall within the defined range when measured according to Hammett's rule. Further, the compounds ofthe present invention contain those which are not benzene derivatives, and as a measure for indicating the electron effect of substituents there is used σp value regardless of substitution position. In the present invention, σp value is used in this sense. The phthalocyanine derivative represented by the general formula (1-2) is normally a mixture of analogues which are unavoidably different in introduction sites of substituents Xn (n = 1 to 4) and Ym (m = 1 to 4) and introduced number of these substituents by synthesis method. Accordingly, the general formula ofthe phtlialocyanine dye is mostly a statistically averaged representation of these analogous mixtures. In the invention, it was found that the classification of these analogous mixtures into the following three classes gives a specific mixture which is particularly preferred. In other words, mixtures of phthalocyanine-based dye analogues represented by the general formula (1-2) or (1-5) are classified into the following classes for definition. In the general formula (1-5), Y₅₁, Y₅₂, Y₅₃, Y5₄, Y₅₅, Y₅6, Y5₇ and Y₅₈ are in 1-, 4-, 5-, 8-, 9-, 12-, 13- and 16-positions, respectively.

(1) β-position substitution type: Phthalocyanine dye having a specific substituent on 2- and or 3-position, 6- and/or 7-position, 10- and or 11-position, or 14- and/or 15-position

(2) -position substitution type: Phtlialocyanine dye having a specific substituent on 1- and/or 4-position, 5- and/or 8-position, 9- and/or 12-position, or 13- and/or 16-position

(3) ,β-position mixed substitution type: Phthalocyanine dye having a specific substituent irregularly on 1- to 16-position In the present specification, in order to describe phtlialocyanine dye derivatives having different structures (particularly different substitution positions), the aforementioned β-position substitution type, opposition substitution type and α,β-position mixed substitution type are used. The phthalocyanine derivative to be used in the invention can be synthesized by, e.g., methods described or cited in Shirai and Kobayashi, "Phthalocyanine - Chemistry and Function -", IPC Co., Ltd., pp. 1 to 62, C. C. Leznoff-AB.P. Lever, "Phthalocyanines - Properties and Applications", VCH, pp. 1 - 54, etc. or analogous methods in combination. The phthalocyanine compound represented by the general formula (1-2) to be used in the invention can be synthesized by, e.g., sulfonation reaction, sulfonylchloration reaction and amidation reaction of unsubstituted phthalocyanine compound as disclosed in WO00/17275, 00/08103, 00/08101 and 98/41853 and JP-A-10-36471. In this case, since sulfonation can occur on any position ofthe phthalocyanine nucleus, it is difficult to control the sulfonated number of substituents. Accordingly, when sulfo groups are incorporated under such a reaction condition, the position and number of sulfo groups incorporated in the reaction product cannot be predetermined, unavoidably giving a mixture of products having different numbers of substituents or substitution positions. Thus, since when this mixture is used as a starting material to synthesize the compound ofthe invention, an α,β-mixed substitution type mixture comprising some compounds having different numbers of substituents or substitution positions is obtained as a phthalocyanine dye because the number of heterocyclic group-substituted sulfamoyl groups or the substitution position cannot be predetermined. As previously mentioned, when many electron-withdrawing groups such as sulfamoyl group are incorporated in the phthalocyanine nucleus, the phthalocyanine dye is provided with a more positive oxidation potential and hence an enlianced ozone fastness. When synthesized according to the aforementioned method, it is unavoidable that the reaction mixture contains a phthalocyanine dye having a small number of electron- withdrawing groups incorporated therein, i.e., more negative oxidation potential. Accordingly, in order to enhance the ozone fastness ofthe phthalocyanine dye, a synthesis method capable of inhibiting the production of a compound having a more negative oxidation potential is preferably employed. The phthalocyanine compound represented by the general formula (1-5) ofthe invention can be derived from a tetiasuffophthalocyanine compound obtained by, e.g., reacting a phthalonitrile derivative (compound P) represented by the following general formula and or a dii inoisoindoline derivative (compound Q) represented by the following general formula with a metal derivative represented by the general formula (1-6) or reacting a 4-sulfophthalocyanine derivative (compound R) represented by the following general formula with a metal derivative represented by the general formula (1-6).

In these general formulae, Xp corresponds to X₅ι, X₅₂, X₅₃ or X₅₄ in tiie general formula (1-5). Yq and Yq' each correspond to Y₅ι, Y₅₂, Y53, Y54, Y55, Yse, Y57 or Y₅₈ in the general formula (1-5). In the compound R, M' represents a cation. Examples ofthe cation represented by M' include alkaline metal ions such as Li, Na and K ions and organic cations such as triethylammomum ion and pyridinium ion. General formula (1-6): M-(Y)d wherein M has the same meaning as M in the general formulae (1-2) or Mi in the general formula (1-5); Y represents a monovalent or divalent ligand such as halogen atom, acetate anion, acetyl acetonate and oxygen; and d represents an integer of from 1 to 4. In other words, when synthesized according to the aforementioned method, desired substituents can be incorporated by a predetermined number. In particular, in order to introduce many electron-withdrawing groups to make the oxidation potential more positive as in the present invention, the aforementioned synthesis method can be used because it is extremely excellent as compared with the aforementioned method for synthesis ofthe phthalocyanine compound ofthe general formula (1-2). The phthalocyanine compound represented by the general formula (1-5) thus obtained is a mixture of compounds represented by the following general formulae (a)-l to (a)-4 which are isomeric with the substitution position on Xp, i.e., β-position substitution type mixture.

General Formula ( ) ^— 1

General Formula ( a ) ^— 2

General Formula ( a ) — 3

In the foregoing synthesis method, when the same compound is used as Xp, a β-position substitution type phthalocyanine dye wherein X₅₁, 5₂, X53 and s₄ are the same substituent can be obtained. On the contrary, when different materials are used in combination as Xp, a dye having substituents ofthe same kind but partially different or a dye having different substituents can be synthesized. Among the dyes ofthe general formula (1-5), tliese dyes having different electron-withdrawing substituents are particularly desirable because they can adjust the solubility and association ofthe dye, the age stability ofthe ink, etc. In the invention, it was found very important for the enhancement of fastness that any of these substitution types has an oxidation potential of more positive than 1.0 V (vs SCE). The degree of this effect could not be expected from the related art. Although its mechanism is not known in detail, a tendency was given that β-position substitution type is obviously better than α,β-position mixed substitution type in hue, light fastness, ozone fastness, etc. Specific examples ofthe phthalocyanine dyes represented by the general formula (1-2) or (1-5) (exemplary compounds I-l to 1-12 and exemplary compounds 101 to 190) will be given below, but the phthalocyanine dye to be used in the present invention is not limited thereto.

example compound

(1-2)

(1-3)

(1-4)

(1-6)

(1-9)

(1-10)

(1-11)

46

SUBSTITUTE SHEEKRULE26)

47

SUBSTITUTE SHEET(RULE2β)

48

SUBSTlϊOiΕSHEET(RULE26)

50

SUBSTllur£SHEET(RULE26)

51

SUBSTITUTE SHEET(RULE2

The structure ofthe phthalocyanine compound represented by M-Pc(Xpι)m(Xp₂)n in Compound Nos.46 to 190 is as follows.

The phthalocyanine dye represented by the general formula (1-2) can be synthesized according to the patent cited above. The phthalocyanine dye represented by the general formula (1-5) can be synthesized by the aforementioned method as well as the method disclosed in JP-A-2001-226275, JP-A-2001-96610, JP-A-2001- 47013 and JP-A-2001-193638. The starting material, intermediate dye and synthesis route are not limited to those according to these methods. The content ofthe phthalocyanine dye represented by the general formula (1-2) in the ink is preferably from 0.2 to 20% by weight, more preferably from 0.5 to 15% by weight. [Magenta dye] The azo dye to be used in the invention is preferably a dye having a maximal absorption at a wavelength of from 500 nm to 580 nm in an aqueous medium and an oxidation potential of more positive than 1.0 V (vs SCE). The first structural characteristic of preferred dye of this azo dye which is a magenta dye is that it is a dye having a chromophore represented by the general formula (heterocyclic ring A)-N=N-(heterocyclic ring B). In this case, the heterocyclic ring A and the heterocyclic ring B in the aforementioned general formula may have the same structure. The heterocyclic ring A and heterocyclic ring B each are in detail a 5- or 6-membered heterocyclic ring which is selected from pyrazole, imidazole, triazole, oxazole, thiazole, selenazole, pyridone, pyrazine, pyrimidine and pyridine. In some detail, they are described in JP-A-2001-279145, JP-A-2001-15614, JP-A-2002-309116, JP-A-2003- 12650, etc. Further, the second preferred structural characteristic ofthe aforesaid azo dye is that the azo group is an azo dye having an aromatic nitrogen-containing 6-membered heterocyclic ring directly connected to at least one end thereof as a coupling component, and specific examples of such an azo dye are described in JP-A-2002- 371214. The third preferred structural characteristic is that the chromophore has an aromatic cyclic amino group or heterocyclic amino group structure, and specific examples ofthe chromophore include anilino group, and heterylamino group. The fourth preferred structural characteristic is that the azo dye has a stereostructure. This is described in detail in Japanese Patent Application 2002-12015. By providing an azo dye with the aforesaid structural characteristics, the oxidation potential ofthe dye can be raised, making it possible to enhance the ozone fastness thereof. As a means of raising the oxidation potential there may be used a metliod involving the removal of α-hydrogen from the azo dye. Further, from the standpoint of rise of oxidation potential, an azo dye ofthe general formula (1-3) is particularly preferred. The means of raising the oxidation potential of an azo dye is described in detail in Japanese Patent Application 2001-254878. The magenta ink ofthe present invention comprising an azo dye having the aforesaid characteristics preferably has λmax (maximal absorption wavelength) of from 500 to 580 nm from the standpoint of hue and has a small half-width on both the long and short wavelengths, i.e., sharp absorption spectrum. This is described in detail in JP-A-2002-309133. Further, if an azo dye ofthe general formula (1-3) is used, by introducing methyl group at α-position, the sharpening of absorption can be realized. The forced fading rate constant ofthe magenta ink comprising the azo dye with respect to ozone gas is preferably not greater than 5.0 x 10^"2 [h¹], more preferably not greater than 3.0 x 10^'2 [h^"1], particularly not greater than 1.5 x 10^"2 [h^"1]. For the measurement ofthe forced fading rate constant with respect to ozone gas, only the magenta ink is printed on a reflective image medium to obtain an image. The color ofthe main spectral absorption range of the ink constituting the image is measured for reflection density through a Status A filter. The colored area at which the reflection density thus measured ranges from 0.90 to 1.10 is predetermined to be initial density point. The initial density is defined to be starting density (= 100%). Using an ozone fading machine in which an ozone concentration of 5 mgL is always kept, the image is then allowed to fading. The time required until the reflection density ofthe initial density point reaches 80% ofthe initial value is then measured. The reciprocal of this value [h^"1] is the determined. On the supposition that the relationship between the density of faded image and the time follows a first-order reaction rate equation, this reciprocal is determined as fading reaction rate constant. Examples ofthe print patch for test employable herein include patch having solid rectangular symbols printed thereon according to JIS code 2223, stepwise color patch of Macbeth chart, and other arbitrary stepwise density patches allowing the measurement of area. The reflection density of reflected image (stepwise color patch) printed for measurement is determined by measuring light ray passing through a Status A filter by a densitometer satisfying IS05-4. The testing chamber for measuring the forced fading rate constant with respect to ozone gas is equipped with an ozone generator (e.g., of high voltage discharge type which applies ac voltage to dried air) capable of keeping the ozone gas concentration in the testing chamber at 5 mg L. The aeration temperature is adjusted to 25°C. The forced fading rate constant is a measure of oxidizability by ambient oixidizing atmosphere such as photochemical smog, automobile emission, organic vapor from coated surface of furniture or carpet and gas generated inside frame in daylight. Ozone gas represents these oxidizing atmospheres. The compound having the aforementioned characteristics represented by the general formula (1-3) as an azo dye which is preferably used in the present invention will be described hereinafter. general formula (1-3):

In the general formula (1-3), A_3J represents a 5-membered heterocyclic ring. B₃ι and B₃₂ each represent =CR₃₁- or -CR₃₂= or one of B₃ι and B₃₂ represents a nitrogen atom while the other represents =CR₃ι- or -CR₃₂=. R₃₅ and R₃₆ each independently represent a hydrogen atom or a substituent which represents an aliphatic group, aromatic group, heterocyclic ring, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group the hydrogen atom of which may be substituted. G₃, R₃₁ and R₃₂ each independently represent a hydrogen atom or a substituent which represents a halogen atom, aliphatic group, aromatic group, heterocyclic ring, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aiyloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfinyl group, arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group or sulfo group the hydrogen atom of which may be substituted. R₃ι and R₃₅ or R₃₅ and R₃₆ may be connected to each other top form a 5- or 6-membered ring. In the general formula (1-3), A₃ι represents a 5-membered heterocyclic ring and examples of hetero atoms in the heterocyclic ring include N, O and S. The 5-membered heterocyclic ring is preferably a nitrogen- containing 5-membered heterocyclic ring which may be condensed with aliphatic rings, aromatic rings or other heterocyclic rings. Preferred examples of A_3Ϊ may include pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazole ring, benzothiazole ring, benzooxazole ring, and benzoisothiazole ring. The various heterocyclic groups may further have substituents. Preferred among these heterocyclic rings are pyrazole ring, imidazole ring, isothiazole ring, thiadiazole ring and benzothiazole ring represented by the following general formulae (a) to (f): (a) (b)

In the aforesaid general formulae (a) to (f), R₃₀7 to R₃₂o represent the same substituents as G₃, R₃₁ and R₃₂ in the general formula (1-3). Preferred among the compounds ofthe general formulae (a) to (f) are pyrazole ring represented by the general formula (a) and isothiazole ring represented by the general formula (b), most preferably pyrazole ring represented by the general formula (a). In the general formula (1-3), B₃ι and B₃₂ each represent =CR₃ι- or -CR₃₂= or one of B₃ι and B₃₂ represents a nitrogen atom while the other represents =CR₃₁- or -CR₃₂=, but B₃ι and B₃₂ preferably each represent =CR₃ι- or -CR₃₂=. Preferred examples of R₃₅ and R₃β may include hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkylsulfonyl group or arylsulfonyl group. More preferably, R₃₅ and R₃₆ each are a hydrogen atom, aromatic group, heterocyclic group, acyl group, alkylsulfonyl group or arylsulfonyl group. Most preferably, R₃₅ and R₃₆ each are a hydrogen atom, aryl group or heterocyclic group. The hydrogen atom of the aforementioned various substituents may be substituted. However, R₃₅ and R₃₆ are not a hydrogen atom at the same time. G₃ is preferably a hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylthio group, arylthio group or heterocyclic thio group, more preferably a hydrogen atom, halogen atom, alkyl group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, amino group or acylamino group, most preferably a hydrogen atom, amino group (preferably anilino group) or acylamino group. The hydrogen atom ofthe aforesaid substituents may be substituted. Preferred examples of R₃₁ and R₃₂ include hydrogen atom, alkyl group, halogen atom, alkoxycarbonyl group, carboxyl group, carbamoyl group, hydroxy group, alkoxy group, and cyano group. The hydrogen atom ofthe aforesaid substituents maybe substituted. R³¹ and R³⁵ or R³⁵ and R³⁶ may be connected to each other to form a 5- or 6-membered ring. Examples ofthe substituents which may substitute on A₃ι or which may substitute on the substituents of R₃₁, R₃₂, ₃₅ or G₃ include those listed above with reference to G₃, R_3X and R₃₂. In the case where the azo dye represented by the general formula (1-3) is a water-soluble dye, an ionic hydrophilic group is further provided on any position on A₃₁, R₃ι, R₃₂, R₃₅, R₃₆ and G₃ as a substituent. Examples ofthe ionic hydrophilic group as a substituent include sulfo group, carboxyl group, phosphono group, quaternary ammonium group, etc. The aforesaid ionic hydrophilic group is preferably a carboxyl group, phosphono group or sulfo group, particularly carboxyl group or sulfo group. The carboxyl group, phosphono group and sulfo group may be in the form of salt, and examples of counter ions constituting the salt include ammonium ion, alkaline metal ion (e.g., lithium ion, sodium ion, potassium ion), and organic cation (e.g., tetramethylammonium ion, tetramethylguanidium ion, tetramethyl phosphonium). The terms (substituent) as used in the description ofthe general formula (1-3) will be described. These terms are common even to the general formula (1-3) and the general formula (3-A) described later. Examples ofthe halogen atom include fluorine atom, chlorine atom, and bromine atom. The aliphatic group means alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkinyl group, substituted alkinyl group, aralkyl group and substituted aralkyl group. In the present specification, the term "substituted" as used in "substituted alkyl group", etc. means that the hydrogen atom in "alkyl group", etc. is substituted by substituents listed above with reference to G₃, R₃ι and R₃₂, etc. The aliphatic group may have branches or may form a ring. The number of carbon atoms in the aliphatic group is preferably from 1 to 20, more preferably from 1 to 16. The aryl moiety ofthe aralkyl group or substituted aralkyl group is preferably a phenyl group or naphthyl group, particularly phenyl group. Examples ofthe aliphatic group include methyl group, ethyl group, butyl group, isopropyl group, t-butyl group, hydroxyethyl group, methoxyethyl group, cyanoethyl group, trifluoroinetliyl group, 3-sulfopropyl group, 4- sulfobutyl group, cyclohexyl group, benzyl group, 2-phenethyl group, vinyl group, and allyl group. The aromatic group means an aryl group or substituted aryl group. The aryl group is preferably a phenyl group or naphthyl group, particularly phenyl group. The number of carbon atoms in the aromatic group is preferably from 6 to 20, more preferably from 6 to 16. Examples ofthe aromatic group include phenyl group, p-tollyl group, p-methoxyphenyl group, 0- chlorophenyl group, and m-(3-sulfopropylamino)phenyl group. Examples ofthe heterocyclic group include substituted heterocyclic groups. The heterocyclic group may have its heterocyclic ring condensed with aliphatic rings, aromatic rings or other heterocyclic rings. The aforesaid heterocyclic group is preferably a 5- or 6-membered heterocyclic ring. Examples ofthe aforesaid substituents include aliphatic group, halogen atom, alkylsulfonyl group, arylsulfonyl group, acyl group, acylamino group, sulfamoyl group, carbamoyl group, ionic hydrophilic group, etc. Examples ofthe aforesaid heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2- benzooxazolyl group, and 2-furyl group. Examples ofthe carbamoyl group include substituted carbamoyl groups. Examples ofthe aforesaid substituents include alkyl group. Examples ofthe aforesaid carbamoyl group include methylcarbamoyl group, and dimethylcarbamoyl group. Examples ofthe alkoxycarbonyl group include substituted alkoxycarbonyl groups. The aforesaid alkoxycarbonyl group is preferably an alkoxycarbonyl group having from 2 to 20 carbon atoms. Examples of the aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid alkoxycarbonyl group include methoxycarbonyl group, and ethoxycarbonyl group. Examples of he aryloxycarbonyl group include substituted aryloxycarbonyl groups. The aforesaid aryloxycarbonyl group is preferably an aryloxycarbonyl group having from 7 to 20 carbon atoms. Examples of the aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid aryloxycarbonyl group include phenoxycarbonyl group. Examples ofthe heterocyclic oxycarbonyl group include substituted heterocyclic oxycarbonyl groups. Examples ofthe heterocyclic ring include those listed above with reference to the heterocyclic group. The aforesaid heterocyclic oxycarbonyl group is preferably a heterocyclic oxycarbonyl group having from 2 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid heterocyclic oxycarbonyl group include 2-pyridyloxycarbonyl group. Examples ofthe acyl group include substituted acyl groups. The aforesaid acyl group is preferably an acyl group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid acyl group include acetyl group and benzoyl group. Examples ofthe alkoxy group include substituted alkoxy groups. Examples ofthe aforesaid alkoxy group is preferably an alkoxy group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include alkoxy groups, hydroxyl groups, and ionic hydrophilic groups. Examples ofthe aforesaid alkoxy group include methoxy group, ethoxy group, isopropoxy group, methoxyethoxy group, hydroxyethoxy group, and 3- carboxypropoxy group. Examples ofthe aryloxy group include substituted aryloxy groups. The aforesaid aryloxy group is preferably an aryloxy group having from 6 to 20 carbon atoms. Examples ofthe aforesaid substituents include alkoxy groups, and ionic hydrophilic groups. Examples ofthe aforesaid aryloxy group include phenoxy group, p-methoxyphenoxy group, and o-methoxyphenoxy group. Examples ofthe heterocyclic oxy group include substituted heterocyclic oxy groups. Examples ofthe heterocyclic ring include those listed above with reference to the heterocyclic group. The aforesaid heterocyclic oxy group is preferably a heterocyclic oxy group having from 2 to 20 carbon atoms. Examples ofthe aforesaid substituents include alkyl groups, alkoxy group, and ionic hydrophilic groups. Examples ofthe aforesaid heterocyclic oxy group include 3-pyridyloxy group, and 3-thienyloxy group. The silyloxy group is preferably a silyloxy group substituted by an aliphatic or aromatic group having from 1 to 20 carbon atoms. Examples ofthe aforesaid sjlyloxy group include trimethylsilyloxy, and diphenylmethyl silyloxy. Examples ofthe acyloxy group include substituted acyloxy groups. The aforesaid acyloxy group is preferably an acyloxy group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples of the aforesaid acyloxy group include acetoxy group, and benzoyloxy group. Examples ofthe carbamoyloxy group include substituted carbamoyloxy groups. Examples ofthe aforesaid substituents include alkyl groups. Examples ofthe aforesaid carbamoyloxy group include N- methylcarbamoyloxy group. Examples ofthe alkoxycarbonyloxy group include substituted alkoxycarbonyloxy groups. The aforesaid alkoxycarbonyloxy group is preferably an alkoxycarbonyloxy group having from 2 to 20 carbon atoms. Examples ofthe aforesaid alkoxycarbonyloxy group include methoxycarbonyloxy group, and isopropoxycarbonyloxy group. Examples ofthe aryloxycarbonyloxy group include substituted aryloxycarbonyloxy groups. The aforesaid aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having from 7 to 20 carbon atoms. Examples ofthe aforesaid aryloxycarbonyloxy group includephenoxycarbonyloxy group. Examples ofthe amino group include substituted amino groups. Examples ofthe aforesaid substituents include alkyl groups, aryl groups, and heterocylic groups, and the alkyl groups, aryl groups and heterocyclic groups may further have substituents. Examples ofthe alkylamino group include substituted alkylamino groups. The alkylamino group is preferably an alkylamino group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid alkylamino group include methylamino group, and diethylamino group. Examples ofthe arylamino group include substituted arylamino groups. The aforesaid arylamino group is preferably an arylamino group having from 6 to 20 carbon atoms. Examples ofthe aforesaid substituents include halogen atoms, and ionic hydrophilic groups. Examples ofthe aforesaid arylamino group include phenylamino group, and 2-chlorophenylamino group. Examples ofthe heterocyclic amino group include substituted heterocyclic amino groups. Examples of the heterocyclic ring include those listed above with reference to the heterocyclic group. The aforesaid heterocyclic amino group is preferably a heterocyclic amino group having from 2 to 20 carbon atoms. Examples ofthe aforesaid substituents include alkyl groups, halogen atoms, and ionic hydrophilic groups. Examples ofthe acylamino group include substituted acrylamino groups. The aforesaid acylamino group is preferably an acylamino group having from 2 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid acylamino group include acetylamino group, propionylamino group, benzoylamino group, N-phenylacetylamino group, and 3,5-disulfobenzoylamino group. Examples ofthe ureido group include substituted ureido groups. The aforesaid ureido group is preferably an ureido group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include alkyl groups, and aryl groups. Examples ofthe aforesaid ureido group include 3-methylureido group, 3,3- dimethylureido group, and 3-phenylureido group. Examples ofthe sulfamoylamino group include substituted sulfamoylamino groups. Examples ofthe aforesaid substituents include alkyl groups. Examples ofthe aforesaid sulfamoylamino group include N,N- dipropylsulfamoylamino group. Examples ofthe all oxycarbonylamino group include substituted alkoxycarbonylamino groups. The aforesaid alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having from 2 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid alkoxycarbonylamino group include ethoxycarbonylamino groups. Examples ofthe aryloxycarbonylamino group include substituted aryloxycarbonylamino groups. The aforesaid aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having from 7 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples of he aforesaid aryloxycarbonylamino group include phenoxycarbonylamino groups. Examples ofthe alkylsulfonylamino group and arylsulfonylamino group include substituted alkylsulfonylamino groups and substituted arylsulfonylamino groups. The aforesaid alkylsulfonylamino group and arylsulfonylamino group are preferably an alkylsulfonylamino group and arylsulfonylamino group each having from 1 to 20 carbon atoms. Examples ofthe substituents include ionic hydrophilic groups. Examples of the aforesaid alkylsulfonylamino group and arylsulfonylamino group include methylsulfonylamino group, N- phenyl-methyl sulfonylamino group, phenylsulfonyl amino group, and 3-carboxyphenylsulfonyl amino group. Examples ofthe heterocyclic sulfonylamino group include substituted sulfonylamino groups. Examples ofthe heterocyclic ring include those listed above with reference to the heterocyclic group. The aforesaid heterocyclic sulfonylamino group is preferably a heterocyclic sulfonylamino group having from 1 to 12 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid heterocyclic sulfonylamino group include 2-thienylsulfonylamino group, and 3-pyridylsulfonyl amino group. Examples ofthe alkylthio group, arylthio group and heterocyclic thio group include substituted alkylthio group, substituted arylthio group, and substituted heterocyclic thio group. Examples ofthe heterocyclic ring include those listed above with reference to the heterocyclic group. The aforesaid alkylthio group, arylthio group and heterocyclic thio group each preferably have from 1 to 20 carbon atoms. Examples of the aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid alkylthio group, arylthio group and heterocyclic thio group include methylthio group, phenylthio group, and 2-pyridylthio group. Examples ofthe alkylsulfonyl group and arylsulfonyl group include substituted alkylsulfonyl groups and substituted arylsulfonyl groups. Examples ofthe alkylsulfonyl group and arylsulfonyl group include methylsulfonyl group and phenylsulfonyl group, respectively. Examples ofthe heterocyclic sulfonyl group include substituted heterocyclic sulfonyl groups. Examples ofthe heterocyclic ring include those listed above with reference to the heterocyclic group. The aforesaid heterocyclic sulfonyl group is preferably a heterocyclic sulfonyl group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid heterocyclic sulfonyl group include 2-tlιienylsulfonyl group and 3-pyridylsulfonyl group. Examples ofthe alkylsulfinyl group and arylsulfinyl group include substituted alkylsulfinyl groups and substituted arylsulfinyl groups. Examples ofthe alkylsulfinyl group and arylsulfinyl group include methylsulfinyl group and phenylsulfinyl group, respectively. Examples ofthe heterocyclic sulfinyl group include substituted heterocyclic sulfinyl groups. Examples ofthe heterocyclic ring include those listed above with reference to the heterocyclic group. The aforesaid heterocyclic sulfinyl group is preferably a heterocyclic sulfinyl group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe heterocyclic sulfinyl group include 4-pyridylsulfinyl group. Examples ofthe sulfamoyl group include substituted sulfamoyl groups. Examples ofthe aforesaid substituents include alkyl groups. Examples ofthe aforesaid sulfamoyl group include dimethylsulfamoyl group, and di-(2-hydroxyethyl)sulfamoyl group. Particularly preferred among the structures ofthe general formula (1-3) is one represented by the following general formula (3-A). general formula (3-A)

wherein R_3J, R₃₂, R₃₅ and R₃₆ are as defined in the general formula (1-3). R₃₃ and R₃₄ each independently represent a hydrogen atom or a substituent which represents an aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group. Prefeπed among these substituents is hydrogen atom, aromatic group, heterocyclic group, acyl group, alkylsulfonyl group or arylsulfonyl group, particularly hydrogen atom, aromatic group and heterocyclic group. Z₃₁ represents an electron-withdrawing group having a Hammett's substituent constant σp of 0.20 or more. Z₃ι is preferably an electron-withdrawing group having a Hammett's substituent constant σp of 0.30 or more, more preferably 0.45 or more, particularly 0.60 or more, but the Hammett's substituent constant σp ofthe electron-withdrawing group is preferably not greater than 1.0. Specific examples ofthe electron-withdrawing group having a Hammett's substituent constant σp of 0.60 or more include cyano group, nitro group, alkylsulfonyl group (e.g., methylsulfonyl group), and arylsulfonyl group (e.g., phenylsulfonyl group). Examples ofthe electron-withdrawing group having a Hammett's substituent constant σp of 0.45 or more include acyl group (e.g., acetyl group), alkoxycarbonyl group (e.g., dodecyloxycarbonyl group), aryloxycarbonyl group (e.g., m-chlorophenoxycarbonyl), alkylsulfinyl group (e.g., n-propylsulfinyl), arylsulfinyl group (e.g., phenylsulfinyl), sulfamoyl group (e.g., N-ethylsulfamoyl, N,N-dimethylsulfamoyl), and halogenated alkyl group (e.g., trifluoromethyl) besides the aforesaid groups. Examples ofthe electron-withdrawing group having a Hammett's substituent constant σp of 0.30 or more include acyloxy group (e.g., acetoxy group), carbamoyl group (e.g., N-ethylcarbamoyl, N,N- dibutylcarbamoyl), halogenated alkoxy group (e.g., trifluoromethyloxy), halogenated aryloxy group (e.g., pentafluorophenyloxy), sulfonyloxy group (e.g., metliylsulfonyloxy), halogenated aU lthio group (e.g., difluoromethyltliio), aryl group substituted by two or more electron-witlidrawing groups having σp of 0.15 or more (e.g., 2,4-dinitrophenyl, pentachlorophenyl), and heterocyclic group (e.g., 2-benzooxazolyl, 2- benzothiazolyl, l-phenyl-2-benzoimidazolyl) besides the aforesaid groups. Specific examples ofthe electron-withdrawing group having σp of 0.20 or more include halogen atoms besides the aforesaid groups. Prefeπed among these groups are C₂-C₂₀ acyl group, C₂-C_2u alkyloxycarbonyl group, nitro group, cyano group, Cι-C₂₀ alkylsulfonyl group, C₆-C₂o arylsulfonyl group, Cι-C₂₀ carbamoyl group, and Cι-C₂₀ halogenated alkyl group. Particularly prefeπed among these groups are cyano group, Cι-C₂₀ alkylsulfonyl group and C₆-C₂₀ arylsulfonyl group, most preferably cyano group. Z₃₂ represents a hydrogen atom or a substituent and the substituent represents an aliphatic group, aromatic group or heterocyclic group. Z₃₂ is preferably an aliphatic group, more preferably a -Cβ alkyl group. Q represents a hydrogen atom or a substituent and the substituent represents an aliphatic group, aromatic group or heterocyclic group. In particular, Q is preferably a group formed by a group of non-metallic atoms required to form a 5- to 8-membered ring. The aforementioned 5- to 8-membered ring may be substituted, may be a saturated ring or may have an unsaturated bond. Particularly preferred among these 5- to 8-membered rings are aromatic group and heterocyclic group. Prefeπed examples ofthe non-metallic atom include nitrogen atom, oxygen atom, sulfur atom, and carbon atom. Specific examples of these cyclic structures include benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, benzoimidazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, oxane ring, sulfolane ring, and thiane ring. The hydrogen atoms in the substituents described with reference to the general formula (3-A) may be substituted. Examples ofthe substituents on these substituents include substituents listed with reference to the general formula (1-3), and groups and ionic hydrophilic groups exemplified with reference to G₃, R₃ι and R₃₂. Referring to a particularly preferred combination of azo dyes represented by the general formula (1-3), R₃₅ and R₃₆ each are preferably a hydrogen atom, alkyl group, aryl group, heterocyclic group, sulfonyl group or acyl group, more preferably hydrogen atom, aryl group, heterocyclic group or sulfonyl group, most preferably hydrogen atom, aryl group or heterocyclic group. However, R₃₅ and R₃6 are not a hydrogen atom at the same time. G₃ is preferably a hydrogen atom, halogen atom, alkyl group, hydroxyl group, amino group or acylamino group, more preferably hydrogen atom, halogen atom, amino group or acylamino group, most preferably hydrogen atom, amino group or acylamino group. A₃ι is preferably a pyrazole ring, imidazole ring, isothiazole ring, thiadiazole ring or benzothiazole ring, more preferably pyrazole ring or isothiazole ring, most preferably pyrazole ring. B₃ι and B₃₂ are =CR₃ι- and -CR₃₂=, respectively, in which R_3Ϊ and R₃₂ each are preferably a hydrogen atom, alkyl group, halogen atom, cyano group, carbamoyl group, carboxyl group, hydroxyl group, alkoxy group or alkoxycarbonyl group, more preferably hydrogen atom, alkyl group, carboxyl group, cyano group or carbamoyl group. Referring to a prefeπed combination of substituents on the compound represented by the general formula (1-3), at least one ofthe various substituents is preferably a compound which is a preferred group as mentioned above, and more preferably, more ofthe various substituents are compounds which are prefeπed groups as mentioned above, and most preferably, all the various substituents are compounds which are prefeπed groups as mentioned above. Specific examples ofthe azo dye represented by the general formula (1-3) will be given below, but the azo dye to be used in the present invention is not limited to the following examples.

a-20 — COCH3 C₈H₁₇(t) C₈H₁₇(t)

71

SUBSTITUTE SHEET(RULE2β)

73

SUBSTITUTE SHEET(RULE36)

74

SUBSTITUTE SI-IEET(RULE26)

77 SUBSTITUTE 3MEET(RULE2β)

The content of the azo dye represented by the general formula (1-3) in the ink is preferably from 0.2% weight, more preferably from 0.5% to 15% by weight. The solubility (or dispersibiiity in stabilized 78

SUBSTITUTE SΪΪEET(RULE26) state) ofthe azo dye represented by the general formula (1-3) in water at 20°C is preferably 5% by weight or more, more preferably 10% by weight or more. [Black dye] As the black ink to be used in the invention there is used a dye (L) having a wavelength λmax of from 500 nm to 700 nm and a half width (Wλ, 1/2) of 100 nm or more (preferably from not lower than 120 nm to not higher than 500 nm, preferably from not lower than 120 nm to not higher than 350 nm) in absorption spectrum of a diluted solution normalized to absorbance of 1.0. In the case where "(sharp) black" having a high image quality, i.e., black which can be difficultly emphasized in any of B, G and R without using an observation light source can be realized with this dye (L) alone, this dye (L) alone can be used as a dye for black ink. In general, however, this dye (L) is used in combination with dyes which compensate the dye (L) in the wavelength range where the dye (L) has a low absorption. It is normally preferred that the dye (L) be used in combination with a dye (S) having main absorption in yellow range (λmax of from 350 to 500 nm). The dye (L) may also be used in combination with other dyes to prepare a black ink. In the invention, these dyes are dissolved or dispersed in an aqueous medium singly or in admixture to prepare a black ink. In order that the black ink for ink jet recording satisfies desired requirements, i.e., (1) excellent weather resistance and or (2) maintenance of black balance even after fading, it is preferred that an ink satisfying the following requirements be prepared. Using the black ink, solid rectangle number of JIS code 2223 is printed at 48 points. The print thus formed is then measured for reflection density (Dvis) through a Status A filter (visual filter). The reflection density thus measured is defined as initial density. As a reflection densitometer having a Status A filter mounted thereon there may be used, X-rite densitometer. In order to measure the density of "black", the value obtained with Dvis as standard observed reflection density is used. This printed matter is then forcedly faded using an ozone fading tester capable of always generating 5 ppm of ozone. The forced fading rate constant (kvis) is then determined from the time (t) required until the reflection density (Dvis) reaches 80% ofthe initial value using the equation (0.8 = exp (-kvis-t)). The black ink preferably exhibits a forced fading rate constant (kvis) of not higher than 5.0 x 10^-2 [h^_1], more preferably not higher than 3.0 x 10^"2 [h^"1], particularly not higher than 1.0 x 10^"2 [h^"1] (Condition 1). Using the black ink, solid rectangle number of JIS code 2223 is printed at 48 points. The print thus formed is then measured for three color (C (cyan), M (magenta), Y (yellow)) reflection densities (D_R, D_G, D_B), which are not Dvis, through a Status A filter. The reflection densities thus measured each are defined as initial densities. D_R, D_G, D_B indicate C reflection density through a red filter, M reflection density through a green filter and Y reflection density through a blue filter, respectively. This printed matter is then forcedly faded using an ozone fading tester capable of always generating 5 ppm of ozone in the aforementioned manner. The forced fading rate constants (k_R, ko, k_B) are then similarly determined from the time required until the reflection densities (D_R, D_G, D_B) reach 80% ofthe initial value. The ratio (R) ofthe maximum value to the minimum value ofthe three rate constants thus determined (R = kκ_. α. if k_R is maximum and k_G is mimmum) is preferably not greater than 1.2, more preferably not greater than 1.1, particularly not greater than 1.05 (Condition 2). The "printed matter obtained by printing a solid rectangle of JIS code 2223 at 48 points" as used hereinabove has a size large enough to cover the aperture ofthe measuring instrument so that a sufficiently large area can be used for density measurement. At least one dye to be used in the black ink has an oxidation potential of more positive than 1.0 V (vs SCE), preferably more positive than 1.1 V (vs SCE), more preferably more positive than 1.2 V (vs SCE) and most preferably more than 1.25 V (vs SCE), and at least one ofthe dyes has λmax of 500 nm or more (Condition 3). Further, the black ink is prepared using the azo dye represented by the general formula (1-4). Examples ofthe azo dye represented by the general formula (1-4) include those corresponding to the dye (L) having λmax of 500 nm to 700 nm and a half width of 100 nm or more in absorption spectrum of a diluted solution normalized to absorbance of 1.0. In addition, the dye (S) having λmax of 350 nm to 500 nm is similarly included as one corresponding to the dye ofthe general formula (1-4). Preferably, at least one ofthe dye (L) is the dye ofthe general formula (1-4), and particularly preferably, at least one of both the dye (L) and the dye (S) are the dyes ofthe general formula (1-4), and among them, it is preferred that the dye ofthe general formula (1-4) amounts 90% by mass ofthe total dyes in the ink (Condition 4). The black ink according to the invention is a black ink that satisfies at least one ofthe conditions 1 to 4. The dye represented by the general formula (1-4) will be described hereinafter. In the general formula (1-4), A₄ι, B_4i and C₄ι each independently represent an aromatic or heterocyclic group which may be substituted (A₄₁ and Gu each are a monovalent group and B₄ι is a divalent group). The substituent on A₄₁, B₄₁ and C₄₁ may be an aromatic azo group or heterocyclic azo group. The azo dye represented by the general formula (1-4) is particularly preferably a dye represented by the following general formula (4-A). general formula (4-A):

In the general formula (4-A), A₄₁ and B₄₁ are as defined in the general formula (1-4). B₄₂ and B₄₃ each represent

or

-C 42⁼. G₄, R₄₁ and R₄₂ each independently represent a hydrogen atom, a halogen atom or an aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxy carbonyloxy group, amino group (including arylamino group and heterocyclic amino group), acylamino group, ureido group, sulfamonylamino group, alkoxycarbonyl amino group, aryloxycarbonylamino group, alkyl sulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfinyl group, arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group or sulfo group which may be further substituted. R45 and R₄6 each independently represent a hydrogen atom, or an aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxy carbonyloxy group, carbamolyl group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group which may be further substituted, with the proviso that R₄5 and ^ are not a hydrogen atom at the same time. R₄₁ and R₄₅ or R₄₅ and ₄₆ may be connected to each other to form a 5- or 6-membered ring. The azo dye represented by the general formula (4-A) is preferably a dye represented by the following general formula (4-B). general formula (4-B):

In the aforementioned general formula (4-B), R₄7 and R₄₈ have the same meaning as R₄₁ in the general formula (4-A). The terms (substituent) used with reference to the general formulae (1-4), (4-A) and (4-B) will be described hereinafter. These terms apply also to the general formulae (4-C) and (4-D). Examples ofthe halogen atom include fluorine atom, chlorine atom, and bromine atom. The aliphatic group means alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkinyl group, substituted alkinyl group, aralkyl group and substituted aralkyl group. The aliphatic group may have branches or may form a ring. The number of carbon atoms in the aliphatic group is preferably from 1 to 20, more preferably from 1 to 16. The aryl moiety ofthe aralkyl group or substituted aralkyl group is preferably a phenyl group or naphthyl group, particularly phenyl group. Examples ofthe aliphatic group include methyl group, ethyl group, butyl group, isopropyl group, t-butyl group, hydroxyethyl group, methoxyethyl group, cyanoethyl group, trifluoromethyl group, 3-sulfopropyl group, 4-sulfobutyl group, cyclohexyl group, benzyl group, 2-phenethyl group, vinyl group, and allyl group. The monovalent aromatic group means an aryl group or substituted aryl group. The aryl group is preferably phenyl or naphthyl, particularly phenyl. The number of carbon atoms in the monovalent aromatic group is preferably from 6 to 20, more preferably from 6 to 16. Examples ofthe monovalent aromatic group include phenyl, p-tollyl, p-methoxyphenyl, o-chlorophenyl, and m-(3-sulfopropylamino)phenyl. The divalent aromatic group is obtained by making the monovalent aromatic group divalent. Examples ofthe divalent aromatic group include phenylene, p-tollylene, p-methoxyphenylene, o-chlorophenylene, m-(3- sulfopropylamino)phenylene, and naphthylene. Examples ofthe heterocyclic group include substituted and unsubstituted heterocyclic groups. The heterocyclic group may have its heterocyclic ring condensed with aliphatic rings, aromatic rings or other heterocyclic rings. The aforesaid heterocyclic group is preferably a 5- or 6-membered heterocyclic ring. Examples of the hetero atom in the heterocycle include nitrogen, oxygen and sulfur atoms. Examples ofthe aforesaid substituents include aliphatic group, halogen atom, alkylsulfonyl group, arylsulfonyl group, acyl group, acylamino group,, sulfamoyl group, carbamoyl group, ionic hydrophilic group, etc. Examples ofthe heterocycle in the monovalent and divalent heterocyclic groups include pyridine, thiophene, thiazole, benozothiazole, benzoxazole, and furane ring. Examples ofthe carbamoyl group include substituted and unsubstituted carbamoyl groups. Examples ofthe substituents on the carbamoyl group include alkyl groups. Examples ofthe carbamoyl group include methylcarbamoyl group, and dimethylcarbamoyl group. Examples ofthe alkoxycarbonylamino group include substituted and unsubstituted alkoxycarbonylamino groups. These alkoxycarbonylamino groups each preferably have from 2 to 20 carbon atoms. Examples ofthe substituents on the a&oxycarbonylamino group include ionic hydrophilic groups. Examples ofthe alkoxycarbonylamino group include methoxycarbonylamino, and ethoxycarbonylamino. Examples ofthe aryloxycarbonyl group include substituted aryloxycarbonyl group and unsubstituted aryloxycarbonyl group. The aforesaid aryloxycarbonyl group is preferably an aryloxycarbonyl group having from 7 to 20 carbon atoms. Examples ofthe aforesaid substituents on aryloxycarbonyl group include ionic hydrophilic groups. Examples ofthe aforesaid aryloxycarbonyl group include phenoxycarbonyl group. Examples ofthe heterocyclic oxycarbonyl group include substituted heterocyclic oxycarbonyl group and unsubstituted heterocyclic oxycarbonyl group. The aforesaid heterocyclic oxycarbonyl group is preferably a heterocyclic oxycarbonyl group having from 2 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid heterocyclic oxycarbonyl group include 2- pyridyloxycarbonyl group. Examples ofthe acyl group include substituted acyl group and unsubstituted acyl group. The aforesaid acyl group is preferably an acyl group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid acyl group include acetyl group and benzoyl group. Examples ofthe alkoxy group include substituted alkoxy group and unsubstituted alkoxy group. Examples ofthe aforesaid alkoxy group is preferably an alkoxy group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include alkoxy groups, hydroxyl groups, and ionic hydrophilic groups. Examples ofthe aforesaid alkoxy group include methoxy group, ethoxy group, isopropoxy group, methoxyethoxy group, hydroxyethoxy group, and 3-carboxypropoxy group. Examples of he aryloxy group include substituted aryloxy group and unsubstituted aryloxy group. The aforesaid aryloxy group is preferably an aryloxy group having from 6 to 20 carbon atoms. Examples ofthe aforesaid substituents include alkoxy groups, and ionic hydrophilic groups. Examples ofthe aforesaid aryloxy group include phenoxy group, p-methoxyphenoxy group, and o-methoxyphenoxy group. Examples ofthe heterocyclic oxy group include substituted heterocyclic oxy group and unsubstituted heterocyclic oxy group. The aforesaid heterocyclic oxy group is preferably a heterocyclic oxy group having from 2 to 20 carbon atoms. Examples ofthe aforesaid substituents include alkyl group, alkoxy group, and ionic hydrophilic groups. Examples ofthe aforesaid heterocyclic oxy group include 3-pyridyloxy group, and 3- thienyloxy group. The silyloxy group is preferably a silyloxy group substituted by an aliphatic or aromatic group having from 1 to 20 carbon atoms. Examples ofthe aforesaid silyloxy group include trimetliylsilyloxy, and diphenylmethyl silyloxy. Examples ofthe acyloxy group include substituted acyloxy group and unsubstituted acyloxy group. The aforesaid acyloxy group is preferably an acyloxy group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid acyloxy group include acetoxy group, and benzoyloxy group. Examples ofthe carbamoyloxy group include substituted carbamoyloxy groups. Examples ofthe aforesaid substituents include alkyl groups. Examples ofthe aforesaid carbamoyloxy group include N- methylcarbamoyloxy group. Examples ofthe alkoxycarbonyloxy group include substituted alkoxycarbonyloxy group and unsubstituted alkoxycarbonyloxy group. The aforesaid alkoxy carbonyloxy group is preferably an alkoxycarbonyloxy group having from 2 to 20 carbon atoms. Examples ofthe aforesaid alkoxycarbonyloxy group include methoxycarbonyloxy group, and isopropoxycarbonyloxy group. Examples ofthe aryloxycarbonyloxy group include substituted aryloxycarbonyloxy group and unsubstituted aryloxycarbonyloxy group. The aforesaid aryloxy carbonyloxy group is preferably an aryloxycarbonyloxy group having from 7 to 20 carbon atoms. Examples ofthe aforesaid aryloxycarbonyloxy group include phenoxycarbonyloxy group. Examples ofthe amino group include substituted amino group and unsubstituted amino group. Examples ofthe aforesaid substituents include alkyl groups, aryl groups, and heterocylic groups, and the alkyl groups, aryl groups and heterocyclic groups may further have substituents. The alkylamino group is preferably an alkylamino group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid alkylamino group include methylamiiio group, and diethylamino group. Examples ofthe arylamino group include substituted arylamino group and unsubstituted arylamino group. The aforesaid arylamino group is preferably an arylamino group having from 6 to 20 carbon atoms. Examples ofthe aforesaid substituents include halogen atoms, and ionic hydrophilic groups. Examples ofthe aforesaid arylamino group include anilino group, and 2-cUorophenylamino group. Examples ofthe heterocyclic amino group include substituted heterocyclic amino group and unsubstituted heterocyclic amino group. The aforesaid heterocyclic amino group is preferably a heterocyclic amino group having from 2 to 20 carbon atoms. Examples ofthe aforesaid substituents include alkyl groups, halogen atoms, and ionic hydrophilic groups. Examples ofthe acylamino group include substituted acylamino group and unsubstituted acylamino group. The aforesaid acylamino group is preferably an acylamino group having from 2 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid acylamino group include acetylamino group, propionylamino group, benzoylamino group, N-phenylacetylamino group, and 3,5-disulfobenzoylamino group. Examples ofthe ureido group include substituted and unsubstituted ureido groups. These ureido groups each preferably have from 1 to 20 carbon atoms. Examples ofthe substituents on the ureido group include alkyl groups, and aryl groups. Examples ofthe ureido group include 3-methylureide group, 3,3-dimethylureido group, and 3-phenylureido group. Examples ofthe sulfamoylamino group include substituted sulfamoylamino group and unsubstituted sulfamoylamino group. Examples ofthe aforesaid substituents include alkyl groups. Examples ofthe aforesaid sulfamoylamino group include N,N-dipropyIsulfamoylamino group. Examples of the alkoxycarbonylamino group include substituted alkoxycarbonylamino group and unsubstituted alkoxycarbonylamino group. The aforesaid alkoxy carbonylamino group is preferably an alkoxycarbonylamino group having from 2 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid alkoxycarbonylamino group include ethoxycarbonylamino groups. Examples ofthe aryloxycarbonylamino group include substituted aryloxycarbonylamino group and unsubstituted aryloxycarbonylamino group. The aforesaid aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having from 7 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid aryloxycarbonylamino group include phenoxycarbonyl amino groups. Examples ofthe aU-ylsulfonylamino group and arylsulfonylamino group include substituted alkylsulfonylamino groups and substituted arylsulfonylamino groups. The aforesaid sulfonyl amino group is preferably a sulfonylamino group having from 1 to 20 carbon atoms. Examples ofthe substituents include ionic hydrophilic groups. Examples ofthe aforesaid sulfonyl groups include methylsulfonylamino group, N-phenyl- methyl sulfonylamino group, phenyl sulfonyl amino group, and 3-carboxyphenylsulfonyl amino group. Examples ofthe heterocyclic sulfonyl group include substituted sulfonylamino group and unsubstituted sulfonylamino group. The aforesaid heterocyclic sulfonyl group is preferably a heterocyclic sulfonylamino group having from 1 to 12 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid heterocyclic sulfonyl group include 2-thiophenesulfonyl group, and 3- pyridylsulfonyl group. Examples ofthe heterocyclic sulfonyl group include substituted heterocyclic sulfonyl group and unsubstituted heterocyclic sulfonyl group. The aforesaid heterocyclic sulfonyl group is preferably a heterocyclic sulfonyl group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe heterocyclic sulfonyl group include 2-thiophene sulfonyl group and 3-pyridylsulfonyl group. Examples of the heterocyclic sulfinyl group include substituted heterocyclic sulfinyl group and unsubstituted heterocyclic sulfinyl group. The aforesaid heterocyclic sulfinyl group is preferably a heterocyclic sulfinyl group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe heterocyclic sulfinyl group include 4-pyridylsulfinyl group. Examples ofthe alkyl group, aryl group and heterocyclic thio group include substituted alkyl, aryl and heterocyclic thio groups and unsubstituted alkyl, aryl and heterocyclic thio groups. The alkyl, aryl and heterocyclic thio groups each preferably have from 1 to 20 carbon atoms. Examples ofthe substituents on the alkyl, aryl and heterocyclic thio groups include ionic hydrophilic groups. Examples ofthe alkyl, aryl and heterocyclic thio groups include metliylthio group, phenylthio group, and 2-pyridylthio group. Examples ofthe alkylsulfonyl and arylsulfonyl groups include substituted alkylsulfonyl and arylsulfonyl groups and unsubstituted alkylsulfonyl and arylsulfonyl groups. Examples ofthe alkylsulfonyl and arylsulfonyl groups include methylsulfonyl group and phenylsulfonyl group. Examples of the alkylsulfinyl and arylsulfinyl groups include substituted alkylsulfinyl and arylsulfinyl groups and unsubstituted alkylsulfinyl and arylsulfinyl groups. Examples of he alkylsulfinyl and arylsulfinyl groups include methylsulfinyl group and phenylsulfinyl group. Examples ofthe sulfamoyl group include substituted and unsubstituted sulfamoyl groups. Examples of the substituents on the sulfamoyl group include alkyl groups. Examples ofthe sulfamoyl group include dimethylsulfamoyl group, and di-(2-hydroxyethyl)sulfamoyl group. The general formulae (1-4), (4-A) and (4-B) will be further described hereinafter. Those described with reference to groups and substituents apply to the following description. In the general formula (1-4), A₄₁, B₄₁ and C ι each independently represent an aromatic group (A41 and C₄ι each are a monovalent aromatic group such as aryl group; B_4J is a divalent aromatic group such as arylene group) which may be substituted or a heterocyclic group (A ₁ and C₄₁ each are a monovalent heterocyclic group; B₄₁ is a divalent heterocyclic group) which may be substituted. Examples ofthe aromatic ring include benzene ring, and naphthalene ring. Examples ofthe hetero atoms in the heterocycle include nitrogen atom, oxygen atom, and sulfur atom. The heterocyclic group may have aliphatic rings,- aromatic rings or other heterocycles condensed thereto. The substituents may be arylazo groups or heterocyclic azo groups. Preferably, at least one of A^, B_4Ϊ and C₄₁ is a heterocyclic group. More preferably, at least two of A₄₁, B ι and C₄₁ are heterocyclic groups. All of A₄₁, B₄₁ and C₄₁ maybe heterocyclic groups. A preferred example ofthe heterocyclic group represented by C₄₁ is an aromatic group-containing 6- membered heterocyclic group represented by the following general formula (4-C). In the case where C₄₁ is an aromatic group-containing 6-membered heterocyclic group represented by the following general formula (4-C), the general formula (1-4) corresponds to the general formula (4-A). general formula (4-C):

In the general formula (4-C), B₄₂ and B₄₃ each represent

or one of B₄₂ and B₄₃ represents a nitrogen atom and the other represents =CRn- or -CR₄₂=. Preferably, B₄₂ and B₄₃ each represent

R₄5 and R₄6 each independently represent a hydrogen atom or an aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group which may further have substituents. Preferred examples ofthe substituents represented by R₄5 and 6 include hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, ah lsulfonyl group, and arylsulfonyl group. More desirable among these substituents are hydrogen atom, aromatic group, heterocyclic group, acyl group, alkylsulfonyl group, and arylsulfonyl group. Most desirable among these substituents are hydrogen atom, aryl group, and heterocyclic group. These substituents may further have substituents. However, R₄₅ and R ₆ are not a hydrogen atom at the same time. G₄, R₄₁ and ₄₂ each independently represent a hydrogen atom, a halogen atom or an aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group, arylamino group and heterocyclic amino group), acylamino group, ureido group, sulfamonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, al lthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfinyl group, arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group, and sulfo group which may be further substituted. Prefeπed among the substituents represented by G₄ are hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, amino group (including alkylamino group, arylamino group and heterocyclic amino group), acylamino group, ureido group, sulfamonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylthio group, arylthio group, and heterocyclic thio group. More desirable among these substituents are hydrogen atom, halogen atom, alkyl group, hydroxyl group, alkoxy group, aryloxy group, acyloxy group, amino group (including alkylamino group, arylamino group and heterocyclic amino group) and acylamino group. Most desirable among these substituents are hydrogen atom, anilino group, and acylamino group. These groups may further have substituents. Prefeπed examples ofthe substituents represented by R₄₁ and R₄₂ include hydrogen atom, alkyl group, halogen atom, alkoxycarbonyl group, carboxyl group, carbamoyl group, hydroxyl group, alkoxy group, and cyano group. These groups may further have substituents. R₄₁ and R₄₂ or R₄5 and R ₆ may be connected to each other to form a 5- or 6-membered ring. Examples ofthe substituents on the substituents represented by A ι, R₄₁, R₄₂, R₄5, R₄6 and G₄ include those listed with reference to G₄, ILπ, and R₄₂. A₄₁, 1^, R₄₂, R₄5, R₄₆ and G₄ preferably further have an ionic hydrophilic group in any position as substituent. Examples ofthe ionic hydrophilic group include sulfo group, carboxyl group, phosphono group, and quaternary ammonium group. Prefeπed among these ionic hydrophilic groups are carboxyl group, phosphono group, and sulfo group, and particularly prefeπed among these ionic hydrophilic groups are carboxyl group and sulfo group. The carboxyl group, phosphono group and sulfo group may be used in the form of salt. Examples ofthe counter ion forming the salt include ammonium ion, alkaline metal ion (e.g., lithium ion, sodium ion, potassium ion), and organic cation (e.g., tetramethyl ammonium ion, tetramethylguanidium ion, tetramethyl phosphonium ion). Prefeπed among tliese counter ions is lithium ion. Prefeπed examples of the heterocyclic structure represented by B₄ι include thiophene ring, thiazole ring, imidazole ring, benzothiazole ring, and thienothiazole ring. These heterocyclic groups may further have substituents. Prefeπed among these heterocyclic groups are thiophene ring, thiazole ring, imidazole ring, benzothiazole ring, and thienothiazole ring represented by the following general formulae (h) to (1). In the case where B₄ι is a thiophene ring represented by the general formula (h) and C ι has a structure represented by the general formula (4-C), the general formula (1-4) coπesponds to the general formula (4-B).

In the general formulae (h) to (1), R₄₀₉ to R₄₁7 have the same meaning as the substituents G₄, R41 and R42 in the general formula (4-A). Particularly prefeπed among the dye structures represented by the general formula (4-B) is one represented by the following general formula (4-D). general formula (4-D):

wherein Z₄ represents an electron-withdrawing group having a Hammett's substituent constant σp of 0.20 or more. Z is preferably an electron-withdrawing group having a Hammett's substituent constant σp of 0.30 or more, more preferably 0.45 or more, particularly 0.60 or more, but the Hammett's substituent constant σp ofthe electron-withdrawing group is preferably not greater than 1.0. Specific examples ofthe electron-witlidrawing group having a Hammett's substituent constant σp of 0.60 or more include cyano group, nitro group, alkylsulfonyl group (e.g., methylsulfonyl group), and arylsulfonyl group (e.g., phenylsulfonyl group). Examples ofthe electron-withdrawing group having a Hammett's substituent constant σp of 0.45 or more include acyl group (e.g., acetyl group), alkoxycarbonyl group (e.g., dodecyloxycarbonyl group), aryloxycarbonyl group (e.g., m-chlorophenoxycarbonyl), alkylsulfinyl group (e.g., n-propylsulfinyl), arylsulfinyl group (e.g., phenylsulfinyl), sulfamoyl group (e.g., N-etliylsulfamoyl, N,N-dimethylsulfamoyl), and halogenated alkyl group (e.g., trifhioromethyi) besides the aforesaid groups. Examples ofthe electron-withdrawing group having a Hammett's substituent constant σp of 0.30 or more include acyloxy group (e.g., acetoxy group), carbamoyl group (e.g., N-ethylcarbamoyl, N,N- dibutylcarbamoyl), halogenated alkoxy group (e.g., trifluoromethyloxy), halogenated aryloxy group (e.g., pentafluorophenyloxy), sulfonyloxy group (e.g., methylsulfonyloxy), halogenated alkylthio group (e.g., difluoromethylthio), aryl group substituted by two or more electron-withdrawing groups having σp of 0.15 or more (e.g., 2,4-dinitrophenyl, pentachlorophenyl), and heterocyclic group'(e.g., 2-benzooxazolyl, 2- benzothiazolyl, l-phenyl-2-benzoimidazolyl) besides the aforesaid groups. Specific examples ofthe electron-withdrawing group having σp of 0.20 or more include halogen atoms besides the aforesaid groups. Prefeπed among these groups are C₂-C₂o acyl group, C₂-C₂o alkyloxycarbonyl group, nitro group, cyano group, -C20 alkylsulfonyl group, C₆-C₂o arylsulfonyl group, C1-C20 carbamoyl group, and C₁-C₂0 halogenated alkyl group as Z₄. Particularly preferred among these groups are cyano group, -C₂₀ alkylsulfonyl group and C₆-C₂o arylsulfonyl group, most preferably cyano group. R₄₁, R₄₂, R₄₅ and R₄6 in the general formula (4-D) are as defined in the general formula (4-A). R₄3 and R₄₄ each independently represent a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group. Prefeπed among these groups are hydrogen atom, aromatic group, heterocyclic group, acyl group, alkylsulfonyl group, and arylsulfonyl group. Particularly prefeπed among these groups are hydrogen atom, aromatic group, and heterocyclic group. The groups described with reference to the general formula (4-D) may further have substituents. In the case where these groups further have substituents, examples of these substituents include the substituents described with reference to the general formula (4-A) and the groups and ionic hydrophilic groups exemplified with reference to G₄, R₄₁ and R42. Referring to a particularly prefeπed combination of azo dyes represented by the general formula (4-B), R₄₅ and R ₆ each are preferably a hydrogen atom, alkyl group, aryl group, heterocyclic group, sulfonyl group or acyl group, more preferably hydrogen atom, aryl group, heterocyclic group or sulfonyl group, most preferably hydrogen atom, aryl group or heterocyclic group. However, R₄5 and R₄₆ are not a hydrogen atom at the same time. G₄ is preferably a hydrogen atom, halogen atom, alkyl group, hydroxyl group, amino group or acylamino group, more preferably hydrogen atom, halogen atom, amino group or acylamino group, most preferably hydrogen atom, amino group or acylamino group. n is preferably a pyrazole ring, imidazole ring, isothiazole ring, thiadiazole ring or benzothiazole ring, more preferably pyrazole ring or isothiazole ring, most preferably pyrazole ring. B₄₂ and B₄₃ are =CR₄i- and -CR)₂=, respectively, in which R₄₁ and R₄₂ each are preferably a hydrogen atom, alkyl group, halogen atom, cyano group, carbamoyl group, carboxyl group, hydroxyl group, alkoxy group or alkoxycarbonyl group, more preferably hydrogen atom, alkyl group, carboxyl group, cyano group or carbamoyl group. Referring to a prefeπed combination of substituents on the aforementioned azo dye, at least one ofthe various substituents is preferably a compound which is a prefeπed group as mentioned above, and more preferably, more ofthe various substituents are compounds which are prefeπed groups as mentioned above, and most preferably, all the various substituents are compounds which are prefeπed groups as mentioned above. Specific examples ofthe azo dye represented by the general formula (1-4) will be given below, but the azo dye to be used in the present invention is not limited to the following examples. In the following specific examples, the carboxyl group, phosphono group and sulfo group may be used in the form of salt. Examples of the counter ion forming the salt include ammonium ion, alkaline metal ion (e.g., lithium ion, sodium ion, potassium ion), and organic cation (e.g., tetramethylammomum ion, tetramethylguanidium ion, tetramethylphosphonium ion). Prefeπed among these counter ions is lithium ion. A— =N— B — N=N— C B

A— N=N— B — N=N— C A B C

A— =N— B — =N— C A B

A— N=N— B — =N— C B

A— N=N— B — =N- A B C

A— N=N— B — N= =N- -C A B C

The azo dyes represented by the aforementioned general formulae (1-4), (4-A), (4-B) and (4-D) can be synthesized by the coupling reaction of diazo component with coupler. As a main synthesis method there may be used one disclosed in Japanese Patent Application No. 2002-113460. As a dyes (S) having λmax of from 350 nm to 500 nm there is preferably used a yellow dye or yellow pigment described below. The content ofthe azo dye represented by the general formula (1^4) in the ink is preferably from 0.2% to 20% by weight, more preferably from 0.5% to 15% by weight. In order to obtain a full-color image or adjust the color tone ofthe image, the ink ofthe invention may comprise other dyes in combination with the dyes ofthe present invention. Examples of these dyes which can be used in combination with the dyes ofthe present invention include the following dyes. Examples of yellow dyes include aryl or heterylazo dyes having phenols, naphthols, anilines, pyrazolones, pyridones or closed-chain type active methylene compounds as coupling components, azomethine dyes having closed-chain type active methylene compounds as coupling components, methine dyes such as benzylidene dyes and monomethine oxonol dyes, and quinone-based dyes such as naphthoquinone dye and anthraquinone dye. Other examples of yellow dyes include quinophthalone dye, nitro-nitroso dye, acridine dye, and acridinone dye. These dyes may assumes yellow only when chromophore is partly dissociated, and, in this case, the counter cation may be an inorganic cation such as alkaline metal ion and ammonium ion or an organic cation such as pyridinium ion and quaternary ammonium salt ion or may be contained in a polymer cation as a partial structure. Examples of magenta dyes include aryl or heterylazo dyes having phenols, naphthols or anilines as coupling components, azomethine dyes having pyrazolones or pyrazolotriazoles as coupling components, methine dyestuffs such as arylidene dye, styryl dye, melocyanine dye and oxonol dye, carbonium dye such as diphenylmethane dye, triphenylmethane dye and xanthene dye, quinone-based dye such as naphthoquinone, anthraquinone and anthrapyridone, and condensed polycyclic dye such as dioxazine dye. These dyes may assume magenta only when chromophore is partly dissociated, and, in this case, the counter cation may be an inorganic cation such as alkaline metal ion and ammonium ion or an organic cation such as pyridinium ion and quaternary ammonium salt ion or may be contained in a polymer cation as a partial structure. Examples of cyan dyes include azomethine dyes such as indoaniline dye and indophenol dye, polymethine dyes such as cyanine dye, oxonol dye and melocyanine dye, carbonium dyes such as diphenylmethane dye, triphenylmethane dye and xanthene dye, phthalocyanine dyes, anthraquinone dyes, aryl or heterylazo dyes having phenols, naphthols or anilines as coupling components, and indigo-thioindigo dyes. These dyes may assume cyan only when chromophore is partly dissociated, and, in this case, the counter cation may be an inorganic cation such as alkaline metal ion and ammonium ion or an organic cation such as pyridinium ion and quaternary ammonium salt ion or may be contained in a polymer cation as a partial structure. Alternatively, a black dyestuff such as polyazo dye may be used. Other examples of dyes employable herein include water-soluble dyes such as direct dye, acidic dye, food dye, basic dye and reactive dye. Prefeπed examples of these water-soluble dyes include: C.I. Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 21, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247; C.I. Direct Violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101; CL Direct Yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 86, 87, 93, 96, 98, 100, 106, 108, 109, 110, 130, 132, 142, 144, 161, 163;

CL Direct Blue 1, 10, 15, 22, 25, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108, 109, 151, 156, 158,

159, 160, 168, 189, 192, 193, 194, 199, 200, 201, 202, 203, 207, 211, 213, 214, 218, 225, 229, 236, 237, 244,

248, 249, 251, 252, 264, 270, 280, 288, 289, 291;

CL Direct Black 9, 17, 19, 22, 32, 51, 56, 62, 69, 77, 80, 91, 94, 97, 108, 112, 113, 114, 117, 118, 121, 122,

125, 132, 146, 154, 166, 168, 173, 199;

C.I. Acid Red 35, 42, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 151, 154, 158, 249, 254, 257,

261, 263, 266, 289, 299, 301, 305, 336, 337, 361, 396, 397;

C Acid Violet 5, 34, 43, 47, 48, 90, 103, 126;

C.I. Acid yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174,

190, 195, 196, 197, 199, 218, 219, 222, 227;

C.I. Acid Blue 9, 25, 40, 41, 62, 72, 76, 78, 80, 82, 92, 106, 112, 113, 120, 127 : 1, 129, 138, 143, 175, 181,

205, 207, 220, 221, 230, 232, 247, 258, 260, 264, 271, 277, 278, 279, 280, 288, 290, 326;

CL Acid Black 7, 24, 48, 52 : 1, 172;

CL Reactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55;

CL Reactive Violet 1, 3, 4, 5, 6, 7, 8, 9, 16,^' 17, 22, 23, 24, 26, 27, 33, 34;

C.I. Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42;

CL Reactive Blue 2, 3, 5, 8, 10, 13, 14, 15, 17, 18, 19, 21, 25, 26, 27, 28, 29, 38;

C.I. Reactive Black 4, 5, 8, 14, 21, 23, 26, 31, 32, 34;

CL Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46;

CL Basic Violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48;

CL Basic Yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40;

CL Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 45, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71;

CL Basic Black 8, etc. Further, the ink composition ofthe invention may comprise pigments incorporated therein as well. As the pigments to be used in the present invention there may be used commercially available products as well as known compounds listed in various literatures. Examples of these literatures include Color Index (compiled by The Society of Dyers and Colourists), "Kaitei Shiriban Ganryo Binran (Revised Edition of Handbook of Pigments)", compiled by Japan Association of Pigment Technology, 1989, "Saishin Ganryo Ouyou Gijutsu (Modern Applied Technology of Pigments)", CMC, 1986, "Insatsu Inki Gijutsu (Printing Ink Technology)", CMC, 1984, and W. Herbst, K. Hunger, "Industrial Organic Pigments", VCH Verlagsgesellschaft, 1993. Specific examples of these pigments include organic pigments such as azo pigment (e.g., azo lake pigment, insoluble azo pigment, condensed azo pigment, chelate azo pigment), polycyclic pigment (e.g., phthalocyanine pigment, anthraquinone-based pigment, peiylene-based pigment, perynone-based pigment, indigo-based pigment, quinacridone-based pigment, dioxazine-based pigment, isoindolinone-based pigment, quinophthalone-based pigment, diketopypyπolopyπole-based pigment), dyed lake pigment (e.g., acidic or basic dye lake pigment) and azine pigment, and inorganic pigments such as yellow pigment (e.g., C.I. Pigment Yellow 34, 37, 42, 53), red pigment (e.g., C.I. Pigment Red 101, 108), blue pigment (e.g., C.I. Pigment blue 27, 29, 17 : 1), black pigment (e.g., C.I. Pigment Black 7, magnetite) and white pigment (e.g., CL Pigment White 4, 6, 18, 21). As a pigment having a color tone suitable for image formation there is preferably used a blue or cyan pigment such as phthalocyanine pigment, anthraquinone-based mdanthrone pigment (e.g., CL Pigment Blue 60) and dyed lake pigment-based triarylcarbonium pigment, particularly phthalocyanine pigment (Prefeπed examples ofthe phthalocyanine pigment include copper phthalocyanine such as CL Pigment Blue 15: 1, 15:2, 15:3, 15:4 and 15:6, monochlorophthalocyanine, low cl orination copper phthalocyanine, aluminum phthalocyanine such as pigment listed in European Patent 860475, metal-free phthalocyanine such as CL Pigment Blue 16, and phthalocyanine having Zn, Ni or Ti as a central metal. Particularly prefeπed among these phthalocyanine dyes are CL Pigment Blue 15:3, 15:4, and aluminum phthalocyanine). Prefeπed examples of red or purple pigments include azo pigments (Prefeπed examples of these dyes include CL Pigment Red 3, 5, 11, 22, 38, 48:1, 48:2, 48:3, 48:4, 49:1, 52:1, 53:1, 57:1, 63:2, 144, 146, 184. Particularly prefeπed among these dyes are CL Pigment Red 57: 1, 146, 184), quinacridone-based pigments (Prefeπed examples of these dyes include CL Pigment Red 122, 192, 202, 207, 209, and CL Pigment Violet 19, 42. Particularly prefeπed among these dyes is C.I. Pigment Red 122), dyed lake-based triarylcarbonium pigments (Prefeπed examples of these dyes include xanfhene-based CL Pigment Red 81:1, CL Pigment Violet 1, 2, 3, 27, 39), dioxazine-based pigments (e.g., CL Pigment Violet 23, 37), diketopyrrolopyπole-based pigments (e.g., CL Pigment Red 254), perylene pigments (e.g., CL Pigment Violet 29), anthraquinone-based pigments (e.g., CL Pigment Violet 5:1, 31, 33), and thioindigo-based pigments (e.g., CL Pigment Red 38, 88). Prefeπed examples of yellow pigments include azo pigments (Prefeπed examples of these dyes include monoazo pigment-based dyes such as CL Pigment Yellow 1, 3, 74, 98, disazo pigment-based dyes such as CL Pigment Yellow 12, 13, 14, 16, 17, 83, general azo-based dyes such as C.I. Pigment Yellow 93, 94, 95, 128, 155 and benzimidazolone-based dyes such as CL Pigment Yellow 120, 151, 154, 156, 180. Particularly prefeπed among these dyes are those prepared from materials other than benzidine-based compounds), isoindoline- isoindolinone-based pigments (Prefeπed examples of these dyes include CL Pigment Yellow 109, 110, 137, 139), quinophthalone pigments (Prefeπed examples of these dyes include C.I. Pigment Yellow 138), and flavanthrone pigment (e.g., CL Pigment Yellow 24). Prefeπed examples of black pigments include inorganic pigments (Prefeπed examples of these pigments include carbon black, and magnetite), and aniline black. Besides these pigments, orange pigments(C.I. Pigment Orange 13, 16), and green pigments (CL Pigment Green 7) may be used. The pigments which may be used in the present technique may be untreated pigments as mentioned above or may be surface-treated pigments. As surface treatment methods there may be proposed a method involving surface coat with a resin or wax, a method involving the attachment of a surface activator, a method involving the bonding of a reactive material (e.g., silane coupling agent, radical produced from an epoxy compound, polyisocyanate or diazonium salt) to the surface of pigment, etc., and these methods are described in the following literatures and patents. (1) Kinzoku Sekken no Seishitsu to Ouyou (Properties and Application of Metal Soap) (Saiwai Shobo) (2) Insatsu Inki Insatsu (Printing with Printing Ink) (CMC Shuppan, 1984) (3) Saishin Ganryo Ouyou Gijutsu (Modern Applied Technology of Pigments (CMC, 1986) (4) US Patents 5,554,739, 5,571,311 (5) JP-A-9-151342, JP-A-10-140065, JP-A-10-292143, JP-A-11-166145 In particular, self-dispersible pigments prepared by reacting the diazonium salt disclosed in the US patents (4) with carbon black and capsulized pigments prepared according to the metliod disclosed in the Japanese patents (5) are useful to obtain dispersion stability without using extra dispersant in the ink. In the ink of the invention, the pigment may be further dispersed with a dispersant. As such a dispersant there may be used any of known compounds depending on the pigment used, e.g., surface active agent type low molecular dispersant or polymer type dispersant. Examples of these dispersants include those disclosed in JP-A-3 -69949 and European Patent 549,486. In order to accelerate the adsorption ofthe pigment to the dispersant used, a pigment derivative called synergist may be added. The particle diameter ofthe pigment which may be used in the present invention is preferably from 0.01 μm to 10 μm, more preferably from 0.05 μm to 1 μm. As a method for dispersing the pigment there may be used a known dispersion technique for use in the production of ink or toner. Examples ofthe dispersing machine include vertical or horizontal agitator mill, attritor, colloid mill, ball mill, three-roll mill, pearl mill, super mill, impeller, disperser, KD mill, dynatron, and pressure kneader. The details of these dispersing machines are described in "Saishin Ganryo Ouyou Gijutsu (Modern Applied Technology of Pigments)", CMC, 1986. The surface active agent to be incorporated in a recording ink (preferably, an ink for inkjet recording) composition ofthe present invention will be described hereinafter. By adding the surface active agent to the recording ink (preferably, an ink for inkjet recording) composition and adjusting the physical properties such as surface tension ofthe ink, the ejection stability ofthe ink can be enhanced, exerting an excellent effect of enhancing the water resistance of image and preventing bleeding of ink printed. Examples ofthe aforementioned surface active agents include anionic surface active agents such as sodium dodecylsulfate, sodium dodecyloxysulfonate and sodium alkylbenzenesulfonate, cationic surface active agents such as cetyl pyridinium chloride, trimethylcetyl ammonium chloride and tetrabutylammonium chloride, and nonionic surface active agents such as polyoxyethylenenonly phenyl ether, polyoxyethylene naphthyl ether and polyoxyethyleneoctylphenyl ether. Prefeπed among tliese surface active agents are nonionic surface active agents. The content of he surface active agent is from 0.001 to 20% by weight, preferably from 0.005 to 10% by weight, more preferably from 0.01 to 5% by weight based on the weight ofthe ink.

[Second Embodiment] The second embodiment ofthe invention will be further described hereinafter. According to the second embodiment ofthe invention, there is provided a recording method comprising ejecting ink drops by using at least two color inks of yellow and magenta each comprising a dye onto a recording material, the recording material comprising a support and an ink-receptive layer provided on the support, according to a recording signal, so as to record an image on the recording material, wherein the percent bleeding ofthe recorded image is 30% or less. The yellow dye will be first described. [Yellow dye] The yellow dye to be used in the invention preferably has an oxidation potential of more positive than 1.0 V (vs SCE), more preferably more positive than 1.1 V (vs SCE), particularly more positive than 1.15 V (vs SCE) from the standpoint of fastness, particularly to ozone gas. As such a yellow dye, an azo dye satisfying the aforementioned requirements is particularly preferred. The oxidation potential (Eox) can be easily measured by those skilled in the art. For the details of the method for measuring the oxidation potential, reference can be made to P. Delahay, "New Instrumental Methods in Electrochemistry", 1954, Interscience Publishers, A. J. Bard et al, "Electrochemical Methods", 1980, John Wiley & Sons, and Akiya Fujishima, "Deriki Kagaku Sokuteiho (Electrochemical Measuring Methods)", 1984, Gihodo Shuppansha. In some detail, the measurement of oxidation potential is carried Out by dissolving the test specimen in a solvent such as dimethylformamide and acetonitrile containing a supporting electrolyte such as sodium perchlorate and tetrapropylammonium perchlorate in a concentration of from 1 x 10^"4 to 1 x 10^"6 mol/1, and then measuring the test solution for oxidation potential with respect to SCE (saturated calomel electrode) using cyclic voltammetry or DC polarography. This value may deviate by scores of millivolts due to the effect of difference in potential between solutions or resistivity of test solution. However, the incorporation of a standard specimen (e.g., hydroquinone) makes it possible to assure the reproducibility of potential. In order to unequivocally define potential, the potential (vs SCE) measured in dimethylformamide containing 0.1 mol dm^"3 of tetrapropylammonium perchlorate as a supporting electrolyte (concentration of dye: 0.001 mol dm³) using DC polarography is defined as oxidation potential of dye. The value of oxidation potential Eox indicates the transferability of electrons from the specimen to the electrode. The greater this value is (the more positive the oxidation potential is), the more difficultly can be transfeπed electrons from the specimen to the electrode, i.e., the more difficultly can be oxidized the specimen. With regard to the structure ofthe compound, the incorporation of electron-withdrawing group causes the oxidation potential to be more positive while the incorporation of electron-donative group causes the oxidation potential to be more negative. In the invention, in order to reduce the reactivity with ozone, which is an electrophilic agent, it is prefeπed that an electron-withdrawing group be introduced into the skeleton of yellow dye to make the oxidation potential thereof more positive. The dye to be used in the invention preferably exhibits a good fastness as well as a good hue. It is particularly prefeπed that the dye ofthe invention show a sharp absorption spectrum on the longer wavelength side thereof. Therefore, the yellow dye to be used in the invention preferably exhibits λmax of from 390 nm to 470 nm and I(λmax + 70 nm)/I(λmax) ratio (ratio of absorbance at λmax + 70 nm (I(λmax + 70 nm)) to absorbance at λmax (I(λmax)) of 0.20 or less, more preferably 0.15 or less, ven more preferably 0.10 or less. The absorption wavelength and absorbance defined herein indicate value measured in a solvent (water or ethyl acetate). As a dye satisfying these oxidation potential and absorption characteristics there is preferably used one represented by the following general formula (2-2). (A_u-N=N-B„)_n-L ... (2-2) wherein An and Bn each independently represent a heterocyclic group which may be substituted; n represents an integer 1 or 2; and L represents a hydrogen atom, mere bond or divalent connecting group, with the proviso that when n is 1, L represents a hydrogen atom and both A_u and B are a monovalent heterocyclic group and when n is 2, L represents a mere bond or divalent connecting group, one of A_π and Bn is a monovalent heterocyclic group and the other is a divalent connecting group, and two n's and Bn's each may be the same or different. The heterocyclic group is preferably a heterocyclic group formed by a 5-membered or 6-membered ring. The heterocyclic group may have a monocyclic structure or a polycyclic structure formed by the condensation of two or more rings or may be an aromatic heterocyclic group or non-aromatic heterocyclic group. As hetero atoms constituting the aforementioned heterocyclic group there are preferably used nitrogen, oxygen and sulfur atoms. The suffix n is more preferably 2. When L is a hydrogen atom, L can be connected to A_π or B_n at arbitrary position. When L is a mere bond or divalent connecting group, L may be connected to Aj ι or Bn at arbitrary position but is preferably connected to the carbon atom or hetero atoms (preferably nitrogen atom) constituting the ring ofthe heterocyclic groups An andBn. Specific examples of An, Bn and L, the prefeπed embodiments and examples ofthe general formula (2-2) are same as those explained in the general formula (1-1) in the first embodiment. Specific examples ofthe yellow dye to be used in the invention will be given below. The magenta ink to be incorporated in the recording ink ofthe invention (preferably ink for inkjet recording) comprises a magenta dye selected from azo dyes dissolved or dispersed in an aqueous medium. The magenta dye to be used herein is basically characterized in that it is a dye having a maximal absorption at a wavelength of from 500 nm to 580 nm in the aqueous medium and an oxidation potential of more positive than 1.0 V (vs SCE). The first structural characteristic of prefeπed dye of this azo dye is that it is a dye having a chromophore represented by the general formula (heterocyclic ring A)-N=N-(heterocyclic ring B). In this case, the heterocyclic ring A and the heterocyclic ring B in the aforementioned general formula may have the same structure. The heterocyclic ring A and heterocyclic ring B each are in detail a 5- or 6-membered heterocyclic ring which is selected from pyrazole, imidazole, triazole, oxazole, thiazole, selenazole, pyridone, pyrazine, pyrimidine and pyridine. In some detail, they are described in JP-A-2001-279145, JP-A-2002-309116, JP-A- 2003-12650, etc. Further, the second prefeπed structural characteristic ofthe aforesaid azo dye is that the azo group is an azo dye having an aromatic mtrogen-containing 6-membered heterocyclic ring directly connected to at least one end thereof as a coupling component, and specific examples of such an azo dye are described in JP-A-2002- 371214. The third prefeπed structural characteristic is that the chromophore has an aromatic cyclic amino group or heterocyclic amino group structure, and specific examples ofthe chromophore include anilino group, and heterylamino group. The fourth prefeπed structural characteristic is that the azo dye has a stereostructure. This is described in detail in JP-A-2002-371214. Among the aforementioned prefeπed structural characteristics of azo dye, the dye represented by the aforementioned general formula (MI) is most desirable for the purpose of accomplishing the aim ofthe invention. The dye ofthe general formula (MI) will be further described hereinafter. In the general formula (MI, A³¹ represents a 5-membered heterocyclic ring. Examples of hetero atoms in the heterocyclic ring include N, O and S. The 5-membered heterocyclic ring is preferably a nitrogen- containing 5-membered heterocyclic ring which may be condensed with aliphatic rings, aromatic rings or other heterocyclic rings. Preferred examples ofthe heterocyclic group include pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazole ring, benzothiazole ring, benzooxazole ring, and benzoisothiazole ring. The various heterocyclic groups may further have substituents. Prefeπed among these heterocyclic rings are pyrazole ring, imidazole ring, isothiazole ring, thiadiazole ring and benzothiazole ring represented by the following general formulae (a) tc ⁾ (f⁾: (a) (b)

(l)

In the aforesaid general formulae (a) to (g), R⁷ to R²² represent the same substituents as G, R¹ and R² in the general formula (MI). Prefeπed among the compounds ofthe general formulae (a) to (g) are pyrazole ring represented by the general formula (a) and isothiazole ring represented by the general formula (b), most preferably pyrazole ring represented by the general formula (a). In the general formula (MI), B³¹ and B³² each represent =CR^:- or -CR²= or one of B³¹ and B³² represents a nitrogen atom while the other represents =CR¹- or -CR²=, but B³¹ and B³² preferably each represent =CR}- or -CR²=. R⁵ and R⁶ each independently represent a hydrogen atom or substituent. The substituent represents an aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group. The hydrogen atom of these substituents may be substituted. Prefeπed examples of R⁵ and R⁶ may include hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkylsulfonyl group, and arylsulfonyl group. More preferably, R⁵ and R⁶ each are a hydrogen atom, aromatic group, heterocyclic group, acyl group, alkylsulfonyl group or arylsulfonyl group. Most preferably, R⁵ and R⁶ each are a hydrogen atom, aryl group or heterocyclic group. The hydrogen atom of the aforementioned various substituents may be substituted. However, R⁵ and R⁶ are not a hydrogen atom at the same time. G³¹, R¹ and R² each independently represent a hydrogen atom or substituent. The substituent represents a halogen atom or an aliphatic group, aromatic group, heterocyclic group,' cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxy carbonyloxy group, amino group (including alkylamino group, arylamino group and heterocyclic amino group), acylamino group, ureido group, sulfamonylamino group, alkoxycarbonyl amino group, aryloxycarbonylamino group, alkyl sulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfinyl group, arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group or sulfo group. The hydrogen atom of these substituents may be further substituted. G³¹ is preferably a hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, amino group (including alkylamino group, arylamino group, and heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylthio group, arylthio group or heterocyclic thio group, more preferably a hydrogen atom, halogen atom, alkyl group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, amino group or acylamino group, most preferably a hydrogen atom, amino group (preferably anilino group) or acylamino group. The hydrogen atom ofthe aforesaid substituents may be substituted. Prefeπed examples of R¹ and R² include hydrogen atom, alkyl group, halogen atom, alkoxycarbonyl group, carboxyl group, carbamoyl group, hydroxy group, alkoxy group, and cyano group. The hydrogen atom ofthe aforesaid substituents may be substituted. R¹ and R⁵ or R⁵ and R^s may be connected to each other to form a 5- or 6-membered ring. Examples ofthe substituents which may substitute on A³¹ or which may substitute on the substituents of R¹, R², R⁵, R⁶ or G include those listed above with reference to G³¹, R¹ and R². In the case where the dye represented by the general formula (MI) is a water-soluble dye, an ionic hydrophilic group is further provided on any position on A³¹, R¹, R², R⁵, R⁶ and G³¹ as a substituent. Examples ofthe ionic hydrophilic group as a substituent include sulfo group, carboxyl group, phosphono group, quaternary ammonium group, etc. The aforesaid ionic hydrophilic group is preferably a carboxyl group, phosphono group or sulfo group, particularly carboxyl group or sulfo group. The carboxyl group, phosphono group and sulfo group may be in the form of salt. Examples of counter ions constituting the salt include ammonium ion, alkaline metal ion (e.g., lithium ion, sodium ion, potassium ion), and organic cation (e.g., tetramethylammonium ion, tetrametliylguanidium ion, tetramethyl phosphonium). The terms (substituent) as used herein will be described. These terms are common to the general formula (MI) and the general formula (Mia) described later even the signs are different. Examples ofthe halogen atom include fluorine atom, chlorine atom, and bromine atom. The aliphatic group means alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkinyl group, substituted alkinyl group, aralkyl group and substituted aralkyl group. In the present specification, the term "substituted" as used in "substituted alkyl group", etc. means that the hydrogen atom in "alkyl group", etc. is substituted by substituents listed above with reference to G³¹, R¹ and R², etc. The aliphatic group may have branches or may form a ring. The number of carbon atoms in the aliphatic group is preferably from 1 to 20, more preferably from 1 to 16. The aryl moiety ofthe aralkyl group or substituted aralkyl group is preferably a phenyl group or naphthyl group, particularly phenyl group. Examples ofthe aliphatic group include methyl group, ethyl group, butyl group, isopropyl group, t-butyl group, hydroxyethyl group, methoxyethyl group, cyanoethyl group, trifluoromethyl group, 3-sulfopropyl group, 4- sulfobutyl group, cyclohexyl group, benzyl group, 2-phenethyl group, vinyl group, and allyl group. The aromatic group means an aryl group or substituted aryl group. The aryl group is preferably a phenyl group or naphthyl group, particularly phenyl group. The number of carbon atoms in the aromatic group is preferably from 6 to 20, more preferably from 6 to 16. Examples ofthe aromatic group include phenyl group, p-tollyl group, p-methoxyphenyl group, o- chlorophenyl group, and m-(3-sulfopropylamino)phenyl group. Examples ofthe heterocyclic group include substituted heterocyclic groups. The heterocyclic group may have its heterocyclic ring condensed with aliphatic rings, aromatic rings or other heterocyclic rings. The aforesaid heterocyclic group is preferably a 5- or 6-membered heterocyclic ring. Examples ofthe aforesaid substituents include aliphatic group, halogen atom, alkylsulfonyl group, arylsulfonyl group, acyl group, acylamino group, sulfamoyl group, carbamoyl group, ionic hydrophilic group, etc. Examples ofthe aforesaid heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2- benzooxazolyl group, and 2-furyl group. Examples ofthe carbamoyl group include substituted carbamoyl groups. Examples ofthe aforesaid substituents include alkyl group. Examples ofthe aforesaid carbamoyl group include methylcarbamoyl group, and dimethylcarbamoyl group. Examples ofthe alkoxycarbonyl group include substituted alkoxycarbonyl groups. The aforesaid alkoxycarbonyl group is preferably an alkoxycarbonyl group having from 2 to 20 carbon atoms. Examples of the aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid alkoxycarbonyl group include methoxycarbonyl group, and ethoxycarbonyl group. Examples ofthe aryloxycarbonyl group include substituted aryloxycarbonyl groups. The aforesaid aryloxycarbonyl group is preferably an aryloxycarbonyl group having from 7 to 20 carbon atoms. Examples of the aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid aryloxycarbonyl group include phenoxycarbonyl group. Examples ofthe heterocyclic oxycarbonyl group include substituted heterocyclic oxycarbonyl groups. Examples ofthe heterocyclic ring include those listed above with reference to the heterocyclic group. The aforesaid heterocyclic oxycarbonyl group is preferably a heterocyclic oxycarbonyl group having from 2 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid heterocyclic oxycarbonyl group include 2-pyridyloxycarbonyl group. Examples ofthe acyl group include substituted acyl groups. The aforesaid acyl group is preferably an acyl group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid acyl group include acetyl group and benzoyl group. Examples ofthe alkoxy group include substituted alkoxy groups. Examples ofthe aforesaid alkoxy group is preferably an alkoxy group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include alkoxy groups, hydroxyl groups, and ionic hydrophilic groups. Examples ofthe aforesaid alkoxy group include methoxy group, ethoxy group, isopropoxy group, methoxyethoxy group, hydroxyethoxy group, and 3- carboxypropoxy group. Examples ofthe aryloxy group include substituted aryloxy groups. The aforesaid aryloxy group is preferably an aryloxy group having from 6 to 20 carbon atoms. Examples ofthe aforesaid substituents include alkoxy groups, and ionic hydrophilic groups. Examples ofthe aforesaid aryloxy group include phenoxy group, p-methoxyphenoxy group, and o-methoxyphenoxy group. Examples ofthe heterocyclic oxy group include substituted heterocyclic oxy groups. Examples ofthe heterocyclic ring include those listed above with reference to the heterocyclic group. The aforesaid heterocyclic oxy group is preferably a heterocyclic oxy group having from 2 to 20 carbon atoms. Examples ofthe aforesaid substituents include alkyl groups, alkoxy group, and ionic hydroplύlic groups. Examples ofthe aforesaid heterocyclic oxy group include 3-pyridyloxy group, and 3-thienyloxy group. The silyloxy group is preferably a silyloxy group substituted by an aliphatic or aromatic group having from 1 to 20 carbon atoms. Examples ofthe aforesaid silyloxy group include trimethylsilyloxy, and diphenylmethyl silyloxy. Examples ofthe acyloxy group include substituted acyloxy groups. The aforesaid acyloxy group is preferably an acyloxy group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid acyloxy group include acetoxy group, and benzoyloxy group. Examples ofthe carbamoyloxy group include substituted carbamoyloxy groups. Examples ofthe aforesaid substituents include alkyl groups. Examples ofthe aforesaid carbamoyloxy group include N- methylcarbamoyloxy group. Examples of the alkoxycarbonyloxy group include substituted alkoxycarbonyloxy groups. The aforesaid alkoxycarbonyloxy group is preferably an alkoxycarbonyl oxy group having from 2 to 20 carbon atoms. Examples ofthe aforesaid alkoxycarbonyloxy group include methoxy carbonyloxy group, and isopropoxycarbonyloxy group. Examples of the aryloxycarbonyloxy group include substituted aryloxycarbonyloxy groups. The aforesaid aryloxycarbonyloxy group is preferably an aryloxy carbonyloxy group having from 7 to 20 carbon atoms. Examples ofthe aforesaid aryloxycarbonyloxy group include phenoxycarbonyloxy group. Examples ofthe amino group include substituted amino groups. Examples ofthe aforesaid substituents include alkyl groups, aryl groups, and heterocylic groups, and the alkyl groups, aryl groups and heterocyclic groups may further have substituents. Examples ofthe alkylamino group include substituted alkylamino groups. The alkylamino group is preferably an alkylamino group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid alkylamino group include methylamino group, and diethylamino group. Examples ofthe arylamino group include substituted arylamino groups. The aforesaid arylamino group is preferably an arylamino group having from 6 to 20 carbon atoms. Examples ofthe aforesaid substituents include halogen atoms, and ionic hydrophilic groups. Examples ofthe aforesaid arylamino group include phenylamino group, and 2-chlorophenylamino group. Examples ofthe heterocyclic amino group include substituted heterocyclic amino groups. Examples of the heterocyclic ring include those listed above with reference to the heterocyclic group. The aforesaid heterocyclic amino group is preferably a heterocyclic amino group having from 2 to 20 carbon atoms. Examples ofthe aforesaid substituents include alkyl groups, halogen atoms, and ionic hydrophilic groups. Examples ofthe acylamino group include substituted acrylamino groups. The aforesaid acylamino group is preferably an acylamino group having from 2 to 20 carbon atoms. Examples of the aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid acylamino group include acetylamino group, propionylamino group, beiizoylamϊno group, N-phenyl acetylamino group, and 3,5-disulfobenzoylamino group. Examples ofthe ureido group include substituted ureido groups. The aforesaid ureido group is preferably an ureido group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include alkyl groups, and aryl groups. Examples ofthe aforesaid ureido group include 3-methylureido group, 3,3- dimethyl ureido group, and 3-phenylureido group. Examples ofthe sulfamoylamino group include substituted sulfamoylamino groups. Examples ofthe aforesaid substituents include alkyl groups. Examples ofthe aforesaid sulfamoylamino group include N,N- dipropylsulfamoylamino group. Examples ofthe alkoxycarbonylamino group include substituted alkoxycarbonylamino groups. The aforesaid alkoxycarbonylamino group is preferably an alkoxy carbonylamino group having from 2 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid alkoxycarbonylamino group include ethoxycarbonylamino groups. Examples ofthe aryloxycarbonylamino group include substituted aryloxycarbonylamino groups. The aforesaid aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having from 7 to 20 carbon atoms. Examples of he aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid aryloxycarbonylamino group include phenoxycarbonyl amino groups. Examples ofthe alkylsulfonylamino group and arylsulfonylamino group include substituted alkyl sulfonylamino groups and substituted arylsulfonylamino groups. The aforesaid altylsulfonylamino group and arylsulfonylamino group are preferably an alkylsulfonyl amino group having from 1 to 20 atoms and arylsulfonylamino group having from 7 to 20 carbon atoms. Examples ofthe substituents include ionic hydrophilic groups. Examples ofthe aforesaid alkylsulfonylamino group and arylsulfonyl amino group include methylsulfonylamino group, N-phenyl-methyl sulfonylamino group, phenylsulfonyl amino group, and 3- carboxyphenylsulfonyl amino group. Examples ofthe heterocyclic sulfonylamino group include substituted sulfonylamino groups. Examples ofthe heterocyclic ring include those listed above with reference to the heterocyclic group. The aforesaid heterocyclic sulfonylamino group is preferably a heterocyclic sulfonylamino group having from 1 to 12 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid heterocyclic sulfonylamino group include 2-tlύenylsulfonylamino group, and 3-pyridylsulfonyl amino group. Examples ofthe alkylthio group, arylthio group and heterocyclic thio group include substituted alkylthio group, substituted arylthio group, and substituted heterocyclic thio group. Examples ofthe heterocyclic ring include those listed above with reference to the heterocyclic group. The aforesaid alkylthio group, arylthio group and heterocyclic thio group each preferably have from 1 to 20 carbon atoms. Examples of the aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid alkylthio group, arylthio group and heterocyclic thio group include methylthio group, phenylthio group, and 2-pyridylthio group. Examples ofthe alkylsulfonyl group and aryl sulfonyl group include substituted alkylsulfonyl groups and substituted arylsulfonyl groups. Examples ofthe alkylsulfonyl group and arylsulfonyl group include methylsulfonyl group and phenylsulfonyl group, respectively. Examples ofthe heterocyclic sulfonyl group include substituted heterocyclic sulfonyl groups. Examples ofthe heterocyclic ring include those listed above with reference to the heterocyclic group. The aforesaid heterocyclic sulfonyl group is preferably a heterocyclic sulfonyl group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe aforesaid heterocyclic sulfonyl group include 2-thienylsulfonyl group and 3-pyridylsulfonyl group. Examples ofthe alkylsulfinyl group and arylsulfinyl group include substituted alkylsulfinyl groups and substituted arylsulfinyl groups. Examples ofthe alkylsulfinyl group and arylsulfinyl group include methylsulfinyl group and phenylsulfinyl group, respectively. Examples ofthe heterocyclic sulfinyl group include substituted heterocyclic sulfinyl groups. Examples ofthe heterocyclic ring include those listed above with reference to the heterocyclic group. The aforesaid heterocyclic sulfinyl group is preferably a heterocyclic sulfinyl group having from 1 to 20 carbon atoms. Examples ofthe aforesaid substituents include ionic hydrophilic groups. Examples ofthe heterocyclic sulfinyl group include 4-pyridylsulfinyl group. Examples ofthe sulfamoyl group include substituted sulfamoyl groups. Examples ofthe aforesaid substituents include alkyl groups. Examples ofthe aforesaid sulfamoyl group include dimethylsulfamoyl group, and di-(2-hydroxyethyl)sulfamoyl group. Particularly prefeπed among the structures ofthe general formula (MI) is one represented by the following general formula (Mia), general formula (Mia):

wherein R¹, R², R⁵ and R⁶ are as defined in the general formula (Ml). R³ and R⁴ each independently represent a hydrogen atom or a substituent which represents an aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group. Preferred among these substituents is hydrogen atom, aromatic group, heterocyclic group, acyl group, alkylsulfonyl group or arylsulfonyl group, particularly hydrogen atom, aromatic group and heterocyclic group- Z¹ represents an electron-withdrawing group having a Hammett's substituent constant σp of 0.20 or more. Z¹ is preferably an electron-withdrawing group having a Hammett's substituent constant σp of 0.30 or more, more preferably 0.45 or more, particularly 0.60 or more, but the Hammett's substituent constant σp ofthe electron-withdrawing group is preferably not greater than 1.0. Specific prefeπed examples of the substituents include electron-withdrawing substituents described later. Prefeπed among these electron-witlidrawing substituents are C₂-C₂o acyl group, C₂-C₂o alkyloxycarbonyl group, nitro group, cyano group, -C₂₀ alkylsulfonyl group, C₆-C₂o arylsulfonyl group, C₁-C₂₀ carbamoyl group, and Cι-C₂₀ halogenated alkyl group. Particularly prefeπed among these electron-withdrawing substituents are cyano group, Cι-C₂₀ alkylsulfonyl group, and C₆-C₂o arylsulfonyl group. Most desirable among these electron-withdrawing substituents is cyano group. Z² represents a hydrogen atom or a substituent and the substituent represents an aliphatic group, aromatic group or heterocyclic group. Z² is preferably an aliphatic group, more preferably a Ci-Cβ alkyl group. Q represents a hydrogen atom or a substituent and the substituent represents an aliphatic group, aromatic group or heterocyclic group. In particular, Q is preferably a group formed by a group of non-metallic atoms required to form a 5- to 8-membered ring. The aforementioned 5- to 8-membered ring may be substituted, may be a saturated ring or may have an unsaturated bond. Particularly prefeπed among these 5- to 8-membered rings are aromatic group and heterocyclic group. Prefeπed examples ofthe non-metallic atom include nitrogen atom, oxygen atom, sulfur atom, and carbon atom. Specific examples of these cyclic structures include benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, benzoimidazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, oxane ring, sulfolane ring, and thiane ring. The hydrogen atoms in the substituents described with reference to the general formula (Mia) maybe substituted. Examples ofthe substituents on these substituents include substituents listed with reference to the general formula (MI), and groups and ionic hydrophilic groups exemplified with reference to G³¹, R¹ and R². The Hammett's substituent constant σp will be described hereinafter. Hammett's rule is an empirical rule which L. P. Hammett proposed in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, and the validity of this empirical rule has been widely accepted today. Substituent constants required in Hammett's rule are σp value and σm value, and these values are found in many general literatures, and for the details of these values, reference can be made to J. A. Dean, "Lange's Handbook of Chemistry", 12th ed., 1979 (Mc Graw-Hill), and "Kagaku no Ryoiki (Region of Chemistry)", extra edition, No. 122, pp. 96 - 103, 1979 (Nankodo). In the present invention, these substituents are defined or described by Hammett's substituent constant σp, but this does not mean that the known values found in the aforementioned literatures are not limited to certain substituents and it goes without saying that even if the values are unknown in literatures, they contain substituents which may fall within the defined range when measured according to Hammett's rule. Further, the compounds ofthe present invention contain those o the general formula (la) which are not benzene derivatives, and as a measure for indicating the electron effect of substituents there is used σp value regardless of substitution position. In the present invention, σp value is used in this sense. Specific examples ofthe election-withdrawing group having a Hammett's substituent constant σp of 0.60 or more include cyano group, nitro group, alkylsulfonyl group (e.g., methylsulfonyl group), and arylsulfonyl group (e.g., phenylsulfonyl group). Examples ofthe electron-withdrawing group having a Hammett's substituent constant σp of 0.45 or more include acyl group (e.g., acetyl group), alkoxycarbonyl group (e.g., dodecyloxycarbonyl group), aryloxycarbonyl group (e.g., m-chlorophenoxycarbonyl), alkylsulfinyl group (e.g., n-propylsulfinyl), arylsulfinyl group (e.g., phenylsulfinyl), sulfamoyl group (e.g., N-ethyl sulfamoyl, N,N-m^ethylsulfamoyl), and halogenated alkyl group (e.g., trifluoromethyl) besides the aforesaid groups. Examples ofthe electron-withdrawing group having a Hammett's substituent constant σp of 0.30 or more include acyloxy group (e.g., acetoxy group), carbamoyl group (e.g., N-ethylcarbamoyl, N,N- dibutylcarbamoyl), halogenated alkoxy group (e.g., trifluoromethyloxy), halogenated aryloxy group (e.g., pentafluorophenyloxy), sulfonyloxy group (e.g., methylsulfonyloxy), halogenated alkylthio group (e.g., difiuoromethylthio), aryl group substituted by two or more electron-withdrawing groups having σp of 0.15 or more (e.g., 2,4-dinitrophenyl, pentachlorophenyl), and heterocyclic group (e.g., 2-benzooxazolyl, 2- benzothiazolyl, l-phenyl-2-benzoimidazolyl) besides the aforesaid groups. Specific examples ofthe electron-withdrawing group having σp of 0.20 or more include halogen atoms besides the aforesaid groups. Referring to a particularly prefeπed combination of azo dyes represented by the general formula (Ml), R⁵ and R⁶ each are preferably a hydrogen atom, alkyl group, aryl group, heterocyclic group, sulfonyl group or acyl group, more preferably hydrogen atom, aryl group, heterocyclic group or sulfonyl group, most preferably hydrogen atom, aryl group or heterocyclic group. However, R⁵ and R⁶ are not a hydrogen atom at the same time. G is preferably a hydrogen atom, halogen atom, alkyl group, hydroxyl group, amino group or acylamino group, more preferably hydrogen atom, halogen atom, amino group or acylamino group, most preferably hydrogen atom, amino group or acylamino group. A³¹ is preferably a pyrazole ring, imidazole ring, isothiazole ring, thiadiazole ring or benzothiazole ring, more preferably pyrazole ring or isothiazole ring, most preferably pyrazole ring. B³¹ and B³² are =CR¹- and -CR²=, respectively, in which R¹ and R² each are preferably a hydrogen atom, alkyl group, halogen atom, cyano group, carbamoyl group, carboxyl group, hydroxyl group, alkoxy group or alkoxycarbonyl group, more preferably hydrogen atom, alkyl group, carboxyl group, cyano group or carbamoyl group. Referring to a prefeπed combination of substituents on the compound represented by the general formula (MI), at least one ofthe various substituents is preferably a compound which is a prefeπed group as mentioned above, and more preferably, more ofthe various substituents are compounds which are prefeπed groups as mentioned above, and most preferably, all the various substituents are compounds wliich are prefeπed groups as mentioned above. Specific examples o the compound (azo dye) represented by the general formula (Ml) are same as those explained in the general formula (1-3) in the first embodiment. The recording ink (preferably ink for inkjet recording) composition ofthe invention (herein simply refeπed to as "ink" also) can be prepared by dissolving and/or dispersing at least one ofthe aforementioned azo magenta dyes in an aqueous medium. The recording ink ofthe invention preferably contains an azo dye in an amount of from 0.2 to 20% by weight, more preferably from 0.5 to 15% by weight. The aforementioned azo magenta dye to be used is substantially water-soluble. The term "substantially water-soluble" as used herein is meant to indicate that the azo magenta dye is dissolved in 20°C water in an amount of 2% by weight or more. The ink composition for in jet recording ofthe invention may comprise other magenta dyes incorporated therein in combination with the aforementioned azo magenta dye. Examples ofthe magenta dyes which can be used in combination with the azo magenta dye include aryl or heterylazo dyes having phenols, naphthols or anilines as coupling components, azomethine dyes having pyrazolones or pyrazolotriazoles as coupling components, methine dyestuffs such as arylidene dye, styryl dye, melocyanine dye and oxonol dye, carbonium dye such as diphenylmethane dye, triphenylmethane dye and xanthene dye, quinone-based dye such as naphthoquinone, anthraquinone and anthrapyridone, and condensed polycyclic dye such as dioxazine dye. These dyes may assume magenta only when chromophore is partly dissociated. In this case, the counter cation may be an inorganic cation such as alkaline metal ion and ammonium ion or an organic cation such as pyridinium ion and quaternary ammonium salt ion or may be contained in a polymer cation as a partial structure. The ink composition containing a compound ofthe general formula (MI) ofthe invention further comprises other dyes incorporated therein so far as it can satisfy the ink precipitation test as defined herein. The ink composition ofthe invention is a recording ink (preferably, an ink for inkjet recording) containing, preferably, a water-miscible organic solvent on a betaine-based surface active agent other than dyes. The betaine-based surface active agent to be used in the invention has both cationic and anionic moieties in its molecule and is defined as a compound having surface activity. Examples of the cationic moiety include aminic nitrogen atom, nitrogen atom in heteroaromatic ring, and boron atom having four bonds to carbon. Prefeπed among these cationic moieties are aminic nitrogen atom and nitrogen atom in heteroaromatic ring. Particularly prefeπed among these cationic moieties is quaternary nitrogen atom. Examples ofthe anionic moiety include hydroxyl group, thio group, sulfonamide group, sulfo group, carboxyl group, imido group, phosphoric acid group, and phosphonic acid group. Particularly prefeπed among these anionic moieties are carboxyl group and sulfo group. The charge ofthe entire surface active agent molecule may be cationic, anionic or neutral but is preferably neutral. It is particularly preferred that the betaine-based surface active agent to be used in the invention be a compound represented by the general formula (2-1). In the general formula (2-1), R represents a hydrogen atom, alkyl group, aryl group or heterocyclic group. L represents a divalent connecting group. M represents a hydrogen atom, alkaline metal atom, ammonium group, protonated organic amine, protonated nittogen-containing heterocyclic group or quaternary ammonium ion, with the proviso that if it is a counter ion of ammonium ion formed by nitrogen atoms in the molecule represented by the general formula (2-1), it represents a group which does not exist as a cation. The suffix q represents an integer of 1 or more. The suffix r, represents an integer of 4 or less. The suffix p represents an integer of from 0 to 4. The sum of p and r is 3 or 4. When the sum of p and r is 4, the nitrogen atom is a protonated ammonium atom (=N⁺=). When m is 2 or more, the plurality of L's may be the same or different. When q is 2 or more, the plurality of COOM groups may be the same or different. When r is 2 or more, the plurality of [L-(COOM)q] groups may be the same or different. When p is 2 or more, the plurality of R's may be the same or different. As the betaine-based surface active agent to be used in the invention there is preferably used a compound represented by the following general formula (2-6) or (2-7) among those represented by the general formula (2-1). general formula (2-6):

In the general formula (2-6), Rι_B to R_3B each represent an alkyl group which may be substituted and preferably has from 1 to 20 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, dodecyl group, cetyl group, stearyl group, oleyl group), aryl group which maybe substituted and preferably has from 6 to 20 carbon atoms (e.g., phenyl group, tollyl group, xylyl group, naphthyl group, cumyl group, dodecylphenyl group) or heterocyclic group which may be Substituted and preferably has from 2 to 20 carbon atoms (e.g., pyridyl group, quinolyl group). R_IB to R_3B maybe connected to each other to form a cyclic structure. Particularly prefeπed among these groups is alkyl group. L represents a divalent connecting group. Prefeπed examples ofthe divalent connecting group include divalent connecting groups containing alkylene group or arylene group as a basic constituent. The connecting main chain may contain hetero atoms such as oxygen atom, sulfur atom and nitrogen atom. R_IB to R_3B or L may be substituted by various substituents. Examples of these substituents include alkyl groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms, particularly from 1 to 8 carbon atoms (e.g., methyl, ethyl, iso- propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl), alkenyl groups preferably having from 2 to 20 carbon atoms, more preferably from 2 to 12 carbon atoms, particularly from 2 to 8 carbon atoms (e.g., vinyl, allyl, 2-butenyl, 3-pentenyl), alkinyl groups preferably having from 2 to 20 carbon atoms, more preferably from 2 to 12 carbon atoms, particularly from 2 to 8 carbon atoms (e.g., propargyl, 3- pentinyl), aryl groups preferably having from 6 to 30 carbon atoms, more preferably from 6 to 20 carbon atoms, particularly from 6 to 12 carbon atoms (e.g., phenyl, p-methylphenyl, naphthyl), amino groups preferably having from 0 to 20 carbon atoms, more preferably from 0 to 12 carbon atoms, particularly from 0 to 6 carbon atoms (e.g., amino, methylamino, dimethylamino, diethylamino, diphenylamino, dibenzylamino), alkoxy groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms, particularly from 1 to 8 carbon atoms (e.g., methoxy, ethoxy, butoxy), aryloxy groups preferably having from 6 to 20 carbon atoms, more preferably from 6 to 16 carbon atoms, particularly from 6 to 12 carbon atoms (e.g., phenyloxy, 2-naphthyl oxy), acyl groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., acetyl, benzoyl, formyl, pivaloyl), alkoxycarbonyl groups preferably having from 2 to 20 carbon atoms, more preferably from 2 to 16 carbon atoms, particularly from 2 to 12 carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl groups preferably having from 7 to 20 carbon atoms, more preferably from 7 to 16 carbon atoms, particularly from 7 to 10 carbon atoms (e.g., phenyloxycarbonyl), acyloxy groups preferably having from 2 to 20 carbon atoms, more preferably from 2 to 16 carbon atoms, particularly from 2 to 10 carbon atoms (e.g., acetoxy, benzoyloxy), acylamino groups preferably having from 2 to 20 carbon atoms, more preferably from 2 to 16 carbon atoms, particularly from 2 to 10 carbon atoms (e.g., acetylamino, benzoylamino), alkoxycarbonylamino groups preferably having from 2 to 20 carbon atoms, more preferably from 2 to 16 carbon atoms, particularly from 2 to 12 carbon atoms (e.g., methoxycarbonylamino), aryloxycarbonyl amino groups preferably having from 7 to 20 carbon atoms, more preferably from 7 to 16 carbon atoms, particularly from 7 to 12 carbon atoms (e.g., phenyloxycarbonyl amino), sulfonylamino groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., methyl sulfonylamino, phenylsulfonylamino), sulfamoyl groups preferably having from 0 to 20 carbon atoms, more preferably from 0 to 16 carbon atoms, particularly from 0 to 12 carbon atoms (e.g., sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl), carbamoyl groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl), alkylthio groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., methylthio, ethylthio), arylthio groups preferably having from 6 to 20 carbon atoms, more preferably from 6 to 16 carbon atoms, particularly from 6 to 12 carbon atoms (e.g., phenylthio), sulfonyl groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., mesyl, tosyl), sulfinyl groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., methyl sulfinyl, phenylsulfinyl), ureido groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., ureido, methylureido, phenylureido), phosphoric acid amide groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., diethylphosphoric acid amide, phenylphosphoric acid amide), hydroxyl groups, mercapto groups, halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), cyano groups, sulfo groups, carboxyl groups, nitro groups, hydroxamic acid groups, sulfino groups, hydrazino groups, imino groups, heterocyclic groups preferably having from 1 to 30 carbon atoms, more preferably from 1 to 12 carbon atoms and containing nitrogen atom, oxygen atom and sulfur atom as hetero atoms (e.g., imidazolyl, benzoimidazolyl, benzothiazolyl, carbazolyl, azepinyl), and silyl groups preferably having from 3 to 40 carbon atoms, more preferably from 3 to 30 carbon atoms, particularly from 3 to 24 carbon atoms (e.g., trimethylsilyl, triphenylsilyl). These substituents may be further substituted. When there are two or more of these substituents, they may be the same or different. If possible, these substituents may be connected to each other to form a ring. A plurality of betaine structures may be contained via Ri to R₃ or L. In the betaine-based surface active agent to be used in the invention, at least one of Rι_B to R_3B and L contains a group having 8 or more carbon atoms. It is particularly prefeπed that R_IB to R_3B contain a long-chain alkyl group, general formula (2-7): (R)_p]-N-[L-(COOM¹)_q]_rl wherein R, L and q are as defined in the general formula (1); pi represents an integer of from 0 to 3; rl represents an integer of from 1 to 3; and M¹ represents an alkaline metal cation or hydrogen atom, with the proviso that the sum of pi and rl is 3, when pi is 2 or more, the plurality of R's may be the same or different, and when rl is 2 or more, the plurality of PACOOM¹),] groups may be the same or different. The general formulae (2-1) and (2-7) will be further described hereinafter. In these general formulae, R represents a hydrogen atom or an alkyl group which may be substituted and preferably has from 1 to 20 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, dodecyl group, cetyl group, stearyl group, oleyl group), aryl group which may be substituted and preferably has from 6 to 20 carbon atoms (e.g., phenyl group, tollyl group, xylyl group, naphthyl group, cumyl group, dodecylphenyl group) or heterocyclic group which may be substituted and preferably has from 2 to 20 carbon atoms (e.g., pyridyl group, quinolyl group). These groups may be connected to each other to form a cyclic structure. Particularly prefeπed among these groups is alkyl group. L represents a divalent connecting group. Prefeπed examples ofthe divalent connecting group include divalent connecting groups containing alkylene group or arylene group as a basic constituent. The connecting main chain may contain hetero atoms such as oxygen atom, sulfur atom and nitrogen atom. R or L may be substituted by various substituents. Examples of these substituents include alkyl groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms, particularly from 1 to 8 carbon atoms (e.g., methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl), alkenyl groups preferably having from 2 to 20 carbon atoms, more preferably from 2 to 12 carbon atoms, particularly from 2 to 8 carbon atoms (e.g., vinyl, allyl, 2-butenyl, 3-pentenyl), alkinyl groups preferably having from 2 to 20 carbon atoms, more preferably from 2 to 12 carbon atoms, particularly from 2 to 8 carbon atoms (e.g., propargyl, 3-pentinyl), aryl groups preferably having from 6 to 30 carbon atoms, more preferably from 6 to 20 carbon atoms, particularly from 6 to 12 carbon atoms (e.g., phenyl, p- methylphenyl, naphthyl), amino groups preferably having from 0 to 20 carbon atoms, more preferably from 0 to 12 carbon atoms, particularly from 0 to 6 carbon atoms (e.g., amino, methylamino, dimethylamino, diethylamino, diphenylamino, dibenzylamino), alkoxy groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms, particularly from 1 to 8 carbon atoms (e.g., methoxy, ethoxy, butoxy), aryloxy groups preferably having from 6 to 20 carbon atoms, more preferably from 6 to 16 carbon atoms, particularly from 6 to 12 carbon atoms (e.g., phenyloxy, 2-naphthyl oxy), acyl groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., acetyl, benzoyl, formyl, pivaloyl), alkoxycarbonyl groups preferably having from 2 to 20 carbon atoms, more preferably from 2 to 16 carbon atoms, particularly from 2 to 12 carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl groups preferably having from 7 to 20 carbon atoms, more preferably from 7 to 16 carbon atoms, particularly from 7 to 10 carbon atoms (e.g., phenyloxycarbonyl), acyloxy groups preferably having from 2 to 20 carbon atoms, more preferably from 2 to 16 carbon atoms, particularly from 2 to 10 carbon atoms (e.g., acetoxy, benzoyloxy), acylamino groups preferably having from 2 to 20 carbon atoms, more preferably from 2 to 16 carbon atoms, particularly from 2 to 10 carbon atoms (e.g., acetylamino, benzoylamino), alkoxycarbonylamino groups preferably having from 2 to 20 carbon atoms, more preferably from 2 to 16 carbon atoms, particularly from 2 to 12 carbon atoms (e.g., methoxycarbonylamino), aryloxycarbonyl amino groups preferably having from 7 to 20 carbon atoms, more preferably from 7 to 16 carbon atoms, particularly from 7 to 12 carbon atoms (e.g., phenyloxycarbonyl amino), sulfonylamino groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., methyl sulfonylamino, phenylsulfonylamino), sulfamoyl groups preferably having from 0 to 20 carbon atoms, more preferably from 0 to 16 carbon atoms, particularly from 0 to 12 carbon atoms (e.g., sulfamoyl, methylsulfamoyl, mmethylsulfamoyl, phenylsulfamoyl), carbamoyl groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl), alkylthio groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., methylthio, ethylthio), arylthio groups preferably having from 6 to 20 carbon atoms, more preferably from 6 to 16 carbon atoms, particularly from 6 to 12 carbon atoms (e.g., phenylthio), sulfonyl groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., mesyl, tosyl), sulfinyl groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., methyl sulfinyl, phenylsulfinyl), ureido groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., ureido, methylureido, phenylureido), phosphoric acid amide groups preferably having from 1 to 20 carbon atoms, more preferably from 1 to 16 carbon atoms, particularly from 1 to 12 carbon atoms (e.g., diefhylphosphoric acid amide, phenylphosphoric acid amide), hydroxyl groups, mercapto groups, halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), cyano groups, sulfo groups, carboxyl groups, nitro groups, hydroxamic acid groups, sulfino groups, hydrazino groups, imino groups, heterocyclic groups preferably having from 1 to 30 carbon atoms, more preferably from 1 to 12 carbon atoms and containing nitrogen atom, oxygen atom and sulfur atom as hetero atoms (e.g., imidazolyl, benzoimidazolyl, benzothiazolyl, carbazolyl, azepinyl), and silyl groups preferably having from 3 to 40 carbon atoms, more preferably from 3 to 30 carbon atoms, particularly from 3 to 24 carbon atoms (e.g., trimethylsilyl, triphenylsilyl). These substituents may be further substituted. When there are two or more of these substituents, they may be the same or different. If possible, these substituents may be connected to each other to form a ring. A plurality of betaine structures may be contained via R or L. M represents a hydrogen atom, alkaline metal cation (e.g., sodium ion, potassium ion, lithium ion, cesium ion), ammonium ion or aminic organic cation (If it is a primary or tertiary amine, it represents a protonated cation such as protonated methylamine, dimethylamine, ethylamine, diethylamine, triethylamine, diazabicycloundecene, diazabicycloctane, piperidine, pyrrolidine, morpholine, N-methylpiperidine, N- methylmoropholine, pyridine, pyrazine, aniline and N,N-dimetlιylaniline. If it is a quaternary ammonium salt, it represents, e.g., tetramethylammonium ion, tetraethylammonium ion, trimethylbenzylammonium ion, methylpyridinium ion, benzylpyridinium ion.). Particularly prefeπed among these groups are alkaline metal cation and hydrogen atom. The suffix q represents an integer of 1 or more (preferably 5 or less, more preferably 2 or less). The suffix r represents an integer of from 1 to 4 (preferably 1 or 2). The suffix p represents an integer of from 0 to 4 (preferably 1 or 2). The sum of p and r is 3 or 4. When the sum of p and 4 is 4, the nitrogen atom is a quaternary ammonium cation and one o the plurality of M's is a dissociated anion. When q is 2 or more, the plurality of (COOM) groups may be the same or different. When r is 2 or more, the plurality of [L-(COOM)_q] groups may be the same or different. When p is 2 or more, the plurality of R's may be the same or different. The suffix pi represents an integer of from 0 to 3 (preferably 2 or less). The suffix rl represents an integer of from 1 to 3 (preferably 2 or less). M¹ represents an alkaline metal cation or hydrogen atom. The sum of pi and rl is 3. When pi is 2 or more, the plurality of R's may be the same or different. When rl is 2 or more, the plurality of PACOOM¹),] groups may be the same or different. R or L preferably contains a hydrocarbon group having 8 or more carbon atoms. Most desirable among the compounds represented by the general formula (2-7) is one represented by the following general formula (2-

general formula (2-8): R-N-(L-COOM^!)₂ R, L and M¹ are as defined in the general formula (2-7). Two (L-COOM¹) groups may be the same or different (The two L's and M^s each may be the same or different). A particularly prefeπed example of R is alkyl group. L is preferably an alkylene group. Prefeπed examples ofthe betaine-based surface active agent will be given below, but it goes without saying that the invention is not limited thereto.

X1-11

XM2

X1-22 C₈H₁₇(n) (n)C₈H₁₇-N-CH₂COO^Θ C₈H₁₇(n)

X1-25

X1-30

X1-31

X1-32 C₁₇H₃₁CONHC₃H₆- _ffi9N^H-C*H₂COO^Θ CH, 1-33 CH₃ (n)C₁₆H₃₃-tf-CH₂CH-CH₂Sθl CH₃ OH

^X1"³⁴ CH₃ (n)C_1βH₃₇- f-CH₂CH-CH₂SO₃ CH₃ OH

X2-1 ^CH₂COOH (n)C₈H₁₇ ^N-cH OOH

X2-2 CH₂COOH (n)C₁₂H_ω ^N-cH OOH

_v„ , „CH₂COONa

*^2"3 (n)C₁₂H₂₅— N._CH2COOH

X2-4 ^CH₂COO (n)C₁₂H₂₅ ^N^CH,COOH

2-5 „CH₂COONa (n)C,₂H₂₅ ^N^CH,COONa

X2-6 „CH₂CH₂COONa (n)C₁₂H₂₅ ^N-CH₂CH₂COOH

_X2.₇ ^CH₂CH₂CH₂COONa (n)C₁₂H₂₅ N-_CH2CH₂CH2COOH

^X2'⁸ ^CH₂COO (n)C₁₆H₃₃ ^N^CH_?COOH

^X2'¹⁶ SO_zC₈H₁₇

X2-17

X2-20 HOOCH₂C_N „CH₂COOH HOOCH₂C^{N C8Hl6 N}"CH₂COOH

X2-21 NaOOCH₂C_N „CH₂COONa HOOCH,C"^{N CδHl6 N}"CH₂COOH

X2-22 NaOOCH₂C_N ,.CH₂COONa HOOCH "^{N Cl2H2 N}"CH₂COOH

X2-23 NaOOCH₂C_N ^CH₂COONa HOOCH,C'^N-Cl6H32W"CH₂COOH

X2-24 KOOCH₂C_χ ^CH₂COOK HOOCH₂C^ ^Cl6H32W"CH₂COOH

X2-25 „CH₂COOK C₁₆H₃₃OOCH₂C-N °_COOH

X2-26 ^CH₂COOK C₁₂H₂₅θOCH₂C— ^_{CH 00H}

The preferred added amount ofthe betaine-based surface active agent may be arbitrary so far as the effect ofthe invention can be exerted but is preferably from 0.001 to 50% by weight, more preferably from 0.01 to 20% by weight based on the weight ofthe ink composition. In the ink set comprising at least two inks having the same hue and different densities, it is preferred that the concentration ofthe betaine-based surface active agent in the ink having the highest dye concentration be higher than that 'of the ink having the lowest dye concentration. It is particularly preferred that as the concentration of dye in the ink increases, the content of betaine-based surface active agent increases. Supposing that the concentration of dye in two inks A and B are Da and Db (Da > Db) and the concentration of betaine-based surface active agent in the two inks A and B are Va and Vb (Va > Vb), k represented by Da Db (Va Vb) is preferably from 0.1 to 10. The ink to be used in the invention is of a type obtained by dissolving and/or dispersing a dye in water or a water-miscible organic solvent. In particular, the ink ofthe invention is preferably a water-soluble type of ink comprising a water-soluble dye incorporated therein. In the ink set, the ink comprising a betaine-based surface active agent may have any color but preferably comprises a betaine-based surface active agent incorporated in a yellow ink and/or magenta ink. In order to adjust the color tone for full-color image, the ink ofthe invention may comprise other dyes in combination with the dyes ofthe present invention. Examples of these dyes which can be used in combination with the dyes ofthe invention include cyan dyes and black dyes. The physical characteristics ofthe dyes which can be used as the cyan dye and black dye is that they have a lύgh oxidation potential, the oxidation potential ofthe dyes is preferably more positive than 1.00 V, more preferably more positive than 1.1 V, most preferably more positive than 1.15 V. As the cyan dyes there are preferably used those described as water-soluble phthalocyanine dye in JP- A-2003-12952 and JP-A-2003-12956. Specific preferred examples ofthe phthalocyanine dye are Exemplary Compounds I-l to 1-12 and 101 to 190 given in the first embodiment. Preferred embodiments and specific examples ofthe black dye are same as those given in the general formula (1-4) in the first embodiment. Incidentally, these dyes may be singly used as a black ink dye but normally is used in combination with dyes which compensate for these dyes in the range where these dyes have a low absorption. In general, the aforementioned dyes are used in combination with dyes or pigments having main absorption in the yellow range to realize desirable black. As yellow dyes there may be used direct dyes or acidic dyes represented by azo dye or azo methine dye which are commonly used. As the dyes to be used for the adjustment of color tone for full- color image there may be used various dyes disclosed in JP-A-2003-306623, paragraph [0090] - [0092]. As a black coloring material there may be used a dispersion of carbon black. Examples ofthe water-miscible organic solvent (including water-soluble organic solvent) employable herein include alcohols (e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t- butanol, pentanol, hexanol, cyclohexanol, benzylalcohol), polyvalent alcohols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexatriol, tliiodiglycol), glycol derivatives (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, triethylene glycol monobutyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amines (e.g., ethanolamine, diethanolamine, triethanolamine, N-methyldiethanol amine, N-ethyldiethanolamine, morpholine, N-ethyl morpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethyl propylenediamine), and other polar solvents (e.g., formamide, N,N-dimethylformamide, N,N-dimethyl acetamide, dimethylsulfoxide, sulfolane, 2-pyrrolidone, N- methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, l,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). Two or more of these water-miscible organic solvents may be used in combination. In the invention, a water-miscible organic solvent (preferably water-soluble organic solvent) having a boiling point of 150°C or more (preferably 200°C or more) is preferably used. In the invention, preferred among the aforementioned water-miscible organic solvents is one (preferably water-soluble organic solvent) having a boiling point of 150°C or more (preferably 170°C or more). The water-miscible organic solvents belonging to the aforementioned glycol derivatives are preferred. Particularly preferred among these glycol derivatives are triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, and dipropylene glycol monomethyl ether. The water-miscible organic solvent may be used in an amount of from 0.01 to 0.95 times, preferably from 0.01 to 0.7 times the weight ofthe ink composition. These water-miscible organic solvents may be used singly or in admixture. The recording ink (preferably ink for inkjet recording) (composition) may comprise a surface active agent incorporated therein. In this arrangement, the liquid physical properties ofthe ink composition can be properly adjusted to enhance the ejection stability ofthe ink composition, making it possible to exert an excellent effect of enhancing the waterproofness ofthe image or preventing the bleeding of ink composition. Examples ofthe aforementioned surface active agents include anionic surface active agents such as sodium dodecylsulfate, sodium dodecyloxysulfbnate and sodium alkylbenzenesulfonate, cationic surface active agents such as cetyl pyridinium chloride, trimethylcetyl ammonium chloride and tetrabutylammonium chloride, and nonionic surface active agents such as polyoxyethylenenonly phenyl ether, polyoxyethylene naphthyl ether and polyoxyethyleneoctylphenyl ether. Preferred among these surface active agents are nonionic surface active agents. The content ofthe surface active agent is from 0.001 to 15% by weight, preferably from 0.005 to 10% by weight, more preferably from 0.01 to 5% by weight based on the weight ofthe ink composition. In the invention, in addition to the betaine-based surface active agent, there may be used nonionic, cationic or anionic surface active agents as surface tension adjuster. Examples ofthe anionic surface active agent include aliphatic acid salts,

acid esters, alkylbenzenesul&nates, alkylnapthalene sulfonates, dialkylsulfosuccinates, alkylphosphoric acid esters, naphthalenesulfonic acid-formalin condensates, and polyoxyethylenealkylsulfuric acid esters. Examples ofthe nonionic surface active agent include polyoxyethylenealkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylenealiphatic acid esters, sorbitanaliphatic acid esters, polyoxyethylene sorbitanaliphatic acid esters, polyoxyethylene alkylamines, glycerinaliphatic acid esters, and oxyethyleneoxypropylene block copolymers. SURFYNOLS (produced by Air Products & Chemicals Inc.), which are acetylene-based polyoxyethylene oxide surface active agents, are preferably used as well. In the first and second embodiments ofthe invention, the ink for inkjet recording ofthe invention can be prepared by dissolving or dispersing the aforementioned dyes and preferably a surface active agent in an aqueous medium. The term "aqueous medium" as used in the invention is meant to indicate water or a mixture of water and a small amount of a water-miscible organic solvent optionally comprising additives such as wetting agent, stabilizer and preservative incorporated therein. In order to prepare the ink solution ofthe invention, which is a water-soluble ink, the dyes are preferably dissolved in water. Thereafter, various solvents and additives are added to and dissolved in the solution which is then stirred to obtain a uniform ink solution. Examples ofthe dissolution method employable herein include dissolution by agitation, dissolution by irradiation with ultrasonic wave, and dissolution by shaking. Particularly preferred among these methods is agitation method. In order to effect stirring, various methods such as fluid agitation known in the art and agitation utilizing shearing force developed by reverse agitator or dissolver may be used. On the other hand, an agitation method utilizing shearing force with respect to the bottom of vessel may be used to advantage. Examples ofthe water-miscible organic solvent employable in the present invention include alcohols (e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent alcohols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amines (e.g., ethanolamine, diethanolamine, triethanolamine, N- methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmoφholine, ethylene diamine, diethylene triamine, triethylene tetramine, polyethyleneimine, tetramethylpropylenediamine), and other polar solvents (e.g., formamide, N,N-dimethylformamide, N,N-dimetlιylacetamide, dimethylsulfoxide, sulfolane, 2-pyrrolidone, N- methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, l,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). Two or more ofthe aforementioned water-miscible organic solvents may be used in combination. In the case where the dye ofthe present invention is oil-soluble, the ink can be prepared by emulsion- dispersing the oil-soluble dye in an aqueous medium in the form of solution in a high boiling organic solvent. The boiling point ofthe aforesaid high boiling organic solvent is 150°C or more, preferably 170°C or more. Examples ofthe high boiling organic solvent employable herein include phthalic acid esters (e.g., dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4- di-tert-amylphenyl) isophthalate, bis(l,l-diethylpropyl)phthalate), phosphoric or phosphonic acid esters (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexyI phenyl phosphate), benzoic acid esters (e.g., 2-ethylhexyl benzoate, 2,4-dichlorobenzoate, dodecyl benzoate, 2- ethylhexyl-p-hydroxybenzoate), amides (e.g., N,N-diethyl dodecaneamide, N,N-diethyllaurylamide), alcohols or phenols (e.g., isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic esters (e.g., clibutoxyethyl succinate, di-2- ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate, trioctyl citrate), aniline derivatives (e.g., N,N-dibutyl-2-butoxy-5-tert-octylaniline), clilorinated paraffins (e.g., paraffins having a chlorine content of from 10% to 80%), trimesic acid esters (e.g., tributyl trimesate), dodecyl benzene, diisopropylene naphthalene, phenols (e.g., 2,4-di-tert-amylphenol, 4-dodecyloxyphenol, 4- dodecyloxycarbonylphenol, 4-(4-dodecyloxy phenylsulfonyl)phenol), carboxylic acids (e.g., 2-(2,4-di-tert- amylphenoxybutyric acid, 2-ethoxy octanedecanoic acid), and alkylphosphoric acids (e.g., di- 2(ethylhexyl)phosphoric acid, dipheylphosphoric acid). The high boiling organic solvent may be used in an amount of from 0.01 to 3 times, preferably from 0.01 to 1.0 times that ofthe oil-soluble dye. These high boiling organic solvents may be used singly or in admixture of two or more thereof (e.g., tricresyl phosphate and dibutyl phthalate, trioctyl phosphate and di(2-ethylhexyl)sebacate, dibutyl phthalate and poly(N-t-butylacrylamide)). For examples of compounds other than the aforementioned high boiling organic solvents to be used in the invention and/or methods for the synthesis of these high boiling organic solvents, reference can be made to US Patents 2,322,027, 2,533, 514, 2,772,163, 2,835,579, 3,594,171, 3,676,137, 3,689,271, 3,700,454, 3,748,141, 3,764,336, 3,765,897, 3,912,515, 3,936,303, 4,004,928, 4,080,209, 4,127,413, 4,193,802, 4,207,393, 4,220,711, 4,239,851, 4,278,757, 4,353,979, 4,363,873, 4,430,421, 4,430,422, 4,464,464, 4,483,918, 4,540,657, 4,684,606, 4,728,599, 4,745,049, 4,935,321, 5,013,639, European Patents 276,319A, 286,253A, 289,820A, 309,158A, 309,159A, 309,160A, 509,311A, 510,576A, East German Patents 147,009, 157,147, 159,573, 225,240A, British Patent 2,091,124A, JP-A-48-47335, JP-A-50-26530, JP-A-51-25133, JP-A-51-26036, JP-A- 51-27921, JP-A-51-27922, JP-A-51-149028, JP-A-52-46816, JP-A-53-1520, JP-A-53-1521, JP-A-53-15127, JP- A-53-146622, JP-A-54-91325, JP-A-54-106228, JP-A-54-118246, JP-A-55-59464, JP-A-56-64333, JP-A-56- 81836, JP-A-59-204041, JP-A-61-84641, JP-A-62-118345, JP-A-62-247364, JP-A-63-167357, JP-A-63-214744, JP-A-63-301941, JP-A-64-9452, JP-A-64-9454, JP-A-64-68745, JP-A-1-101543, JP-A-1-102454, JP-A-2-792, JP-A-2-4239, JP-A-2-43541, JP-A-4-29237, JP-A-4-30165, JP-A-4-232946, and JP-A-4-346338. The aforementioned high boiling organic solvents are used in an amount of preferably from 0.01 to 3.0 times, pre preferably from 0.01 to 1.0 times that ofthe oil-soluble dye by weight. In the invention, the oil-soluble dye and the high boiling organic solvent are used in the form of emulsion dispersion in an aqueous medium. During emulsion dispersion, a low boiling organic solvent may be used in some cases from the standpoint of emulsifiability. As such a low boiling organic solvent there may be used an organic solvent having a boiling point of from about 30°C to 150°C at atmospheric pressure. Preferred examples ofthe organic solvent employable herein include esters (e.g., ethyl acetate, butyl acetate, ethyl propionate, β-ethoxyethyl acetate, methyl cellosolve acetate), alcohols (e.g., isopropyl alcohol, n-butyl alcohol, secondary butyl alcohol), ketones (e.g., methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone), amides (e.g., dimethylformamide, N-methylpyrrolidone), and ethers (e.g., tetrahydrofurane, dioxane). However, the present invention is not limited to these organic solvents. The emulsion dispersion is effected to disperse an oil phase having a dye dissolved in a high boiling organic solvent optionally mixed with a low boiling organic solvent in an aqueous phase mainly composed of water to make minute oil droplets of oil phase. During this procedure, additives such as surface active agent, wetting agent, dye stabilizer, emulsion stabilizer, preservative and antifungal agent described later may be added to either or both ofthe aqueous phase and the oil phase as necessary. The emulsification is normally accomplished by adding the oil phase to the aqueous phase, but a so- called phase inversion emulsification method involving the dropwise addition of an aqueous phase to an oil phase is preferably used. The aforementioned emulsification method may be used also in the case where the dye to be used in the invention is water-soluble and the additives are oil-soluble. The emulsion dispersion may be effected with the aforesaid surface active agents. Preferred examples o the surface active agents employable herein include amonic surface active agents such as aliphatic acid salt, alkylsulfuric acid ester, alkylberizenesulfonate, alkylnaphthalenesulfonate, dialkylsulfosuccinate, alkylphosphoric acid esters, naphthalenesulfonic acid-formalin condensate and polyoxyethyleneaLkylsulfuric acid ester, and nonionic surface active agents such as polyoxyethylenealkyl ether, polyoxyethylenealkylallyl ether, polyoxyethylene aliphatic acid ester, sorbitanaliphatic acid ester, polyoxyethylenesorbitanaliphatic acid ester, polyoxyethylenealkylamine, glycerinaliphatic acid ester and oxyethyleneoxypropylene block copolymer. Alternatively, SURFYNOLS (produced by Air Products & Chemicals Inc.), which are acetylene-based polyoxyethylene oxide surface active agents, are preferably used as well. Further, amine oxide-based amphoteric surface active agents such as N,N-dimethyl-N-alkylamine oxide may be used. Those listed as surface active agents in JP-A-59-157,636, pp. 37 - 38, and Research Disclosure No. 308119 (1989) may be used. For the purpose of stabilizing the ink shortly after emulsification, the aforementioned surface active agents may be used in combination with a water-soluble polymer. As such a water-soluble polymer there may be preferably used a polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, polyacrylic acid, polyacrylamide or copolymer thereof. Further, natural water-soluble polymers such as polysaccharides, casein and gelatin may be preferably used. For the purpose of stabilizing the dye dispersion, polyvinyls obtained by the polymerization of acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins, styrenes, vinylethers or acrylonitriles, polymethanes, polyesters, polyamides, polyureas, polycarbonates, etc., which are substantially insoluble in an aqueous medium, may be used. These polymers preferably have - S0₃ ^" or -COO^". In the case where these polymers substantially insoluble in an aqueous medium are used, they are preferably used in an amount of not greater than 20% by weight, preferably not greater than 10% by weight based on the amount ofthe high boiling organic solvent. In the case where emulsion dispersion is effected to disperse the oil-soluble dye or high boiling organic solvent to make an aqueous ink, a particularly important factor is control over the particle size ofthe aqueous ink. In order to enhance the color purity or density during the formation of an image by ink ejection, it is essential to reduce the average particle size. The volume-average particle diameter ofthe aqueous ink is preferably not greater than 1 μm, more preferably from 5 nm to 100 nm. The measurement ofthe volume-average particle diameter and the particle size distribution ofthe dispersed particles can be easily accomplished by any known method such as static light scattering method, dynamic light scattering method, centrifugal sedimentation method and method as disclosed in "Jikken Kagaku Koza (Institute of Experimental Chemistry)", 4th ed., pp. 417 - 418. For example, measurement can be easily carried out by diluting the ink with distilled water such that the particle concentration in the ink reaches 0.1% to 1% by weight, and then subjecting the solution to measurement using a commercially available volume-average particle diameter measuring instrument (e.g., Microtrack UPA (produced by NIKKISO CO., LTD.). Further, dynamic light scattering method utilizing laser doppler effect is particularly preferred because it is capable of measuring even small particle size. The term "volume-average particle diameter" as used herein is meant to indicate average particle diameter weighted with particle volume, which is obtained by dividing the sum ofthe product ofthe diameter and the volume of individual particles in the aggregate of particles by the total volume of the particles. For the details of volume-average particle diameter, reference can be made to Souic i Muroi, "Koubunshi Ratekkusu no Kagaku (Chemistry of Polymer Latexes)", Koubunshi Kankokai, page 119. It was also made obvious that the presence of coarse particles has an extremely great effect on the printing properties. In other words, coarse particles clog the head nozzle. Even if coarse particles do not go so far as to clog the head nozzle, the ink cannot be ejected or can be deviated when ejected, giving a serious effect on the printing properties. In order to prevent this trouble, it is important to keep the number of particles having a diameter of not smaller than 5 μm and not smaller than 1 μm in the resulting ink to 10 or less and 1,000 or less, respectively. The removal of these coarse particles can be accomplished by any known method such as centrifugal separation method and precision filtration method. The separation step may be effected shortly after emulsion dispersion or shortly before the filling ofthe emulsion dispersion comprising various additives such as wetting agent and surface active agent in the ink cartridge. As an effective unit for reducing the average particle diameter of particles and eliminating coarse particles there maybe used a mechanical emulsifier. As such an emulsifier there may be used any known device such as simple stirrer, impeller type agitator, in-line agitator, mill type agitator (e.g., colloid mill) and ultrasonic agitator. The use of a high pressure homogenizer is particularly preferred. For the details of the mechanism of high pressure homogenizer, reference can be made to US Patent 4,533,254, JP-A-6-47264, etc., and examples of commercially available high pressure homogenizers include Gaulin homogenizer (produced by A. P. V GAULLN INC.), microfluidizer (produced by MICROFLUIDEX INC.) and altimizer (produced by SUGINO MACHINE LIMITED). In recent years, a high pressure homogenizer having a mechanism for atomizing a material in a ultrahigh pressure jet stream as disclosed in US Patent 5,720,551 is particularly useful in the emulsion dispersion of the invention. An example of the emulsifier using a ultrahigh jet stream is De BEE2000 (produced by BEE TNTERNATIONAL LTD.). The pressure at which emulsion is carried out by a high pressure emulsion disperser is not lower than 50 MPa, preferably not lower than 60 MPa, more preferably not lower than 180 MPa. For example, the combined use of two or more emulsifiers as in a method involving the emulsification by an agitated emulsifier followed by the passage through a high pressure homogenizer is particularly preferred. Alternatively, a method is preferably used which comprises effecting the emulsion ofthe material using such an emulsifier, adding additives such as wetting agent and surface active agent, and then passing the ink composition again through the high pressure homogenizer before being filled in the cartridge. In the case where the dye composition comprises a low boiling organic solvent incorporated therein in addition to the high boiling organic solvent, it is preferred to remove the low boiling organic solvent from the standpoint of emulsion stability and safety/hygiene. The removal of the low boiling solvent can be accomplished by any known method such as evaporation method, vacuum evaporation method and ultrafiltration method depending on the solvent to be removed. The step of removing the low boiling organic solvent is preferably effected as rapidly as possible shortly after emulsification. For the details ofthe process for the preparation of ink for in jet recording, reference can be made to JP-A-5-148436, JP-A-5-295312, JP-A-7-97541, JP-A-7-82515, and JP-A-7-118584. These preparation processes can be used also in the preparation ofthe ink for inkjet recording ofthe invention. During the production ofthe ink for inkjet recording ofthe invention, ultrasonic vibration may be applied at the step of dissolving additives such as dye and like steps. Referring further to ultrasonic vibration, an ultrasonic energy equal to or greater than the energy received by the recording head has been previously applied during the production ofthe ink to remove bubbles, preventing the generation of bubbles due to the pressure applied to the ink by the recording head. The ultrasonic vibration is an ultrasonic wave having a frequency of normally 20 kHz or more, preferably 40 kHz or more, more preferably 50 kHz. The energy applied to the solution by the ultrasonic vibration is normally 2 x 10⁷ J/m³ or more, preferably 5 x 10⁷ J/m³ or more, more preferably 1 x 10⁸ J/m³ or more. The time during which the ultrasonic vibration is applied is normally from about 10 minutes to 1 hour. The step of applying ultrasonic vibration may be effected at any time after the incorporation ofthe dye in the medium to exert the effect. Even when the ultrasonic vibration is applied after the storage ofthe ink completed, the effect can be exerted. However, it is preferred that the ultrasonic vibration be applied during the dissolution and/or dispersion of the dye in the medium because the effect of removing bubbles can be more exerted and the dissolution and/or dispersion ofthe dyestuff in the medium can be accelerated by the ultrasonic vibration. In other words, the aforementioned step of applying at least ultrasonic vibration may be effected either during or after the step of dissolving and/or dispersing the dye in the medium. In other words, the aforementioned step of applying at least ultrasonic vibration may be effect one or more times between after the preparation ofthe ink and the completion ofthe product. In an embodiment of implementation of the invention of the invention, the step of dissolving and or dispersing the dye in the medium preferably involves a step of dissolving the aforementioned dye in a part ofthe entire medium and a step of adding the rest ofthe medium, and it is preferred that ultrasonic vibration be applied at any ofthe aforementioned steps, more preferably at the step of dissolving the dye in a part ofthe entire medium. The aforementioned step of adding the rest ofthe medium may consist of a single step or a plurality of steps. Further, the process for the production of the ink according to the present invention is preferably accompanied by heat deaeration or deaeration under reduced pressure to enhance the effect of removing bubbles from the ink. Heat deaeration or vacuum deaeration is preferably effected at the same time with or after the step of adding the rest of the medium to the solution. Examples ofthe unit for generating sound vibration at the step of giving sound vibration include known devices such as ultrasonic dispersing machine. In the process for the preparation ofthe ink composition according to the invention, it is important to effect a step of removing dust as solid content by filtration after the preparation ofthe ink solution. For this job, a filter is used, and, as such a filter there is used a filter having an effective pore diameter of 1 μm or less, preferably from 0.05 μm to 0.3 μm, particularly from 0.25 μm to 0.3 μm. As the filter material there may be used any of various known materials, and, in the case where a water-soluble dye ink is used, a filter prepared for aqueous solvent is preferably used. In particular, a filter made of a polymer material which can difficultly give dust is preferably used. Filtration may be accomplished by pumping the solution through the jacket or may be effected under pressure or reduced pressure. Filtration is often accompanied by the entrapment of air in the solution. Since bubbles due to air thus entrapped can often cause disturbance in image in the inkjet recording, the aforementioned deaeration step is preferably provided separately. As the deaeration method there may be used a method which comprises allowing the solution thus filtered to stand or various methods such as ultrasonic deaeration and vacuum deaeration using commercially available apparatus. The ultrasonic deaeration process, if effected, preferably lasts for about 30 seconds to 2 hours, more preferably for about 5 minutes to 1 hour. These jobs are preferably effected in a space such as clean room and clean bench to prevent the contamination by dust. In the present invention, these jobs are preferably effected in a space having a cleanness degree of 1,000 class or less. The term "cleanness" as used herein is meant to indicate the value counted by a dust counter. The ink for inkjet recording ofthe invention may comprise properly selected additives incorporated therein in a proper amount such as drying inhibitor for preventing the clogging ofthe ejection nozzle with dried ink, penetration accelerator for helping the ink to penetrate in the page, ultraviolet absorber, oxidation inhibitor, viscosity adjuster, surface tension adjuster, dispersant, dispersion stabilizer, antifungal agent, rust preventive, pH adjuster, anti-foaming agent and chelating agent. As the drying inhibitor there is preferably used a water-soluble organic solvent having a lower vapor pressure than water. Specific examples ofthe water-soluble organic solvent include polyvalent alcohols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodigycol, 2-methyl- 1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivative, glycerin and trimethylolpropane, lower alkylethers of polyvalent alcohol such as ethylene glycol monomethyl(or ethyl) ether, diethylene glycol monomethyl(or ethyl)ether and triethylene glycol monoethyl(or butyl)ether, heterocyclic compounds such as 2- pyrrolidone, N-methyl-2-pyrrolidone, l,3-dimethyl-2-imidazolidinone and N-ethylmoφholine, sulfur-containing compounds such as sulfolane, dimethylsulfoxide and 3-sulfolene, polyfunctional compounds such as diacetone alcohol and ( ethanolamine, and urea derivatives. Preferred among these water-soluble organic solvents are polyvalent alcohols such as glycerin and diethylene glycol. These drying inhibitors may be used singly or in combination of two or more thereof. These drying inhibitors are preferably incorporated in the ink in an amount of from 10% to 50% by weight. Examples ofthe penetration accelerator employable in the present invention include alcohols such as ethanol, isopropanol, butanol, di(tri)ethylene glycol monobutyl ether and 1,2-hexanediol, sodium laurylsulfate, sodium oleate, and nonionic surface active agents. These penetration accelerators can exert a sufficient effect when incorporated in the ink in an amount of from 10% to 30% by weight. These penetration accelerators are preferably used in an amount such that no printing run or print through occurs. Examples ofthe ultraviolet absorber to be used to enhance the preservability ofthe image in the present invention include benzotriazole-based compounds as disclosed in JP-A-58-185677, JP-A-61-190537, JP-A-2- 782, JP-A-5-197075 and JP-A-9-34057, benzophenone-based compounds as disclosed in JP-A-46-2784, JP-A-5- 194483 and US Patent 3,214,463, cinnamic acid-based compounds as disclosed in JP-B-48-30492, JP-A-56- 21141 and JP-A- 10-88106, triazine-based compounds as disclosed in JP-A-4-298503, JP-A-8-53427, JP-A-8- 239368, JP-A-10-182621 and JP-T-8-501291, compounds as disclosed in Research Disclosure No. 24239, and compounds which absorb ultraviolet rays to emit fluorescence, i.e., so-called fluorescent brighteners, such as stilbene-based and benzoxazole-based compounds. In the present invention, as the oxidation inhibitor to be used to enhance the image preservability there may be used any of various organic and metal complex-based discoloration inhibitors. Examples ofthe organic discoloration inhibitors include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocyclic compounds. Examples ofthe metal complex-based discoloration inhibitors include nickel complex, and zinc complex. Specific examples of these oxidation inhibitors include compounds listed in the patents cited in Research Disclosure No. 18716, Articles VI-I and J, Research Disclosure No. 15162, Research Disclosure No. 17643, left column, page 650, Research Disclosure No. 36544, page 527, Research Disclosure No. 307105, page 872, and Research Disclosure No. 15162, and compounds included in the general formula and examples of representative compounds listed in JP-A-62- 215272, pp. 127 - 137. Examples ofthe antifungal agent to be incorporated in the present invention include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1 -oxide, ethyl p-hydroxybenzoate, 1,2- benzoisothiazoline-3-one, and salts thereof. These antifungal agents are preferably incorporated in the ink in an amount of from 0.02% to 5.00% by weight. For the details of these antifungal agents, reference can be made to "Bokin Bobizai Jiten (Dictionary of Anti-bacterial and Antifungal Agents)", compiled by Dictionary Compilation Committee of The Society for Antibacterial and Antifungal Agents, Japan. Examples ofthe rust preventive employable herein include acidic sulfites, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerthyritol tetranitrate, dicyclohexylammonium nitrite, and benzotriazole. These rust preventives are preferably incorporated in the ink in an amount of from 0.02% to 5.00% by weight. The pH adjustor to be incorporated in the ink for ink set of the invention is preferably used for the purpose of adjusting the pH value ofthe ink, providing dispersion stability or like purposes. It is preferred that the pH value ofthe ink be adjusted to a range of from 8 to 11 at 25°C. When the pH value ofthe ink falls below 8, the resulting dye composition exhibits a deteriorated solubility, causing nozzle clogging. On the contrary, when the pH value ofthe ink exceeds 11, the resulting ink tends to exhibit a deteriorated water resistance. Examples ofthe pH adjustor include basic pH adjustors such as organic base and inorganic alkali, and acidic pH adjustors such as organic acid and inorganic acid. Examples ofthe basic compounds employable herein include inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium acetate, potassium acetate, sodium phosphate and disodium hydrogenphosphate, and organic bass such as aqueous ammonia, methylamine, ethylamine, dietliylamine, triethylamine, etlianolamine, cuethanolamine, triethanolamine, ethylenediamine, piperidine, diazabicyclooctane, diazabicycloundecene, pyridine, quinoline, picoline, lutidine and collidine. Examples ofthe acidic compounds employable herein include inorganic compounds such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, sodium hydrogensulfate, potassium hydrogensulfate, potassium dihydrogenphosphate and sodium dihydrogenphosphate, and organic compounds such as acetic acid, tartaric acid, benzoic acid, trifluoroacetic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfbnic acid, saccharinic acid, phthalic acid, picolic acid and quinolinic acid. The electrical conductance ofthe ink ofthe invention falls within a range of from 0.01 to 10 S/m. A particularly preferred range of electrical conductance is from 0.05 to 5 S/m. The measurement of electric conductance can be accomplished by en electrode method using a commercially available saturated potassium chloride. The electric conductance ofthe ink can be controlled mainly by the ionic concentration ofthe aqueous solution. In the case where the salt concentration is high, desalting may be effected using a ultrafiltration membrane or the like. Further, in the case where salts or the like are added to adjust electric conductance, various organic or inorganic salts may be added. As the inorganic salts there may be used inorganic compounds such as potassium halide, sodium halide, sodium sulfate, potassium sulfate, sodium hydrogensulfate, potassium hydrogensulfate, sodium nitrate, potassium nitrate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate, disodium hydrogenphosphate, boric acid, potassium dihydrogenphosphate and sodium dihydrogenphosphate. Organic compounds such as sodium acetate, potassium acetate, potassium tartrate, sodium tartrate, sodium benzoate, potassium benzoate, sodium p-toluenesulfbnate, potassium saccharinate, potassium phthalate and sodium picolate may be used. Alternatively, the selection of other additive components makes it possible to adjust the electric conductance ofthe ink. The ink ofthe invention exliibits a viscosity of from 1 to 20 mPa-s, more preferably from 2 to 15 mPa-s, particularly from 2 to 10 mPa-s at 25°C. When the viscosity ofthe ink exceeds 30 mPa-s, the resulting recorded image can be fixed only at a reduced rate. Further, the resulting ink exliibits a deteriorated ejectability. On the contrary, when the viscosity ofthe ink falls below 1 mPa-s, the resulting recorded image runs and thus exhibits a reduced quality. The adjustment of viscosity can be arbitrarily carried out by controlling the added amount ofthe ink solvent. Examples ofthe ink solvent employable herein include glycerin, diethylene glycol, triethanolamine, 2- pyrrolidone, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether. Further, a viscosity adjustor may be used. Examples ofthe viscosity adjustor employable herein include celluloses, water-soluble polymers such as polyvinyl alcohol, and nonionic surface active agents. For the details of these viscosity adjustors, reference can be made to "Nendo Chousei Gijutsu (Technology for Viscosity Adjustment)", Gijutsu Joho Kyoukai, Article 9, 1999, and "Iriku Jetto Purintayou Kemikaruzu (98 zouho) - Zairyou no Kaihatsu Doko/Tenbo Chousa (Chemicals for Ink Jet Printer (98 enlarged edition) - Research on Trend and View of Development of Materials)", CMC, pp. 162 - 174, 1997. For the details of the metliod for the measurement of viscosity of liquid, reference can be made to JIS Z8803. In practice, however, the viscosity of liquid can be simply measured using a commercially available viscometer. Examples ofthe rotary viscometer include Type B viscometer and Type E viscometer produced by Tokyo Keiki Kogyo K.K. In the invention, a Type VM-100A-L vibration viscometer (produced by YAMAICHI ELECTRONICS CO., LTD.) was used to measure viscosity at 25°C. The unit of viscosity is Pa-s. In practice, however, mPa-s is used. The surface tension, regardless of which it is static or dynamic, of the ink to be used in the invention is preferably from 20 to not greater than 50 mN/m, more preferably from 20 to not greater than 40 mN/m at 25°C. When the surface tension ofthe ink exceeds 50 mN/m, the resulting ink exhibits a drastic deterioration in print quality such as ejection stability and resistance to running and whisker during color mixing. On the contrary, when the surface tension ofthe ink falls below 20 mN/m, the resulting ink can be attached to hard surface when ejected, causing defective printing. The aforementioned various cationic, anionic and nonionic surface active agents may be added also for the pmpose of adjusting surface tension. These surface active agents are preferably used in an amount of from 0.01 to 20% by weight, more preferably from 0.1 to 10% by weight based on the weight ofthe ink for inkjet recording. Two or more of these surface active agents may be used in combination. Known examples ofthe static surface tension measuring method include capillary rise method, dropping method, and ring method. In the invention, as the static surface tension measuring method there is used a peφendicular plate method. When a thin glass or platinum plate is hanged partially dipped in a liquid, surface tension ofthe liquid acts downward along the length ofthe plate in contact with the liquid. The surface tension is measured by balancing this force by a upward force. As dynamic surface tension measuring methods there are known vibration jet metliod, meniscus dropping method and maximum bubble pressure method as disclosed in "Shinjikken Kagaku Koza (New Institute of Experimental Chemistry), 18th ed., Kaimen to Koroido (Interface and Colloid)", Maruzen, pp. 69 - 90 (1977). Further, a liquid film destruction method is known as disclosed in JP-A-3-2064. In the invention, as the dynamic viscosity measuring method there is used a differential bubble pressure method. The principle and method of effecting this measuring method will be described hereinafter. When bubbles are formed in a solution which has been stirred to uniformity, a new gas-liquid interface is produced. Surface active agent molecules in the solution then gather on the surface of water at a constant rate. The bubble rate (rate of formation of bubbles) is changed. As the formation rate decreases, more surface active agent components gather on the surface of bubbles, reducing the maximum bubble pressure shortly before the burst of bubbles. Thus, the maximum bubble pressure (surface tension) with respect to bubble rate can be detected. As a method for the measurement of dynamic surface tension there is preferably used a method which comprises forming bubbles in a solution using a large probe and a small probe, measuring the differential pressure ofthe two probes in the state of maximum bubble pressure, and then calculating the dynamic surface tension from the differential pressure. The content of no-volatile components in the ink ofthe invention is preferably from 10% to 70% by weight based on the total amount of the ink from the standpoint of enhancement of ejection stability of ink, printed image quality and various fastnesses of image and elimination of running of printed image and stickiness of printed surface, more preferably from 20% to 60% by weight from the standpoint of enhancement of ejection stability of ink and elimination of running of printed image. The term "non-volatile component" as used herein is meant to indicate a liquid, solid or polymer component having a boiling point of not lower than 150°C at 1 atm. Examples ofthe non-volatile components to be incoφorated in the ink for inkjet recording include dyes, and high boiling solvents, and polymer latexes, surface active agents, dye stabilizers, antifungal agents and buffers which are optically added. Most of these non-volatile components but dye stabilizers deteriorate the dispersion stability ofthe ink. Further, these nonvolatile components are still present on the inkjet image-receiving paper after printing, inhibiting the stabilization of dyes by association on the image-receiving paper and hence deteriorating various fastnesses of the image area and worsening the image running at high temperature and humidity. In the invention, the ink may comprise a polymer compound incoφorated therein. The term "polymer compound" as used herein is meant to indicate all polymer compounds having a number-average molecular weight of not smaller than 5,000 contained in the ink. Examples of these polymer compounds include water- soluble polymer compounds substantially soluble in an aqueous medium, water-dispersible polymer compounds such as polymer latex and polymer emulsion, and alcohol-soluble polymer compounds soluble in polyvalent alcohols used as auxiliary solvents. All polymer compounds are included in the polymer compounds ofthe invention so far as they can be substantially uniformly dissolved or dispersed in the ink solution. Specific examples ofthe water-soluble polymer compounds employable herein include water-soluble polymers such as polyvinyl alcohol, silanol-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, polyalkylene oxide (e.g., polyethylene oxide, polypropylene oxide) and polyalkylene oxide derivative, natural water-soluble polymers such as polysaccharide, starch, cationated starch, casein and gelatin, aqueous acrylic resins such as polyacrylic acid, polyacrylamide and copolymer thereof, aqueous alkyd resins, and water-soluble compounds which have -S0₃ ^~ or -COO^" group and thus are substantially soluble in an aqueous medium. Examples ofthe polymer latexes include styrene-butadiene latexes, styrene-acryl latexes, and polyurethane latexes. Examples ofthe polymer emulsions include acryl emulsions. These water-soluble polymer compounds may be used singly or in combination of two or more thereof. Such a water-soluble polymer compound is used as a viscosity adjustor to adjust the ink viscosity to a value falling within a range that provides the ink a good ejectability. When the added amount ofthe water- soluble polymer compound is too great, the resulting ink exhibits too high a viscosity that deteriorates the ejection stabihty ofthe ink solution. Thus, when time elapses, the ink undergoes precipitation, causing clogging ofthe nozzle. The added amount ofthe polymer compound to be used as a viscosity adjustor depends on the molecular weight ofthe polymer compound added (The greater the molecular weight ofthe polymer compound to be added is, the smaller is the added amount thereof) but is normally from 0% to 5% by weight, preferably from 0% to 3% by weight, more preferably from 0% to 1% by weight based on the total amount ofthe ink composition. In the invention, in addition to the surface active agent,, there may be used nonionic, cationic or amonic surface active agents as surface tension adjustor. Examples ofthe anionic surface active agent include aliphatic acid salts, alkylsulfuric acid esters, alkylbenzenesulfonates, alkylnapthalenesulfonates, dialkylsulfosuccinates, alkylphosphoric acid esters, naphthalenesulfonic acid-formalin condensates, and polyoxyethylenealkylsulfuric acid esters. Examples ofthe nonionic surface active agent include polyoxyethylenealkyl ethers, polyoxyethylenealkyl allyl ethers, polyoxyethylenealiphatic acid esters, sorbitanaliphatic acid esters, polyoxyethylene sorbitanaliphatic acid esters, polyoxyethylene alkylamines, glycerinaliphatic acid esters, and oxyethyleneoxypropylene block copolymers. SURFYNOLS (produced by Air Products & Chemicals Inc.), which are acetylene-based polyoxyethylene oxide surface active agents, are preferably used as well. Further, amine oxide-based amphoteric surface active agents such as N,N-mmethyl-N-alkylamine oxide are preferred. Moreover, those listed as surface active agents in JP-A-59-157, 636, pp. 37 - 38, and Research Disclosure No. 308119, 1989, ma be used. In the invention, as the dispersant and dispersion stabilizer there may be used the aforementioned various cationic, anionic and nonionic surface active agents as necessary. As the anti-forming agent there may be used a fluorine-based or silicone-based compound or a chelating agent such as EDTA as necessary. [Image-receiving material] As the image-receiving material there may be used a recording paper or recording film which is a reflection medium described hereinafter. As the support in the recording paper or recording film there may be used one obtained by processing a chemical pulp such as LBKP and NBKP, a mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP and CGP, used paper pulp such as DIP or the like, optionally mixed with known additives such as pigment, binder, sizing agent, fixing agent, cationic agent and paper strength improver, through various paper machines such as foundrinier paper machine and cylinder paper machine. As the support there may be used either a synthetic paper or plastic film sheet besides tliese support materials. The thickness of the support is preferably from 10 μm to 250 μm. The basis weight ofthe support is preferably from 10 to 250 g/m². An ink-receiving layer and a back coat layer may be provided on the support directly or with a size press or anchor coat layer of starch, polyvinyl alcohol or the like inteφosed therebetween to prepare a material for receiving the ink ofthe invention. The support may be further subjected to leveling using a calendering machine such as machine calender, TG calender and soft calender. As the support there is preferably used a paper or plastic film laminated with a polyolefin (e.g., polyethylene, polystyrene, polybutene, copolymer thereof) or polyethylene terephthalate on both sides thereof. The polyolefin preferably comprises a white pigment (e.g., titanium oxide, zinc oxide) or a tinting dye (e.g., cobalt blue, ultramarine, neodymium oxide) incoφorated therein. The ink-receiving layer to be provided on the support comprises a porous material or aqueous binder incoφorated therein. The image receiving layer (ink-receiving layer) also preferably comprises a pigment incoφorated therein. As such a pigment there is preferably used an inorganic white pigment (particles). Examples ofthe inorganic white pigments include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amoφhous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulfate and zinc carbonate, and organic pigments such as styrene-based pigment, acrylic pigment, urea resin and melamine resin. Particularly preferred among these pigments are porous inorganic white pigments. In particular, synthetic amoφhous silica having a large pore area, etc. are preferred. As the synthetic amoφhous silica there may be also used anhydrous silicate obtained by dry method or hydrous silicate obtained by wet method, but hydrous silicate is particularly preferred. These pigments may be used in combination of two or more thereof. Specific examples ofthe recording paper comprising the aforementioned pigments incoφorated in the image-receiving layer include those disclosed in JP-A-10-81064, JP-A-10-119423, JP-A-10-157277, JP-A-10- 217601, JP-A-11-348409, JP-A-2001-138621, JP-A-2000-43401, JP-A-2000-211235, JP-A-2000-309157, JP-A- 2001-96897, JP-A-2001-138627, JP-A-11-91242, JP-A-8-2087, JP-A-8-2090, JP-A-8-2091, JP-A-8-2093, JP-A- 174992, JP-A-11-192777, and JP-A-2001-301314. Examples ofthe aqueous binder to be incoφorated in the image-receiving layer include water-soluble polymers such as polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationated starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, polyalkylene oxide and polyalkylene oxide derivative, and water-dispersible polymers such as styrene butadiene latex and acryl emulsion. These aqueous binders may be used singly or in combination of two or more thereof. In the invention, particularly preferred among tliese aqueous binders are polyvinyl alcohol and silanol-modified polyvinyl alcohol from the standpoint of adhesion to pigment and exfoliation resistance of ink-receiving layer. The ink-receiving layer may comprise a mordant, a wateφroofing agent, a light-resistance improver, a gas resistance improver, a surface active agent, a film hardener and other additives incoφorated therein besides the pigments and aqueous binders. The mordant to be incoφorated in the image-receiving layer is preferably passivated. To this end, a polymer mordant is preferably used. For the details ofthe polymer mordant, reference can be made to JP-A-48-28325, JP-A-54-74430, JP- A-54-124726, JP-A-55-22766, JP-A-55-142339, JP-A-60-23850, JP-A-60-23851, JP-A-60-23852, JP-A-60- 23853, JP-A-60-57836, JP-A-60-60643, JP-A-60-118834, JP-A-60-122940, JP-A-60-122941, JP-A-60-122942, JP-A-60-235134, JP-A-1-161236, US Patents 2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386, 4,193,800, 4,273,853, 4,282,305 and 4,450,224. An image-receiving material containing a polymer mordant disclosed in JP-A-1-161236, pp. 212 to 215 is particularly preferred. The use ofthe polymer mordant disclosed in the above cited patent makes it possible to obtain an image having an excellent quality and hence improve the light-resistance ofthe image. The wateφroofing agent can be used to render the image wateφroof. As such a wateφroofing agent there is preferably used a cationic resin in particular. Examples of such a cationic resin include polyamide polyamine epichlorohydnn, polyethylenimine, polyamine sulfone, dimethyl diallyl ammonium chloride polymer, and cation polyacrylamide. Particularly preferred among these cationic resins is polyamine epichlorohydrin. The content of such a cationic resin is preferably from 1% to 15% by weight, particularly from 3% to 10% by weight based on the total solid content ofthe ink-receiving layer. Examples ofthe light-resistance improver and gas resistance improver include phenol compounds, hindered phenol compounds, thioether compounds, thiourea compounds, thiocyanic acid compounds, amine compounds, hindered amine compounds, TEMPO compounds, hydrazine compounds, hydrazide compounds, amidine compounds, vinyl-containing compounds, ester compounds, amide compounds, ether compounds, alcohol compounds, sulfinic acid compounds, saccharides, water-soluble reducing compounds, organic acids, inorganic acids, hydroxyl-containing organic acids, benzotriazole compounds, benzophenone compounds, triazine compounds, heterocyclic compounds, water-soluble metal salts, organic metal compounds, and metal complexes. Specific examples of these compounds include those disclosed in JP-A-10-182621, JP-A-2001-260519, JP-A-2000-260519, JP-B-4-34953, JP-B-4-34513, JP-B-4-34512, JP-A-11-170686, JP-A-60-67190, JP-A-7- 276808, JP-A-2000-94829, JP-T-8-512258, and JP-A-11-321090. Examples ofthe light-resistance improver include zinc sulfate, zinc oxide, hindered amine-based oxidation inhibitor, and benzotriazole-based ultraviolet absorber such as benzophenone. Particularly preferred among these light-resistance improvers is zinc sulfate. The surface active agent acts as a coating aid, releasability improver, slipperiness improver or antistat. For the details ofthe surface active agent, reference can be made to JP-A-62-173463 and JP-A-62-183457. An organic fluoro-compounds may be used instead ofthe surface active agent. The organic fluoro- compound is preferably hydrophobic. Examples ofthe organic fluoro-compound include fluorine-based surface active agents, oil-based fluorine compounds (e.g., fluorine-based oil), and solid fluorine-based compound resins (e.g., tetrafluoroethylene resin). For the details ofthe organic fluoro-compound, reference can be made to JP-B- 57-9053 (8th to 17th columns), JP-A-61-20994, and JP-A-62-135826. As the film hardener there may be used any of materials disclosed in JP-A-1-161236, page 222, JP-A-9- 263036, JP-A-10-119423, and JP-A-2001-310547. Other examples of additives to be incoφorated in the image-receiving layer include pigment dispersants, thickening agents, antifoaming agents, dyes, fluorescent brighteners, preservatives, pH adjustors, matting agents, and film hardeners. There may be provided one or two ink-receiving layers. The recording paper and recording film may comprise a back coat layer provided thereon. Examples of the components which can be incoφorated in the back coat layer include white pigments, aqueous binders, and other components. Examples ofthe white pigments to be incoφorated in the back coat layer include inorganic white pigments such as light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amoφhous silica, colloidal silica, colloidal alumina, pseudo- boehmite, aluminum hydroxide, alumina, lithopone, hydrated halloysite, magnesium carbonate and magnesium hydroxide, and organic pigments such as styrene-based plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin and melamine resin. Examples ofthe aqueous binder to be incoφorated in the back coat layer include water-soluble polymers such as styrene/maleate copolymer, styrene/acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationated starch, casein, gelatin, carboxymefhyl cellulose, hydroxyethyl cellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrenebutadiene latex and acryl emulsion. Examples of other components to be incoφorated in the back coat layer include antifoaming agents, foaming inhibitors, dyes, fluorescent brightening agents, preservatives, and wateφroofing agents. The layers (including back layer) constituting the ink et recording paper and film may comprise a fine dispersion of polymer incoφorated therein. The fine dispersion of polymer is used for the puφose of improving physical properties of film, e.g., stabilizing dimension, inhibiting curling, adhesion and film cracking. For the details ofthe fine dispersion of polymer, reference can be made to JP-A-62-245258, JP-A-62-1316648, and JP- A-62-110066. The incoφoration of a fine dispersion of polymer having a glass transition temperature as low as not higher than 40°C in a layer containing a mordant makes it possible to prevent the cracking or curling ofthe layer. The incoφoration of a fine dispersion of polymer having a high glass transition temperature, too, in the back layer makes it possible to prevent the curling ofthe back layer. [Inkjet recording] The volume ofthe droplet to be ejected onto the ink recording material ofthe invention is from not smaller than 0.1 pi to not greater than 100 pi, preferably from not smaller than 0.5 pi to not greater than 50 pi, particularly from not smaller than 2 pi to not greater than 50 pi. In the present invention, the inkjet recording method is not limited. The ink of the present invention may be used in any known recording method such as electrostatic control method which utilizes electrostatic attraction to eject ink, drop-on-demand method (pressure pulse method) utilizing vibrational pressure of piezoelectric element, acoustic inkjet method which comprises converting electrical signal to acoustic beam with which the ink is irradiated to produce a radiation pressme that is utilized to eject the ink and thermal inkjet (bubble jet (registered trademark)) method which comprises heating the ink to form bubbles that raise the pressure to eject the ink. Examples ofthe inkjet recording method include a method which comprises ejecting many portions of an ink having a low concentration called photoink in a small volume, a method which comprises using a plurality of inks having substantially the same hue but different densities to improve the image quality, and a method involving the use of a colorless transparent ink. The volume ofthe ink droplet to be ejected is controlled mainly by the print head. For example, in the thermal ink jet recording system, the volume of the ink droplet to be ejected can be controlled by the structure ofthe print head. In some detail, the ink droplet can be ejected in a desired size by properly changing the size ofthe ink chamber, heating zone and nozzle. Even in the thermal inkjet recording system, the ink droplet can be ejected in a plurality of sizes by using a plurality of print heads comprising heating zones and nozzles having different sizes. In the case of drop-on-demand system using a piezoelectric element, the volume ofthe ink droplet to be ejected can be varied due to the structure of the print head as in the thermal ink jet recording system. As described later, however, by controlling the waveform ofthe driving signal for driving the piezoelectric element, the ink droplet can be ejected in a plurality of sizes by the same structure of print head. In the invention, the frequency at which the ink droplet is ejected onto the recording material is not lower than 1 kHz. In order to record a high quality image as in photographic system, it is necessary that the ejection density be not smaller than 600 dpi (number of dots per inch) to reproduce an image having a high shaφness with small ink droplets. In the system involving the ejection ofthe ink droplet through a head having a plurality of nozzles, on the other hand, the number of heads which can be driven at the same time in a type of recording system involving the cross movement ofthe recording paper and the head is from scores to about 200. Even in a type having heads called line heads fixed therein, the number of heads which can be driven at the same time is limited to hundreds. This is because the driving electric power is limited or the heat generated on the head gives an adverse effect on the image thus formed, making it impossible to drive a large number of head nozzles at the same time. Therefore, the recording rate tends to be prolonged to raise the ejection density. By raising the driving frequency, the recording rate can be raised. The control over the ejection frequency in the case of thermal inkjet recording system can be accomplished by controlling the frequency ofthe head driving signal for heating the head. In the piezoelectric system, the control over the ejection frequency can be accomplished by controlling the frequency ofthe signal for driving the piezoelectric element. The driving of piezoelectric element will be described hereinafter. The image signal to be printed is made as follows. In some detail, the size of ink droplet to be ejected, the ejection rate and the ejection frequency are determined at the printer control. Thus, the signal for driving the print head is developed. The driving signal thus developed is then supplied into the print head. The size of ink droplet to be ejected, the ejection rate and the ejection frequency are controlled by the signal for driving the piezoelectric element. The size of ink droplet to be ejected and the ejection rate are determined by the shape and amplitude ofthe driving waveform and the ejection frequency is determined by the repetition frequency ofthe signal. When the ejection frequency is predetermined to 10 kHz, the head is driven every 100 microseconds. One line of recording is finished in 400 microseconds. By predetermining the moving rate ofthe recording paper such that it moves at a rate of 1/600 inch or about 42 micrometers per 400 microseconds, printing can be made at a rate of one sheet per 1.2 seconds. The configuration ofthe printing device using the ink for inkjet recording ofthe invention can be applied is preferably in an embodiment disclosed in JP-A-11-170527. The configuration ofthe ink cartridge to which the invention can be applied is preferably in an embodiment disclosed in JP-A-5-229133. The configuration ofthe suction system and the cap covering the print head 28 are preferably in an embodiment disclosed in JP-A-7-276671. It is preferred that a filter for evacuating bubbles as disclosed in JP-A-9-277552 be provided in the vicinity ofthe head. The surface ofthe nozzle is preferably subjected to water repellent treatment as disclosed in Japanese Patent No. 2001-016738. The invention may be used with a printer connected to computer. The invention may be used with an apparatus dedicated for printing photograph. The ink for inkjet recording ofthe invention is preferably ejected onto the recording material at an average rate of not smaller than 2 m/sec, preferably not smaller than 5 m/sec. The control over the ejection rate is accomplished by controlling the form and amplitude of the signal for driving the head. By using a plurality of driving waveforms properly, ink droplets having a plurality of sizes can be ejected by the same head. [Puφose of ink for inkjet recording] The ink for inkjet recording medium ofthe present invention may be used pmposes other than inkjet recording such as display image material, image-forming material for indoor decoration material, and image- forming material for outdoor decoration material. Examples ofthe display image material include various materials such as poster, wall paper, small decoration articles (ornament, doll, etc.), commercial flyer, wrapping paper, wrapping material, paper bag, vinyl bag, packaging material, signboard, picture drawn or attached to the side of traffic facilities (automobile, bus, train, etc.) and clothing with logogram. In the case where the dye ofthe invention is used as a material for forming a display image, the term "image" as used herein means an image in a narrow sense as well as all dye patterns perceivable by human being such as abstract design, letter and geometrical pattern. The term "indoor decoration material" as used herein is meant to include various materials such as wall paper, small decoration articles (ornament, doll, etc.), members of lighting fixture, members of furniture and design members of floor and ceiling. In the case where the dye ofthe invention is used as an image-forming material, the term "image" as used herein means an image in a narrow sense as well as all dye patterns perceivable by human being such as abstract design, letter and geometrical pattern. The term "outdoor decoration material" as used herein is meant to include various materials such as wall material, roofing material, signboard, gardening material, small outdoor decoration articles (ornament, doll, etc.) and members of outdoor lighting fixture. In the case where the dye ofthe invention is used as an image- forming material, the term "image" as used herein means an image in a narrow sense as well as all dye patterns perceivable by human being such as abstract design, letter and geometrical pattern. Examples ofthe media on which patterns are formed in these uses include various materials such as paper, fiber, cloth (including nonwoven cloth), plastic, metal and ceramics. Dyeing can be carried out by mordanting or printing. Alternatively, a dye can be fixed in the form of reactive dye having a reactive group incoφorated therein. Preferred among these dyeing methods is mordanting. (Example) The first embodiment ofthe invention will be further described in the following examples, but the invention is not construed as being limited thereto. (Example 1-1) To the following components was added ultrapure water having a resistivity of 18 MΩ or more to make 1 1. The mixture was then heated to a temperature of from 30°C to 40°C with stirring for 1 hour. Thereafter, the solution was filtered through a microfilter having an average pore diameter of 0.25 μm under reduced pressure to prepare various color ink solutions. [Formulation of light cyan ink] (Solid component) Cyan dye (C-l-1) shown below 20 g 1 Urea (UR) 15 g 1 Benzotriazole (BTZ) 0.08 g/1 PROXEL XL2 (PXL) 3.5 gΛ (Liquid component) Triethylene glycol (TEG) 110 gΛ Glycerin (GR) 130 g/1 Triethylene glycol monobutyl ether (TGB) 110 g/1 2-Pyrrolidone (PRD) 60 g/1 Triethanolamine (TEA) 7 g/1 Surfynol STG (SW) 10 g/1

[Formulation of cyan ink] (Solid component) Cyan dye (C-l-1) shown above 60 g/1 Urea (UR) 30 g/1 Benzotriazole (BTZ) 0.08 g/1 PROXEL XL2 (PXL) 3.5 g/1 (Liquid component) Triethylene glycol (TEG) 110 g/1 Glycerin (GR) 130 g/1 Triethylene glycol monobutyl ether (TGB) 130 g/1 2-Pyrrolidone (PRD) 60 g/1 Triethanolamine (TEA) 7 g/l Surfynol STG (SW) 10 g/1

[Formulation of light magenta ink] (Solid component) Cyan dye (C-l) shown below 7.5 gΛ Urea (UR) 10 gΛ PROXEL XL2 (PXL) 5 gΛ (Liquid component) Triethylene glycol (TEG) 90 gΛ Glycerin (GR) 70 g 1 Triethylene glycol monobutyl ether (TGB) 70 g 1 Triethanolamine (TEA) 6.9 g/1 Surfynol STG (SW) 10 g/1

[Formulation of magenta ink] (Solid component) Magenta dye (M-1) shown above 23 gΛ Urea (UR) 15 gΛ PROXEL XL2 (PXL) 5 g/1 (Liquid component) Diethylene glycol (DEG) 90 gΛ Glycerin (GR) 70 gΛ Triethylene glycol monobutyl ether (TGB) 70 g/1 Triethanolamine (TEA) 6.9 gΛ Surfynol STG (SW) 10 g/1

[Formulation of yellow ink] (Solid component) Yellow dyes (Y-l - Y-8)) shown below 35 gΛ PROXEL XL2 (PXL) 3.5 gΛ Benzotriazole 0.08 gΛ Urea 10 gΛ (Liquid component) Triethylene glycol monobutyl ether (TGB) 130 gΛ Glycerin (GR) 115 g 1 Diethylene glycol (DEG) 120 gΛ 2-Pynolidone (PRD) 35 g 1 Triethanolamine (TEA) 8 g/1 Surfynol STG (SW) 10 g/1

[Formulation of black ink] (Solid component) Black dye (Bk-1) shown below 75 g/1 Black dye (Bk-2) shown below 30 gΛ PROXEL XL2 (PXL) 5 gΛ Urea 10 gΛ Benzotriazole 3 g/1 (Liquid component) Diethylene glycol monobutyl ether (DGB) 120 g/1 Glycerin (GR) 125 g/1 Diethylene glycol (DEG) 100 gΛ 2-Pynolidone (PRD) 35 gΛ Triethanolamine (TEA) 8 gΛ Surfynol STG (SW) 10 g/1

An ink set comprising these inks was refened to as "IS-101". Ink sets IS-102 to 108 shown below were then prepared from the same inks except that the dye for yellow ink was changed to one according to the invention or other compounds.

Table 1-1

Y-1-5:Dye

Y-1-8: Dye

The aforementioned dyes ofthe invention were each measured for potential in the form of 1 mmolTl aqueous solution by dropping mercury electrode polarography. As a result, all these dyes showed a higher potential than 1.2 V/vsSCE. These inks were each packed in the ink cartridge of a Type PM-980C ink jet printer (produced by EPSON Co., Ltd.). Using this inkjet printer, a standard image pattern was printed in a 6-color mode. The image sheet used herein was prepared according to the following fonnulation. (Preparation of coating solution A for coloring material-receiving layer) The gas phase process particulate silica (1), the ion-exchanged water (2) and "PAS-M-1" (3) in the following formulation were mixed, and then subjected to dispersion at a rotary speed of 10,000 φm using KD-P (produced by SHINMARU ENTERPRISES CORPORATION) for 20 minutes. To the dispersion a solution of a polyvinyl alcohol (4), boric acid (5) and a polyoxyethylene lauryl ether (6) in ion-exchanged water (7). The mixture was then again subjected to dispersion at a rotary speed of 10,000 φm for 20 minutes to prepare a coating solution A for coloring material-receiving layer. The weight ratio (PB ratio = (1) : (4)) of particulate silica to water-soluble resin was 4.5 : 1. The pH value ofthe coating solution A for coloring material-receiving layer was 3.5, which is acidic. <Formulation of coating solution A for coloring material-receiving layer>

(1) Gas phase process particulate silica (inorganic particulate material) (Reolosil QS-30; average primary particle diameter: 7 nm; produced by TOKUYAMA CORP.) 10.0 parts

(2) Ion-exchanged water 51.7 parts

(3) "PAS-M-1" (60% aqueous solution) 0.83 parts (dispersant produced by Nitto Boseki Co., Ltd.)

(4) 8% Aqueous solution of polyvinyl alcohol 27.8 parts ("PVA124", produced by KURARAY CO., LTD.; saponification degree: 98.5%; polymerization degree: 2,400)

(5) Boric acid (crosslinking agent) 0.4 parts

(6) Polyoxyethylene lauryl ether (surface 1.2 parts active agent) ("Emulgen 109P; produced by Kao Coφ; 10% aqueous solution; HLB value: 13.6)

(7) Ion-exchanged water 33.0 parts

(Preparation of inkjet recording sheet) A 200-μm thick paper support laminated with a polyethylene was subjected to corona discharge treatment on one surface thereof. The coating solution A for coloring material-receiving layer obtained above was spread over the same surface ofthe support at a rate of 200 ml/m² (coating step), and then dried at 80°C in a hot air drier (wind velocity: 3 to 8 m/second) until the solid concentration ofthe coat layer reached 20%. The coat layer exhibited a constant drying rate. The coated support was immediately dipped in a mordant solution B having the following formulation for 30 seconds so that the mordant solution B was attached to the coat layer in an amount of 20 g/m² (step of providing a mordant solution), and then dried at 80°C for 10 minutes (drying step). In this manner, an inventive inkjet recording sheet R-l having a coloring material-receiving layer provided thereon to a dried thickness of 32 μm was prepared.

(1) Boric acid (crosslinking agent) 0.65 parts

(2) 10% Aqueous solution of polyallylamine "PAA-10C" (mordant produced by Nitto Boseki Co., Ltd.) 25 parts

(3) Ion-exchanged water 59.7 parts

(4) Ammonium chloride (surface pH adjustor) 0.8 parts

(5) Polyoxyethylene lauryl ether (surface 10 parts active agent) ("Emulgen 109P; produced by Kao Coφ; 2% aqueous solution; HLB value: 13.6)

(6) 10% Aqueous solution of Megafac "F1405" (fluorine-based surface active agent produced by DATNIPPON INK AND CHEMICALS, INCORPORATED) 2.0 parts Image-receiving papers R-2 and R-3 were prepared in the same manner as the inkjet recording sheet R- 1 except that the mordant polymer was changed from the polyarylamine to the inventive polymers P-1 and P-3, respectively.

<Evaluation of image bleeding> For the evaluation of image bleeding under high humidity conditions, the image sample printed on the image-receiving material was stored at 25°C and 90%RH for 7 days relative to the aforementioned standard image. Those showing bleeding of yellow dye on the white background were judged poor. Those showing no yellow bleeding were judged good. The results of evaluation are set forth in the table below.

Table 1-2

As can be seen in the table above, the samples according to the invention showed no dye bleeding. The second embodiment ofthe invention will be further described in the following examples, but the invention is not construed as being limited thereto. (Example 2-1) To the following components was added deionized water to make 1 liter. The mixture was then heated to a temperature of from 30°C to 40°C with stirring for 1 hour. Thereafter, the solution was adjusted with 10 ml/1 of KOH to pH 9, and then filtered through a microfilter having an average pore diameter of 0.25 μm under reduced pressure to prepare a light magenta ink solution. Magenta dye (a-36) ■ 8.2 g/L Diethylene glycol 43 g/L Urea 4 g L Glycerin 124 g L Triethylene glycol monobutyl ether 114 g/L 2-Pyrrolidone 3 g/L, Triethanolamine 3 g/L Benzotriazole 0.02 gΛL. PROXEL XL2 2 g L Surface active agent (w-1) 10 g L Further, the kind of dyes and additives were changed to prepare a magenta ink, a light cyan ink, a cyan ink, a yellow ink, a dark yellow ink and a black ink from which an ink set 101 set forth in Table 2-1 was then prepared. [Table 2-1]

Deionized water added to make 1 liter

C-2-1

Ink sets 102 to 107 were then prepared in the same manner as the ink set 101 except that the surface active agent, the water-miscible organic solvent and the dye were changed as set forth in Table 2-2.

W-1: (n-C₅H„)₂CHO(CH₂CH₂O)₁₀H Subsequently, these ink sets 101 to 107 were each packed in the cartridge of a Type PM920C inkjet printer (produced by EPSON CO., LTD.) by which an image was then printed on an inkjet paper photographic gloss paper produced by Fuji Photo Film Co., Ltd. and evaluated for the following properties.

1) For the evaluation of printing properties, the cartridge was mounted on the printer. The ejection of ink from all the nozzles was then confirmed. Thereafter, the nozzles were allowed to stand with their cap removed for 3 days. The nozzle check pattern was then printed. The number of times of cleaning required until no ejection was observed on the nozzle check pattern thus printed was then counted.

2) For the evaluation of image storage properties (light-fastness), a solid gray print image sample was prepared. The sample thus prepared was then evaluated as follows. The image density Ci ofthe image which had been just printed on the sample was measured using X-rite 310. The image was inadiated with xenon light (85,000 lux) for 7 days, and then again measured for image density Cf to determine percent remaining of dye (Cf/Ci x 100). The percent remaining of dye was evaluated at three initial reflection density points of 1, 1.5 and 2. Those showing a percent dye remaining of 85% or more at any density point were ranked A, those showing a percent dye remaining of less than 85% at two of these density points were ranked B, and those showing a percent dye remaining of less than 85% at all the density points were ranked C.

3) For the evaluation of ozone resistance, the sample was allowed to stand in a box having an ozone gas concentration predetermined to 5 ppm for 3 days. The image density before and after aging in the presence of ozone gas was measured using a reflection densitometer (X-Rite 310TR) to determine percent dye remaining which was then evaluated. The percent remaining of dye was evaluated at three initial reflection density points of 1, 1.5 and 2. Those showing a percent dye remaining of 80% or more at any density point were ranked A, those showing a percent dye remaining of less than 85% at two of these density points were ranked B, and those showing a percent dye remaining of less than 70% at all the density points were ranked C.

4) For the evaluation of percent bleeding, a neutral gray data comprising a white line having a width of 0.2 mm extending through the center of a 10 mm square prepared using an imaging software (Adobe Photoshop) was outputted to a color printer wliich then printed a gray image having a reflection density of 1.5 (neutral color according to CIE) using a plurality of color inks. The percent bleeding is represented by the following equation: % Bleeding = (DC - Db)/Da x 100 where Da represents the density ofthe gray image whiςh has been just printed; Db represents the density ofthe white line which has been just printed; and Dc represents the density of the white line which has been allowed to stand at 23 °C and 90%RH for 7 days shortly after printing. The density was measured using a microdensitometer. A percent bleeding of cyan, magenta, yellow and visual of gray image sites having a reflection density of 1.5. The results ofthe evaluations (1) to (4) are set forth in Table 2-3. [Table 2-3]

As can be seen in the results of Table 33, the ink sets comprising the ink compositions ofthe invention exhibit an excellent ejection stability and image fastness. Even when the image-receiving paper to be used in the invention was changed to PM photographic paper produced by EPSON Co., LTD. or PR101 (produced by Canon Inc.), the same effect as in the aforementioned results was exerted. [Example 2-2] The inks prepared in Example 2-1 were each packed in the cartridge of a Type BJ-F850 inkjet printer (produced by Canon Inc.). Using this inkjet printer, an image was then printed on an in jet photographic gloss paper EX produced by Fuji Photo Film Co., Ltd. The image thus printed was then evaluated in the same manner as in Example 2-1. The results thus obtained were similar to that of Example 2-1. Similar effects were exerted also with PM photographic paper produced by EPSON CO., LTD. or PR101 (produced by Canon Inc.). In accordance with the invention, an ink set for inkjet recording in the form of aqueous ink advantageous from the standpoint of handleability, odor, safety, etc. can be provided which exhibits a high ejection stability and can provide an image having an excellent weather resistance.

Industrial Applicability In accordance with the invention, an inkjet recording method can be provided which is little subject to image bleeding even under high humidity conditions. The invention can provide a recording method (preferably inkjet recording method) which exhibits a high ejection stability and gives an image having an excellent hue and little bleeding and thus can be expected to be widely spread for office use.

Claims

CLAIMS 1. An inkjet recording method comprising printing an image with an ink on an image-receiving material, according to an image data, so as to form an image, wherein the ink includes: an anionic dye; and at least one of water and a water-soluble organic solvent, and wherein the anionic dye has three or more hydrogen-bonding functional groups.

2. The inkjet recording method according to claim 1, wherein a printing surface ofthe image- receiving material contains a compound having four or more hydrogen-bonding functional groups.

3. The inkjet recording metliod according to claim 1 or 2, wherein a printing surface ofthe image- receiving material contains a mordant.

4. The inkjet recording method according to any one of claims 1 to 3, wherein as the anionic dye there is used at least one compound having an oxidation potential of more positive than 1.0 V.

5. The inkjet recording method according to any one of claims 1 to 4, wherein as the anionic dye there is used at least one ofthe compounds represented by the following general formulae (1-1) to (1-4): general formula (1-1): (A„-N=N-B„)_n-L wherein An and B each independently represents a heterocyclic group which may be substituted; n represents an integer 1 or 2; and L represents a substituent bonded to A or Bn at arbitrary position, with the proviso that when n is 1, L represents a hydrogen atom or monovalent substituent and when n is 2, L represents a mere bond or divalent connecting group; general formula (1-2):

wherein X21, X22, X23 and X₂₄ each independently represents -SO-Z2, -SO₂-Z2, -S0₂NR₂iR₂2, sulfo group, - CON ₂]R₂₂ or -COOR₂₁ in which Z₂'s each independently represents a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, aralkyl, aryl or heterocyclic group and R2₁ and R₂₂ each independently represents a hydrogen atom or substituted or unsubstituted alkyl, cycloalkyl, alkenyl, aralkyl, aryl or heterocyclic group; Y_2i, Y₂₂, Y2₃ and Y₂4 each independently represents a monovalent substituent;- a₂ι to a₂₄ andb₂ι tob₂ represent the number ofthe substituents X₂ι to X₂₄ and Y₂₁ to Y₂₄, respectively; a₂i to a₂₄ each independently represents a number of from 0 to 4 and at least one of a₂i to a₂₄ is not zero; b₂ι to b₂₄ each independently represents a number of from 0 to 4, with the proviso that when a₂ι to a₂4 and b ι to b₂₄ each represent a number of 2 or more, the plurality of X ι's to X₂₄'s and Y₂ι's to Y₂₄'s may be the same or different; and M represents a hydrogen atom, metal atom or oxide, hydroxide or halide thereof; general formula (1-3):

wherein A₃₁ represents a 5-membered heterocyclic group; B3₁ and B₃₂ each represents =CR₃ι- or -CR₃₂- or one of B₃ι and B₃₂ represents a nitrogen atom and the other represents =CR₃ι- or -CR₃₂=; R₃₅ and R₃₆ each independently represents a hydrogen atom or an aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group or sulfamoyl group which may further have substituents; G₃, R2₁ and R₃₂ each independently represents a hydrogen atom, a halogen atom or an aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including arylamino group and heterocyclic amino group), acylamino group, ureido group, sulfamonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfinyl group, arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group, sulfo group or heterocyclic thio group which may be further substituted; R₃j and R35 or R₃₅ and R3₆ may be connected to each other to form a 5- or 6-membered ring; and general formula (1-4):

wherein A_, , B₄ι and C₄₁ each independently represent an aromatic or heterocyclic group which may be substituted.

6. The inkjet recording method according to claim 5, wherein the anionic dye represented by the general formula (1-2) is one represented by the following general formula (1-5): general formula (1-5):

wherein X_5J to X₅₄, Y₅₁ to Ys₈ and Mi have the same meaning as X₂ι to X2₄, Y₂₁ to Y₂₄ and M in the general formula (1-2); and asi to as₄ each independently represents an integer of 1 or 2.

7. A recording method comprising ejecting ink drops onto a recording material according to a recording signal, the recording material comprising a support and an ink-receptive layer provided on the support, by using at least two color inks comprising a yellow ink and a magenta ink, so as to record an image on the recording material, wherein the percent bleeding of the recorded image is 30% or less.

8. The recording method according to claim 7, wherein, supposing that an gray image having a 10 mm square and a reflection density of 1.5 (neutral color according to CIE) is prepared using a plurality of color inks according to a neutral gray data outputted to a color printer, the gray image comprising a white line having a width of 0.2 mm extending through the center of the 10 mm square, the percent bleeding is represented by the following equation: % Bleeding = (DC - Db)Λ)a x 100 where Da represents a density ofthe gray image which has been just printed; Db represents a density ofthe white line which has been just printed; and Dc represents a density ofthe white line wliich has been allowed to stand at 23°C and 90%RH for 7 days shortly after printing.

9. The inkjet recording method according to claim 7 or 8, wherein the yellow and magenta inks each further comprise a surface active agent and the surface active agent is a betaine-based surface active agent.

10. The inkjet recording method according to any one of claims 7 to 9, wherein the betaine-based surface active agent is represented by the following general formula (2-1): (R)_p-N-|L-(COOM)_q]_r ... (2-1) wherein R represents a hydrogen atom, alkyl group, aryl group or heterocyclic group; L represents a divalent connecting group; M represents a hydrogen atom, alkaline metal atom, ammonium group, protonated organic amine, protonated nitrogen-containing heterocyclic group or quaternary ammonium ion, with the proviso that if one "COO" of at least one (COOM) group is a counter ion of ammonium ion formed by nitrogen atoms in the molecule represented by the general formula (2-1), conesponding M ofthe "COO" represents a group which does not exist as a cation; q represents an integer of 1 or more; r represents an integer of 1 or more and 4 or less; and p represents an integer of from 0 to 4, with the proviso that: the sum of p and r is 3 or 4; when the sum of p and r is 4, the nitrogen atom is a protonated ammonium atom (=N⁺=); when q is 2 or more, the plurality of COOM groups may be the same or different; when r is 2 or more, the plurality of [L-(COOM)_q] groups may be the same or different; and when p is 2 or more, the plurality of R's may be the same or different.

11. The recording method according to any one of claims 7 to 10, wherein the yellow and magenta inks each further contain a water-miscible organic solvent and the water-miscible organic solvent is selected from the group consisting of triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, tripropylene glycol monomethyl ether and dipropylene glycol monomethyl ether.

12. The recording method according to any one of claims 7 to 11, wherein at least one ofthe dyes is a dye having an oxidation potential of more positive than 1.0 V (vs SCE).

13. The recording method as defined in any one of claims 7 to 12, wherein the dye for yellow ink is a yellow dye represented by the following general formula (2-2): (Aιι-N=N-B_π)_n-L ... (2-2) wherein A and Bn each independently represents a heterocyclic group which may be substituted; n represents an integer 1 or 2; and L represents a hydrogen atom, mere bond or divalent connecting group, with the proviso that: when n is 1, L represents a hydrogen atom and both An and Bn are a monovalent heterocyclic group; and when n is 2, L represents a mere bond or divalent connecting group, one of An and Bn is a monovalent heterocyclic group and the other is a divalent connecting group, and two An's and Bn's each may be the same or different.

14. The recording method according to any one of claims 7 to 13, wherein the dye for magenta ink is a magenta dye represented by the following general formula (Ml) :

wherein A³¹ represents a 5-membered heterocyclic group; B³¹ and B³² represent =CR¹- and -CR²=, respectively, or one of B³¹ and B³² represents nitrogen atom and the other represents =CR¹- or -CR²=; R⁵ and R⁶ each independently represents a hydrogen atom or substituent; and G³¹, R¹ and R² each independently represents a hydrogen atom or substituent.

15. The recording method according to any one of claims 7 to 14, wherein the ink-receptive layer comprises an inorganic white particulate material.

16. The recording method according to any one of claims 7 to 15, which is adapted for inkjet recording.