JP4518728B2 - Ink set and inkjet recording method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ink set excellent in image fastness and an ink jet recording method using the ink set.
[0002]
[Prior art]
In recent years, a material for forming a color image has been mainly used as an image recording material. Specifically, an inkjet recording material, a thermal transfer type image recording material, a recording material using an electrophotographic system, a transfer type halogen, and the like. Silver halide photosensitive materials, printing inks, recording pens and the like are actively used.
In these color image recording materials, three primary colors (dyes and pigments) of the so-called subtractive color mixing method are used to reproduce or record a full color image, but it has an absorption characteristic that can realize a preferable color reproduction range. However, the fact is that there are no fast-moving dyes that can withstand various use conditions, and improvements are strongly desired.
The ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording.
[0003]
Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. There are a method of discharging bubbles, a method of generating bubbles in the ink by heat and discharging droplets, a method of using ultrasonic waves, and a method of sucking and discharging droplets by electrostatic force. As the ink for ink jet recording, water-based ink, oil-based ink, or solid (melted type) ink is used.
[0004]
For the colorant used in such ink for ink jet recording, the solvent has good solubility or dispersibility, high density recording is possible, hue is good, light, heat, environment Active gas (NO_xIn addition to oxidizing gases such as ozone, SO_xFastness to water and chemicals, good fixability to image-receiving materials, difficult to bleed, excellent storability as ink, and no toxicity Therefore, it is required to have high purity and to be available at low cost. However, it is extremely difficult to search for colorants that meet these requirements at a high level. Especially when printing on an image receiving material having a good three primary color hue and being robust to light, humidity and heat, especially having an ink receiving layer containing porous white inorganic pigment particles. The colorant is strongly desired to be robust against oxidizing gases such as ozone therein.
[0005]
Conventionally, as magenta dyes, azo dyes using phenol, naphthol, aniline or the like as a coupling component have been widely used. As azo dyes having good hues, there are known dyes disclosed in JP-A-11-209673, Tokuto No. 3020660 and the like, but have a problem that light fastness is inferior. As an improvement, a dye having a good hue and improved light fastness has been disclosed in JP-A No. 2001-335714. However, all of the dyes known in these patents are extremely insufficient in fastness to oxidizing gases such as ozone.
[0006]
Typical cyan dyes are phthalocyanine dyes and triphenylmethane dyes.
The most widely used phthalocyanine dyes are C.I. I. DirectBlue 86, 87, and 199, which are superior in light resistance compared to magenta and yellow dyes, are discolored by oxidizing gases such as nitrogen oxide gas and ozone, which are often taken up as environmental problems in recent years. And faint.
Up to now, as phthalocyanine dyes imparted with ozone gas resistance, JP-A-3-103484, JP-A-4-39365, JP-A-2000-30309, etc. have been disclosed. The improvement effect is extremely insufficient, and further improvement has been desired.
On the other hand, a triphenylmethane dye represented by Acid Blue 9 has a good hue, but is extremely inferior in light resistance and ozone gas resistance.
[0007]
As yellow dyes, azobenzene dyes represented by Direct Yellow 86 and 120, or heterocyclic azo dyes such as pyrazolone azo dyes and pyridone azo dyes such as Acid Yellow 17 have been used. Also, quinophthalone dyes are often proposed. However, among these conventionally known dyes, those having good hues, particularly long-wave tails in the absorption spectrum, such as quinophthalone dyes, are often not fast against ozone and light. The current situation is that there are no dyes that have both hue and fastness, such as being fast, but having a poor slash on the long wave side.
[0008]
In order to obtain a robust full color image having excellent color reproducibility, the following requirements are required for the dye constituting the image.
(1) Each primary dye has excellent absorption characteristics
(2) Optimal combination of the three primary color dyes to achieve a wide color gamut
(3) Each dye of the three primary colors has high fastness
(4) No deterioration of fastness due to dye interaction
(5) Balance of fastness of the three primary color dyes
However, fastness, particularly fastness to oxidizing gases such as ozone, which has become a major problem in ink jet printing these days, relates to the properties of dyes such as what structure or physical properties work effectively against ozone fastness. Since there are no reports, there is no guideline for dye selection. Furthermore, it becomes extremely difficult to select one that also has light fastness.
[0009]
[Problems to be solved by the invention]
The object of the present invention, which has been made in consideration of the above-mentioned drawbacks of the prior art, is to provide an improved guideline capable of drastically solving gas fading common to various dyes, and by using an ink composition based on the guideline, To provide an ink set for ink jet recording capable of forming an image excellent in gas fastness (especially ozone gas) fastness and light fastness, and further to provide an ink jet recording method using the ink set and a method for preventing discoloration of the ink jet recorded image. With the goal.
[0010]
[Means for Solving the Problems]
The present inventors have examined in detail a dye having a good hue, light fastness and gas fastness (especially ozone gas), and as a result of the combination of dyes having a specific oxidation potential not conventionally known, As a result, the present invention has been completed. That is, when the three primary color dyes satisfy such potential characteristics, the reactivity of each dye to ozone is greatly suppressed, and the light fastness is improved, and there is no interaction between different color dyes. It was found that there was no problem with the discoloration of the part. On the contrary, it was found that when a magenta dye or cyan dye that does not satisfy these potential conditions is used, the balance of the entire image is greatly lost and the quality of the full-color image is greatly deteriorated. Also, it has been found that there is no problem with the light fastness of light-colored inks even when using inks of different densities that have been used recently to improve color reproducibility. Furthermore, it has been found that the improved stability of the dye itself improves the oxidative stability of the ink and extends the warranty period as a product.
That is, the following are mentioned as a preferable aspect for solving the said subject.
[0011]
  <1> At least oneOxidation potential is nobler than 0.99V (vs SCE)A yellow ink containing a yellow dye, a magenta ink containing at least one magenta dye, and at least one kindCopper phthalocyanine dyeAn ink set having a cyan ink containing a cyan dye as a minimum component, wherein the oxidation potential of the magenta dye and the cyan dye is nobler than 0.8 V (vs SCE), and the oxidation potential of the magenta dye Is nobler than the oxidation potential of the cyan dye.The magenta dye is a compound represented by the following general formula (M-II), a compound represented by the following structural formula M-25, or a compound represented by the following structural formula M-26.An ink set characterized by that.
[0012]
[Chemical 1]
[0013]
  General formula (M-II)During, R ⁵And R⁶Each independently represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, or a sulfamoyl group, May have a substituent. R ¹And R²Each independently represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, an acyl group, Hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including heterocyclic amino group and anilino group), Acylamino, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkyl or arylsulfonylamino, heterocyclic sulfonylamino, nitro, alkyl or arylthio, alkyl or Arylsulfonyl group, heterocyclic sulfonyl group, an alkyl- or arylsulfinyl group, heterocyclic sulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group, and each group may be further substituted. R¹And R^FiveOr R^FiveAnd R⁶May combine to form a 5- or 6-membered ring.
  R ^Three , R ^Four Each independently represents a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl and arylsulfonyl group, or sulfamoyl group. Z ₁ Represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ₂ Represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
  In Structural Formulas M-25 and M-26, the numerical value in parentheses represents the oxidation potential of the dye.
<2> The ink set according to <1>, wherein the cyan dye is a dye represented by the following general formula (C-II).
[0014]
[Chemical 2]
[0015]
  In general formula (C-II), X₁₁, X₁₂, X₁₃And X₁₄Each independently represents an electron-withdrawing group having σp of 0.40 or more. Y₁₁~ Y₁₈Represents a hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, carboxyl group, and sulfo group. M is,copperoriginalChildTo express. a₁₁~ A₁₄Are each X₁₁~ X₁₄Represents the number of substituents. a₁₁~ A₁₄Each independently represents an integer of 0 to 4. Where a₁₁~ A₁₄Is the sum of 2 or more. If the dye is a water-soluble dye, X₁₁, X₁₂, X₁₃, X₁₄, Y₁₁, Y₁₂, Y₁₃, Y₁₄It has an ionic hydrophilic group as a substituent at any of the above positions.
<3> Above <1>Or<2The ink set for ink-jet recording according to the item 1, wherein at least magenta ink and cyan ink are composed of two or more types of inks having different densities.
<4> From <1> above <3>Any one ofA container containing the ink set for ink jet recording described in 1.
<5> On the image receiving material having an ink image receiving layer containing white inorganic pigment particles on the support, the above <1>To any one of <3>An ink jet recording method comprising forming an image using the ink set for ink jet recording described in 1.
<6> From <1> above <3>Any one ofA method for preventing discoloration of an ink jet recorded image, wherein ink jet recording is performed using the ink set described in 1.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
  The present invention is described in detail below.
[dye]
  In the present invention, a magenta dye and a cyan dye having an oxidation potential nobler than 0.8 V (vs SCE) are used.In the present invention, the magenta dye is a compound represented by general formula (M-II), a compound represented by structural formula (specific example) M-25, or a structural formula (specific example) M-. The cyan dye is a copper phthalocyanine dye.
  The oxidation potential is more preferable as it is noble, the oxidation potential is more noble than 1.0 V (vs SCE), more preferably noble than 1.1 V (vs SCE), and 1.15 V ( Those more noble than (vs SCE) are more preferred, and those nobler than 1.2 V (vs SCE) are most preferred.
[0017]
The value of the oxidation potential represents the ease of transfer of electrons from the sample to the electrode. The larger the value (the higher the oxidation potential), the less transfer of electrons from the sample to the electrode, in other words, less oxidation. Represent. In relation to the structure of the compound, the oxidation potential becomes more noble by introducing an electron withdrawing group, and the oxidation potential becomes lower by introducing an electron donating group.
[0018]
The value of the oxidation potential, which will be described in detail below, means the potential at which the compound is an anode in voltammetry and the electron of the compound is extracted, and is considered to approximately match the energy level of HOMO in the ground state of the compound. Yes.
[0019]
The inventors have studied the ozone fastness of the colored image. As a result, there is a correlation between the oxidation potential of the compound used in the colored image and the ozone fastness, and the oxidation potential value is higher than that of the saturated calomel electrode (SCE). It has been found that ozone fastness is improved by using noble compounds.
[0020]
The reason why the ozone fastness of the colored image is improved can be explained by the relationship between the HOMO (highest occupied orbit) and LUMO (lowest empty orbit) of the compound and ozone gas. That is, it is considered that the colorant is oxidized by the reaction of the colorant HOMO and the ozone gas LUMO, and as a result, the ozone fastness of the colored image is lowered. The reactivity with ozone gas may be lowered by lowering the HOMO.
[0021]
A person skilled in the art can easily measure the value (Eox) of the oxidation potential. Regarding this method, for example Delahay, “New Instrumental Methods in Electrochemistry” (1954 Interscience Publishers) and A.D. J. et al. “Electrochemical Methods” by Bard et al. (1980 John Wiley & Sons) and “Electrochemical Measurement Method” by Akira Fujishima et al. (1984, Gihodo Publishing Co., Ltd.).
[0022]
The measurement of the oxidation potential will be specifically described. The oxidation potential is 1 × 10 5 for the test sample in a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate.^-Four~ 1x10^-6mol · dm^-3Dissolve and measure as a value for SCE (saturated calomel electrode) using cyclic voltammetry or direct current polarography.
The supporting electrolyte and solvent to be used can be selected appropriately depending on the oxidation potential and solubility of the test sample. The supporting electrolytes and solvents that can be used are described in Akira Fujishima et al., “Electrochemical measurement method” (published by Gihodo Publishing Co., Ltd., 1984), pages 101 to 118.
[0023]
The value of the oxidation potential may be deviated by several tens of mil volts due to the influence of the inter-liquid potential difference or the liquid resistance of the sample solution, but the potential measured by calibrating with a standard sample (for example, hydroquinone). The reproducibility of the value of can be guaranteed.
[0024]
The oxidation potential in the present invention is 0.1 mol · dm.^-3In N, N-dimethylformamide containing 1 mol of tetrapropylammonium perchlorate as the supporting electrolyte^-3mol · dm^-3), SCE (saturated calomel electrode) as a reference electrode, a graphite electrode as a working electrode, and a platinum electrode as a counter electrode, and values measured by DC polarography are used.
[0025]
The dye used in the present invention may have any structure as long as it satisfies the above oxidation potential. In particular, yellow dyes have no structural restrictions because they have noble oxidation potential (low HOMO). The dye structure necessary for satisfying the oxidation potential will be described in detail below.
In the present invention, in order to lower the reactivity with ozone as an electrophile, it is desirable to introduce an electron withdrawing group into the dye skeleton to make the oxidation potential more noble. Therefore, using Hammett's substituent constant σp value, which is a measure of the electron withdrawing property and electron donating property of the substituent, the σp value is as in nitro, cyano, sulfinyl, sulfonyl, and sulfamoyl groups. It can be said that the oxidation potential can be made more noble by introducing a large substituent.
[0026]
Hammett's substituent constant σp value will be described briefly. Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo).
[0027]
In addition to the above-described substituents, the oxidation potential can be made noble as the number of atoms having high electronegativity generally increases as the constituent atoms of the chromophore. Therefore, for example, when an unsaturated heterocycle is used as a constituent of a chromophore rather than an aryl group, the oxidation potential can be made noble. Examples of the heteroatom having a high electronegativity include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom is particularly preferable.
[0028]
Accordingly, the dye used in the present invention is preferably one in which the chromophore is composed of a heteroatom, one containing an unsaturated heterocycle, or one containing an electron-withdrawing group.
Preferred chromophores composed of heteroatoms include azo dyes, azomethine dyes, phthalocyanine dyes and the like, with azo dyes being particularly preferred.
As the unsaturated heterocycle, a 5- or 6-membered unsaturated heterocycle is preferable, and a thiophene ring, furan ring, pyrrole ring, thiazole ring, oxazole ring, imidazole ring, isothiazole ring, isoxazole ring, pyrazole ring, thiadiazole ring And oxadiazole ring, triazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and the like. The unsaturated heterocycle may form a condensed ring with a hydrocarbon ring or a heterocycle. In the case of a nitrogen-containing heterocycle, the nitrogen atom may be quaternized. In addition, as for the heterocycle that can be tautomeric, even when only one tautomer is described, other tautomers are also included. Of these, preferred are a thiazole ring, an isothiazole ring, a pyrazole ring, a thiadiazole ring, a pyridine ring, a pyrimidine ring, and a pyrazine ring. Most preferred are an isothiazole ring, a pyrazole ring, a 1,2,4-thiadiazole ring, a 1,3,4-thiadiazole ring, and a pyridine ring.
[0029]
As a preferred electron-withdrawing substituent, a substituent having a Hammett's σp value of 0.40 or more is preferable, a substituent of 0.45 or more is more preferable, and a substituent of 0.50 or more is most preferable. Further, when a plurality of electron-withdrawing groups are present as substituents on the chromophore, the sum of the σp values of the substituents is preferably 0.50 or more, more preferably 0.60 or more, and 0.70 The above is most preferable. Specific examples of the electron-withdrawing group having σp of 0.40 or more are described in J. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (McGraw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo) .
[0030]
Preferred dyes of the present invention are combinations of those represented by the following general formula (I).
(Ch)-(EWG)_n        Formula (I)
In the general formula (I), Ch represents a chromophore containing an unsaturated heterocycle, and EWG represents an electron-withdrawing substituent having a σp value of 0.40 or more, which will be described later. n is an integer from 1 to 8.
Ch is an azo dye having an unsaturated heterocyclic ring as a chromophore, a phthalocyanine dye, an azomethine dye, a quinone dye (anthraquinone dye, anthrapyridone dye, etc.), a carbonium dye (triphenylmethane dye, xanthene dye, acridine dye, etc.), And chromophores of azine dyes (oxazine, thiazine, etc.). Preferred are azo dyes, phthalocyanine dyes, azomethine dyes, and anthrapyridone dyes having an unsaturated heterocyclic ring in the chromophore, and most preferred are azo dyes and phthalocyanine dyes having an unsaturated heterocyclic ring in the chromophore.
[0031]
Preferred azo dyes that can be used as magenta and yellow dyes are those represented by the following general formula (II).
Het (A) -N = N-Het (B) General formula (II)
In the general formula (II), Het (A) and Het (B) represent a 5- or 6-membered unsaturated heterocycle. Examples of unsaturated heterocycles represented by Het (A) and Het (B) include thiophene ring, furan ring, pyrrole ring, thiazole ring, oxazole ring, imidazole ring, isothiazole ring, isoxazole ring, pyrazole ring, Examples include a thiadiazole ring, an oxadiazole ring, a triazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring. These unsaturated heterocycles further have a substituent. When the substituents on the unsaturated heterocycle are bonded to each other, a condensed ring with a hydrocarbon ring or an unsaturated heterocycle may be formed, and further a substituent may be present on the condensed ring. In the case of a nitrogen-containing unsaturated heterocycle, the nitrogen atom may be quaternized. Moreover, about the unsaturated heterocycle which can become tautomerism, even when only one tautomer is described, other tautomers are also included.
When the dye is a water-soluble dye, it preferably has an ionic hydrophilic group as a substituent. Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group.
[0032]
The heterocyclic ring represented by Het (A) and Het (B) is preferably a thiazole ring, isothiazole ring, pyrazole ring, thiadiazole ring, pyridine ring or pyrazine ring. More preferably, they are an isothiazole ring, a pyrazole ring, a thiadiazole ring, and a pyridine ring. Most preferred are a pyrazole ring, a 1,2,4-thiadiazole ring and a pyridine ring.
[0033]
Het (A) and Het (B) may have a substituent. Substituents include halogen atoms, alkyl groups (including cycloalkyl groups), alkenyl groups (including cycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxy Carbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and Arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphono groups, phosphinyl groups, phosphinyloxy groups, Examples include a phosphinylamino group and a silyl group. Among them, halogen atom, heterocyclic group, cyano group, nitro group, carboxyl group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl Raising substituents such as groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, imide groups, phosphoryl groups, phosphono groups, phosphinoyl groups, phosphonyl groups, phosphinoyloxy groups, phosphinoylamino groups Among them, an electron-withdrawing group is preferable, and a substituent having σp of 0.40 or more is particularly preferable. Substituents with σp of 0.40 or more include cyano group, nitro group, carboxyl group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl Groups, imide groups, phosphono groups, phosphoryl groups, etc., alkyl groups substituted with electron-withdrawing groups (trihalomethyl groups, perfluoroalkyl groups, dicyanomethyl groups, iminomethyl groups, etc.), alkenyl substituted with electron-withdrawing groups Groups (such as tricyanovinyl groups) and quaternary salt substituents (sulfonium groups, ammonium groups, phosphonium groups) can also be mentioned. Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, an arylsulfonylaminocarbonyl group, and the like.
Moreover, when the substituents on the heterocycle are bonded to each other, a heterocycle and a condensed ring may be formed, and a substituent may be further provided on the condensed ring.
[0034]
Preferred magenta dyes are those represented by the general formula (M-I). In general formula (MI), A is a 5-membered heterocyclic diazo component A-NH.₂Represents the residue. B¹And B²Are each -CR¹= And -CR²= Or either one is a nitrogen atom and the other is -CR¹= Or -CR²=. R^FiveAnd R⁶Each independently represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, or a sulfamoyl group, It may have a substituent.
[0035]
G, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, an acyl group, Hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including heterocyclic amino group and anilino group), Acylamino, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkyl or arylsulfonylamino, heterocyclic sulfonylamino, nitro, alkyl or arylthio, alkyl or Arylsulfonyl group, heterocyclic sulfonyl group, an alkyl- or arylsulfinyl group, heterocyclic sulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group, and each group may be further substituted. R¹And R^FiveOr R^FiveAnd R⁶May combine to form a 5- or 6-membered ring.
[0036]
In the general formula (MI), A is a 5-membered heterocyclic diazo component A-NH.₂Represents the residue. Examples of heteroatoms for heterocycles include N, O, and S. A nitrogen-containing 5-membered heterocyclic ring is preferable, and an aliphatic ring, an aromatic ring or another heterocyclic ring may be condensed to the heterocyclic ring. Examples of preferred heterocyclic rings for A include pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazole ring, benzothiazole ring, benzoxazole ring, and benzoisothiazole ring. Each heterocyclic group may further have a substituent. Of these, the pyrazole ring, imidazole ring, isothiazole ring, thiadiazole ring and benzothiazole ring represented by the following general formulas (a) to (f) are preferable.
[0037]
[Chemical Formula 3]
[0038]
In the general formulas (a) to (f), R⁷To R²⁰Is G, R¹, R²It represents the same substituent as the substituent described in 1. Of the general formulas (a) to (f), preferred are the pyrazole ring and isothiazole ring represented by the general formulas (a) and (b), and the most preferred is represented by the general formula (a). It is a pyrazole ring.
[0039]
In the general formula (MI), B¹And B²Are each -CR¹= And -CR²= Or either one is a nitrogen atom and the other is -CR¹= Or -CR²=, But each -CR¹=, -CR²What represents = is more preferable.
[0040]
R^Five, R⁶Each independently represents a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or arylsulfonyl group, sulfamoyl group, and each group is further substituted. It may have a group. R^Five, R⁶Preferred examples of the substituent represented by can include a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkyl group, or an arylsulfonyl group. More preferred are a hydrogen atom, aromatic group, heterocyclic group, acyl group, alkyl or arylsulfonyl group. Most preferably, they are a hydrogen atom, an aryl group, and a heterocyclic group. Each group may further have a substituent. However, R^Five, R⁶Are not simultaneously hydrogen atoms.
[0041]
G, R¹And R²Are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, 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 (including anilino group and heterocyclic amino group) , Acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl and arylthio group, heterocyclic thio group, A Kill or arylsulfonyl group, heterocyclic sulfonyl group, an alkyl- or arylsulfinyl group, heterocyclic sulfinyl group, a sulfamoyl group, a sulfo group, each group may be further substituted.
[0042]
Examples of the substituent represented by G include a hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, amino group (anilino group, heterocyclic amino group). Group), an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl and arylthio group, or a heterocyclic thio group, more preferably a hydrogen atom, a halogen atom, An alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group (including an anilino group and a heterocyclic amino group) or an acylamino group, and among them, a hydrogen atom, an anilino group and an acylamino group are most preferable. Each group may further have a substituent.
[0043]
R¹, R²Preferred examples of the substituent represented by can include a hydrogen atom, an alkyl group, a halogen atom, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group, a hydroxy group, an alkoxy group, and a cyano group. Each group may further have a substituent. R¹And R^FiveOr R^FiveAnd R⁶May combine to form a 5- or 6-membered ring.
[0044]
A, R¹, R², R^Five, R⁶In the case where each substituent represented by G further has a substituent, the above-mentioned G, R¹, R²The substituents mentioned in the above can be mentioned.
[0045]
When the dye of the present invention is a water-soluble dye, A, R¹, R², R^Five, R⁶, G preferably further has an ionic hydrophilic group as a substituent at any position on G. Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. Examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic cation. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium).
[0046]
In this specification, an aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The aliphatic group may have a branch and may form a ring. The number of carbon atoms in the aliphatic group is preferably 1-20, and more preferably 1-16. The aryl part of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, particularly preferably phenyl. Examples of aliphatic groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl, cyclohexyl group, benzyl group, 2-phenethyl Groups, vinyl groups, and allyl groups.
[0047]
In the present specification, the aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably phenyl or naphthyl, particularly preferably phenyl. The number of carbon atoms in the aromatic group is preferably 6 to 20, and more preferably 6 to 16. Examples of the aromatic group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.
[0048]
The heterocyclic group includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent include aliphatic groups, halogen atoms, alkyl and arylsulfonyl groups, acyl groups, acylamino groups, sulfamoyl groups, carbamoyl groups, and ionic hydrophilic groups. Examples of the heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group and 2-furyl group.
[0049]
The alkyl and arylsulfonyl groups include substituted alkyl and arylsulfonyl groups, unsubstituted alkyl and arylsulfonyl groups. Examples of the alkyl and arylsulfonyl groups include a methylsulfonyl group and a phenylsulfonyl group, respectively.
[0050]
Alkyl and arylsulfinyl groups include substituted alkyl and arylsulfinyl groups, unsubstituted alkyl and arylsulfinyl groups. Examples of the alkyl and arylsulfinyl groups include a methylsulfinyl group and a phenylsulfinyl group, respectively.
[0051]
The acyl group includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.
[0052]
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
[0053]
The amino group includes an amino group substituted with an alkyl group, an aryl group or a heterocyclic group, and the alkyl group, aryl group and heterocyclic group may further have a substituent. As the alkylamino group, an alkylamino group having 1 to 20 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.
[0054]
The arylamino group includes an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 20 carbon atoms. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include a phenylamino group and a 2-chlorophenylamino group.
[0055]
The heterocyclic amino group includes a heterocyclic amino group having a substituent and an unsubstituted heterocyclic amino group. The heterocyclic amino group is preferably a heterocyclic amino group having 2 to 20 carbon atoms. Examples of the substituent include an alkyl group, a halogen atom, and an ionic hydrophilic group.
[0056]
The alkoxy group includes an alkoxy group having a substituent and an unsubstituted alkoxy group. As said alkoxy group, a C1-C20 alkoxy group is preferable. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.
[0057]
The aryloxy group includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.
[0058]
The silyloxy group is preferably a silyloxy group substituted with an aliphatic group or aromatic group having 1 to 20 carbon atoms. Examples of the silyloxy group include trimethylsilyloxy and diphenylmethylsilyloxy.
[0059]
The heterocyclic oxy group includes a heterocyclic oxy group having a substituent and an unsubstituted heterocyclic oxy group. The heterocyclic oxy group is preferably a heterocyclic oxy group having 2 to 20 carbon atoms. Examples of the substituent include an alkyl group, an alkoxy group, and an ionic hydrophilic group. Examples of the heterocyclic oxy group include a 3-pyridyloxy group and a 3-thienyloxy group.
[0060]
The alkoxycarbonyloxy group includes an alkoxycarbonyloxy group having a substituent and an unsubstituted alkoxycarbonyloxy group. The alkoxycarbonyloxy group is preferably an alkoxycarbonyloxy group having 2 to 20 carbon atoms. Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group and an isopropoxycarbonyloxy group.
[0061]
The aryloxycarbonyloxy group includes an aryloxycarbonyloxy group having a substituent and an unsubstituted aryloxycarbonyloxy group. The aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having 7 to 20 carbon atoms. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group.
[0062]
The acylamino group includes an acylamino group having a substituent and an unsubstituted acylamino group. The acylamino group is preferably an acylamino group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-disulfobenzoylamino group.
[0063]
The ureido group includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 20 carbon atoms. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.
[0064]
The sulfamoylamino group includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino group.
[0065]
The alkoxycarbonylamino group includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.
[0066]
The alkyl and arylsulfonylamino groups include substituted alkyl and arylsulfonylamino groups, and unsubstituted alkyl and arylsulfonylamino groups. The sulfonylamino group is preferably a sulfonylamino group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonylamino group include a methylsulfonylamino group, an N-phenyl-methylsulfonylamino group, a phenylsulfonylamino group, and a 3-carboxyphenylsulfonylamino group.
[0067]
The carbamoyl group includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.
[0068]
The sulfamoyl group includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.
[0069]
The alkoxycarbonyl group includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.
[0070]
The acyloxy group includes an acyloxy group having a substituent and an unsubstituted acyloxy group. The acyloxy group is preferably an acyloxy group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.
[0071]
The carbamoyloxy group includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.
[0072]
The aryloxycarbonyl group includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.
[0073]
The aryloxycarbonylamino group includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.
[0074]
The alkyl, aryl and heterocyclic thio groups include substituted alkyl, aryl and heterocyclic thio groups and unsubstituted alkyl, aryl and heterocyclic thio groups. The alkyl, aryl and heterocyclic thio groups are preferably those having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkyl, aryl and heterocyclic thio groups include a methylthio group, a phenylthio group, and a 2-pyridylthio group.
[0075]
The heterocyclic oxycarbonyl group includes a heterocyclic oxycarbonyl group having a substituent and an unsubstituted heterocyclic oxycarbonyl group. The heterocyclic oxycarbonyl group is preferably a heterocyclic oxycarbonyl group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic oxycarbonyl group include a 2-pyridyloxycarbonyl group.
[0076]
The heterocyclic sulfonylamino group includes a substituted heterocyclic sulfonylamino group and an unsubstituted heterocyclic sulfonylamino group. The heterocyclic sulfonylamino group is preferably a heterocyclic sulfonylamino group having 1 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfonylamino group include a 2-thiophenesulfonylamino group and a 3-pyridinesulfonylamino group.
[0077]
The heterocyclic sulfonyl group includes a heterocyclic sulfonyl group having a substituent and an unsubstituted heterocyclic sulfonyl group. The heterocyclic sulfonyl group is preferably a heterocyclic sulfonyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfonyl group include a 2-thiophenesulfonyl group and a 3-pyridinesulfonyl group.
[0078]
The heterocyclic sulfinyl group includes a heterocyclic sulfinyl group having a substituent and an unsubstituted heterocyclic sulfinyl group. The heterocyclic sulfinyl group is preferably a heterocyclic sulfinyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfinyl group include a 4-pyridinesulfinyl group.
[0079]
In the present invention, the dye represented by the general formula (M-I) is preferably a dye represented by the following general formula (M-II).
[0080]
[Formula 4]
[0081]
In general formula (M-II), Z₁Represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z₁Is preferably an electron-withdrawing group having a σp value of 0.30 or more, more preferably an electron-withdrawing group of 0.45 or more, and particularly preferably an electron-withdrawing group of 0.60 or more. It is desirable not to exceed. Specific examples of the preferred substituent include an electron-withdrawing substituent described later. Among them, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, An alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, and a halogenated alkyl group having 1 to 20 carbon atoms are preferable. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group.
[0082]
  R¹, R², R^Five, R⁶Is synonymous with the general formula (MI). R^Three, R^FourEach independently represents a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl and arylsulfonyl group, or sulfamoyl group. Of these, a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group is preferable, and a hydrogen atom, an aromatic group, and a heterocyclic group are particularly preferable. Z₂Represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Among them, Q is preferably a group consisting of a nonmetallic atom group necessary for forming a 5- to 8-membered ring. The 5- to 8-membered ring may be substituted, may be a saturated ring, or may have an unsaturated bond. Of these, aromatic groups and heterocyclic groups are particularly preferred. Preferred nonmetallic atoms include nitrogen atoms, oxygen atoms, sulfur atoms or carbon atoms. Specific examples of such a ring structure include, for example, a benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring. , Benzimidazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, oxane ring, sulfolane ring and thiane ring.ThisThe
[0083]
Each group described in formula (M-II) may further have a substituent. When each of these groups further has a substituent, examples of the substituent include the substituents described in the general formula (MI), G, R¹, R²And the groups exemplified in 1) and ionic hydrophilic groups.
[0084]
Hammett substituent constant σ_pExamples of the electron-withdrawing group having a value of 0.60 or more include a cyano group, a nitro group, and an alkylsulfonyl group (for example, a methanesulfonyl group and an arylsulfonyl group (for example, a benzenesulfonyl group)).
Hammett σ_pAs the electron-withdrawing group having a value of 0.45 or more, in addition to the above, an acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, m-chlorophenoxycarbonyl), An alkylsulfinyl group (for example, n-propylsulfinyl), an arylsulfinyl group (for example, phenylsulfinyl), a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), a halogenated alkyl group (for example, Trifluoromethyl).
Hammett substituent constant σ_pAs an electron-withdrawing group having a value of 0.30 or more, in addition to the above, an acyloxy group (for example, acetoxy), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), a halogenated alkoxy group (for example, , Trifluoromethyloxy), halogenated aryloxy group (eg, pentafluorophenyloxy), sulfonyloxy group (eg, methylsulfonyloxy group), halogenated alkylthio group (eg, difluoromethylthio), two or more σ_pAn aryl group substituted with an electron-withdrawing group having a value of 0.15 or more (for example, 2,4-dinitrophenyl, pentachlorophenyl) and a heterocycle (for example, 2-benzoxazolyl, 2-benzothiazolyl, 1- Phenyl-2-benzimidazolyl). Specific examples of the electron withdrawing group having a σp value of 0.20 or more include a halogen atom in addition to the above.
[0085]
A particularly preferred combination of substituents as the azo dye represented by the general formula (MI) is R^FiveAnd R⁶And preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group or an acyl group, more preferably a hydrogen atom, an aryl group, a heterocyclic group or a sulfonyl group, most preferably a hydrogen atom, An aryl group and a heterocyclic group. However, R^FiveAnd R⁶Are not hydrogen atoms.
[0086]
G is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an amino group or an acylamino group, more preferably a hydrogen atom, a halogen atom, an amino group or an acylamino group, most preferably a hydrogen atom or an amino group. An acylamino group.
[0087]
Among A, a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring, and a benzothiazole ring are preferable, a pyrazole ring and an isothiazole ring are further preferable, and a pyrazole ring is most preferable.
[0088]
B¹And B²Each -CR¹=, -CR²= Yes, R¹, R²Are each preferably a hydrogen atom, an alkyl group, a halogen atom, a cyano group, a carbamoyl group, a carboxyl group, a hydroxyl group, an alkoxy group or an alkoxycarbonyl group, more preferably a hydrogen atom, an alkyl group, a carboxyl group, a cyano group or a carbamoyl group. It is a group.
[0089]
Examples of preferable cyan dyes include dyes represented by the following general formula (CI).
[0090]
[Chemical formula 5]
[0091]
In the general formula (CI), X₁, X₂, X_ThreeAnd X_FourEach independently represents an electron-withdrawing group having σp of 0.40 or more. Y₁, Y₂, Y_ThreeAnd Y_FourEach independently represents a monovalent substituent. M represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof. a₁~ A_Four, B₁~ B_FourAre each X₁~ X_Four, And Y₁~ Y_FourRepresents the number of substituents. a₁~ A_FourEach independently represents an integer of 0 to 4;₁~ B_FourEach independently represents an integer of 0 to 4. Where a₁~ A_FourIs 2 or more, preferably 3 or more, particularly a₁= A₂= A_Three= A_Four= 1 is most preferred. If the dye is a water-soluble dye, X₁, X₂, X_Three, X_Four, Y₁, Y₂, Y_Three, Y_FourIt is preferable to further have an ionic hydrophilic group as a substituent at any of the above positions. Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group.
[0092]
Among the phthalocyanine dyes represented by the general formula (CI), a phthalocyanine dye having a structure represented by the general formula (C-II) is more preferable. The phthalocyanine dye represented by formula (C-II) of the present invention is described in detail below.
[0093]
  In the general formula (C-II), X₁₁~ X₁₄Are independently -SO-Z, -SO₂-Z, -SO₂NR₁R₂, Sulfo group, -CONR₁R₂Or -CO₂R₁Represents. Y₁₁~ Y₁₈Each independently represents a monovalent substituent.. MIs a hydrogen atom, metal atom or oxide, hydroxide or halide thereofIn the present invention, M is copper.originalThe child copper phthalocyanine dye is used. In the general formula (C-II),a₁₁~ A₁₄Is thatX ₁₁~ X₁₄And represents an integer of 1 or 2 independently.
  Z is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, substituted or unsubstituted Represents a heterocyclic group. R₁, R₂Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted Alternatively, it represents an unsubstituted heterocyclic group.
[0094]
In general formula (C-II), a₁₁~ A₁₄Each independently represents an integer of 1 or 2, particularly preferably 4 ≦ a₁₁+ A₁₂+ A₁₃+ A₁₄≦ 6, and among these, a is particularly preferable₁₁= A₁₂= A₁₃= A₁₄= 1.
[0095]
X₁₁, X₁₂, X₁₃And X₁₄Each may be exactly the same substituent or, for example, X₁₁, X₁₂, X₁₃And X₁₄Is all -SO₂-Z but each Z may be the same type of substituent, but may be partially different from each other, as in the case where each Z includes different ones.₂-Z and -SO₂NR₁R₂May contain different substituents as in the case of simultaneously substituted.
[0096]
Among the phthalocyanine dyes represented by the general formula (C-II), particularly preferred combinations of substituents are as follows.
[0097]
X₁₁~ X₁₄Are each independently -SO-Z, -SO₂-Z, -SO₂NR₁R₂Or -CONR₁R₂In particular, -SO₂-Z or -SO₂NR₁R₂Is preferred, -SO₂-Z is most preferred.
[0098]
Z is independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and most preferably a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group. . In particular, the case of having an asymmetric carbon in the substituent (use in a racemic form) is preferable because of increasing the solubility of the dye and the ink stability. In addition, for the reason of increasing the association property and improving the fastness, it is preferable that a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group have in the substituent.
[0099]
R₁, R₂Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group is preferable. A ring group is most preferred. However, it is not preferable that both R1 and R2 are hydrogen atoms. In particular, the case of having an asymmetric carbon in the substituent (use in a racemic form) is preferable because of increasing the solubility of the dye and the ink stability. In addition, for the reason of increasing the association property and improving the fastness, it is preferable that a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group have in the substituent.
[0100]
Y₁₁~ Y₁₈Is preferably a hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, carboxyl group, and sulfo group, particularly hydrogen. An atom, a halogen atom, a cyano group, a carboxyl group, and a sulfo group are preferable, and a hydrogen atom is most preferable. a₁₁~ A₁₄Are preferably each independently 1 or 2, particularly preferably all 1. M represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof, and Cu, Ni, Zn and Al are particularly preferable, and Cu is particularly preferable.
[0101]
When the phthalocyanine dye represented by the above (CI) or (C-II) is water-soluble, it preferably has an ionic hydrophilic group. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. Examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic cation. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, an alkali metal salt is preferable, and a lithium salt is particularly preferable because it increases the solubility of the dye and improves the ink stability.
As the number of ionic hydrophilic groups, those having at least two or more in one molecule of phthalocyanine dye are preferable, and those having at least two sulfo groups and / or carboxyl groups are particularly preferable.
[0102]
Regarding the preferred combination of substituents of the compound represented by the general formula (C-II), a compound in which at least one of various substituents is the above-mentioned preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.
[0103]
As the chemical structure of the phthalocyanine dye preferably used in the present invention, an electron-withdrawing group such as a sulfinyl group, a sulfonyl group, and a sulfamoyl group is substituted on each of the four benzene rings of phthalocyanine to replace the entire phthalocyanine skeleton. It is preferable to introduce the group so that the total σp value of the group is 1.6 or more.
[0104]
The phthalocyanine derivative represented by the general formula (CI) inevitably has different introduction positions and introduction numbers of the substituents Xn (n = 1 to 4) and Ym (m = 1 to 4) depending on the synthesis method. It is common to be analog mixtures, and therefore the general formula often represents a statistical average of these analog mixtures. In the present invention, it has been found that a specific mixture is particularly preferable when these analog mixtures are classified into the following three types. That is, the phthalocyanine dye analog mixture represented by the general formulas (CI) and (C-II) is defined by classifying into the following three types based on the substitution positions.
[0105]
(1) β-position substitution type: phthalocyanine dye having a specific substituent at the 2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and / or 15 position.
[0106]
(2) α-position substitution type: phthalocyanine dyes having specific substituents at 1 and / or 4 position, 5 and / or 8 position, 9 and / or 12 position, 13 and / or 16 position
[0107]
(3) α, β-position mixed substitution type: phthalocyanine dye having a specific substituent without regularity at positions 1 to 16
[0108]
In the present specification, when describing derivatives of phthalocyanine dyes having different structures (particularly, different substitution positions), the β-position substitution type, α-position substitution type, and α, β-position mixed substitution type are used. .
[0109]
Examples of the phthalocyanine derivatives used in the present invention include “Phthalocyanine—Chemistry and Function” (P. 1-62), C.I. C. Leznoff-A. B. P. Lever co-authored by VCH and published in 'Phthalogians-Properties and Applications' (P. 1-54), etc., can be synthesized by combining quoted or similar methods.
[0110]
The phthalocyanine compounds represented by the general formula (CI) of the present invention are described in World Patents 00/17275, 00/08103, 00/08101, 98/41853, and JP-A-10-36471. As shown, for example, it can be synthesized through sulfonation, sulfonyl chlorideation, and amidation reaction of an unsubstituted phthalocyanine compound. In this case, sulfonation can occur at any position of the phthalocyanine nucleus, and the number of sulfonation is difficult to control. Therefore, when a sulfo group is introduced under such reaction conditions, the position and number of the sulfo group introduced into the product cannot be specified, and a mixture in which the number of substituents and the substitution position are different is always given. Therefore, when synthesizing the compound of the present invention using it as a raw material, the number and substitution position of the heterocyclic substituted sulfamoyl group cannot be specified, so the compound of the present invention includes several types of compounds having different numbers of substituents and substitution positions. Α, β-position mixed substitution mixture.
[0111]
As described above, for example, when a large number of electron withdrawing groups such as sulfamoyl groups are introduced into the phthalocyanine nucleus, the oxidation potential becomes more noble and the ozone resistance is enhanced. According to the above synthesis method, it is inevitable that a small amount of electron-withdrawing groups are introduced, that is, a phthalocyanine dye having a lower oxidation potential is mixed. Therefore, in order to improve ozone resistance, it is more preferable to use a synthesis method that suppresses the formation of a compound having a lower oxidation potential.
[0112]
On the other hand, the phthalocyanine compound represented by the general formula (C-II) of the present invention is generally a phthalonitrile derivative (compound P) and / or a diiminoisoindoline derivative (compound Q) represented by the following formula, for example. It is obtained by reacting with a metal derivative represented by the formula (C-III). Alternatively, it can be derived from a tetrasulfophthalocyanine compound obtained by reacting a 4-sulfophthalic acid derivative (compound R) represented by the following formula and a metal derivative represented by the general formula (C-III).
[0113]
[Chemical 6]
[0114]
In the above formulas, Xp represents X in the general formula (C-II).₁, X₂, X_ThreeOr X_FourIt corresponds to. Yq and Yq ′ are each Y in the general formula (C-II).₁₁, Y₁₂, Y₁₃, Y₁₄, Y₁₅, Y₁₆, Y₁₇Or Y₁₈It corresponds to. In the compound R, M ′ represents a cation.
[0115]
Formula (C-III): M- (Y) d
In the general formula (C-III), M is the same as M in the general formula (C-II), and Y is monovalent or divalent coordination such as halogen atom, acetate anion, acetylacetonate, oxygen, etc. Child is shown, d is an integer of 1-4.
[0116]
That is, according to the above synthesis method, a specific number of desired substituents can be introduced. In particular, when it is desired to introduce a large number of electron withdrawing groups in order to make the oxidation potential noble as in the present invention, the above synthesis method is extremely superior to the synthesis method of the general formula (CI). It is.
[0117]
The phthalocyanine compound represented by the above general formula (C-II) thus obtained is usually a compound represented by the following general formula (a) -1 to (a) -4 which is an isomer at each substitution position of Xp. In the β-position substitution type.
[0118]
[Chemical 7]
[0119]
In the above synthesis method, if all the same Xp are used, X₁₁, X₁₂, X₁₃And X₁₄Β-substituted phthalocyanine dyes having the same substituent can be obtained. On the other hand, by using different combinations of Xp, it is possible to synthesize dyes having the same type of substituents but partially different from each other, or dyes having different types of substituents. . Among the dyes of the general formula (C-II), these dyes having different electron-withdrawing substituents are particularly preferable because they can adjust the solubility of the dye, the associability, the stability with time of the ink, and the like.
[0120]
In the present invention, it is found that it is very important to improve the fastness that the oxidation potential is noble than 0.8 V (vs SCE) in any substitution type. It was completely unpredictable from the prior art. Although the cause is unknown in detail, the β-position substitution type tends to be clearly superior in terms of hue, light fastness, ozone gas resistance, etc., than the α, β-position mixed substitution type. .
[0121]
The phthalocyanine dyes represented by the general formulas (C-I) and (C-II) can be synthesized according to the above-mentioned patents. Japanese Patent Application Nos. 2001-226275, 2001-96610, It can synthesize | combine by the method as described in 2001-47013 and 2001-193638. Further, the starting material, dye intermediate and synthetic route are not limited by these.
[0122]
The magenta dye and cyan dye used in the present invention are characterized in that the oxidation potential is nobler than 0.8 V. However, since phthalocyanine widely used as a cyan dye forms an aggregate, However, the magenta dye does not form an association even if it is somewhat lower, but it is preferable that the oxidation potential is set higher than that of the cyan dye in order to increase the fastness.
[0123]
Although the preferable example of the dye which can be used by this invention below is shown, these are for explaining this invention in detail, and this invention is not limited by these. The oxidation potential of the dye is shown in parentheses.
[0124]
First, specific examples [Y-1 to Y-35] of yellow dyes that can be used in the present invention are listed.
[0125]
[Chemical 8]
[0126]
[Chemical 9]
[0127]
[Chemical Formula 10]
[0128]
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[0129]
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[0130]
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[0131]
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[0132]
  next, MaSpecifics of Zenta dyeExampleI will give you.However, magenta dyes that can be used in the present invention are M-3 to M-26 among the following M-1 to M-26.
[0133]
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[0134]
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[0135]
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[0136]
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[0137]
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[0138]
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[0139]
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[0140]
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[0141]
Next, specific examples [C-1 to C-50] of cyan dyes that can be used in the present invention will be given.
[0142]
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[0143]
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[0144]
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[0145]
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[0146]
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[0147]
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[0148]
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[0149]
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[0150]
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[0151]
Other examples of compounds that can be applied to the present invention include Japanese Patent Application Nos. 2001-96610, 2001-24352, 2001-47013, 2001-57063, 2001-76689, 2001-193638, Although described also in 2001-15614, 2001-110457, and 2001-110335, it is not limited to these. In addition, each of the above compounds can be easily synthesized by the method described in the patents listed here.
[0152]
[Ink for inkjet recording]
The ink set for ink-jet recording of the present invention is composed of a yellow ink containing at least one yellow dye, a magenta ink containing at least one magenta dye, and a cyan ink containing at least one cyan dye. And The various dyes described above are used as the dye contained in each ink. Usually, each ink can be prepared by dissolving and / or dispersing a dye in a lipophilic medium or an aqueous medium. Preferably, an aqueous medium is used.
If necessary, other additives may be added within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are directly added to the ink liquid in the case of water-soluble ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.
[0153]
The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink-jet ink at the ink jet port of the nozzle used in the ink-jet recording method.
[0154]
The anti-drying agent is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said drying inhibitor may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by weight.
[0155]
The penetration enhancer is preferably used for the purpose of allowing ink jet ink to penetrate better into paper. Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants. it can. If these are contained in the ink in an amount of 5 to 30% by weight, they usually have a sufficient effect, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print-through).
[0156]
The ultraviolet absorber is used for the purpose of improving image storage stability. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492, 56-211141, Cinnamic acid compounds described in, for example, Kaihei 10-88106, JP-A-4-298503, 8-53427, 8-239368, 10-182621, JP-A-8- No. 501291, etc., triazine compounds, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.
[0157]
The anti-fading agent is used for the purpose of improving image storage stability. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, Nos. VII to I, J; 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in pages 127 to 137 of JP-A-62-215272 can be used.
[0158]
Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in an amount of 0.02 to 1.00% by weight in the ink.
[0159]
The neutralizer (organic base, inorganic alkali) can be used as the pH adjuster. For the purpose of improving the storage stability of the ink-jet ink, the pH adjuster is preferably added so that the ink-jet ink has a pH of 6 to 10 for summer, and more preferably pH 7 to 10.
[0160]
Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. The surface tension of the inkjet ink according to the present invention is preferably 25 to 70 mPa · s. Furthermore, 25-60 mN / m is preferable. The viscosity of the inkjet ink according to the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less. Examples of surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates. Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Further, JP-A-59-157,636, pages (37) to (38), Research Disclosure No. The surfactants described in 308119 (1989) can also be used.
[0161]
As the antifoaming agent, fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.
[0162]
In the case where the dye according to the present invention is oil-soluble, a method for dispersing in an aqueous medium may be a dye and oil as disclosed in JP-A-11-286637, JP-A-2001-267639, JP-A-2001-262039, JP-A-2001-247788 Colored fine particles containing a soluble polymer are dispersed in an aqueous medium, or dissolved in a high-boiling organic solvent as disclosed in JP-A-2001-262018, JP-A-2001-240763, JP-A-2001-335734, and Japanese Patent Application No. 2000-203857. It is preferred to disperse the dye in the invention in an aqueous medium. The specific method for dispersing the dye in the present invention in the aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount used thereof are preferably those described in the above patent. it can. Or you may disperse | distribute dye to a fine particle state with solid. At the time of dispersion, a dispersant or a surfactant can be used. Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high-pressure emulsification dispersion method (high-pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. In addition to the above-mentioned patents, the ink jet recording ink preparation method described above is disclosed in JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7-118584. Details are described in Japanese Laid-Open Patent Publication No. 11-286637 and Japanese Patent Application No. 2000-87539, and can also be used for preparing the ink for ink jet recording according to the present invention.
[0163]
As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohol (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol 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), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine) , Triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl- 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may use 2 or more types together.
[0164]
The ink used in the ink set of the present invention preferably contains 0.1 to 20 parts by weight of the dye with respect to 100 parts by weight of the ink. Further, yellow, magenta, and cyan inks may be used in combination with two or more dyes as long as the oxidation potential is nobler than 0.8V. When two or more kinds of dyes are used in combination, the total dye content is preferably within the above range.
In recent years, yellow, magenta, and cyan inks are often composed of two or more types of inks having different dye concentrations for the purpose of improving the image quality. In the present invention, the dyes used in the light and dark inks are all oxidized. It is desirable that the potential is nobler than 0.8V.
[0165]
In the present invention, when two or more kinds of different inks are used as the ink of the same hue, the density of the other kinds of ink is preferably 0.05 to 0.5 times the density of one kind of ink.
[0166]
The ink set of the present invention is used for forming a full-color image, but in order to adjust the color tone, a black color ink may be further used. Applicable black materials include disazo, trisazo, tetraazo dyes, and carbon black dispersions.
[0167]
[Inkjet recording method]
In the ink jet recording method of the present invention, energy is supplied to each ink in the ink set for ink jet recording of the present invention, and a known image receiving material, that is, plain paper, resin-coated paper, for example, JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153898, JP-A-10-217473. 10-235995, 10-337947, 10-217597, 10-337947, etc., inkjet paper, film, electrophotographic co-paper, fabric, glass, metal An image is formed on ceramics.
[0168]
When forming an image, a polymer latex compound may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing of applying the latex compound to the image receiving material may be before, after, or simultaneously with the application of the colorant, and therefore the addition location may be in the image receiving paper. It may be in ink or may be used as a liquid material of polymer latex alone. Specifically, the methods described in Japanese Patent Application Nos. 2000-363090, 2000-315231, 2000-354380, 2000-343944, and 2000-268952 can be preferably used.
[0169]
Hereinafter, a recording paper and a recording film used for ink jet printing using the ink of the present invention will be described. The support in recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMPMP, CGP, and waste paper pulp such as DIP. Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there. In addition to these supports, either synthetic paper or plastic film sheet may be used. The thickness of the support is 10 to 250 μm, and the basis weight is 10 to 250 g / m.²Is desirable. The support may be provided with an ink receiving layer and a backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar. In the present invention, as the support, paper and plastic films laminated on both sides with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. It is preferable to add a white pigment (for example, titanium oxide or zinc oxide) or a tinting dye (for example, cobalt blue, ultramarine blue, or neodymium oxide) to the polyolefin.
[0170]
The ink receiving layer provided on the support contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins, and melamine resins. As the white pigment contained in the ink receiving layer, porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either anhydrous silicic acid obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but it is particularly desirable to use hydrous silicic acid.
[0171]
Examples of the aqueous binder contained in the ink receiving layer include water-soluble polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivatives, and the like. Water-dispersible polymers such as water-soluble polymers, styrene butadiene latexes, and acrylic emulsions. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and resistance to peeling of the ink receiving layer.
The ink receiving layer can contain a mordant, a water resistance agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.
[0172]
The mordant added to the ink receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used.
For the polymer mordant, JP-A-48-28325, 54-74430, 54-124726, 55-22766, 55-142339, 60-23850, 60-23835, 60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122942, 60- No. 235134, JP-A-1-161236, U.S. Pat.Nos. 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, It is described in each specification of the same No. 4450224. An image receiving material containing a polymer mordant described in JP-A-1-161236, pages 212 to 215 is particularly preferred. When the polymer mordant described in the publication is used, an image with excellent image quality is obtained and the light resistance of the image is improved.
[0173]
The water-proofing agent is effective in making the image water-resistant. As these water-proofing agents, cationic resins are particularly desirable. Examples of such cationic resins include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, colloidal silica, etc. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably 1 to 15% by weight, particularly preferably 3 to 10% by weight, based on the total solid content of the ink receiving layer.
[0174]
Examples of the light fastness improver include zinc sulfate, zinc oxide, hindered amine-based antioxidants, benzophenone-based and benzotriazole-based ultraviolet absorbers, and the like. Of these, zinc sulfate is particularly preferred.
[0175]
The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. The surfactant is described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil), and a solid fluorine compound resin (for example, tetrafluoroethylene resin). The organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20994, and 62-135826. Examples of other additives added to the ink receiving layer include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusters, matting agents, and hardening agents. . The ink receiving layer may be one layer or two layers.
[0176]
The recording paper and the recording film can be provided with a back coat layer, and examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. White inorganic pigments such as diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide And organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin and melamine resin.
[0177]
As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.
[0178]
Polymer latex may be added to the constituent layers (including the backcoat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer latex is described in JP-A Nos. 62-245258, 62-136648, and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.
[0179]
In the ink jet recording method of the present invention, the ink jet recording method is not limited, and a known method, for example, a charge control method in which ink is ejected using electrostatic attraction, or a drop-on-demand method using vibration pressure of a piezo element. Method (pressure pulse method), acoustic ink method that converts electrical signals into acoustic beams, irradiates ink, and ejects ink using radiation pressure, and forms bubbles by heating ink and uses generated pressure It is used for thermal ink jet system. Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving the image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.
[0180]
[Method of preventing discoloration of inkjet recording image]
The method for preventing discoloration of an ink jet recorded image according to the present invention is performed by performing ink jet recording using the ink set of the present invention.
As described above, the ink set for ink-jet recording of the present invention has light fastness and gas (especially ozone gas) fastness because the oxidation potentials of the magenta dye and cyan dye are each nobler than 0.8 V (vs SCE). A high image can be obtained and fading of the image can be prevented.
[0181]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to these examples.
[Example 1]
(Preparation of water-based ink)
After adding deionized water to the following components to make 1 liter, the mixture was stirred for 1 hour while being heated at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with KOH 10 mol / L, and filtration under reduced pressure was performed using a microfilter having an average pore size of 0.25 μm to prepare an ink liquid for light magenta.
[0182]
[0183]
Further, magenta ink, light cyan ink, cyan ink, yellow ink, and black ink were adjusted by changing the dye species and additives, and ink set 101 having the density shown in Table 1 was produced.
[0184]
[Table 1]
[0185]
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[0186]
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[0187]
Next, the dye types of the light magenta, magenta, light cyan, cyan, and yellow inks of the ink set 101 were changed as shown in Table 2, and ink sets 102 to 112 were produced. When changing the dye, the dye concentration was adjusted so that the transmission density of each ink liquid was equivalent to that of the ink set 101 on the basis of equimolar replacement. Moreover, when using together dye, it used equimolar.
[0188]
[Table 2]
[0189]
(Image recording and evaluation)
The ink sets 101 to 112 were packed in a cartridge of an ink jet printer PM-770C (manufactured by Seiko Epson Corporation), images were printed on the ink jet paper PM photographic paper made by Seiko Epson Corporation using the same machine, and the following evaluation was performed. .
[0190]
<Print performance (1)>
After setting the cartridge in the printer and confirming the ejection of ink from all the nozzles, 50 sheets of A4 were output, and printing disturbance was evaluated.
A: No printing disturbance from the start to the end of printing.
B: Output with printing disturbance occurs.
C: Disturbance of printing from the start to the end of printing
<Print performance (2)>
After leaving the cartridge at 60 ° C. for 10 days, the printing disturbance was evaluated by the same method as in the printing performance (1).
[0191]
<Drying>
The stain when touched with a finger immediately after printing was visually evaluated.
<Thin lines blur>
A thin line pattern of yellow, magenta, cyan and black was printed and visually evaluated (1). For black, magenta ink was printed on a solid surface, black fine lines were printed, and evaluation of bleeding due to contact of two colors (2) was also performed.
<Water resistance>
The obtained image was immersed in deionized water for 5 seconds, and then bleeding of the image was visually evaluated.
<Image robustness>
For image fastness, a gray print sample was prepared and evaluated as follows.
(1. Light fastness: “Light resistance” is described in the table below)
Immediately after printing, the chromaticity (a * 1, b * 1) and lightness (L1) were measured with Gretag SPM100-II, and then irradiated with xenon light (85000 lux) using an Atlas weather meter for 7 days. After that, chromaticity (a * 2, b * 2) and lightness (L2) were measured again, and the color difference (ΔE) before and after the light irradiation was determined and evaluated according to the following formula (I).
For color differences, the reflection density is evaluated at three points of 1.0, 1.3, and 1.6, and when the color difference is less than 5 at any density, A includes both evaluations of less than 5 and 5 or more depending on the density. The case was B, and the case of 5 or more at all concentrations was C.
[0192]
(2. Heat fastness: The following table describes “heat resistance”)
The color difference before and after storing the sample for 6 days at 80 ° C. was evaluated by the same method as the light fastness. The residual ratio of dye is evaluated at three points of reflection density of 1.0, 1.3, and 1.6. A is a case where the color difference is less than 3 at any density, and both less than 3 and 3 or more are evaluated depending on the density. Was included, and C was defined as 3 or more at all concentrations.
(3. Ozone resistance)
The color difference before and after storing the sample for 7 days in a box where the ozone gas concentration was set to 0.5 ppm was evaluated by the same method as the light fastness. The residual ratio of dye is evaluated at three points of reflection density of 1.0, 1.3, and 1.6. When the color difference is less than 10 at any density, A, both less than 10 and 10 or more depending on the density Was included, and C was defined as 10 or more at all concentrations. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
As described above, all evaluation results in Example 1 are shown in Table 3 below.
[0193]
[Table 3]
[0194]
When the ink composition according to the present invention is used, it can be seen that the image fastness is particularly excellent. In addition, the ink composition according to the present invention has excellent ejection stability without clogging, has excellent bleeding performance, and has excellent water resistance.
In addition, even when the image receiving paper used in the present invention is changed to Fuji Photo Film's inkjet paper image photographic finish and Canon's PR101, the same effect as above can be seen.
[0195]
[Example 2]
The same ink prepared in Example 1 is packed in an ink jet printer BJ-F850 (Canon), and the image is printed on the ink jet paper color photo finish made by Fuji Photo Film, and the same evaluation as in Example is performed. As a result, the same result as in Example 1 was obtained. The same effect was observed when the image receiving paper was PM photo paper manufactured by Epson and PR101 manufactured by Canon.
[0196]
Example 3
Ink set 201 was prepared by changing light magenta, magenta, light cyan, cyan, and yellow from the ink set 101 of Example 1 to oil-soluble dye inks prepared by the following method.
8 g of dye (M-24), 60 g of a surfactant (product name: EMAL 20C), 6 g of high boiling organic solvent (S-1), 10 g of high boiling organic solvent (S-2), additive (A- 1) Dissolved in 70 g of 1.0 g and 50 mL of ethyl acetate. 500 mL of deionized water was added to this solution while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion.
Structural formulas of the high-boiling organic solvents (S-1) and (S-2) and the additive (A-1) are shown below.
[0197]
Embedded image
[0198]
Next, the coarse particle dispersion was passed through a microfluidizer (MICROFLUIDEXINC) at a pressure of 60 MPa for 5 times to make fine particles. Further, the resulting emulsion was removed with a rotary evaporator until the odor of ethyl acetate disappeared.
After adding additives such as diethylene glycol 140 g, glycerin 64 g, and urea to the fine emulsion of the hydrophobic dye obtained as described above, deionized water is added so that the total amount becomes 1 liter, and KOH The light magenta ink according to the density | concentration of Table 4 was created by adjusting pH = 9 at 10 mol / L. The volume average particle size of the obtained emulsified and dispersed ink was measured using Microtrac UPA (manufactured by Nikkiso Co., Ltd.) and found to be 40 nm.
Further, the kind and amount of the dye used, the amount of the high-boiling organic solvent, and the kinds and amounts of various additives were changed to prepare magenta ink, light cyan ink, cyan ink, and yellow ink of the ink set 201 shown in Table 4. Table 4 shows the composition of the final composition after evaporation of the solvent.
[0199]
[Table 4]
[0200]
For each ink, ink sets 202 to 209 were produced in the same manner as 201 except that the dye type was changed as shown in Table 5. When changing the dye, the dye concentration was adjusted so that the transmission density of each ink liquid was equivalent to that of the ink set 201, based on the fact that it was used by replacing it in equimolar amounts.
[0201]
[Table 5]
[0202]
(Image recording and evaluation)
Next, the ink sets 201 to 209 are packed in a cartridge of an ink jet printer PM-770C (manufactured by Seiko Epson Corp.), and images are printed on the Fuji Photo Film ink jet paper photo finish with the same machine, and the following evaluation is performed. It was.
[0203]
<Print performance (1)>
After setting the cartridge in the printer and confirming the ink ejection from all the nozzles, 30 sheets of A4 were output and the printing disturbance was evaluated.
A: No printing disturbance from the start to the end of printing.
B: Output with printing disturbance occurs.
C: Disturbance of printing from the start to the end of printing
<Print performance (2)>
After the cartridge was left at 60 ° C. for 2 days, printing disturbance was evaluated in the same manner as in the printing performance (1).
[0204]
<Drying>
The stain when touched with a finger immediately after printing was visually evaluated.
<Thin lines blur>
A thin line pattern of yellow, magenta, cyan and black was printed and visually evaluated (1). For black, magenta ink was printed on a solid surface, black fine lines were printed, and evaluation of bleeding due to contact of two colors (2) was also performed.
<Water resistance>
The obtained image was immersed in deionized water for 60 seconds, and then bleeding of the image was visually evaluated.
<Image robustness>
For image fastness, a gray print sample was prepared and evaluated as follows.
(1. Light fastness: “Light resistance” is described in the table below)
Immediately after printing, the chromaticity (a * 1, b * 1) and lightness (L1) were measured with Gretag SPM100-II and then irradiated with xenon light (85000 lux) using an Atlas weather meter for 14 days. After that, chromaticity (a * 2, b * 2) and lightness (L2) were measured again, and the color difference (ΔE) before and after the light irradiation was determined and evaluated according to the following formula (I).
For color differences, the reflection density is evaluated at three points of 1.0, 1.3, and 1.6, and when the color difference is less than 5 at any density, A includes both evaluations of less than 5 and 5 or more depending on the density. The case was B, and the case of 5 or more at all concentrations was C.
[0205]
(2. Heat fastness: The following table describes “heat resistance”)
The color difference before and after storing the sample for 6 days under the condition of 85 ° C. was evaluated by the same method as the light fastness. The residual ratio of dye is evaluated at three points of reflection density of 1.0, 1.3, and 1.6. A is a case where the color difference is less than 3 at any density, and both less than 3 and 3 or more are evaluated depending on the density. Was included, and C was defined as 3 or more at all concentrations.
(3. Ozone resistance)
The color difference before and after storing the sample for 7 days in a box where the ozone gas concentration was set to 1.0 ppm was evaluated by the same method as the light fastness. The residual ratio of dye is evaluated at three points of reflection density of 1.0, 1.3, and 1.6. When the color difference is less than 10 at any density, A, both less than 10 and 10 or more depending on the density Was included, and C was defined as 10 or more at all concentrations. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
All the evaluation results in Example 3 are shown in Table 6 below.
[0206]
[Table 6]
[0207]
When the ink composition according to the present invention is used as an oil-soluble dye dispersion, it can be seen that the image fastness is particularly excellent. In addition, the ink composition according to the present invention has excellent ejection stability without clogging, the performance when outputting fine lines is excellent without bleeding, and the water resistance is further improved.
Even when the image receiving paper used in the present invention is changed to Epson PM photographic paper or Canon PR101, the same effect as the above results can be seen.
[0208]
Example 4
The same ink prepared in Example 3 is packed in an ink jet printer BJ-F850 (Canon), and the image is printed on Fuji Photo Film ink jet paper color photo finish with the same machine, and the same evaluation as in Example is performed. As a result, the same results as in Example 3 were obtained. The same effect was observed when the image receiving paper was PM photo paper manufactured by Epson and PR101 manufactured by Canon.
[0209]
As demonstrated in the Examples, the ink jet recording liquid according to the present invention has excellent fastness, particularly light resistance and ozone resistance, and excellent ejection stability, water resistance and bleeding as an ink for ink jet recording.
[0210]
【The invention's effect】
The ink set for ink-jet recording of the present invention is excellent in light fastness because gas (especially ozone gas) fading is suppressed, and according to the ink jet recording method using this ink set, it is excellent in gas fastness and light fastness. A high image can be formed. Furthermore, according to the ink jet recording method of the present invention, the use of the ink set can effectively prevent image fading.

Claims (6)

A yellow ink containing a yellow dye having an oxidation potential no less than 0.99 V (vs SCE), a magenta ink containing at least one magenta dye, and cyan being at least one copper phthalocyanine dye An ink set having a cyan ink containing a dye as a minimum component, wherein the oxidation potential of the magenta dye and the cyan dye is nobler than 0.8 V (vs SCE), and the oxidation potential of the magenta dye is Ri noble der than the oxidation potential of the cyan dye, the compound wherein the magenta dye is represented by the following general formula (M-II), a compound represented by the following structural formula M-25, or the following structural formula M-26 ink set features a compound der Rukoto represented.
In general formula (M- II ) , R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or Represents an arylsulfonyl group or a sulfamoyl group, and each group may further have a substituent . R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, 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 (heterocyclic amino group, anilino Group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl or arylthio group Alkyl or arylsulfonyl group, heterocyclic sulfonyl group, an alkyl- or arylsulfinyl group, heterocyclic sulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group, and each group may be further substituted. R ¹ and R ⁵ , or R ⁵ and R ⁶ may combine to form a 5- or 6-membered ring.
R ³ and R ⁴ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl and arylsulfonyl group, or a sulfamoyl group. . Z ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ₂ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
In Structural Formulas M-25 and M-26, the numerical value in parentheses represents the oxidation potential of the dye. The ink set according to claim 1, wherein the cyan dye is a dye represented by the following general formula (C-II).
In the general formula (C-II), X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ each independently represents an electron-withdrawing group having σp of 0.40 or more. Y _{11 to} Y ₁₈ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a carboxyl group, and a sulfo group. Represents. M represents a copper atom. a ₁₁ ~a ₁₄ each represent the number of substituents of X ₁₁ to X _14. a ₁₁ ~a ₁₄ each independently represents an integer of 0-4. However the sum of a ₁₁ ~a ₁₄ is 2 or more. When the dye is a water-soluble dye, an ionic hydrophilic group is further added as a substituent at any position on X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , Y ₁₁ , Y ₁₂ , Y ₁₃ , Y _14. Have The ink set according to claim 1 or 2, wherein the magenta ink and the cyan ink are composed of two or more types of inks having different densities. A container in which the ink set according to any one of claims 1 to 3 is stored. An image is formed using the ink set according to any one of claims 1 to 3 on an image receiving material having an ink image receiving layer containing white inorganic pigment particles on a support. Recording method. An ink jet recording image fading prevention method, wherein ink jet recording is performed using the ink set according to any one of claims 1 to 3 .