JP2005264085A - Ink composition, ink for inkjet recording and inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition and ink for inkjet recording having good color reproducibility, high color density and excellent in light resistance and ozone resistance. <P>SOLUTION: The ink composition comprises at least two kinds of yellow dyes having 390-470 nm λmax and the difference between λmax of a dye in which λmax is positioned on the longest wave side and λmax of a dye in which λmax is the shortest wave side in these yellow dyes is ≥12 nm. The ink for inkjet recording comprises the ink composition. The fading rate constant of the dye in which λmax is positioned on the longest side is preferably ≤1×10<SP>-3</SP>[hour<SP>-1</SP>]. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an ink composition having good color reproducibility and excellent light resistance, and an ink for inkjet recording. The present invention also relates to an ink jet recording method for providing an image having good hue and excellent light resistance.

In recent years, with the spread of computers, inkjet printers are widely used for printing on paper, film, cloth and the like not only in offices but also at home.
Ink jet recording methods include a method of ejecting droplets by applying pressure with a piezo element, a method of ejecting droplets by generating bubbles in ink by heat, a method of using ultrasonic waves, or a droplet by electrostatic force. There is a method of sucking and discharging. As these inks for inkjet recording, water-based inks, oil-based inks, or solid (melting type) inks are used.

  For dyes used in these inkjet recording inks, high density recording is possible, hue is good, fastness to light, heat, air, water and chemicals is excellent, and recording The material (image receiving material) is required to have good fixability, excellent storage stability as an ink, no toxicity, high purity, and availability at low cost. However, it is extremely difficult to search for pigments that meet these requirements at a high level. In particular, a dye having a good yellow hue, excellent color reproducibility, high color density, and high fastness is strongly desired.

An ink having excellent color reproducibility, high color density, and high weather resistance against light, heat, and ozone is also desired.
For yellow ink, two or more kinds of yellow dyes are used in order to maintain a balance of ozone fading (see, for example, Patent Document 1). However, the level of ozone fading balance is insufficient, the color reproducibility is still insufficient, and improvement in light resistance is particularly desired.
JP 2003-238850 A

  An object of the present invention is to provide an ink composition and ink jet recording ink that have good color reproducibility, high color density, and excellent light resistance and ozone resistance. Another object of the present invention is to provide an ink jet recording method capable of obtaining an image having good hue and excellent light resistance and ozone resistance.

The problems of the present invention are solved by the following means.
(1) An ink composition containing at least two or more yellow dyes having a λmax of 390 to 470 nm, and the difference in λmax between the dye having the λmax of the longest wave side and the dye having the shortest wave side of the yellow dye An ink composition having a thickness of 12 nm or more.
(2) The absorbance ratio I (λmax + 70 nm) / I (λmax) between the absorbance I (λmax) at λmax and the absorbance I (λmax + 70 nm) at λmax + 70 nm of the mixture of the yellow dye is 0.20 or less. The ink composition as described in (1) above.
(3) In the above (1) or (2), the following fading rate constant of the dye having the longest wave side of λmax is 1 × 10 ⁻³ [hour ⁻¹ ] or less among the yellow dyes Ink composition.
Here, the fading rate constant of a dye is a value obtained by measuring the reflection density of a printed image through a status A filter after printing ink containing only one of the dyes on a reflective medium, and measuring the reflection density ( One point where D _B ) is 0.9 to 1.10 is defined as an initial density, and the image is forcibly faded by irradiating the image with 85000 Lux xenon light. The value obtained from the time t until the concentration reaches 70% of the initial concentration ((−ln 0.7) / t).
(4) The above (1) to (3), wherein in any two of the yellow dyes, λmax has a fading rate constant of a long wave side dye smaller than a fading rate constant of a short wave side dye The ink composition according to any one of the above.
(5) Any one of the above-mentioned (1) to (3), wherein in any two of the yellow dyes, λmax is higher in oxidation potential of the long-wave dye than in the short-wave dye An ink composition according to any one of the above.
(6) In any two of the yellow dyes, λmax is greater than Δλmax (sol) of the short-wave dye, and λmax is greater than Δλmax (sol) of the short-wave dye. The ink for inkjet recording according to any one of (3).
Here, Δλmax (sol) is the difference between λmax of the dye in the N, N-dimethylformamide solution and λmax of the dye in the aqueous solution (Δλmax (sol) = λmax (N, N-dimethylformamide solution). ) -Λmax (aqueous solution)).
(7) In any one of the yellow dyes, in any one of the above (1) to (6), a dye having a long wave side of λmax is represented by the following general formula (1) The ink composition as described.

In general formula (1), R ¹⁰ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group or an aryl group. Any of these groups may have a substituent. R ¹¹ and R ¹² each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a sulfo group or a heterocyclic group. Het represents an aromatic heterocyclic group.

  (8) In any one of the yellow dyes, the short-wave side dye is represented by the following general formula (2), according to any one of (1) to (7), Ink composition.

In the general formula (2), R ⁴ represents a monovalent group, R ⁵ represents —OR ⁶ or —NHR ⁷ , R ⁶ and R ⁷ represent a hydrogen atom or a monovalent group, and X ₃ represents 2 N3 represents 0 or 1, Ar ₃ represents an arylene group or a divalent heterocyclic group, and Ar ₄ represents an alkyl group, an aryl group, or a monovalent triazine ring group.

(9) An ink for inkjet recording comprising the ink composition according to any one of (1) to (8) above.
(10) An ink jet recording method using the ink for ink jet recording described in (9) above.

  According to the present invention, it is possible to provide an ink composition having good color reproducibility, high color density, and excellent light resistance and ozone resistance. By using the ink composition of the present invention, it is possible to obtain an image having a good hue and high weather resistance, particularly light resistance.

Hereinafter, the present invention will be described in detail.
In the ink composition of the present invention, at least two kinds of yellow dyes having an absorption maximum wavelength λmax of 390 to 470 nm are used, and among the yellow dyes, λmax is the λmax between the dye having the longest wave side and the dye having the shortest wave side. Is set to 12 nm or more. Thus, by using two or more kinds of yellow dyes having a difference in λmax, a yellow ink having a good color density can be obtained.
The λmax of the yellow dye is preferably 390 to 450 nm. The difference in λmax between the dye having λmax on the longest wave side and the dye on the shortest wave side is preferably 15 nm or more, more preferably 20 nm or more and 100 nm or less.

The two or more yellow dyes in the mixture state have an absorbance ratio I (λmax + 70 nm) / I (λmax) of absorbance I (λmax) at λmax and absorbance I (λmax + 70 nm) at λmax + 70 nm of 0.20 or less. It is preferable that It is preferable that the absorbance ratio is 0.20 or less because the tail on the long wave side is good in the absorption spectrum, and such a dye exhibits a better hue. The absorbance ratio I (λmax + 70 nm) / I (λmax) is more preferably 0.15 or less, and further preferably 0.10 or less.
The absorption maximum wavelength λmax and absorbance I (λ) are values in a solvent (water or ethyl acetate).

In the ink composition of the present invention, it is preferable that the discoloration rate constant of the dye having the longest wave side of λmax is 1 × 10 ⁻³ [hour ⁻¹ ] or less. Here, the fading rate constant of a dye is a value obtained by measuring the reflection density of a printed image through a status A filter after printing ink containing only one of the dyes on a reflective medium, and measuring the reflection density ( One point where D _B ) is 0.9 to 1.10 is defined as an initial density, and the image is forcibly faded by irradiating the image with 85000 Lux xenon light. It is a value ((−ln 0.7) / t) obtained from the time t until the concentration reaches 70% of the initial concentration. The smaller this value, the more excellent the light resistance.
The yellow dye with λmax on the long wave side tends to be less light-resistant than the short wave side. However, by setting λmax to 1 × 10 ⁻³ [hour ⁻¹ ] or less of the longest wave side dye, Light resistance can be improved. More preferably, it is 5 × 10 ⁻⁴ [hour ⁻¹ ] or less.

Furthermore, in the case of yellow dyes, the color of λmax with a long-wave side dye is more strongly perceived by human eyes because of its visual sensitivity, so the ink composition of the present invention reduces the hue change due to fading. In order to maintain good color reproducibility, it is preferable that any two of the yellow dyes satisfy at least one of the following conditions 1) to 3).
1) λmax is smaller than the fading rate constant of the long-wave side dye.
2) The acid value potential of the long wave side dye is higher than the acid value potential of the short wave side dye.
3) λmax is greater than Δλmax (sol) of the dye on the long wave side and Δλmax (sol) of the dye on the short wave side.
When three or more kinds of yellow dyes are included, it is particularly preferable that the longer wavelength side dye satisfies the above conditions 1) to 3) with respect to the shorter wavelength side dye.

  The value of the oxidation potential (Eox) can be easily measured by those skilled in the art. Regarding the measuring method, for example, P.I. Delahay's “New Instrumental Methods in Electrochemistry” (1954, published by Interscience Publishers) and A.D. J. et al. "Electrochemical Methods" by Bard et al. (1980, published by John Wiley & Sons), Akira Fujishima et al., "Electrochemical Measurement Method" (published by Gihodo Publishing Co., Ltd., 1984), and the like.

Specifically, the test sample is dissolved 1 × 10 ⁻² to 1 × 10 ⁻⁶ mol / liter in a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate. And it can measure as a value with respect to SCE (saturated calomel electrode) using cyclic voltammetry. Although this value may be deviated by several tens of mil volts due to the influence of the liquid potential difference or the liquid resistance of the sample solution, the reproducibility of the potential can be ensured by inserting a standard sample (for example, hydroquinone). In order to uniquely define the potential, in the present invention, a value measured in dimethylformamide containing 0.1 moldm ⁻³ of tetrapropylammonium perchlorate as a supporting electrolyte (the concentration of the dye is 0.001 moldm ⁻³ ). Let (vs SCE) be the oxidation potential of the dye.

  The value of Eox represents the ease of transfer of electrons from the sample to the electrode, and the greater the value (the higher the oxidation potential), the less transfer of electrons from the sample to the electrode, in other words, less oxidation. . 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. In the present invention, in order to lower the reactivity with ozone, which is an electrophile, it is desirable to introduce an electron withdrawing group into the yellow dye skeleton to make the oxidation potential more noble.

  The oxidation potential of the dye is preferably nobler than 1.0 V (vs SCE) and more nobly than 1.1 V (vs SCE) in terms of improving fastness, particularly fastness to ozone gas. More preferably, it is more preferable than 1.2 V (vs SCE). As the kind of dye, an azo dye satisfying the above physical property requirements is particularly preferable.

The Δλmax (sol) is the difference between the λmax of the dye in the N, N-dimethylformamide solution and the λmax of the dye in the aqueous solution (Δλmax (sol) = λmax (N, N-dimethylformamide solution). ) -Λmax (aqueous solution)). In the present invention, Δλmax (sol) is a value obtained from λmax measured at a dye concentration of 3 × 10 ⁻² g / l in each solution.

  As the yellow dye having such absorption characteristics and acid value potential, a dye represented by the following general formula (1) or general formula (2) is preferable. In particular, a dye represented by the following general formula (1) is preferable as the dye having λmax of the long wave side, and a dye represented by the following general formula (2) is preferable as the dye having the λmax of the short wave side.

In general formula (1), R ¹⁰ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group or an aryl group. Any of these groups may have a substituent. R ¹¹ and R ¹² each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a sulfo group or a heterocyclic group. Het represents an aromatic heterocyclic group.

In the general formula (2), R ⁴ represents a monovalent group, R ⁵ represents —OR ⁶ or —NHR ⁷ , R ⁶ and R ⁷ represent a hydrogen atom or a monovalent group, and X ₃ represents 2 N3 represents 0 or 1, Ar ₃ represents an arylene group or a divalent heterocyclic group, and Ar ₄ represents an alkyl group, an aryl group, or a monovalent triazine ring group.

Hereinafter, first, the general formula (1) will be described in detail.
The alkyl group represented by R ¹⁰ includes a substituted or unsubstituted alkyl group. The substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. As an example of a substituent, what is mentioned to the below-mentioned substituent group A is preferable. Of these, a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom, a sulfo group (which may be in a salt form) and a carboxyl group (which may be in a salt form) are preferable. Examples of alkyl groups include methyl, ethyl, butyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, hydroxyethyl, cyanoethyl and 4-sulfobutyl.

The cycloalkyl group represented by R ¹⁰ includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 5 to 30 carbon atoms. As an example of a substituent, what is mentioned to the below-mentioned substituent group A is preferable. Examples of cycloalkyl groups include cyclohexyl, cyclopentyl, and 4-n-dodecylcyclohexyl.

The aralkyl group represented by R ¹⁰ includes a substituted or unsubstituted aralkyl group. As the substituted or unsubstituted aralkyl group, an aralkyl group having 7 to 30 carbon atoms is preferable. As an example of a substituent, what is mentioned to the below-mentioned substituent group A is preferable. Examples of aralkyl groups include benzyl and 2-phenethyl.

The alkoxy group represented by R ¹⁰ includes a substituted or unsubstituted alkoxy group. As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. As an example of a substituent, what is mentioned to the below-mentioned substituent group A is preferable. Examples of alkoxy groups include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryl group represented by R ¹⁰ includes a substituted or unsubstituted aryl group. As the substituted or unsubstituted aryl group, an aryl group having 6 to 30 carbon atoms is preferable. As examples of the substituent, those listed in the following substituent group A are preferable.

(Ring group A)
Halogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic ring Oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfur Famoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or Arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a silyl group.

Each group listed in the substituent group A will be described in detail.
A halogen atom represents a chlorine atom, a bromine atom, an iodine atom, or the like.
The alkyl group, alkoxy group, cycloalkyl group and aralkyl group have the same meaning as in the case of R ¹⁰ described above.
An alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They include C2-C30 substituted or unsubstituted alkenyl groups such as vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl.
The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include ethynyl and propargyl.
Examples of the aryl group include substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, and o-hexadecanoylaminophenyl.
The heterocyclic group is a group obtained by removing a hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. Preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Examples include 2-furyl, 2-thienyl, 2-pyrimidinyl, and 2-benzothiazolyl.

Examples of the aryloxy group include substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, and 2-tetradecanoylaminophenoxy. It is done.
Examples of the silyloxy group include silyloxy groups having 3 to 20 carbon atoms, such as trimethylsilyloxy and t-butyldimethylsilyloxy.
Examples of the heterocyclic oxy group include substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms, such as 1-phenyltetrazole-5-oxy and 2-tetrahydropyranyloxy.
The acyloxy group is a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, Stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy may be mentioned.
The carbamoyloxy group is a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-. Examples include octylaminocarbonyloxy and Nn-octylcarbamoyloxy.
Examples of the alkoxycarbonyloxy group include substituted or unsubstituted alkoxycarbonyloxy groups having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, and n-octylcarbonyloxy.
Examples of the aryloxycarbonyloxy group include substituted or unsubstituted aryloxycarbonyloxy groups having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, and pn-hexadecyloxyphenoxycarbonyloxy. .

The amino group is a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino And diphenylamino.
The acylamino group is a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, Examples include lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino.
Examples of the aminocarbonylamino group include substituted or unsubstituted aminocarbonylamino groups having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, and morpholinocarbonylamino. .
The alkoxycarbonylamino group is a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonyl. Amino is mentioned.
Examples of the aryloxycarbonylamino group include substituted or unsubstituted aryloxycarbonylamino groups having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, and mn-octyloxyphenoxycarbonylamino.
Examples of the sulfamoylamino group include substituted or unsubstituted sulfamoylamino groups having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, and Nn-octylaminosulfonylamino. It is done.
The alkyl or arylsulfonylamino group is a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, Examples include phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, and p-methylphenylsulfonylamino.

Examples of the alkylthio group include substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, such as methylthio, ethylthio, and n-hexadecylthio.
Examples of the arylthio group include substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, and m-methoxyphenylthio.
The heterocyclic thio group includes a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio and 1-phenyltetrazol-5-ylthio.

The sulfamoyl group is a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetyl. Sulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl).
The alkyl or arylsulfinyl group is a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenyl. And sulfinyl.
The alkyl or arylsulfonyl group is a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenyl. And sulfonyl.

  The acyl group includes a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted to unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, and a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms. And a heterocyclic carbonyl group bonded to a carbonyl group, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl.

Examples of the aryloxycarbonyl group include substituted or unsubstituted aryloxycarbonyl groups having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, and pt-butylphenoxycarbonyl.
Examples of the alkoxycarbonyl group include substituted or unsubstituted alkoxycarbonyl groups having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, and n-octadecyloxycarbonyl.
The carbamoyl group is a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl). ) Carbamoyl.

Examples of the phosphino group include substituted or unsubstituted phosphino groups having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, and methylphenoxyphosphino.
Examples of the phosphinyl group include substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, and diethoxyphosphinyl.
Examples of the phosphinyloxy group include substituted or unsubstituted phosphinyloxy groups having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.
Examples of the phosphinylamino group include substituted or unsubstituted phosphinylamino groups having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino and dimethylaminophosphinylamino.
Examples of the silyl group include substituted or unsubstituted silyl groups having 3 to 30 carbon atoms, such as trimethylsilyl, t-butyldimethylsilyl, and phenyldimethylsilyl.

  Among the substituents mentioned in the above-mentioned ring group group A, those having a hydrogen atom may be removed and further substituted with groups mentioned in the above ring group group A. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. More specific examples include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

In general formula (1), the halogen atom, alkoxy group, and amino group represented by R ¹¹ and R ¹² have the same meanings as the groups listed in the above-mentioned ring group A.
The heterocyclic group represented by R ¹¹ and R ¹² is preferably a 5-membered or 6-membered ring, and they may be further condensed. Further, it may be an aromatic heterocyclic ring or a non-aromatic heterocyclic ring. For example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole , Thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, morpholine, piperidine and the like. Of these, aromatic heterocyclic groups are preferable, pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, and thiadiazole are preferable, and thiadiazole is most preferable. . They may have a substituent, and examples of the substituent are preferably those mentioned in the above-mentioned substituent group A.

In general formula (1), R ¹⁰ is preferably an alkyl group, R ¹¹ is preferably an amino group or a hydroxyl group, and R ¹² is preferably an amino group or a heterocyclic group.

In the general formula (1), Het represents an aromatic heterocyclic group, and preferred examples thereof include pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benz. Examples include isothiazole and thiadiazole, and pyrazole is particularly preferable. They may have a substituent, and examples of the substituent include those mentioned in the above-mentioned Substituent group A and arylazo groups or heterocyclic azo groups.
Here, examples of the arylazo group include the aryl groups mentioned in the above-mentioned Substituent group A, preferably azo groups having a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Examples of the heterocyclic azo group include the heterocyclic groups mentioned in the above-mentioned substituent group A, preferably azo groups having a 5- to 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.

  As Het, a group represented by the following general formula (a) is particularly preferable.

In general formula (a), one of X and Y is a nitrogen atom, and the other is —C (R ¹³ ) ═. More preferably, X is —C (R ¹³ ) and Y is a nitrogen atom. R ¹³ is a halogen atom, alkyl group, alkylthio group, alkylsulfonyl group, alkylsulfinyl group, alkoxycarbonyl, carbamoyl group, alkoxy group, aryl group, arylthio group, arylsulfonyl group, arylsulfinyl group, aryloxy group or acylamino group And each group is preferably those exemplified in the above-mentioned group A. R ¹³ is preferably a hydrogen atom, an alkyl group, an alkylthio group, or an aryl group.

  In the present invention, the dye represented by the general formula (1) is also preferably a dye represented by the following general formula (1-1).

In general formula (1-1), R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, or an aryl group. R ²³ represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a sulfo group or a heterocyclic group. Het represents an aromatic heterocyclic group.
A preferred group of each group, an optionally substituted group, and the like include R ¹⁰ of the general formula (1) for R ²¹ and R ²² , and R ¹¹ or R ¹² of the general formula (1) for R ^23. And Het has the same meaning as Het in the general formula (1).

  Specific examples of the dye represented by the general formula (1) are shown below, but the dye used in the present invention is not limited to the following examples. In specific examples, Me means methyl, Et means ethyl, and Ph means phenyl.

  The synthesis of the dye represented by the general formula (1) can be performed by a known method. For example, it is compoundable by the method of Unexamined-Japanese-Patent No. 2003-277661 and 2003-277661.

Next, the general formula (2) will be described in detail.
In the general formula (2), the monovalent group represented by R ⁴ is preferably those listed in the above-mentioned substituent group A. More preferably, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryl group, an amino group, a carboxyl group (may be a salt) or a carbamoyl group is preferable, and an alkyl group (preferably a lower alkyl having 1 to 5 carbon atoms) is preferable. Most preferred are groups such as methyl, ethyl, butyl, t-butyl).

R ⁵ represents —OR ⁶ or —NHR ⁷ , and R ⁶ and R ⁷ represent a hydrogen atom or a monovalent group. The monovalent group represented by R ⁶ and R ⁷ has the same meaning as the substituent group A described above.
X ₃ represents a divalent linking group, an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene), an alkenylene group (eg, ethenylene, propenylene), an alkynylene group (eg, ethynylene, propynylene), an arylene group ( Examples, phenylene, naphthylene), divalent heterocyclic groups (eg, 6-chloro-1,3,5-triazine-2,4-diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3- diyl group), - O -, - CO -, - NR- (R is a hydrogen atom, an alkyl group or an aryl group), - S -, - SO 2 -, - SO- or is preferably a combination thereof.
The alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, alkyl group or aryl group represented by R may have a substituent. Examples of the substituent include the group of the substituent group A described above. Moreover, the alkyl group and aryl group represented by R are synonymous with the alkyl group and aryl group of the above-mentioned substituent group A.
Examples of the divalent linking group represented by X ₃ include an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, and a divalent complex. More preferably, it is a cyclic group, —O—, —S—, or a combination thereof.
The total number of carbon atoms in the divalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

  n3 is 0 or 1, preferably 1.

Examples of the arylene group represented by Ar ₃ include an arylene group having 6 to 30 carbon atoms, preferably a phenylene group or a naphthalene group. These groups may further have a substituent, and as the substituent, those exemplified in the aforementioned substituent group A are preferable.
Examples of the divalent heterocyclic group represented by Ar ₃ include pyridine, pyrazine, pyrimidine, pyrazole, thiazole, benzothiazole and thiadiazole, preferably thiadiazole. These groups may further have a substituent, and as the substituent, those mentioned in the above-mentioned substituent group A are preferable.

As the alkyl group and aryl group represented by Ar ₄ , those exemplified in the aforementioned substituent group A are preferable. Ar ₄ is preferably a monovalent triazine ring group.

  Specific examples of the dye represented by the general formula (2) are shown below, but the dye used in the present invention is not limited to the following examples.

  The synthesis of the dye represented by the general formula (2) can be performed by a known method. For example, it is compoundable by the method of Unexamined-Japanese-Patent No. 2003-277661 and 2003-277661.

The ink composition of the present invention can be made into various inks by containing a medium. However, when a solvent is used as the medium, it is particularly suitable as an ink for ink jet recording.
The ink for ink jet recording of the present invention can be produced by using a lipophilic medium or an aqueous medium as a medium and dissolving and / or dispersing a dye therein. Preferably, an aqueous medium is used.
The ink for ink jet recording of the present invention may contain other additives as necessary 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, Known additives (described in JP-A No. 2003-306623) such as a foaming agent, a viscosity modifier, a dispersant, a dispersion stabilizer, a rust inhibitor, and a chelating agent can be used. 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.

When the dye used in the present invention is dispersed in an aqueous medium, the dye and the oil-soluble polymer are used as described in JP-A-11-286637, JP-A-2001-240763, JP-A-2001-262039, JP-A-2001-247788. Or dispersed in an aqueous medium or dissolved in a high-boiling organic solvent as in JP-A-2001-262018, JP-A-2001-240763, JP-A-2001-335734, JP-A-2002-80772 It is preferable to disperse the dye of the present invention in an aqueous medium.
The specific method for dispersing the dye used in the present invention in an 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-mentioned patent documents. can do. 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 patent documents, the method for preparing the ink for ink jet recording is described in JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, 7-118584, Details are described in JP-A Nos. 11-286637 and JP-A-2001-271003, and can also be used for preparing the ink for inkjet recording of the present invention.

  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 alcohols (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.

The ink for inkjet recording of the present invention preferably contains 0.1 to 20 parts by mass in total of two or more of the yellow dye in 100 parts by mass of ink, and is 0.2 to 10 parts by mass. More preferably, it is more preferably 0.5-9 parts by mass.
In addition to the yellow dye, other dyes may be used in combination with the inkjet recording ink of the present invention. Also when other dyes are used in combination, the total of the dye contents is preferably within the above range.

  The ink for ink jet recording used in the present invention is preferably used not only for forming a single color image but also for forming a full color image. In order to form a full color image, magenta ink, cyan ink, and yellow ink can be used, and in order to adjust the color tone, black ink may be further used.

  Examples of yellow dyes that can be used in these inks include phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, and open-chain active methylene compounds as coupling components (hereinafter also referred to as coupler components). Aryl or heteryl azo dyes having, for example, azomethine dyes having open-chain active methylene compounds as coupler components; methine dyes such as benzylidene dyes or monomethine oxonol dyes; for example, naphthoquinone dyes, anthraquinone dyes, etc. Such quinone dyes can be selected, and other dye species can be selected from quinophthalone dyes, nitro / nitroso dyes, acridine dyes, acridinone dyes and the like.

  Examples of magenta dyes include aryl or heteryl azo dyes having, for example, phenols, naphthols, anilines as coupler components; azomethine dyes having, for example, pyrazolones, pyrazolotriazoles, etc. as coupler components; for example arylidene dyes, styryl dyes, merocyanine Methine dyes such as dyes, cyanine dyes, oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., such as dioxazine dyes Examples thereof include condensed polycyclic dyes.

  Examples of cyan dyes include aryl or heteryl azo dyes having, for example, phenols, naphthols, and anilines as coupler components; for example, azomethine dyes having phenols, naphthols, and heterocyclic rings such as pyrrolotriazole as coupler components; Examples thereof include polymethine dyes such as dyes, oxonol dyes and merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; phthalocyanine dyes; anthraquinone dyes;

  Examples of black dyes include disazo, trisazo, and tetraazo dyes, and carbon black dispersions.

  The ink for ink jet recording of the present invention is recorded on a recording material. Known image receiving materials as recording materials, that is, plain paper, resin-coated paper, for example, JP-A-8-169172, 8-27693, 2-276670, 7-276789, 9 -323475, JP-A-62-238783, JP-A-10-153899, JP-A-10-217473, JP-A-10-235995, JP-A-10-337947, and JP-A-10-217597, Examples thereof include ink jet exclusive paper, film, electrophotographic co-paper, cloth, glass, metal, ceramics, and the like described in JP-A-10-337947. As the ink jet recording method of the present invention, the description in paragraph numbers 0093 to 0105 of JP-A No. 2003-306623 can be applied.

  When forming an image, a polymer latex compound may be added to the recording material for the purpose of giving glossiness or water resistance or improving weather resistance. The timing of applying the latex compound to the recording material may be before, after or at the same time as adding the colorant. Alternatively, it may be in ink, or may be used as a liquid material of polymer latex alone. Specifically, JP 2002-166638, JP 2002-121440, JP 2002-154201, JP 2002-144696, JP 2002-080759, JP 2002-187342, JP 2002 The method described in each publication of Japanese Patent No. 172774 can be preferably used.

Hereinafter, recording paper and recording film will be described as typical image receiving materials that can be used in the present invention. 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, and the thickness of the support is preferably 10 to 250 μm and the basis weight is preferably 10 to 250 g / m ² . 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.

  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.

  The ink jet recording method of the present invention is not limited to the ink jet recording method, and is a known method, for example, a charge control method for ejecting ink using electrostatic attraction, or a drop-on-demand method using vibration pressure of a piezo element. (Pressure pulse method), acoustic ink jet method that converts electrical signals into acoustic beams, irradiates ink, and discharges ink using radiation pressure, and heats the ink to form bubbles and uses the generated pressure 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 image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

  After adding ultrapure water (resistance value 18 MΩ or more) to the following components to make 1 liter, the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, the mixture was filtered under reduced pressure through a microfilter having an average pore diameter of 0.25 μm to prepare yellow ink Y-101.

[Yellow ink Y-101 prescription]
(Solid content)
Yellow dye (Y-1 / Y-2 / Y-3 = 10/20/20; mass ratio) 50g / l
Proxel 2g / l
Urea 10g / l
(Liquid component)
Triethylene glycol monobutyl ether 100g / l
Glycerin 100g / l
Triethylene glycol 100g / l
2-pyrrolidone 20g / l
Triethanolamine 2g / l
Surfynol 465 (AirProducts & Chemical) 10g / l

Similarly to Y-101, yellow inks Y-102 to 107 using the yellow dyes shown in Table 1 were produced in the same manner. The ratio and amount of yellow dye were adjusted to match the yellow density of Y-101.
The speed constant (fading speed constant) of each yellow dye shown in Table 1 is the same as that of the Xenon Weather-Ometer “ATLAS” for the ink prepared by using each yellow dye alone in the Y-101 formulation. It is a value measured using “Ci4000” (manufactured by TOYO SEIKI). Δλmax is the difference in λmax between the longest wave side dye and the short wave side dye.

  Further, a PM-950C yellow ink cartridge manufactured by Epson Corporation was used as an ink comparison type.

These inks are loaded into the yellow ink cartridge of the EPSON Inkjet Printer PM-950C, and other color inks are used with the PM-950C ink. The image pattern was printed.
The image-receiving sheet was printed on an inkjet paper photo glossy paper “Image” manufactured by Fuji Photo Film Co., Ltd., and the image quality, ink ejection properties, image storage stability (weather resistance), and image bleeding were evaluated.

(Evaluation experiment)
1) About discharge stability, after setting a cartridge in a printer and confirming the protrusion of the ink from all the nozzles, 20 sheets of A4 were output and evaluated according to the following criteria.
A: No printing disturbance from the start to the end of printing,
B: Output with printing disturbance occurs.
C: Print disorder from start to finish.
This experiment was performed immediately after ink filling (ejection performance A) and after the ink cartridge was stored at 40 ° C. and 80% RH for 2 weeks (ejection performance B).

2) Regarding the image storage stability, the following evaluation was performed using print samples.
(i) Light fastness is determined by measuring the image density Ci immediately after printing with X-Rite 310, irradiating the image with xenon light (85,000 lux) for 10 days using a weather meter manufactured by Atlas, and then re-image The density Cf was measured and the dye residual ratio Cf / Ci × 100 was determined and evaluated. The afterimage rate of the dye is evaluated at three points of reflection density of 1, 1.5, and 2. A is the case where the dye remaining rate is 70% or more at any concentration, and B is the case where the reflection rate is less than 70%. When the concentration was less than 70%, C was designated.

  (ii) About heat fastness, the density | concentration before and behind storing a sample for 10 days on 80 degreeC70% RH conditions was measured by X-Rite310, and the dye residual rate was calculated | required and evaluated. The afterimage rate of the dye is evaluated at three points of reflection density of 1, 1.5, and 2. A is the case where the dye residual rate is 90% or more at any concentration, and B is the case where the reflection point is less than 90%. The concentration of less than 90% was defined as C.

(iii) For ozone resistance, the photo glossy paper on which the image has been formed is left in a box where the ozone gas concentration is set to 0.5 ppm for 7 days, and the image density before and after being left under ozone gas is measured by a reflection densitometer (X -Rite310TR), and evaluated as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
The evaluation was made in three stages, with A being a dye residual ratio of 80% or higher at any concentration, A being 1 or 2 points being less than 80% B, and C being less than 70% at all concentrations.

  3) For blurring of the image, a yellow 3 cm × 3 cn square pattern was prepared in which a 4 mm square pattern was formed so as to form a 1 mm white space, and this image sample was obtained at 25 ° C. After storage for 72 hours under the condition of 90% RH, an increase in density due to yellow dye bleeding in the white space was observed. In the yellow filter of status A, the yellow density increase of the white background immediately after printing was set to A when 0.01 or less, B as 0.01 to 0.05, and C as 0.05 or more.

Apart from these evaluations, the color tone of the image was visually evaluated using a test image chart of ISO / JIS 12640. Those with good color tone were marked with ◯, and those with better color were marked with ◎.
The above evaluation results are shown in Table 2.

  As shown in Table 2, it was found that the system using the ink of the present invention was excellent in all performance, and particularly superior in light fastness and light resistance to the comparative example. Further, the ink of the present invention has a high color density and a small amount of dye.

Claims (10)

  An ink composition containing at least two or more yellow dyes having a λmax of 390 to 470 nm, wherein a difference in λmax between a dye having the λmax of the longest wave side and a dye having the shortest wave side of the yellow dye is 12 nm or more An ink composition characterized by the above.   The absorbance ratio I (λmax + 70 nm) / I (λmax) between the absorbance I (λmax) at λmax and the absorbance I (λmax + 70 nm) at λmax + 70 nm of the mixture of yellow dyes is 0.20 or less. Item 2. The ink composition according to Item 1. 3. The ink composition according to claim 1, wherein the yellowing dye has the following fading rate constant of 1 × 10 ⁻³ [hour ⁻¹ ] or less for a dye having λmax having the longest wavelength side.
Here, the fading rate constant of a dye is a value obtained by measuring the reflection density of a printed image through a status A filter after printing ink containing only one of the dyes on a reflective medium, and measuring the reflection density ( One point where D _B ) is 0.9 to 1.10 is defined as an initial density, and the image is forcibly faded by irradiating the image with 85000 Lux xenon light. It is a value ((−ln 0.7) / t) obtained from the time t until the concentration reaches 70% of the initial concentration.   4. The dye according to claim 1, wherein in any two of the yellow dyes, λmax has a fading rate constant of a long-wave side dye smaller than a fading rate constant of a short-wave side dye. Ink composition.   4. The ink composition according to claim 1, wherein, in any two of the yellow dyes, λmax has a higher oxidation potential of a long wave side dye than an oxidation potential of a short wave side dye. 5. Stuff. 4. Any one of the two dyes among the yellow dyes, wherein [lambda] max is greater than [Delta] [lambda] max (sol) of the long-wave side dye and [Delta] [lambda] max (sol) of the short-wave side dye. 2. Ink for ink jet recording described in 1.
Here, Δλmax (sol) is a difference between λmax of the dye in the N, N-dimethylformamide solution and λmax of the dye in the aqueous solution (Δλmax (sol) = λmax (N, N-dimethylformamide solution). ) -Λmax (aqueous solution)). 7. The ink composition according to claim 1, wherein in any two of the yellow dyes, a dye having a long wavelength side of λmax is represented by the following general formula (1).

In general formula (1), R ¹⁰ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group or an aryl group. Any of these groups may have a substituent. R ¹¹ and R ¹² each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a sulfo group or a heterocyclic group. Het represents an aromatic heterocyclic group. The ink composition according to any one of claims 1 to 7, wherein in any two of the yellow dyes, the short-wave side dye is represented by the following general formula (2).

In the general formula (2), R ⁴ represents a monovalent group, R ⁵ represents —OR ⁶ or —NHR ⁷ , R ⁶ and R ⁷ represent a hydrogen atom or a monovalent group, and X ₃ represents 2 N3 represents 0 or 1, Ar ₃ represents an arylene group or a divalent heterocyclic group, and Ar ₄ represents an alkyl group, an aryl group, or a monovalent triazine ring group.   An ink for ink-jet recording comprising the ink composition according to claim 1.   An ink jet recording method using the ink for ink jet recording according to claim 9.