JP2003238863A - Ink set and inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set for use in inkjet recording capable of forming an image having excellent color reproducibility and light fastness, an inkjet recording method and a method for prevention of color fading. <P>SOLUTION: This ink set comprises a yellow ink containing at least one yellow dye, a magenta ink containing at least one magenta dye, a cyan ink containing at least one cyan dye and a black ink containing at least one self- dispersible pigment, wherein oxidation potentials of the magnet dye and the cyan dye are each higher than 0.8 V (vs. SCE). The inkjet recording method and the method for prevention of color fading of the inkjet recorded image are provided by using the ink set. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink set having excellent image fastness, an ink jet recording method using the ink set, and a fading prevention method.

[0002]

2. Description of the Related Art Color image recording materials use dyes (dyes and pigments) of three primary colors of a so-called subtractive color mixture method in order to reproduce or record a full color image. The fact is that there is no fast dye that has characteristics and can withstand various use conditions, and improvement is strongly desired. The ink jet recording method has a low material cost, enables high-speed recording,
Since the noise during recording is small and color recording is easy, it is rapidly spreading and further developing.

Ink jet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in response to an image information signal, and the ejection method involves applying pressure by a piezo element. There is a method of ejecting droplets by means of a method, a method of ejecting droplets by generating bubbles in the ink by heat, a method of using ultrasonic waves, or a method of sucking and ejecting droplets by electrostatic force. Inkjet recording inks include water-based inks, oil-based inks,
Alternatively, solid (melting type) ink is used.

With respect to the colorant used in such ink jet recording ink, the solubility or dispersibility in a solvent is good, high density recording is possible, the hue is good, the light, It is robust against heat and active gases in the environment (NOx, oxidizing gases such as ozone, as well as SOx, etc.), has excellent fastness to water and chemicals, and has good fixability to image receiving materials. It is required that the ink does not easily bleed, that it has excellent storage stability as an ink, that it has no toxicity, that it has high purity, and that it can be obtained at low cost. However, it is extremely difficult to find a colorant that meets these requirements at a high level. In particular, it has a good hue of three primary colors and is a colorant that is robust against light, humidity, and heat, and a colorant that is robust against light, humidity, and heat, has less light source disparity, and has a sharp edge. A black colorant having excellent quality, especially a color that is robust against oxidizing gases such as ozone in the environment when printing on an image receiving material having an ink receiving layer containing porous white inorganic pigment particles, and A black colorant is highly desired.

Conventionally, as the magenta dye, an azo dye using phenol, naphthol, aniline or the like as a coupling component has been widely used. As the azo dye having a good hue, dyes disclosed in JP-A No. 11-209673 and Tokubo No. 3020660 are known, but they have a problem that light fastness is poor. To improve this, a dye having a good hue and improved light fastness is recently disclosed in Japanese Patent Application No. 2000-220649. However, all of the dyes known in these patents have extremely insufficient fastness to oxidizing gases such as ozone.

Typical cyan dyes are phthalocyanine dyes and triphenylmethane dyes. The most widely used phthalocyanine dye is CI
As represented by Direct Blue 86, 87, 199,
Although these are characterized by being superior in light resistance to magenta and yellow dyes, discoloration and fading due to oxidizing gases such as nitric oxide gas and ozone, which are often taken up as environmental problems these days, are remarkable. Heretofore, as a phthalocyanine-based dye imparted with ozone gas resistance, JP-A-3-
103484, JP-A-4-39365, JP-A-200
No. 0-303009 and the like are disclosed, but in any case, the effect of improving the robustness of oxidizing gas is extremely insufficient, and further improvement has been desired. On the other hand, the triphenylmethane dye represented by Acid Blue 9 has a good hue but is extremely inferior in light resistance and ozone gas resistance.

As a yellow dye, Direct Ye
Azobenzene dyes represented by Llow 86 and 120, or heterocyclic azo dyes such as pyrazolone azo dyes such as Acid Yellow 17 and pyridone azo dyes have been used. Also, quinophthalone dyes are often proposed. However, among these conventionally known dyes, those having a good hue, especially the tail of the absorption spectrum on the long-wave side, like the quinophthalone dye, are often not robust to ozone and light, and the azobenzene dye is Although it is tough, it is the current situation that there is no dye that has both hue and toughness, such as poor shortness on the long wave side.

For the black dye, Food Black 2
Among them, bisazo or trisazo dyes are typical, but at present, none of them show good performance in both light fastness and ozone fastness. On the other hand, pigments typified by carbon black are also frequently used. JP-A-3-21037
Japanese Patent Publication No. 3 describes an ink using acidic carbon black and an alkali-soluble polymer. In addition, JP-A-3-134073 describes an inkjet ink in which a dispersion having excellent storage stability and dischargeability in a bubble jet (registered trademark) recording device can be easily obtained.

However, ink jet inks containing carbon black together with a dispersant have technical problems such as unstable ejection and insufficient print density. In order to solve these problems, JP-A-8-34
No. 98 and JP-A-10-120958, a functional group having a dissociative hydrogen of a certain amount or a salt thereof is introduced into carbon black, and a surface modification treatment is performed without a surfactant or a polymer dispersant. Further, a dispersion liquid using a self-dispersing carbon black that can be spontaneously dispersed by the carbon black alone is described. Alternatively, JP-A-10-11
Japanese Patent No. 0127 describes a method of introducing a sulfone group into carbon black. Furthermore, JP-A-10-
Japanese Patent No. 95941 proposes an inkjet ink containing the above-mentioned surface-modified carbon black and glycol ethers. The self-dispersing carbon black has improved the above-mentioned problems, but in the present situation it is not possible to obtain a satisfactory result because the fastness of the water-soluble dye to be combined is significantly inferior when performing high-quality full-color printing. there were.

In order to obtain a full-color image which is excellent in color reproducibility and is robust, the dye constituting the image is required to have the following requirements. (1) Each of the three primary color and black colorants has excellent absorption characteristics. (2) Optimal combination of the three primary color and black colorants that realize a wide color reproduction range. (3) Each of the three primary color and black. The colorant has high fastness. (4) When the three primary colors and the black colorants are brought into contact with or mixed with each other on the image-receiving paper, the fastness is deteriorated due to the interaction, and bleeding,
Image quality deterioration such as bleeding should not occur. (5) The fastness of each of the three primary color and black colorants is balanced.

However, with respect to the fastness, in particular, the fastness to oxidizing gases such as ozone, which has been a big problem in inkjet printing these days, dyes such as what structure or physical property works effectively to the ozone fastness. Since there are no reports on the properties of the above, it is the current situation that no guideline for dye selection can be obtained. It is extremely difficult to select a colorant that does not cause deterioration in fastness due to the interaction of each colorant and does not cause deterioration of image quality such as bleeding and bleeding as in the above (4).

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in the prior art and achieve the following objects. That is, the present invention is 1) common to various colorants,
The improved guideline that can fundamentally solve ozone fading is shown 2).
PROBLEM TO BE SOLVED: To provide an ink composition for inkjet printing capable of giving a color-colored image having excellent fastness to ozone gas. 3) An ink set capable of forming an image having excellent color reproducibility and high light fastness. It is an object of the present invention to provide an inkjet recording method using the.

[0013]

DISCLOSURE OF THE INVENTION The inventors of the present invention have studied in detail a dye having good hue and high light fastness and gas fastness (especially ozone gas). The inventors have found that the above problems can be solved by a combination of a dye that they have and a self-dispersing black pigment, and have completed the present invention. That is, when a dye of three primary colors satisfying the above potential characteristics and a self-dispersing black pigment are used together, not only the reactivity of each colorant to ozone is greatly suppressed but also the light fastness is improved, and coloring of different colors is achieved. It was found that there was no interaction between the agents and there was no problem with fading or bleeding of the mixed color and bleeding. On the contrary, magenta dye,
Alternatively, it has been found that when a cyan dye that does not satisfy the conditions of these potentials is used, the balance of the entire image is largely lost, and the quality as a full-color image is greatly deteriorated.

Further, it has been found that the light fastness of the light color ink does not become a problem even when the inks of different densities which have been used in recent years are used to improve the color reproducibility.
Furthermore, it was also found that the stability of the colorant itself was improved, so that the stability of the ink against oxidation, precipitation and aggregation was improved, and the warranty period as a product could be extended. The following are mentioned as a preferable aspect for solving the said subject.

<1> A yellow ink containing at least one yellow dye, a magenta ink containing at least one magenta dye, a cyan ink containing at least one cyan dye, and at least one self-dispersing property. An ink set having a black ink containing a pigment, wherein the oxidation potentials of the magenta dye and the cyan dye are respectively higher than 0.8 V (vs SCE). <2> The ink set according to claim 1, wherein the magenta dye is a dye represented by the following general formula (MI).

[0016]

[Chemical 1]

In the general formula (MI), A represents the residue of the 5-membered heterocyclic diazo component A-NH ₂ . B ¹ and B ² are each −
Either CR ¹ ═ and —CR ² ═, or one of them represents a nitrogen atom and the other represents —CR ¹ ═ or —CR ² ═. R ⁵ and R ⁶ each independently represent 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. Each group may further have a substituent. G, R ¹ and R ² are each independently 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 group. 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 groups), acylamino groups, ureido groups, sulfamoylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, alkyl or arylsulfonylamino groups, heterocyclic sulfonylamino groups, nitro groups, alkyl or arylthio groups. , An alkyl or aryl sulfonyl group, a heterocyclic sulfonyl group, an alkyl or aryl sulfinyl group, a 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. <3> The ink set according to claim 1, wherein the cyan dye is a dye represented by the following general formula (C-II).

[0018]

[Chemical 2]

In the general formula (C-II), X ₁₁ , X ₁₂ ,
X ₁₃ and X ₁₄ each independently represent an electron withdrawing group having a σp of 0.40 or more. Y ₁₁ , Y ₁₂ , Y ₁₃ and Y ₁₄ each independently represent a monovalent substituent. M represents a hydrogen atom, a metal element or its oxide, hydroxide or halide. a _{11 to} a ₁₄ and b _{11 to} b ₁₄ are each X ₁₁ to
It represents the number of substituents of X ₁₄ and Y _{11 to} Y ₁₄ . a _{11 to} a ₁₄
Each independently represent an integer of 0 to 4, and b _{11 to} b ₁₄ each independently represent an integer of 0 to 4. However, the total sum of a _{11 to} a ₁₄ is 2 or more. When the dye is a water-soluble dye, X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄
It further has an ionic hydrophilic group as a substituent at any of the above positions. <4> The oxidation potential of the yellow dye is 0.8 V (vs
The ink set according to claim 1, which is more noble than SCE). <5> The ink set according to claim 1, wherein at least each of the magenta ink and the cyan ink is composed of two or more kinds of ink having different densities. <6> A container containing the ink set according to any one of <1> to <5>. <7> An inkjet recording method, wherein an image is formed by an inkjet method using the ink set according to any one of <1> to <5>. <8> An image fading preventing method, which comprises inkjet recording using the ink set according to any one of <1> to <5>.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Ink] The ink of the present invention has an oxidation potential of 0.8 V (v
Magenta dyes and cyan dyes (hereinafter sometimes referred to as dyes of the present invention), which are more noble than s SCE), are used. The more preferable the oxidation potential is, the more preferable the oxidation potential is 1.0 V (vs SCE), the more preferable the oxidation potential is 1.1 V (vs SCE), and the 1.15 V ( It is more preferable that it is more noble than vs SCE, and 1.2 V (vs SC)
Those more noble than E) are most preferred.

The value of the oxidation potential represents the ease with which electrons move from the sample to the electrode. The larger the value (the higher the oxidation potential is), the more difficult it is for electrons to move from the sample to the electrode. Indicates difficult. In relation to the structure of the compound, the oxidation potential becomes more noble by introducing the electron-withdrawing group, and the oxidation potential becomes less by introducing the electron-donating group.

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 electrons of the compound are abstracted, and it is approximately the same as the energy level of HOMO in the ground state of the compound. It is considered.

The inventors have studied the ozone fastness of a colored image. As a result, there is a correlation between the oxidation potential of the compound used for the colored image and the ozone fastness, and the value of the oxidation potential is similar to that of a saturated calomel electrode (SCE). It has been found that ozone fastness is improved by using a compound that is more noble.

The reason why the ozone fastness of the colored image is improved can be explained by the relationship between the HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) of the compound and ozone gas. That is, HOMO of colorant and LU of ozone gas
It is considered that the colorant is oxidized by the reaction with MO, and as a result, the ozone fastness of the colored image is deteriorated.
In order to improve ozone fastness, the HOMO of the colorant may be lowered to lower the reactivity with ozone gas.

The oxidation potential value (Eox) can be easily measured by those skilled in the art. For this method, see P. D.
elahay “New Instrumental Methods in Electrochemi
stry ”(1954 Interscience Publishers) and AJ B
ard et al., “Electrochemical Methods” (1980 John W.
iley & Sons), Aki Fujishima et al., "Electrochemical measurement method" (1984)
Annual Gihodo Publishing Co., Ltd.).

The measurement of the oxidation potential will be specifically described.
It The oxidation potential is sodium perchlorate or tetrachlorate tetrachloride.
Dimethy containing supporting electrolytes such as propylammonium
In a solvent such as ruformamide or acetonitrile,
1 x 10 test samples^-Four~ 1 x 10 ^-6mol · dm^-3Melted
, Cyclic voltammetry and DC polarography
Value for SCE (saturated calomel electrode) using fee
To measure. The supporting electrolyte and solvent to be used are
Choose an appropriate one depending on the oxidation potential and solubility of the sample.
it can. Supporting electrolytes and solvents that can be used
Is Aki Fujishima et al. "Electrochemical measurement method" (Published by Gihodo in 1984)
(Published by the company) See pages 101-118.

The value of the oxidation potential may deviate by about several tens of mil volts due to the influence of the potential difference between the liquids and the liquid resistance of the sample solution, but it is measured by calibrating with a standard sample (for example, hydroquinone). It is possible to guarantee the reproducibility of the value of the applied potential.

The oxidation potential in the present invention is 0.1 mol.
-In N, N-dimethylformamide containing dm ^-3 tetrapropylammonium perchlorate as a supporting electrolyte (compound concentration is 1 x 10 ^-3 mol dm ^-3 ), SCE (saturated calomel electrode) as a reference electrode A graphite electrode is used as a working electrode, a platinum electrode is used as a counter electrode, and a value measured by direct current polarography is used.

The dye used in the present invention may have any structure as long as it satisfies the above oxidation potential. Especially, yellow dye originally has a high oxidation potential (H
Since the OMO is low), there are few structural restrictions. The structure of the dye required to satisfy the above oxidation potential will be described in detail below.

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 dye skeleton to make the oxidation potential more noble. Therefore, using the Hammett's substituent constant σp value, which is a measure of the electron withdrawing property and electron donating property of a substituent, the σp value is the same as in the nitro group, cyano group, sulfinyl group, sulfonyl group, and sulfamoyl group. It can be said that the oxidation potential can be made more noble by introducing a large substituent.

The Hammett's substituent constant σp value will be briefly described. Hammett's rule is 193 to quantitatively discuss the effect of a substituent on the reaction or equilibrium of a benzene derivative.
5 years L. P. The rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σp values and σm values, and these values can be found in many general textbooks. A. Dean edition, "Lange '
s Handbook of Chemistry ", 12th Edition, 1979 (McGrow-Hill) and" The Area of Chemistry "Special Issue, No. 122, pp. 96-103, 19
Detailed in 1979 (Nankodo).

In addition to the above-mentioned substituents, generally, the more the number of atoms having a high electronegativity as the constituent atoms of the chromophore, the more the oxidation potential can be made noble. Therefore, for example, when an unsaturated heterocycle is used as a constituent element of the chromophore, the oxidation potential can be made higher than that of the aryl group. Examples of the hetero atom having a high electronegativity include a nitrogen atom, an oxygen atom and a sulfur atom, and a nitrogen atom is particularly preferable.

Therefore, the dye used in the present invention is preferably a dye whose chromophore is composed of a hetero atom, an unsaturated hetero ring, or an electron-withdrawing group. Preferred chromophores composed of heteroatoms include azo dyes,
Examples thereof include azomethine dyes and phthalocyanine dyes, and azo dyes are particularly preferable. The unsaturated heterocycle is preferably a 5- or 6-membered unsaturated heterocycle, such as thiophene ring, furan ring, pyrrole ring, thiazole ring, oxazole ring, imidazole ring, isothiazole ring, isoxazole ring, pyrazole ring, thiadiazole ring. , 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. Further, with regard to a heterocycle which may be tautomeric, even when only one tautomer is described, other tautomers are also included. Of the above, preferred are thiazole ring, isothiazole ring, pyrazole ring, thiadiazole ring, pyridine ring, pyrimidine ring and pyrazine ring. Most preferably, isothiazole ring, pyrazole ring, 1,2,4
-Thiadiazole ring, 1,3,4-thiadiazole ring,
It is a pyridine ring.

As a preferable electron-withdrawing substituent, a substituent having a Hammett's σp value of 0.4 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. Also, when there are a plurality of electron-withdrawing groups as substituents on the chromophore, the sum of the σp values of the substituents is
It is preferably 0.50 or more, more preferably 0.60 or more,
0.70 or more is the most preferable. Specific examples of the electron withdrawing group having a σp of 0.40 or more are described in J. A. Dean edition,
"Lange's Handbook of Chemi
12th edition, 1979 (McGraw-H
ill) and "Chemical Area" special edition, No. 122, 96-10
One can cite page 3, 1979 (Nankodo).

Preferred specific azo dyes which can be used as the magenta and yellow dyes are represented by the following general formula (I). General formula (I) Het (A) -N = N-Het (B) In general formula (I), Het (A) and Het (B)
Represents a 5- or 6-membered unsaturated heterocycle having a substituent.
Examples of unsaturated heterocycles represented by Het (A) and Het (B) include thiophene ring, furan ring, pyrrole ring, thiazole ring, oxazole ring, imidazole ring,
Examples thereof include an isothiazole ring, an isoxazole ring, a pyrazole ring, 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 the hydrocarbon ring or the unsaturated heterocycle may be formed, and the condensed ring may have a substituent. In the case of a nitrogen-containing unsaturated heterocycle, the nitrogen atom may be quaternized. Further, regarding the unsaturated heterocycle which may be tautomeric, even when only one tautomer is described, other tautomers are also included.

When the above dye is a water-soluble dye, it is preferable that it further has an ionic hydrophilic group as a substituent. The ionic hydrophilic group as a substituent includes a sulfo group, a carboxyl group, a phosphono group, a quaternary ammonium group and the like.

The hetero ring represented by Het (A) and Het (B) is preferably a thiazole ring, an isothiazole ring, a pyrazole ring, a thiadiazole ring, a pyridine ring or a pyrazine ring. More preferred are isothiazole ring, pyrazole ring, thiadiazole ring and pyridine ring. Most preferably a pyrazole ring, 1,2,4-
Thiadiazole ring and pyridine ring.

Het (A) and Het (B) may have a substituent. As the substituent, a halogen atom, an alkyl group (including a cycloalkyl group), an alkenyl group (including a cycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, 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 group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphono group, phosphinyl group, phosphinyloxy group, Examples thereof 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. Group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, phosphoryl group, phosphono group, phosphinoyl group, phosphonyl group,
Substituents such as a phosphinoyloxy group and a phosphinoylamino group can be raised, but among them, an electron-withdrawing group is preferable, and a substituent having σp of 0.40 or more is particularly preferable. σp is a substituent of 0.40 or more, a cyano group, a nitro group, a carboxyl group, a sulfamoyl group, an alkyl and arylsulfinyl group, an alkyl and arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an imide Groups, phosphono groups, phosphoryl groups, etc., alkyl groups substituted with electron-withdrawing groups (trihalomethyl groups, perfluoroalkyl groups, dicyanomethyl groups, iminomethyl groups, etc.), alkenyl groups substituted with electron-withdrawing groups (Trisia And a quaternary salt substituent (sulfonium group, ammonium group, phosphonium group). Among the above-mentioned functional groups, those having a hydrogen atom may be substituted with the above-mentioned group after removing the hydrogen atom. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, an arylsulfonylaminocarbonyl group, and the like. Further, the substituents on the heterocycle may be bonded to each other to form a condensed ring with the heterocycle, and further, the condensed ring may have a substituent.

Preferred magenta dyes are those represented by the general formula (MI). General formula (MI)
In the above, A represents a residue of the 5-membered heterocyclic diazo component A-NH ₂ . B ¹ and B ² are each -CR ¹ = and -CR ² = or represents, or one nitrogen atom and the other -CR ¹
= Or represents a -CR ² =. R ⁵ and R ⁶ each independently represent 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. Each group may further have a substituent.

G, R ¹ and R ² are each independently 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. , 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 (complex Ring amino group, including anilino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl Or It represents a reelthio group, an alkyl or aryl sulfonyl group, a heterocyclic sulfonyl group, an alkyl or aryl sulfinyl group, a 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.

In the general formula (MI), A represents the residue of the 5-membered heterocyclic diazo component A-NH ₂ . Examples of heteroatoms in the heterocycle can include N, O, and S.
It is preferably a nitrogen-containing 5-membered heterocycle, and the heterocycle may be condensed with an aliphatic ring, an aromatic ring or another heterocycle. A
Examples of the preferred heterocycle include a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a benzothiazole ring, a benzoxazole ring, and a benzisothiazole ring. Each heterocyclic group may further have a substituent. Among them, a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring and a benzothiazole ring represented by the following general formulas (a) to (f) are preferable.

[0042]

[Chemical 3]

In the above general formulas (a) to (f), R
⁷ to R ²⁰ represent the same substituents as described in G, R ¹ and R ² . Among the general formulas (a) to (f), the pyrazole ring and the isothiazole ring represented by the general formulas (a) and (b) are preferable, and the most preferable are the general formula (a). It is a pyrazole ring.

In the general formula (MI), B ¹ and B ²
Each -CR ¹ = and -CR ² = or represents, or either one nitrogen atom and the other -CR ¹ = or -CR ² =
Represents an each -CR ¹ =, - represents a CR ² = is more preferable.

R ⁵ and R ⁶ are each independently 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. And each group may further have a substituent.
Preferred substituents represented by R ⁵ and R ⁶ include a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group. More preferably, it is a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group. Most preferably, it is a hydrogen atom, an aryl group or a heterocyclic group. Each group may further have a substituent. However, R ⁵ and R ⁶ are not hydrogen atoms at the same time.

G, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a 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, heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, Alkyl or aryl sulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl and arylthio group, heterocyclic thio group, alkyl and aryl sulfonyl group, heterocyclic sulfonyl group,
It represents an alkyl and aryl sulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfo group, and each group may be further substituted.

The substituent represented by G includes a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, a heterocyclic oxy group, an amino group (anilino group, Heterocyclic amino groups), acylamino groups, ureido groups, sulfamoylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, alkyl and arylthio groups,
Or a heterocyclic thio group is preferable, 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. Of these, a hydrogen atom, an anilino group, and an acylamino group are most preferable. Each group may further have a substituent.

Preferred substituents represented by R ¹ and R ² 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. R ¹ and R ⁵ , or R
⁵ and R ⁶ may combine to form a 5- or 6-membered ring.

When each of the substituents represented by A, R ¹ , R ² , R ⁵ , R ⁶ and G further has a substituent, the substituents listed above in G, R ¹ and R ^{2 can} be used. You can name the group.

When the dye of the present invention is a water-soluble dye, it further has an ionic hydrophilic group as a substituent at any position on A, R ¹ , R ² , R ⁵ , R ⁶ and G. It is preferable. The ionic hydrophilic group as a substituent includes a sulfo group, a carboxyl group, a phosphono group, a quaternary ammonium group and the like. 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, the phosphono group and the sulfo group may be in a salt state, and 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,
And tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium).

In the present specification, the 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 of the aliphatic group is preferably 1-20, 1-1
More preferably, it is 6. The aryl part of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, particularly preferably phenyl. Examples of aliphatic groups are methyl, ethyl, butyl, isopropyl,
t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl,
4-sulfobutyl, cyclohexyl group, benzyl group, 2
-A phenethyl group, a vinyl group, and an allyl group can be mentioned.

In the present specification, the aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably phenyl or naphthyl, with phenyl being particularly preferred. The aromatic group preferably has 6 to 20 carbon atoms, and more preferably has 6 to 16 carbon atoms. Examples of aromatic groups include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

The heterocyclic group includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. An aliphatic ring, an aromatic ring or another heterocycle may be condensed with the heterocycle. The heterocyclic group is preferably a 5- or 6-membered heterocyclic group. Examples of the substituent include an aliphatic group, a halogen atom, an alkyl and aryl sulfonyl group, an acyl group, an acylamino group, a sulfamoyl group, a carbamoyl group, an ionic hydrophilic group and the like. Examples of the heterocyclic group include 2-pyridyl group,
A 2-thienyl group, a 2-thiazolyl group, a 2-benzothiazolyl group, a 2-benzoxazolyl group and a 2-furyl group are included.

Alkyl and arylsulfonyl groups include
The alkyl and aryl sulfonyl groups having a substituent and the unsubstituted alkyl and aryl sulfonyl groups are included.
Examples of the alkyl and aryl sulfonyl groups include a methyl sulfonyl group and a phenyl sulfonyl group, respectively.

The alkyl and aryl sulfinyl groups include an alkyl and aryl sulfinyl group having a substituent and an unsubstituted alkyl and aryl sulfinyl group. Examples of the alkyl and arylsulfinyl groups include a methylsulfinyl group and a phenylsulfinyl group, respectively.

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.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

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. The alkylamino group has from 1 to 1 carbon atoms.
20 alkylamino groups are preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.

The arylamino group includes an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group has 6 to 6 carbon atoms.
20 arylamino groups are preferred. 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.

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.

The alkoxy group includes an alkoxy group having a substituent and an unsubstituted alkoxy group. The alkoxy group is preferably an alkoxy group having 1 to 20 carbon atoms. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include methoxy group, ethoxy group, isopropoxy group, methoxyethoxy group, hydroxyethoxy group and 3-carboxypropoxy group.

The aryloxy group includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group has 6 to 6 carbon atoms.
20 aryloxy groups are preferred. 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.

The silyloxy group has 1 carbon atom.
A silyloxy group substituted with an aliphatic group or an aromatic group of 20 is preferable. Examples of the silyloxy group include trimethylsilyloxy and diphenylmethylsilyloxy.

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.

The alkoxycarbonyloxy group includes an alkoxycarbonyloxy group having a substituent and an unsubstituted alkoxycarbonyloxy group. The alkoxycarbonyloxy group has 2 to 2 carbon atoms.
An alkoxycarbonyloxy group of 0 is preferred. Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group and an isopropoxycarbonyloxy group.

The aryloxycarbonyloxy group includes
The aryloxycarbonyloxy group having a substituent and the unsubstituted aryloxycarbonyloxy group are included. As the aryloxycarbonyloxy group,
An aryloxycarbonyloxy group having 7 to 20 carbon atoms is preferable. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group.

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 acetylamino group, propionylamino group, benzoylamino group, N-phenylacetylamino and 3,5-
A disulfobenzoylamino group is included.

The ureido group includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably an 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.

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:
Includes N, N-dipropylsulfamoylamino groups.

The alkoxycarbonylamino group includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group has 2 to 2 carbon atoms.
An alkoxycarbonylamino group of 0 is preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

The alkyl- and aryl-sulfonylamino group includes an alkyl- and aryl-sulfonylamino group having a substituent and an unsubstituted alkyl- and aryl-sulfonylamino group. 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, a methylsulfonylamino group, N-phenyl-methylsulfonylamino group,
A phenylsulfonylamino group and a 3-carboxyphenylsulfonylamino group are included.

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.

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.

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 methoxycarbonyl group and ethoxycarbonyl group.

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.

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.

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.

The aryloxycarbonylamino group includes
The aryloxycarbonylamino group having a substituent and the unsubstituted aryloxycarbonylamino group are included.
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.

The alkyl, aryl and heterocyclic thio groups include an alkyl, aryl and heterocyclic thio group having a substituent and an unsubstituted alkyl, aryl and heterocyclic thio group. The alkyl, aryl and heterocyclic thio groups preferably have 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.

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 2-pyridyloxycarbonyl group.

The heterocyclic sulfonylamino group includes a heterocyclic sulfonylamino group having a substituent 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.

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 2-thiophene sulfonyl group and 3-pyridine sulfonyl group.

The heterocyclic sulfinyl group includes a heterocyclic sulfinyl group having a substituent and an unsubstituted heterocyclic sulfinyl group. As the heterocyclic sulfinyl group,
A heterocyclic sulfinyl group having 1 to 20 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfinyl group include 4-pyridinesulfinyl group.

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).

[0085]

[Chemical 4]

In the general formula (M-II), Z ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.
Z ₁ is 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, particularly preferably an electron-withdrawing group of 0.60 or more,
It is desirable not to exceed 1.0. Examples of preferable specific substituents include electron-withdrawing substituents described later, but among them, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group,
Cyano group, C1-C20 alkylsulfonyl group, C6-C20 arylsulfonyl group, C1-C20
The carbamoyl group and the halogenated alkyl group having 1 to 20 carbon atoms are preferable. Particularly preferred are cyano group, alkylsulfonyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms.
Is an arylsulfonyl group, and the most preferred is a cyano group.

R ¹ , R ² , R ⁵ and R ⁶ have the same meanings as in formula (MI). R ³ and R ⁴ each independently represent 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. . 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, or a heterocyclic group is particularly preferable. 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. Among them, Q is preferably a group consisting of a non-metal atom group necessary for forming a 5- to 8-membered ring. 5 above
The to 8-membered ring may be substituted, may be a saturated ring or may have an unsaturated bond. Among them, aromatic groups and heterocyclic groups are particularly preferable. Preferred non-metal atoms include nitrogen atom, oxygen atom, sulfur atom or carbon atom. Specific examples of such a ring structure include, for example, a benzene ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring and an imidazole ring. Examples thereof include benzimidazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, oxane ring, sulfolane ring and thian ring.

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), the groups exemplified by G, R ¹ and R ² and the ionic hydrophilic groups. To be

Examples of the electron-withdrawing group having a Hammett substituent constant σ _p value of 0.60 or more include cyano group, nitro group, alkylsulfonyl group (eg, methanesulfonyl group, arylsulfonyl group (eg, benzenesulfonyl group)). Examples of the electron-withdrawing group having a Hammett σ _p value of 0.45 or more include an acyl group (eg, acetyl group), an alkoxycarbonyl group (eg, dodecyloxycarbonyl group), an aryloxycarbonyl group (eg, , 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). , Halogenated alkyl groups (eg , Trifluoromethyl) The Hammett substituent constant σ _p value is 0.30
Examples of the electron-withdrawing group include, in addition to the above, an acyloxy group (eg, acetoxy), a carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), a halogenated alkoxy group (eg, trifluoromethyloxy). ), A halogenated aryloxy group (for example, pentafluorophenyloxy), a sulfonyloxy group (for example, methylsulfonyloxy group), a halogenated alkylthio group (for example, difluoromethylthio), and two or more σ _p values of 0.15. An aryl group (for example, 2,4-dinitrophenyl, pentachlorophenyl) substituted with the above electron-withdrawing group, and a heterocycle (for example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl) ) Can be mentioned. σ
Specific examples of the electron withdrawing group having a p value of 0.20 or more include:
In addition to the above, examples thereof include a halogen atom.

Particularly preferred combinations of substituents for the azo dye represented by formula (MI) are R ⁵ and R ^6.
As, preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group, an acyl group, more preferably a hydrogen atom, an aryl group, a heterocyclic group, a sulfonyl group, most preferably a hydrogen atom, An aryl group,
It is a heterocyclic group. However, R ⁵ and R ⁶ are not both hydrogen atoms.

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, and most preferably a hydrogen atom. , An amino group and an acylamino group.

Of 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 more preferable, and a pyrazole ring is most preferable.

B ¹ and B ² are -CR ¹ =, -C, respectively.
R ² = Yes, R ¹ and R ² are 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, and a carbamoyl group.

Preferred cyan dyes include dyes represented by the following general formula (CI).

[0095]

[Chemical 5]

In the general formula (CI), X ₁ , X ₂ , X
₃ and X ₄ each independently represent an electron-withdrawing group having σp of 0.40 or more. Y ₁ , Y ₂ , Y ₃ and Y ₄ each independently represent a monovalent substituent. M represents a hydrogen atom, a metal element or its oxide, hydroxide or halide. _{a 1 ~a 4, b 1 ~b} 4 are each X ₁ to X _4, and represents the number of substituents Y ₁ to Y _4. a _{1 to} a ₄ each independently represent an integer of 0 to 4, and b _{1 to} b ₄ each independently represent 0 to 4.
Represents an integer of 4. However, the total sum of a _{1 to} a ₄ is 2 or more, preferably 3 or more, and particularly a ₁ = a ₂ = a ₃ = a ₄ =
Most preferably, it is 1. When the dye is a water-soluble dye, an ionic hydrophilic group is further added as a substituent at any position on X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y ₃ and Y _4. It is preferable to have The ionic hydrophilic group as a substituent includes a sulfo group, a carboxyl group, a phosphono group, a quaternary ammonium group and the like.

Among the phthalocyanine dyes represented by the general formula (CI), the phthalocyanine dye having the 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.

In the general formula (C-II), X _{11 to} X
-SO-Z are each independently _14, -SO ₂ -Z, -SO ₂
NR ₁ R ₂ , sulfo group, -CONR ₁ R ₂ , or -CO ₂ R ₁
Represents Y _{11 to} Y ₁₈ each independently represent a monovalent substituent. M is a hydrogen atom, a metal atom or its oxide, hydroxide or halide. a ₁₁ ~a ₁₄ each represents a number of substituents X ₁₁ to X ₁₄ each independently 1 or 2
Represents the integer. 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, a substituted or unsubstituted Represents a heterocyclic group. R ₁ and R ₂ are each independently 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 Represents an aryl group or a substituted or unsubstituted heterocyclic group.

In formula (C-II), a _{11 to} a ₁₄ each independently represent an integer of 1 or 2, and 4 is particularly preferable.
≦ a ₁₁ + a ₁₂ + a ₁₃ + a ₁₄ ≦ 6, and among them, particularly preferable is when a ₁₁ = a ₁₂ = a ₁₃ = a ₁₄ = 1.

X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ may each be the same substituent, or, for example, X ₁₁ , X ₁₂ ,
X ₁₂ , X ₁₃ and X ₁₄ are all —SO ₂ —Z, but each Z
Are substituents of the same kind but may be partially different from each other, for example, when -SO ₂ -Z and -SO ₂ NR ₁ R ₂ are simultaneously substituted. As described above, the substituents may be different from each other.

Among the phthalocyanine dyes represented by the general formula (C-II), a particularly preferred combination of substituents is
It is as follows.

X _{11 to} X ₁₄ are each independently --SO--
_{Z, -SO 2 -Z, -SO 2} NR 1 R 2 or -CONR,
₁ R ₂ is preferable, especially —SO ₂ —Z, or —SO ₂ NR
₁ R ₂ is preferred, and —SO ₂ —Z is most preferred.

Z is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, among which a substituted alkyl group, a substituted aryl group and a substituted heterocyclic group are preferable. Is most preferred. In particular, it is preferable to have an asymmetric carbon atom in the substituent (use in a racemic form) for the reason of improving the solubility of the dye and the stability of the ink. Further, it is preferable that the substituent has a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group for the reason of increasing the association property and improving the fastness.

R ₁ and R ₂ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, among which a hydrogen atom and a substituted alkyl group are preferable. Most preferred are groups, substituted aryl groups, and substituted heterocyclic groups. However, it is not preferable that both R ₁ and R ₂ are hydrogen atoms. In particular, it is preferable to have an asymmetric carbon atom in the substituent (use in a racemic form) for the reason of improving the solubility of the dye and the stability of the ink. Further, it is preferable that the substituent has a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group for the reason of increasing the association property and improving the fastness.

Y _{11 to} Y ₁₈ are hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, carboxyl group, And a sulfo group are preferable, particularly a hydrogen atom,
A halogen atom, a cyano group, a carboxyl group, and a sulfo group are preferable, and a hydrogen atom is most preferable. It is preferable that a _{11 to} a ₁₄ are each independently 1 or 2, and particularly preferably all 1 are 1. M represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof, particularly Cu, Ni, Zn and Al are preferable, and Cu is particularly preferable.

When the phthalocyanine dye represented by the above (C-I) or (C-II) is water-soluble, it preferably has an ionic hydrophilic group. Ionic hydrophilic groups include sulfo group, carboxyl group, phosphono group and 4
Includes primary ammonium groups and the like. 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, the phosphono group and the sulfo group may be in a salt state, and 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 enhances the solubility of the dye and improves the ink stability. The number of ionic hydrophilic groups is preferably one having at least 2 or more in one molecule of the phthalocyanine dye, particularly a sulfo group and / or
Alternatively, those having at least two carboxyl groups are particularly preferable.

With respect to the preferable combination of the substituents of the compound represented by the general formula (C-II), the compound in which at least one of the various substituents is the preferable group described above is preferable, and more various substituents are preferable. Are more preferred, and those in which all substituents are the preferred groups are most preferred.

The chemical structure of the phthalocyanine dye preferably used in the present invention has at least one electron-withdrawing group such as a sulfinyl group, a sulfonyl group or a sulfamoyl group in each of the four benzene rings of the phthalocyanine skeleton. The sum of the σp values of all substituents
It is preferable to introduce so as to be 1.6 or more.

The phthalocyanine derivative represented by the above general formula (C-I) is inevitably introduced by the synthetic method thereof at the introduction positions and introduction positions of the substituents Xn (n = 1 to 4) and Ym (m = 1 to 4). It is general that the analog mixtures are different in number, and therefore the general formula often represents these analog mixtures by statistically averaging. In the present invention, it has been found that when these analog mixture is classified into the following three types, a specific mixture is particularly preferable. That is, the phthalocyanine dye analog mixture represented by the general formulas (C-I) and (C-II) is defined by classifying into the following three types based on the substitution position.

(1) β-position substitution type: 2 and / or 3 position, 6
And / or 7th, 10 and / or 11th, 14 and / or 15th
Phthalocyanine Dye Having Specific Substituent at Position

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

(3) α, β-position mixed substitution type: a phthalocyanine dye having a specific substituent in the 1st to 16th positions without regularity

In the present specification, when a derivative of a phthalocyanine dye having a different structure (in particular, a different substitution position) is described, the above β-position substitution type, α-position substitution type, α, β
-Use mixed substitution type.

The phthalocyanine derivative used in the present invention is, for example, by Shirai-Kobayashi, "Phthalocyanine-Chemistry and Function" published by IPC Co., Ltd. (P. 1-62),
C. C. Leznoff-A. B. P. Lever co-authored, VCH issue'Phthalocyanines-P
properties and Application
s' (P.1 to 54) and the like, and can be synthesized by quoting or combining methods similar thereto.

The phthalocyanine compound represented by the general formula (C-I) of the present invention can be prepared according to International Publication WO00 / 17275,
00/08103, 00/08101, 98/4
1853, Japanese Patent Application Laid-Open No. 10-36471 and the like, for example, it can be synthesized through a sulfonation, sulfonyl chloride formation, or amidation reaction of an unsubstituted phthalocyanine compound. In this case, sulfonation can occur at any position of the phthalocyanine nucleus, and the number of sulfonates is also difficult to control. Therefore, when the sulfo group is introduced under such reaction conditions, the position and the number of the sulfo group introduced into the product cannot be specified, and a mixture having different numbers of substituents and different substitution positions is always provided. Therefore, when synthesizing the compound of the present invention using it as a raw material, the number and the substitution position of the heterocyclic-substituted sulfamoyl group cannot be specified.Therefore, the compound of the present invention includes some compounds having different numbers of substituents and different substitution positions. It is obtained as an α, β-position mixed substitution type mixture.

As described above, 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 ozone resistance is enhanced.
According to the above-mentioned synthetic method, it is inevitable that a phthalocyanine dye having a small number of electron-withdrawing groups introduced, that is, a phthalocyanine dye having a more base oxidation potential, is mixed. Therefore,
In order to improve the ozone resistance, it is more preferable to use a synthetic method that suppresses the formation of a compound having a more base oxidation potential.

On the other hand, the general formula (C-II) of the present invention
The phthalocyanine compound represented by, for example, a phthalonitrile derivative (compound P) and / or a diiminoisoindoline derivative (compound Q) represented by the following formula is represented by the general formula (C
-III) It is obtained by reacting with a metal derivative.
Alternatively, it can be derived from a tetrasulfophthalocyanine compound obtained by reacting a 4-sulfophthalic acid derivative (compound R) represented by the following formula with a metal derivative represented by the general formula (C-III).

[0118]

[Chemical 6]

In each of the above formulas, Xp is the above general formula (C-II).
Corresponds to X ₁ , X ₂ , X ₃ , or X ₄ . Also, Y
q and Yq ′ are each Y in the above general formula (C-II).
_{It corresponds to 11} , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ , or Y ₁₈ . In the compound R, M ′ represents a cation.

General formula (C-III): M- (Y) d In general formula (C-III), M is M in the general formula (C-II).
Y is a halogen atom, acetic acid anion, acetylacetonate, oxygen or other monovalent or divalent ligand, and d is an integer of 1 to 4.

That is, a desired number of substituents can be introduced according to the above synthetic method. In particular, when a large number of electron-withdrawing groups are to be introduced in order to make the oxidation potential noble as in the present invention, the above synthetic method can be carried out by the general formula (C
It is extremely superior to the synthetic method of -I).

The thus obtained phthalocyanine compound represented by the general formula (C-II) is usually an isomer at each substitution position of Xp, represented by the following general formula (a) -1.
It is a mixture of compounds represented by (a) -4, that is, a β-position substitution type.

[0123]

[Chemical 7]

In the above synthetic method, all Xp are the same.
If you use the one X₁₁, X₁₂, X ₁₃And X₁₄Is totally
Obtained β-position substituted phthalocyanine dye having the same substituent
You can On the other hand, combine different Xp
If used together, they are the same kind of substituents but partially
Dyes with different substituents or different dyes
Dyes with certain types of substituents can be synthesized.
Different electron withdrawing among the dyes of the general formula (C-II)
These dyes that have a functional substituent are
Properties, ink stability over time, etc. can be adjusted.
Good

In the present invention, it was found that the oxidation potential of any substitution type is nobler than 1.0 V (vs SCE) is very important for improving the fastness, and its effect is large. This was completely unpredictable from the prior art. The cause is not clear in detail, but among them, the β-position substitution type tends to be obviously superior in hue, light fastness, ozone gas resistance and the like to the α, β-position mixed substitution type. .

The phthalocyanine dyes represented by the general formulas (C-I) and (C-II) can be synthesized according to the above-mentioned patents, and Japanese Patent Application Nos. 2001-226275 and 2001-226275 can be used.
It can be synthesized by the method described in 96610, 2001-47013 and 2001-193638. The starting materials, dye intermediates, and synthetic routes are not limited to these.

The magenta dye and cyan dye used in the present invention are characterized by having an oxidation potential nobler than 0.8 V, but phthalocyanine widely used as a cyan dye forms an aggregate. Although the fastness can be compensated even if the oxidation potential is somewhat low, the magenta dye does not form an association. Therefore, in order to enhance the fastness, it is preferable to set the oxidation potential to be nobler than that of the cyan dye.

Preferred examples of dyes usable in the present invention are shown below, but these are for explaining the present invention in detail, and the present invention is not limited by these. The oxidation potential of the dye is shown in parentheses.

[0129]

[Chemical 8]

[0130]

[Chemical 9]

[0131]

[Chemical 10]

[0132]

[Chemical 11]

[0133]

[Chemical 12]

[0134]

[Chemical 13]

[0135]

[Chemical 14]

[0136]

[Chemical 15]

[0137]

[Chemical 16]

[0138]

[Chemical 17]

[0139]

[Chemical 18]

[0140]

[Chemical 19]

[0141]

[Chemical 20]

[0142]

[Chemical 21]

[0143]

[Chemical formula 22]

[0144]

[Chemical formula 23]

[0145]

[Chemical formula 24]

[0146]

[Chemical 25]

[0147]

[Chemical formula 26]

[0148]

[Chemical 27]

[0149]

[Chemical 28]

[0150]

[Chemical 29]

[0151]

[Chemical 30]

Other examples of the compound of the present invention include Japanese Patent Application No. 2001-9.
6610, 2001-24352, 2001-47013, 2001-570
63, 2001-76689, 2001-193638, 2001-1561
No. 4, 2001-110457, and 2001-110335, but not limited thereto. Also, the compounds of the present invention can be readily synthesized by the methods described in the patents listed here.

[Black Ink] The self-dispersible pigment which can be dispersed in a medium without the dispersant of the present invention will be described. The black ink in the present invention contains a self-dispersing pigment that can be dispersed in a medium without a dispersant. The medium is preferably an aqueous medium. "Pigment dispersible in a medium without a dispersant" is a pigment having a solubilizing group for the medium bound to the surface thereof directly or through another atomic group, and is stable even without a dispersant. Can be dispersed. In order to be a “pigment that can be dispersed in a medium without a dispersant”, a dispersing device such as an ultrasonic homogenizer, a nanomizer, a microfluidizer, or a ball mill is used, and 95% by mass of the medium and pigment 5 are used without using the dispersant. The pigment is dispersed in a dispersion medium so that the concentration becomes mass%, the dispersant is put into a glass bottle, and left for one day and night. When the pigment concentration of the supernatant is measured, the pigment concentration is 98% or more of the initial concentration. If

The "pigment which can be dispersed in a medium without a dispersant" of the present invention is a pigment which has been prepared by treating an ordinary pigment with an acid / base, a coupling agent such as a diazonium salt, a polymer graft treatment, a plasma treatment or a hypochlorous acid. Alternatively, it can be produced by subjecting the salt or a hydrogen peroxide solution to an oxidation treatment or a surface modification treatment such as a reduction treatment. Regarding such a process, JP-A-8-3498 and JP-A-10-9898
-120958, JP-A-10-110127,
International publication WO96 / 18695, same 00/75246,
No. 01/10963 or Japanese Patent Application Laid-Open No. 10-95941, and more specifically, Japanese Patent Application Laid-Open No. 2001-89688.
Describes various self-dispersing carbon blacks in detail, and these can be referred to in the present invention. By performing such a surface treatment, the solubilizing group for the medium is contained in a larger amount than that of a normal pigment, and dispersion without a dispersant becomes possible.

Usual pigments which are subjected to the surface modification treatment include Raven7000, Raven5750 and Rav.
en5250, Raven5000 ULTRAII, R
aven3500, Raven2000, Raven1
500, Raven1250, Raven1200, R
aven1190 ULTRAII, Raven117
0, Raven1255, Raven1080, Rav
en1060 (above, Columbian Carbon Co., Ltd.),
Regal400R, Regal330R, Regal
660R, Mogul L, Black Pearls
L, Monarch 700, Monarch 800,
Monarch 880, Monarch 900, Mo
narch 1000, Monarch 1100, Mo
narch 1300, Monarch 1400 (above, manufactured by Cabot), ColorBlack FW
1, Color Black FW2, Color Bl
ackFW2V, Color Black 18, Col
or Black FW200, Color Black
S150, Color Black S160, Colo
rBlack S170, Printex35, Print
exU, PritexVrintex140U, Pri
ntex140V, Special Black 6, S
special Black 5, Special Bla
ck 4A, Special Black 4 (above, manufactured by Degussa), No. 25, No. 33, No. 40, No.
47, No. 52, No. 900, No. 2300, MC
F-88, MA600, MA7, MA8, MA100
(Above, manufactured by Mitsubishi Chemical Co., Ltd.) can be used,
It is not limited to these. Further, magnetic fine particles such as magnetite and ferrite, titanium black and the like may be used.

As the “pigment dispersible in water without a dispersant” of the present invention, a commercially available product can be used as it is. Examples of such commercially available pigments include Cabojet-2.
00, Cabojet-300, IJX-55, IJX
-164 (above, Cabot), Microjet
Black CW-1 (BONJET Black CW
-1, manufactured by Orient Chemical Industry Co., Ltd.) and the like.

The solubilizing group for the medium contained in the "pigment dispersible in the medium without a dispersant" of the present invention may be any of nonionic, cationic and anionic groups. Acid, carboxylic acid, hydroxyl group,
A phosphate group or the like is desirable. In the case of a sulfonic acid, carboxylic acid or phosphoric acid group, it can be used as it is in the free acid state, but it may form a salt. When forming a salt, the acid counterion is typically Li, Na,
Preference is given to K, NH ₄ and organic amines.

In the present invention, it is desirable to use a purified product as the pigment. The impurities can be removed by, for example, washing with water, an ultrafiltration membrane method, an ion exchange treatment, adsorption by activated carbon, zeolite or the like. Although not particularly limited, the concentration of the inorganic substance derived from the impurities of the coloring material in the ink is preferably 500 ppm or less, more preferably 300 ppm or less.

In the present invention, the content of the pigment in the black ink is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, based on the total weight of the ink.
And particularly preferably 1.0 to 8.0% by mass.
When the content of the pigment exceeds 15% by mass, the nozzle tip of the print head is likely to be clogged, and when it is less than 0.1% by mass, a sufficient image density cannot be obtained.

Even when the self-dispersing pigment is used, a surfactant may be added to the black ink for adjusting the surface tension. The surfactant is preferably a nonionic or anionic surfactant that hardly affects the dispersed state of the water-insoluble coloring material or the dissolved state of the water-soluble dye.

Examples of nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene fatty acid ester. Examples thereof include oxyethylene sorbitan fatty acid ester, fatty acid alkylol amide, acetylene alcohol ethylene oxide adduct, polyethylene glycol polypropylene glycol block copolymer, polyoxyethylene ether of glycerin ester, and polyoxyethylene ether of sorbitol ester.

As the anionic surfactant, alkylbenzene sulfonate, alkylphenyl sulfonate,
Examples thereof include alkylnaphthalene sulfonates, higher fatty acid salts, sulfuric acid ester salts of higher fatty acid esters and sulfonates, and higher alkyl sulfosuccinates.

Amphoteric surfactants can be used, and examples thereof include betaine, sulfobetaine, sulfate betaine, imidazoline and the like. Further, silicone-based surfactants such as polysiloxane polyoxyethylene adducts, fluorine-based surfactants such as oxyethylene perfluoroalkyl ethers, biosurfactants such as spiculisporic acid, rhamnolipid, and lysolecithin can also be used.

In the present invention, pure water, ultrapure water, ion-exchanged water or the like can be used as the water contained in the black ink.

The dispersed particle size of the pigment in the ink is 20 to 120 nm in volume average particle size, and 50
The number of coarse particles of 0 nm or more is 5 × 10 ^{5 in} 1 μl of ink.
It is preferable that the number is not more than the number. Volume average particle size is 20n
If it is smaller than m, a sufficient image density cannot be obtained and 120n
If it is larger than m, clogging easily occurs in the print head, and ejection stability cannot be obtained. Further, if the number of coarse particles of 500 nm or more is larger than 5 × 10 ⁵ particles in 2 μl of ink, similarly, clogging easily occurs in the print head, and ejection stability cannot be obtained. The number of coarse particles is more preferably 3 × 10 ⁵ or less, particularly preferably 2 × 1.
No more than 0 ⁵ . Furthermore, when used under the above conditions,
The surface tension of the ink at 20 ° C. is 20-40 mN /
m, and the viscosity is preferably 1.5 to 5.0 mPas.

The pigment contained in the black ink has a storage elastic modulus of 5 × 10 ⁻⁴ to 1 × 10 at 24 ° C. when measured in a low shear rate region at an angular velocity of 1 to 10 rad / s.
^-2 Pa is preferable. When the storage elastic modulus is out of this range, bleeding between colors and color unevenness are likely to occur, and the image fixability is deteriorated, which is not preferable. The pigment of the black ink has an appropriate elasticity in this region, so that the behavior on paper becomes favorable. These can be easily measured by an apparatus capable of measuring viscoelasticity in the low shear rate region. As such a device, for example, a VE-type viscoelasticity analyzer (VILASTIC SCIENTIFI
C, INC.), DCR ultra-low viscosity viscoelasticity measuring device (Paar Physica), and the like.

[Inkjet recording ink]

The ink jet recording ink can be prepared by dissolving and / or dispersing the colorant in a lipophilic medium or an aqueous medium. Preferably, an aqueous medium is used. If necessary, other additives are contained 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, permeation accelerators, UV absorbers, antiseptics, mildew-proofing agents, pH adjusting agents, surface tension adjusting agents, and deodorizing agents. Known additives such as foaming agents, viscosity modifiers, dispersants, dispersion stabilizers, rust preventives and chelating agents can be used. In the case of water-soluble ink, these various additives are added directly to the ink liquid. When the oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the dye dispersion is prepared, but it may be added to the oil phase or the water phase during the preparation.

The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the inkjet ink at the ink ejection port of the nozzle used in the inkjet recording system.

As the anti-drying agent, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivative, glycerin. , Lower alkyl ethers of polyhydric alcohols such as trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, etc. , 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocycles 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 preferable. The above-mentioned anti-drying agents may be used alone or in combination of two or more kinds. These drying inhibitors are contained in the ink in an amount of 10 to 50% by mass.
It is preferable to contain.

The penetration enhancer is preferably used for the purpose of allowing the ink jet ink to better penetrate the paper.
As the penetration enhancer, alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants may be used. it can. When these are contained in the ink in an amount of 5 to 30% by mass, a sufficient effect is usually obtained, and it is preferable to use them in an addition amount range that does not cause bleeding of printing and paper drop (print through).

The ultraviolet absorber is used for the purpose of improving the storability of images. Examples of the ultraviolet absorber include JP-A-58-185677 and JP-A-61-190537.
Japanese Patent Laid-Open No. 2-782 and Japanese Patent Laid-Open No. 5-97075.
And benzotriazole compounds described in JP-A-9-34057, JP-A-46-2784,
Japanese Unexamined Patent Publication No. 5-194843, U.S. Pat. No. 32,144
No. 63, etc., benzophenone compounds, JP-B-48-30492, JP-A-56-21141,
Cinnamic acid compounds described in JP-A-10-88106 and the like, JP-A-4-298503 and 8-534.
No. 27, No. 8-239368, No. 10-18.
No. 2621, Japanese Patent Publication No. 8-501291, etc., triazine compounds, Research Disclosure No. Compounds described in JP-A No. 24239, stilbene compounds and benzoxazole compounds, which fluoresce by absorbing ultraviolet rays, so-called fluorescent whitening agents can also be used.

The anti-fading agent is used for the purpose of improving the storability of images. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Hydroquinones as organic anti-fading agents,
Alkoxyphenols, dialkoxyphenols,
There are phenols, anilines, amines, indanes, chromanes, alkoxyanilines, heterocycles and the like, and metal complexes include nickel complexes and zinc complexes. More specifically, Research Disclosure No.
17643, items VII, I through J, ibid. 1516
2, the same No. 18716, page 650, left column, same No. 36
544, page 527, ibid. 307105, page 872,
Same No. The compounds described in the patent cited in 15162 and pages 127 to 13 of JP-A No. 62-215272.
The compounds included in the general formulas of the representative compounds and the compound examples described on page 7 can be used.

As the antifungal agent, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-
Examples thereof include 1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are 0.02-1.
It is preferable to use 100% by mass.

The neutralizer (organic base, inorganic alkali) can be used as the pH adjuster. The pH
The adjusting agent has a pH of 6 to 10 for the purpose of improving the storage stability of the inkjet ink.
It is preferable to add it for summer, and it is more preferable to add it so as to have a pH of 7 to 10.

Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. still,
The surface tension of the inkjet ink of the present invention is 25 to 7
0 mN / m is preferred. Furthermore, 25-60 mN / m is preferable. The viscosity of the inkjet ink of the present invention is preferably 30 mPa · s or less. It is more preferable to adjust to 20 mPa · s or less. Examples of the surfactant include fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, dialkylsulfosuccinate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkyl sulfate. Anionic surfactants such as ester salts, polyoxyethylene alkyl ethers,
Nonionic surfactants such as polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, and oxyethyleneoxypropylene block copolymer are preferable. In addition, SURFYNOLS (Air Products & Ch), which is an acetylene-based polyoxyethylene oxide surfactant, is used.
(Medicals, Inc.) is also preferably used. Also, N,
Also preferred are amine oxide type amphoteric surfactants such as N-dimethyl-N-alkylamine oxide. Furthermore,
Research Disclosure No. pp. 37-38, JP-A-59-157,636. 308119 (198
Those listed as the surfactants described in (9 years) can also be used.

As the antifoaming agent, a fluorine-based compound, a silicone-based compound, a chelating agent typified by EDTA, or the like can be used if necessary.

When the dye of the present invention is oil-soluble, a method for dispersing it in an aqueous medium is described in JP-A No. 11-286637 and Japanese Patent Application No.
No. 0-78491, No. 2000-80259, No. 2000-62370 colored particles containing a dye and an oil-soluble polymer are dispersed in an aqueous medium, or Japanese Patent Application Nos. 2000-78454 and 2000-78491. ,
It is preferable to disperse the dye of the present invention dissolved in a high-boiling point organic solvent in an aqueous medium as described in 2000-203856 and 2000-203857. The specific method for dispersing the dye of the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive and the amount thereof are preferably those described in the above patent. it can. Alternatively, the dye may be dispersed in a fine particle state as it is as a solid. At the time of dispersion, a dispersant or a surfactant can be used. As a dispersing device, a simple stirrer or impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor,
A roll mill, an agitator mill, etc.), an ultrasonic system, a high-pressure emulsification dispersion system (high-pressure homogenizer; specific commercially available devices: Gorin homogenizer, microfluidizer, DeBEE2000, etc.) can be used. Regarding the method for preparing the above ink jet recording ink, in addition to the above-mentioned patent, JP-A-5-148436
No. 5, No. 5-295312, No. 7-97541, No. 7
-82515, 7-118584, JP-A-11-
Details are described in JP-A-286637 and Japanese Patent Application No. 2000-87539, and can be used for preparing the ink for inkjet recording of the invention.

As the aqueous medium, a mixture containing water as a main component and, if desired, a water-miscible organic solvent added thereto can be used. Examples of the water-miscible organic solvent include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec.
-Butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol),
Polyhydric 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 (For example, 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. 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, dimethylsulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, Acetone) is included. The water-miscible organic solvent may be used in combination of two or more kinds.

Inkjet recording ink 10 of the present invention
20 parts by weight of each of the dyes of the present invention are contained in an amount of 0.1 parts by weight or more and 20
It is preferably contained in an amount of not more than parts by weight. The yellow, magenta, and cyan inks of the present invention have an oxidation potential of 0.8V.
If more noble, two or more dyes may be used in combination. Two
When two or more kinds of dyes are used in combination, the total content of dyes is preferably within the above range.

In recent years, for the purpose of improving image quality, each of yellow, magenta, and cyan inks is often composed of two or more kinds of inks having different dye densities.
The dye used in each of the dark and light inks preferably has an oxidation potential higher than 0.8 V, more preferably higher than 1.0 V, further preferably higher than 1.1 V, More preferably it is nobler than 1.15V, most preferably it is nobler than 1.2V.

In the present invention, two inks having the same hue are used.
When using one or more kinds of different inks, it is preferable that the ink density of one kind of ink is 0.05 to 0.5 times.

In addition, for controlling ink characteristics, polyethyleneimine, polyamines, polyvinylpyrrolidone,
Use cellulose derivatives such as polyethylene glycol, ethyl cellulose, carboxyethyl cellulose, polysaccharides and their derivatives, other water-soluble polymers and polymer emulsions, cyclodextrins, macrocyclic amines, dendrimers, crown ethers, urea and its derivatives, acetamide, etc. You can

As chelating agents, ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid (IDA), ethylenediamine di (o-hydroxyphenylacetic acid)
(EDDHA), nitrilotriacetic acid (NTA), dihydroxyethylglycine (DHEG), trans-1,2-
Cyclohexanediaminetetraacetic acid (CyDTA), diethylenetriamine-N, N, N ', N', N'-pentaacetic acid (DTPA), glycol etherdiamine-N, N,
N ', N'- tetraacetic acid (GEDTA) etc. are mentioned.

As the viscosity modifier, methyl cellulose,
Examples include ethyl cellulose and its derivatives, glycerins and polyglycerins and their polyethylene oxide and polypropylene oxide adducts, and polysaccharides and their derivatives. Specific examples of these include glucose, fructose, mannitol, D-sorbit, dextran, xanthan gum, curdlan, cycloamylose, maltitol and their derivatives.

In order to prevent bleeding between cyan, magenta and yellow inks and black ink in the ink set of the present invention, these inks may contain a pH buffering agent. As the pH buffer, the pH of the ink is 7.0
Any material may be used as long as it can be stably maintained at up to 9.5. If the pH of the ink is less than 7.0, bleeding between colors and color unevenness are likely to occur, and the image fixability deteriorates. If it exceeds 9.5, the head member may be damaged. Examples of pH buffering agents are potassium dihydrogen phosphate / sodium hydroxide, sodium tetraborate / hydrochloric acid, potassium dihydrogen phosphate / disodium hydrogen phosphate, ammonium chloride / ammonia, trisaminomethane / hydrochloric acid,
Good buffers, ACES, ADA, BES,
Bicine, Bis-Tris, CHES, DISP
O, EPPS, HEPES, HEPPSO, MES, M
OPS, MOPSO, POPSO, TAPS, TAPS
A combination of O, TES, and Tricine with sodium hydroxide, potassium hydroxide, and ammonia is preferably used. Among these, a pH buffer agent using sodium hydroxide, potassium hydroxide, or ammonia as an alkali is particularly preferable. The effect of these pH buffer agents is particularly remarkable when used with an ink drop amount of 1 to 20 pl, preferably 2 to 18 pl. Further, the effect is good by the thermal ink jet method.

The surface tension of the cyan, magenta and yellow inks is preferably 20 to 70 mN / m, more preferably 25 to 60 mN / m at 20 ° C. 20m
When it is lower than N / m, bleeding on paper becomes remarkable, and stable ejection is difficult to obtain, which is not preferable. In addition, 70mN /
If it is larger than m, ink penetration into the paper does not occur sufficiently and blue,
The color developability of secondary colors such as red and green deteriorates, which is not preferable.
The surface tension of the black ink at 20 ° C. is cyan,
It is more effective when it is lower than the surface tension of both magenta and yellow inks.

The viscosities of cyan, magenta, yellow and black inks are the same for all inks, and are 30 mP at 20 ° C.
a · s or less is preferable, more preferably 1.5 to 20 m
Pa · s, and the best result is obtained. 1.5m
If it is lower than Pas, it is difficult to obtain ejection stability, and 20 mPa.
If it is higher than s, clogging easily occurs, which is not preferable.

[Inkjet recording method] In the inkjet recording method of the present invention, energy is applied to the inkjet recording ink so that a known image receiving material, that is, plain paper or resin coated paper, for example, JP-A-8-169172, is disclosed. No. 8-27693, No. 2-276670, No. 7-276789, No. 9-323475, No. 62-23878, No. 10-
No. 153989, No. 10-217473, No. 10-235995, No. 10-337947, No. 10-21797, No. 10-33794.
An image is formed on inkjet-dedicated paper, film, electrophotographic co-paper, cloth, glass, metal, porcelain, etc. described in Japanese Patent Publication No.

When forming an image, a polymer latex compound may be used together for the purpose of imparting glossiness, water resistance and improving weather resistance. The latex compound may be applied to the image receiving material before, after, or at the same time as the application of the colorant, so that the place of addition is also in the image receiving paper, It may be in the ink or may be used as a liquid substance of the polymer latex alone. Specifically, Japanese Patent Application No. 2000-36
3090, 2000-315231, 2000-3
54380, 2000-343944, 2000-
The method described in 268952 can be preferably used.

The recording paper and recording film used for ink jet printing using the ink of the present invention will be described below. Supports for recording paper and recording film are chemical pulp such as LBKP and NBKP, G
P, PGW, RMP, TMP, CTMP, CMP, CG
It consists of mechanical pulp such as P, waste paper pulp such as DIP,
If necessary, conventionally known pigments, binders, sizing agents,
Mixing additives such as fixing agent, cationic agent, paper strengthening agent,
Those manufactured by various devices such as a Fourdrinier paper machine and a cylinder paper machine can be used. In addition to these supports, 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 ² is desirable. The support may be provided with the ink receiving layer and the back coat layer as it is, or may be provided with the ink receiving layer and the back coat layer after the size press or the anchor coat layer is provided with starch, polyvinyl alcohol or the like. Further, the support may be subjected to flattening treatment by a calendar device such as a machine calendar, a TG calendar and a soft calendar. In the present invention, as the support,
A paper and a plastic film having both surfaces laminated with a polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and their copolymers) are more preferably used. It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine blue, neodymium oxide) to the polyolefin.

The ink receiving layer provided on the support is
It 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, a porous inorganic pigment is preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, both silicic acid anhydride obtained by the dry production method and hydrous silicic acid obtained by the wet production method can be used, but it is particularly preferable to use hydrous silicic acid.

The aqueous binder contained in the ink receiving layer includes polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivative. Water soluble polymer such as styrene butadiene latex,
Examples thereof include water-dispersible polymers such as acrylic emulsion. These aqueous binders can be used alone or in combination of two or more. In the present invention, among them, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peeling resistance of the ink receiving layer. The ink receiving layer may contain a mordant, a water-proofing agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used. Regarding the polymer mordant, JP-A-48-28325 and JP-A-54-74430 are used.
No. 54-124726, No. 55-22766,
No. 55-142339, No. 60-23850, No. 6
0-23851, 60-2852, 60-2
3853, 60-57836, 60-6064.
No. 3, No. 60-118834, No. 60-122940
No. 60-122941, No. 60-122942
No. 60-235134, JP-A-1-161236.
Publications, US Pat. Nos. 2,484,430 and 25,485.
No. 64, No. 3148061, No. 3309690, No. 4115124, No. 4124386, No. 41938.
No. 00, No. 4273853, No. 4282305, and No. 4450224. JP-A-1-
An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A-161236 is particularly preferable. When the polymer mordant described in the publication is used, an image with excellent image quality can be obtained and the light resistance of the image can be improved.

The water-proofing agent is effective for making images water-proof, and as these water-proofing agents, cationic resins are particularly desirable. As such a cationic resin, polyamide polyamine epichlorohydrin, polyethyleneimine,
Examples thereof include polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. The content of these cationic resins is preferably 1 to 15% by mass based on the total solid content of the ink receiving layer, and particularly 3
It is preferably from 10 to 10% by mass.

Examples of the light resistance improver include zinc sulfate, zinc oxide, hindered amine antioxidants, and benzophenone or benzotriazole ultraviolet absorbers. Of these, zinc sulfate is particularly preferable.

The above-mentioned surfactant functions as a coating aid, a peeling property improving agent, a slipping property improving agent or an antistatic agent. For the surfactant, see JP-A-62-17346.
No. 3 and No. 62-183457.
An organic fluoro compound may be used instead 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). Regarding organic fluoro compounds, JP-B-57-9053 (columns 8 to 17), JP-A-61-2
It is described in each publication of 0994 and 62-135826. Other additives added to the ink receiving layer include pigment dispersants, thickeners, defoamers, dyes, optical brighteners,
Preservatives, pH adjusters, matting agents, hardeners and the like can be mentioned. The ink receiving layer may be one layer or two layers.

A back coat layer may be provided on the recording paper and the recording film, and components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of the white pigment contained in the back coat 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. , Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite,
Examples thereof include white inorganic pigments such as hydrolyzed halloysite, magnesium carbonate and magnesium hydroxide, organic pigments such as styrene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, urea resins and melamine resins.

The aqueous binder contained in the back coat layer includes styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin. , Water-soluble polymers such as carboxymethyl cellulose, hydroxyethyl cellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the back coat layer include a defoaming agent, a defoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water resistance agent.

Polymer latex may be added to the constituent layers (including the back coat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, and film crack prevention. Regarding the polymer latex, JP-A Nos. 62-245258 and 62-1
It is described in each publication of No. 36648 and No. 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 or curling of the layer can be prevented. Curling can also be prevented by adding a polymer latex having a high glass transition temperature to the back coat layer.

The ink of the present invention is not limited to an ink jet recording system, and is a known system, for example, a charge control system in which ink is ejected by using electrostatic attraction, a drop-on-demand system in which vibration pressure of a piezo element is used. (Pressure pulse method), an acoustic ink jet method in which an electric signal is converted into an acoustic beam to irradiate the ink and the ink is ejected by using radiation pressure, and a bubble is formed by heating the ink and the generated pressure is used. It is used in thermal inkjet systems. The inkjet recording method uses a method of ejecting a large number of low density inks called photo ink in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue but different densities, and a colorless transparent ink. Method is included.

[0202]

[Example 1]

(Preparation of Self-Dispersing Pigment) A pigment dispersion A in which self-dispersing carbon black was dispersed was prepared according to the example of JP-A-2001-89688. JP 2001-72904 A
A pigment dispersion B in which self-dispersing carbon black was dispersed was prepared according to the example of No. (Preparation of Black Ink) Bonjet Black CW-1
(Orient Chemical Co., Ltd.) was diluted with water to a pigment concentration of 10% by mass and then centrifuged (7,000 r.p.m.).
pm, 30 minutes) to obtain a pigment dispersion (pigment concentration 8.3% by mass).

Pigment dispersion 50% by mass Diethylene glycol 15% by mass Urea 5% by mass C ₄ H ₉ (CH ₂ CH ₂ O) ₂ H 2% by mass Surfactant 1% by mass (Orifin E1010: manufactured by Nisshin Chemical Co., Ltd.) Pure water 27% by mass

While the above components were thoroughly mixed, a 1N aqueous sodium hydroxide solution was added dropwise until the pH reached 7.5. Then, pressure filtration was performed using a 1 μm filter to prepare black ink C. Similarly, Bonjet Bla
ck CW-1 (manufactured by Orient Chemical Co.), the above pigment dispersions A and B were used in place of the dispersions, and pure amounts were adjusted so that the same optical density was obtained to prepare black ink A and black ink B, respectively. did.

On the other hand, as a comparative black ink, a black ink D was prepared in the same manner as in the preparation of the aqueous light magenta ink solution described below.

(Preparation of Aqueous Color Ink) Deionized water was added to the following components to make 1 liter, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then KOH 10mo
The pH was adjusted to 9 with 1 / L, and vacuum filtration was performed using a microfilter having an average pore size of 0.25 μm to prepare a light magenta ink liquid.

[0207] ・ Magenta dye (T-1) 7.5g / L ・ Diethylene glycol 150g / L ・ Urea 37g / L ・ Glycerin 130 g / L ・ Triethylene glycol monobutyl ether 130g / L ・ Triethanolamine 6.9g / L ・ Benzotriazole 0.08g / L ・ Surfynol 465 10.5 g / L ・ PROXEL XL2 3.5g / L

Further, magenta ink, light cyan ink, cyan ink, and yellow ink were adjusted by changing the dye species and additives to prepare color ink set 101 having the density shown in Table 1.

[0209]

[Table 1]

[0210]

[Chemical 31]

Next, the dye species of each of the light magenta, magenta, light cyan, cyan, and yellow inks of the color ink set 101 was changed as shown in Table 2 to prepare ink sets 102-112. In addition, when changing the dye, the standard is to use it by replacing it in equimolar amounts,
The dye concentration was adjusted so that the transmission density of each ink liquid was the same as that of the ink set 101. When a dye was used in combination, they were used in equimolar amounts.

[0212]

[Table 2]

(Image recording and evaluation) Color ink set
101-112 and black inks A to D are packed in a cartridge of an inkjet printer PM-770C (manufactured by Seiko Epson Corporation), and an image is printed on the inkjet paper PM photo paper manufactured by Seiko Epson Corporation by the same machine. An evaluation was made.

<Bleed of fine line> A fine line pattern of yellow, magenta, cyan and black is printed at 40 ° C and 80%.
After standing for 1 day under the conditions described above, evaluation was performed visually. For black, magenta ink was solidly printed, then black fine lines were printed, and bleeding due to contact of two colors was also evaluated.

<Water resistance> After immersing the obtained image in deionized water for 30 seconds, the blurring of the image was visually evaluated.

<Light fastness> For the image fastness, a gray print sample was prepared and evaluated as follows. Chromaticity (a * 1, b * 1) and brightness (L1) immediately after printing were measured with Gretag SPM100-II, and then irradiated with xenon light (85000 lux) for 14 days using an Atlas weather meter. After that, the chromaticity (a * 2, b * 2) and the lightness (L2) were measured again, and the color difference (ΔE) before and after light irradiation was obtained and evaluated according to the following formula. ΔE = {(a * 1-a * 2) ² + (b * 1-b * 2) ² + (L1-
L2) ² } ^1/2 color difference was evaluated at three points with reflection densities of 1.0, 1.3 and 1.6, and A was used when the color difference was less than 5 and A was less than 5 and 5 depending on the density. The case in which both of the above evaluations are included is B, and the case in which all the concentrations are 5 or more is C.

<Thermal Fastness> The color difference before and after storing the sample at 80 ° C. for 14 days was evaluated by the same method as the light fastness. Regarding the residual ratio of the dye, the reflection density is 1.0, 1.
Evaluation was made at 3 points of 3 and 1.6, and A in the case where the color difference was less than 3 in any density, B in the case of including both evaluations of less than 3 and 3 or more depending on the density, and 3 or more in all the density. The case was designated as C.

<Ozone resistance> Ozone gas concentration is 0.5 p
The color difference before and after storing the sample in a box set to pm for 14 days was evaluated by the same method as the light fastness.
Regarding the residual ratio of dye, the reflection density is 1.0, 1.3, 1.6
The color difference was less than 10 at any of the densities, A was designated as A, the case of including both the ratings of less than 10 and 10 or more depending on the densities was designated as B, and the case of 10 or more at all densities was designated as C. . The ozone gas concentration in the box is APP
LICS ozone gas monitor (model: OZG-EM
-01).

[0219]

[Table 3]

It can be seen that when the ink composition of the present invention is used, it exhibits particularly excellent fastness. In addition, the ink composition of the present invention is excellent in performance in outputting fine lines without bleeding, and is also excellent in water resistance. The image-receiving paper used in the present invention is an inkjet paper image photographic finish manufactured by Fuji Photo Film Co., Ltd., and PR1 manufactured by Canon Inc.
Even when the value is changed to 01, the same effect as the above result can be seen.

[Example 2] The same ink prepared in Example 1 was packed in an inkjet printer BJ-F850 (manufactured by Canon Inc.), and an image was printed on the inkjet paper with a photographic finish of Fuji Photo Film by the same machine. When the same evaluation as that of the example was performed, the same result as that of the example 1 was obtained. Similar effects were observed when the image receiving paper was PM photo paper manufactured by Epson and PR101 manufactured by Canon.

[Example 3] Ink set 101 of Example 1
Ink set 201 was prepared by changing light magenta, magenta, light cyan, cyan, and yellow to the oil-soluble dye inks prepared by the following method.

Dye (M-24) 8 g, surfactant (manufactured by Kao, trade name Emal 20C) 60 g, high boiling organic solvent (S-1) 6 g, high boiling organic solvent (S-2) 10 g, additive 7 in 1.0 g of (T-1) and 50 mL of ethyl acetate
It was dissolved at 0 ° C. To this solution, add 500 mL of deionized water while stirring with a magnetic stirrer,
An oil-in-water type coarse particle dispersion was prepared. Next, this coarse particle dispersion is mixed with a microfluidizer (MICROFLUIDE).
(XINC) was made into fine particles by passing it 5 times at a pressure of 60 MPa. Further, the resulting emulsion was desolvated by a rotary evaporator until the odor of ethyl acetate disappeared.

To the fine emulsion of the hydrophobic dye obtained as described above, 140 g of diethylene glycol, 64 g of glycerin, and additives such as urea were added, and the total amount of deionized water was adjusted to 1 liter. In addition, KOH 1
A light magenta ink according to the density of Table 4 was prepared by adjusting the pH to 9 at 0 mol / L. The volume average particle size of the obtained emulsion-dispersed ink was measured by using Microtrac UPA (manufactured by Nikkiso Co., Ltd.).
was nm.

Further, by changing the type and amount of dye used, the amount of high boiling point organic solvent and the type and amount of various additives, the magenta ink, light cyan ink, cyan ink and yellow ink of the ink set 201 shown in Table 4 were changed. Prepared.
Table 4 shows the composition of the final composition after solvent evaporation.

[0226]

[Table 4]

[0227]

[Chemical 32]

With respect to each ink, the ink set 20 was prepared in the same manner as 201 except that the dye type was changed as shown in Table 5.
2-209 was produced. When the dyes were changed, the dyes were adjusted so that the transmission densities of the respective ink liquids were equivalent to those of the ink set 201, based on the fact that they were used by replacing them in equimolar amounts. Next, the ink set 201-209 was packed in a cartridge of an inkjet printer PM-770C (manufactured by Seiko Epson Co., Ltd.), and the image was printed on the inkjet paper coloring photo finish made by Fuji Photo Film, and the following evaluation was performed. It was

<Bleed of fine line> A fine line pattern of yellow, magenta, cyan and black is printed, and the temperature is 40% at 80%.
After standing for 1 day under the conditions described above, evaluation was performed visually. For black, magenta ink was solidly printed, then black fine lines were printed, and bleeding due to contact of two colors was also evaluated.

<Water resistance> After immersing the obtained image in deionized water for 5 minutes, bleeding of the image was visually evaluated.

<Light fastness> For the image fastness, a gray print sample was prepared and evaluated as follows. After measuring the chromaticity (a * 1, b * 1) and brightness (L1) immediately after printing with SPM100-II made by Gretag, irradiate with xenon light (85000 lux) for 18 days using a weather meter made by Atlas. After that, the chromaticity (a * 2, b * 2) and the lightness (L2) were measured again, and the color difference (ΔE) before and after the light irradiation was obtained and evaluated according to the following formula. ΔE = {(a * 1-a * 2) ² + (b * 1-b * 2) ² + (L1-
L2) ² } ^1/2 color difference was evaluated at three points with reflection densities of 1.0, 1.3 and 1.6, and A was used when the color difference was less than 5 and A was less than 5 and 5 depending on the density. The case in which both of the above evaluations are included is B, and the case in which all the concentrations are 5 or more is C.

<Thermal Fastness> The color difference before and after storing the sample at 85 ° C. for 10 days was evaluated by the same method as the light fastness. Regarding the residual ratio of dye, the reflection density is 1.0,
Evaluation was made at three points of 1.3 and 1.6, and A in the case where the color difference was less than 3 in any of the densities, B in the case of including both evaluations of less than 3 and 3 or more depending on the density, and 3 in all the densities. The above case was designated as C.

<Ozone resistance> Ozone gas concentration is 1.0 p
The color difference before and after storing the sample for 14 days in the box set to pm was evaluated by the same method as the light fastness. Regarding the residual ratio of dye, the reflection density is 1.0, 1.3,
Evaluation was made with 3 points of 1.6, and the color difference was 10 at any density.
The case of less than was designated as A, the case of including both ratings of less than 10 and 10 or more depending on the concentration was designated as B, and the case of 10 or more at all concentrations was designated as C. The ozone gas concentration in the box is
Ozone gas monitor made by APPLICS (Model: OZG
-EM-01).

[0234]

[Table 5]

[0235]

[Table 6]

It can be seen that when the ink composition of the present invention is used as an oil-soluble dye dispersion, it exhibits particularly excellent fastness. Further, the ink composition of the present invention provides excellent ejection stability without clogging, has excellent performance when outputting fine lines without bleeding, and further improves water resistance. Even when the image receiving paper used in the present invention is changed to PM photo paper manufactured by Epson Corp. or PR101 manufactured by Canon Inc., the same effect as the above result can be seen.

[Example 4] The same ink prepared in Example 3 was packed in an inkjet printer BJ-F850 (manufactured by Canon Inc.), and the image was printed on the inkjet paper image photographic finish made by Fuji Photo Film by the same machine, When the same evaluation as that of the example was performed, the same result as that of the example 3 was obtained. Similar effects were observed when the image receiving paper was PM photo paper manufactured by Epson and PR101 manufactured by Canon.

[0238]

As demonstrated in the examples, the ink jet recording liquid according to the present invention has good fastness, particularly light resistance and ozone resistance as an ink for ink jet recording, and excellent ejection stability, water resistance and bleeding. ing.

Claims (3)

[Claims] 1. A yellow ink containing at least one yellow dye, a magenta ink containing at least one magenta dye, a cyan ink containing at least one cyan dye, and at least one self-dispersing pigment. An ink set having a black ink containing the ink, wherein the oxidation potentials of the magenta dye and the cyan dye are noble than 0.8 V (vs SCE), respectively. 2. A container containing the ink set according to claim 1. 3. An ink jet recording method, wherein an image is formed by an ink jet method using the ink set according to claim 1.