JP2008255330A - Ink set and inkjet recording method - Google Patents

Abstract

An object of the present invention is to suppress a bronzing phenomenon in a colored image material formed by combining ink compositions of a plurality of colors, and to form an image having good fixability to an image receiving material even under high-temperature and high-humidity conditions and with little blur. An ink set is provided.
An ink set comprising a magenta ink composition and a cyan ink composition, wherein the magenta ink composition comprises at least one selected from a specific azo dye as a colorant and a specific anthrapyridone dye. 50% or more of the total number of counter ions is a lithium ion as a counter ion of the ionic hydrophilic group of the total colorant included in the magenta ink composition, including at least one selected from the above, and the cyan ink composition Is an ink set containing at least one selected from phthalocyanine compounds as a colorant.
[Selection figure] None

Description

  The present invention suppresses the bronzing phenomenon of a colored image material formed by combining a plurality of color ink compositions, and forms an image with good fixability to the image receiving material even under high-temperature and high-humidity conditions and with less blur. And an ink jet recording method.

The ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording.
Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. There are a method of discharging bubbles, a method of generating bubbles in the ink by heat and discharging droplets, a method of using ultrasonic waves, and a method of sucking and discharging droplets by electrostatic force. As the ink for ink jet recording, water-based ink, oil-based ink, or solid (melting type) ink is used.

For the colorant used in such ink for ink jet recording, the solvent has good solubility or dispersibility, high density recording is possible, hue is good, light, heat, environment It is robust against active gases (NOx, oxidizing gases such as ozone, SOx, etc.), has excellent fastness to water and chemicals, and has good fixability to image receiving materials and is difficult to bleed. The ink is required to have excellent storage stability, no toxicity, high purity, and availability at low cost.
However, it is extremely difficult to search for pigments that meet these requirements at a high level. In particular, there is a strong demand for a colorant that has a good hue, is robust against light and ozone, has good fixability to an image receiving material even under high temperature and high humidity conditions, and has little blur.

  In recent years, it has been practiced to form a color image by an ink jet recording method using a plurality of color ink compositions to obtain a recorded matter. In general, a color image is formed by three colors, ie, a yellow ink composition, a magenta ink composition, and a cyan ink composition, and further, if desired, four colors including a black ink composition. In some cases, color images are formed with six colors obtained by adding a light cyan ink composition and a light magenta ink composition to these four colors, or seven colors obtained by further adding a dark yellow ink composition thereto. A combination of two or more ink compositions is an ink set.

  In the ink composition used for forming the color image described above, the ink composition for each color has a good color developability, and in addition, a recording obtained when combining a plurality of color ink compositions. It is required that an object does not discolor during storage and that a bronze phenomenon does not occur.

  In an ink set, when the light resistance or ozone resistance of a specific ink composition is significantly lower than other ink compositions, the color formed by the specific ink composition fades faster than other colors. The color changes, and the balance of the color tone of the entire image becomes worse. Accordingly, in addition to improving the light resistance and ozone resistance of each ink composition constituting the ink set, the deterioration rate of the image formed by each ink composition by light and ozone, for example, the fading speed is as much as possible. Preferably there is. In other words, it is preferable that each ink composition constituting the ink set is excellent in light resistance and ozone resistance, and that the difference in light resistance and ozone resistance between the ink compositions is small.

  In addition, when a recorded image having a high optical density is formed, a dye crystal precipitates on the surface of the image receiving material as it dries, and a so-called bronze phenomenon occurs in which the recorded image reflects light and emits a metallic luster. was there. This phenomenon is due to the increase in dye association (aggregation) by reducing the water solubility of the dye in order to improve water resistance or by introducing an amino group of a hydrogen bond group into the dye structure. This is likely to occur. Since the light is reflected by the occurrence of the bronze phenomenon, not only the optical density of the recorded image is lowered, but also the hue of the recorded image is greatly different from the desired one. This is one of the important performance requirements.

  As the skeleton of the cyan dye used in the ink for inkjet recording, a phthalocyanine compound is representative. In recent years, when an image is formed using a phthalocyanine compound described in JP-A No. 2003-213167 in a cyan ink composition, the bronze phenomenon in a single color is suppressed, and light resistance and ozone resistance are excellent. Has been reported. However, there is no description of the presence or absence of bronzing in a colored image (mixed color portion) formed by combining ink compositions of a plurality of colors.

On the other hand, the skeleton of the magenta dye used in the ink for ink jet recording includes xanthene dyes found in JP-A-8-60053, H-azo dyes found in JP-A-7-090211, etc. Heterocycles such as anthrapyridone dyes found in 192930, WO04 / 104108, WO06 / 075706, and JP-A-2002-371214, 2006-143389 -Heterocyclic azo dyes are typical.
Among these, xanthene dyes and H acid azo dyes are excellent in hue, but have problems in light resistance and ozone resistance. Anthrapyridone dyes are excellent in sharpness and light resistance, but have a problem in ozone resistance. On the other hand, the heterocyclic-heterocyclic azo dye is excellent in light resistance and ozone resistance, but has a problem in fixability to an image receiving material under high temperature and high humidity conditions.
Therefore, to date, there has been no report of a magenta dye that has excellent hue, light resistance, and ozone resistance, good fixability to an image receiving material under high temperature and high humidity conditions, and does not cause bronzing in a mixed color portion.
JP 2003-213167 A JP 2003-192930 A International Publication No. 04/104108 Pamphlet International Publication No. 06/075706 Pamphlet JP 2002-371214 A JP 2006-143989 A

An object of the present invention is to solve the above problems and achieve the following objects.
That is, a first object of the present invention is an inkjet recording magenta that has good fixability to an image receiving material under high-temperature and high-humidity conditions, has little blurring, and can form a robust image against light and ozone. The object is to provide an ink set containing ink.
The second object of the present invention is to provide a good balance of light resistance and ozone resistance between the ink compositions constituting the ink set, and a colored image (mixed color portion) formed by combining a plurality of color ink compositions. The object is to provide an ink set that does not cause bronzing.

The present inventors have made it possible to solve the above problems by adopting the following configuration.
1. At least an ink set comprising a magenta ink composition and a cyan ink composition, wherein the magenta ink composition is at least one selected from azo dyes represented by the following general formula (1) as a colorant: It contains at least one selected from the anthrapyridone dyes represented by the following general formula (2), and the counter ion of the ionic hydrophilic group of all the colorants contained in the magenta ink composition has a total counter ion number of 50. % Or more of lithium ions, and the cyan ink composition contains at least one selected from phthalocyanine compounds as a colorant.
General formula (1):

In general formula (1), A represents a 5-membered heterocyclic ring. B ₁ and _{B 2} are each _-CR 13 =, - or represents _{CR 14} =, or, in either a nitrogen atom and the other represents a _{-CR 13} = or _{-CR 14} =. R ₁₁ and R ₁₂ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl. Represents a group. However, R ₁₁ and R ₁₂ are not simultaneously hydrogen atoms. R ₁₃ and R ₁₄ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group Group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, sulfamoylamino group, alkoxy Carbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, nitro group, alkyl and arylthio group, alkyl and arylsulfonyl group, alkyl and arylsulfinyl group, sulfamoyl group, It represents a heterocyclic thio group or an ionic hydrophilic group. R ₁₃ and R ₁₁ or R ₁₁ and R ₁₂ may be bonded to form a 5- to 6-membered ring. a and e each independently represent an alkyl group, an alkoxy group, or a halogen atom; b, c, and d are each independently synonymous with R ₁₃ and R ₁₄ ; a to e are bonded to each other to form a ring; May be. However, general formula (1) has at least one ionic hydrophilic group.
General formula (2):

In general formula (2), R ₁ represents a hydrogen atom or an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, and R ₃ and R ₅ each independently represents a hydrogen atom or a substituent. R ₂ and R ₄ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. However, general formula (2) has at least one ionic hydrophilic group.
2. 2. The ink set according to 1 above, wherein the cyan ink composition contains at least one selected from phthalocyanine compounds represented by the following general formula (3) as a colorant.
General formula (3):

In the general formula (3), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NV ₁ V ₂ , —CONV ₁ V ₂ , —CO ₂ represents any one of Z, —CO—Z and a sulfo group. Here, Z represents an aliphatic group, an aromatic group, or a heterocyclic group each independently. V ₁ and V ₂ may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkylamino group, Alkoxy group, aryloxy group, amide group, arylamino group, aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, Heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group, or ionic hydrophilic group To express. a ₁ ~a ₄ and _b 1 ~b ₄ each represent the number of substituents of _X 1 to X ₄ and _Y 1 to Y _4. A _{1 to} a ₄ are each independently an integer of 0 to 4, and all do not simultaneously become 0. b ₁ ~b ₄ represents each independently an integer of 0-4. M is a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof. However, at least one of X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y ₃ and Y ₄ is an ionic hydrophilic group or an ionic hydrophilic group as a substituent. It is group which has.
3. 3. The ink set according to 1 or 2 above, wherein the concentration of free copper ions in the cyan ink composition is 10 ppm or less.
4). As described in any one of 1 to 3 above, wherein 80% or more of the total counter ions are lithium ions as counter ions of the ionic hydrophilic groups of all colorants contained in the magenta ink composition. The ink set described.
5. As counter ions of ionic hydrophilic groups of all colorants contained in the magenta ink composition, 80% or more of the total counter ions are lithium ions, and ions of all colorants contained in the cyan ink composition The ink set according to any one of 1 to 4 above, wherein 80% or more of the total number of counter ions is a lithium ion as a counter ion of the hydrophilic hydrophilic group.
6). The ink set according to any one of the above 1 to 5, wherein the azo dye of the general formula (1) is represented by the following general formula (4).
General formula (4):

In the general formula (4), Z ₁₁ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ₁₂ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or an acyl group. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , a, b, c, d, and e are as defined in the general formula (1). Q represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. However, general formula (4) has at least one ionic hydrophilic group.
7). In the azo dye of the general formula (1), a and e are both alkyl groups, and the total number of carbon atoms constituting the alkyl group is 3 or more. The ink set described in 1.
8). 8. The ink set according to any one of 1 to 7, wherein in the anthrapyridone dye of the general formula (2), at least one of the ionic hydrophilic groups is a carboxyl group.
9. The magenta ink composition according to any one of 1 to 8 above, wherein the magenta ink composition includes two types of magenta ink compositions having different color densities, and at least one magenta ink composition is the magenta ink composition according to any one of 1 to 8 above. An ink set characterized by being.
10. The cyan ink composition according to any one of 1 to 9 above, wherein the cyan ink composition includes two types of cyan ink compositions having different color densities, and at least one type of cyan ink composition is the cyan ink composition according to any one of 1 to 9 above. An ink set characterized by being.
11. An ink cartridge that accommodates the ink set described in any one of 1 to 10 integrally or independently.
12 An ink jet printer, wherein the ink cartridge according to 11 is loaded.
13. 11. An ink jet recording method comprising recording using the ink set according to any one of 1 to 10 or the ink cartridge according to 11 above.
14 Forming an image on the image receiving material having an ink receiving layer containing a white inorganic pigment on a support using the ink set according to any one of 1 to 10 or the ink cartridge according to 11 above. An ink jet recording method.
15. 11. A method for suppressing a bronze phenomenon of a colored image material, wherein the ink set according to any one of 1 to 10 is used.
16. A method for improving bleeding under high-temperature and high-humidity conditions of a colored image material, wherein the ink set according to any one of 1 to 10 is used.

The present invention provides a magenta ink composition that is excellent in light resistance and ozone resistance, has good fixability to an image receiving material under high-temperature and high-humidity conditions, and can give a colored image with less blurring, and has excellent light resistance and ozone resistance. An ink set including a cyan ink composition capable of providing an excellent colored image.
The ink set of the present invention has a small difference in light fastness and ozone fastness between ink compositions, a small hue change under high temperature and high humidity conditions, and a color mixture portion formed by combining a plurality of color ink compositions A colored image that does not cause bronzing is obtained.

Hereinafter, implementation of the present invention will be described in detail.
First, the substituent used in this specification is demonstrated. Examples of the substituent used in the present specification include the following groups (hereinafter referred to as “substituent W”).
For example, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group , Carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group , Mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryl group Aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a silyl group.

  The aliphatic group used in the present specification means an alkyl group, an alkenyl group, and an alkynyl group. Moreover, an aryl group can be mentioned as an aromatic group used by this specification.

  More specifically, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkyl group include linear, branched, and cyclic substituted or unsubstituted alkyl groups, and also include cycloalkyl groups, bicycloalkyl groups, and tricyclo structures having many ring structures. An alkyl group (for example, an alkyl group of an alkoxy group or an alkylthio group) in a substituent described below also represents such an alkyl group. Specifically, the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, eicosyl group, A 2-chloroethyl group, a 2-cyanoethyl group, a 2-ethylhexyl group, and the like. The cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as a cyclohexyl group or a cyclopentyl group. 4-n-dodecylcyclohexyl group and the like, and the bicycloalkyl group is preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a bicyclic alkane having 5 to 30 carbon atoms to a hydrogen atom. A monovalent group such as a bicyclo [1,2,2] heptan-2-yl group, B [2,2,2] octan-3-yl group.

Examples of the alkenyl group include linear, branched, and cyclic substituted or unsubstituted alkenyl groups, and include cycloalkenyl groups and bicycloalkenyl groups. Specifically, the alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group, and the like. Is preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as 2-cyclopentene-1 -Yl group, 2-cyclohexen-1-yl group and the like. As the bicycloalkenyl group, a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, That is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond, for example, bicyclo [ , 2,1] hept-2-en-1-yl group, a bicyclo [2,2,2] oct-2-en-4-yl group and the like.
The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, or a trimethylsilylethynyl group.

The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group, and the like. Can be mentioned.
The heterocyclic group is preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a carbon number. Examples thereof include 3 to 30 5- or 6-membered aromatic heterocyclic groups such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.
The alkoxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or a 2-methoxyethoxy group. Etc.

The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as a phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, 3-nitrophenoxy group, 2 -Tetradecanoylaminophenoxy group etc. are mentioned.
The silyloxy group is preferably a substituted or unsubstituted silyloxy group having 0 to 20 carbon atoms, such as a trimethylsilyloxy group or a diphenylmethylsilyloxy group.
Preferred examples of the heterocyclic oxy group include substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms, such as a 1-phenyltetrazole-5-oxy group and a 2-tetrahydropyranyloxy group.
The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as an acetyloxy group, Examples include a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, and a p-methoxyphenylcarbonyloxy group.
The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N , N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group and the like.

The alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, or an n-octylcarbonyloxy group. Etc.
The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxy. Examples include phenoxycarbonyloxy group.
The amino group includes an alkylamino group, an arylamino group, and a heterocyclic amino group, preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 6 to 30 carbon atoms. Examples of the substituted anilino group include a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, and a diphenylamino group.
The acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as an acetylamino group, Examples include pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, and the like.

The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as a carbamoylamino group, an N, N-dimethylaminocarbonylamino group, or an N, N-diethylaminocarbonylamino group. And a morpholinocarbonylamino group.
The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, or an n-octadecyloxycarbonylamino group. Group, N-methyl-methoxycarbonylamino group and the like.
The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxy. Examples thereof include a carbonylamino group.
The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as a sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn- Examples include octylaminosulfonylamino group.

The alkyl or arylsulfonylamino group is preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as a methylsulfonylamino group. Butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, and the like.
The alkylthio group is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, and an n-hexadecylthio group.
Preferred examples of the arylthio group include substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms such as a phenylthio group, a p-chlorophenylthio group, and an m-methoxyphenylthio group.
Preferred examples of the heterocyclic thio group include substituted or unsubstituted heterocyclic thio groups having 2 to 30 carbon atoms such as a 2-benzothiazolylthio group and a 1-phenyltetrazol-5-ylthio group.
The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfuryl group. Examples include a famoyl group, an N-acetylsulfamoyl group, an N-benzoylsulfamoyl group, and an N- (N′-phenylcarbamoyl) sulfamoyl group.

The alkyl or arylsulfinyl group is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group, an ethylsulfinyl group, phenyl. Examples thereof include a sulfinyl group and a p-methylphenylsulfinyl group.
The alkyl or arylsulfonyl group is preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, a phenyl group. A sulfonyl group, p-methylphenylsulfonyl group, etc. are mentioned.
The acyl group is preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted group having 2 to 30 carbon atoms. Heterocyclic carbonyl groups bonded to carbonyl groups at substituted carbon atoms, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridyl Examples thereof include a carbonyl group and a 2-furylcarbonyl group.
The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt- A butylphenoxycarbonyl group etc. are mentioned.

Preferred examples of the alkoxycarbonyl group include substituted or unsubstituted alkoxycarbonyl groups having 2 to 30 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, and an n-octadecyloxycarbonyl group.
The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, or an N, N-di-n-octyl group. Examples thereof include a carbamoyl group and an N- (methylsulfonyl) carbamoyl group.
The aryl or heterocyclic azo group is preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo and the like.

Preferred examples of the imide group include an N-succinimide group and an N-phthalimide group.
Preferred examples of the phosphino group include substituted or unsubstituted phosphino groups having 0 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, and a methylphenoxyphosphino group.
The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 0 to 30 carbon atoms, such as a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, and the like.
Preferred examples of the phosphinyloxy group include substituted or unsubstituted phosphinyloxy groups having 0 to 30 carbon atoms such as a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group.
The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 0 to 30 carbon atoms, such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group.
The silyl group is preferably a substituted or unsubstituted silyl group having 0 to 30 carbon atoms, such as a trimethylsilyl group, a t-butyldimethylsilyl group, and a phenyldimethylsilyl group.

  Among the above substituents, those having a hydrogen atom may be substituted with the above substituent. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

  Examples of the ionic hydrophilic group include an anionic group such as a sulfo group, a carboxyl group, and a phosphono group, and a cationic group such as a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and among them, a carboxyl group and a sulfo group are preferable. The carboxyl group, phosphono group, sulfo and the like may be in the form of a salt, and as a counter ion forming the salt, ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion), organic cation ( Examples thereof include tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal ions are preferable. Of the alkali metal ions, potassium ions, sodium ions, and lithium ions are preferable.

The magenta dye used as the colorant of the magenta ink composition in the ink set of the present invention is represented by the general formula (1) and the general formula (2). First, the azo dye represented by the following general formula (1) will be described.
General formula (1):

In general formula (1), A represents a 5-membered heterocyclic group. B ₁ and _{B 2} are each _-CR 13 =, - or represents _{CR 14} =, or, in either a nitrogen atom and the other represents a _{-CR 13} = or _{-CR 14} =. R ₁₁ and R ₁₂ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl. Represents a group. However, R ₁₁ and R ₁₂ are not simultaneously hydrogen atoms. R ₁₃ and R ₁₄ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group Group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, sulfamoylamino group, alkoxy Carbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, nitro group, alkyl and arylthio group, alkyl and arylsulfonyl group, alkyl and arylsulfinyl group, sulfamoyl group, It represents a heterocyclic thio group or an ionic hydrophilic group. R ₁₃ and R ₁₁ or R ₁₁ and R ₁₂ may be bonded to form a 5- to 6-membered ring. a and e each independently represent an alkyl group, an alkoxy group, or a halogen atom; b, c, and d are each independently synonymous with R ₁₃ and R ₁₄ ; a to e are bonded to each other to form a ring; May be. However, general formula (1) has at least one ionic hydrophilic group.

  In the general formula (1), A represents a 5-membered heterocyclic ring, and examples of the heteroatom of the 5-membered heterocyclic ring represented by A include N, O, and S. A is preferably a nitrogen-containing 5-membered heterocyclic ring, and the heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring, or another heterocyclic ring. Examples of a preferable heterocyclic ring for A include a pyrazole ring, an imidazole ring, a triazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a benzothiazole ring, a benzoxazole ring, and a benzoisothiazole ring. Each heterocyclic group may further have a substituent (the aforementioned substituent W). Among these, heterocyclic rings represented by the following general formulas (a) to (i) are preferable.

In formula _{(a) ~ (i),} Rm 1 ~Rm 20 have the same meanings as in formula (1) _{R 13, R 14} in.

In general formula (1), preferred R ₁₁ and R ₁₂ each independently represents a hydrogen atom, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, substituted or unsubstituted A substituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, more preferably a hydrogen atom, a substituted aryl group, or a substituted heterocyclic group, a substituted aryl group, or a substituted Heterocyclic groups are particularly preferred. However, R ₁₁ and R ₁₂ are not simultaneously hydrogen atoms.

In the general formula (1), the case where B ₁ and B ₂ represent —CR ₁₃ ═ and —CR ₁₄ ═ is preferable in that more excellent performance can be exhibited.

In the general formula (1), preferable R ₁₃ and R ₁₄ are each independently a hydrogen atom, an alkyl group, a cyano group, a carboxyl group, a carbamoyl group, or an alkoxycarbonyl group. Each group may be further substituted. More specifically, a hydrogen atom, an alkyl group, or a cyano group is preferable. Among them, R ₁₃ is preferably a hydrogen atom, R ₁₄ is preferably an alkyl group, R ₁₃ is a hydrogen atom, and R ₁₄ is particularly preferably a combination of methyl groups.

  In the general formula (1), preferable a and e are cases where both a and e are alkyl groups and the total number of carbon atoms constituting the alkyl group is 3 or more. More preferable a and e are each independently a methyl group, an ethyl group, or an isopropyl group, and among them, an ethyl group or an isopropyl group is preferable, and in particular, both a and e are most preferably an ethyl group or an isopropyl group.

  In General formula (1), preferable c is a hydrogen atom, an alkyl group, or an ionic hydrophilic group, and a hydrogen atom, a methyl group, or a sulfo group is more preferable. Preferred b and d are each independently a hydrogen atom or an ionic hydrophilic group, more preferably a hydrogen atom, a sulfo group or a carboxy group, and the combination of b and d may be a hydrogen atom and a sulfo group. Further preferred.

In the present invention, among the azo dyes represented by the general formula (1), an azo dye represented by the following general formula (4) is preferable.
General formula (4):

In the general formula (4), Z ₁₁ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ₁₂ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or an acyl group. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , a, b, c, d, and e are as defined in the general formula (1). Q represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. However, general formula (4) has at least one ionic hydrophilic group.

In the general formula _(4), R _{13, R 14} has the same meaning as _{R 13, R 14} in the general formula (1), and preferred examples are also the same.

In the general formula _(4), R _{11, R 12} has the same meaning as _{R 11, R 12} in the general formula (1), and preferred examples are also the same.

  In the general formula (4), a, b, c, d and e have the same meanings as a, b, c, d and e in the general formula (1), and preferred examples are also the same.

In the general formula (4), the electron withdrawing group of Z _{11 is} an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, preferably 0.30 or more. The upper limit of the σp value is preferably 1.0 or less.

Here, Hammett's substituent constant σp value used in this specification will be described.
Hammett's rule is a method for determining the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it is limited only to a substituent having a known value that can be found in the above-mentioned book. However, it goes without saying that even if the value is unknown, it also includes a substituent that would be included in the range when measured based on Hammett's rule. In the present invention, the σp value is used in this sense.

Specific examples of the electron withdrawing group having a σp value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphospho group Group, diarylphosphinyl group, alkylsulfinyl group , arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy Substituent, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, heterocyclic group, halogen atom, azo group, selenocyanate group, other electron withdrawing groups with σp value of 0.20 or more Aryl group etc. The

Z ₁₁ is preferably a cyano group, a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, or a halogen atom, and more preferably a cyano group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group. A cyano group is most preferred.

In the general formula (4), Z ₁₂ is preferably a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group, more preferably a hydrogen atom or an alkyl group. Each substituent may be further substituted. More specifically, Z ₁₂ is preferably an alkyl group having 1 to 12 carbon atoms excluding the carbon atoms of the substituent, and more preferably an alkyl group having 1 to 6 carbon atoms.
Examples of alkyl groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, or 4-sulfobutyl, among which methyl, ethyl, Isopropyl or t-butyl is preferred, isopropyl or t-butyl is preferred, and t-butyl is particularly preferred.

In the general formula (4), Q is preferably an aryl group or a heterocyclic group substituted with an electron withdrawing group, and the electron withdrawing group serving as a substituent for Q is Hammett's substituent constant σp value. Is an electron withdrawing group of 0.20 or more, preferably 0.30 or more. The upper limit of the σp value is preferably 1.0 or less. Specific examples of the electron withdrawing group having a σp value of 0.20 or more are the same as Z ₁₁ in the general formula (4). More specifically, Q is preferably a heterocyclic group substituted with an electron withdrawing group, and among them, a sulfo group, a substituted or unsubstituted carbamoyl group, a benzoxazole ring substituted with a substituted or unsubstituted sulfamoyl group, A benzothiazole ring substituted with a sulfo group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group is preferred, and a benzothiazole ring substituted with a sulfo group or a substituted sulfamoyl group is particularly preferred.

  The azo dyes represented by the general formulas (1) and (4) have at least one ionic hydrophilic group in the molecule. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and among them, a carboxyl group and a sulfo group are preferable. It is particularly preferred that at least one is a sulfo group. The carboxyl group, phosphono group, and sulfo group may be in a salt state. Examples of counter ions that form the salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), organic Cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) are included. Among the counter ions, alkali metal ions are preferable. Of the alkali metal ions, potassium ions, sodium ions, and lithium ions are preferable, and lithium ions are most preferable. From the viewpoint of improving solubility and suppressing the bronze phenomenon in ink jet printing, a combination of a ionic hydrophilic group as a sulfo group and a counter ion as lithium ion is particularly preferable.

  The azo dye represented by the general formula (1) and the general formula (4) preferably has 3 or more and 6 or less ionic hydrophilic groups in its molecule, and has 3 or more and 6 or less sulfo groups. More preferably, it has 3 or more and 5 or less sulfo groups.

Examples of the azo dyes represented by the general formulas (1) and (4) of the present invention include ionic hydrophilic groups in the molecule among the azo dyes described in Patent Documents 5 to 9 shown below. Preferred is an azo dye having at least one.
Patent Document 5 JP 2002-371214 A Patent Document 6 JP 2006-143989 JP Patent Document 7 JP 2002-309116 JP Patent Document 8 JP 2003-064275 JP Patent Document 9 International Publication No. 02/083795 pamphlet Specific examples of the azo dyes represented by the general formulas (1) and (4) of the present invention are shown below. However, the azo dyes used in the present invention are limited to the following examples. It is not something.
An azo dye represented by a-27, f-1, and f-3 described in Patent Document 5 a-2, a-6, d-3, d-4, and d-5 described in Patent Document 6 Azo dye represented by d-6, azo dye represented by 143,145,148 described in Patent Document 8

  An azo dye represented by a-27, f-1, and f-3 described in Patent Document 5, and a-2, a-6, d-3, d-4, d-5, described in Patent Document 6 azo dye represented by d-6, azo dye represented by 143,145,148 described in Patent Document 8

Next, an anthrapyridone dye represented by the following general formula (2) used as a colorant for the magenta ink composition in the ink set of the present invention will be described.
General formula (2):

In general formula (2), R ₁ represents a hydrogen atom or an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, and R ₃ and R ₅ each independently represents a hydrogen atom or a substituent. (The substituent W described above), and R ₂ and R ₄ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. However, general formula (2) has at least one ionic hydrophilic group.

In the general formula (2), the electron withdrawing group of R ₁ is preferably an electron withdrawing group having Hammett's substituent constant σp value of 0.20 or more, more preferably 0.30 or more, and σp value. The upper limit is preferably 1.0 or less. R ₁ is preferably a hydrogen atom, substituted benzoyl group, acyl group, carbamoyl group, alkoxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, aryl A sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, or a sulfamoyl group, more preferably a hydrogen atom, a substituted benzoyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, or an acyl group, particularly A substituted benzoyl group (3-sulfobenzoyl group, 4-sulfobenzoyl group, 3,5-disulfobenzoyl group, 3-sulfo-4-methoxybenzoyl group, etc. ) is preferable.

In general formula (2), R ₂ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. The heterocyclic group for R ₂ is preferably a 5- to 6-membered heterocyclic group, and may be a monocyclic structure or a polycyclic structure in which two or more rings are condensed. Further, the heterocyclic group is preferably a heterocyclic group containing at least one of N, O, and S atoms. Preferred examples of the 5- to 6-membered heterocyclic group represented by R ₂ include thienyl group, furyl group, pyrrolyl group, indolyl group, imidazolyl group, benzimidazolyl group, pyrazolyl group, indazolyl group, thiazolyl group, Benzothiazolyl group, isothiazolyl group, benzoisothiazolyl group, oxazolyl group, benzoxazolyl group, isoxazolyl group, 1,2,4-thiadiazolyl group, 1,3,4-thiadiazolyl group, 1,2,4-oxadiazolyl group 1,3,4-oxadiazolyl group, triazolyl group, pyridyl group, pyrazyl group, pyrimidyl group, pyridazyl group, 1,3,5-triazyl group, quinolyl group, isoquinolyl group, phthalazinyl group and the like. These may have a substituent (the aforementioned substituent W). Two substituents on the heterocyclic group may combine to form a condensed ring. Further, when the heterocyclic group contains a nitrogen atom, the nitrogen atom may be quaternized.

R ₂ is more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom or a methyl group.

In general formula (2), R ₃ is preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carboxyl group, or a sulfo group, and particularly preferably a hydrogen atom. Or a substituted aryloxy group.

In the general formula (2), R ₄ is preferably an aromatic group or a heterocyclic group, more preferably a substituted aryl group, and particularly preferably an aryl group substituted with an ionic hydrophilic group.

In general formula (2), R ₅ is preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an amino group, a carboxyl group, or a sulfo group, and particularly preferably a hydrogen atom.

The anthrapyridone dye represented by the general formula (2) has at least one ionic hydrophilic group in the molecule. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and among them, a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group, and sulfo group may be in a salt state. Examples of counter ions that form the salt include ammonium ions, alkali metal ions (for example, lithium ions, sodium ions, potassium ions), and organic cations. (For example, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal ions are preferable. From the viewpoint of fixability to an image receiving material under high temperature and high humidity conditions, at least one of the ionic hydrophilic groups is particularly preferably a carboxyl group. The counter ions are preferably lithium ions, sodium ions, potassium ions and ammonium ions, and particularly preferably lithium ions from the viewpoint of improving the solubility and suppressing the bronzing phenomenon in ink jet printing.
The anthrapyridone dye preferably has 2 or more and 12 or less ionic hydrophilic groups in its molecule, and more preferably 4 or more and 10 or less.

As an anthrapyridone dye represented by General formula (2) of this invention, the anthrapyridone dye of the patent documents 2-4 shown below and the patent documents 10-22 is mentioned as a preferable thing.
Patent Document 2: No. described in Japanese Patent Application Laid-Open No. 2003-192930. 1-60 and no. Compounds 1-1 to 1-17 / Patent Document 3: No. described in WO 04/104108 pamphlet Compounds Nos. 1 to 37 and Patent Document 4: No. described in pamphlet of International Publication No. 06/075706. Compounds of 1 to 22 / Patent Document 10: Compounds of (1) to (7) described in JP-A No. 2001-072884 / Patent Document 11: Compounds of formula (1) described in JP-A No. 2001-139836 Patent Document 12: Compounds (4), (5), (12), and (15) to (22) described in JP-A-2002-332418. Patent Document 13: described in JP-A-2005-008868. No. Compound No. 1 to 40 / Patent Document 14: Compound of formula (3) described in JP-A-2005-041846 / Patent Document 15: No. described in JP-A-2005-139377 Compound Nos. 1 to 14, Patent Document 16: No. 1 to 41, described in JP-A 2005-314514, Patent Document 17: Compounds A1 and A2, and JP-A 2005-320480, Patents 18: Compounds described in Table 1 of JP-A No. 2006-124475 / Patent Document 19: No. described in JP-A No. 2006-188706 1 to 48 compounds / Patent Document 20: No. described in JP 2007-077256 A Compounds Nos. 1 to 17 and Patent Document 21: No. Compounds of 1 to 15 / Patent Document 22: Compounds of Exemplified Compounds 1 to 7 described in JP-A-2007-277314

  More preferably, the anthrapyridone dye represented by the general formula (2) of the present invention has at least one carboxyl group as an ionic hydrophilic group and is described in Patent Documents 2 to 4 and Patent Documents 13 to 22 described above. For example, No. 2 described in Patent Document 2 is a dye. Nos. 21 to 24, 30, and 31; 23-31, no. Nos. 34 to 37, Nos. The compound of 1-22 is mentioned. When a magenta ink composition using these anthrapyridone dyes and the azo dye represented by the general formula (1) of the present invention in combination is used, it is robust to good hue, light and ozone, and receives images under high temperature and high humidity conditions. A colored image having good fixability to the material and less blur is obtained.

  Particularly preferably, the anthrapyridone dye represented by the general formula (2) of the present invention has at least one carboxyl group as an ionic hydrophilic group, and a lithium ion is included as a counter ion of the ionic hydrophilic group. Is the case. The ratio of the number of lithium ions to the total number of counter ions of the ionic hydrophilic group substituted with the anthrapyridone dye represented by the general formula (2) is preferably 40% or more, more preferably 60% or more. Is the case. As the proportion of lithium ions increases, the solubility of the anthrapyridone dye in water can be improved. Further, when these anthrapyridone dyes and the azo dyes represented by the general formula (1) of the present invention are used in combination, in addition to the above effects, a bronze is formed in a colored image (color mixture portion) formed in combination with a cyan ink composition. The phenomenon can be suppressed.

The cyan dye used as the colorant for the cyan ink composition contained in the ink set of the present invention is not particularly limited as long as it is a phthalocyanine compound, but is preferably a phthalocyanine compound represented by the following general formula (3). Next, the following general formula (3) will be described in detail.
General formula (3):

In the general formula (3), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NV ₁ V ₂ , —CONV ₁ V ₂ , —CO ₂ represents any one of Z, —CO—Z and a sulfo group. Here, Z represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted heterocyclic group. V ₁ and V ₂ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted heterocyclic group.
Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkylamino group, Alkoxy group, aryloxy group, amide group, arylamino group, aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, Heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group, or ionic hydrophilic group To express.
a ₁ ~a ₄ and _b 1 ~b ₄ each represent the number of substituents of _X 1 to X ₄ and _Y 1 to Y _4.
A _{1 to} a ₄ are each independently an integer of 0 to 4, and all do not simultaneously become 0. b ₁ ~b ₄ represents each independently an integer of 0-4.
M is a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof. However, at least one of X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y _3, and Y ₄ is an ionic hydrophilic group or a ionic hydrophilic group as a substituent. As a group possessed as

In the general formula (3), a ₁ , a ₂ , a ₃ and a ₄ are preferably 0 or 1, and two or more of a ₁ , a ₂ , a ₃ and a ₄ are 1; Furthermore, b ₁ , b ₂ , b ₃ and b ₄ are preferably integers such that the sum of a ₁ , a ₂ , a ₃ and a ₄ is ₄ , respectively.

In the general formula (3), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NV ₁ V ₂ , —CONV ₁ V ₂ , —CO ₂ represents any one of Z, —CO—Z and a sulfo group.
Z is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group is preferable. Particularly preferred are substituted alkyl groups.

V ₁ and V ₂ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom, a substituted alkyl group, a substituted An aryl group or a substituted heterocyclic group is most preferred.

The substituted or unsubstituted aliphatic group represented by Z, V ₁ or V ₂ is preferably an aliphatic group having 1 to 50 carbon atoms. In particular, an aliphatic group having a branched carbon chain is preferable because of increasing the solubility of the dye and the ink stability, and a case where the group has an asymmetric carbon (use in a racemic form) is particularly preferable. As a preferred substituent for substitution with an aliphatic group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group, an amino group, an amide group, and a sulfamoyl group are particularly preferable because they enhance the association of the dye and improve the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

As the substituted or unsubstituted aromatic group represented by Z, V ₁ and V ₂ , an aromatic group having 6 to 30 carbon atoms is preferable. As a preferable substituent substituted with an aromatic group, an electron withdrawing group is particularly preferable because the oxidation potential of the dye is noble and fastness is improved.

The heterocyclic group represented by Z, V ₁ and V ₂ is preferably a 5- or 6-membered ring group, which may be further condensed. Further, it may be an aromatic heterocyclic ring or a non-aromatic heterocyclic ring. Hereinafter, the heterocyclic groups represented by Z, V ₁ and V ₂ are exemplified in the form of a heterocyclic ring with the substitution position omitted, but the substitution position is not limited. It is possible to substitute at position 3, 3 and 4. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole Benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. Among them, an aromatic heterocyclic group is preferable, and preferable examples thereof are exemplified in the same manner as described above. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole Or thiadiazole. They may have a substituent (the aforementioned substituent W) and are preferably substituted with an electron withdrawing group.

  When the phthalocyanine dye of the present invention is water-soluble, it preferably has an ionic hydrophilic group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, or a sulfo group is preferable, and a carboxyl group or a sulfo group is particularly preferable. The carboxyl group, phosphono group, and sulfo group may be in a salt state. Examples of counter ions that form the salt include ammonium ions, alkali metal ions (for example, lithium ions, sodium ions, potassium ions), and organic cations. (For example, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal ions are preferable, and thyllium ions are particularly preferable from the viewpoint of improving solubility and suppressing bronzing in ink jet printing. The most preferred ionic hydrophilic group is a lithium salt of a sulfo group.

  As the number of ionic hydrophilic groups, those having at least two or more in one molecule of the phthalocyanine dye of the present invention are preferable, and those having at least two sulfo groups and / or carboxyl groups are particularly preferable.

Preferable examples of M include hydrogen atoms and metal atoms such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi and the like can be mentioned. Examples of the oxide include VO and GeO. Moreover, Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _2, etc. are mentioned as a hydroxide. Furthermore, examples of the halide include AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl, FeCl, GaCl, and ZrCl. Of these, Cu, Ni, Zn, Al and the like are preferable, and Cu is particularly preferable.

Examples of the phthalocyanine compound used in the present invention include sulfinyl group (—SO—Z); sulfonyl group (—SO ₂ —Z); sulfamoyl group (—SO ₂ NV ₁ V ₂ ); carbamoyl group (—CONV ₁ V ₂ ). An alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group (—CO ₂ Z); an acyl group (—CO—Z); and an electron-attracting group such as a sulfo group on each benzene ring of the phthalocyanine compound; It is particularly preferable to introduce at least one by one so that the total of the σp values of the substituents of the entire phthalocyanine skeleton is 1.2 or more. Among them, a sulfinyl group (—SO—Z); a sulfonyl group (—SO ₂ —Z); a sulfamoyl group (—SO ₂ NV ₁ V ₂ ) is preferable, and a sulfonyl group (—SO ₂ —Z); a sulfamoyl group ( -SO ₂ NV ₁ V ₂₎ are preferred, a sulfonyl group _(-SO 2 -Z) is more preferable.

Among the phthalocyanine compounds represented by the general formula (3), a phthalocyanine compound represented by the following general formula (6) is preferable.
General formula (6):

In general formula (6), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, complex Ring group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, Alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfinyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxy Carbonylamino group, imide group, heterocyclic thio group, phosphoryl group, It represents a sill group or an ionic hydrophilic group. These groups may further have a substituent (the aforementioned substituent W).
Z ₁ , Z ₂ , Z ₃ and Z ₄ each independently represent a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₁ , Z ₂ , Z ₃ and Z ₄ has an ionic hydrophilic group as a substituent.
l, m, n, p, q ₁ , q ₂ , q ₃ , and q ₄ each independently represent an integer of 1 or 2, and M has the same meaning as in the general formula (3).

  In general formula (6), two or more of l, m, n, and p are preferably 1, and l = m = n = p = 1 is most preferred.

In general formula (6), two or more of q ₁ , q ₂ , q ₃ , and q ₄ are preferably 2, and most preferably q ₁ = q ₂ = q ₃ = q ₄ = 2.

In general formula (6), Z ₁ , Z ₂ , Z ₃ , and Z ₄ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, Among these, a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group is preferable, and a substituted alkyl group is particularly preferable. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent.

In the general formula (6), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ are preferably each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a complex A ring group, cyano group, hydroxyl group, nitro group, carbamoyl group, sulfamoyl group, sulfinyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, phosphoryl group, acyl group, or ionic hydrophilic group, and further hydrogen An atom, a halogen atom, a cyano group, a hydroxyl group, a sulfamoyl group, a sulfinyl group, a sulfonyl group, or an ionic hydrophilic group is more preferable, and a hydrogen atom is particularly preferable.

  In General formula (6), M is synonymous with M in the said General formula (3), and its preferable example is also the same.

As a phthalocyanine compound represented by General Formula (3) and General Formula (6) used for this invention, the phthalocyanine compound of the patent document 1 shown below and patent documents 23-27 is mentioned as a preferable thing, for example.
Patent Document 1: Compound Nos. 101 to 215 described in Paragraph Nos. 0207 to 0226 of JP 2003-192930 A Patent Document 23: 101 to 143 described in Paragraph Nos. 0173 to 0183 of JP 2002-285050 A Compounds of Patent No. 24: 101-175 compounds described in paragraph Nos. 0195 to 0204 of JP-A No. 2002-309118 / 101 of Patent Reference No. 25: paragraphs of 0208 to 0216 of JP-A No. 2004-002670 -145 compound, compounds of 146-150 described in paragraph number 0219, compounds of 151-155 described in paragraph number 0222, and Patent Document 26: No. described in International Publication No. 04/085541 pamphlet. Compounds Nos. 1 to 55 and Patent Document 27: No. described in WO 04/087815 pamphlet. The compound of 1-47 Although the specific example of a compound especially preferable as a phthalocyanine compound represented by General formula (3) and General formula (6) used for this invention is shown below, the phthalocyanine compound used for this invention is the following. It is not limited to the example.
-Compound No. described in Patent Document 24 101, 105, 108, 112, 131, 132, 133 phthalocyanine dyes, dye Nos. No. 103, 108, 110, 146, 154, No. described in Patent Document 27 Phthalocyanine dyes represented by 1,5,12

[Use of coloring composition, etc.]
Applications of the colored composition of the present invention include image recording materials for forming images, particularly color images, and specifically, thermal transfer type images including ink jet recording materials described in detail below. There are recording materials, pressure-sensitive recording materials, recording materials using electrophotographic methods, transfer type silver halide photosensitive materials, printing inks, recording pens, etc., preferably inkjet recording materials, thermal transfer type image recording materials, electrophotographic methods In particular, an ink jet recording material is preferable. In addition, color filters used in solid-state imaging devices such as LCDs and CCDs described in US Pat. No. 4,808,501 and JP-A-6-35182, and dyeing solutions for dyeing various fibers. Is also applicable.
The colorant of the present invention can be used by adjusting the physical properties such as solubility and heat mobility suitable for the application with a substituent. The colorant of the present invention can be used in a uniform dissolved state, a dispersed dissolved state such as an emulsified dispersion, or a solid dispersed state depending on the system used.

[Ink composition for inkjet recording]
The ink composition for inkjet recording can be prepared by dissolving and / or dispersing the colorant compound of the present invention in an oleophilic medium or an aqueous medium. Preferably, an aqueous medium is used. If necessary, other additives may be 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, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives (the thing of Unexamined-Japanese-Patent No. 2002-371214 is applicable), such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, and a chelating agent. These various additives are directly added to the ink liquid in the case of water-soluble ink. When an oil-soluble colorant is used in the form of a dispersion, it is generally added to the dispersion after preparation of the colorant dispersion, but it may be added to the oil phase or aqueous phase during preparation.

  As an aqueous medium, the mixture which has water as a main component and added the water miscible organic solvent as needed can be used. Examples of the water-miscible organic solvent include alcohol (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine) , Triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl- 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). Two or more of these water-miscible organic solvents may be used in combination.

  The ink set of the present invention can include a dark magenta ink composition and a light magenta ink composition as a magenta ink composition. When both the dark magenta ink composition and the light magenta ink composition are included in the ink set, it is preferable that at least one of them contains the compounds of the general formula (1) and the general formula (2) as a colorant. More preferably, the composition contains the compounds of general formula (1) and general formula (2) as a colorant. Most preferably, both the dark magenta ink composition and the light magenta ink composition contain the compounds of general formula (1) and general formula (2) as colorants.

  In the ink for inkjet recording of the present invention, the concentration of magenta dye in the magenta ink composition can be appropriately determined based on the color value of the dye used. Generally, it is preferable that 0.2 to 10 parts by mass of the total of the magenta dyes represented by the general formula (1) and the general formula (2) is contained in 100 parts by mass of the ink for inkjet recording. By setting the colorant (dye) concentration to 0.2% by mass or more, sufficient color developability can be secured as an ink, and by using the colorant (dye) concentration to 10% by mass or less, the ink used for the ink jet recording method As a composition, it becomes easy to ensure dischargeability from a nozzle, prevent nozzle clogging, and the like.

  The mass ratio of the azo dye represented by the general formula (1) and the anthrapyridone dye represented by the general formula (2) in the magenta ink composition is the total number of counter ions contained in the total colorant. Although it will not specifically limit if 50% or more satisfy | fills that it is a lithium ion, Preferably it is 4: 1-1: 8, Most preferably, it is 2: 1-1: 4.

  Furthermore, as a colorant for the magenta ink composition, other magenta dyes may be used in combination with the magenta dyes represented by the general formulas (1) and (2). Even when three or more kinds of colorants are used in combination, it is sufficient that 50% or more of the total number of counter ions contained in all colorants is lithium ions, and the total content of all colorants is within the above range. It is preferable that

  Examples of magenta dyes that can be used in combination with the magenta dyes represented by the general formulas (1) and (2) include C.I. I. Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, C.I. I. Direct violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101, C.I. I. Acid Red 35, 42, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 151, 154, 158, 249, 254, 257, 261, 263, 266, 289, 299, 301, 305, 336, 337, 361, 396, 397, C.I. I. Acid Violet 5, 34, 43, 47, 48, 90, 103, 126, C.I. I. Reactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55, C.I. I. Reactive violet 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34, C.I. I. Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46, C.I. I. Basic violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48 etc. are mentioned. Further, as coupling components (hereinafter referred to as coupler components), phenols, naphthols, anilines, heterocycles such as pyrazine, aryl or heteryl azo dyes having open-chain active methylene compounds, etc., open-chain types as coupler components Examples include azomethine dyes having an active methylene compound, anthrapyridone dyes, and the like.

As a magenta dye that can be used in combination with the magenta dye represented by the general formula (1) and the general formula (2), a monoazo dye represented by the following general formula (7) is preferable.
General formula (7):

In general formula (7), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an optionally substituted alkyl group having 1 to 9 carbon atoms, An alkoxy group having 1 to 9 carbon atoms, an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, an optionally substituted amino group, a sulfonate group, and an alkylsulfonyl group having 1 to 9 carbon atoms Represents an arylsulfonyl group having 6 to 15 carbon atoms or an alkoxycarbonyl group. a represents 0, 1 or 2. Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. G ¹ and G ² are each independently a group represented by a halogen atom, NR ⁴ R ⁵ or OR ⁶ , and R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a carbon number of 1-18. An alkyl group, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aromatic hydrocarbon ring group, or a heterocyclic group, and a hydrogen atom other than a hydrogen atom may be substituted.

  When a magenta ink composition is prepared by using a magenta dye represented by the general formula (1) and the general formula (2) in combination with another magenta dye as a colorant, the general formula (1) and the general formula (2) The ratio of the total mass of the magenta dye represented by) and the mass of the magenta dye to be used together is not particularly limited, but is preferably 50:50 to 100: 0, and more preferably 70:30 to 100: 0, particularly preferably 80:20 to 100/0.

  In the inkjet recording ink of the present invention, ammonium ions, alkali metal ions (for example, lithium ions, sodium ions, potassium ions) are used as counter ions of the ionic hydrophilic groups of all colorants contained in the magenta ink composition. And organic cations (for example, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) are used. In the present invention, the proportion of lithium ions in the total number of counter ions is 50% or more, more preferably. Is 70% or more, particularly preferably 80% or more. Thus, as the lithium ion ratio increases, the bronze phenomenon in the mixed color (blue) portion formed by combining the magenta ink composition and the cyan ink composition can be suppressed.

  Furthermore, in the magenta ink composition of the present invention, a betaine surfactant may be used in combination with the magenta dyes represented by the general formulas (1) and (2). As specific betaine-type surfactants, those described in International Publication No. 03/066656 pamphlet and Japanese Patent Application Laid-Open No. 2007-204631 can be applied. The betaine surfactant is preferably a compound of X-1 to X-16 described in WO 03/066756. The betaine type surfactant is preferably contained in an amount of 0.02 to 20 parts by mass in 100 parts by mass of the ink for inkjet recording. In addition, a plurality of betaine surfactants having different structures may be used. In that case, the total content of all the betaine surfactants is preferably within the above range.

  By adding a betaine surfactant to the magenta ink composition in the above range, the image receiving material has good fixability under high temperature and high humidity conditions, and bleeding can be suppressed.

  In the ink set of the present invention, a dark cyan ink composition and a light cyan ink composition can be included in the ink set as the cyan ink composition. When both the deep cyan ink composition and the light cyan ink composition are included in the ink set, it is preferable that at least one of them contains a cyan dye of the general formula (3) or the general formula (6) as a colorant. More preferably, the ink composition contains a cyan dye of the general formula (3) or the general formula (6) as a colorant. Most preferably, both the deep cyan ink composition and the light cyan ink composition contain the cyan dye of the general formula (3) or the general formula (6) as a colorant.

  In the inkjet recording ink of the present invention, the concentration of the cyan dye in the cyan ink composition can be appropriately determined based on the color value of the dye used. Generally, it is preferable that the cyan dye represented by the general formula (3) or the general formula (6) is contained in an amount of 0.2 to 10 parts by mass in 100 parts by mass of the ink for inkjet recording.

  Moreover, as a colorant of the cyan ink composition used in the ink for inkjet recording of the present invention, other cyan dyes may be used in combination with the cyan dye represented by the general formula (3) or the general formula (6). Good. When two or more colorants are used in combination, the total content of all colorants is preferably within the above range.

Any cyan dye that can be used in combination with the cyan dye represented by formula (3) or formula (6) can be used. Preferable specific examples of the cyan dye include C.I. I. Direct Blue 1, 10, 15, 22, 25, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108, 109, 151, 156, 158, 159, 160, 168, 189, 192, 193, 194, 199, 200, 201, 202, 203, 207, 211, 213, 214, 218, 225, 229, 236, 237, 244, 248, 249, 251, 252, 264, 270, 280, 288, 289, 291, C.I. I. Acid Blue 9, 25, 40, 41, 62, 72, 76, 78, 80, 82, 92, 106, 112, 113, 120, 127, 128, 129, 138, 143, 175, 181, 205, 207, 220, 221, 230, 232, 247, 258, 260, 264, 271, 277, 278, 279, 280, 288, 290, 326, C.I. I. Reactive Blue 2, 3, 5, 8, 10, 13, 14, 15, 17, 18, 19, 21, 25, 26, 27, 28, 29, 38, C.I. I. Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 45, 46, 47, 54, 57, 60, 62, 65, 66, 69, or a hydrolyzate thereof. Further, aryl or hetaryl azo dyes having phenols, naphthols, anilines, etc. as coupler components, for example, azomethine dyes, cyanine dyes, oxonols having heterocycles such as phenols, naphthols, pyrrolotriazole, etc. as coupler components Examples thereof include polymethine dyes such as dyes and merocyanine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, phthalocyanine dyes, anthraquinone dyes, and indigo / thioindigo dyes.
The cyan dye may have a cyan color only after a part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal or an inorganic cation such as ammonium. Further, it may be an organic cation such as pyridinium, quaternary ammonium salt, or may be a polymer cation having a partial structure thereof.

  When the central metal (M) of the phthalocyanine dye represented by the general formula (3) or the general formula (6) is copper, the free copper ion concentration in the cyan ink composition is 10 ppm or less, more preferably 5 ppm or less. is there. Examples of the method for controlling the free copper ion concentration include increasing the degree of purification of the colorant or sequestering free copper ions with a metal ion sequestering agent. Preferable examples of the sequestering agent include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, uramildiacetic acid, and metal salts thereof (for example, sodium salt).

  By setting the free copper ion concentration within the above range, it is possible to prevent the generation of precipitates after the production of the ink. Moreover, good storage stability, ejection stability, and the effect of preventing clogging can also be obtained. Furthermore, the ozone fastness of the mixed color (blue) portion formed by combining the magenta ink composition and the cyan ink composition can be improved.

  The free copper ion concentration can be measured by ion chromatography, induction plasma mass spectrometry (ICP-MS), capillary electrophoresis, or the like.

  The ink for inkjet recording of the present invention can be used not only for forming a single color image but also for forming a full color image. A magenta ink composition, a cyan ink composition, and a yellow ink composition can be used to form a full-color image, and a black ink composition may be further used to adjust the color tone.

In the ink set of the present invention, the yellow dye used as the colorant of the yellow ink composition is not particularly limited, and any one can be used. For example, C.I. I. Direct yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 86, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 120, 130, 132, 142, 144, 161, 163, C.I. I. Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195, 196, 197, 199, 218, 219, 222, 227, C.I. I. Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, C.I. I. Basic yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40 etc. are mentioned. Furthermore, aryl or heteryl azo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone as coupling components, and open-chain active methylene compounds, for example, open-chain active methylene compounds as coupler components Azomethine dyes such as benzylidene dyes and monomethine oxonol dyes, for example, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dye species include quinophthalone dyes, Examples thereof include nitro / nitroso dyes, acridine dyes, and acridinone dyes. The yellow dye may have a yellow color only after a part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal or an inorganic cation such as ammonium. Further, it may be an organic cation such as pyridinium, quaternary ammonium salt, or may be a polymer cation having a partial structure thereof.
Preferred examples of the yellow dye used as the colorant for the yellow ink composition include compounds described in International Publication No. 05/075753 pamphlet and Japanese Patent Application Laid-Open No. 2007-63520.

  The ink set of the present invention can be configured to contain a black ink composition as desired. By including the black ink composition in the ink set of the present invention, an image having good contrast can be formed on a recording medium. In the ink set of the present invention, the colorant used in the black ink composition is not limited to the colorant having a specific structure, but the black ink composition has the light resistance and ozone resistance of the ink composition of other colors. It is preferable that the difference between the light resistance and the ozone resistance is small. Applicable black dyes include disazo, trisazo, and tetraazo dyes as well as carbon black dispersions.

[Inkjet recording method]
In the ink jet recording method of the present invention, energy is supplied to the ink for ink jet recording, and a known image receiving material, that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153989, JP-A-10-217473, JP-A-10-235995 10-337947, 10-217597, 10-337947, etc. Form images on inkjet paper, film, electrophotographic co-paper, fabric, glass, metal, ceramics, etc. To do.

In forming an image, a polymer latex compound may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing of applying the latex compound to the image receiving material may be before, after, or simultaneously with the application of the colorant, and therefore the addition location may be in the image receiving paper. It may be in ink or may be used as a liquid material of polymer latex alone. Specifically, JP 2002-166638, the 2002-121440 JP, same 2002-154201 JP, same 2002-144696 JP, same 2002-80759 JP, same 2002-187342 Patent, each publication of JP same 2002-172774 Can be preferably used.

  A recording paper and a recording film used for inkjet printing using the ink composition of the present invention are described in JP-A-2002-371214.

  The ink composition constituting the ink set of the present invention is prepared by including components appropriately selected from the above-mentioned components, and the viscosity of the obtained ink composition is preferably less than 10 mPa · s at 20 ° C. . Furthermore, in the present invention, the surface tension of the ink composition is preferably 45 mN / m or less at 20 ° C., and particularly preferably in the range of 25 to 45 mN / m. By adjusting the viscosity and the surface tension in this way, an ink composition having desirable characteristics for use in the ink jet recording method can be obtained. The adjustment of the viscosity and the surface tension can be performed by appropriately adjusting and selecting the addition amount of the solvent and various additives to be contained in the ink composition, the kind thereof, and the like.

  The ink composition constituting the ink set of the present invention preferably has a pH of 7.0 to 10.5 at 20 ° C., more preferably 7.5 to 10.0. By making the pH of the ink composition at 20 ° C. 7.0 or more, it is possible to prevent the eutectoid plating of the ink jet head from being peeled off, and to stabilize the ejection characteristics of the ink composition from the ink jet head. Can do. In addition, by setting the pH of the ink composition to 10.5 or less at 20 ° C., it is possible to prevent deterioration of various members that come into contact with the ink composition, for example, members constituting an ink cartridge or an inkjet head. .

  As a method for preparing the ink composition in the present invention, for example, various components contained in the ink composition are sufficiently mixed and dissolved as uniformly as possible, and then subjected to pressure filtration with a membrane filter having a pore size of 0.8 μm, Although the method of preparing the obtained solution by deaerating with a vacuum pump can be illustrated, it is not limited to this.

  Next, the ink set of the present invention using the above-described ink composition can be used as an ink cartridge containing these integrally or independently, and is preferable from the viewpoint of convenient handling. An ink cartridge including an ink set is known in the art, and can be formed into an ink cartridge by appropriately using a known method.

  The ink set or ink cartridge of the present invention can be used for general writing instruments, recorders, pen plotters, and the like, but is particularly preferably used for an ink jet recording method. The ink jet recording method in which the ink set or the ink cartridge of the present invention can be used includes any recording method in which the ink composition is ejected as droplets from a thin nozzle and the droplets are attached to a recording medium. Specific examples of the ink jet recording method in which the ink composition of the present invention can be used will be described below.

  The first method is a method called an electrostatic attraction method. In the electrostatic suction method, a strong electric field is applied between the nozzle and the acceleration electrode arranged in front of the nozzle, and droplet-like ink is continuously ejected from the nozzle, and the ink droplet passes between the deflection electrodes. In the meantime, by supplying a printing information signal to the deflection electrode, the ink droplets are blown toward the recording medium and the ink is fixed on the recording medium, or the image is recorded, or the ink droplets are not deflected, In this method, an image is fixed on a recording medium by ejecting ink droplets from a nozzle onto the recording medium in accordance with a print information signal.

  The second method is a method for forcibly ejecting ink droplets from the nozzles by applying pressure to the ink liquid with a small pump and mechanically vibrating the ink jet nozzles with a quartz vibrator or the like. The ink droplet ejected from the nozzle is charged at the same time as it is ejected, and while the ink droplet passes between the deflection electrodes, a print information signal is given to the deflection electrode to fly the ink droplet toward the recording medium, This is a method for recording an image on a recording medium.

  The third method is a method in which an image is recorded on a recording medium by simultaneously applying a pressure and a printing information signal to the ink liquid by a piezoelectric element, and ejecting ink droplets from a nozzle toward the recording medium.

  In the fourth method, the ink liquid is heated and foamed using microelectrodes according to the print signal information, and the bubbles are expanded to eject the ink liquid from the nozzle toward the recording medium, thereby forming an image on the recording medium. It is a method of recording.

  The ink set or ink cartridge of the present invention is particularly preferable as an ink composition used when an image is recorded on a recording medium using an image recording method based on an ink jet recording method including the four methods described above. The recorded matter recorded using the ink set of the present invention has excellent image quality, and is excellent in light resistance and ozone resistance.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples at all.
[Example 1]

[Preparation of each ink composition]
Based on the composition shown in Table 1 below, each component was stirred at room temperature for 30 minutes, and then the resulting solution was filtered using a membrane filter having an aperture of 1.0 μm to obtain each ink composition. In Table 1, the numerical value of each component indicates the mass% of each component when the mass of the ink composition is 100%, and “remaining” indicating the amount of water is the total including the components other than water. The amount to be 100% is shown.

In Table 1, Y-01 represents a yellow ink composition, M-01 to M-16 represent magenta ink compositions, and C-01 to C-04 represent cyan ink compositions. In Table 1, the following formula (Y-1) is used as the yellow dye, the following formulas (M-1) to (M-7) are used as the magenta dye, and the following formula (A-1) is used as the betaine surfactant. As the cyan dye, compounds represented by the following formulas (C-1) to (C-2) were used.
(Y-1): Compound described in JP-A-2007-63520

(M-1): Compound described in JP-A-2002-371214

(M-2): Compound described in JP-A-2006-143898

(M-3): Compound described in JP-A No. 2003-192930

(M-4): Compound described in International Publication No. 04/104108 pamphlet

(M-5): Compound described in International Publication No. 06/075706 Pamphlet

(M-6): Compound described in paragraph No. 0078 of JP-A-2005-105137

(M-7): Occupational Safety and Health Act / Gazette Publication Number 8- (7) -1527

(A-1): Compound described in International Publication No. 03/066756 Pamphlet

(C-1): Compound described in JP-A-2004-002670

(C-2): Compound described in International Publication No. 04/087815 pamphlet

In the table, TEGmBE is triethylene glycol monobutyl ether, and DEGmBE is diethylene glycol monobutyl ether.
Next, A to Q ink sets were prepared using the combinations shown in Table 2 using the prepared ink compositions. The ink set of the combinations shown in Table 2 does not include a light ink composition, that is, a light magenta ink composition and a light cyan ink composition. The Li conversion rate in Table 2 represents the ratio of lithium ions to the total number of counter ions contained in all colorants in the magenta ink composition.

(Image recording and evaluation)
Using an ink jet printer Stylus Color 880 (trade name) (trade name, manufactured by Seiko Epson Corporation) and further using the ink set shown in Table 2, an ink jet recording medium {photo paper <gloss> (trade name, Seiko Epson) (Made by Co., Ltd.)}, each color single-color image pattern in which the density is changed in a stepwise manner so that the OD value of each color becomes 0.7 to 1.8, and green, red, and blue. An image pattern was printed, and light fastness and ozone fastness were evaluated. In addition, in order to evaluate the fixability to a recording medium under a high temperature and high humidity condition, the hue change of a gray portion formed by combining yellow, magenta, and cyan ink compositions was observed. Furthermore, the presence or absence of bronzing in the mixed color portion was evaluated using a blue image formed by combining magenta and cyan ink compositions.

  Regarding the light fastness, after measuring the image density Ci immediately after recording, the image was irradiated with xenon light (85,000 lux) for 7 days using a weather meter (Atlas C.165), and the image was again displayed. The density Cf was measured, and the dye residual ratio ({(Ci-Cf) / Ci} × 100%) was calculated and evaluated from the difference in image density before and after the xenon light irradiation. The image density was measured using a reflection densitometer (X-Rite 310TR). The dye residual ratio was measured at three points with reflection densities of 1, 1.5 and 2.0. The evaluation results are shown in Table 3 below. In Table 3 below, the evaluation was made in three stages, with ◯ when the dye residual ratio was 80% or more at any concentration, △ when 2 points were less than 80%, and x when less than 80% at all concentrations. .

  For ozone fastness, the image immediately after recording is left in a box where the ozone gas concentration is set to 5 ppm for 24 hours, and the image density before and after being left under ozone gas is measured using a reflection densitometer (X-Rite 310TR). The dye residual ratio was evaluated. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS. The evaluation results are shown in Table 3 below. In Table 3 below, evaluation was made in three stages, with ◯ when the dye residual ratio was 70% or more at any concentration, Δ when 1 or 2 points were less than 70%, and X when less than 70% at all concentrations.

  Regarding the hue change under high temperature and high humidity conditions, the image immediately after recording was left for 3 days under the condition of 40 ° C. and 85% RH, and the hue change was measured by the Δa * value of the gray part. Under any condition, the value of Δa * is less than 2.0. When the value of Δa * is 2.0 or more and less than 4.0 under any condition, Δ. When any value, the value of Δa * is The evaluation was made in three stages with x being 4.0 or more.

  The presence or absence of bronze phenomenon was evaluated by visually observing the image immediately after recording for 24 hours and then visually observing it. The case where bronze gloss was not confirmed at all was rated as “◯”, the case where slight bronze gloss was confirmed as Δ, and the case where bronze gloss was clearly confirmed as “X”. In addition, when the bronze phenomenon occurs, it can be confirmed that the print density is lower than that without the bronze phenomenon.

As shown in Table 3, the images obtained from the ink sets B to C, E to H, N, P, and Q of the present invention were compared with the images obtained from the comparative ink sets A and D and I to M and O. However, it can be seen that the difference in light fastness and ozone fastness between the ink compositions was small, and the hue change in the gray portion was small, so that the bronzing phenomenon of the blue image could be improved.
[Example 2]

  When the same ink produced in Example 1 was packed in a cartridge of an inkjet printer BJ-F850 (manufactured by CANON), an image was printed on the professional photo paper PR-101 of the same machine, and the same evaluation was performed. The same results as in Example 1 were obtained.

Claims (16)

At least an ink set comprising a magenta ink composition and a cyan ink composition, wherein the magenta ink composition is at least one selected from azo dyes represented by the following general formula (1) as a colorant: It contains at least one selected from the anthrapyridone dyes represented by the following general formula (2), and the counter ion of the ionic hydrophilic group of all the colorants contained in the magenta ink composition has a total counter ion number of 50. % Or more of lithium ions, and the cyan ink composition contains at least one selected from phthalocyanine compounds as a colorant.
General formula (1):

In general formula (1), A represents a 5-membered heterocyclic ring. B ₁ and _{B 2} are each _-CR 13 =, - or represents _{CR 14} =, or, in either a nitrogen atom and the other represents a _{-CR 13} = or _{-CR 14} =. R ₁₁ and R ₁₂ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl. Represents a group. However, R ₁₁ and R ₁₂ are not simultaneously hydrogen atoms. R ₁₃ and R ₁₄ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group Group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, sulfamoylamino group, alkoxy Carbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, nitro group, alkyl and arylthio group, alkyl and arylsulfonyl group, alkyl and arylsulfinyl group, sulfamoyl group, It represents a heterocyclic thio group or an ionic hydrophilic group. R ₁₃ and R ₁₁ or R ₁₁ and R ₁₂ may be bonded to form a 5- to 6-membered ring. a and e each independently represent an alkyl group, an alkoxy group, or a halogen atom; b, c, and d are each independently synonymous with R ₁₃ and R ₁₄ ; a to e are bonded to each other to form a ring; May be. However, general formula (1) has at least one ionic hydrophilic group.
General formula (2):

In general formula (2), R ₁ represents a hydrogen atom or an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, and R ₃ and R ₅ each independently represents a hydrogen atom or a substituent. R ₂ and R ₄ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. However, general formula (2) has at least one ionic hydrophilic group. The ink set according to claim 1, wherein the cyan ink composition contains at least one selected from phthalocyanine compounds represented by the following general formula (3) as a colorant.
General formula (3):

In the general formula (3), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NV ₁ V ₂ , —CONV ₁ V ₂ , —CO ₂ represents any one of Z, —CO—Z and a sulfo group. Here, Z represents an aliphatic group, an aromatic group, or a heterocyclic group each independently. V ₁ and V ₂ may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkylamino group, Alkoxy group, aryloxy group, amide group, arylamino group, aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, Heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group, or ionic hydrophilic group To express. a ₁ ~a ₄ and _b 1 ~b ₄ each represent the number of substituents of _X 1 to X ₄ and _Y 1 to Y _4. A _{1 to} a ₄ are each independently an integer of 0 to 4, and all do not simultaneously become 0. b ₁ ~b ₄ represents each independently an integer of 0-4. M is a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof. However, at least one of X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y ₃ and Y ₄ is an ionic hydrophilic group or an ionic hydrophilic group as a substituent. It is group which has.   The ink set according to claim 1 or 2, wherein a concentration of free copper ions in the cyan ink composition is 10 ppm or less.   4. The counter ion of the ionic hydrophilic group of the total colorant contained in the magenta ink composition, wherein 80% or more of the total counter ion number is lithium ion. The ink set described in 1.   As counter ions of ionic hydrophilic groups of all colorants contained in the magenta ink composition, 80% or more of the total counter ions are lithium ions, and ions of all colorants contained in the cyan ink composition The ink set according to any one of claims 1 to 4, wherein 80% or more of all counter ions are lithium ions as counter ions of the hydrophilic hydrophilic group. The ink set according to any one of claims 1 to 5, wherein the azo dye of the general formula (1) is represented by the following general formula (4).
General formula (4):

In the general formula (4), Z ₁₁ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ₁₂ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , a, b, c, d, and e are as defined in the general formula (1). Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. However, general formula (4) has at least one ionic hydrophilic group.   In the azo dye represented by the general formula (1), a and e are both alkyl groups, and the total number of carbon atoms constituting the alkyl group is 3 or more. The ink set according to any one of the above.   The ink set according to any one of claims 1 to 7, wherein in the anthrapyridone dye represented by the general formula (2), at least one of the ionic hydrophilic groups is a carboxyl group. .   The magenta ink composition according to any one of claims 1 to 8, wherein the magenta ink composition has two types of magenta ink compositions having different color densities, and at least one type of magenta ink composition. An ink set characterized by   The cyan ink composition according to any one of claims 1 to 9, wherein the cyan ink composition has two cyan ink compositions having different color densities, and at least one cyan ink composition is present. An ink set characterized by   An ink cartridge that accommodates the ink set according to any one of claims 1 to 10 integrally or independently.   An ink jet printer having the ink cartridge according to claim 11 loaded therein.   An ink jet recording method comprising: recording using the ink set according to claim 1 or the ink cartridge according to claim 11.   An image is formed on an image receiving material having an ink receiving layer containing a white inorganic pigment on a support, using the ink set according to any one of claims 1 to 10 or the ink cartridge according to claim 11. An ink jet recording method.   A method for suppressing a bronzing phenomenon of a colored image material, wherein the ink set according to any one of claims 1 to 10 is used.   A method for improving the bleeding of a colored image material under high-temperature and high-humidity conditions, wherein the ink set according to any one of claims 1 to 10 is used.