JP2007224119A - Ink composition, ink for ink jet recording, ink set and ink jet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition which is used for ink jet recording and forms images having good magenta hues, excellent in fixity, and having high fastness to light and active gases, especially ozone gas in environments. <P>SOLUTION: This ink composition is characterized by containing at least one compound represented by the general formula (1) having at least one ionic hydrophilic group in the molecule as a colorant. Wherein, R<SB>1</SB>is H or an electron-attractive group having a Hammett substituent constant ρp value of 0.20 to 0.55; R<SB>2</SB>is an aromatic group or a heterocyclic group; R<SB>3</SB>is H or a substituent; R<SB>4</SB>and R<SB>5</SB>are each H, an aliphatic group or an aromatic group; and Z is a non-metallic atom group necessary for forming a 5 to 7-membered aromatic ring or heterogeneous ring together with carbon atoms. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel ink composition, in particular, a magenta ink composition capable of forming an image excellent in light resistance and ozone resistance, an ink set including the ink composition, 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 magenta hue, has good fixability to an image receiving material even under high humidity conditions, and is robust against active gases in the light and environment, especially oxidizing gases such as ozone. It is rare.

Typical examples of magenta dye skeletons used in ink jet recording inks include xanthene dyes found in JP-A-8-60053 and the like, H-acid azo dyes and anthrapyridone dyes found in JP-A-7-157698 and the like. . Among these, xanthene dyes are excellent in hue and sharpness but have a problem in light resistance. H acid azo dyes are excellent in hue and water resistance, but have problems in light resistance and sharpness.
On the other hand, the anthrapyridone dyes found in JP-A-57-195775, JP-A-59-074173, JP-A-10-306221, JP-A-2000-191660, JP-A-2001-072884, etc. Although it was excellent in light resistance, there was a problem in ozone resistance. In recent years, JP 2002-332418, JP 2003-192930, and WO 04/104108, which have improved the ozone resistance of anthrapyridone dyes, have been disclosed, but they are not yet satisfactory.

  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 itself has a good color developability, and a good intermediate color when a plurality of color ink compositions are combined. And the like, and the recorded material obtained should not discolor during storage.

In an ink set, when the light resistance or ozone resistance of a specific ink composition is significantly lower than the light resistance or ozone resistance of another ink composition, the color formed by that specific ink composition The color fades and discolors earlier than the color of the image, and the balance of the color tone of the entire image becomes worse, but then the observer can recognize that the image formed by the single ink composition is faded. Image quality degradation can be recognized within a short time. Therefore, in the ink set, in addition to improving the light resistance and ozone resistance of each ink composition constituting the ink set, the light resistance and ozone resistance level of each ink composition, that is, each ink composition. It is preferable that the deterioration rate of the image formed by the light and ozone, for example, the fading rate is as much as possible. 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.
JP 2002-332418 A JP 2003-192930 A International Publication No. 04/104108 Pamphlet

An object of the present invention is to solve the above problems and achieve the following objects.
That is, the first object of the present invention is to form an image having a good magenta hue, excellent fixability to an image receiving material, and high fastness to light and environmental active gas, particularly ozone gas. Another object is to provide a magenta ink composition for inkjet recording.
The second object of the present invention is that each ink composition itself constituting the ink set has good light resistance and ozone resistance, and a good balance of light resistance and ozone resistance between the ink compositions. Another object of the present invention is to provide an ink set in which a specific color does not fade or discolor faster than other colors with respect to ozone or ozone.

The inventors have studied in detail an anthrapyridone compound derivative excellent in magenta hue and light resistance. As a result, an ink composition containing a compound represented by the following general formula (1) into which a specific substituent not conventionally known has been introduced. Found an ink set having a good balance of light resistance and ozone resistance between ink compositions by combining each color dye having a specific structure which is excellent in ozone resistance and has not been known so far, and completes the present invention. It came to.
1. An ink composition comprising at least one compound represented by the following general formula (1) having at least one ionic hydrophilic group in a molecule as a colorant.

In the general formula (1), 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 0.55 or less, and R ₂ represents an aromatic group or a heterocyclic group. R ₃ represents a hydrogen atom or a substituent, R ₄ and R ₅ each independently represent a hydrogen atom, an aliphatic group or an aromatic group, and Z represents a 5- to 7-membered aromatic group together with a carbon atom. It represents a nonmetallic atom group necessary for forming a ring or a heterocyclic ring. However, general formula (1) has at least one ionic hydrophilic group.
2. 2. The ink composition as described in 1 above, wherein Z is an anthrapyridone compound represented by the following general formula (2), wherein an aromatic ring formed with a carbon atom is a benzene ring.

In general formula (2), R ₆ represents a hydrogen atom or a substituent. However, the general formula (2) has at least one (preferably 2 or more and 6 or less) ionic hydrophilic group.
3. 3. The ink composition according to 1 or 2 above, wherein R ₁ is an acyl group, an alkoxycarbonyl group, or a carbamoyl group.
4). R ₂ is an ionic hydrophilic substituted aromatic group or a group ink composition according to any one of the above 1 to 3, wherein the heterocyclic group substituted with an ionic hydrophilic group.
5). _5. The ink composition as described in any one of 1 to 4 above, wherein one of R ₄ and R ₅ is a hydrogen atom and the other is an aromatic group substituted with an ionic hydrophilic group.
6). An ink for ink-jet recording, wherein an ink composition containing at least one compound according to any one of 1 to 5 above is used as a colorant.
7). An ink jet recording method comprising forming an image on an image receiving material having an ink receiving layer containing a white inorganic pigment on a support, using the ink for ink jet recording described in 6 above.
8). An ink set comprising at least a yellow ink composition, a magenta ink composition, and a cyan ink composition, wherein the magenta ink composition includes at least the compound according to any one of 1 to 5 as a colorant. An ink set comprising one type.

  The ink composition of the present invention has a good magenta hue and can give a colored image or coloring material excellent in sharpness, water resistance, light resistance and ozone resistance. In particular, the ink for ink jet recording using the ink composition of the present invention and the ink jet recording method using the ink have a good magenta hue, and are magenta having high fastness to light and environmental active gases, particularly ozone gas. An image can be formed. Further, by combining each color dye having a specific structure, an ink set having a good balance of light resistance and ozone resistance between the ink compositions can be obtained.

Hereinafter, implementation of the present invention will be described in detail.
First, some of the substituents used in this specification will be described. 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 Oxycarbonyl 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 or a silyl group may be mentioned as examples.

  The aliphatic group used in this specification means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, or a substituted alkynyl group. Moreover, the aromatic group used in this specification means an aryl group and a substituted aryl group.

  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, and preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, or a substitution having 6 to 30 carbon atoms. Or an unsubstituted anilino group, for example, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, etc. are mentioned.
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, or a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as 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, or a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group, an ethylsulfinyl group, Examples thereof include a phenylsulfinyl group and a p-methylphenylsulfinyl group.
As the alkyl or arylsulfonyl group, a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms such as a methylsulfonyl group, an ethylsulfonyl group, A phenylsulfonyl 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, or a substituted or unsubstituted carbon group having 2 to 30 carbon atoms. A heterocyclic carbonyl group bonded to a carbonyl group with an unsubstituted carbon atom, for example, an acetyl group, a pivaloyl group, a 2-chloroacetyl group, a stearoyl group, a benzoyl group, a pn-octyloxyphenylcarbonyl group, 2- A pyridylcarbonyl group, 2-furylcarbonyl group, etc. are mentioned.
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, or 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, or an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, or a benzoylaminosulfonyl group.

  In the present invention, the magenta dye used as the colorant of the ink composition is a compound represented by the following general formula (1).

In the general formula (1), 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 0.55 or less, and R ₂ represents an aromatic group or a heterocyclic group. R ₃ represents a hydrogen atom or a substituent, R ₄ and R ₅ each independently represent a hydrogen atom, an aliphatic group or an aromatic group, and Z represents a 5- to 7-membered aromatic group together with a carbon atom. It represents a nonmetallic atom group necessary for forming a ring or a heterocyclic ring. However, general formula (1) has at least one ionic hydrophilic group.

In the general formula (1), R ₁ represents a hydrogen atom or an electron-withdrawing group having a Hammett substituent constant σp value of 0.20 or more and 0.55 or less. R ₁ is preferably _{one in} which an electron withdrawing group having a σp value of 0.20 or more and 0.55 or less is substituted with at least one ionic hydrophilic group. Here, Hammett's substituent constant σp value used in the present specification will be described briefly. 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 and 0.55 or less include an acyl group, a carboxyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfinyl group, and an arylsulfinyl group. Group, sulfonyloxy group, acylthio group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, heterocyclic group, halogen atom, Examples thereof include an azo group, a selenocyanate group, and an aryl group substituted with another electron-withdrawing group having a σp value of 0.20 or more.
R ₁ is preferably a hydrogen atom, an acyl group, an alkoxycarbonyl group, a carbamoyl group or a heterocyclic group, more preferably an acyl group, an alkoxycarbonyl group or a carbamoyl group, and particularly preferably a benzoyl group.

In the general formula (1), R ₂ is preferably an aromatic group or a heterocyclic group which may have a substituent, and examples of the substituent include the substituent W.
The heterocyclic group represented by 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.
The heterocyclic group represented by R ₂ is preferably thienyl group, furyl group, pyrrolyl group, indolyl group, imidazolyl group, benzimidazolyl group, pyrazolyl group, indazolyl group, thiazolyl group, benzothiazolyl group, isothiazolyl group, benzoisothiazolyl group. Ryl 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 substituent W described above). 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 an aromatic group substituted with an ionic hydrophilic group or a heterocyclic group substituted with an ionic hydrophilic group, particularly preferably an aryl group or thiazolyl group substituted with an ionic hydrophilic group. , A benzothiazolyl group, or a 1,3,5-triazyl group.

In the general formula (1), R ₃ represents a hydrogen atom or a substituent (substituent W), and R ₃ is preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, amino Group, carbamoyl group, carboxyl group or sulfo group, particularly preferably a hydrogen atom or an aryloxy group.

In the general formula (1), R ₄ and R ₅ are preferably one of R ₄ and R ₅ is a hydrogen atom, the other is an aliphatic group or an aromatic group, and more preferably one of R ₄ and R ₅ . Is an aromatic group substituted with a hydrogen atom and the other is replaced with an ionic hydrophilic group, and particularly preferably one of R ₄ and R ₅ is a hydrogen atom and the other is an aryl group substituted with a carboxyl group and / or a sulfo group is there.

  In the general formula (1), Z represents a group of nonmetallic atoms necessary for forming a 5- to 7-membered aromatic ring or heterocyclic ring together with a carbon atom, and the 5- to 7-membered aromatic ring or heterocyclic ring further represents You may have a substituent (the said substituent W). Examples of the 5- to 7-membered heterocycle formed by Z together with the carbon atom include thiophene ring, furan ring, pyrrole ring, indole ring, imidazole ring, pyrazole ring, indazole ring, thiazole ring, isothiazole ring, oxazole ring, isoxazole Ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring and the like.

  The 5- to 7-membered aromatic ring or heterocyclic ring formed by Z together with the carbon atom is preferably a benzene ring, a thiophene ring, a furan ring, or a pyridine ring. An anthrapyridone compound represented by the following general formula (2) in which the aromatic ring formed by Z together with the carbon atom is a benzene ring is particularly preferable.

In the general formula (2), R ₆ represents a hydrogen atom or a substituent (the substituent W), and R ₆ 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.
In the general formula _(2), R 1 to R ₅ are the same as _R 1 to R ₅ in the general formula (1), and preferred examples are also the same.

The dye compound represented by the general formula (1) and the general formula (2) has 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, or a sulfo group is preferable, and among them, a carboxyl group or a sulfo group is particularly preferable. Most preferably, 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), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal salts are preferable.
The dye compound preferably has 2 or more and 6 or less ionic hydrophilic groups in the molecule, and more preferably 3 or more and 5 or less.

  The preferred combinations of substituents of the compounds represented by the general formula (1) and the general formula (2) are preferably compounds in which at least one of the various substituents is the preferred group, and more More preferred are compounds in which the above substituents are the above preferred groups, and most preferred are compounds in which all the substituents are the above preferred groups.

  Specific examples of the compounds represented by the general formulas (1) and (2) of the present invention are shown below, but the compounds used in the present invention are not limited to the following examples.

  In the present invention, even when a tautomer exists depending on the structure of the compound, it is described in one of the representative forms in the present invention, but a tautomer different from the description of the present invention is also present in the present invention. It is contained in the compound.

  Moreover, in this invention, even if it contains isotopes (for example, 2H, 3H, 13C, 15N) in the compound represented by General formula (1) or General formula (2), it is applicable.

[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. Further, 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. It can also be applied to.
The compound (pigment compound) of the present invention can be used by adjusting the physical properties such as solubility and heat transfer property suitable for the application with a substituent. The dye compound of the present invention can also 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]
An ink composition for ink jet recording (synonymous with ink for ink jet recording) can be prepared by dissolving and / or dispersing the coloring 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, Known additives such as foaming agents, viscosity modifiers, dispersants, dispersion stabilizers, rust preventives, chelating agents (the ones described in JP 2002-371214 A can be applied). These various additives are directly added to the ink liquid in the case of water-soluble ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.

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

In the inkjet recording ink of the present invention, the concentration of the magenta coloring matter (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 dye compound represented by the general formula (1) or the general formula (2) is contained in 100 parts by mass of the ink for inkjet recording. By setting the dye concentration to 0.2% by mass or more, sufficient color developability can be secured as an ink. Further, by setting the dye concentration to 10% by mass or less, the ink composition used in the ink jet recording method can be ejected from a nozzle. It is easy to ensure the property and prevent nozzle clogging.
In addition, as a colorant for the magenta ink composition used in the inkjet recording ink of the present invention, other magenta dyes may be added to the magenta dye compound represented by the general formula (1) or the general formula (2) of the present invention. You may use together. When two or more colorants are used in combination, the total content of all colorants is preferably within the above range.

  Examples of the magenta dye that can be used in combination with the magenta dye compound represented by formula (1) or formula (2) of the present invention 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 thereof include azomethine dyes having an active methylene compound, anthrapyridone dyes, and the like.

  As the magenta dye used in combination with the coloring compound represented by the general formula (1) or the general formula (2), an anthrapyridone dye (for example, JP-A Nos. 2001-139936, 2003-192930, and 2005-2005) is preferable. And compounds described in Examples of pamphlet of JP-A-2005868, JP-A-2005-320480, and WO04 / 104108), heteryl-heterylazo dyes (JP-A-2002-309115, JP-A-2002-309116, And compounds described in Examples of JP-A-2002-371079, JP-A-2002-371214, and JP-A-2004-075742), and more preferably an azo dye comprising an aminopyrazole diazo component and a pyridine coupler. For example, in JP-A-2002-371214 It shows compound (f-1) can be mentioned.

  When a magenta ink composition is prepared by using another magenta dye in combination with the coloring compound represented by the general formula (1) or the general formula (2) as a colorant, the general formula (1) or the general formula (2) The mass ratio of the magenta dye to be used in combination with the pigment compound represented by () is not particularly limited, but is preferably 90/10 to 10/90, and more preferably 30/70 to 70/30.

  Furthermore, in the ink composition of the present invention, a betaine surfactant may be used in combination with the dye compound represented by the general formula (1) or the general formula (2). As specific betaine type surfactants, those described in International Publication No. 03/066756 pamphlet can be applied. 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.

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. In order to form a full color image, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.
That is, the ink composition of the present invention can be used as a magenta ink composition of an ink set including a yellow ink composition, a magenta ink composition, and a cyan ink composition. In the ink set of the present invention, the structure of the yellow dye and the cyan dye used as the colorant of the yellow ink composition and the cyan ink composition is not particularly limited, but each ink composition can be further combined by combining each color dye having a specific structure. An ink set having a good balance of light resistance and ozone resistance between objects can be provided.

  Next, the colorant used in the yellow ink composition constituting the ink set of the present invention will be described.

  In the ink set of the present invention, any yellow dye that can be applied as a colorant used in the yellow ink composition 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. In this case, the counter cation may be an alkali metal or an inorganic cation such as ammonium. Organic cation such as pyridinium, quaternary ammonium salt, and polymer cation having them in a partial structure may be used.

A preferred yellow dye for the ink set of the present invention is an azo dye represented by the following general formula (4).

  In General Formula (4), G represents a heterocyclic group, and n represents an integer of 1 to 3. When n is 1, R, X, Y, Z, Q, and G represent a monovalent group, and represent a monoazo dye shown in parentheses. When n is 2, R, X, Y, Z, Q, G represents a monovalent or divalent substituent. However, at least one represents a divalent substituent, and represents a bis-type azo dye of the dye shown in parentheses. When n is 3, R, X, Y, Z, Q, and G represent a monovalent, divalent, or trivalent substituent. However, at least two represent a divalent substituent, or at least one represents a trivalent substituent, and represents a tris-type azo dye of a dye shown in parentheses.

  Hereinafter, the general formula (4) will be described in more detail.

  In the general formula (4), examples of preferable substituents for G are preferably 5- to 8-membered heterocyclic groups, and more preferably 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic groups. , They may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.

  Examples of the heterocyclic group represented by G include pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, and the like. Benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine , Thiazoline, sulfolane and the like.

  In the general formula (4), preferable examples of substituents of Q, R, X, Y and Z will be described in detail.

When Q, R, X, Y, Z represents a monovalent group, the monovalent group represents a hydrogen atom or a monovalent substituent. The monovalent substituent will be described in more detail. Examples of the monovalent substituent include a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an alkoxy group, and an aryl group. Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonyl Amino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, A silyl group, an azo group, or an imide group can be mentioned, and each may further have a substituent.

  Among them, particularly preferred are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amide group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group. An arylsulfonyl group, a carbamoyl group, or an alkoxycarbonyl group, particularly preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic group, a hydrogen atom, Alkyl groups, aryl groups, cyano groups, or alkylsulfonyl groups are most preferred.

When Q, R, X, Y, Z represents a divalent group, examples of the divalent group include an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene) and an alkenylene group (eg, ethenylene, propylene). Nylene), alkynylene groups (eg, ethynylene, propynylene), arylene groups (eg, phenylene, naphthylene), divalent heterocyclic groups (eg, 6-chloro-1, 3,5-triazine-2, 4-diyl group, pyrimidine-2, 4 -Diyl group, pyrimidine-4,6-diyl group, quinoxaline-2,3-diyl group, pyridazine-3,6-diyl), -O-, -CO-, -NR'- (R 'is a hydrogen atom, alkyl group, aryl group) _{, -S -, - SO 2 -} , - SO- , or a combination thereof (e.g., _{-NHCH 2 CH 2 NH -, -} NHCONH- , etc.) preferably be .

  The alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, R 'alkyl group or aryl group may have a substituent.

More preferably, an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, a divalent heterocyclic group, -S-,- More preferably, it is SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.).

  The total number of carbon atoms in the divalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

When Q, R, X, Y and Z represent a trivalent group, the trivalent group includes a trivalent hydrocarbon group, a trivalent heterocyclic group,> N-, or a divalent group thereof. (For example,> NCH ₂ CH ₂ NH—,> NCONH—, etc.).

  The total carbon number of the trivalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

  In formula (4), preferred examples of the substituent for Q are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted aryl. A sulfonyl group is preferable, and a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted acyl group is particularly preferable, and among them, a hydrogen atom is particularly preferable.

  In the general formula (4), preferred examples of the substituent for R include a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and a substituted or unsubstituted carbon number. A 4-12 heterocyclic group is preferable, and among them, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, a secondary or tertiary alkyl group is particularly preferable, and a t-butyl group is most preferable. .

  In the general formula (4), a preferred substituent example of X is an electron withdrawing group. Particularly, an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, more preferably an electron-withdrawing group having a σp value of 0.30 or more, and the upper limit is 1.0 or less. It is an electron withdrawing group.

  X is preferably an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, or an aryl having 7 to 18 carbon atoms. Oxycarbonyl group, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, arylsulfinyl group having 6 to 18 carbon atoms, alkylsulfonyl group having 1 to 12 carbon atoms, and 6 to 18 carbon atoms Arylsulfonyl group, sulfamoyl group having 0 to 12 carbon atoms, halogenated alkyl group having 1 to 12 carbon atoms, halogenated alkyloxy group having 1 to 12 carbon atoms, halogenated alkylthio group having 1 to 12 carbon atoms, carbon number 7 A halogenated aryloxy group having ˜18, a C7-18 aryl group substituted with two or more electron-withdrawing groups having a σp value of 0.20 or more, a nitrogen atom, an acid Atom include a heterocyclic group having 1 to 18 carbon atoms in the 5- to 8-membered ring having a sulfur atom.

  More preferred are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, and a sulfamoyl group having 0 to 12 carbon atoms. In particular, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and a cyano group and an alkylsulfonyl group having 1 to 12 carbon atoms are most preferable.

In the general formula (4), preferred examples of the substituent for Y are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, substituted or unsubstituted. Of these, a C 4-12 heterocyclic group is preferable, and among them, a hydrogen atom or an alkyl group having 1 to 8 carbon atoms is preferable, and a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is particularly preferable. And a hydrogen atom is most preferable.

  In the general formula (4), preferred examples of the substituent for Z are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group. Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. A particularly preferred substituent represented by Z is a substituted aryl group or a substituted heterocyclic group, and among these, a substituted aryl group is particularly preferred.

  In general formula (4), the preferable example of n is 1 or 2, and 2 is especially preferable.

Regarding the preferred combination of substituents of the azo dye represented by the general formula (4) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substituents are the above-mentioned A compound that is a preferred group is more preferred, and a compound in which all substituents are the preferred groups is most preferred.
Of the azo dyes represented by the general formula (4), a dye represented by the general formula (5) is preferable.

In the general formula (5), R ₁ , R ₂ , Y ₁ and Y _{2 each} represent a monovalent group, and X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett σp value of 0.20 or more. Show. Z ₁ and Z ₂ are each independently a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl A group, or a substituted or unsubstituted heterocyclic group; M represents a hydrogen atom or a cation.

Hereinafter, R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , Z ₂ and M will be described in detail.

In the general formula (5), examples of the substituents for R ₁ and R ₂ are the same as the examples of the substituent for R described in the general formula (4), and preferred examples are also the same.
In the general formula (5), examples of the substituents of X ₁ and X ₂ are the same as the examples of the substituent of X described in the general formula (4), and preferred examples are also the same.
In the general formula (5), examples of the substituents Y ₁ and Y ₂ are the same as the examples of the substituent of Y described in the general formula (4), and preferred examples are also the same.
In the general formula (5), examples of the substituents Z ₁ and Z ₂ are the same as the examples of the substituent of Z described in the general formula (4), and preferred examples are also the same.

  In the general formula (5), examples of M are the same as the examples of M described in the general formula (4), and preferred examples are also the same.

  Regarding the preferred combination of substituents of the dye represented by the general formula (5) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  In the present invention, when the compounds represented by the general formulas (4) and (5) require hydrophilicity, it preferably has 2 or more ionic hydrophilic groups in the molecule. It is more preferable to have an ionic hydrophilic group, and it is particularly preferable to have 3 to 6 ionic hydrophilic groups.

  A sulfo group, a carboxyl group or a hydroxyl group (including salts thereof) is preferred. When the ionic hydrophilic group is a salt, preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, and organic cations (eg, pyridinium, tetramethylammonium, guanidinium), among them Alkali metals are preferred. In particular, a lithium salt is preferred for the sulfo group, and a sodium salt and / or potassium salt is preferred for the carboxy group.

  Specific examples of the compounds represented by formulas (4) and (5) of the present invention are shown below, but the compounds used in the present invention are not limited to the following examples.

  Next, the colorant used in the cyan ink composition constituting the ink set of the present invention will be described.

In the ink set of the present invention, any cyan dye that can be applied as a colorant used in the cyan ink composition can be used. For example, C.I. I. Direct Blue 1, 10, 15, 22, 25, 55, 67, 68, 71, 76, 77, 78, 80, 884, 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, 71, and the like. 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.

  Preferred cyan dyes for the ink set of the present invention are phthalocyanine dyes, for example, compounds described in Examples of Japanese Patent Application Laid-Open Nos. 2004-002670 and 2004-075986. Particularly preferred is JP-A No. 2004-002670 (Exemplary Compounds 103 and 105).

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

In the present invention, the black dye used as the colorant of the black ink composition may be any known black dye, but preferably JP-A Nos. 2003-306623, 2005-97359, and 2005-120346. And dyes described in Examples of JP-A-2005-139427. Particularly preferred black dyes are JP-A No. 2005-120346 (Exemplary Compounds D-1, D-9) and JP-A No. 2005-139427 (Exemplary Compounds b-3, c-4).
Also, red, green, blue and white ink compositions other than yellow, magenta and cyan ink compositions can be used.

[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-A Nos. 2002-166638, 2002-121440, 2002-154201, 2002-144696, 2002-80759, 2002-187342, 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, but 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 manner, 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 deaeration using 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.

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

<Synthesis Method of Exemplary Compound (D-2)>
(1) Synthesis method of intermediate (a-1) Intermediate (a-1) Org. Chem. USSR (Engl. Transl); 16; 2039-2044 (1980).
(2) Synthesis method of intermediate (a-2) 18.9 g (50 mmol) of intermediate (a-1), 19.2 g (100 mmol) of ethyl benzoyl acetate, 0.79 g (7.5 mmol) of sodium carbonate To the mixture, 60 mL of orthodichlorobenzene was added and stirred at an internal temperature of 175 ° C. for 12 hours. The reaction solution was air-cooled, and the precipitated crystals were collected by filtration, washed with methanol, dried, and purified by column chromatography to obtain 15.7 g of intermediate (a-2) (31.0 mmol, yield 62%). )
(3) Synthesis method of intermediate (a-3) 15.7 g (31.0 mmol) of intermediate (a-2), 9.7 g (46.5 mmol) of dimethyl 5-aminoisophthalate, copper powder To 9 g and 4.9 g (46.5 mmol) of sodium carbonate, 45 mL of 1,3-dimethyl-2-imidazolidinone (DMI) was added and stirred at an internal temperature of 200 ° C. for 4 hours. After cooling this reaction liquid, 150 mL of ethyl acetate was added, and insoluble matters (unreacted copper and inorganic salts) were removed by filtration. The filtrate was concentrated with an evaporator and purified by column chromatography to obtain 10.0 g (15.8 mmol, yield 51%) of intermediate (a-3).
(4) Method for synthesizing exemplary compound (D-2) 6.3 g of stabilized sulfuric anhydride (sulfane) in a suspension obtained by adding 40 mL of sulfolane to 10.0 g (15.8 mmol) of intermediate (a-3) (79.0 mmol) was slowly added dropwise. After stirring this reaction liquid at 50 degreeC for 4 hours, 5.0 mL of water was dripped slowly, and also it stirred at 70 degreeC for 1 hour. After cooling this reaction liquid and neutralizing with 4M aqueous sodium hydroxide solution, 113 mL of ethanol was added and the precipitated crystals were collected by filtration, washed with methanol and dried to give 6.8 g (7) of the exemplary compound (D-2). 0.6 mmol, yield 48%). The synthesis route is shown below.

(Preparation of water-based ink)
The following components were stirred for 1 hour while heating at 30 to 40 ° C., adjusted to pH 9 with KOH 10 mol / L as necessary, and filtered under pressure using a microfilter having an average pore size of 0.45 μm and a diameter of 47 mm. Thus, an ink liquid A was prepared.
-Composition of ink liquid A-
Dye (D-2) 5 parts by mass Diethylene glycol 9 parts by mass Tetraethylene glycol monobutyl ether 9 parts by mass Glycerol 7 parts by mass Diethanolamine 1 part by mass Water 70 parts by mass

  Ink liquids B to H were prepared in the same manner as the ink liquid A except that the dye was changed as shown in Table 1 below. When two or more dyes were used in combination, they were used in equal mass.

(Image recording and evaluation)
Using ink liquids A to H, an image was recorded on photo glossy paper (inkjet paper manufactured by Fuji Photo Film Co., Ltd., Super Photo Grade) with an ink jet printer (PM-700C, manufactured by Seiko Epson Corporation). The obtained images were evaluated for light fastness, ozone fastness, and hue change under high humidity conditions.

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 1 below.
In Table 1 below, evaluation was made in three stages, with ◯ when the dye residual ratio was 80% or more at any concentration, Δ when two points were less than 80%, and × 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. In Table 1 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.

  About the hue change under high-humidity conditions, it was allowed to stand 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. In Table 1 below, if any value of Δa * is less than 2.0 in any condition, ○, if any value, Δa * value is 2.0 or more and less than 4.0, Δ, any condition The case where Δa * was 4.0 or more was evaluated as x and evaluated in three stages.

  As shown in Table 1, the images obtained from the ink liquids A and E of the present invention are superior to the images obtained from the comparative ink liquids F and H in terms of light fastness and ozone fastness, under high humidity conditions. It can be seen that the hue change at is small. It can be seen that the comparative ink liquid H has a small hue change but is inferior in ozone and light fastness to the ink liquid of the present invention.

  Furthermore, an image was recorded on photographic paper <glossy> (KA450PSK, manufactured by Seiko Epson Corporation) using the ink liquids A to H by an ink jet printer (PM-700C, manufactured by Seiko Epson Corporation). When the obtained images were evaluated for light fastness, ozone gas resistance and hue change under high humidity conditions, the same results as in Table 1 were obtained.

  The same ink produced in Example 2 is packed in a cartridge of an ink jet printer BJ-F850 (manufactured by CANON), and an image is printed on the professional photo paper PR-101 of the same machine, and the same evaluation as in Example 2 is performed. As a result, the same result as in Example 2 was obtained.

[Preparation of each ink composition]
Based on the composition shown in Table 2 below, each component was stirred at room temperature for 30 minutes, and then the resulting solution was filtered using a membrane filter having an opening of 1.0 μm to obtain each ink composition. In Table 2, 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 2, Y represents a yellow ink composition, M represents a magenta ink composition, C represents a cyan ink composition, and B represents a black ink composition.

  In Table 2, the following formula (YELLOW-1) is used as a yellow dye, the following formula (CYAN-1) is used as a cyan dye, and the following formula (BLACK-1) is used as a black dye. A compound represented by the general formula (BLACK-2) was used.

  In the table, TEGmBE is triethylene glycol monobutyl ether, and DEGmBE is diethylene glycol monobutyl ether.

  Next, an ink set of I to N was created using the prepared ink compositions in combinations shown in Table 3. The ink set of the combinations shown in Table 3 does not include a light ink composition, that is, a light magenta ink composition and a light cyan ink composition.

  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 3, an ink jet recording medium {photo paper <gloss> (trade name, Seiko Epson) Manufactured by Co., Ltd.)}, yellow, magenta, cyan, and black (however, black is included only when the ink set includes a black ink composition), and the OD value of each color is 0.7 to 1.8. Each color single-color image pattern in which the density changed stepwise and green, red, and gray image patterns were printed, and image fastness (light resistance and ozone gas resistance) was evaluated.

  As shown in Table 4, the images obtained from the ink sets I to L of the present invention are superior to the images obtained from the comparative ink sets M and N in light fastness and ozone fastness, and each ink. It can be seen that the difference in light fastness and ozone fastness between the compositions is small.

Claims (8)

An ink composition comprising at least one compound represented by the following general formula (1) having at least one ionic hydrophilic group in a molecule as a colorant.

In the general formula (1), 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 0.55 or less, and R ₂ represents an aromatic group or a heterocyclic group. R ₃ represents a hydrogen atom or a substituent, R ₄ and R ₅ each independently represent a hydrogen atom, an aliphatic group or an aromatic group, and Z represents a 5- to 7-membered aromatic group together with a carbon atom. It represents a nonmetallic atom group necessary for forming a ring or a heterocyclic ring. However, general formula (1) has at least one ionic hydrophilic group. 2. The ink composition according to claim 1, wherein the aromatic ring formed by Z together with the carbon atom is an anthrapyridone compound represented by the following general formula (2), wherein the aromatic ring is a benzene ring.

In general formula (2), R ₆ represents a hydrogen atom or a substituent. _{R 1, R 2, R 3} , R 4 and _{R 5} have the same meanings as _{R 1, R 2, R 3} , R 4 and _{R 5} in the general formula (1). However, general formula (2) has at least one ionic hydrophilic group. The ink composition according to claim 1 or 2, wherein R ₁ is an acyl group, an alkoxycarbonyl group, or a carbamoyl group. The ink composition according to claim 1, wherein R ₂ is an aromatic group substituted with an ionic hydrophilic group or a heterocyclic group substituted with an ionic hydrophilic group. The ink composition according to claim 1, wherein one of R ₄ and R ₅ is a hydrogen atom and the other is an aromatic group substituted with an ionic hydrophilic group.   An ink for ink jet recording using an ink composition containing at least one compound according to any one of claims 1 to 5 as a colorant.   An ink jet recording method comprising forming an image on an image receiving material having an ink receiving layer containing a white inorganic pigment on a support using the ink for ink jet recording according to claim 6.   An ink set comprising at least a yellow ink composition, a magenta ink composition, and a cyan ink composition, wherein the magenta ink composition comprises the compound according to any one of claims 1 to 5 as a colorant. An ink set comprising at least one kind.