JP2013129804A - Azaphthalocyanine compound, coloring composition, inkjet ink, inkjet recording method, color filter and color toner - Google Patents

Abstract

【選択図】なしAn object of the present invention is to provide a coloring composition capable of achieving both ozone resistance and printing density.
For example, the following compounds are included.

[Selection figure] None

Description

  The present invention relates to an azaphthalocyanine compound, a colored composition containing an azaphthalocyanine compound, an inkjet ink, an inkjet recording method, a color filter, and a color toner.

  In recent years, a material for forming a color image has been mainly used as an image recording material, and specifically, an ink jet recording material, a thermal transfer recording material, an electrophotographic recording material, a transfer halogen. Silver halide photosensitive materials, printing inks, recording pens and the like are actively used. Further, a color filter is used for recording and reproducing a color image in an imaging device such as a CCD in a photographing apparatus and in an LCD or PDP in a display.

  In these color image recording materials and color filters, three primary colors (dyes and pigments) of so-called additive color mixing and subtractive color mixing are used to reproduce or record full color images. The fact is that there are no fast-acting dyes that have realizable absorption characteristics and can withstand various use conditions, and improvements are strongly desired.

  The ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording.

  Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. There are a method of discharging bubbles, a method of generating bubbles in the ink by heat and discharging droplets, a method of using ultrasonic waves, and a method of sucking and discharging droplets by electrostatic force.

  As the ink for ink jet recording, water-based ink, oil-based ink, or solid (melted type) ink is used.

  For dyes used in such inks for ink jet recording, the solvent has good solubility or dispersibility, high-density recording is possible, hue is good, light, heat, in the environment Fast against active gases (NOx, ozone and other oxidizing gases, SOx, etc.), excellent fastness to water and chemicals, good fixability to image-receiving materials, and low bleeding. It is required that the ink has excellent storability, has no toxicity, has high purity, and can be obtained at low cost.

  However, it is extremely difficult to search for pigments that meet these requirements at a high level. In particular, when printing on an image receiving material having an ink receiving layer that has a good cyan hue and is robust to light, humidity, and heat, especially containing porous white inorganic pigment particles, It is strongly desired to be robust against oxidizing gases such as ozone.

  Cyan dye skeletons used in such inks for ink jet recording include phthalocyanine, anthraquinone, and triphenylmethane, and phthalocyanine compounds with excellent hue and light fastness are used. In particular, since it does not have sufficient fastness to ozone and ink stability cannot be satisfied, improvement is desired.

  The phthalocyanine dye represented by Direct Blue 87 or Direct Blue 199, which is currently widely used, and also described in the above publications, etc., has a feature that it is superior in light resistance compared to magenta and yellow, but is soluble in dye. In many cases, for example, a dissolution failure occurs at the time of manufacturing, resulting in a manufacturing trouble, or an insoluble material precipitates during product storage or use. In particular, the above-described ink jet recording has problems such as clogging of the print head and ejection failure due to poor ink storage stability such as precipitation of dye, leading to significant deterioration of the printed image.

  Currently, inkjet recording is rapidly expanding in the field of use, and as it becomes increasingly widely used in general households, SOHO, business fields, etc., it will be exposed to various usage conditions and environments, resulting in the dissolution of cyan dye. There are many cases where troubles in ink storage stability due to inferiority of the ink occur or exposure to light or an active gas in the environment causes a problem of fading of the printed image. Accordingly, a dye and ink composition having particularly good hue, excellent light fastness and fastness in active gases in the environment (oxidizing gases such as NOx, ozone, etc., SOx, etc.) and high solubility are provided. It is increasingly strongly desired.

Various characteristics of ink, particularly ink used in an ink jet recording system, largely depend on characteristics inherent to the pigment, and selection of the pigment is extremely important. Recently, phthalocyanine compounds having a benzene ring are disclosed in Patent Documents 1 and 2 as dyes that improve the above problems.
Patent Document 3 discloses an azaphthalocyanine dye having a sulfo group and a substituted sulfamoyl group, and Patent Document 4 discloses a specific azaphthalocyanine dye.
In any case, the specific phthalocyanine structure and the specific azaphthalocyanine structure improve the image fastness such as ozone resistance and storage stability, and contribute to the improvement of the performance as an inkjet ink.

Japanese Patent Laid-Open No. 2002-249677 JP 2004-323605 A International Publication No. 2010/020802 Pamphlet Japanese Laid-Open Patent Publication No. 2005-179469

However, the dyes described in Patent Documents 1 to 4 are required to be further improved in terms of performance when used as inkjet inks.
In particular, the dyes used in these ink-jet inks have been designed to promote association of phthalocyanine dyes and increase fastness typified by ozone resistance. On the other hand, there has been a problem that the print density decreases. .
In addition, Patent Documents 1 to 4 do not describe a dye that can achieve both high printing density and excellent ozone resistance, and there is room for study.
An object of this invention is to provide the pigment | dye which can make the performance of the outstanding ozone resistance and the high printing density compatible.

  In the prior art, there is a trade-off relationship between printing density and ozone resistance in a colored composition using a phthalocyanine dye. This is a result designed by the association control of the phthalocyanine dye. When the association is strengthened, the ozone resistance is improved, but the printing density is lowered, and further, bronze gloss is generated in the printed matter, resulting in poor printing quality. On the other hand, when the association is weakened, the printing density is improved, but the ozone resistance is remarkably lowered.

  As a result of intensive studies in view of the above circumstances, the present inventors contain an azaphthalocyanine compound having a sulfonyl group at the α-position (positions 1, 4, 5, 8, 9, 12, 13 and 16), and a phthalocyanine compound. It was found that the coloring composition to be used has both excellent ozone resistance and high print density performance, and the present invention has been completed. Moreover, it turned out that the coloring composition of this invention has bronze glossiness suppressed, has a favorable hue, and is unexpectedly excellent in storage stability.

（一般式（１）中、環Ａ〜Ｄは、それぞれ独立に、下記一般式（３）で表される環、又は下記一般式（４）で表される環を表す。但し、環Ａ〜Ｄのうち少なくとも１つは下記一般式（４）で表される環である。

（一般式（３）中、Ｚ_１は、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表す。＊はフタロシアニン骨格内のピロール環との結合手を表す。一般式（４）中、Ｘ^１〜Ｘ^４はそれぞれ独立に窒素原子またはＣＨを表す。但し、Ｘ^１〜Ｘ^４のうち少なくとも１つは窒素原子を表す。＊はフタロシアニン骨格内のピロール環との結合手を表す。）

一般式（２）中、Ｒ_１及びＲ_２はそれぞれ独立して水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のヘテロ環基、置換もしくは無置換のアルケニル基を表す。 Ａは連結基をそれぞれ表し、隣接するＲ_１、Ｒ_２及びＡは互いに連結して環を形成しても良い。
Ｙ及びＺは、それぞれ独立してハロゲン原子、ヒドロキシル基、スルホン酸基、カルボキシル基、アミノ基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のシクロアルキルオキシ基、置換もしくは無置換のアリールオキシ基、置換もしくは無置換のヘテロ環オキシ基、置換もしくは無置換のアラルキルオキシ基、置換もしくは無置換のアルケニルオキシ基、置換もしくは無置換のアルキルアミノ基、置換もしくは無置換のシクロアルキルアミノ基、置換もしくは無置換のアリールアミノ基、置換もしくは無置換のヘテロ環アミノ基、置換もしくは無置換のアラルキルアミノ基、置換もしくは無置換のアルケニルアミノ基、置換もしくは無置換のジアルキルアミノ基、置換もしくは無置換のアルキルチオ基、置換もしくは無置換のアリールチオ基、置換もしくは無置換のヘテロ環チオ基、置換もしくは無置換のアラルキルチオ基、置換もしくは無置換のアルケニルチオ基を表す。但し、Ｙ、Ｚのうち少なくとも１つは、スルホン酸基、カルボキシル基、またはイオン性親水性基を置換基として有する基である。ｍ_１は０〜３を表し、ｍ_２は１〜３を表し、ｍ_３は１〜３を表し、且つｍ_１、ｍ_２及びｍ_３の和は２〜４である。）
〔２〕
前記一般式（１）において、環Ａ〜Ｄのうち、３つの環が一般式（３）で表される環であり、１つの環が一般式（４）で表される環であることを特徴とする、〔１〕に記載の着色組成物。
〔３〕
前記一般式（４）において、Ｘ^１〜Ｘ^４のうち１つが窒素原子を表し、３つがＣＨを表すことを特徴とする、〔１〕又は〔２〕に記載の着色組成物。
〔４〕
前記一般式（３）で表される環が、下記一般式（５）で表される環であることを特徴とする〔１〕〜〔３〕のいずれか一項に記載の着色組成物。

（一般式（５）中、Ｚ_２は置換若しくは無置換のアルキレン基、置換若しくは無置換のシクロアルキレン基、置換若しくは無置換のアルケニレン基、置換若しくは無置換のアラルキレン基、置換若しくは無置換のアリーレン基、又は置換若しくは無置換のヘテロ環基を表す。＊はフタロシアニン骨格内のピロール環との結合手を表す。）
〔５〕
前記着色組成物において、一般式（１）で表される化合物の着色組成物全体に対する含有量と、一般式（２）で表される化合物の着色組成物全体に対する含有量の比率が、２：１〜１：１０であることを特徴とする、〔１〕〜〔４〕のいずれか一項に記載の着色組成物。
〔６〕
〔１〕〜〔５〕のいずれか一項に記載の着色組成物を含有するインクジェット用インク。
〔７〕
〔１〕〜〔５〕のいずれか一項に記載の着色組成物又は〔６〕に記載のインクジェット用インクを用いて、画像形成することを特徴とするインクジェット記録方法。
〔８〕
〔１〕〜〔５〕のいずれか１項に記載の着色組成物を含有するカラーフィルター。
〔９〕
〔１〕〜〔５〕のいずれか１項に記載の着色組成物を含有するカラートナー。
〔１０〕
一般式（１）で表されるアザフタロシアニン化合物。

（一般式（１）中、環Ａ〜Ｄは、それぞれ独立に、下記一般式（３）で表される環、又は下記一般式（４）で表される環を表す。）

（一般式（３）中、Ｚ_１は、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表す。＊はフタロシアニン骨格内のピロール環との結合手を表す。一般式（４）中、Ｘ^１〜Ｘ^４はそれぞれ独立に窒素原子またはＣＨを表し、Ｘ^１〜Ｘ^４のうち、少なくとも１つが窒素原子である。＊はフタロシアニン骨格内のピロール環との結合手を表す。） That is, the present invention is as follows.
[1]
A coloring composition comprising an azaphthalocyanine compound represented by the following general formula (1) and a phthalocyanine compound represented by the following general formula (2).

(In the general formula (1), the rings A to D each independently represent a ring represented by the following general formula (3) or a ring represented by the following general formula (4). At least one of D is a ring represented by the following general formula (4).

(In the general formula (3), Z ₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted Represents an aryl group or a substituted or unsubstituted heterocyclic group, * represents a bond to a pyrrole ring in the phthalocyanine skeleton, and in formula (4), X ^{1 to} X ⁴ each independently represent a nitrogen atom or CH (However, at least one of X ^{1 to} X ⁴ represents a nitrogen atom. * Represents a bond with a pyrrole ring in the phthalocyanine skeleton.)

In general formula (2), R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted group. An aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group is represented. A represents a linking group, and adjacent R ₁ , R ₂ and A may be connected to each other to form a ring.
Y and Z are each independently a halogen atom, hydroxyl group, sulfonic acid group, carboxyl group, amino group, substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkyloxy group, substituted or unsubstituted aryloxy Group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted cycloalkylamino group, substituted Or an unsubstituted arylamino group, a substituted or unsubstituted heterocyclic amino group, a substituted or unsubstituted aralkylamino group, a substituted or unsubstituted alkenylamino group, a substituted or unsubstituted dialkylamino group, a substituted or unsubstituted Alkylthio group, substituted or unsubstituted Riruchio represents group, a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted aralkylthio group, a substituted or unsubstituted alkenylthio group. However, at least one of Y and Z is a group having a sulfonic acid group, a carboxyl group, or an ionic hydrophilic group as a substituent. m ₁ represents 0 to 3, _{m 2} represents 1-3, _{m 3} represents 1-3, the sum of and _m 1, _{m 2} and _{m 3} are 2 to 4. )
[2]
In the general formula (1), among the rings A to D, three rings are rings represented by the general formula (3), and one ring is a ring represented by the general formula (4). The coloring composition according to [1], which is characterized.
[3]
In the general formula (4) represents one of the nitrogen atoms of the X ¹ to X ^4, 3 one is characterized to represent CH, colored composition according to [1] or [2].
[4]
The ring composition represented by the general formula (3) is a ring represented by the following general formula (5), wherein the colored composition according to any one of [1] to [3].

(In the general formula (5), Z ₂ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted aralkylene group, or a substituted or unsubstituted arylene. Represents a group, or a substituted or unsubstituted heterocyclic group, * represents a bond to a pyrrole ring in the phthalocyanine skeleton.)
[5]
In the colored composition, the ratio of the content of the compound represented by the general formula (1) to the entire colored composition and the ratio of the content of the compound represented by the general formula (2) to the entire colored composition is 2: It is 1-1: 10, The coloring composition as described in any one of [1]-[4] characterized by the above-mentioned.
[6]
[1] to [5] An inkjet ink containing the colored composition according to any one of [5].
[7]
An ink jet recording method comprising forming an image using the colored composition according to any one of [1] to [5] or the ink jet ink according to [6].
[8]
The color filter containing the coloring composition of any one of [1]-[5].
[9]
A color toner containing the coloring composition according to any one of [1] to [5].
[10]
An azaphthalocyanine compound represented by the general formula (1).

(In General Formula (1), Rings A to D each independently represent a ring represented by the following General Formula (3) or a ring represented by the following General Formula (4).)

(In the general formula (3), Z ₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted Represents an aryl group or a substituted or unsubstituted heterocyclic group, * represents a bond to a pyrrole ring in the phthalocyanine skeleton, and in formula (4), X ^{1 to} X ⁴ each independently represent a nitrogen atom or CH And at least one of X ^{1 to} X ⁴ is a nitrogen atom. * Represents a bond with a pyrrole ring in the phthalocyanine skeleton.)

According to the present invention, an azaphthalocyanine compound having a sulfonyl group at the α-position (positions 1, 4, 5, 8, 9, 12, 13 and 16) capable of achieving both excellent ozone resistance and high printing density, And a coloring composition containing the phthalocyanine compound, an inkjet ink containing the coloring composition, and an inkjet recording method.
Furthermore, a color filter and a color toner containing the coloring composition are provided.

Hereinafter, the present invention will be described in detail.
The present invention includes an azaphthalocyanine compound represented by the general formula (1) and a phthalocyanine compound represented by the general formula (2). We believe that it is possible to appropriately control the association state that cannot be controlled well with the seed alone, and to achieve both excellent ozone resistance and high print density.

Here, in the present invention, Hammett's substituent constant σp value is defined.
(Hammett's substituent constant σp value)
Hammett's substituent constant σp value used in this specification will be described.
Hammett's rule is a method described in 1935 in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, but this means that it is limited to only a substituent having a value known in the literature, which can be found in the above-mentioned book. Needless to say, even if the value is unknown, it includes a substituent that would be included in the range when measured based on Hammett's rule. Although the compound concerning this invention is not a benzene derivative, (sigma) p value is used as a scale which shows the electronic effect of a substituent irrespective of a substitution position. In the present invention, the σp value will be used in this sense.

  In the present invention, when the compound is a salt, the salt is dissociated into ions in the ink, but is expressed as “contains a salt” for convenience.

  Hereinafter, the azaphthalocyanine compound represented by the general formula (1) will be described in detail.

  In General Formula (1), Rings A to D each independently represent a ring represented by General Formula (3) or a ring represented by General Formula (4). However, at least one of the rings A to D is a ring represented by the following general formula (4).

In general formula (3), Z ₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl. Represents a group or a substituted or unsubstituted heterocyclic group. * Represents a bond with the pyrrole ring in the phthalocyanine skeleton.
In General Formula (4), X ^{1 to} X ⁴ each independently represent a nitrogen atom or CH. However, at least one of X ^{1 to} X ⁴ represents a nitrogen atom. * Represents a bond with the pyrrole ring in the phthalocyanine skeleton.

  In general formula (1), at least one of rings A to D is a ring represented by general formula (4), and one or two of rings A to D are represented by general formula (4). It is preferable that one ring among the rings A to D is a ring represented by the general formula (4).

Examples of the substituent in the case where Z ₁ has a substituent, may be mentioned the following substituent group A.
(Substituent group A)
For example, halogen atom, alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro 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, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarboni Examples include groups, alkoxycarbonyl groups, carbamoyl groups, aryl or heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, silyl groups, and ionic hydrophilic groups. . These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group A described above.

  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 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, for example, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-octyl group, eicosyl. Group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group and the like, and the cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms such as cyclohexyl group, A cyclopentyl group, 4-n-dodecylcyclohexyl group and the like. The bicycloalkyl group is preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a bicycloalkane having 5 to 30 carbon atoms. Monovalent groups from which one hydrogen atom has been removed, for example, bicyclo [1,2,2] heptan-2-yl group, bicycl [2,2,2] octan-3-yl group.

  Examples of the aralkyl group include a substituted or unsubstituted aralkyl group, and the substituted or unsubstituted aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms. For example, a benzyl group and a 2-phenethyl group can be mentioned.

  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, and 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 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, and 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.

  Preferred examples of the silyloxy group include substituted or unsubstituted silyloxy groups having 0 to 20 carbon atoms such as a trimethylsilyloxy group and 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, a diphenylamino group, and a triazinylamino 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, N, N-dimethylaminocarbonylamino group, or 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 methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino. 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.
Preferred examples of the alkylthio group include substituted or unsubstituted alkylthio groups 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, or 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, such as 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.

  The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group 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.

  The phosphino group is preferably a substituted or unsubstituted phosphino group having 0 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group, and the like.

  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.

  Preferred examples of the silyl group include substituted or unsubstituted silyl groups having 0 to 30 carbon atoms such as a trimethylsilyl group, a t-butyldimethylsilyl group, and a phenyldimethylsilyl group.

(Ionic hydrophilic group)
A sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, a quaternary ammonium group and the like can be mentioned. Particularly preferred are a sulfo group and a carboxyl group. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. Examples of counter cations that form a salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic. Cation (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) is included, lithium salt, sodium salt, potassium salt, ammonium salt is preferable, lithium salt or mixed salt containing lithium salt as a main component Are more preferred, and lithium salts are most preferred.

Z ₁ is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, more preferably a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group. Preferably, it is a substituted alkyl group. Examples of the substituent when Z ₁ has a substituent include the substituent group A, and an ionic hydrophilic group or a substituted or unsubstituted sulfamoyl group is preferable, and an ionic hydrophilic group or hydrocarbyl. A sulfamoyl group having a group as a substituent is more preferable, and a sulfo group or a carboxyl group is still more preferable.

In the general formula ^(4), X 1 ~X 4 represents a nitrogen atom or a CH ^{independently} preferably representing at least one nitrogen atom of X 1 to X ^4, 1 of the X 1 to X ⁴ It is more preferable that ~ 2 represents a nitrogen atom, and it is still more preferable that ^one of X ^{1 to} X ⁴ represents a nitrogen atom.

  Of the rings represented by the general formula (3), a ring represented by the following general formula (5) is preferable.

(In the general formula (5), Z ₂ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted aralkylene group, or a substituted or unsubstituted arylene. Represents a group, or a substituted or unsubstituted heterocyclic group, * represents a bond to a pyrrole ring in the phthalocyanine skeleton.)

In the general formula (5), Z ₂ is preferably a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heterocyclic group, an unsubstituted alkylene group, an unsubstituted arylene group, Or an unsubstituted heterocyclic group is more preferred, and an unsubstituted alkylene group is still more preferred. Examples of the substituent when Z ₂ has a substituent include the substituent group A, and an ionic hydrophilic group, a substituted or unsubstituted alkyl group, or a hydroxyl group is preferable, an ionic hydrophilic group, or An unsubstituted alkyl group is more preferable, and a sulfo group, a carboxyl group, or a hydroxyl group is still more preferable.

  The azaphthalocyanine compound represented by the general formula (1) is an α-position substituted type (the azaphthalocyanine compound having a substituent at the following 1 or 2 position in the benzene ring as the rings A to D in the general formula (1) ).

(* Represents a bond with the pyrrole ring in the phthalocyanine skeleton.)

For example, a benzene ring (α-position substituted type) substituted with a substituent represented by —SO ₂ Z ₁ at the α-position is represented by the following ring, and the following ring is a ring represented by the general formula (3) of the present application. Corresponding to

(Z ₁ represents a hydrogen atom or a substituent. * Represents a bond with a pyrrole ring in the phthalocyanine skeleton.)

  Specific examples of the compound represented by the general formula (1) are listed below, but the present invention is not limited to these specific examples.

  The azaphthalocyanine compound represented by the general formula (1) according to the present invention replaces 4-nitrophthalimide with 3-phthalimide in accordance with the method described in paragraph No. [0263] of JP-A-2005-179469. Can be synthesized.

  Hereinafter, the phthalocyanine compound represented by the general formula (2) will be described in detail.

(In general formula (2), R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted. An aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, wherein A represents a linking group, and adjacent R ₁ , R ₂ and A are connected to each other to form a ring. Y and Z are each independently a halogen atom, hydroxyl group, sulfonic acid group, carboxyl group, amino group, substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkyloxy group, substituted or unsubstituted Aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted Alkenyloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted cycloalkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted heterocyclic amino group, substituted or unsubstituted aralkylamino Group, substituted or unsubstituted alkenylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted An aralkylthio group or a substituted or unsubstituted alkenylthio group, provided that at least one of Y and Z is a group having a sulfonic acid group, a carboxyl group, or an ionic hydrophilic group as a substituent. m ₁ represents 0 to 3, m ₂ represents 1 to 3, and m ₃ represents 1 to 3. And the sum of m ₁ , m ₂ and m ₃ is 2-4.)

In general formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or a substituent, and are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group. It preferably represents an aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group, and more preferably represents a hydrogen atom or a substituted or unsubstituted alkyl group. Preferably, it represents a hydrogen atom.
When the substituent represented by R ₁ and R ₂ further has a substituent, the substituent is preferably a hydroxyl group.

  Examples of the substituted or unsubstituted alkyl group include an alkyl group having 1 to 12 carbon atoms. Examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group and an acetyl group), an aryl group, a halogen atom, And a cyano group.

  Examples of the substituted or unsubstituted cycloalkyl group include alkyl groups having 1 to 12 carbon atoms. Examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group and an acetyl group), an aryl group, a halogen atom, And a cyano group.

  Examples of the substituted or unsubstituted aralkyl group include an alkyl group having 1 to 12 carbon atoms. Examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group and an acetyl group), an aryl group, a halogen atom, And a cyano group.

  Examples of the substituted or unsubstituted aryl group include a phenyl group and a naphthyl group. Examples of substituents include, for example, sulfonic acid groups, carboxyl groups, phosphoric acid groups, hydroxyl groups, amino groups (which may be substituted with alkyl groups, aryl groups and acetyl groups), ureido groups, alkyl groups, alkoxy groups, Examples thereof include a nitro group, a cyano group, a heterocyclic group, and a halogen atom.

  The substituted or unsubstituted heterocyclic group is preferably a 5-membered or 6-membered ring, and they may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. Examples of heterocycles include, for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, Examples include triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. These heterocyclic rings may have a substituent, and examples of the substituent include a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an amino group (an alkyl group, an aryl group, and an acetyl group). Ureido group, alkyl group, alkoxy group, nitro group, cyano group, and halogen atom.

  Examples of the substituted or unsubstituted alkenyl group include alkenyl groups having 1 to 12 carbon atoms. Examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group, and an acetyl group), an aryl group, and a halogen atom. And a cyano group.

In general formula (2), A represents a divalent linking group. Examples of the divalent linking group include, for example, an alkylene group, a cycloalkylene group, and an arylene group, and a group formed by combining these may be used, and an alkylene group is preferable. Examples of groups formed by combining these include xylylene. It is also possible to form a connection with _{R 1} and _{R 2.} The divalent linking group may have a substituent. Examples of the substituent include a sulfonic acid group, a carboxyl group, and a hydroxyl group.

  Examples of the alkylene group include alkylene groups having 1 to 16 carbon atoms. A part of the carbon atoms of the alkylene group may be substituted with nitrogen, oxygen and sulfur atoms. Further, it may be a group formed by combining alkylene and cycloalkylene.

  Examples of the cycloalkylene group include cycloalkylene groups having 1 to 16 carbon atoms. Some of the carbon atoms of the cycloalkylene group may be substituted with nitrogen, oxygen and sulfur atoms. It may be a group formed by combining cycloalkylene and alkylene. The cycloalkylene group may be a bridged cyclic hydrocarbon or a spiro ring hydrocarbon.

  Examples of the arylene group include a phenylene group and a naphthylene group. These may have a substituent. Examples of substituents include, for example, sulfonic acid groups, carboxyl groups, phosphoric acid groups, hydroxyl groups, amino groups (which may be substituted with alkyl groups, aryl groups and acetyl groups), ureido groups, alkyl groups, alkoxy groups, A nitro group, a cyano group, and a halogen atom are mentioned.

  In general formula (2), Y and Z are each independently a halogen atom, hydroxyl group, sulfonic acid group, carboxyl group, amino group, substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkoxy group, substituted Or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted Dialkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted heterocyclic amino group, substituted or unsubstituted aralkylamino group, substituted or unsubstituted alkenylamino group, substituted or unsubstituted alkylthio group, substituted Or unsubstituted arylthio group, substituted or unsubstituted Represents a heterocyclic thio group, a substituted or unsubstituted aralkylthio group, a substituted or unsubstituted alkenylthio group, and at least one of Y and Z is substituted with a sulfonic acid group, a carboxyl group, or an ionic hydrophilic group It is a group possessed as a group. It has an ionic hydrophilic group as a substituent. As the ionic hydrophilic group, an anionic hydrophilic group is preferable, and examples thereof include a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group. These ionic hydrophilic groups may be free forms, or may be alkali metal salts, alkaline earth metal salts, onium ion salts or ammonium salts of organic amines. Examples of the alkali metal include sodium, potassium, lithium and the like. Examples of the alkaline earth metal include calcium and magnesium. As the organic amine, examples of the alkylamine include lower alkylamines having 1 to 4 carbon atoms such as methylamine and ethylamine. Examples of the alkanolamine include mono-, di- or tri (lower alkanol having 1 to 4 carbon atoms) amines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine. Preferred are ammonium, sodium, potassium, lithium, monoethanolamine, diethanolamine, trienolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine salts.

  Examples of the substituted or unsubstituted alkoxy group include an alkoxy group having 1 to 12 carbon atoms. Examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group and an acetyl group), an aryl group, a halogen atom, And a cyano group. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted cycloalkoxy group include cycloalkoxy groups having 1 to 12 carbon atoms. Examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group and an acetyl group), an aryl group, a halogen atom, And a cyano group. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted aryloxy group include a phenoxy group and a naphthoxy group. Examples of substituents include, for example, sulfonic acid groups, carboxyl groups, phosphoric acid groups, hydroxyl groups, amino groups (which may be substituted with alkyl groups, aryl groups and acetyl groups), ureido groups, alkyl groups, alkoxy groups, Examples thereof include a nitro group, a cyano group, a heterocyclic group, and a halogen atom. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  The substituted or unsubstituted heterocyclic oxy group is preferably a 5-membered or 6-membered ring, and they may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. Examples of heterocycles include, for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, Examples include triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. These heterocyclic rings may have a substituent, and examples of the substituent include a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an amino group (an alkyl group, an aryl group, and an acetyl group). Ureido group, alkyl group, alkoxy group, nitro group, cyano group, and halogen atom.

  Examples of the substituted or unsubstituted aralkyloxy group include aralkyloxy groups having 1 to 12 carbon atoms. Examples of substituents include, for example, sulfonic acid groups, carboxyl groups, phosphoric acid groups, hydroxyl groups, amino groups (which may be substituted with alkyl groups, aryl groups and acetyl groups), ureido groups, alkyl groups, alkoxy groups, Examples thereof include a nitro group, a cyano group, a heterocyclic group, and a halogen atom. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted alkenyloxy group include alkenyloxy groups having 1 to 12 carbon atoms. Examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group and an acetyl group), an aryl group, a halogen atom, And a cyano group. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted alkylamino group include an alkylamino group having 1 to 12 carbon atoms. Examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group and an acetyl group), an aryl group, a halogen atom, And a cyano group. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted dialkylamino group include a dialkylamino group having 1 to 12 carbon atoms. Examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group and an acetyl group), an aryl group, a halogen atom, And a cyano group. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted cycloalkylamino group include cycloalkylamino groups having 1 to 12 carbon atoms. Examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group and an acetyl group), an aryl group, a halogen atom, And a cyano group. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted arylamino group include an anilino group and a naltylamino group. Examples of substituents include, for example, sulfonic acid groups, carboxyl groups, phosphoric acid groups, hydroxyl groups, amino groups (which may be substituted with alkyl groups, aryl groups and acetyl groups), ureido groups, alkyl groups, alkoxy groups, Examples thereof include a nitro group, a cyano group, a heterocyclic group, and a halogen atom. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  The substituted or unsubstituted heterocyclic amino group is preferably a 5-membered or 6-membered ring, and they may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. Examples of heterocycles include, for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, Examples include triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. These heterocyclic rings may have a substituent, and examples of the substituent include a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an amino group (an alkyl group, an aryl group, and an acetyl group). Ureido group, alkyl group, alkoxy group, nitro group, cyano group, and halogen atom.

  Examples of the substituted or unsubstituted aralkylamino group include aralkylamino groups having 1 to 12 carbon atoms. Examples of substituents include, for example, sulfonic acid groups, carboxyl groups, phosphoric acid groups, hydroxyl groups, amino groups (which may be substituted with alkyl groups, aryl groups and acetyl groups), ureido groups, alkyl groups, alkoxy groups, Examples thereof include a nitro group, a cyano group, a heterocyclic group, and a halogen atom. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted alkenylamino group include alkenylamino groups having 1 to 12 carbon atoms. Examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group and an acetyl group), an aryl group, a halogen atom, And a cyano group. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted alkylthio group include an alkylthio group having 1 to 12 carbon atoms. Examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group and an acetyl group), an aryl group, a halogen atom, And a cyano group. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted cycloalkylthio group include a cycloalkylthio group having 1 to 12 carbon atoms. Examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group and an acetyl group), an aryl group, a halogen atom, And a cyano group. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted arylthio group include a phenylthio group and a naphthylthio group. Examples of substituents include, for example, sulfonic acid groups, carboxyl groups, phosphoric acid groups, hydroxyl groups, amino groups (which may be substituted with alkyl groups, aryl groups and acetyl groups), ureido groups, alkyl groups, alkoxy groups, Examples thereof include a nitro group, a cyano group, a heterocyclic group, and a halogen atom. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  The substituted or unsubstituted heterocyclic thio group is preferably a 5-membered or 6-membered ring, and they may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. Examples of heterocycles include, for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, Examples include triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. These heterocyclic rings may have a substituent, and examples of the substituent include a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an amino group (an alkyl group, an aryl group, and an acetyl group). Ureido group, alkyl group, alkoxy group, nitro group, cyano group, and halogen atom.

  Examples of the substituted or unsubstituted aralkylthio group include an aralkylthio group having 1 to 12 carbon atoms. Examples of substituents include, for example, sulfonic acid groups, carboxyl groups, phosphoric acid groups, hydroxyl groups, amino groups (which may be substituted with alkyl groups, aryl groups and acetyl groups), ureido groups, alkyl groups, alkoxy groups, Examples thereof include a nitro group, a cyano group, a heterocyclic group, and a halogen atom. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

  Examples of the substituted or unsubstituted alkenylthio group include alkenylthio groups having 1 to 12 carbon atoms. Examples of the substituent include, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an alkoxy group, an amino group (which may be substituted with an alkyl group, an aryl group and an acetyl group), an aryl group, a halogen atom, And a cyano group. Of these, a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a hydroxyl group are preferable.

In general formula (2), Y and Z each independently represent a hydrogen atom or a substituent, an amino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted hetero It preferably represents a cyclic amino group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryloxy group or an ionic hydrophilic group, and is an amino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted group. More preferably, it represents a substituted or unsubstituted heterocyclic amino group, and further represents a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a sulfonic acid group, or a carboxyl group. preferable.
When the substituent represented by Y and / or Z further has a substituent, the substituent is preferably an alkylamino group, a hydroxyl group or an ionic hydrophilic group, more preferably an alkylamino group, a carboxyl group or a sulfonic acid group.

In the general formula (2), the number (m ₁ ) of ionic hydrophilic groups directly bonded to the phthalocyanine skeleton is 0 to 3, more preferably 0 to 2, and still more preferably 0 to 1. The number (m ₂ ) of unsubstituted sulfamoyl groups not containing group A is 1 to 3, more preferably 2 to 3, and the number of substituents containing linking group A (m ₃ ) is 1 to 3. More preferably, it is 1-2. The sum of _m 1, _{m 2} and _{m 3} is 2 to 4, more preferably from 3 to 4.

  In the general formula (2), the substituent containing the linking group A is preferably a group represented by the following general formula (6).

In General Formula (6), A ² represents a single bond or a substituted or unsubstituted alkylene group. R ¹⁰ , R ¹¹ , R ¹² and R ¹⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ¹³ and R ¹⁵ are substituted or unsubstituted. It represents an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and has at least one ionic hydrophilic group as a substituent.

In General Formula (6), A ² represents a single bond or a substituted or unsubstituted alkylene group, and preferably represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and is unsubstituted having 1 to 10 carbon atoms. More preferably, an unsubstituted alkylene group having 2 to 6 carbon atoms is more preferable.
The substituent when A ² has a substituent is preferably a hydroxyl group.

In general formula (6), R ¹⁰ , R ¹¹ , R ¹² and R ¹⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, It preferably represents an unsubstituted alkyl group or a substituted or unsubstituted aryl group, and more preferably represents a hydrogen atom. When the substituent represented by R ¹⁰ , R ¹¹ , R ¹² and / or R ¹⁴ further has a substituent, the substituent is preferably an alkylamino group, a hydroxyl group or an ionic hydrophilic group, an alkylamino group or a carboxyl group. A sulfonic acid group is more preferable. A carboxyl group and a sulfonic acid group are more preferable.

In General Formula (6), R ¹³ and R ¹⁵ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, It preferably represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and more preferably represents a hydrogen atom or a substituted or unsubstituted aryl group. When the substituent represented by R ¹³ and / or R ¹⁵ further has a substituent, the substituent is preferably an alkylamino group, a hydroxyl group or an ionic hydrophilic group, more preferably an alkylamino group, a carboxyl group or a sulfonic acid group. A carboxyl group and a sulfonic acid group are more preferable.

  Specific examples of the substituent containing the linking group A are given below, but the present invention is not limited to these specific examples.

  Specific examples of the compound represented by the general formula (2) are given below, but the present invention is not limited to these specific examples.

  The phthalocyanine compound represented by the general formula (2) according to the present invention can be synthesized by the method described in JP-A-2004-323605.

(Coloring composition)
The coloring composition of the present invention contains at least one azaphthalocyanine compound of the present invention and at least one phthalocyanine compound of the present invention. The coloring composition of the present invention can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for inkjet recording. The coloring composition of the present invention is prepared by dissolving and / or dispersing the azaphthalocyanine compound of the present invention and the phthalocyanine compound of the present invention in a lipophilic medium or an aqueous medium as a medium. Can do. Preferably, an aqueous medium is used. The coloring composition of the present invention includes an ink composition excluding a medium.

  In the present invention, the ratio of the content of the azaphthalocyanine compound represented by the general formula (1) and the content of the phthalocyanine compound represented by the general formula (2) contained in the coloring composition is the general formula used. It is determined by the kind of substituent in the azaphthalocyanine compound represented by (1), the kind of substituent in the phthalocyanine compound represented by general formula (2), and the kind of solvent component used for producing the colored composition. It is done. The ratio of the content of the azaphthalocyanine compound represented by the general formula (1) and the content of the phthalocyanine compound represented by the general formula (2) contained in the coloring composition is 3: 1 to 1:20. It is preferable that the ratio is 2: 1 to 1:10.

  The sum of the content of the azaphthalocyanine compound represented by the general formula (1) and the content of the phthalocyanine compound represented by the general formula (2) contained in the coloring composition is 1 to 10% by mass. Is preferable, and it is still more preferable that it is 2-6 mass%. This is because, when the content is in the above range, the physical properties suitable for the ink jet ink can be obtained (viscosity, surface tension, etc.).

  The coloring composition of the present invention may contain other additives as necessary within a range that does not impair the effects of the present invention. Examples of other additives include additives that can be used in ink jet recording inks described later.

[Ink for inkjet recording]
Next, the ink for inkjet recording of the present invention will be described.
The ink for inkjet recording can be produced by dissolving and / or dispersing the azaphthalocyanine compound and the phthalocyanine compound (mixture) in an oleophilic medium or an aqueous medium. Preferably, the ink uses an aqueous medium.
If necessary, other additives are contained within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are directly added to the ink liquid in the case of water-soluble ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.

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

  As the anti-drying agent, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said anti-drying agent may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

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

  The ultraviolet absorber is used for the purpose of improving image storability. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, U.S. Pat. No. 3,214,463, etc., JP-B Nos. 48-30492, 56-21114, Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP-A-8 No. -502911, etc., triazine compounds, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  The anti-fading agent is used for the purpose of improving image storage stability. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in pages 127 to 137 of JP-A-62-215272 can be used.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

  As the pH adjuster, the neutralizing agent (organic base, inorganic alkali) can be used. For the purpose of improving the storage stability of the ink for ink jet recording, the pH adjuster is preferably added to summer for pH 6 to 10 and more preferably pH 7 to 10 for summer. preferable.

  Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. The surface tension of the inkjet ink of the present invention is preferably 25 to 70 mN / m. Furthermore, 25-60 mN / m is preferable. Further, the viscosity of the ink for ink jet recording of the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less. Examples of surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates. Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Further, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

  As the antifoaming agent, fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.

  When the azaphthalocyanine compound of the present invention and the phthalocyanine compound are dispersed in an aqueous medium, JP-A-11-286637, Japanese Patent Application Nos. 2000-78491, 2000-80259, 2000-62370, etc. As described in JP-A No. 2000-78454, 2000-78491, 2000-203856, 2000-203857, colored fine particles containing a compound and an oil-soluble polymer are dispersed in an aqueous medium. It is preferable to disperse the compound of the present invention dissolved in a high boiling point organic solvent in an aqueous medium as described in each specification of No. The specific method for dispersing the compound of the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount used thereof are preferably those described in the above-mentioned patent publications. be able to. Or you may disperse | distribute the said azaphthalocyanine compound to a fine particle state with a solid. At the time of dispersion, a dispersant or a surfactant can be used. Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high pressure emulsification dispersion method (high pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. In addition to the above-mentioned patents, the ink jet recording ink preparation method described above is disclosed in JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7-118584. Details are described in Japanese Laid-Open Patent Publication No. 11-286637 and Japanese Patent Application No. 2000-87539, and can also be used to prepare the ink for inkjet recording of the present invention.

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

  In 100 parts by mass of the ink for inkjet recording of the present invention, the azaphthalocyanine compound and the phthalocyanine compound are preferably contained in an amount of 0.2 parts by mass or more and 10 parts by mass or less, and preferably 1 part by mass or more and 7 parts by mass or less. Is more preferable. In addition, in the inkjet ink of the present invention, other pigments may be used in combination with the azaphthalocyanine compound. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range.

  The ink for inkjet recording of the present invention preferably has a viscosity of 30 mPa · s or less. The surface tension is preferably 25 mN / m or more and 70 mN / m or less. Viscosity and surface tension are various additives such as viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, UV absorbers, antioxidants, antifading agents, antifungal agents, and rust inhibitors. It can be adjusted by adding a dispersant and a surfactant.

  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.

  Any applicable yellow dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, open-chain active methylene compounds, etc. as coupling components (hereinafter referred to as coupler components); for example, coupler components Azomethine dyes having open-chain active methylene compounds as examples; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dyes Examples of the species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

  Any applicable magenta dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles, etc. as coupler components; for example arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, Methine dyes such as oxonol dyes; Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc., quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycycles such as dioxazine dyes, etc. And dyes.

  Any applicable cyan dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines and the like as coupler components; for example, azomethine dyes having phenols, naphthols, heterocyclic rings such as pyrrolotriazole as coupler components; cyanine dyes, oxonol dyes, Examples include polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, and xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes.

Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated. In this case, the counter cation is an alkali metal or an inorganic cation such as ammonium. Alternatively, it may be an organic cation such as pyridinium or quaternary ammonium salt, and may further be a polymer cation having these in a partial structure.
Applicable black materials include disazo, trisazo, tetraazo dyes, and 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 paper, cloth, glass, metal, ceramics, etc. To do.

  When forming an image, a polymer fine particle dispersion (also referred to as polymer latex) may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing of applying the polymer latex to the image receiving material may be before, after, or simultaneously with the application of the colorant, and therefore the addition place 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, Japanese Patent Application Nos. 2000-363090, 2000-315231, 2000-354380, 2000-343944, 2000-268952, 2000-299465, 2000-297365, etc. The method described in the specification can be preferably used.

Hereinafter, a recording paper and a recording film used for ink jet printing using the ink of the present invention will be described.
The support in recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMPMP, CGP, and waste paper pulp such as DIP. Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there. In addition to these supports, either synthetic paper or plastic film sheets may be used. The thickness of the support is preferably 10 to 250 μm and the basis weight is preferably 10 to 250 g / m ² .
The support may be provided with an ink receiving layer and a backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar. In the present invention, paper and plastic films laminated on both sides with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used as the support.
It is preferable to add a white pigment (for example, titanium oxide or zinc oxide) or a tinting dye (for example, cobalt blue, ultramarine blue, or neodymium oxide) to the polyolefin.

  The ink receiving layer provided on the support contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. As the white pigment contained in the ink receiving layer, porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either anhydrous silicic acid obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but it is particularly desirable to use hydrous silicic acid.

Examples of the aqueous binder contained in the ink receiving layer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. Water-dispersible polymers such as water-soluble polymers, styrene butadiene latexes, and acrylic emulsions. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and resistance to peeling of the ink receiving layer.
The ink receiving layer can contain a mordant, a water resistance agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used.
For the polymer mordant, JP-A-48-28325, 54-74430, 54-124726, 55-22766, 55-142339, 60-23850, 60-23835, 60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122942, 60- No. 235134, JP-A-1-161236, U.S. Pat.Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386, 4,193,800, 4,283,853, 4,282,305, It is described in each specification of the same No. 4450224. An image receiving material containing a polymer mordant described in JP-A-1-161236, pages 212 to 215 is particularly preferred. When the polymer mordant described in the publication is used, an image with excellent image quality is obtained and the light resistance of the image is improved.

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

  Examples of the light fastness improver include zinc sulfate, zinc oxide, hindered amine antioxidants, and benzotriazole ultraviolet absorbers such as benzophenone. Of these, zinc sulfate is particularly preferred.

  The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. The surfactant is described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil), and a solid fluorine compound resin (for example, tetrafluoroethylene resin). The organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20994, and 62-135826. Examples of other additives added to the ink receiving layer include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusters, matting agents, and hardening agents. . The ink receiving layer may be one layer or two layers.

  The recording paper and the recording film can be provided with a back coat layer, and examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. White inorganic pigments such as diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide And organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin and melamine resin.

  As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.

  Polymer latex may be added to the constituent layers (including the backcoat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer latex is described in JP-A Nos. 62-245258, 62-136648, and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.

  The ink of the present invention is not limited to an ink jet recording system, and is a known system, for example, a charge control system that discharges ink using electrostatic attraction, a drop-on-demand system (pressure) that uses the vibration pressure of a piezo element. Pulse method), acoustic ink jet method that converts electrical signal into acoustic beam and irradiates ink and uses ink to discharge ink, and thermal ink jet that heats ink to form bubbles and uses generated pressure Used for systems. Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.

[Color filter]
The present invention also relates to a color filter containing the azaphthalocyanine compound represented by the general formula (1) and the phthalocyanine compound.
As a color filter forming method, a pattern is first formed with a photoresist and then dyed, or disclosed in JP-A-4-163552, JP-A-4-128703, and JP-A-4-175653. Thus, there is a method of forming a pattern with a photoresist to which a dye is added. Any of these methods may be used as a method used when the compound of the present invention is introduced into a color filter. Preferred methods are described in JP-A-4-175753 and JP-A-6-35182. The positive resist composition comprising a thermosetting resin, a quinonediazide compound, a cross-linking agent, a dye and a solvent, and after coating on a substrate, exposing through a mask and developing the exposed portion. Then, a positive resist pattern is formed, the positive resist pattern is exposed on the entire surface, and then the exposed positive resist pattern is cured, and a color filter forming method can be mentioned. In addition, a black matrix is formed according to a conventional method, and an RGB primary color system or Y, M, C complementary color system color filter can be obtained. In the case of a color filter, the amount of the azaphthalocyanine compound of the present invention is not limited, but is preferably 0.1 to 50% by mass.

  Regarding the thermosetting resin, quinonediazide compound, crosslinking agent, and solvent used in this case, and those used, those described in the above-mentioned patent documents can be preferably used.

[Color toner]
The present invention also relates to a color toner containing the azaphthalocyanine compound represented by the general formula (1) and the phthalocyanine compound.
The content of the azaphthalocyanine compound in 100 parts by weight of the color toner is not particularly limited, but is preferably 0.1 parts by weight or more, more preferably 1 to 20 parts by weight, and 2 to 10 parts by weight. Most preferred. As a binder resin for a color toner into which an azaphthalocyanine compound is introduced, all commonly used binders can be used. Examples thereof include styrene resin, acrylic resin, styrene / acrylic resin, and polyester resin.
Inorganic fine powders and organic fine particles may be externally added to the toner for the purpose of improving fluidity and controlling charging. Silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. These have a number average primary particle size of preferably 10 to 500 nm, and more preferably 0.1 to 20% by mass in the toner.

  As the release agent, all conventionally used release agents can be used. Specific examples include olefins such as low molecular weight polypropylene, low molecular weight polyethylene, and ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax. These addition amounts are preferably 1 to 5% by mass in the toner.

  The charge control agent may be added as necessary, but is preferably colorless from the viewpoint of color development. Examples thereof include those having a quaternary ammonium salt structure and those having a calixarene structure.

  As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron and ferrite, or a resin-coated carrier whose magnetic material particle surface is coated with a resin or the like may be used. The average particle diameter of this carrier is preferably 30 to 150 μm in terms of volume average particle diameter.

  The image forming method to which the toner is applied is not particularly limited. For example, a method of forming a color image by repeatedly forming a color image on a photoconductor to form an image, or an image formed on a photoconductor For example, a method of sequentially transferring to an intermediate transfer member or the like and forming a color image on the intermediate transfer member or the like and then transferring it to an image forming member such as paper to form a color image, or the like.

(Synthesis example)
Hereinafter, although the synthesis method of the coloring composition of this invention is demonstrated in detail to an Example, this invention is not limited to these Examples at all.

The representative azaphthalocyanine compound of the present invention can be derived from, for example, the following synthetic route. A typical phthalocyanine compound of the present invention can be synthesized by the method described in JP-A-2004-323605.
[Synthesis Example 1]
Synthesis of azaphthalocyanine compounds

  In a 1000 mL three-necked flask, 134 g of diethylene glycol (manufactured by Fischer), 21.2 g of ethyl orthoacetate (manufactured by Fischer), 0.63 g of acetic acid (manufactured by Fischer), 2.73 g of pyridine-2,3-dicarbonitrile (manufactured by Tokyo Chemical Industry) 2- (2,3-dicyanobenzene-1-ylsulfonyl) propanesulfonic acid (24.1 g (synthesized by the method described in WO2007 / 37039A1, page 67)), and heated and stirred at 100 ° C. Copper chloride 3.0 g (manufactured by Fischer) and ammonium benzoate 24.8 g (manufactured by Acros) were added and reacted at 100 ° C. for 24 hours. Concentrated hydrochloric acid 40mL was added to the reaction liquid, it cooled to 85 degreeC, acetone 360mL was dripped there, and the crystal | crystallization was deposited. After cooling to room temperature, the crystals were filtered off and washed thoroughly with acetone. The crystals separated by filtration are dissolved in 1000 mL of water, passed through a cation exchange resin (Amberlite IR-120Na, manufactured by Organo), desalted to 10 μS using a dialysis tube, Dust removal was performed with a 2 μm Millipore filter, and drying was performed in an oven at 60 ° C. to obtain 18.6 g of green glossy crystals of Exemplary Compound 1-1. The absorption maximum wavelength in the visible region in the dilute aqueous solution was 656 nm, and a waveform having another maximum wavelength at 611 nm was also shown.

  Deionized water was added to the following components to make 100 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with KOH 10 mol / L, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.25 μm to prepare an ink solution for cyan.

Composition of ink liquid A:
Azaphthalocyanine dye of the present invention (Exemplary Compound 1-1) 2.5 g
Illustrative compound (2-1) 2.5 g
Diethylene glycol 10.65g
Glycerin 14.70g
Diethylene glycol monobutyl ether 12.70g
Triethanolamine 0.65g
Olfin E1010 (Nissin Chemical Industry Co., Ltd.) 0.9g
Surfynol TG (Air Products) 0.85g
PROXEL XL2 (manufactured by Fuji Film Imaging Colorant) 0.18g

  Except having changed the pigment | dye as shown in following Table 5, it carried out similarly to preparation of the ink liquid 1, and adjusted the ink liquids 2-5 and the comparative ink liquids 1-4, and Examples 1-5 and Comparative Example 1 It was set to ~ 4.

<Image recording and evaluation>
The following evaluation was performed about the ink for inkjet of each of the above Examples and Comparative Examples.
Ozone resistance, presence or absence of bronze gloss, and hue were evaluated after each ink-jet ink was recorded on photo glossy paper (Seiko Epson Photographic Paper (KA420PSK)) with an inkjet printer (Seiko Epson PM700C). Is. The print density was evaluated after an image was recorded on plain paper (Canon, GF500) using the printer.

<Ozone gas resistance>
While passing dry air through the double glass tube of the Siemens type ozonizer, an AC voltage of 5 kV was applied, and using this, the ozone gas concentration was 0.5 ± 0.1 ppm, the room temperature was set in a dark place, The photo glossy paper on which the image was formed was allowed to stand for 14 days, and the image density before and after being left under ozone gas was measured using a reflection densitometer (X-Rite 310TR) and evaluated as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
The evaluation was made in three stages, with A being a dye residual ratio of 70% or more at any concentration, A being 1 or 2 points being less than 70% B, and C being less than 70% at all concentrations.

<Print density>
The print density at a print density of 100% is measured using a reflection densitometer (X-Rite 310TR), and when the print density is 1.1 or more, A, when 1.0 or less and less than 1.1, B. A case of less than 0 was evaluated as C, and evaluated in three stages.
As is apparent from the results in Table 6, the inks of the examples using the dyes of the present invention can achieve both excellent ozone resistance and printing density, and are extremely high in comparison with the other comparative examples. You can see that both are compatible.

<Bronze glossiness>
When an image at a printing density of 100% is visually observed under a fluorescent lamp, the cyan image portion does not have a bronze-like gloss, A is slightly generated, B is clearly generated, and C is clearly generated. Evaluation was made in three stages.

<Hue evaluation>
When visually observed under a fluorescent lamp, a sample exhibiting a vivid cyan color was evaluated in two stages, A indicating a slightly turbid cyan color, and B.

  Table 6 shows the ozone gas resistance evaluation results, the print density evaluation results, the bronze gloss evaluation results, and the hue evaluation results of the recorded ink images obtained in Examples 1 to 5 and Comparative Examples 1 to 4. .

  As apparent from the above, Examples 1 to 5 all have excellent ozone resistance, high printing density, no bronze gloss, good hue, and can be suitably used as a cyan ink for inkjet.

  In addition, prints printed with ink containing partial azaphthalocyanine containing a pyridine ring are much more excellent in light resistance test results than partial azaphthalocyanine containing a pyrazine ring. Inks using partial azaphthalocyanine containing are particularly useful for this application.

(Example 101)
Preparation of high-concentration aqueous solution Ion exchange water was added to the following components to make 33.3 g and dissolved by heating.
Exemplified Compound 1-1 2.5g
Exemplified Compound 2-1 2.5g

(Examples 102 to 105 and Comparative Examples 101 to 104)
A highly concentrated aqueous solution was prepared in the same manner except that the dye used in Example 101 was changed as shown in Table 7 below.

<Storage stability over time>
With respect to the prepared high-concentration aqueous solutions of Examples 101 to 105 and comparative high-concentration aqueous solutions of Comparative Examples 101 to 104, a temporal stability test was conducted after the high-concentration aqueous solution was left at 20 ° C. for 14 days. Evaluation was made in two stages: A, which maintained a good aqueous solution form even after aging, and B, which had abnormalities such as precipitation and increased viscosity. The results are shown in Table 8 below.

  As is clear from the above results, it can be seen that Examples 101 to 105 of the present invention are all excellent in storage stability with time in a high concentration aqueous solution. When the storage stability in a high concentration aqueous solution is high, since a high concentration is sufficient for transportation and storage, the cost for this can be suppressed as compared with a dilute solution, and thus the industrial utility value is great.

Claims (10)

A coloring composition comprising an azaphthalocyanine compound represented by the following general formula (1) and a phthalocyanine compound represented by the following general formula (2).

(In the general formula (1), the rings A to D each independently represent a ring represented by the following general formula (3) or a ring represented by the following general formula (4). At least one of D is a ring represented by the following general formula (4).

(In the general formula (3), Z ₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted Represents an aryl group or a substituted or unsubstituted heterocyclic group, * represents a bond to a pyrrole ring in the phthalocyanine skeleton, and in formula (4), X ^{1 to} X ⁴ each independently represent a nitrogen atom or CH (However, at least one of X ^{1 to} X ⁴ represents a nitrogen atom. * Represents a bond with a pyrrole ring in the phthalocyanine skeleton.)

In general formula (2), R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted group. An aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group is represented. A represents a linking group, and adjacent R ₁ , R ₂ and A may be connected to each other to form a ring.
Y and Z are each independently a halogen atom, hydroxyl group, sulfonic acid group, carboxyl group, amino group, substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkyloxy group, substituted or unsubstituted aryloxy Group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted cycloalkylamino group, substituted Or an unsubstituted arylamino group, a substituted or unsubstituted heterocyclic amino group, a substituted or unsubstituted aralkylamino group, a substituted or unsubstituted alkenylamino group, a substituted or unsubstituted dialkylamino group, a substituted or unsubstituted Alkylthio group, substituted or unsubstituted Riruchio represents group, a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted aralkylthio group, a substituted or unsubstituted alkenylthio group. However, at least one of Y and Z is a group having a sulfonic acid group, a carboxyl group, or an ionic hydrophilic group as a substituent. m ₁ represents 0 to 3, _{m 2} represents 1-3, _{m 3} represents 1-3, the sum of and _m 1, _{m 2} and _{m 3} are 2 to 4. )   In the general formula (1), among the rings A to D, three rings are rings represented by the general formula (3), and one ring is a ring represented by the general formula (4). The colored composition according to claim 1, characterized in that 3. The colored composition according to claim 1, wherein in the general formula (4), one of X ^{1 to} X ⁴ represents a nitrogen atom, and three represents CH. The colored composition according to any one of claims 1 to 3, wherein the ring represented by the general formula (3) is a ring represented by the following general formula (5).

(In the general formula (5), Z ₂ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted aralkylene group, or a substituted or unsubstituted arylene. Represents a group, or a substituted or unsubstituted heterocyclic group, * represents a bond to a pyrrole ring in the phthalocyanine skeleton.)   In the colored composition, the ratio of the content of the compound represented by the general formula (1) to the entire colored composition and the ratio of the content of the compound represented by the general formula (2) to the entire colored composition is 2: The coloring composition according to claim 1, wherein the coloring composition is 1 to 1:10.   An ink-jet ink containing the coloring composition according to any one of claims 1 to 5.   An ink jet recording method comprising forming an image using the colored composition according to claim 1 or the ink jet ink according to claim 6.   The color filter containing the coloring composition of any one of Claims 1-5.   A color toner containing the coloring composition according to claim 1. An azaphthalocyanine compound represented by the general formula (1).

(In General Formula (1), Rings A to D each independently represent a ring represented by the following General Formula (3) or a ring represented by the following General Formula (4).)

(In the general formula (3), Z ₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted Represents an aryl group or a substituted or unsubstituted heterocyclic group, * represents a bond to a pyrrole ring in the phthalocyanine skeleton, and in formula (4), X ^{1 to} X ⁴ each independently represent a nitrogen atom or CH And at least one of X ^{1 to} X ⁴ is a nitrogen atom. * Represents a bond with a pyrrole ring in the phthalocyanine skeleton.)