JP2013049799A - Azaphthalocyanine compound, coloring composition, inkjet ink, inkjet recording method, color filter and color toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an azaphthalocyanine compound satisfiable of both ozone resistance and print density.SOLUTION: The coloring composition includes a specific azaphthalocyanine compound having at least one ionic hydrophilic group as a substituent, in which the ratio (n/n) of the number (n) of substituents where the substituting position to the phthalocyanine skeleton is α-position and the number (n) of substituents where the substituting position to the phthalocyanine skeleton is β-position is larger than 1, provided that nand nare not 0 in any case.

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, as a coloring matter for improving the above problem, Patent Document 1 discloses a phthalocyanine compound (mixture) having a pyridine ring, a pyrazine ring, and a benzene ring. Patent Documents 2 and 3 disclose phthalocyanine compounds in which substituents and substitution positions of a phthalocyanine compound (mixture) having a pyridine ring, a pyrazine ring, and a benzene ring are limited. In any case, the specific phthalocyanine structure improves the image fastness such as ozone resistance and the storage stability, and contributes to the improvement of the performance as an inkjet ink.

JP 2003-34758 A Japanese Patent No. 4516744 JP 2006-070662 A

However, the dyes described in Patent Documents 2 and 3 are required to be further improved in performance when used as ink-jet 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 2 and 3 do not describe a dye that can achieve both high print 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, in a coloring composition in which the number of substituents at the β-position of the phthalocyanine compound contained in the coloring composition is larger than the number of substituents at the α-position, stacking of the dye in the coloring composition occurs and apparent Increases molecular weight. As a result, proper penetration of the printing medium in the depth direction is hindered, causing a reduction in printing density.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that the number of substituents substituted at the α-position of the azaphthalocyanine compound contained in the colored composition is larger than the number of substituents substituted at the β-position of the azaphthalocyanine The present inventors have found that the coloring composition achieves both excellent ozone resistance and high printing density performance, and have completed the present invention.

（一般式（１）中、環Ａ１〜Ａ４は、それぞれ独立に、ベンゼン環、ピリジン環、又はピラジン環を表す。
但し、環Ａ１〜Ａ４のいずれか少なくとも１つはピリジン環、又はピラジン環であり、
Ｒは水素原子又は置換基を表し、ｎは１から１５までの整数を表し、一般式（１）で表されるアザフタロシアニン化合物は、少なくとも１つはイオン性親水性基を置換基として有する。）
〔２〕
前記着色組成物において、前記フタロシアニン骨格への置換位置がα位である置換基数（Ｎ_α）と、前記フタロシアニン骨格への置換位置がβ位である置換基数（Ｎ_β）との比率（Ｎ_α／Ｎ_β）が１．５以上９９以下であることを特徴とする、〔１〕に記載の着色組成物。
〔３〕
前記環Ａ１〜Ａ４のうち、１つの環がピリジン環又はピラジン環であり、３つの環がベンゼン環であることを特徴とする、〔１〕又は〔２〕に記載の着色組成物。
〔４〕
〔１〕に記載の一般式（１）で表されるアザフタロシアニン化合物が、下記一般式（３）で表され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。

（式中、Ｒ_１は水素原子又は置換基を表し、
Ｘ_１は置換基を有していてもよい炭素数２〜２０のアルキレン基を表し、
Ｌ_１は単結合又は２価の連結基を表し、
Ｒ_１２〜Ｒ_１４はそれぞれ独立に水素原子又は置換基を表し、
ｍ_１は０〜２までの整数を表し、ｍ_２は１〜３までの整数を表し、ｍ_１＋ｍ_２＝３を満たす。）
〔５〕
前記イオン性親水性基が、対イオンとしてリチウムイオンを含むことを特徴とする〔１〕〜〔４〕のいずれか１項に記載の着色組成物。
〔６〕
〔１〕〜〔５〕のいずれか１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１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項に記載の一般式（１）で表されるアザフタロシアニン化合物を含有するカラーフィルター。
〔９〕
〔１〕〜〔５〕のいずれか１項に記載の一般式（１）で表されるアザフタロシアニン化合物を含有するカラートナー。
〔１０〕
一般式（Ａ）で表されるアザフタロシアニン化合物。

（一般式（Ａ）中、環ａ１〜ａ４は、それぞれ独立に、ベンゼン環、ピリジン環、又はピラジン環を表す。
Ｒ_Ａは水素原子又は置換基を表す。
但し、環ａ１〜ａ４のいずれか少なくとも１つはピリジン環、又はピラジン環であり、
ｎ_１は１から１５までの整数を表し、一般式（Ａ）で表されるアザフタロシアニン化合物は、少なくとも１つはイオン性親水性基を置換基として有し、フタロシアニン骨格への置換位置がα位である置換基の数が、フタロシアニン骨格への置換位置がβ位である置換基の数より大きい。） That is, the present invention is as follows.
[1]
Containing at least one azaphthalocyanine compound represented by the general formula (1), the number of substituents (N _α ) having a substitution position on the phthalocyanine skeleton at the _α- position, and the substitution position on the phthalocyanine skeleton at the β-position A coloring composition having a ratio (N _α / N _β ) to a number of substituents (N _β ) of greater than 1. However, N _α and N _β are never 0.

(In General Formula (1), Rings A1 to A4 each independently represent a benzene ring, a pyridine ring, or a pyrazine ring.
However, at least one of the rings A1 to A4 is a pyridine ring or a pyrazine ring,
R represents a hydrogen atom or a substituent, n represents an integer of 1 to 15, and at least one of the azaphthalocyanine compounds represented by the general formula (1) has an ionic hydrophilic group as a substituent. )
[2]
In the coloring composition, the ratio (N _α ) of the number of substituents (N _α ) whose substitution position to the phthalocyanine skeleton is α-position and the number of substituents (N _β ) whose substitution position to the phthalocyanine skeleton is β-position / _Nβ ) is 1.5 or more and 99 or less, The coloring composition as described in [1].
[3]
The colored composition according to [1] or [2], wherein one of the rings A1 to A4 is a pyridine ring or a pyrazine ring, and three rings are benzene rings.
[4]
The azaphthalocyanine compound represented by the general formula (1) according to [1] is represented by the following general formula (3), according to any one of [1] to [3] Coloring composition.

(Wherein R ₁ represents a hydrogen atom or a substituent,
X ₁ represents an alkylene group having 2 to 20 carbon atoms which may have a substituent,
L ₁ represents a single bond or a divalent linking group,
R _{12 to} R ₁₄ each independently represent a hydrogen atom or a substituent,
m ₁ represents an integer from 0 to ₂ , m ₂ represents an integer from 1 to 3, and satisfies m ₁ + m ₂ = 3. )
[5]
The colored composition according to any one of [1] to [4], wherein the ionic hydrophilic group contains lithium ions as a counter ion.
[6]
[1] to [5] An inkjet ink containing the colored composition according to any one of [5].
[7]
An inkjet recording method comprising forming an image using the colored composition according to any one of [1] to [5] or the inkjet ink according to [6].
[8]
The color filter containing the azaphthalocyanine compound represented by General formula (1) of any one of [1]-[5].
[9]
A color toner containing an azaphthalocyanine compound represented by the general formula (1) described in any one of [1] to [5].
[10]
An azaphthalocyanine compound represented by the general formula (A).

(In General Formula (A), rings a1 to a4 each independently represent a benzene ring, a pyridine ring, or a pyrazine ring.
R _A represents a hydrogen atom or a substituent.
However, at least one of the rings a1 to a4 is a pyridine ring or a pyrazine ring,
n ₁ represents an integer of 1 to 15, and at least one of the azaphthalocyanine compounds represented by the general formula (A) has an ionic hydrophilic group as a substituent, and the substitution position on the phthalocyanine skeleton is α The number of substituents at the position is larger than the number of substituents at the β-position at the substitution position on the phthalocyanine skeleton. )

According to the present invention, the number of substituents substituted at the α-position of the azaphthalocyanine compound contained in the coloring composition, which can achieve both excellent ozone resistance and high printing density, is substituted at the β-position of the azaphthalocyanine. There are provided a coloring composition having a larger number of substituents, 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.
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.

The colored composition of the present invention contains a compound represented by the general formula (1), and the number of substituents (N _α ) whose substitution position to the phthalocyanine skeleton is _α- position and the substitution position to the phthalocyanine skeleton are Since the ratio (N _α / N _β ) to the number of substituents at the β-position (N _β ) is greater than 1, dye stacking is suppressed due to steric hindrance of the α-position substituent, and the apparent molecular weight decreases. We believe that the print density will improve. In addition, the pyridine ring or pyrazine ring present in the azaphthalocyanine compound provides a high oxidation potential, and ozone resistance can be achieved at a high level. Therefore, the coloring composition of the present invention has the effect of achieving both excellent ozone resistance and high print density.

The N _beta in the present application, in all of the compounds represented by the general formula (1) contained in the coloring composition of the present invention, ring A1~ benzene ring as ring A4, the following in a pyridine ring or a pyrazine ring 1 or 2 Means the total number of substituents represented by —SO ₂ R substituted at the position (β-position). The compound in one molecule, represented by the herein n _beta general formula (1), a benzene ring as ring A1~ ring A4, to 1 or 2 of the following positions in the pyridine ring or a pyrazine ring (beta-position) It means the number of substituents represented by substituted -SO 2 _R. * Represents the bonding position of the azaphthalocyanine ring.

In the present application, N _α is the following 3 or 4 in the benzene ring, pyridine ring or pyrazine ring as ring A1 to ring A4 in all the compounds represented by the general formula (1) included in the colored composition of the present invention. Means the total number of substituents represented by —SO ₂ R substituted at the position (α position). In the present application, n _α is in the following 3 or 4 position (α-position) in the benzene ring, pyridine ring or pyrazine ring as ring A1 to ring A4 in one molecule of the compound represented by the general formula (1). It means the number of substituents represented by substituted -SO 2 _R. * Represents the bonding position of the azaphthalocyanine ring.

For example, a benzene ring (β-position substituted type) in which the substituent represented by —SO ₂ R is substituted at the β-position is represented by the following ring.

（Ｒは水素原子又は置換基を表す。）

(R represents a hydrogen atom or a substituent.)

Further, for example, a benzene ring (α-position substituted type) substituted with a substituent represented by —SO ₂ R at the α-position is represented by the following ring.

（Ｒは水素原子又は置換基を表す。）
本発明の着色組成物において、フタロシアニン骨格への置換位置がα位である置換基の数（Ｎ_α）と、フタロシアニン骨格への置換位置がβ位である置換基の数（Ｎ_β）との比率（Ｎ_α／Ｎ_β）が１より大きくなる態様としては、着色組成物に含まれる全てのアザフタロシアニン化合物のＮ_αがＮ_βより大きくなる限り特に限定されないが、例えば以下の（ｉ）又は（ｉｉ）で表される態様が挙げられる。また、Ｎ_α及びＮ_βはそれぞれ０になることはない。すなわち、本発明の着色組成物は、フタロシアニン骨格への置換位置がα位である置換基を少なくとも１つ以上有し、フタロシアニン骨格への置換位置がβ位である置換基を少なくとも１つ以上有する。

(R represents a hydrogen atom or a substituent.)
In the colored composition of the present invention, the number of substituents whose substitution position to the phthalocyanine skeleton is α-position (N _α ) and the number of substituents whose substitution position to the phthalocyanine skeleton is β-position (N _β ) The aspect in which the ratio (N _α / N _β ) is larger than 1 is not particularly limited as long as N _{α of} all azaphthalocyanine compounds contained in the colored composition is larger than N _β . For example, the following (i) or The mode represented by (ii) is mentioned. Also, N _α and N _β are never 0. That is, the colored composition of the present invention has at least one substituent whose substitution position to the phthalocyanine skeleton is α-position and has at least one substituent whose substitution position to the phthalocyanine skeleton is β-position. .

(I) All the compounds represented by the general formula (1) contained in the coloring composition are compounds in which the number of substituents at the α-position (n _α ) is larger than the number of substituents at the β-position (n _β ) in one molecule. is there.

(Ii) The coloring composition contains a compound represented by the general formula (1) in which the number of substituents at the α-position (n _α ) is larger than the number of substituents at the β-position (n _β ), and n _α and n _β Containing the same compound and / or a compound in which n _β is larger than n _{α and} the total number of α-position substituents (N _α ) contained in the entire colored composition is β-position substitution contained in the entire colored composition Greater than the total number of groups ( _Nβ ).

In the case of (i), the ratio of the number of substituents (n _α ) whose substitution position to the phthalocyanine skeleton is α-position and the number of substituents (n _β ) whose substitution position to the phthalocyanine skeleton is β-position ( n _α / n _β ) is preferably 1.05 to 7.0, more preferably n _α / n _β is 1.10 to 5.0, and 1.25 to 3.0. Is more preferable.

In the case of (ii), the ratio of the number of substituents whose substitution position to the phthalocyanine skeleton is α-position (N _α ) and the number of substituents whose substitution position to the phthalocyanine skeleton is β-position (N _β ) ( N _α / N _β ) is preferably 1.05 to 7.0, N _α / N _β is more preferably 1.10 to 5.0, and 1.25 to 3.5. Is more preferable.

Hereinafter, the azaphthalocyanine compound represented by the general formula (1) contained in the colored composition of the present invention will be described in detail.
[Azaphthalocyanine compound represented by general formula (1)]
The azaphthalocyanine compound represented by the general formula (1) includes an azaphthalocyanine compound represented by the general formula (1), a salt thereof, and a hydrate thereof.

（一般式（１）中、環Ａ１〜Ａ４は、それぞれ独立に、ベンゼン環、ピリジン環、又はピラジン環を表す。
但し、環Ａ１〜Ａ４のいずれか少なくとも１つはピリジン環、又はピラジン環であり、
Ｒは水素原子又は置換基を表す。
ｎは１から１５までの整数を表し、一般式（１）で表されるアザフタロシアニン化合物は、少なくとも１つはイオン性親水性基を置換基として有する。）

(In General Formula (1), Rings A1 to A4 each independently represent a benzene ring, a pyridine ring, or a pyrazine ring.
However, at least one of the rings A1 to A4 is a pyridine ring or a pyrazine ring,
R represents a hydrogen atom or a substituent.
n represents an integer of 1 to 15, and at least one of the azaphthalocyanine compounds represented by the general formula (1) has an ionic hydrophilic group as a substituent. )

In general formula (1), R represents a hydrogen atom or a substituent. The following substituent group A can be mentioned as a substituent.
(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.

  In general formula (1), at least one of R is preferably a group represented by the following general formula (2).

（式中、Ｒ_２〜Ｒ_４はそれぞれ独立に水素原子又は置換基を表し、
Ｘは置換基を有していてもよい炭素数２〜２０のアルキレン基を表し、
Ｌは単結合又は２価の連結基を表す。）

(Wherein R _{2 to} R ₄ each independently represents a hydrogen atom or a substituent,
X represents an alkylene group having 2 to 20 carbon atoms which may have a substituent,
L represents a single bond or a divalent linking group. )

R ₂ represents a hydrogen atom or a substituent, and examples of the substituent include the substituent group A, and include a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group. An aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group is preferable, and a hydrogen atom is more preferable.

R ₃ and R ₄ each independently represent a hydrogen atom or a substituent, and examples of the substituent include the substituent group A and the ionic hydrophilic group. R ₃ and R ₄ are preferably a hydrogen atom or the substituent group A, and include a hydrogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, and a substituted group. Alternatively, an unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, or a substituted or unsubstituted heterocyclic thio group is preferable, and a substituted or unsubstituted amino group is more preferable.
Examples of the substituent when the substituent represented by R ₃ and R ₄ further has a substituent include the substituent group A, and an alkyl group, an aryl group, or a heterocyclic group is preferable. These may be further substituted with the substituent group A, and more preferably substituted with an ionic hydrophilic group.

At least one of R and R _{2 to} R ₄ is preferably a group having a sulfonic acid group, a carboxyl group, or an ionic hydrophilic group as a substituent. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group, and sulfo group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal salts are preferable, and lithium ions are particularly preferable because they increase the solubility of the compound and improve the ink stability. As the number of ionic hydrophilic groups, those having at least two in one molecule of an azaphthalocyanine compound are preferable, and those having at least 2 to 8 ionic hydrophilic groups selected from a sulfo group and a carboxyl group are particularly preferable. Those having 2 to 4 are particularly preferred.

In general formula (2), X represents a C2-C20 alkylene group which may have a single bond or a substituent.
X preferably represents a single bond, ethylene or n-propylene, more preferably a single bond or n-propylene. An alkyl group is mentioned as a substituent in the case of having a substituent.

In general formula (2), L represents a single bond or a divalent linking group. Examples of the divalent linking group include an oxy group (—O—), a thio group (—S—), a carbonyl group (—CO—), a sulfonyl group (—SO ₂ —), an imino group (—NH—), and methylene. Group (—CH ₂ —), an arylene group, a cycloalkylene group, and a group formed by a combination thereof, such as a phenylene group, a cyclohexylene group, a methylene group, a sulfonyl group, —NH—R ₂₀ — or —SO _2. A group represented by NH—R ₂₁ — is preferred, and a group represented by —SO ₂ NH—R ₂₁ — or a sulfonyl group is more preferred.
R ₂₀ and R ₂₁ represent an alkylene group having 1 to 20 carbon atoms, and preferably represent an alkylene group having 1 to 6 carbon atoms.

In general formula (1), A1 to A4 each independently represents a benzene ring, a pyridine ring, or a pyrazine ring.
However, at least one of the rings A1 to A4 is a pyridine ring or a pyrazine ring, and at least one of the rings A1 to A4 is a benzene ring.

  Among the rings A1 to A4, the number of pyridine rings or pyrazine rings is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.

  N represents an integer of 1 to 15, preferably 2 to 6, more preferably 3 to 4, and still more preferably 3.

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

  Of the compounds represented by the general formula (1), a compound represented by the following general formula (3) is preferable.

（式中、Ｒ_１は水素原子又は置換基を表し、
Ｘ_１は置換基を有していてもよい炭素数２〜２０のアルキレン基を表し、
Ｌ_１は単結合又は２価の連結基を表し、
Ｒ_１２〜Ｒ_１４はそれぞれ独立に水素原子又は置換基を表し、
ｍ_１は０から２までの整数を表し、ｍ_２は１から３までの整数を表し、ｍ_１＋ｍ_２＝３を満たす。）

(Wherein R ₁ represents a hydrogen atom or a substituent,
X ₁ represents an alkylene group having 2 to 20 carbon atoms which may have a substituent,
L ₁ represents a single bond or a divalent linking group,
R _{12 to} R ₁₄ each independently represent a hydrogen atom or a substituent,
m ₁ represents an integer from 0 to 2, m ₂ represents an integer from 1 to 3, and satisfies m ₁ + m ₂ = 3. )

R ₁ represents a hydrogen atom or a substituent, and examples of the substituent group include the substituent group A, including a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or An unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group is preferred, and a substituted or unsubstituted amino group, substituted Or an unsubstituted heterocyclic group and a substituted alkyl group are more preferable.
Examples of the substituent when the substituent represented by R ₁ further has a substituent include the substituent group A, and a substituted or unsubstituted hydroxyalkyl group and the ionic hydrophilic group are preferable, and a substituted hydroxy An alkyl group and a sulfo group are more preferable.

R < ₁₂ > -R < ₁₄ > is synonymous with R < ₂ > -R < ₄ > in the above-mentioned general formula (2), and its preferable range is also the same.

X ₁ has the same meaning as X in the general formula (2), and the preferred range is also the same.

L ₁ has the same meaning as L in the above general formula (2), and preferred ranges are also the same.

m ₁ represents an integer from 0 to 2, m ₂ represents an integer from 1 to 3, and satisfies m ₁ + m ₂ = 3. A preferable embodiment of m ₁ and m _{2 is} an embodiment in which m ₁ represents an integer of 1 or 2, m ₂ represents an integer of 1 or 2, and m ₁ + m ₂ = 3 is satisfied. A more preferable embodiment of m ₁ and m ₂ is an embodiment in which m ₁ is 2 and m ₂ is 1.

The present invention also relates to a phthalocyanine compound represented by the following general formula (A), wherein the number of substituents at the α-position is larger than the number of substituents at the β-position in one molecule.
Such a compound can be suitably used in the embodiment (i).

（一般式（Ａ）中、環ａ１〜ａ４は、それぞれ独立に、ベンゼン環、ピリジン環、又はピラジン環を表す。
Ｒ_Ａは水素原子又は置換基を表す。
但し、環ａ１〜ａ４のいずれか少なくとも１つはピリジン環、又はピラジン環であり、
ｎ_１は１から１５までの整数を表し、一般式（Ａ）で表されるアザフタロシアニン化合物は、少なくとも１つはイオン性親水性基を置換基として有し、フタロシアニン骨格への置換位置がα位である置換基の数が、フタロシアニン骨格への置換位置がβ位である置換基の数より大きい。）

(In General Formula (A), rings a1 to a4 each independently represent a benzene ring, a pyridine ring, or a pyrazine ring.
R _A represents a hydrogen atom or a substituent.
However, at least one of the rings a1 to a4 is a pyridine ring or a pyrazine ring,
n ₁ represents an integer of 1 to 15, and at least one of the azaphthalocyanine compounds represented by the general formula (A) has an ionic hydrophilic group as a substituent, and the substitution position on the phthalocyanine skeleton is α The number of substituents at the position is larger than the number of substituents at the β-position at the substitution position on the phthalocyanine skeleton. )

  In general formula (A), a1-a4 are synonymous with A1-A4 in the above-mentioned general formula (1), and a preferable range is also the same.

In General Formula (A), R _A has the same meaning as R in General Formula (1) described above, and the preferred range is also the same.

In the general formula (A), n ₁ is as defined n in the above general formula (1), and preferred ranges are also the same.

Hereinafter, specific examples of the ring A1-A4 substituents of the azaphthalocyanine compound of the present invention represented by the general formulas (1) and (A) and N _α / N _β will be described. It is not limited.

  In the table, examples of four rings (A1) (A2) (A3) (A4) of the azaphthalocyanine mother nucleus are derived from preparation ratios (eq./eq.) Having different structures in the synthesis of the azaphthalocyanine compound of the present invention. It is derived and represents the average value of the mixing ratio of the obtained azaphthalocyanine compounds. In the table, the ionic hydrophilic group is described in the form of a free acid. The colored composition of the present invention may have a form in which the following exemplary compounds are mixed.

The azaphthalocyanine of the present invention is a phthalonitrile or phthalic acid derivative (phthalic acid, phthalic anhydride, phthalimide, diiminoisoindoline, etc.) in which —SO ₂ R is substituted at the α-position and β-position as a starting material for the azaphthalocyanine ring formation reaction. ) In order to be within the scope of the present invention.
When synthesizing by the phthalonitrile method, a nitrogen-containing ring compound (for example, pyridine-2,3-dinitrile), α-SO ₂ R-substituted phthalonitrile and β-SO ₂ R-substituted phthalonitrile are adjusted to a desired ratio. Azaphthalocyanine may be synthesized by mixing. However, in the conventionally known literature, α and β are not mixed and synthesized in a desired ratio in advance, and it cannot be imagined that there is an effect described in the present application.
Similarly, when synthesizing by the Weiler method, a nitrogen-containing ring compound (for example, quinolinic acid), an α-SO ₂ R-substituted phthalic acid derivative and a β-SO ₂ R-substituted phthalic acid derivative are mixed in a desired ratio. Azaphthalocyanine may be synthesized. In particular, when synthesizing by the Weiler method, the reactivity of a conventionally known pigment base is completely random in chlorosulfonylation, so that Nα / Nβ≈1 (α-position substitution 50% / β-position substitution 50%). . Since sulfophthalic acid derived from phthalic acid has different sulfonation reactivity, α-position substitution 25% / β-position substitution 75%, and (aza) phthalocyanine using this as a starting material is Nα / Nβ≈ 0.33 (α-position substitution 25% / β-position substitution 75%). Further, 4-sulfophthalic acid (β-substituted) obtained by purifying the above-mentioned sulfophthalic acid is industrially available, but 3-sulfophthalic acid (α-substituted) cannot be obtained. It was not easy to make.

(Coloring composition)
The coloring composition of the present invention contains at least one azaphthalocyanine 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 can be prepared by dissolving and / or dispersing the azaphthalocyanine compound of the present invention in a lipophilic medium or an aqueous medium as a medium. 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 content of the azaphthalocyanine compound contained in the colored composition is determined by the type of substituent in the general formula (1) used, the type of solvent component used to produce the colored composition, and the like. However, the content of the compound represented by the general formula (1) or the salt thereof in the colored composition is preferably 1 to 10% by mass with respect to the total mass of the colored composition, and 2 to 6% by mass. More preferably it is included.

  By making the content of the compound represented by the general formula (1) contained in the coloring composition 1% by mass or more, it is possible to improve the color developability of the ink on the recording medium when printed, and it is necessary. Image density can be ensured. Moreover, when the total amount of the compounds represented by the general formula (1) contained in the coloring composition is 10% by mass or less, the discharging property of the coloring composition can be improved when used in the ink jet recording method. In addition, it is possible to obtain an effect such that the inkjet nozzle is not easily clogged.

  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 (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 is dispersed in an aqueous medium, as described in JP-A-11-286637, Japanese Patent Application Nos. 2000-78491, 2000-80259, 2000-62370, and the like. In addition, colored fine particles containing a compound and an oil-soluble polymer are dispersed in an aqueous medium, or each specification of Japanese Patent Application Nos. 2000-78454, 2000-78491, 2000-203856, 2000-203857. Thus, it is preferable to disperse the compound of the present invention dissolved in a high boiling point organic solvent in an aqueous medium. 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 is preferably contained in an amount of 0.2 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 7 parts by mass or less. 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 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 hetaryl 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, Polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, 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).
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).
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)
EXAMPLES Hereinafter, although the synthesis method of the azaphthalocyanine compound 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.
[Synthesis Example 1]

<Synthesis of Intermediate A>
Sodium carbonate (165 g) was added to a mixture of 3-nitrophthalonitrile (250 g), DMSO (2 L) and 3-mercaptopropanesulfonic acid sodium salt (320 g), heated to 60 ° C. and stirred for 3 hours. The reaction mixture was poured into 10% brine (3 kg), and the precipitated solid was collected by filtration and washed with an isopropanol / water (3/1) mixture. Water (2 L), acetic acid (30 mL) and sodium tungstate (20 g) were added to the obtained solid, and 31% hydrogen peroxide solution (500 mL) was added, followed by heating and stirring at 60 ° C. After stirring for 4 hours, the reaction mixture was poured into isopropanol (5 L), and the precipitated solid was collected by filtration and washed with an isopropanol / water (3/1) mixture. The solid obtained here was dried to obtain 250 g of intermediate A white crystals. MS (m / z, posi) 315 (M + 1, 100%)

<Synthesis of Intermediate B>
Intermediate B was synthesized by the method described in JP-A-2004-075986.

<Synthesis of Intermediate C2>
To 300 g of ice water, 1.1 g of calsolene oil and 36.8 g of cyanuric chloride were added and stirred for 30 minutes. Next, 58.0 g of aniline-2,5-disulfonic acid monosodium salt was added, and the pH was maintained at 2.7 to 3.0 while adding a 25% aqueous sodium hydroxide solution. Reaction was performed at -30 degreeC for 1 hour. Next, the reaction solution was cooled to 10 ° C. or lower, and 18.2 g of 28% aqueous ammonia was added to the reaction solution. While adding a 25% aqueous sodium hydroxide solution, the pH was maintained at 9.0 to 10.0, and the reaction was performed at 10 to 15 ° C for 0.5 hours and at 27 to 30 ° C for 1 hour. Next, ice was added to the reaction solution to adjust to 5 ° C. or lower. 120 g of ethylenediamine was added to this reaction solution, and the reaction was performed at 20 to 30 ° C. for 3 hours. The liquid volume was adjusted to 750 g, and 150 g of sodium chloride was added to precipitate crystals. The precipitated crystals were separated by filtration and washed with 250 g of a 20% aqueous sodium chloride solution to obtain 92.1 g of a wet cake. 92.1 g of the obtained wet cake was put into 200 g of methanol, 20 g of water was added and suspended and stirred at 60 ° C. for 1 hour, then filtered, washed with methanol, and dried, and 55.3 g of white powder of Intermediate C2 Got. MS (m / z, posi) 406 (M + 1, 100%)

<Synthesis of Exemplary Compound 2 (m = 3, n = 0, N _α / N _β = 2)>
Intermediate A 14.3 g (0.0446 mol), Intermediate B 7.1 g (0.0223 mol), Pyridine-2,3-carbodinitrile 2.9 g (0.0223 mol), Diethylene glycol 134 g, Ortho 21.1 g of ethyl acetate and 0.63 g of acetic acid were mixed and stirred at 110 ° C. for 15 minutes.
The internal temperature was cooled to 80 ° C., 3 g of copper chloride and 24.8 g of ammonium benzoate were added, and the mixture was reacted at an internal temperature of 100 ° C. for 24 hours. After 40 mL of concentrated hydrochloric acid and then 5 g of sodium chloride were added, the internal temperature was cooled to 90 ° C., 360 mL of isopropyl alcohol was added dropwise, and the mixture was stirred at this temperature for 2 hours. After cooling to room temperature, it is filtered, washed thoroughly with isopropyl alcohol and then with acetone, this solid is dissolved in about 1000 mL of water, the pH is adjusted to 8.5 with 2N aqueous sodium hydroxide solution, and dialyzed. Then, the electrical conductivity is purified to 20 μS, filtered through a membrane filter, and the filtrate is concentrated and solidified to obtain 23 g of glossy crystals of exemplary compound 2 (m = 3, n = 0, N _α / N _β = 2). It was. MS (m / z, negative) 1133 (M-H), 566 (M-2H / 2, 100%)

<Synthesis of Exemplified Compound 2 (m = 2, n = 1, N _α / N _β = 2)>
To 100 g of chlorosulfonic acid, 5.7 g (0.005 mol) of the above exemplified compound 2 (m = 3, n = 0, N _α / N _β = 2) was added, and 10 g of phosphorus oxychloride was added. Was reacted at 130 ° C. for 6 hours. The reaction solution was cooled to room temperature, poured slowly into 1000 g of ice water, and the precipitated crystals were filtered to obtain a blue paste (Paste A).
Separately, the intermediate C2 (10.9 g, 0.027 mol) was dispersed in 100 mL of water, and the pH was adjusted to 9.0 with a 2N lithium hydroxide aqueous solution and completely dissolved. The paste A was added at 5 ° C. or lower, and then reacted at 60 ° C. for 3 hours while maintaining a pH of 9.0 with a 2N aqueous lithium hydroxide solution. The reaction was carried out at 1 ° C. for 1 hour. The reaction solution was almost completely dissolved. The reaction solution was neutralized with aqueous hydrochloric acid, the reaction solution was passed through a membrane filter, and dialyzed to an electric conductivity of 20 μS. The dialyzed solution is concentrated, unreacted intermediate C2 is removed by column purification with Pharmacia Sephadex, and dried to obtain an exemplary compound (m = 2, n = 1, N _α / N _β = 2). It was. Here, the values of m and n are estimated from the ratio of C and N by elemental analysis. N _α / N _β is calculated from the charge ratio of the cyclization reaction described above.

  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) 3.5 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

  Ink liquids B to I were prepared in the same manner as in the preparation of ink liquid A, except that the dye was changed as shown in Table 6 below. Illustrative compounds 1 and 3 used Li salts.

(Image recording and evaluation)
The following evaluation was performed on the ink jet inks of the above Examples (and Comparative Examples (Ink Liquids A to I)). The results are shown in Table 6.
In Table 6, the ozone resistance indicates that each ink-jet ink is a photo glossy paper (PMSON paper made by EPSON <gloss> (KA420PSK, EPSON)) using an ink jet printer (manufactured by EPSON Corporation; PM-700C). The printing density was measured using a standard paper (Canon plain paper (GF500, Canon)) using an inkjet printer (manufactured by EPSON Corporation; PM-700C). ) And evaluated after recording the image.

<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.
In particular, the effect of the dye of the present invention having a triazine side chain is remarkable.

[Example 2] Preparation and evaluation of color toner <Preparation of color toner>
3 parts by mass of the pigment of the present invention (Exemplary Compound 1) and 100 parts by mass of a resin for toner [styrene-acrylate copolymer; Hymer TB-1000F (trade name, manufactured by Sanyo Chemical Co., Ltd.)] are mixed and pulverized by a ball mill. Thereafter, the mixture was heated and mixed at 150 ° C., and after cooling, coarsely pulverized using a hammer mill, and then finely pulverized by an air jet type pulverizer. Further, classification was performed to select particles having a size of 1 to 20 μm to obtain toner.

<Evaluation>
To 10 parts by mass of this toner, 900 parts by mass of carrier iron powder (EFV250 / 400, trade name, manufactured by Nippon Iron Powder Co., Ltd.) was uniformly mixed to obtain a developer. When this developer is used for copying with a dry plain paper electrophotographic copying machine (NP-5000, trade name, manufactured by Canon Inc.), it has excellent spectral characteristics and exhibits excellent properties as a toner. I understood.

[Example 3]: Production and evaluation of color filter <Production of color filter>
(Preparation of positive resist composition)
Using 3.4 parts by mass of a cresol novolak resin (polystyrene-converted mass average molecular weight 4300) obtained from a mixture of m-cresol / p-cresol / formaldehyde (reaction molar ratio = 5/5 / 7.5), a phenol compound of the following formula O-naphthoquinonediazide-5-sulfonic acid ester (average of two hydroxyl groups esterified) 1.8 parts by mass, hexamethoxymethylolated melamine 0.8 parts by mass, ethyl lactate 20 parts by mass, and 1 part by mass of Exemplified Compound 1 was mixed to obtain a positive resist composition.

(Production of color filter)
The obtained positive resist composition was spin-coated on a silicon wafer, and then the solvent was evaporated. Next, the silicon wafer was exposed through a mask to decompose the quinonediazide compound. Thereafter, heating was performed at 100 ° C., and then the exposed portion was removed by alkali development to obtain a positive colored pattern having a resolution of 0.8 μm. After the entire surface was exposed, it was heated at 150 ° C. for 15 minutes to obtain a cyan complementary color filter. The exposure was performed with an i-line exposure stepper HITACHILD-5010-i (trade name, manufactured by Hitachi, Ltd., NA = 0.40). The developer used was SOPD or SOPD-B (both trade names, manufactured by Sumitomo Chemical Co., Ltd.).
The obtained color filter had good color purity, high transparency, and good performance.

Claims (10)

Containing at least one azaphthalocyanine compound represented by the general formula (1), the number of substituents (N _α ) having a substitution position on the phthalocyanine skeleton at the _α- position, and the substitution position on the phthalocyanine skeleton at the β-position A coloring composition having a ratio (N _α / N _β ) to a number of substituents (N _β ) of greater than 1. However, N _α and N _β are never 0.

(In General Formula (1), Rings A1 to A4 each independently represent a benzene ring, a pyridine ring, or a pyrazine ring.
However, at least one of the rings A1 to A4 is a pyridine ring or a pyrazine ring,
R represents a hydrogen atom or a substituent, n represents an integer of 1 to 15, and at least one of the azaphthalocyanine compounds represented by the general formula (1) has an ionic hydrophilic group as a substituent. ) In the coloring composition, the ratio (N _α ) of the number of substituents (N _α ) whose substitution position to the phthalocyanine skeleton is α-position and the number of substituents (N _β ) whose substitution position to the phthalocyanine skeleton is β-position The coloring composition according to claim 1, wherein / N _β ) is 1.5 or more and 99 or less.   The colored composition according to claim 1 or 2, wherein one of the rings A1 to A4 is a pyridine ring or a pyrazine ring, and three rings are benzene rings. The coloring composition according to any one of claims 1 to 3, wherein the azaphthalocyanine compound represented by the general formula (1) according to claim 1 is represented by the following general formula (3). object.

(Wherein R ₁ represents a hydrogen atom or a substituent,
X ₁ represents an alkylene group having 2 to 20 carbon atoms which may have a substituent,
L ₁ represents a single bond or a divalent linking group,
R _{12 to} R ₁₄ each independently represent a hydrogen atom or a substituent,
m ₁ represents an integer from 0 to ₂ , m ₂ represents an integer from 1 to 3, and satisfies m ₁ + m ₂ = 3. )   The coloring composition according to claim 1, wherein the ionic hydrophilic group contains lithium ions as counter ions.   An ink-jet ink comprising the colored composition according to claim 1.   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 azaphthalocyanine compound represented by General formula (1) of any one of Claims 1-5.   A color toner containing the azaphthalocyanine compound represented by the general formula (1) according to any one of claims 1 to 5. An azaphthalocyanine compound represented by the general formula (A).

(In General Formula (A), rings a1 to a4 each independently represent a benzene ring, a pyridine ring, or a pyrazine ring.
R _A represents a hydrogen atom or a substituent.
However, at least one of the rings a1 to a4 is a pyridine ring or a pyrazine ring,
n ₁ represents an integer of 1 to 15, and at least one of the azaphthalocyanine compounds represented by the general formula (A) has an ionic hydrophilic group as a substituent, and the substitution position on the phthalocyanine skeleton is α The number of substituents at the position is larger than the number of substituents at the β-position at the substitution position on the phthalocyanine skeleton. )