JP2013049800A - 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 achieving high print density and giving printed matter excellent in image robustness such as ozone resistance.SOLUTION: This azaphthalocyanine compound is expressed by general formula (1). In the general formula (1), rings A1 to A4 each independently represents an electron-attracting group or a benzene ring, pyridine ring or pyrazine ring which may be substituted with a group represented by general formula (V1), provided that at least anyone of rings A1 to A4 is a pyridine ring or pyrazine ring substituted by the electron attractive group, and at least anyone of rings A1 to A4 is a benzene ring substituted by the group represented by general formula (V1); Rrepresents H or a monovalent substituent. Also the azaphthalocyanine compound expressed by general formula (1) has at least one ionic hydrophilic group as a substituent.

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.

  Moreover, it is easy to fade with oxidizing gases such as ozone, which are often cited as environmental problems, and the print density is greatly reduced.

  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 Document 2 discloses a phthalocyanine compound in which substituents and substitution positions of a phthalocyanine compound (mixture) having a pyridine ring, a pyrazine ring, and a benzene ring are limited. Patent Documents 3 to 5 disclose phthalocyanine compounds having a structure having a pyridine ring, a pyrazine ring, a pyrimidine ring, and a benzene ring and having or having a specific substituent on a nitrogen-containing ring. . In any case, the specific phthalocyanine structure improves the image fastness and storage stability including ozone resistance, light resistance and water resistance, and contributes to the improvement of the performance as an inkjet ink.

JP 2003-34758 A Japanese Patent No. 4516744 JP 2007-249160 A JP 2006-070662 A International Publication No. 05/021658

However, the dyes described in Patent Documents 2 to 5 have no description of quality such as print density, and there is room for further study.
An object of the present invention is to provide a dye capable of realizing a high printing density while maintaining image fastness such as ozone resistance.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that a compound having an electron withdrawing group on the nitrogen-containing ring of azaphthalocyanine is high while maintaining image fastness such as ozone resistance. The present inventors have found that a print density can be realized and have completed the present invention.

（一般式（１）中、環Ａ１〜Ａ４は、それぞれ独立に、電子求引性基又は一般式（Ｖ１）で表される基で置換されていてもよい、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つは電子求引性基で置換されているピリジン環又はピラジン環であり、かつ環Ａ１〜Ａ４のいずれか少なくとも１つは一般式（Ｖ１）で表される基で置換されたベンゼン環である。
Ｒ_１は水素原子又は１価の置換基を表す。複数のＲ_１は同じであっても異なっていてもよい。
環Ａ１〜Ａ４はさらに−Ｒ_１１で置換されていてもよい。Ｒ_１１は１価の置換基を表す。複数のＲ_１１は同じであっても異なっていてもよい。
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〕
前記環Ａ１〜Ａ４のうち、１つの環が電子求引性基で置換されているピリジン環又はピラジン環であり、１つの環が一般式（Ｖ１）で表される基で置換されたベンゼン環であり、２つの環がベンゼン環又は一般式（Ｖ１）で表される基で置換されたベンゼン環であることを特徴とする、〔１〕に記載の着色組成物。
環Ａ１〜Ａ４はさらにーＲ_１１で置換されていてもよい。Ｒ_１１は１価の置換基を表す。複数のＲ_１１は同じであっても異なっていてもよい。
〔３〕
前記環Ａ１〜Ａ４のうち、１つの環が一般式（Ｖ０）で表される環であり、１つの環が一般式（Ｖ１）で表される基で置換されたベンゼン環であり、２つの環がベンゼン環又は一般式（Ｖ１）で表される基で置換された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。

（一般式（Ｖ０）中、ＥＷＧは電子求引性基を表す。Ｒ_１１は１価の置換基を表す。ｍは１または２である。）
〔４〕
前記一般式（Ｖ１）で表される基で置換されたベンゼン環が下記（Ｖ１−α）であることを特徴とする、〔１〕〜〔３〕のいずれか１項に記載の着色組成物。*はアザフタロシアニン環の結合位置を表す。

（Ｒ_１はそれぞれ独立に水素原子又は１価の置換基を表す。）
〔５〕
前記一般式（Ｖ１）で表される基で置換されたベンゼン環が下記（Ｖ１−β）であることを特徴とする、〔１〕〜〔３〕のいずれか１項に記載の着色組成物。*はアザフタロシアニン環の結合位置を表す。

（Ｒ_１はそれぞれ独立に水素原子又は１価の置換基を表す。）
〔６〕
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〕〜〔５〕のいずれか１項に記載の着色組成物。
〔７〕
〔１〕〜〔６〕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。
〔８〕
〔１〕〜〔６〕のいずれか１項に記載の着色組成物又は〔７〕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。
〔９〕
〔１〕〜〔６〕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。
〔１０〕
〔１〕〜〔６〕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。
〔１１〕
一般式（１）で表されるアザフタロシアニン化合物。

（一般式（１）中、環Ａ１〜Ａ４は、それぞれ独立に、電子求引性基又は一般式（Ｖ１）で表される基で置換されていてもよい、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つは電子求引性基で置換されているピリジン環又はピラジン環であり、かつ環Ａ１〜Ａ４のいずれか少なくとも１つは一般式（Ｖ１）で表される基で置換されたベンゼン環である。
Ｒ_１は水素原子又は１価の置換基を表す。複数のＲ_１は同じであっても異なっていてもよい。
環Ａ１〜Ａ４はさらに−Ｒ_１１で置換されていてもよい。Ｒ_１１は１価の置換基を表す。複数のＲ_１１は同じであっても異なっていてもよい。
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。） That is, the present invention is as follows.
[1]
A coloring composition comprising an azaphthalocyanine compound represented by the general formula (1).

(In General Formula (1), Rings A1 to A4 are each independently a benzene ring, a pyridine ring, or a pyrazine, which may be substituted with an electron-withdrawing group or a group represented by General Formula (V1). Represents a ring.
However, at least one of the rings A1 to A4 is a pyridine ring or a pyrazine ring substituted with an electron withdrawing group, and at least one of the rings A1 to A4 is represented by the general formula (V1). A benzene ring substituted with
R ₁ represents a hydrogen atom or a monovalent substituent. The plurality of R ₁ may be the same or different.
Ring A1~A4 may be further substituted by _{-R 11.} R ₁₁ represents a monovalent substituent. The plurality of R ₁₁ may be the same or different.
At least one of the azaphthalocyanine compounds represented by the general formula (1) has an ionic hydrophilic group as a substituent. )
[2]
Among the rings A1 to A4, one ring is a pyridine ring or a pyrazine ring substituted with an electron withdrawing group, and one ring is substituted with a group represented by the general formula (V1) The coloring composition according to [1], wherein the two rings are benzene rings or benzene rings substituted with a group represented by formula (V1).
Ring A1~A4 may be substituted by Sarani _{R 11.} R ₁₁ represents a monovalent substituent. The plurality of R ₁₁ may be the same or different.
[3]
Among the rings A1 to A4, one ring is a ring represented by the general formula (V0), one ring is a benzene ring substituted with a group represented by the general formula (V1), and two rings The colored composition as described in [1] or [2], wherein the ring is a benzene ring or a benzene ring substituted with a group represented by formula (V1).

(In General Formula (V0), EWG represents an electron-withdrawing group. R ₁₁ represents a monovalent substituent. M is 1 or 2.)
[4]
The colored composition according to any one of [1] to [3], wherein the benzene ring substituted with the group represented by the general formula (V1) is the following (V1-α): . * Represents the bonding position of the azaphthalocyanine ring.

(R ₁ independently represents a hydrogen atom or a monovalent substituent.)
[5]
The colored composition according to any one of [1] to [3], wherein the benzene ring substituted with the group represented by the general formula (V1) is the following (V1-β): . * Represents the bonding position of the azaphthalocyanine ring.

(R ₁ independently represents a hydrogen atom or a monovalent substituent.)
[6]
The colored composition according to any one of [1] to [5], wherein the ionic hydrophilic group contains lithium ions as a counter ion.
[7]
[1] An inkjet ink containing the coloring composition according to any one of [6].
[8]
An inkjet recording method comprising forming an image using the colored composition according to any one of [1] to [6] or the inkjet ink according to [7].
[9]
A color filter containing an azaphthalocyanine compound represented by the general formula (1) according to any one of [1] to [6].
[10]
A color toner containing an azaphthalocyanine compound represented by the general formula (1) according to any one of [1] to [6].
[11]
An azaphthalocyanine compound represented by the general formula (1).

(In General Formula (1), Rings A1 to A4 are each independently a benzene ring, a pyridine ring, or a pyrazine, which may be substituted with an electron-withdrawing group or a group represented by General Formula (V1). Represents a ring.
However, at least one of the rings A1 to A4 is a pyridine ring or a pyrazine ring substituted with an electron withdrawing group, and at least one of the rings A1 to A4 is represented by the general formula (V1). A benzene ring substituted with
R ₁ represents a hydrogen atom or a monovalent substituent. The plurality of R ₁ may be the same or different.
Ring A1~A4 may be further substituted by _{-R 11.} R ₁₁ represents a monovalent substituent. The plurality of R ₁₁ may be the same or different.
At least one of the azaphthalocyanine compounds represented by the general formula (1) has an ionic hydrophilic group as a substituent. )

According to the present invention, an azaphthalocyanine compound in which an electron-attracting group is introduced on a nitrogen-containing ring, which can achieve high printing density while maintaining image fastness including ozone resistance, and coloring containing the compound Compositions, inkjet inks, and inkjet recording methods are provided.
Furthermore, a color filter and a color toner containing the azaphthalocyanine compound are provided.

  In the azaphthalocyanine compound represented by the general formula (1) used in the present invention, for example, at least one specific ring (for example, a pyridine ring having an electron withdrawing group) is introduced into the phthalocyanine mother nucleus, and further, at least one It is a substituted azaphthalocyanine compound (mixture) into which two specific substituents {for example, a group represented by the above general formula (V1)} are introduced. In the present invention, all of the possibilities when synthesizing an azaphthalocyanine compound Azaphthalocyanine mixtures {for example, a mixing ratio of a pyridine ring having an electron withdrawing group and a benzene ring substituted with a group represented by the general formula (V1)} may be included, and a specific mixing ratio { For example, a specific mixture of pyridine ring / benzene ring substituted with a group represented by formula (V1) = 99.9 / 0.1 to 0.1 / 99.9 (eq./eq.)} Also used only things, or it can be used several of them as a mixture. Therefore, crystallization can be inhibited by using a mixture in which azaphthalocyanine compounds having a plurality of specific substituents are present, and improvement in storage stability of the dye (azaphthalocyanine compound) in the ink can be expected. .

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.

Hereinafter, the azaphthalocyanine compound represented by the general formula (1) 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) of the present invention includes a compound, a salt thereof, and a hydrate thereof.
The azaphthalocyanine compound of the present invention has a nitrogen-containing ring substituted with an electronic attractive group. Since this structure has an electron-attracting group in the nitrogen-containing ring, for example, in a conventional synthesis method such as chlorosulfonylation of unsubstituted azaphthalocyanine, low reactivity due to electron deficiency of the nitrogen-containing ring It cannot be synthesized because it does not react with any part, and can be synthesized by the synthesis method described later (a nitrogen-containing heterocyclic derivative containing an electron-withdrawing group is selected in advance and phthalocyanine cyclized). .
Since the azaphthalocyanine compound of the present invention has a nitrogen-containing ring substituted with an electronic attractive group,
Due to the electron withdrawing ability, the HOMO level of the dye is lowered, and the effect of the present application that the image fastness such as ozone resistance is excellent is achieved. Further, by selecting a low molecular weight substituent as the electron withdrawing group, the molar extinction coefficient per unit weight is increased, and the effect of the present application that the printing density in the printed matter can be improved is achieved.

(In General Formula (1), Rings A1 to A4 are each independently a benzene ring, a pyridine ring, or a pyrazine, which may be substituted with an electron-withdrawing group or a group represented by General Formula (V1). Represents a ring.
However, at least one of the rings A1 to A4 is a pyridine ring or a pyrazine ring substituted with an electron withdrawing group, and at least one of the rings A1 to A4 is represented by the general formula (V1). A benzene ring substituted with
R ₁ represents a hydrogen atom or a monovalent substituent. The plurality of R ₁ may be the same or different.
Ring A1~A4 may be further substituted by _{-R 11.} R ₁₁ represents a monovalent substituent. The plurality of R ₁₁ may be the same or different.
At least one of the azaphthalocyanine compounds represented by the general formula (1) has an ionic hydrophilic group as a substituent. )

  Azaphthalocyanine derivatives having different substitution positions are defined by classifying them into the following three types. Hereinafter, when describing azaphthalocyanine derivatives having different substitution positions, the following (1) β-position substitution type and (2) α-position substitution: Type, (3) α, β-position mixed substitution type.

  (1) β-position substitution type: when each of rings A1 to A4 represents any one of the rings having a group represented by formula (V1) as a substituent at the following 1 or 2 position (β position) . * Represents the bonding position of the azaphthalocyanine ring.

  (2) α-position substitution type: when each of rings A1 to A4 represents any of the rings having a group represented by formula (V1) as a substituent at the following 3 or 4 position (α position) . * Represents the bonding position of the azaphthalocyanine ring.

  (3) α, β-position mixed substitution type: When the group represented by formula (V1) is present as a substituent at the β-position and the α-position.

  In general formula (1), at least one of rings A1 to A4 is a pyridine ring or a pyrazine ring substituted with an electron withdrawing group. The electron withdrawing group is an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, preferably 0.30 or more. The upper limit of the σp value is preferably 1.0 or less.

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

  Preferred as the electron withdrawing group are a cyano group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, a halogen atom, an alkylsulfonyl group, an arylsulfonyl group, a halogenated alkyl group, a cyano group, an alkoxycarbonyl group, a halogen atom, An alkylsulfonyl group and a halogenated alkyl group are more preferable, and a cyano group and an alkylsulfonyl group are most preferable.

In general formula (1), at least one of rings A1 to A4 is a ring substituted with a group represented by general formula (V1).
R ₁ in the general formula (V1) represents a hydrogen atom or a monovalent substituent. If R ₁ is more present in one molecule, a plurality of R ₁ may be the same or different. 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.

R ₁ represents a hydrogen atom or a monovalent substituent, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl Group, a substituted or unsubstituted heterocyclic group, and a substituted or unsubstituted alkenyl group are preferable, and a substituted alkyl group is more preferable.
Examples of the substituent when the substituent represented by R ₁ further has a substituent include the substituent group A, and include the ionic hydrophilic group or a substituted or unsubstituted sulfamoyl group (substitution of a substituted sulfamoyl group). The group is preferably a substituted or unsubstituted alkyl group, and the substituent of the alkyl group is preferably an amino group, an alkyl group or a hydroxy group substituted with a heterocyclic group, and the heterocyclic group is an amino group or an arylamino group. Or optionally substituted by an alkylamino group).

Ring A1~A4 may be further substituted by _{-R 11.} R ₁₁ represents a monovalent substituent. If R ₁₁ is to plurality of in one molecule, a plurality of R ₁₁ may be the same or different. Examples of the monovalent substituent include the substituent group A described above, and a substituted or unsubstituted alkyl group, a halogen atom, and an ionic hydrophilic group are preferable, an unsubstituted alkyl group and a halogen atom are preferable, and methyl More preferably, they are a group, a chlorine atom, and a bromine atom.

At least one of the plurality of R ₁ and R ₁₁ 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.

  At least one of the azaphthalocyanine compounds represented by the general formula (1) has an ionic hydrophilic group as a substituent. As the number of ionic hydrophilic groups, those having at least two in one molecule of an azaphthalocyanine compound are preferable, those having at least 2 to 8 ionic hydrophilic groups selected from a sulfo group and a carboxyl group are more preferable, Those having 2 to 4 are particularly preferred.

In the general formula (1), the rings A1 to A4 are each independently a benzene ring, a pyridine ring, or a pyrazine ring which may be substituted with an electron withdrawing group or a group represented by the general formula (V1). Represents.
However, at least one of the rings A1 to A4 is a pyridine ring or a pyrazine ring substituted with an electron withdrawing group, and at least one of the rings A1 to A4 is represented by the general formula (V1). Is a ring substituted with a group.

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.
At least one of the rings A1 to A4 is a pyridine ring or a pyrazine ring substituted with an electron withdrawing group, more preferably 1 or 2, and even more preferably 1.
At least one of the rings A1 to A4 is a ring substituted with a group represented by the general formula (V1), and is preferably a benzene ring substituted with a group represented by the general formula (V1). 1 to 3 are preferably benzene rings substituted with a group represented by the general formula (V1).
Among the rings A1 to A4, one ring is a pyridine ring or a pyrazine ring substituted with an electron withdrawing group, and one ring is a benzene ring substituted with a group represented by the general formula (V1) It is more preferable that the two rings are benzene rings or benzene rings substituted with a group represented by formula (V1).

  Among the rings A1 to A4, one ring is a ring represented by the general formula (V0), one ring is a benzene ring substituted with a group represented by the general formula (V1), and two rings It is particularly preferable that the ring is a benzene ring or a benzene ring substituted with a group represented by the general formula (V1).

In General Formula (V0), EWG represents an electron withdrawing group. R ₁₁ represents a monovalent substituent. m is 1 or 2.

  In General Formula (V0), EWG represents an electron withdrawing group. Specific examples and preferred examples of the electron withdrawing group are the same as the specific examples and preferred examples of the electron withdrawing group having a σp value of 0.20 or more.

R ₁₁ represents a monovalent substituent. Specific examples and preferred examples are the same as the specific examples and preferred examples of R ₁₁ described above. m is 1 or 2, and is preferably 1.
As represented by the general formula (V0), having R ₁₁ on a pyridine ring substituted with an electron withdrawing group is preferable from the viewpoint of availability of raw materials (ease of synthesis).

  The embodiment (α-position substituted type) in which the benzene ring substituted with the group represented by the general formula (V1) is the following (V1-α) is preferable from the viewpoint of achieving high print density by suppressing dye association.

(R ₁ independently represents a hydrogen atom or a monovalent substituent.)

  In the embodiment (β-position substituted type) in which the benzene ring substituted with the group represented by the general formula (V1) is the following (V1-β), the association of the dye is promoted, and from the viewpoint of image fastness of the printed matter preferable.

(R ₁ independently represents a hydrogen atom or a monovalent substituent.)
Specific examples and preferred examples of R ₁ are the same as R ₁ in the general formula (1).

  Hereinafter, although the specific example of the azaphthalocyanine compound of this invention represented by General formula (1) is given, this invention is not necessarily limited to these specific examples.

  In the table, examples of the four rings (A1), (A2), (A3), and (A4) of the azaphthalocyanine mother nucleus are the phthalonitrile derivatives and nitrogen-containing ring dinitrile derivatives having different structures in the synthesis of the azaphthalocyanine compound of the present invention. The mixing ratio of the obtained azaphthalocyanine compound derived from the charging ratio (eq./eq.) Or the charging ratio of phthaloic acid derivatives and nitrogen-containing cyclic dicarboxylic acid derivatives having different structures (eq./eq.) Represents the average ratio. In the table, the ionic hydrophilic group is described in the form of a free acid. The following exemplary compounds include (1) β-position substitution type, (2) α-position substitution type, and (3) α, β-position mixed substitution type, respectively.

The azaphthalocyanine compound of the present invention is difficult to produce by ordinary synthesis methods. The method for synthesizing an azaphthalocyanine compound of the present invention is characterized in that a nitrogen-containing derivative having an electron withdrawing group is used in advance in the ring formation stage of azaphthalocyanine. These derivatives can be obtained by methods known in the literature (for example, DE 2230392 A1).
The ring formation reaction may be synthesized according to conventionally known conditions called the Weiler method or the phthalonitrile method, and a part of this may be replaced with the above-mentioned nitrogen-containing derivative.

(R ₁ independently represents a hydrogen atom or a monovalent substituent. EWG represents an electron withdrawing group.)
Specific examples and preferred examples of R ₁ are the same as R ₁ in the general formula (1). Specific examples and preferred examples of EWG are the same as those of EWG in general formula (V0).

The substitution position of the substituent of the nitrogen-containing ring is determined by the nitrogen-containing ring derivative used for the ring-forming reaction, and if the desired derivative cannot be obtained, the nitrogen-containing ring derivative itself may be newly synthesized.
It is preferable that the substitution position of the substituent other than the nitrogen-containing ring (benzene ring) is determined in advance as a substituent of the phthalonitrile derivative or phthalic acid derivative at the stage of the ring formation reaction. There is also a synthesis method in which an azaphthalocyanine ring is formed with the above nitrogen-containing derivative having an electron-withdrawing group using an unsubstituted phthalonitrile derivative or a phthalic acid derivative, followed by sulfonation or chlorosulfonylation. This is because the α-position and β-position are completely random substitutions. Therefore, when it is desired to control the substitution position of the substituent, it is preferable that the substitution position of the phthalonitrile derivative or phthalic acid derivative is determined in advance at the stage of the ring formation reaction. In order to synthesize a 100% α-substituted aza-substituted product, a phthalonitrile derivative or a phthalic acid derivative having a substituent at the 3-position may be used. To synthesize a 100% β-substituted aza-substituted product Can use a phthalonitrile derivative or a phthalic acid derivative having a substituent at the 4-position, and if you want to arbitrarily adjust the ratio of substituents at the α and β positions, adjust the amount charged during the synthesis as appropriate Just do it.

(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 8 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.

  EXAMPLES Hereinafter, although the synthesis method of the azaphthalocyanine compound (mixture) of this invention is demonstrated in detail to an Example, this invention is not limited to these Examples at all.

  A typical azaphthalocyanine compound (mixture) of the present invention can be derived from, for example, the following synthetic route.

[Synthesis Example 1: Synthesis of Exemplified Compound 1 (Li Salt)]
Precursor A (synthesized by the method described in DE2230392A1 paragraph number) 4.93 g, Precursor P1 (synthesized by the method described in JP-A-2004-075986) 21.5 g, diethylene glycol 134 g, ethyl orthoacetate 21.1 g, acetic acid 0.63 g 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, the solid is dissolved in about 1000 mL of water, the pH is adjusted to 8.5 with 2N aqueous lithium hydroxide, and dialyzed. Then, the electrical conductivity was purified to 20 μS, filtered through a membrane filter, purified by column Kumato (Sephadex LH-20 manufactured by Pharmacia), and concentrated and solidified to obtain 10 g of glossy crystals of Exemplified Compound 1. MS (m / z, Nega) 1222.80 [M-H] ^- , 613.5 [(M-2H) / 2] ^- .

[Example 1]
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) 5.0 g
Diethylene glycol 10.65g
Glycerin 14.70g
Diethylene glycol monobutyl ether 12.70g
Triethanolamine 0.65g
Orphin E 1010 (manufactured by Nissin Chemical Industry Co., Ltd.) 0.9g

  Except that the coloring matter was changed as shown in Table 9 below, ink liquids B to G and ink liquids for comparison were used as the ink liquids A to C, and the following comparative compounds 1 and 2 were used. H and I were adjusted.

(Image recording and evaluation)
The following evaluations were performed on the inkjet inks of the above Examples (Ink Liquids A to G) and Comparative Examples (Ink Liquids H to I). The results are shown in Table 9.
In Table 9, 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). The print density is 1.05 or more, A is 0.95 or more and less than 1.05, B is 0. The case of less than 95 was defined as C and evaluated in three stages.

  As is apparent from the results of Table 9, the inks of the examples using the dyes of the present invention are compatible with each other at a very high level in terms of ozone resistance and printing density as compared with the other comparative examples. Recognize.

[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.

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 using an i-line exposure stepper HITACHI LD-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 (11)

A coloring composition comprising an azaphthalocyanine compound represented by the general formula (1).

(In General Formula (1), Rings A1 to A4 are each independently a benzene ring, a pyridine ring, or a pyrazine, which may be substituted with an electron-withdrawing group or a group represented by General Formula (V1). Represents a ring.
However, at least one of the rings A1 to A4 is a pyridine ring or a pyrazine ring substituted with an electron withdrawing group, and at least one of the rings A1 to A4 is represented by the general formula (V1). A benzene ring substituted with
R ₁ represents a hydrogen atom or a monovalent substituent. The plurality of R ₁ may be the same or different.
Ring A1~A4 may be further substituted by _{-R 11.} R ₁₁ represents a monovalent substituent. The plurality of R ₁₁ may be the same or different.
At least one of the azaphthalocyanine compounds represented by the general formula (1) has an ionic hydrophilic group as a substituent. ) Among the rings A1 to A4, one ring is a pyridine ring or a pyrazine ring substituted with an electron withdrawing group, and one ring is substituted with a group represented by the general formula (V1) The coloring composition according to claim 1, wherein the two rings are benzene rings or benzene rings substituted with a group represented by formula (V1).
Ring A1~A4 may be substituted by Sarani _{R 11.} R ₁₁ represents a monovalent substituent. The plurality of R ₁₁ may be the same or different. Among the rings A1 to A4, one ring is a ring represented by the general formula (V0), one ring is a benzene ring substituted with a group represented by the general formula (V1), and two rings The colored composition according to claim 1 or 2, wherein the ring is a benzene ring or a benzene ring substituted with a group represented by formula (V1).

(In General Formula (V0), EWG represents an electron-withdrawing group. R ₁₁ represents a monovalent substituent. M is 1 or 2.) The colored composition according to any one of claims 1 to 3, wherein the benzene ring substituted with the group represented by the general formula (V1) is the following (V1-α). * Represents the bonding position of the azaphthalocyanine ring.

(R ₁ independently represents a hydrogen atom or a monovalent substituent.) The colored composition according to any one of claims 1 to 3, wherein the benzene ring substituted with the group represented by the general formula (V1) is the following (V1-β). * Represents the bonding position of the azaphthalocyanine ring.

(R ₁ independently represents a hydrogen atom or a monovalent substituent.)   The colored composition according to claim 1, wherein the ionic hydrophilic group contains lithium ions as counter ions.   An ink-jet ink containing the colored composition according to claim 1.   An ink-jet recording method comprising forming an image using the colored composition according to any one of claims 1 to 6 or the ink-jet ink according to claim 7.   The color filter containing the azaphthalocyanine compound represented by General formula (1) of any one of Claims 1-6.   A color toner containing the azaphthalocyanine compound represented by the general formula (1) according to any one of claims 1 to 6. An azaphthalocyanine compound represented by the general formula (1).

(In General Formula (1), Rings A1 to A4 are each independently a benzene ring, a pyridine ring, or a pyrazine, which may be substituted with an electron-withdrawing group or a group represented by General Formula (V1). Represents a ring.
However, at least one of the rings A1 to A4 is a pyridine ring or a pyrazine ring substituted with an electron withdrawing group, and at least one of the rings A1 to A4 is represented by the general formula (V1). A benzene ring substituted with
R ₁ represents a hydrogen atom or a monovalent substituent. The plurality of R ₁ may be the same or different.
Ring A1~A4 may be further substituted by _{-R 11.} R ₁₁ represents a monovalent substituent. The plurality of R ₁₁ may be the same or different.
At least one of the azaphthalocyanine compounds represented by the general formula (1) has an ionic hydrophilic group as a substituent. )