JP2010189638A - Ink composition, inkjet recording method by using the same, and recorded matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition excellent in gas resistance, and light fastness, and capable of producing a printed matter without yielding bronze phenomena. <P>SOLUTION: This ink composition is provided by containing at least water, a metal phthalocyanine-based dyestuff having -SO2NR1R2 and/or a sulfo group, an aromatic compound having carboxyl group and/or its salt. It is preferable that the above metal is a copper element, the aromatic compound having the carboxyl group and/or its salt is the aromatic compound having one carboxyl group and/or its salt. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to an ink composition suitable for ink jet recording, in particular, an ink composition excellent in bronze resistance, an ink jet recording method using the ink composition, and a recorded matter recorded by the recording method.

Inkjet recording is a method of recording characters and images (hereinafter sometimes simply referred to as “images”) on the surface of a recording medium by ejecting ink compositions as small droplets from fine nozzles. As an ink jet recording method, an electric signal is converted into a mechanical signal using an electrostrictive element, and an ink composition stored in a nozzle head portion is intermittently ejected to record characters and images on the surface of the recording medium. The ink composition stored in the nozzle head part is rapidly heated at a part close to the ejection part to generate bubbles, and ejected intermittently by volume expansion due to the bubbles, and characters and images are printed on the surface of the recording medium. A recording method has been put to practical use.

In addition, as an ink composition for ink jet recording, in general, those obtained by dissolving various dyes in water or an organic solvent, or a mixture thereof from the viewpoint of safety and printing characteristics,
In various characteristics, more strict conditions are required as compared with ink compositions for writing instruments such as fountain pens and ballpoint pens.

In particular, in recent years, inkjet printers have come to be used for the production of printed materials for advertisement, and when forming a color image using a plurality of ink compositions, it is much more. Strict demands are being made.
This is because, in a color image formed by a plurality of ink compositions, if there is one color that is inferior in hue, the color balance of the entire image is inferior because of the hue, and a high-quality image cannot be obtained. Because it will be.
In particular, in an ink composition using a metal phthalocyanine dye as a coloring material, a red floating phenomenon (hereinafter referred to as a “bronze phenomenon”) occurs in a portion printed at a high duty such as solid printing (100% duty printing). Is seen. In such a case, since the color balance of the entire image becomes non-uniform and the image quality is lowered, the improvement is desired.
In recent years, glossy paper has been widely used as a recording medium with a texture close to that of a photographic tone, but due to the bronze phenomenon of specific colors, the glossiness on the surface of the printed matter varies, and the image Therefore, the improvement is strongly desired from the viewpoint of maintaining the glossiness of the entire image.

In addition, since printed matter created using the ink composition as described above may be installed not only indoors but also outdoors, various kinds of light such as sunlight and outside air (ozone, nitrogen oxides) Ink compositions with excellent light resistance and gas resistance have been developed. In particular, cyan ink compositions with improved gas resistance have a bronze phenomenon. Conspicuous improvement is desired.

In addition, it is known that a so-called bronzing phenomenon occurs when printing is performed on a recording medium having a high acidity when, for example, a dye having poor water solubility is used in an ink composition for ink jet recording.
As countermeasures against this, it is common practice to add alcohol amines as pH maintainers and to increase the penetration into paper. Basically, the bronze phenomenon is caused by crystallization of the dye due to drying of the ink composition on the paper surface, and the above method prevents crystallization by increasing this solubility, or prevents the crystallization in the paper before crystallization. It is effective from the viewpoint of penetration into However, in the former, the pH easily rises to around 11 due to the addition, causing concern about corrosion of the nozzles of the printer and further affecting the human body. The latter is a so-called case where the permeability is excessively increased. Other print quality deterioration such as bleed phenomenon is caused,
It is not a perfect solution.
As an alternative to these, in order to solve this problem, 2-oxo-oxazolidone,
An ink composition to which 1,3-bis (β-hydroxyethyl) urea has been added has been proposed (see, for example, Patent Document 1).
In addition, an ink composition has been proposed that solves this problem by adding a basic amino acid (see, for example, Patent Document 2).
However, unfortunately, based on the results of various investigations and researches by the present inventors, the printed matter robustness (light resistance and gas resistance), which is the subject of the present invention, even if the measures described above are used. It has been found that an ink composition using a cyan dye having excellent properties has no effect on the elimination or alleviation of the bronze phenomenon.

JP-A-6-25575 JP 7-228810 A

Accordingly, the present invention has been made in consideration of the above-described circumstances, and an object of the present invention is to provide an ink composition excellent in printed matter fastness (mainly gas resistance and light resistance). Further providing an ink composition improved in terms of bronzing, further providing an ink composition improved in terms of clogging resistance, an ink jet recording method using them, and the recording method It is to provide a recorded matter recorded by.

As a result of further investigations and researches on the light resistance, gas resistance, prevention of bronze phenomenon, etc. of various known cyan dyes, the present inventors have found that an ink composition containing a cyan dye has a carboxyl group. When an aromatic compound and / or a salt thereof having a carboxylic acid is added, the improvement is further observed with respect to a specific cyan dye, and further, when the salt of the compound having a carboxyl group to be added is a lithium salt, bronze The present inventors have found that the effect of improving the phenomenon is remarkably excellent and that the result is extremely good in clogging resistance, and the present invention has been completed based on this finding.

That is, the said subject was solved by the following invention.
(1) An ink composition comprising at least water, a cyan dye represented by the following general formula (I), an aromatic compound having a carboxyl group, and / or a salt thereof.

  Formula (I)

（式中、Ｘ₁₁、Ｘ₁₂、Ｘ₁₃およびＸ₁₄は、それぞれ独立に、−ＳＯ₂ＮＲ₁Ｒ₂及び／又は
スルホ基を表す。但しＸ₁₁、Ｘ₁₂、Ｘ₁₃及びＸ₁₄のすべてが同時にスルホ基になることは
ない。ここで、Ｒ₁は、複数個存在する場合それぞれ独立に、水素原子、置換もしくは無
置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換のアル
ケニル基、置換もしくは無置換のアラルキル基、置換もしくは無置換のアリール基、また
は置換もしくは無置換のヘテロ環基を表す。Ｒ₂は、複数個存在する場合それぞれ独立に
、置換もしくは無置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もし
くは無置換のアルケニル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の
アリール基、または置換もしくは無置換のヘテロ環基を表す。Ｒ₁とＲ₂は互いに結合して
５〜６員含窒素ヘテロ環を形成してもよい。
Ｙ₁₁、Ｙ₁₂、Ｙ₁₃、Ｙ₁₄、Ｙ₁₅、Ｙ₁₆、Ｙ₁₇およびＹ₁₈は、それぞれ独立に、水素原子
、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリー
ル基、ヘテロ環基、シアノ基、ヒドロキシ基、ニトロ基、アミノ基、アルキルアミノ基、
アルコキシ基、アリールオキシ基、アミド基、アリールアミノ基、ウレイド基、スルファ
モイルアミノ基、アルキルチオ基、アリールチオ基、アルコキシカルボニルアミノ基、ス
ルホンアミド基、カルバモイル基、アルコキシカルボニル基、ヘテロ環オキシ基、アゾ基
、アシルオキシ基、カルバモイルオキシ基、シリルオキシ基、アリールオキシカルボニル
基、アリールオキシカルボニルアミノ基、イミド基、ヘテロ環チオ基、ホスホリル基、ア
シル基またはイオン性親水性基を表し、各々の基はさらに置換基を有していてもよい。
ａ₁₁〜ａ₁₄は、それぞれＸ₁₁〜Ｘ₁₄の置換基数を表し、それぞれ独立に、０〜２の整数
であるが、すべてが同時に０になることはない。
Ｍは、水素原子、金属元素またはその酸化物、水酸化物もしくはハロゲン化物である。
但し、Ｘ₁₁、Ｘ₁₂、Ｘ₁₃、Ｘ₁₄、Ｙ₁₁、Ｙ₁₂、Ｙ₁₃、Ｙ₁₄、Ｙ₁₅、Ｙ₁₆、Ｙ₁₇およびＹ
₁₈のうちの少なくとも１つは、イオン性親水性基であるかまたはイオン性親水性基を置換
基として有する基である。）

Wherein X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ each independently represent —SO ₂ NR ₁ R ₂ and / or a sulfo group, provided that all of X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ At the same time, when there are a plurality of R _{1 s} , each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group. R ₂ represents an independently substituted or unsubstituted alkenyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted heterocyclic group. Alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group, or substituted R ₁ and R ₂ may be bonded to each other to form a 5- to 6-membered nitrogen-containing heterocyclic ring.
Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ and Y ₁₈ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkylamino group,
Alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, alkoxycarbonyl group, heterocyclic oxy group, Azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group or ionic hydrophilic group, each group is Furthermore, you may have a substituent.
a ₁₁ ~a ₁₄ each represent a number of substituents X ₁₁ to X _14, independently, is an integer of 0 to 2, but all are not 0 at the same time.
M is a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof.
_{However, X 11, X 12, X} 13, X 14, Y 11, Y 12, Y 13, Y 14, Y 15, Y 16, Y 17 and Y
_At least one of ₁₈ is an ionic hydrophilic group or a group having an ionic hydrophilic group as a substituent. )

(2) The ink composition according to (1), wherein the cyan dye represented by the general formula (I) is represented by the following general formula (II).

  Formula (II)

（式中、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃およびＲ₁₄は、それぞれ独立に、水素原子、置換もしくは無置
換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換のアルケ
ニル基、置換もしくは無置換のアラルキル基、置換もしくは無置換のアリール基、または
置換もしくは無置換のヘテロ環基を表す。
Ｖ₁、Ｖ₂、Ｖ₃およびＶ₄は、それぞれ独立に、置換もしくは無置換のアルキル基、置換
もしくは無置換のシクロアルキル基、置換もしくは無置換のアルケニル基、置換もしくは
無置換のアラルキル基、置換もしくは無置換のアリール基、または置換もしくは無置換の
ヘテロ環基を表す。
Ｙ₃₁、Ｙ₃₂、Ｙ₃₃、Ｙ₃₄、Ｙ₃₅、Ｙ₃₆、Ｙ₃₇およびＹ₃₈は、それぞれ独立に、水素原子
、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリー
ル基、ヘテロ環基、シアノ基、ヒドロキシ基、ニトロ基、アミノ基、アルキルアミノ基、
アルコキシ基、アリールオキシ基、アミド基、アリールアミノ基、ウレイド基、スルファ
モイルアミノ基、アルキルチオ基、アリールチオ基、アルコキシカルボニルアミノ基、ス
ルホンアミド基、カルバモイル基、アルコキシカルボニル基、ヘテロ環オキシ基、アゾ基
、アシルオキシ基、カルバモイルオキシ基、シリルオキシ基、アリールオキシカルボニル
基、アリールオキシカルボニルアミノ基、イミド基、ヘテロ環チオ基、ホスホリル基、ア
シル基またはイオン性親水性基を表し、各々の基はさらに置換基を有していてもよい。
Ｍは一般式（Ｉ）におけるＭと同義である。
Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、Ｖ₁、Ｖ₂、Ｖ₃、Ｖ₄、Ｙ₃₁、Ｙ₃₂、Ｙ₃₃、Ｙ₃₄、Ｙ₃₅、Ｙ₃₆
、Ｙ₃₇およびＹ₃₈のうちの少なくとも１つはイオン性親水性基であるかまたはイオン性親
水性基を置換基として有する基である。）

Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, substituted Alternatively, it represents an unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
V ₁ , V ₂ , V ₃ and V ₄ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, It represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
Y ₃₁ , Y ₃₂ , Y ₃₃ , Y ₃₄ , Y ₃₅ , Y ₃₆ , Y ₃₇ and Y ₃₈ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkylamino group,
Alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, alkoxycarbonyl group, heterocyclic oxy group, Azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group or ionic hydrophilic group, each group is Furthermore, you may have a substituent.
M has the same meaning as M in formula (I).
_{R 11, R 12, R 13} , R 14, V 1, V 2, V 3, V 4, Y 31, Y 32, Y 33, Y 34, Y 35, Y 36
, Y ₃₇ and Y ₃₈ are ionic hydrophilic groups or groups having an ionic hydrophilic group as a substituent. )

(3) The ink composition according to (1), wherein the cyan dye represented by the general formula (I) is represented by the following general formula (III).

  General formula (III)

（式中、Ｒ₂₁、Ｒ₂₂、Ｒ₂₃およびＲ₂₄は、それぞれ独立に、水素原子、置換もしくは無置
換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換のアルケ
ニル基、置換もしくは無置換のアラルキル基、置換もしくは無置換のアリール基、または
置換もしくは無置換のヘテロ環基を表す。
Ｖ₁₁、Ｖ₁₂、Ｖ₁₃およびＶ₁₄は、それぞれ独立に、置換もしくは無置換のアルキル基、
置換もしくは無置換のシクロアルキル基、置換もしくは無置換のアルケニル基、置換もし
くは無置換のアラルキル基、置換もしくは無置換のアリール基、または置換もしくは無置
換のヘテロ環基を表す。
Ｍは一般式（Ｉ）におけるＭと同義である。
但し、Ｒ₂₁、Ｒ₂₂、Ｒ₂₃、Ｒ₂₄、Ｖ₁₁、Ｖ₁₂、Ｖ₁₃およびＶ₁₄のうちの少なくとも１つ
は、イオン性親水性基を置換基として有する。）

(Wherein R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, substituted Alternatively, it represents an unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ are each independently a substituted or unsubstituted alkyl group,
A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is represented.
M has the same meaning as M in formula (I).
However, at least one of R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ has an ionic hydrophilic group as a substituent. )

(4) The ink composition according to (3), wherein M in the general formula (III) is a copper element.
(5) The ink composition according to (3), wherein M in the general formula (III) is a copper element, and the counter cation of the ionic hydrophilic group is a lithium cation.
(6) The aromatic compound having a carboxyl group and / or a salt thereof is the aromatic compound having one carboxyl group and / or a salt thereof, according to any one of (1) to (5). Ink composition.
(7) The ink composition according to any one of (1) to (6), wherein the aromatic compound having a carboxyl group and / or a salt thereof is a compound having a naphthalene skeleton and / or a salt thereof.

(8) The compound having a naphthalene skeleton and / or a salt thereof is a compound having a carboxyl group and an —OR group (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the naphthalene skeleton. ) Ink composition.
(9) The compound having a naphthalene skeleton and / or a salt thereof is a compound having one carboxyl group and one -OR group (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the naphthalene skeleton. The ink composition as described in (8).

(10) The ink composition according to any one of (7) to (9), wherein the compound having a naphthalene skeleton and / or a salt thereof is a compound having a carboxyl group at the 2-position and / or a salt thereof.

(11) The compound having a carboxyl group at the 2-position and having a naphthalene skeleton and / or a salt thereof are 1-hydroxy-2-naphthoic acid, 2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 6- At least one of hydroxy-2-naphthoic acid, 3-methoxy-2-naphthoic acid, 6-methoxy-2-naphthoic acid, 6-ethoxy-2-naphthoic acid, 6-propoxy-2-naphthoic acid and salts thereof The ink composition according to (10), wherein
(12) The ink composition according to any one of (1) to (11), wherein the salt is a lithium salt.

(13) The aromatic compound having a carboxyl group and / or its salt is contained in an amount of 0.1 to 10% by weight based on the total amount of the ink composition, as described in any one of (1) to (12). Ink composition.
(14) The content ratio of the cyan dye and the aromatic compound having a carboxyl group and / or a salt thereof is in the range of 1: 0.1 to 1:10 by weight, (1) to (13 ). The ink composition according to any one of the above.

(15) The ink composition according to any one of (1) to (14), further comprising a nonionic surfactant.
(16) The nonionic surfactant is an acetylene glycol surfactant,
The ink composition according to 15).

(17) The ink composition according to (15) or (16), comprising 0.1 to 5% by weight of the nonionic surfactant based on the total amount of the ink composition.
(18) The ink composition according to any one of (1) to (17), further comprising a penetration accelerator.

(19) The ink composition according to (18), wherein the penetration accelerator is glycol ether.
(20) The pH of the ink composition at 20 ° C. is 8.0 to 10.5.
The ink composition according to any one of 19).

(21) The ink composition according to any one of (1) to (20), which is used in an inkjet recording method.
(22) The ink composition according to (21), wherein the inkjet recording method is a recording method using an inkjet head that forms ink droplets by mechanical deformation of an electrostrictive element.

(23) An ink jet recording method for performing recording by discharging a droplet of an ink composition and attaching the droplet to a recording medium, wherein the ink composition is any one of (1) to (22) An ink jet recording method using the ink composition described above.

(24) Recorded using the ink composition according to any one of (1) to (22),
Or a recorded matter recorded by the recording method described in (23).

The present invention uses a metal phthalocyanine dye represented by the above general formula (I) as a colorant of an ink composition, and contains an aromatic compound having a carboxyl group and / or a salt thereof, thereby the ink composition. The recorded material is fastness to printed matter (mainly gas resistance,
It has an excellent effect that an image having excellent light resistance and no bronzing can be obtained.

It is a figure which shows the spectral characteristic (absorption wavelength) of the dye (CI direct blue 199) used by the comparative example.

The ink composition of the present invention comprises an aromatic compound having at least a cyan dye and a carboxyl group represented by the following general formula (I) and / or an aqueous compound composed of water or water and a water-soluble organic solvent. It contains a salt, and may contain a moisturizing agent, a viscosity adjusting agent, a pH adjusting agent and other additives as necessary.

First, the phthalocyanine compound represented by formula (I) used in the ink composition of the present invention will be described in detail.

  Formula (I)

前記一般式（Ｉ）において、Ｘ₁₁、Ｘ₁₂、Ｘ₁₃およびＸ₁₄は、それぞれ独立に、−ＳＯ
₂ＮＲ₁Ｒ₂又はスルホ基を表し、特に−ＳＯ₂ＮＲ₁Ｒ₂が好ましい。但しＸ₁₁、Ｘ₁₂、Ｘ₁₃
及びＸ₁₄のすべてが同時にスルホ基になることはない。Ｒ₁とＲ₂は互いに結合して５〜６
員含窒素ヘテロ環を形成してもよい。

In the general formula (I), X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ are each independently —SO
₂ represents NR ₁ R ₂ or a sulfo group, and —SO ₂ NR ₁ R ₂ is particularly preferable. However, X ₁₁ , X ₁₂ , X ₁₃
And all of X ₁₄ do not become a sulfo group at the same time. R ₁ and R ₂ are bonded to each other to form 5-6
A membered nitrogen-containing heterocycle may be formed.

Each R ₁ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, particularly preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, among which a hydrogen atom, a substituted An alkyl group, a substituted aryl group and a substituted heterocyclic group are preferred, a hydrogen atom, a substituted alkyl group and a substituted aryl group are more preferred, and a hydrogen atom is most preferred.

Each R ₂ independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or Represents a substituted or unsubstituted heterocyclic group,
Among them, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group is preferable, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are more preferable, and a substituted alkyl group is particularly preferable. , Substituted aryl groups are preferred, and substituted alkyl groups are most preferred.

The substituted or unsubstituted alkyl group represented by R ₁ and R ₂ is preferably an alkyl group having 1 to 30 carbon atoms. Examples of the substituent are R ₁ , R ₂ , Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ described later.
, Y ₁₆ , Y ₁₇ and Y ₁₈ may be the same as the substituents when it is possible to further have a substituent.

The substituted or unsubstituted cycloalkyl group represented by R ₁ and R ₂ is preferably a cycloalkyl group having 5 to 30 carbon atoms. Examples of the substituent are R ₁ , R ₂ , Y ₁₁ , Y ₁₂ , Y ₁₃ described later.
, Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ and Y ₁₈ are the same as the substituents in the case where they can further have a substituent.

The substituted or unsubstituted alkenyl group represented by R ₁ and R ₂ is preferably an alkenyl group having 2 to 30 carbon atoms. Examples of the substituent include R ₁ , R ₂ , Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , which will be described later.
Examples thereof include the same substituents as those in the case where Y ₁₅ , Y ₁₆ , Y ₁₇ and Y ₁₈ can further have a substituent.

The substituted or unsubstituted aralkyl group represented by R ₁ and R ₂ is preferably an aralkyl group having 7 to 30 carbon atoms. Examples of the substituent include R ₁ , R ₂ , Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , which will be described later.
Examples thereof include the same substituents as those in the case where Y ₁₅ , Y ₁₆ , Y ₁₇ and Y ₁₈ can further have a substituent.

The substituted or unsubstituted aryl group represented by R ₁ and R ₂ is preferably an aryl group having 6 to 30 carbon atoms. Examples of the substituent are R ₁ , R ₂ , Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ described later.
, Y ₁₆ , Y ₁₇ and Y ₁₈ may be the same as the substituents when it is possible to further have a substituent.

The heterocyclic group represented by R ₁ and R ₂ is preferably a 5-membered or 6-membered ring, which may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. In the following, the heterocyclic group represented by R ₁ and R ₂ is exemplified in the form of a heterocyclic ring by omitting the substitution position, but the substitution position is not limited. 3
It is possible to substitute at the 4-position. Pyridine, pyrazine, pyrimidine, pyridazine,
Triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene,
Examples include pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. Among them, an aromatic heterocyclic group is preferable, and preferable examples thereof are exemplified in the same manner as above. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benziso Examples include thiazole and thiadiazole.

These may have a substituent, and examples of the substituent include R ₁ , R ₂ , Y ₁₁ , Y described later.
Examples thereof include the same substituents as those in the case where ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ and Y ₁₈ can further have a substituent.

Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ and Y ₁₈ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkylamino group,
Alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, alkoxycarbonyl group, heterocyclic oxy group, Represents an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a phosphoryl group, an acyl group, a carboxyl group, or a sulfo group, each of which It may have a substituent.

Among these, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamido group, a carbamoyl group, an alkoxycarbonyl group, a carboxyl group, and a sulfo group are preferable, and in particular, a hydrogen atom, A halogen atom, a cyano group, a carboxyl group and a sulfo group are preferred, and a hydrogen atom is most preferred.

When R ₁ , R ₂ , Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ and Y ₁₈ are groups that can further have a substituent, as listed below Further substituents may be included.

A halogen atom (for example, a chlorine atom or a bromine atom); a linear or branched alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or 2 to 2 carbon atoms
12 straight-chain or branched-chain alkynyl groups, a cycloalkyl group having 3 to 12 carbon atoms which may have a side chain, a cycloalkenyl group having 3 to 12 carbon atoms which may have a side chain (the above group) As specific examples of, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl)
: Aryl group (eg, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl); heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl) , 2-benzothiazolyl); alkoxy groups (for example,
Methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy); aryloxy groups (eg, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy,
3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenoxy); acylamino groups (eg, acetamide, benzamide, 4- (3
-T-butyl-4-hydroxyphenoxy) butanamide); alkylamino groups (eg methylamino, butylamino, diethylamino, methylbutylamino); anilino groups (
For example, phenylamino, 2-chloroanilino); ureido group (eg, phenylureido, methylureido, N, N-dibutylureido); sulfamoylamino group (eg,
N, N-dipropylsulfamoylamino); alkylthio groups (eg methylthio, octylthio, 2-phenoxyethylthio); arylthio groups (eg phenylthio, 2
-Butoxy-5-t-octylphenylthio, 2-carboxyphenylthio); alkyloxycarbonylamino group (for example, methoxycarbonylamino); sulfonamide group (
For example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide); carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl); sulfamoyl group (eg, N-ethylsulfamoyl, N, N) -Dipropylsulfamoyl, N, N-diethylsulfamoyl); sulfonyl groups (eg methylsulfonyl, octylsulfonyl, phenylsulfonyl, 4-methylphenylsulfonyl); alkyloxycarbonyl groups (eg methoxycarbonyl, butyloxycarbonyl) A heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy); an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, -Hydroxy-4-propanoylphenylazo); acyloxy groups (eg acetoxy); carbamoyloxy groups (eg N-methylcarbamoyloxy, N-phenylcarbamoyloxy); silyloxy groups (eg trimethylsilyloxy, dibutylmethylsilyloxy) ); Aryloxycarbonylamino group (for example, phenoxycarbonylamino); imide group (for example, N-succinimide, N-phthalimide); heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy) -1,3,5-triazole-6-thio, 2-pyridylthio); sulfinyl group (
For example, 3-phenoxypropylsulfinyl); phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl); aryloxycarbonyl group (eg, phenoxycarbonyl); acyl group (eg, acetyl, 3-phenylpropanoyl) Noyl, benzoyl); ionic hydrophilic group (for example, carboxyl group, sulfo group, 4
Secondary ammonium group, sulfonylsulfamoyl group and acylsulfamoyl group); other examples include cyano group, hydroxy group, nitro group and amino group. Among these substituents, a hydroxy group, an alkoxy group, a sulfamoyl group, a sulfonamide group, an acylamino group, a carbamoyl group, a cyano group, and an ionic hydrophilic group are preferable, and among them, a hydroxy group, a sulfamoyl group, and an ionic hydrophilic group are preferable. Particularly preferred.

A ₁₁ ~a ₁₄ in the general formula (I), each represent the number of substituents X ₁₁ to X _14, each independently, represent an integer of 0 to 2. However, all of a _{11 to} a ₁₄ do not become 0 at the same time. a
₁₁ ~a ₁₄ are particularly preferably each 1.

M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.

What is preferable as M is Li, Na, K, Mg, Ti, Zr as a metal element in addition to a hydrogen atom.
, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn
Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi and the like. As oxide, VO,
Preferred examples include GeO. Preferred examples of the hydroxide include Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _{2 and the} like. Further, as the _{halides, AlCl, SiCl 2, VCl,} VCl 2, VOCl,
FeCl, GaCl, ZrCl and the like can be mentioned. Of these, Cu, Ni, Zn, Al and the like are preferable, and Cu is most preferable.

Further, in the phthalocyanine compound represented by the general formula (I), Pc (phthalocyanine ring) is a dimer (for example, Pc-MLMMM-Pc) or 3 via L (a divalent linking group). A monomer may be formed, and a plurality of M present at that time may be the same or different.

The divalent linking group represented by L is an oxy group —O—, a thio group —S—, or a carbonyl group —CO—.
, A sulfonyl group —SO ₂ —, an imino group —NH—, a methylene group —CH ₂ —, and a group formed by combining these are preferable.

In the general formula (I), the molecular weight of the phthalocyanine compound is preferably in the range of 750 to 3000, more preferably in the range of 995 to 2500, of which 995-2.
A molecular weight of 000 is preferred, and a molecular weight in the range of 995 to 1800 is most preferred.

The phthalocyanine compound represented by the general formula (I) is converted to Pc (L) via L (divalent linking group).
In the case where the phthalocyanine ring) forms a dimer (for example, Pc-MLM-Pc) or a trimer, a preferable molecular weight, for example, a particularly preferable molecular weight is the particularly preferable molecular weight described above (995-1800). 2) (in the case of a dimer) or 3 times (in the case of a trimer). Here, the preferable molecular weight of the dimer or trimer is a value including the linking group L.

The phthalocyanine compound represented by the general formula (I) is X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , Y ₁₁ , Y
_At least one of ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ and Y ₁₈ is an ionic hydrophilic group or a group having an ionic hydrophilic group as a substituent.

Examples of the ionic hydrophilic group as a substituent, a sulfo group (-SO ₃ ^- X ^+), a carboxyl group (
-CO ₂ ^- X ^+), and quaternary ammonium group ^{(-N + RR'R "X -)} , acyl sulfamoyl group ^{_{(-SO 2 N + X - COR}} ), a sulfonylcarbamoyl group (-CON ⁺ X ^- SO ₂ R),
Acylsulfamoyl group ^{_{(-SO 2 N + X - SO}} 2 R) , etc. are included. Of these, a sulfo group, a carboxyl group, and a quaternary ammonium group are preferable, and a sulfo group is particularly preferable. A sulfo group, a carboxyl group, an acylsulfamoyl group, a sulfonylcarbamoyl group and a sulfonylsulfamoyl group may be in the form of a salt. Examples of counter ions that form salts include alkali metal ions (eg, sodium ions). , Potassium ion, lithium ion), ammonium ion, organic cation (eg, tetramethylguanidinium ion), organic and / or inorganic anion (eg, halogen ion, methanesulfonate ion, benzenesulfonate ion). X in the parentheses is a hydrogen atom or a counter ion, R, R ′, R
"" Represents a substituent.

Since the phthalocyanine compound represented by the general formula (I) has at least one ionic hydrophilic group or a group having an ionic hydrophilic group as a substituent in one molecule, it is soluble in an aqueous medium. Or dispersibility becomes favorable. From such a viewpoint, as the phthalocyanine compound represented by the general formula (I), those having at least two ionic hydrophilic groups in one molecule are preferable, and at least one of a plurality of ionic hydrophilic groups is used. Is more preferably a sulfo group, and most preferably one having at least two sulfo groups in one molecule.

Particularly preferred compounds as the phthalocyanine compound represented by the general formula (I) are compounds having the following combinations (a) to (g).

(A) Regarding X _{11 to} X ₁₄ , these are each independently preferably —SO ₂ NR ₁ R ₂ .
(B) R ₁ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, A substituted heterocyclic group is preferred, and a hydrogen atom is most preferred.
(C) R ₂ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
A substituted or unsubstituted heterocyclic group is preferable, and among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are preferable, and a substituted alkyl group is most preferable. Furthermore, it is more preferable that at least one of R ₁ and R ₂ has an ionic hydrophilic group or a group having an ionic hydrophilic group as a substituent.

(D) For Y _{11 to} Y ₁₈ , these are each independently a hydrogen atom, a halogen atom,
Alkyl groups, aryl groups, cyano groups, alkoxy groups, amide groups, ureido groups, sulfonamido groups, carbamoyl groups, sulfamoyl groups, alkoxycarbonyl groups, carboxyl groups, and sulfo groups are preferred, especially hydrogen atoms, halogen atoms, cyano groups , A carboxyl group, and a sulfo group are preferable, and a hydrogen atom is most preferable.
(E) is preferably a ₁₁ ~a ₁₄ are each 1.
(F) M is preferably Cu, Ni, Zn, or Al, and most preferably Cu.
(G) The molecular weight of the phthalocyanine compound is preferably in the range of 750 to 3000, and more preferably 9
A molecular weight in the range of 95-2500 is preferred, a molecular weight in the range of 995-2000 is preferred, and a molecular weight in the range of 995-1800 is most preferred.

As for the preferred combination of substituents of the compound represented by the general formula (I), a compound in which at least one of various substituents is the preferred group is preferred, and more various substituents are preferred groups. Certain compounds are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

Among the phthalocyanine compounds represented by the general formula (I), a phthalocyanine compound having a structure represented by the following general formula (II) is more preferable. The phthalocyanine compound represented by the general formula (II) used in the present invention is described in detail below.

  Formula (II)

前記一般式(II)中、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃およびＲ₁₄は、それぞれ独立に、水素原子、置換
もしくは無置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無
置換のアルケニル基、置換もしくは無置換のアラルキル基、置換もしくは無置換のアリー
ル基、または置換もしくは無置換のヘテロ環基を表す。
Ｒ₁₁、Ｒ₁₂、Ｒ₁₃およびＲ₁₄に関する好ましい例は、一般式（Ｉ）の中のＲ₁と同義で
ある。

In the general formula (II), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group. An alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is represented.
Preferred examples of R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are the same as R ₁ in the general formula (I).

V ₁ , V ₂ , V ₃ and V ₄ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, It represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
Preferred examples of V ₁ , V ₂ , V ₃ and V ₄ are the same as R ₂ in the general formula (I).
Y _{31 to} Y ₃₈ are each independently represented by Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ ,
Y ₁₅ , Y ₁₆ , Y ₁₇ and Y ₁₈ have the same meanings, and preferred examples are also the same.

M has the same meaning as M in formula (I), and preferred examples are also the same.
_{However, R 11, R 12, R} 13, R 14, V 1, V 2, V 3, V 4, Y 31, Y 32, Y 33, Y 34, Y 35
, Y ₃₆ , Y ₃₇ and Y ₃₈ are ionic hydrophilic groups or groups having an ionic hydrophilic group as a substituent.
Examples of the ionic hydrophilic group, X ₁₁ in the general formula _{(I), X 12, X} 13, are the same as examples of X _14, and preferred examples thereof are also the same.

Since the phthalocyanine compound represented by the general formula (II) has at least one ionic hydrophilic group or a group having an ionic hydrophilic group as a substituent in one molecule, it is soluble in an aqueous medium. Or dispersibility becomes favorable. From such a viewpoint, the phthalocyanine compound represented by the general formula (II) preferably has at least two ionic hydrophilic groups in one molecule, and has at least one of a plurality of ionic hydrophilic groups. Those having a sulfo group are more preferable, and those having at least two sulfo groups in one molecule are most preferable.

In the general formula (II), the molecular weight of the phthalocyanine compound is preferably in the range of 750 to 3000, more preferably in the range of 995 to 2500, of which 995-2.
A molecular weight of 000 is preferred, and a molecular weight in the range of 995 to 1800 is most preferred.
However, in the phthalocyanine compound represented by the general formula (II) in the present invention, Pc (phthalocyanine ring) is dimerized via L (divalent linking group) (for example, Pc-MLMLM-Pc). )
Or in the case of forming a trimer, a preferred molecular weight, for example, a particularly preferred molecular weight is
It is 2 times (in the case of a dimer) or 3 times (in the case of a trimer) of a particularly preferable molecular weight (in the range of 995 to 1800) described above. Here, the preferable molecular weight of the dimer or trimer is a value including the linking group L.

Particularly preferred compounds as the phthalocyanine compound represented by the general formula (II) are compounds having the following combinations (a) to (e).

(A) R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are a hydrogen atom, a substituted or unsubstituted alkyl group,
A substituted or unsubstituted aryl group and a substituted or unsubstituted heterocyclic group are preferable, and among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are preferable, and a hydrogen atom is most preferable.
(B) V ₁ , V ₂ , V ₃ and V ₄ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group or a substituted group An aryl group and a substituted heterocyclic group are preferred, and a substituted alkyl group is most preferred. Further, at least one of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , V ₁ , V ₂ , V ₃ and V ₄ is an ionic hydrophilic group or has an ionic hydrophilic group as a substituent. More preferably, it is a group.
(C) Regarding Y _{31 to} Y ₃₈ , these are each independently a hydrogen atom, a halogen atom,
Alkyl groups, aryl groups, cyano groups, alkoxy groups, amide groups, ureido groups, sulfonamido groups, carbamoyl groups, sulfamoyl groups, alkoxycarbonyl groups, carboxyl groups, and sulfo groups are preferred, especially hydrogen atoms, halogen atoms, cyano groups , A carboxyl group, and a sulfo group are preferable, and a hydrogen atom is most preferable.
(D) M is preferably Cu, Ni, Zn, or Al, and most preferably Cu.
(E) The molecular weight of the phthalocyanine compound is preferably in the range of 750 to 2500, and further 9
A molecular weight in the range of 95-2500 is preferred, a molecular weight in the range of 995-2000 is preferred, and a molecular weight in the range of 995-1800 is most preferred.

Regarding the preferred combination of substituents of the compound represented by the general formula (II), a compound in which at least one of various substituents is the preferred group is preferred, and more various substituents are preferred groups. Certain compounds are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

Among the phthalocyanine compounds represented by the general formula (II), a phthalocyanine compound having a structure represented by the following general formula (III) is more preferable. The general formula (III) used in the present invention is as follows.
The phthalocyanine compound represented by) will be described in detail.

  General formula (III)

前記一般式(III)中、Ｒ₂₁、Ｒ₂₂、Ｒ₂₃およびＲ₂₄は、それぞれ独立に、水素原子、置
換もしくは無置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは
無置換のアルケニル基、置換もしくは無置換のアラルキル基、置換もしくは無置換のアリ
ール基、または置換もしくは無置換のヘテロ環基を表し、特に水素原子、置換アルキル基
、置換アリール基、置換ヘテロ環基が好ましく、その中でも水素原子、置換アルキル基が
好ましく、水素原子が最も好ましい。

In the general formula (III), R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group. Represents an alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, particularly preferably a hydrogen atom, a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group; Among these, a hydrogen atom and a substituted alkyl group are preferable, and a hydrogen atom is most preferable.

V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ are each independently a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, particularly a substituted alkyl group; A substituted aryl group and a substituted heterocyclic group are preferred, and a substituted alkyl group is most preferred among them.

The alkyl group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ includes an alkyl group having a substituent and an unsubstituted alkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include a hydroxy group, an alkoxy group, a cyano group, and a halogen atom and an ionic hydrophilic group. Examples of alkyl groups include methyl, ethyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoroethyl, 3-sulfopropyl and 4
-Sulfobutyl is included.

The cycloalkyl group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ includes
A cycloalkyl group having a substituent and an unsubstituted cycloalkyl group are included. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The alkenyl group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ includes an alkenyl group having a substituent and an unsubstituted alkenyl group. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include a vinyl group and an allyl group.

The aralkyl group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

The aryl group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ includes an aryl group having a substituent and an unsubstituted aryl group. As the aryl group, an aryl group having 6 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

The heterocyclic group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group.
The heterocyclic groups represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ are each independently a saturated heterocyclic ring or an unsaturated heterocyclic ring. Also good.
The heterocyclic groups represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ may each independently form a condensed ring with another ring.
The heterocyclic group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ is 5
A membered or 6-membered heterocyclic group is preferred.
Preferred examples of the heterocyclic group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ and condensed rings thereof include 5- to 6-membered nitrogen-containing heterocycles (further other rings And a condensed ring can be formed).
The heterocyclic group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ is exemplified in the form of a heterocyclic ring with the substitution position omitted, but the substitution position is limited. For example, pyridine can be substituted at the 2-position, 3-position, and 4-position.

Pyridine, pyrazine, pyrimidine, pyridazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, benzopyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, benzopyrazole, imidazole, benzimidazole, triazole, Examples include oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. Among them, an aromatic heterocyclic group is preferable, and preferable examples thereof are exemplified in the same manner as described above, and pyridine, pyrazine, pyrimidine,
Examples include pyridazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, and thiadiazole.

Examples of the substituent when the heterocyclic group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ further has a substituent include an alkyl group (R—), an alkoxy group (RO-), an alkylamino group (RNH-, RR'N-), a carbamoyl group (-CONHR), a sulfamoyl group (-SO ₂ NHR), sulfonylamino groups (-NHSO ₂ R), a halogen atom, ion (In addition, R and R ′ represent an alkyl group and a phenyl group, and these may have an ionic hydrophilic group).

M has the same meaning as M in formula (I), and preferred examples are also the same.
However, at least one of R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ has an ionic hydrophilic group as a substituent.
The example of an ionic hydrophilic group is synonymous with the example of X < ₁₁ >, X < ₁₂ >, X <_13> , X < ₁₄ > in the said general formula (I), and its preferable example is also the same.
The molecular weight of the phthalocyanine compound is preferably in the range of 750 to 2500, more preferably 995
A molecular weight in the range of 2500 is preferred, a molecular weight in the range of 995 to 2000 is preferred, and a molecular weight in the range of 995 to 1800 is most preferred.
Since the phthalocyanine compound represented by the general formula (III) is an ionic hydrophilic group or a group having an ionic hydrophilic group as a substituent in one molecule, it can be dissolved in an aqueous medium. Or dispersibility is improved. From such a viewpoint, the phthalocyanine compound represented by the general formula (III) preferably has at least two ionic hydrophilic groups in one molecule, and at least one of a plurality of ionic hydrophilic groups. Those having a sulfo group are preferred, and among them, those having at least two sulfo groups in one molecule of the phthalocyanine compound are most preferred.

Particularly preferred compounds as the phthalocyanine compound represented by the general formula (III) are compounds having the following combinations (a) to (e).

(A) R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl. Represents a group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, particularly preferably a hydrogen atom, a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group. A hydrogen atom is most preferred.
(B) With respect to V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ , these are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted Or an unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, particularly preferably a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group, and among them, an ionic hydrophilic group Most preferred is an alkyl group as a substituent.
(C) M is preferably Cu, Ni, Zn, or Al, and most preferably Cu.
(D) The molecular weight of the phthalocyanine compound is preferably in the range of 750 to 2500, and further 9
A molecular weight in the range of 95-2500 is preferred, a molecular weight in the range of 995-2000 is preferred, and a molecular weight in the range of 995-1800 is most preferred.
(E) Since the phthalocyanine compound represented by the general formula (III) has at least one ionic hydrophilic group in the molecule, the solubility or dispersibility in an aqueous medium is good. From such a viewpoint, the phthalocyanine compound represented by the general formula (III) preferably has at least two ionic hydrophilic groups in one molecule, and is at least one of a plurality of ionic hydrophilic groups. Is a sulfo group, and among them, one having at least two sulfo groups in one molecule is most preferable.

As for the preferred combination of substituents of the compound represented by the general formula (III), a compound in which at least one of various substituents is the preferred group is preferred, and more various substituents are preferred groups. Certain compounds are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

In general, it is known to use various phthalocyanine derivatives in an ink composition for ink jet recording. The phthalocyanine derivative represented by the following general formula (IV) inevitably has a substitution position (R ₁ : 1 position to R ₁₆ : 16 position) of the substituent R _n (n = 1 to 16) at the time of synthesis. In some cases, these substitution position isomers are regarded as the same derivative without being distinguished from each other. Further, even when isomers are included in the substituent of R, they are often regarded as the same phthalocyanine derivative without distinction.

  Formula (IV)

本明細書中で定義するフタロシアニン系色素において構造が異なる場合とは、一般式（
IV）で説明すると、置換基（Ｒ_n（ｎ＝１〜１６））の構成原子種が異なる場合、置換基
Ｒ_nの数が異なる場合または置換基Ｒ_nの位置が異なる場合のいずれかである。

The case where the structure is different in the phthalocyanine dye defined in the present specification is the general formula (
As described in IV), when the constituent atomic species of the substituent (R _n (n = 1 to 16)) are different, the number of substituents R _n is different, or the position of the substituent R _n is different is there.

In the present invention, the structure of the phthalocyanine dye represented by the general formula (IV) is different (
In particular, the substitution position) derivatives are classified into the following three types and defined.

β-position substitution type: (phthalocyanine compound having a specific substituent at positions 2 and / or 3, position 6 and / or 7, position 10 and / or 11, position 14 and / or 15).
α-position substitution type: (1 and / or 4 position, 5 and / or 8 position, 9 and / or 1
A phthalocyanine compound having a specific substituent at the 2-position, the 13-position and / or the 16-position).
α, β-position mixed substitution type: (phthalocyanine compound having a specific substituent without regularity at positions 1 to 16).

In the present specification, when a derivative of a phthalocyanine dye having a different structure (especially a substitution position) is described, the β-position substitution type, α-position substitution type, and α, β-position mixed substitution type are used.

Examples of the phthalocyanine derivative used in the present invention include “Phthalocyanine—Chemistry and Function” (P. 1-62), C.K. C. Leznoff
-A. B. P. Authored by Lever and published by VCH 'Phthalogicanes-Pro
described in “parties and Applications ′” (P. 1 to 54) and the like, or can be synthesized by combining similar methods.

The phthalocyanine compound represented by the general formula (I) used in the present invention is WO00 / 1727.
5, 00/08103, 00/08101, 98/41853, JP-A-10-36
As described in No. 471 and the like, it can be synthesized through, for example, sulfonation, sulfonyl chlorideation, and amidation reaction of an unsubstituted phthalocyanine compound.
In this case, sulfonation can occur at any position of the phthalocyanine nucleus, and the number of sulfonation is difficult to control.

Therefore, when a sulfo group is introduced under such reaction conditions, the position and number of the sulfo group introduced into the product cannot be specified, and a mixture in which the number of substituents and the substitution position are different is always given.
Therefore, when synthesizing the compound of the present invention using it as a raw material, the number and substitution position of the heterocyclic substituted sulfamoyl group cannot be specified, so that the compound is a mixture containing several kinds of compounds having different numbers of substitution groups and substitution positions. can get.

Among the phthalocyanine compounds represented by the general formulas (I) to (III) of the present invention, for example, the phthalocyanine compound represented by the following general formula (V) is, for example, a phthalonitrile represented by the following general formula (VI) It is synthesized by reacting a derivative and / or a diiminoisoindoline derivative represented by the following general formula (VII) with a metal derivative represented by the general formula (VIII).
On the other hand, the phthalocyanine compound represented by the general formula (V) is a 4-
By reacting a sulfophthalic acid-sodium salt with a metal derivative represented by the general formula (VIII), phthalocyanine copper (II) -tetrasulfonic acid-4sodium was synthesized, and then derived into the corresponding sulfonyl chloride. Can also be synthesized by reacting with an amine and / or aniline derivative (eg, G ₁ , G ₂ , G ₃ and G ₄ are G ₁ : {-S
_{O 2 N (R 21) (} V 11)}, G 2: {- SO 2 N (R 22) (V 12)}, G 3: {- SO 2 N (
_{R 23) (V 13)}} , G 4: {- SO 2 N (R 24) when the (V _14)}).
In addition, l, m, n, and p in the general formula (V) are synonymous with t in the general formula (VI) and / or the general formula (VII). G ₁ , G ₂ , G ₃ and G ₄ in the general formula (V) are each independently
General formula (III) in _{G 1: {- SO 2 N} (R 21) (V 11)}, G 2: {- SO 2 N (R 22) (
_{V 12)}, G 3:} {- SO 2 N (R 23) (V 13)}, G 4: {- SO 2 N (R 24) (V 14)}
Represents.

In general formula (VIII), M has the same meaning as M in general formula (I). Y represents a monovalent or divalent ligand such as a halogen atom, acetate anion, acetylacetonate, oxygen, and d is 1 to 1
It is an integer of 4. Examples of the metal derivative represented by M- (Y) d include Al, Si, Ti, V,
Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In, Sn, Pt, P
b halides, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides, complexes and the like. Specific examples include copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, iron chloride, zinc chloride, zinc bromide, zinc iodide, acetic acid. Examples include zinc, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, acetylacetone manganese, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride, and tin chloride.

The compound represented by the general formula (V) thus obtained (for example, l = m = n = p =
1) is usually an isomer at each substitution position of G _{1 to} G _4.
It is a mixture of compounds represented by (a) -4.
Furthermore, when preparing a dye using two or more types of general formula (VI) and / or general formula (VII) having different substituents, the compound represented by general formula (V) is the type of substituent. , The dye mixture in different positions.

Examples of the cyan dye used in the present invention include JP-A No. 2002-256167,
2002-275386, 2002-285050, 2002-294097
No., 2002-302623, 2002-309118, 2003-2131
Nos. 67 and 2003-213168 can be exemplified by compounds having the corresponding structure, and particularly preferred ones are listed in the following table. About the compound of Table 1, it is compoundable by the method as described in the said gazette or specification. Of course, the starting compound, the dye intermediate and the synthesis method are not limited to these.

In general, an ink jet recording medium using an ink composition containing a cyan dye (
In particular, a bronzing phenomenon may be observed when solid printing is performed on a glossy recording medium). Among such cyan dyes, the more cyan dyes excellent in both light resistance and gas resistance,
Ink jet recording medium using ink composition containing the same (particularly glossy recording medium)
In the case of solid printing, etc., the bronze phenomenon tends to become strong.
In order to obtain a high-quality ink-jet recorded product that is excellent in both light resistance and gas resistance and has no bronze phenomenon, it is further necessary to be in the presence of ozone, nitrogen oxides or sulfur oxides present in the air. In order to obtain an ink jet recorded product capable of preventing discoloration and fading under such an oxidizing gas atmosphere, it can be achieved by incorporating the following aromatic compound having a carboxyl group into the cyan dye.

The content of the dye is determined by the type of the compound represented by the general formula (I), the type of the solvent component, etc., but is preferably 0.1 to 10% by weight, more preferably based on the total weight of the ink composition. It is in the range of 0.5 to 5% by weight. By setting the content to 0.1% by weight or more, it is possible to ensure color developability or image density on the recording medium, and by setting the content to 10% by weight or less, it becomes easy to adjust the viscosity of the ink composition, and discharge reliability and clogging properties. Such characteristics can be easily secured.

The ink composition of the present invention is an aromatic compound having a carboxyl group in order to weaken or eliminate the bronzing phenomenon observed when solid printing is performed using an ink composition containing a cyan dye as described above. Or it contains at least one salt thereof.
In the present invention, as long as the ink composition contains water, the cyan dye represented by the general formula (I), and an aromatic compound having a carboxyl group or a salt thereof, the cyan ink composition is of course. For example, even an ink composition having a color different from cyan, such as a black ink composition, can weaken or eliminate the bronzing phenomenon seen in solid printing. In order to produce these various ink compositions, they can be used in combination with other conventionally known dyes.

The aromatic compound having a carboxyl group or a salt thereof used in the present invention may be any aromatic compound or salt thereof having at least one carboxyl group in the molecular structure, but one carboxyl group. Are preferred, and those having a naphthalene skeleton are preferred. Those having an —OR group (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) together with a carboxyl group in the naphthalene skeleton can also be preferably used. In the compound having a naphthalene skeleton or a salt thereof, the carboxyl group and the —OR group are One is preferred. Further, a compound having a carboxyl group at the 2-position and having a naphthalene skeleton or a salt thereof is more preferable, and a more preferable one is an alkali metal salt of a compound having a carboxyl group at the 2-position and having a naphthalene skeleton. . Of the alkali metal salts of compounds having a carboxyl group at the 2-position and having a naphthalene skeleton, lithium salts are not only particularly preferred from the viewpoint of improving bronzing resistance but also from the viewpoint of clogging resistance.

Specific examples of the aromatic compound having a carboxyl group or a salt thereof include 2-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid, 3-hydroxy- 2-naphthoic acid, 6-hydroxy-2-naphthoic acid, 3-methoxy-2-naphthoic acid, 6-methoxy-2-naphthoic acid, 6-ethoxy-2-naphthoic acid, 6
-Propoxy-2-naphthoic acid, 4-hydroxybenzoic acid, 2,6-naphthalenedicarboxylic acid and the like and salts thereof (particularly lithium salts).
The salt of the aromatic compound having a carboxyl group is added in the form of a salt and can be contained in the ink. In addition, the aromatic compound having a carboxyl group and the base are added separately, It is also possible to contain.

The content of the aromatic compound having a carboxyl group and / or a salt thereof is determined by the kind of the aromatic compound having a carboxyl group and / or a salt thereof, the kind of the dye, the kind of the solvent component, and the like. Preferably it is 0.1 to 10 weight% with respect to the total weight of a thing, More preferably, it is the range of 0.5 to 5 weight%.

In the ink composition of the present invention, the content ratio of the cyan dye and the aromatic compound having a carboxyl group and / or a salt thereof is preferably in a weight ratio of 1: 0.1 to 1:10, more preferably 1. : 0.3 to 1: 6. The effect of improving the bronze phenomenon can be sufficiently obtained by increasing the ratio of the aromatic compound having a carboxyl group and / or a salt thereof higher than 1: 0.1, and the aromatic having a carboxyl group than 1:10. By reducing the ratio of the group compound and / or salt thereof, clogging reliability and the like can be easily secured.

In order to stably dissolve the amount of the predetermined dye and the aromatic compound having a carboxyl group and / or a salt thereof, the pH (20 ° C.) of the ink composition is preferably 8.0 or more. Also, considering the material resistance with various members in contact with the ink composition, the p of the ink composition
H is preferably 10.5 or less. To make these matters better,
It is more preferable to adjust the pH of the ink composition to 8.5 to 10.0.

The ink composition of the present invention may further contain a humectant selected from water-soluble organic solvents and / or saccharides having a vapor pressure lower than that of pure water.
By including the humectant, the ink can be moisturized by suppressing evaporation of moisture in the ink jet recording system. In addition, if it is a water-soluble organic solvent, the ejection stability can be improved, and the viscosity can be easily changed without changing the ink characteristics.

The water-soluble organic solvent refers to a medium having an ability to dissolve a solute, and is selected from organic and water-soluble solvents having a vapor pressure smaller than that of water. Specifically, ethylene glycol, propylene glycol, butanediol, pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, glycerin, 1,2,6-hexanetriol, diethylene glycol Desirable are polyhydric alcohols such as triethylene glycol and dipropylene glycol, ketones such as acetonyl acetone, esters such as γ-butyrolactone and triethyl phosphate, furfuryl alcohol, tetrahydrofurfuryl alcohol, thiodiglycol and the like. .

The saccharide is preferably maltitol, sorbitol, gluconolactone, maltose or the like.
The humectant is preferably 5 to 50% by weight, more preferably 5%, based on the total amount of the ink composition.
It is added in the range of -30% by weight, more preferably 5-20% by weight. If it is 5% by weight or more, moisture retention can be obtained, and if it is 50% by weight or less, it is easy to adjust the viscosity used for inkjet recording.

The ink composition of the present invention preferably contains a nitrogen-containing organic solvent as a solvent. Examples of the nitrogen-containing organic solvent include 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidone, N-methyl-2-pyrrolidone, and ε-caprolactam.
-Pyrrolidone can be suitably used. They can be used alone or in combination of two or more.
The content is preferably 0.5 to 10% by weight, and more preferably 1 to 5% by weight. By making the content 0.5% by weight or more, it is possible to improve the solubility of the coloring material of the present invention by adding, and by making the content 10% by weight or less, various kinds of ink compositions that come into contact with it. The material resistance with the member is not deteriorated.

In addition, the ink composition of the present invention provides rapid fixing (penetration) of the ink and at the same time, 1
It is preferable to include a nonionic surfactant as an additive effective for maintaining the roundness of the dots.

Examples of nonionic surfactants used in the present invention include acetylene glycol surfactants. Specific examples of acetylene glycol surfactants include Surfinol (registered trademark) 465 and Surfinol 104 (above, Air Products and Chemi).
cals, Inc., trade name), Orphine (registered trademark) STG, Olphine E1010, Olfin PD001 (above, trade name, manufactured by Nissin Chemical Industry Co., Ltd.) and the like. The addition amount is preferably 0.1 to 5% by weight, more preferably 0.5 to 2% by weight. When the addition amount is 0.1% by weight or more, sufficient penetrability can be obtained, and when the addition amount is 5% by weight or less, it is easy to prevent image blurring.

Furthermore, by adding glycol ethers as penetration enhancers in addition to nonionic surfactants, the permeability is further increased and the bleed at the boundary between adjacent color inks is reduced when color printing is performed. And a very clear image can be obtained.

The glycol ethers that can be used in the present invention include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol mono Examples include butyl ether and triethylene glycol monobutyl ether. The addition amount is preferably 3 to 30% by weight, more preferably 5 to 15% by weight. If the addition amount is less than 3% by weight, the effect of preventing bleeding cannot be obtained. If the amount exceeds 30% by weight, not only the image will bleed, but also oily separation will occur, so the dissolution aid for these glycol ethers will be required, which will increase the viscosity of the ink. Becomes difficult.

Furthermore, the ink composition of the present invention includes a pH adjuster such as triethanolamine or alkali metal hydroxide, a hydrotrope such as urea and its derivatives, a water-soluble polymer such as sodium alginate, if necessary. A water-soluble resin, a fluorine-based surfactant, a fungicide, a rust inhibitor, and the like may be added.

As a method for preparing the ink composition of the present invention, for example, each component is sufficiently mixed and dissolved, pressure-filtered through a membrane filter having a pore size of 0.8 μm, and then degassed using a vacuum pump. There is.

Next, the recording method of the present invention using the above-described ink composition will be described. In the recording method of the present invention, an ink jet recording method in which an ink composition is ejected as droplets from fine holes and the droplets are attached to a recording medium for recording can be used particularly preferably. Needless to say, it can also be used for applications such as pen plotters.

As the ink jet recording method, any of the conventionally known methods can be used, and in particular, a method of ejecting droplets using vibration of a piezoelectric element (using an ink jet head that forms ink droplets by mechanical deformation of an electrostrictive element). Recording method) and a method using thermal energy, it is possible to perform excellent image recording.

Next, the present invention will be specifically described with reference to examples and comparative examples of the present invention.
The present invention is not limited to the following examples.

[Examples 1 to 13 and Comparative Examples 1 to 5]
The ink compositions of Examples 1 to 13 and Comparative Examples 1 to 5 were mixed and dissolved at the blending ratios shown in Table 2, and subjected to pressure filtration with a membrane filter having a pore size of 1 μm. Was prepared.

In addition, each component of the ink composition shown in the table indicates weight% of each component with respect to the total amount of the ink composition, and the remaining amount is water.

Using the ink compositions described in Examples 1 to 13 and Comparative Examples 1 to 5 using an inkjet printer EM930C (manufactured by Seiko Epson Corporation), a dedicated cartridge (
Cyan chamber) was filled and printed on an inkjet recording medium (PM photographic paper, dedicated glossy film: both manufactured by Seiko Epson Corporation), and each evaluation was performed. The obtained results are shown in Table 3.

《Bronze evaluation》
A gloss meter (PG-1M: Nippon Denshoku Industries Co., Ltd.) was printed using the above cartridge to obtain a solid printing amount of 1.5 to 2.2 mg per inch square meter.
(Measurement angle 60 °) and the glossiness was determined. Printing was performed in an environment of 25 ° C. and 40% RH.
The glossiness obtained and the value obtained from the following equation were used as the bronze criteria.

Glossiness (printed matter) -Glossiness (recording medium) [Evaluation criteria] Evaluation A: Less than 15 Evaluation B: 15 or more and less than 35 Evaluation C: 35 or more and less than 55 Evaluation D: 55 or more

<Ozone resistance evaluation>
Using the above cartridge, printed matter obtained by performing printing while adjusting the applied duty so that OD (Optical Density) falls within the range of 0.9 to 1.1 is obtained as an ozone weather meter O.
Using a MS-H type (trade name, manufactured by Suga Test Instruments Co., Ltd.), the printed matter was exposed for a predetermined time (6, 12 hours) under the conditions of 24 ° C., relative humidity 60% RH, and ozone concentration 20 ppm.
After the exposure, the OD of each printed matter was measured using a densitometer (“Spectrolino” manufactured by Gretag), an optical density residual ratio (ROD) was determined by the following formula, and evaluated according to the following criteria.

ROD (%) = (D / D ₀ ) × 100
D: OD after exposure test
D ₀ : OD before exposure test
(However, the measurement conditions are Filter: Red, light source: D50, viewing angle: 2 degrees)
[Criteria] Evaluation A: ROD is 90% or more Evaluation B: ROD is 80% or more and less than 90% Evaluation C: ROD is 70% or more and less than 80% Evaluation D: ROD is less than 70%

<Evaluation of clogging resistance>
After charging the above cartridge into an ink jet printer EM930C (manufactured by Seiko Epson Corporation) and confirming that the ink is normally discharged initially, the main body power is turned off, and the ink cartridge is loaded and the temperature is 40 ° C. and 20% RH. Left in the environment. Predetermined time (3
(0 days, 180 days) After leaving, the EM930C was taken out, the power was turned on after the temperature dropped to room temperature, and it was checked whether the ink was ejected normally. In addition, when it does not discharge normally, EM93
A predetermined cleaning recovery operation of 0C was performed, printing was performed thereafter, and the number of cleaning recovery operations required until normal ejection was obtained was obtained and evaluated according to the following criteria.

[Judgment Criteria] Evaluation A: Power is turned on or ejection is normally performed after one cleaning operation B: Normal ejection is evaluated after 2 to 3 cleaning operations C: Normal ejection evaluation is performed after 4 to 6 cleaning operations D: Cleaning operation Does not discharge normally even after 6 times

Each ink composition was subjected to pH measurement using a pH meter (Model PH82: Yokogawa Electric Corporation).
The obtained values are shown together in Table 3.

Claims (14)

An ink composition comprising at least water, a cyan dye represented by the following general formula (I), an aromatic compound having a carboxyl group, and / or a salt thereof.
Formula (I)

Wherein X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ each independently represent —SO ₂ NR ₁ R ₂ and / or a sulfo group, provided that all of X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ At the same time, when there are a plurality of R _{1 s} , each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group. R ₂ represents an independently substituted or unsubstituted alkenyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted heterocyclic group. Alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group, or substituted R ₁ and R ₂ may be bonded to each other to form a 5- to 6-membered nitrogen-containing heterocyclic ring.
Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ and Y ₁₈ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkylamino group,
Alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, alkoxycarbonyl group, heterocyclic oxy group, Azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group or ionic hydrophilic group, each group is Furthermore, you may have a substituent.
a ₁₁ ~a ₁₄ each represent a number of substituents X ₁₁ to X _14, independently, is an integer of 0 to 2, but all are not 0 at the same time.
M is a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof.
_{However, X 11, X 12, X} 13, X 14, Y 11, Y 12, Y 13, Y 14, Y 15, Y 16, Y 17 and Y
_At least one of ₁₈ is an ionic hydrophilic group or a group having an ionic hydrophilic group as a substituent. ) The ink composition according to claim 1, wherein the cyan dye represented by the general formula (I) is represented by the following general formula (II).
Formula (II)

Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, substituted Alternatively, it represents an unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
V ₁ , V ₂ , V ₃ and V ₄ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, It represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
Y ₃₁ , Y ₃₂ , Y ₃₃ , Y ₃₄ , Y ₃₅ , Y ₃₆ , Y ₃₇ and Y ₃₈ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkylamino group,
Alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, alkoxycarbonyl group, heterocyclic oxy group, Azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group or ionic hydrophilic group, each group is Furthermore, you may have a substituent.
M has the same meaning as M in formula (I).
_{R 11, R 12, R 13} , R 14, V 1, V 2, V 3, V 4, Y 31, Y 32, Y 33, Y 34, Y 35, Y 36
, Y ₃₇ and Y ₃₈ are ionic hydrophilic groups or groups having an ionic hydrophilic group as a substituent. ) The ink composition according to claim 1, wherein the cyan dye represented by the general formula (I) is represented by the following general formula (III).
General formula (III)

(Wherein R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, substituted Alternatively, it represents an unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ are each independently a substituted or unsubstituted alkyl group,
A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is represented.
M has the same meaning as M in formula (I).
However, at least one of R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ has an ionic hydrophilic group as a substituent. )   The ink composition according to claim 3, wherein M in the general formula (III) is a copper element. The ink composition according to claim 3, wherein M in the general formula (III) is a copper element, and the counter cation of the ionic hydrophilic group is a lithium cation. The ink composition according to claim 1, wherein the aromatic compound having a carboxyl group and / or a salt thereof is an aromatic compound having one carboxyl group and / or a salt thereof. The ink composition according to any one of claims 1 to 6, wherein the aromatic compound having a carboxyl group and / or a salt thereof is a compound having a naphthalene skeleton and / or a salt thereof. The compound having a naphthalene skeleton and / or a salt thereof is a compound having a carboxyl group and an -OR group (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the naphthalene skeleton. Ink composition. The compound having a naphthalene skeleton and / or a salt thereof is a compound having one carboxyl group and one -OR group (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the naphthalene skeleton. Item 9. The ink composition according to Item 8. The ink composition according to any one of claims 7 to 9, wherein the compound having a naphthalene skeleton and / or a salt thereof is a compound having a carboxyl group at the 2-position and / or a salt thereof. The compound having a carboxyl group at the 2-position and having a naphthalene skeleton and / or a salt thereof,
1-hydroxy-2-naphthoic acid, 2-naphthoic acid, 3-hydroxy-2-naphthoic acid,
6-hydroxy-2-naphthoic acid, 3-methoxy-2-naphthoic acid, 6-methoxy-2-
The ink composition according to claim 10, which is at least one of naphthoic acid, 6-ethoxy-2-naphthoic acid, 6-propoxy-2-naphthoic acid and salts thereof.   The ink composition according to any one of claims 1 to 11, wherein the salt is a lithium salt. The ink composition according to any one of claims 1 to 12, comprising 0.1 to 10% by weight of the aromatic compound having a carboxyl group and / or a salt thereof based on the total amount of the ink composition. 14. The content ratio of the cyan dye and the aromatic compound having a carboxyl group and / or a salt thereof is in the range of 1: 0.1 to 1:10 by weight ratio. Item 4. The ink composition according to item.

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