JP2014098119A - Coloring composition, ink jet recording ink, ink jet recording method, ink jet printer cartridge, and ink jet recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition with excellent discharge accuracy, and an ink jet recording ink, an ink jet recording method, an ink jet printer cartridge, and an ink jet recording material.SOLUTION: A coloring composition contains a phthalocyanine dye represented by general formula (2), another phthalocyanine dye, and further a phosphonate compound or an organic monophosphonic acid of a specific structure.

Description

  The present invention relates to a coloring composition, an ink for ink jet recording, an ink jet recording method, an ink jet printer cartridge, and an ink jet recorded matter.

In recent years, with the spread of computers, ink jet printers are widely used for printing on paper, film, cloth and the like not only in offices but also at home.
Ink jet recording methods include a method of ejecting droplets by applying pressure with a piezo element, a method of ejecting droplets by generating bubbles in ink by heat, a method of using ultrasonic waves, or a droplet by electrostatic force. There is a method of sucking and discharging. As these inks for inkjet recording, water-based inks, oil-based inks, or solid (melting type) inks are used. Among these inks, water-based inks are mainly used from the viewpoints of production, handleability, odor, safety, and the like.

  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.

  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 a good cyan hue and being robust against light, humidity, and heat, especially an ink receiving layer containing porous white inorganic pigment particles, It is strongly desired to be robust against an oxidizing gas such as ozone therein, and at the same time, it is strongly desired to achieve both ink storage stability as described later.

  Cyan dye skeletons used in such inks for ink jet recording include phthalocyanine-based, anthraquinone-based, and triphenylmethane-based phthalocyanine compounds that are excellent in hue and light fastness. 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.

  Further, it is a big problem that the printing density is greatly reduced due to the fading easily by an oxidizing gas such as ozone, which is often taken up as an environmental problem in recent years.

  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. In many cases, the ink ejection accuracy is deteriorated due to the poor quality. Therefore, a coloring composition excellent in ink ejection accuracy is strongly desired.

Patent Document 1 discloses a phthalocyanine dye having a specific sulfonyl group or sulfinyl group as a phthalocyanine dye that achieves both hue and light and ozone fastness. Further, in the phthalocyanine dye described in this document, the substitution position of the substituent is a β-position substitution type (the following general formula) rather than the α, β-position mixed type (the substitution position of the substitution group is not regular). In the case where R _{1 to} R ₁₆ in (IV) are 1st to 16th positions, respectively, 2nd and / or 3rd position, 6th and / or 7th position, 10th and / or 11th position, 14th and / or 15th position It is described that a compound having a specific sulfonyl group or sulfinyl group is excellent in hue, light and ozone fastness.

Patent Document 2 describes that a phosphonate additive is used as a compound capable of preventing the occurrence of kogation against the heat of a recording liquid such as ink for inkjet recording.
Patent Document 3 describes the use of organic monophosphonic acid as a compound that can prevent the occurrence of kogation against the heat of a recording liquid such as ink for inkjet recording.

Japanese Patent Laid-Open No. 2002-249677 JP 2002-317136 A Japanese Patent No. 3896921

  The subject of this invention is providing the coloring composition excellent in the discharge precision, the ink for inkjet recording, the inkjet recording method, an inkjet printer cartridge, and an inkjet recorded matter.

  The present inventors have a dye represented by the general formula (2) having a strong associative property and excellent fastness, and a dye represented by the general formula (1) having a weak associative property and excellent print density, It has been found that a coloring composition excellent in ejection accuracy can be obtained by incorporating a phosphonate compound or an organic monophosphonic acid having a specific structure into the coloring composition. Although the mechanism of action is unknown, the dye and phosphonate compound or specific structure represented by the general formula (1) with respect to the time-dependent precipitation of the dye in the ink (probably a dye represented by the general formula (2) having a strong association) It is considered that a colored composition having high ejection accuracy could be obtained by highly suppressing association and aggregation due to the synergistic effect of the organic monophosphonic acid.

  The object of the present invention has been achieved by the following method.

[1]
A coloring composition comprising a phthalocyanine dye represented by the following general formula (1) and a phthalocyanine dye represented by the following general formula (2),
Furthermore, the coloring composition containing the organic monophosphonic acid represented by a phosphonate compound or following General formula (3).

In general formula (1),
R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl 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, sulfonamide group, carbamoyl group, sulfamoyl 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, an acyl group or an ionic hydrophilic group. These groups may further have a substituent.
Z ₁ , Z ₂ , Z ₃ and Z 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. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent.
l, m, n, p, q ₁ , q ₂ , q ₃ and q ₄ each independently represent 1 or 2.
M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
General formula (2):

In general formula (2),
R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl 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, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group , Heterocyclic thio group, phosphoryl Represents an acyl group or an ionic hydrophilic group. These groups may further have a substituent.
Z ₅ , Z ₆ , Z ₇ and Z ₈ 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. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₅ , Z ₆ , Z ₇ , and Z ₈ has an ionic hydrophilic group as a substituent.
t, u, v, w, q ₅ , q ₆ , q ₇ and q ₈ each independently represent 1 or 2.
M ₂ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.

(In general formula (3), R represents a group selected from the following 1) or 2).
1) an unsubstituted alkyl group, or an alkyl group substituted with a hydroxyl group, amino group, nitro group or carboxyl group,
2) An unsubstituted phenyl group or a phenyl group substituted with an amino group, an alkyl group or a hydroxyl group. )
[2]
The colored composition according to [1], wherein R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ in the phthalocyanine dye represented by the general formula (2) are hydrogen atoms. .
[3]
Z ₅ , Z ₆ , Z ₇ and Z ₈ in the phthalocyanine dye represented by the general formula (2) are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. The coloring composition according to [1] or [2], which represents a substituted heterocyclic group.
[4]
In the phthalocyanine dye represented by the general formula (2), Z ₅ , Z ₆ , Z ₇ , and Z ₈ represent a substituted alkyl group, and at least one of the substituents of the alkyl group is a —SONHR group (where R is a substituted group). Or represents an unsubstituted alkyl group or a substituted or unsubstituted phenyl group). [1] to [3] The colored composition according to any one of [1] to [3].
[5]
The coloring composition according to any one of [1] to [4], wherein t, u, v and w in the phthalocyanine dye represented by the general formula (2) are 1.
[6]
The colored composition according to any one of [1] to [5], wherein q ₅ , q ₆ , q ₇ and q ₈ in the phthalocyanine dye represented by the general formula (2) are 2.
[7]
Any of [1] to [6], in which R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ in the phthalocyanine dye represented by the general formula (1) are hydrogen atoms 2. The coloring composition according to claim 1.
[8]
Z ₁ , Z ₂ , Z ₃ and Z ₄ in the phthalocyanine dye represented by the general formula (1) are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. The coloring composition according to any one of [1] to [7], which represents a substituted heterocyclic group.
[9]
The coloring composition according to any one of [1] to [8], wherein l, m, n, and p in the phthalocyanine dye represented by the general formula (1) are 1.
[10]
The coloring composition according to any one of [1] to [9], wherein q ₁ , q ₂ , q ₃ and q ₄ in the phthalocyanine dye represented by the general formula (1) are 2.
[11]
Any one of [1] to [10], wherein the mass ratio of the phthalocyanine dye represented by the general formula (1) and the phthalocyanine dye represented by the general formula (2) is 50/50 to 10/90. The coloring composition as described in.
[12]
The coloring composition according to any one of [1] to [11], wherein the content of the phthalocyanine dye represented by the general formula (1) is 0.1 to 10% by mass.
[13]
The phosphonate compound comprises a sodium salt of aminotri (methylene-phosphonic acid), a sodium salt of hydroxyethylidene diphosphonic acid, a sodium salt of diethylenetriaminepenta (methylenephosphonic acid), and a potassium salt of hexamethylenediaminetetra (methylenephosphonic acid). The coloring composition according to any one of [1] to [12], which is at least one selected from the group consisting of:
[14]
The coloring composition according to any one of [1] to [13], wherein the content of the phosphonate compound is 0.05% by mass or more and 0.8% by mass or less based on the total mass of the coloring composition.
[15]
In the general formula (3), according to any one of [1] to [12], R is an alkyl group substituted with a carboxyl group, an unsubstituted alkyl group, or an unsubstituted phenyl group. Coloring composition.
[16]
In any one of [1] to [12] and [15], the compound represented by the general formula (3) is contained in an amount of 0.01 to 0.25% by mass based on the total mass of the colored composition. The coloring composition as described.
[17]
The mass ratio of the total amount of the phthalocyanine dyes represented by the general formula (1) and the general formula (2) and the phosphonate compound or the compound represented by the general formula (3) is 500/1 to 25/4. The coloring composition according to any one of [1] to [16].
[18]
[1] to [17] An inkjet recording ink comprising the colored composition according to any one of [17].
[19]
An inkjet recording method using the inkjet recording ink according to [18].
[20]
An ink cartridge filled with the ink for ink jet recording according to [18].
[21]
[18] An ink-jet recorded matter in which a colored image is formed on a recording material using the ink for ink-jet recording described in [18].

  ADVANTAGE OF THE INVENTION According to this invention, the coloring composition excellent in the discharge precision, the ink for inkjet recording, the inkjet recording method, an inkjet printer cartridge, and an inkjet recorded matter are provided.

  In the present invention, the substituent group A is defined as follows.

(Substituent group A)
Halogen atom (for example, chlorine atom, bromine atom); linear or branched alkyl group having 1 to 12 carbon atoms, aralkyl group having 7 to 18 carbon atoms, alkenyl group having 2 to 12 carbon atoms, 2 to 2 carbon atoms 12 linear or branched 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 ( Specific examples of the above group include, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl): aryl group (for example, phenyl, 4-t- Butylphenyl, 2,4-di-t-amylphenyl); heterocyclic groups (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2- Alkyloxy groups (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy); aryloxy groups (eg, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3 -Nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl); acylamino groups (eg acetamide, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide); alkylamino groups (eg , Methylamino, butylamino, diethylamino, methylbutylamino); anilino group (eg, phenylamino, 2-chloroanilino; ureido group (eg, phenylureido, methylureido, N, N-dibutylureido); Famoylamino group (eg, N, N-dipropylsulfamoylamino); alkylthio group (eg, methylthio, octylthio, 2-phenoxyethylthio); arylthio group (eg, phenylthio, 2-butoxy-5-t-octyl) Phenylthio, 2-carboxyphenylthio); alkyloxycarbonylamino group (eg methoxycarbonylamino); sulfonamide group (eg methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecane); carbamoyl group (eg , N-ethylcarbamoyl, N, N-dibutylcarbamoyl); sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-diethylsulfamoyl); sulfonyl group (eg, , Methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl); alkyloxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl); heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyl) Oxy); azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo); acyloxy group (for example, acetoxy); carbamoyloxy group (for example, , N-methylcarbamoyloxy, N-phenylcarbamoyloxy); silyloxy groups (eg, trimethylsilyloxy, dibutylmethylsilyloxy); aryloxycarbonylamino groups (eg, phenoxycal) Nilamino); imide group (for example, N-succinimide, N-phthalimi); heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio) , 2-pyridylthio); sulfinyl group (eg, 3-phenoxypropylsulfinyl); phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl); aryloxycarbonyl group (eg, phenoxycarbonyl); acyl group (For example, acetyl, 3-phenylpropanoyl, benzoyl); ionic hydrophilic groups (for example, carboxyl group, sulfo group, and quaternary ammonium group); other cyano group, hydroxyl group, nitro group, amino group.

  The coloring composition of the present invention is a coloring composition comprising a phthalocyanine dye represented by the following general formula (1) and a phthalocyanine dye represented by the following general formula (2), and further, a phosphonate compound or a general An organic monophosphonic acid represented by the formula (3) is contained. The coloring composition contains a phthalocyanine dye represented by the general formula (1) and a phthalocyanine dye represented by the general formula (2), and further contains a phosphonate compound or an organic monophosphonic acid represented by the general formula (3). By containing, the coloring composition excellent in the discharge precision is provided.

[Phthalocyanine dye represented by formula (1)]
First, the phthalocyanine dye represented by the general formula (1) will be described in detail.

In general formula (1),
R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl 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, sulfonamide group, carbamoyl group, sulfamoyl 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, an acyl group or an ionic hydrophilic group. These groups may further have a substituent.
Z ₁ , Z ₂ , Z ₃ and Z 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. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent.
l, m, n, p, q ₁ , q ₂ , q ₃ and q ₄ each independently represent 1 or 2.
M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.

In general formula (1), R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or an alkenyl. Group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl 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, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryl Oxycarbonylamino group, imide group, heterocycle It represents an OH group, a phosphoryl group, an acyl group or an ionic hydrophilic group. These groups may further have a substituent. Examples of the substituent include the substituents described in the above substituent group A.

Examples of the halogen atom represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ include a fluorine atom, a chlorine atom and a bromine atom.

The alkyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ 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 hydroxyl group, an alkoxy group, a cyano group, and a halogen atom and an ionic hydrophilic group. Examples of the alkyl group include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.

The cycloalkyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. 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 ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ 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 ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ 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 ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ 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 ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic group include a 2-pyridyl group, a 2-thienyl group, and a 2-furyl group.

The alkylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkylamino group having a substituent and an unsubstituted alkylamino group. The alkylamino group is preferably an alkylamino group having 1 to 6 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.

The alkoxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkoxy group having a substituent and an unsubstituted alkoxy group. As an alkoxy group when a substituent is removed, an alkoxy group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

The aryloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

The amide group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an amide group having a substituent and an unsubstituted amide group. The amide group is preferably an amide group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the amide group include an acetamide group, a propionamide group, a benzamide group, and a 3,5-disulfobenzamide group.

The arylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 12 carbon atoms when a substituent is removed. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.

The ureido group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

The sulfamoylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. A group is included. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include an N, N-dipropylsulfamoylamino group.

The alkylthio group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkylthio group having a substituent and an unsubstituted alkylthio group. The alkylthio group is preferably an alkylthio group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group include a methylthio group and an ethylthio group.

The arylthio group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an arylthio group having a substituent and an unsubstituted arylthio group. The arylthio group is preferably an arylthio group having 6 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an alkyl group and an ionic hydrophilic group. Examples of the arylthio group include a phenylthio group and a p-tolylthio group.

The alkoxycarbonylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. It is. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

The sulfonamide group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a sulfonamide group having a substituent and an unsubstituted sulfonamide group. The sulfonamide group is preferably a sulfonamide group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonamide group include methanesulfonamide, benzenesulfonamide, and 3-carboxybenzenesulfonamide.

The carbamoyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

The sulfamoyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group and an aryl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group, a di- (2-hydroxyethyl) sulfamoyl group, and a phenylsulfamoyl group.

The alkoxycarbonyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

The heterocyclic oxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R _{15 includes} a heterocyclic oxy group having a substituent and an unsubstituted heterocyclic oxy group. It is. The heterocyclic oxy group is preferably a heterocyclic oxy group having a 5-membered or 6-membered heterocyclic ring. Examples of the substituent include a hydroxyl group and an ionic hydrophilic group. Examples of the heterocyclic oxy group include a 2-tetrahydropyranyloxy group.

The azo group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an azo group having a substituent and an unsubstituted azo group. Examples of the azo group include a p-nitrophenylazo group.

The acyloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an acyloxy group having a substituent and an unsubstituted acyloxy group. The acyloxy group is preferably an acyloxy group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

The carbamoyloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

The silyloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a silyloxy group having a substituent and an unsubstituted silyloxy group. Examples of the substituent include an alkyl group. Examples of the silyloxy group include a trimethylsilyloxy group.

The aryloxycarbonyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. It is. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

The aryloxycarbonylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino A group is included. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

The imide group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an imide group having a substituent and an unsubstituted imide group. Examples of the imide group include an N-phthalimide group and an N-succinimide group.

The heterocyclic thio group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R _{15 includes} a heterocyclic thio group having a substituent and an unsubstituted heterocyclic thio group. It is. The heterocyclic thio group preferably has a 5-membered or 6-membered heterocyclic ring. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic thio group include a 2-pyridylthio group.

The phosphoryl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a phosphoryl group having a substituent and an unsubstituted phosphoryl group. Examples of the phosphoryl group include a phenoxyphosphoryl group and a phenylphosphoryl group.

The acyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

The ionic hydrophilic group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a sulfo group, a carboxyl group, a quaternary ammonium group, and the like. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.

R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido, among others Group, sulfonamido group, carbamoyl group, sulfamoyl group and alkoxycarbonyl group are preferable, hydrogen atom, halogen atom and cyano group are particularly preferable, and hydrogen atom is most preferable.

In general formula (1), Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, It represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent. Examples of the substituent include the substituents described in the above substituent group A.

The alkyl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms when a substituent is excluded. Examples of the substituent group, a hydroxyl group, an alkoxy group, a cyano group, an alkylamino group (RNH-, RR'N-), a carbamoyl group (-CONHR), a sulfamoyl group _{(-SO 2 NHR, -SO 2 NRR} ') , A sulfonylamino group (—NHSO ₂ R), a —SONHR group, a —SONRR ′ group, a halogen atom and an ionic hydrophilic group. (Note that R and R ′ represent an alkyl group and a phenyl group, and these may have a substituent. Examples of the substituent include an alkylamino group, a hydroxyl group, and an ionic hydrophilic group. R and R ′ may form a ring by a chemical bond.) Examples of the alkyl group include methyl, ethyl, butyl, n-propyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trimethyl. Fluoromethyl, 3-sulfopropyl and 4-sulfobutyl are included.

The cycloalkyl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. 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 Z ₁ , Z ₂ , Z ₃ , and Z ₄ 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 Z ₁ , Z ₂ , Z ₃ and Z ₄ 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 Z ₁ , Z ₂ , Z ₃ , and Z ₄ 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 aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl, m-sulfophenyl. Examples of the 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), A sulfonylamino group (—NHSO ₂ R), a halogen atom, and an ionic hydrophilic group are included (note that R and R ′ represent an alkyl group and a phenyl group, and these may also have an ionic hydrophilic group. Good).

The heterocyclic group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group, and may form a condensed ring with another ring. Good. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. The heterocyclic group may form a condensed ring with another ring. Examples of the heterocyclic group include, but are not limited to, the substitution position of the heterocyclic ring. Oxazole, benzoxazole, thiadiazole, oxadiazole, pyrrole, benzopyrrole, indole, isoxazole, benzoisoxazole, thiophene, benzothiophene, furan, benzofuran, pyridine, quinoline, isoquinoline, pyridazine, pyrimidine, pyrazine, cinnoline, phthalazine, Quinazoline, quinoxaline, triazine and the like are included. Examples of the substituent include an alkyl group (R-), an aryl group (R-), an alkoxy group (RO-), an alkylamino group (RNH-, RR'N-), a carbamoyl group (-CONHR), and a sulfamoyl group. (—SO ₂ NHR), a sulfonylamino group (—NHSO ₂ R), a sulfonyl group (—SO ₂ R), an acylamino group (—NHCOR), a halogen atom, and an ionic hydrophilic group are included (note that R, R above) 'Represents an alkyl group or an aryl group, and these may have an ionic hydrophilic group or a substituent having an ionic hydrophilic group).

Z ₁ , Z ₂ , Z ₃ and Z ₄ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted alkyl group or a substituted aryl group. A substituted heterocyclic group is more preferred, and a substituted alkyl group is more preferred.

At least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent. Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.

  In general formula (1), l, m, n and p each independently represent 1 or 2. That is, 4 ≦ l + m + n + p ≦ 8 is satisfied. Preferably, 4 ≦ l + m + n + p ≦ 6 is satisfied, and most preferably, each is 1 (1 = m = n = p = 1).

In general formula (1), q ₁ , q ₂ , q ₃ and q ₄ each independently represent 1 or 2. In particular, q ₁ = q ₂ = q ₃ = q ₄ = 2 is preferable.

In General Formula (1), M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.

What is preferable as M ₁ is a metal element other than a hydrogen atom, such as Li, Na, K, Mg, Ti, Zr, 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. Of these, Cu, Ni, Zn, Al and the like are particularly preferable, and Cu is most preferable. Preferred examples of the metal oxide include VO and GeO. Moreover, as a metal hydroxide, Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _2, etc. are mentioned preferably. Further, as the metal _{halide, AlCl, SiCl 2, VCl,} VCl 2, VOCl, FeCl, GaCl, ZrCl , and the like.

[Phthalocyanine dye represented by formula (2)]
Next, the phthalocyanine dye represented by the general formula (2) will be described in detail.

In general formula (2),
R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ are each independently R ₂ , R ₃ , R ₆ , R ₇ , R in the general formula (1). ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are synonymous with each other.
Z ₅ , Z ₆ , Z ₇ , and Z ₈ are each independently synonymous with Z ₁ , Z ₂ , Z ₃ , and Z _{4 in the} general formula (1).
t, u, v, w, q ₅ , q ₆ , q ₇ and q ₈ each independently represent 1 or 2.
M ₂ has the same meaning as M ₁ in the general formula (1).

R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ are each independently R ₂ , R ₃ , R ₆ , R ₇ , R in the general formula (1). ₁₀ , R ₁₁ , R _14, and R ₁₅ , each having the same meaning, 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 sulfonamide group, a carbamoyl group, a sulfamoyl group, and An alkoxycarbonyl group is preferable, a hydrogen atom, a halogen atom, or a cyano group is particularly preferable, and a hydrogen atom is most preferable.
These groups may further have a substituent. Examples of the substituent include the substituents described in the above substituent group A.

Z ₅ , Z ₆ , Z ₇ , and Z ₈ are each independently synonymous with Z ₁ , Z ₂ , Z ₃ , and Z _{4 in the} general formula (1).
Z ₅ , Z ₆ , Z ₇ and Z ₈ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted alkyl group or a substituted aryl group. A substituted heterocyclic group is more preferred, and a substituted alkyl group is more preferred. Further, at least one of the substituents of the substituted alkyl group is most preferably a —SONHR group from the viewpoint of ozone fastness.
The ionic hydrophilic group which at least one of Z ₅ , Z ₆ , Z ₇ and Z ₈ has as a substituent is substituted by Z ₁ , Z ₂ , Z ₃ and Z _{4 in the} general formula (1). It is synonymous with the ionic hydrophilic group which has as group, and its preferable example is also the same.

  In general formula (2), t, u, v, and w each independently represent 1 or 2. That is, 4 ≦ t + u + v + w ≦ 8 is satisfied. Preferably, 4 ≦ t + u + v + w ≦ 6 is satisfied, and most preferably, each is 1 (t = u = v = w = 1).

In general formula (2), q ₅ , q ₆ , q ₇ and q ₈ each independently represent 1 or 2. In particular, q ₅ = q ₆ = q ₇ = q ₈ = 2 is preferable.

M ₂ has the same meaning as M ₁ in the general formula (1), and preferred examples thereof are also the same.

[Synthesis of phthalocyanine dyes]
Examples of the phthalocyanine derivatives used in the present invention include “Phthalocyanine—Chemistry and Function” (P. 1-62), C.I. C. Leznoff-A. B. P. Lever co-authored, published by VCH, “Phthalogicanes-Properties and Applications” (P. 1-54), etc., can be synthesized by combining quoted or similar methods.

Hereinafter, the synthesis of the phthalocyanine dye represented by the general formula (2) of the present invention will be described as an example.
Of the phthalocyanine dyes represented by the general formula (2) of the present invention, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ are hydrogen, q ₅ , q ₆ , q _7. And the compound in which q ₈ is 2 is, for example, a phthalonitrile derivative represented by the following general formula (V) and / or a diiminoisoindoline derivative represented by the following general formula (VI) and the following M- (Y) d: It is synthesize | combined by making the metal derivative represented by these react.

In general formula (2),
R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ are each independently R ₂ , R ₃ , R ₆ , R ₇ , R in the general formula (1). ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are synonymous with each other.
Z ₅ , Z ₆ , Z ₇ , and Z ₈ are each independently synonymous with Z ₁ , Z ₂ , Z ₃ , and Z _{4 in the} general formula (1).
t, u, v, w, q ₅ , q ₆ , q ₇ and q ₈ each independently represent 1 or 2.
M and _{M 2} has the same meaning as _{M 1} in the general formula (1), and M = _{M 2.}

In general formula (V) and / or general formula (VI), x is synonymous with t, u, v, and w in general formula (2). Z represents a substituent corresponding to Z ₅ , Z ₆ , Z ₇ , and Z ₈ .
Y represents a monovalent or divalent ligand such as a halogen atom, acetate anion, acetylacetonate, or oxygen, and d is an integer of 1 to 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, and Pb. 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, tin chloride and the like.

  The use amount of the metal derivative and the phthalonitrile compound represented by the general formula (V) is preferably 1: 3 to 1: 6 in molar ratio. The amount of the metal derivative and the diiminoisoindoline derivative represented by the general formula (VI) is preferably 1: 3 to 1: 6 in terms of molar ratio.

  The reaction is usually performed in the presence of a solvent. As the solvent, an organic solvent having a boiling point of 80 ° C. or higher, preferably 130 ° C. or higher is used. For example, n-amyl alcohol, n-xanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, ethoxyethanol , Propoxyethanol, butoxyethanol, dimethylaminoethanol, diethylaminoethanol, trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene, quinoline, urea and the like. The usage-amount of a solvent is 1-100 mass times of a phthalonitrile compound, Preferably it is 5-20 mass times.

  In the reaction, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) or ammonium molybdate may be added as a catalyst. The addition amount is 0.1 to 10 times mol, preferably 0.5 to 2 times mol, per 1 mol of the phthalonitrile compound and / or diiminoisoindoline derivative.

  The reaction temperature is preferably 80 to 300 ° C, preferably 100 to 250 ° C, particularly preferably 130 to 230 ° C. Below 80 ° C, the reaction rate is extremely slow. If it exceeds 300 ° C, the phthalocyanine compound may be decomposed.

  The reaction time is preferably 2 to 20 hours, preferably 5 to 15 hours, and particularly preferably 5 to 10 hours. If it is less than 2 hours, there are many unreacted raw materials, and if it exceeds 20 hours, decomposition of the phthalocyanine compound may occur.

  The product obtained by these reactions is processed according to a post-treatment method of a normal organic synthesis reaction, and then used as a product with or without purification. That is, for example, the operation of purifying the product liberated from the reaction system without purification or by recrystallization or column chromatography (for example, gel permeation chromatography (SEPHADEX ™ LH-20: manufactured by Pharmacia) or the like alone or in combination. In addition, after completion of the reaction, the reaction solvent is distilled off or is poured into water or ice without being distilled off, and is neutralized or liberated without being neutralized. After purification, the product can be provided as a product after it has been purified by recrystallization, column chromatography, etc. alone or in combination. Left or put into water or ice without distilling off, and extracted with organic solvent / water solution with or without neutralization Ones without purification, or crystallization, after performing either alone or in combination of purification operations by column chromatography, can be provided as a product.

Of the phthalocyanine dyes represented by the general formula (2) thus obtained, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ are hydrogen, q ₅ , q ₆ , A phthalocyanine compound in which q ₇ and q ₈ are represented by 2 (for example: when t = u = v = w = 1) is usually Ra (SO ₂ -Z ₅ ), Rb (SO ₂ -Z ₆ ), rc _{(SO 2} -Z 7), and a mixture of the following general formula (a) -1~ (a) a compound represented -4 which are isomers with respect to the substitution site of each Rd _(SO 2 -Z ₈₎ Yes.

That is, the compounds represented by the above general formulas (a) -1 to (a) -4 are β-position substituted type (R _{1 to} R ₁₆ in the following general formula (IV) are respectively in the 1st to 16th positions. In the case, a phthalocyanine compound having a specific substituent at the 2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and / or 15 position).

The phthalocyanine dye represented by the general formula (1) of the present invention has a α-position substitution type (1 and / or 4 position, 5 and / or 8 position, 9 and or 12 position, 13 and or 16 position specific substituent Phthalocyanine dyes represented by the general formula (2) are β-position substituted types (2 and 3 position, 6 and or 7 position, 10 and or 11 position, 14 and or 15 position) A phthalocyanine compound having a substituent of In the present invention, in any substitution type, having a specific substituent represented by —SO—Z and / or —SO ₂ —Z is important for good robustness.

  Specific examples of the phthalocyanine dye represented by the general formula (1) or (2) are shown below using the following general formula (IV), but the phthalocyanine dye used in the present invention is limited to the following examples. Is not to be done.

(Example of phthalocyanine dye represented by formula (1))

[Phosphonate compound]
Next, the phosphonate compound will be described.
By containing the phosphonate compound, the coloring composition of the present invention can improve the ejection accuracy, and the redispersibility of the ink in which the water has evaporated after being allowed to stand is good, so that the standstill recovery property of the printer head is ensured. be able to. That is, when the ink for ink jet recording of the present invention is used, cleaning of the printer head after printing, which is necessary when normal ink is used, is unnecessary or the number of times can be reduced.
The present inventors have a dye represented by the general formula (2) having a strong associative property and excellent fastness, and a dye represented by the general formula (1) having a weak associative property and excellent print density, It has been found that by adding a phosphonate compound to the coloring composition, it is possible to obtain a coloring composition that is excellent in storage stability and ejection accuracy and that is excellent in securing the storage stability of the printer head. Although the mechanism of action is unknown, regarding the time-dependent precipitation of the dye in the ink (perhaps a dye represented by the general formula (2) having a strong association), the synergistic effect of the dye represented by the general formula (1) and the phosphonate Since the association and aggregation can be suppressed to a high degree, it is considered that a colored composition with little unevenness of stripes and unevenness of density and high discharge accuracy can be obtained even when exposed to high temperatures for a long time. In addition, according to the present invention, even when the dye represented by the general formula (2) is precipitated, the dye represented by the general formula (1) and the phosphonate compound accelerate the re-dissolution of the precipitate. It is considered that the recoverability of the printer head can be obtained.

  Examples of the phosphonate compound include a sodium salt of aminotri (methylene-phosphonic acid), a sodium salt of hydroxyethylidene diphosphonic acid such as 1-hydroxyethylene-1,1, -diphosphonic acid, a sodium salt of diethylenetriaminepenta (methylenephosphonic acid), And potassium salt of hexamethylenediaminetetra (methylenephosphonic acid) can be preferably used. These phosphonates can be used in any form of phosphonates and phosphonic acids as long as the pH of the final aqueous ink is within a desired range.

The phosphonate compounds are available, for example, as the “DEQUEST®” series from Solutia.
Specifically, Dequest 2016 (1-hydroxyethylene-1,1, -diphosphonic acid tetrasodium salt), which is a sodium salt of an acid represented by the following formula, can be mentioned.

  Moreover, Dequest 2054, which is a potassium salt of hexamethylenediaminetetra (methylenephosphonic acid) represented by the following formula, can be mentioned.

  Furthermore, Dequest 2006 (aminotri (methylenephosphonic acid) pentasodium salt), which is a sodium salt of an acid represented by the following formula, can be mentioned.

In addition, Dequest 2010 (1-hydroxyethylidene-1,1-diphosphonic acid), Dequest 2041 [ethylenediaminetetra (methylenephosphonic acid)], Dequest 2066 [diethylenetriaminepenta (methylenephosphonic acid) 7Na salt], and the like Can do.
In the colored composition of the present invention, only one kind of phosphonate compound may be used, or a plurality of kinds may be mixed and used.

[Compound represented by formula (3)]
Next, the compound (organic monophosphonic acid) represented by the general formula (3) will be described.

(In general formula (3), R represents a group selected from the following 1) or 2).
1) an unsubstituted alkyl group, or an alkyl group substituted with a hydroxyl group, an amino group, a nitro group or a carboxyl group,
2) An unsubstituted phenyl group or a phenyl group substituted with an amino group, an alkyl group or a hydroxyl group. )

By containing the organic monophosphonic acid represented by the general formula (3), the coloring composition of the present invention can improve discharge accuracy and improve image clarity.
The present inventors have a dye represented by the general formula (2) having a strong associative property and excellent fastness, and a dye represented by the general formula (1) having a weak associative property and excellent print density, It has been found that by including an organic monophosphonic acid in a colored composition, a colored composition having excellent ejection accuracy and excellent image clarity can be obtained. Although the mechanism of this action is unknown, the addition of organic monophosphonic acid relaxes the organic monophosphonic acid by acting on the salt exchange reaction, and particularly the solubility of the dye represented by the general formula (2) by salt exchange. By suppressing the decrease, it is considered that there is an effect that foreign matters such as precipitates are not generated, and the ink ejection accuracy is excellent. Also in the printed image, strong association aggregation of the dye represented by the general formula (2) is caused by the dye represented by the general formula (1) (capping effect at the association end) and the organic monophosphonic acid (relaxing effect on salt exchange). It is considered that excellent image clarity is exhibited by achieving high levels of ensuring transparency, suppressing bronze gloss, and suppressing printing unevenness due to inhibition by a synergistic effect.

R in the compound represented by the general formula (3) will be described.
When R represents an unsubstituted alkyl group or an alkyl group substituted by a hydroxyl group, amino group, nitro group or carboxyl group, the unsubstituted alkyl group includes a linear or branched chain or cyclic group Any of an alkyl group may be sufficient, a C1-C6 alkyl group is preferable and a C2-C4 alkyl group is more preferable.
Examples of the linear or branched chain alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, Isopentyl group, tert-pentyl group, sec-pentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethylbutyl group, 2 -Ethylbutyl group, 1-ethyl-2-methylpropyl group, etc. are mentioned.
Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
When R is 1), an unsubstituted alkyl group, or an alkyl group substituted with a hydroxyl group or a carboxyl group is preferred. In this case, the substituent that the alkyl group has is preferably a hydroxyl group or a carboxyl group, and more preferably a carboxyl group.

When R is an unsubstituted phenyl group or a phenyl group substituted with an amino group, an alkyl group or a hydroxyl group, the alkyl group substituted on the phenyl group is preferably an alkyl group having 1 to 6 carbon atoms. And an alkyl group having 2 to 4 carbon atoms is more preferred. Specific examples include those exemplified as the alkyl group when R is 1).
As the substituent substituted on the phenyl group, an alkyl group is preferable.
Specific examples of the compound represented by the general formula (3) when R is 2) include phenylphosphonic acid, methylphenylphosphonic acid, ethylphenylphosphonic acid, butylphenylphosphonic acid, hydroxyphenylphosphonic acid, and aminophenylphosphonic. An acid etc. are mentioned.

  Among the compounds represented by the general formula (3), a compound in which R is an alkyl group substituted with a carboxyl group, an unsubstituted alkyl group, or an unsubstituted phenyl group is preferable.

Specific examples of the compound represented by the general formula (3) include ethylphosphonic acid, n-propylphosphonic acid, i-propylphosphonic acid, n-butylphosphonic acid, t-butylphosphonic acid, phenylphosphonic acid, o -Methyl-phenylphosphonic acid, m-methyl-phenylphosphonic acid, p-methyl-phenylphosphonic acid, o-ethyl-phenylphosphonic acid, m-ethyl-phenylphosphonic acid, p-ethyl-phenylphosphonic acid, ot -Butyl-phenylphosphonic acid, m-t-butyl-phenylphosphonic acid, p-t-butyl-phenylphosphonic acid, p-hydroxy-phenylphosphonic acid, m-hydroxy-phenylphosphonic acid, o-hydroxy-phenylphosphonic acid 2,2-dimethylpropylphosphonic acid, cyclohexylphosphonic acid, n-hexylphosphonic acid Acid, o-aminophenylphosphonic acid, m-aminophenylphosphonic acid, p-aminophenylphosphonic acid, and those having the following structure (referred to as phosphonic acid A).
Among these, phenylphosphonic acid, ethylphosphonic acid, n-propylphosphonic acid, phosphonic acid A or n-butylphosphonic acid is preferable, and phenylphosphonic acid, ethylphosphonic acid or phosphonic acid A is more preferable.

  In the colored composition of the present invention, only one type of compound represented by the general formula (3) may be used, or a plurality of types may be mixed and used.

(Coloring composition)
The coloring composition of the present invention comprises a phthalocyanine dye represented by the above general formula (1), a phthalocyanine dye represented by the above general formula (2), and a phosphonate compound or an organic material represented by the above general formula (3). Monophosphonic acid. A dye represented by the general formula (2) having a strong associative property and excellent fastness, a dye represented by the general formula (1) having a weak associative property and excellent print density, and a phosphonate compound or the above general formula By including the organic monophosphonic acid represented by (3) in the coloring composition, it is possible to obtain a coloring composition having excellent discharge accuracy.
The colored composition of the present invention can be preferably used as a colored composition for image formation. Applications of the colored composition of the present invention include image recording materials for forming images, particularly color images, and specifically, thermal transfer type images including ink jet recording materials described in detail below. Recording materials, pressure-sensitive recording materials, recording materials using electrophotographic methods, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc., preferably ink-jet recording materials, thermal transfer type image recording materials, electrophotographic methods In particular, an ink jet recording material is preferable. Further, it can also be applied to dyeing solutions for dyeing various fibers of color filters used in solid-state imaging devices such as LCDs and CCDs described in US Pat. No. 4,808,501 and JP-A-6-35182. . The phthalocyanine dye used in the present invention is used by adjusting physical properties such as solubility and heat transfer properties suitable for the intended use with a substituent. The phthalocyanine dye used in the present invention can be used in a uniform dissolved state or a dispersed dissolved state such as an emulsified dispersion depending on the system used.

  In the coloring composition, the mass ratio of the phthalocyanine dye represented by the general formula (1) and the phthalocyanine dye represented by the general formula (2) is preferably 50/50 to 10/90, and 40/60 ~ 20/80 is more preferred. By making the mass ratio of the dye within the above range, the colored composition is excellent in stability over time (viscosity change, precipitation, etc.) at a high concentration, and is excellent in ozone fastness of a print sample using the colored composition. Further, it is possible to obtain a feature that the print density is excellent.

  Moreover, it is preferable that content of the phthalocyanine dye represented by General formula (1) is 0.1-10 mass% in a coloring composition. If it is 0.1% by mass or more, the color composition is excellent in stability over time and printing density at a high concentration, and if it is 10% by mass or less, the printing sample is excellent in ozone fastness.

  The addition amount of the phosphonate compound in the present invention is preferably in the range of 0.05% by mass or more and 0.8% by mass or less, and 0.1% by mass or more with respect to the total mass of the colored composition, from the viewpoint of dissolution stability. 0.6 mass% or less is more preferable, and 0.3 mass% or more and 0.5 mass% or less is still more preferable.

  In the colored composition of the present invention, the content of the compound represented by the general formula (3) is 0 based on the total mass of the colored composition in terms of discharge accuracy of the colored composition and image clarity of the printed material. 0.01 to 0.25% by mass is preferable, 0.05 to 0.2% by mass is more preferable, and 0.1 to 0.2% by mass is even more preferable.

  Moreover, in this invention, mass ratio of the sum total of the phthalocyanine dye represented by General formula (1) and General formula (2) in a coloring composition, and a phosphonate compound is 500/1-25/4. Is more preferable, 500/1 to 25/2 is more preferable, 500/1 to 20/1 is further preferable, 100/1 to 25/1 is particularly preferable, and 50/1 to 25 is preferable. / 1 is most preferred. Further, in the colored composition, the mass ratio of the sum of the phthalocyanine dyes represented by the general formula (1) and the general formula (2) to the organic monophosphonic acid represented by the general formula (3) is 500/1 to 1. It is preferably 25/4, more preferably 100/1 to 25/4, still more preferably 50/1 to 25/3, and particularly preferably 50/3 to 10/1. . By making the mass ratio of the dye within the above range, even after storage for a long period of time or after being exposed to high temperature, the occurrence of density unevenness and streak unevenness is suppressed, so that storage stability is excellent, and the discharge accuracy, Excellent image clarity and excellent printer head retention recovery.

[Surfactant]
The coloring composition of the present invention can contain a surfactant. Examples of the surfactant used in the present invention include anionic surfactants such as fatty acid salts, higher alcohol ester salts, alkylbenzene sulfonate salts, sulfosuccinic acid ester salts, higher alcohol phosphoric acid ester salts, aliphatic amine salts, 4 Nonionic surfactants such as cationic surfactants such as quaternary ammonium salts, ethylene oxide adducts of higher alcohols, ethylene oxide adducts of alkylphenols, polyhydric alcohol fatty acid esters, acetylene glycol and its ethylene oxide adducts And amphoteric surfactants such as amino acid type and betaine type, fluorine-based compounds, and silicon-based compounds. These may be used alone or in combination of two or more.

By adding a surfactant to the coloring composition of the present invention and adjusting the liquid physical properties of the ink such as surface tension, the ink ejection stability is improved, the water resistance of the image is improved, and the printed ink bleeds. It is possible to have an excellent effect in prevention and the like. Further, two or more kinds of the above surfactants may be used in combination.
The coloring composition used in the present invention preferably contains 0.005 to 5 mass% of a surfactant, more preferably 0.005 to 3 mass%. When the content of the surfactant in the coloring composition is in the range of 0.005 to 5% by mass, the discharge stability is not lowered, the occurrence of bleeding at the time of color mixing, the printing quality is not lowered such as the generation of whiskers, At the time of ejection, it is possible to suppress printing defects due to adhesion of ink to the periphery of the nozzle.

[Ink for inkjet recording]
Next, the ink for inkjet recording of the present invention will be described. The ink for inkjet recording of the present invention contains the above colored composition. The ink for inkjet recording can be produced by dissolving and / or dispersing the phthalocyanine compound 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 the 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.

  In the ink for ink jet recording of the present invention, the phosphonate compound or the organic monophosphonic acid represented by the general formula (3) may be used alone or in combination.

  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 penetration enhancers, alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, nonionic surfactants, etc. 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, Nos. VII to I, J; 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 so that the ink for ink jet recording has a pH of 6 to 10, and more preferably added to have a pH of 7 to 10. 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-59-157636, 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 phthalocyanine 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, it is possible to disperse colored fine particles containing a dye and an oil-soluble polymer in an aqueous medium, or to each specification of Japanese Patent Application Nos. 2000-78454, 2000-78491, 2000-203856, and 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. Alternatively, the phthalocyanine compound may be dispersed in a fine particle state as 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 inkjet recording ink of the present invention, the phthalocyanine compound is preferably contained in an amount of 0.2 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less. More preferred are those containing from 5 parts by weight to 5 parts by weight, and most preferred are those containing from 4 parts by weight to 5 parts by weight. In addition, in the inkjet ink of the present invention, other pigments may be used in combination with the phthalocyanine 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 40 cp or less. The surface tension is preferably 20 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 and 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 and 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]
The present invention also relates to an ink jet recording method using the ink for ink jet recording according to the present invention. In the ink jet recording method of the present invention, energy is supplied to the ink for ink jet recording, and a known image receiving material, that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153989, JP-A-10-217473, JP-A-10-235995 10-337947, 10-217597, 10-337947, etc. Form images on inkjet paper, film, electrophotographic co-paper, fabric, glass, metal, ceramics, etc. To do.

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.
A preferred combination of a recording material and a recording method is an inkjet recording in which an image receiving material having an image receiving layer containing white inorganic pigment particles on a support is ejected with ink droplets according to a recording signal, and an image is recorded on the image receiving material. Is the method.

  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.

[Ink cartridge for ink jet recording and ink jet recorded matter]
The ink cartridge for ink jet recording of the present invention is filled with the ink for ink jet recording of the present invention described above. Further, the ink-jet recorded matter of the present invention is obtained by forming a colored image on a recording material using the above-described ink for ink-jet recording of the present invention.

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 resistance 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, 62-1316648, 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 present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

(Synthesis example)
Hereinafter, the synthesis method of the phthalocyanine dye derivative of the present invention will be described in detail in Examples, but the starting material, the dye intermediate and the synthesis route are not limited.

  The phthalocyanine compound of the present invention can be derived from, for example, the following synthetic route. In the following examples, λmax is the absorption maximum wavelength, and εmax is the molar extinction coefficient at the absorption maximum wavelength.

Synthesis Example 1: Synthesis of Compound (A) In a nitrogen stream, 26.0 g of 4-nitrophthalonitrile (Tokyo Kasei) was dissolved in 200 mL of DMSO (dimethyl sulfoxide) and stirred at an internal temperature of 20 ° C. 30.3 g of sodium 3-mercapto-propane-sulfonate (Aldrich) was added. Subsequently, 24.4 g of anhydrous sodium carbonate was gradually added to the mixture being stirred at an internal temperature of 20 ° C. While stirring the reaction solution, it was heated to 30 ° C. and stirred at the same temperature for 1 hour. After cooling to 20 ° C., the reaction solution is filtered with Nutsche, the filtrate is poured into 15000 mL of ethyl acetate for crystallization, and subsequently stirred at room temperature for 30 minutes, and the precipitated crude crystals are filtered with Nutsche, and ethyl acetate is filtered. Washed with and dried. The obtained crude crystals were recrystallized from methanol / ethyl acetate to obtain 42.5 g of Compound A. ¹ H-NMR (DMSO-d6), δ value TMS standard: 1.9 to 2.0 (2H, t); 2.5 to 2.6 (2H, m); 3.2 to 3.3 (2H , T); 7.75 to 7.85 (1H, d); 7.93 to 8.03 (1H, d); 8.05 to 8.13 (1H, s)

Synthesis Example 2: Synthesis The compounds of 42.0g of compound (B) (A) was dissolved in acetic acid 300 mL, the resultant mixture was stirred at an internal temperature of 20 ° C., 2.5 g of _Na 2 _WO 4 · _2H 2 O Then, the mixture was cooled to an internal temperature of 10 ° C. in an ice bath. Subsequently, 32 mL of hydrogen peroxide (30%) was gradually added dropwise while paying attention to heat generation. After stirring at an internal temperature of 15 to 20 ° C. for 30 minutes, the reaction solution was heated to an internal temperature of 60 ° C. and stirred at the same temperature for 1 hour. After cooling to 20 ° C., 1500 mL of ethyl acetate was poured into the reaction solution, followed by stirring at the same temperature for 30 minutes, and then the precipitated crude crystals were filtered with Nutsche, washed with 200 mL of ethyl acetate, and dried. The obtained crude crystals were purified by heating and washing with methanol / ethyl acetate to obtain 40.0 g of Compound B. ¹ H-NMR (DMSO-d6), δ value TMS standard: 1.8 to 1.9 (2H, t); 2.4 to 2.5 (2H, m); 3.6 to 3.7 (2H , T); 8.3-8.4 (1H, d); 8.4-8.5 (1H, d); 8.6-8.7 (1H, s)

Synthesis Example 3: Synthesis of Exemplified Compound 102β (Dye 1A of General Formula (1)) To a three-necked flask equipped with a cooling tube, 70 mL of n-amyl alcohol was added, and 6.7 g of compound B and copper (II) chloride 1 were added thereto. 0.0 g was added and 7.0 mL of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) was added dropwise at room temperature with stirring. Subsequently, the reaction solution was heated to an internal temperature of 100 ° C. and stirred at the same temperature for 10 hours. After cooling to 40 ° C., 250 mL of heated methanol at 50 ° C. was poured and stirred for 1 hour under reflux. Next, after cooling the reaction liquid to room temperature, the obtained solid was filtered with Nutsche and washed with 200 mL of methanol. Subsequently, the obtained solid was added to 100 mL of 1M aqueous hydrochloric acid saturated with sodium chloride, and the unreacted copper salt was dissolved. After filtering insoluble matter, 300 mL of methanol was added dropwise to the filtrate for crystallization, and the resulting crude crystals were filtered with Nutsche and washed with 200 mL of methanol. After the crude crystals were dissolved in 50 mL of water, 100 mL of a saturated methanol solution of sodium acetate was gradually added while stirring the aqueous solution to form a salt. Further, the mixture was heated to the reflux temperature while stirring and stirred at the same temperature for 1 hour. After cooling to room temperature, the precipitated crystals were filtered and washed with methanol. Subsequently, the obtained crystal was added to 100 mL of 80% methanol, stirred for 1 hour under reflux, and cooled to room temperature. Then, the precipitated crystal was filtered, and further, the obtained crystal was added to 100 mL of 70% aqueous methanol solution. After stirring at reflux for an hour and cooling to room temperature, the precipitated crystals were filtered, washed with 100 mL of methanol and dried to give 3.8 g of exemplary compound 102β as blue crystals.
λmax (absorption maximum wavelength): 629.1 nm; εmax (molar extinction coefficient at absorption maximum wavelength) = 6.19 × 10 ⁴ (in aqueous solution). As a result of analyzing the obtained compound (measured by various instrumental analysis methods such as mass spectrometry: ESI-MS, elemental analysis, neutralization titration), the phthalocyanine copper (II) -substitution position defined in this specification is β-position substitution type {(2- or 3-position), (6- or 7-position), (10- or 11-position), (14- or 15-position) of each benzene nucleus at — {SO ₂ — (CH ₂ ) ₃ It was confirmed that one —SO ₃ Na} group was included and one copper phthalocyanine molecule had — {SO ₂ — (CH ₂ ) ₃ —SO ₃ Na} groups in total}.

<Examples using phosphonate compounds>
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 NaOH 10 mol / L, and filtered under reduced pressure with a microfilter having an average pore size of 0.25 μm to prepare an ink solution for cyan.

Phthalocyanine dye (Compound 1A) 0.5g
Phthalocyanine dye (compound 2B) 4.5 g
Phosphonate compound (Daiquest 2016 (Compound 3A)) 0.4 g
Diethylene glycol 2g
Glycerin 12g
Diethylene glycol monobutyl ether 23g
2-pyrrolidone 8g
1.79 g of triethanolamine
Benzotriazole 0.006g
Surfynol TG 0.85g
PROXEL XL2 0.18g

(Examples 2-36, Comparative Examples 1-6)
Except for changing the type and addition amount of the dye, and the type and addition amount of the phosphonate compound as shown in Tables 17 and 18 below, Examples 2 to 36 and Ink liquids of Comparative Examples 1 to 6 were prepared.

<Image recording and evaluation>
The following evaluation was performed about the ink liquid of each of the above Examples (Examples 1 to 36) and Comparative Examples (Comparative Examples 1 to 6). The results are shown in Tables 17 and 18.

(Discharge accuracy evaluation)
As the ink jet recording apparatus, an ink jet printer (trade name: PIXUS iP8600; manufactured by Canon Inc.) was used. A photo gloss film HG201 manufactured by Canon Inc. was used as a recording medium. Using the inks of the examples and comparative examples as inks for inkjet recording, the distance between the lines at a site of 5 cm from the droplet ejection start part of the print sample was measured with a dot analyzer EDA-6000 manufactured by Oji Scientific Instruments, and its standard deviation Was calculated, and the direction accuracy of ejection was evaluated according to the following criteria.

<Evaluation criteria>
A: Standard deviation is less than 3 μm B: Standard deviation is 3 μm or more and less than 4 μm C ... Standard deviation is 4 μm or more and less than 5 μm D ... Standard deviation is 5 μm or more

(Ink storage stability)
Each colored composition was put in a PET container, sealed, and stored in a constant temperature bath at 60 ° C. for 14 days, and the viscosity and spectral absorption after storage were measured. Further, the viscosity and spectral absorption of the ink before storage were measured by the same method. The viscosity was measured with an R100 viscometer (manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and a cone rotation speed of 20 to 100 rpm. Spectral absorption was measured by using V-570 (manufactured by JASCO Corporation), diluting the ink 2000 times with ultrapure water, using a quartz cell and ultrapure water as a control, and measuring the change in absorbance around 500 nm. Compared. The stability of the ink was evaluated according to the following evaluation criteria using the measured value as an index.

<Evaluation criteria>
AA: Both changes in viscosity and absorbance were less than ± 5% of the values before storage.
A: Both the viscosity and absorbance change were ± 5% or more and less than 10% of the values before storage.
B: The value of either viscosity or absorbance change was ± 10% or more of the value before storage.
C: Both viscosity and absorbance change were ± 10% or more of the values before storage.

(Leave recovery test)
As an ink jet recording apparatus, an ink jet printer BJ-F850 (manufactured by Canon Inc.) was used.
Using the ink liquids of the examples and comparative examples as inks for ink jet recording, after confirming that printing can be performed normally, leave the ink in an environment of 23 ° C. and 50% RH for 6 weeks, and print the recovery operation by head cleaning normally. Repeatedly until possible, recovery was recorded and evaluated according to the following criteria.

<Evaluation criteria>
A: Recovery after 1 time B: Recovery after 2-4 times C: Recovery after 5 times

  From the results shown in Tables 17 and 18, when the ink of the present invention is used for inkjet recording, density unevenness and streak unevenness are generated even after storage for a long period of time or after exposure to high temperatures, as compared with Comparative Examples. Is suppressed, the storage stability is excellent, the ejection accuracy is excellent, and the printer head is left to recover.

  The structures of the compounds used in the examples are shown below.

Compound 3A: Day Quest 2016
Compound 3B: Day Quest 2054
Compound 3C: Day Quest 2006

<Examples using organic monophosphonic acid>
(Example 101)
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 NaOH 10 mol / L, and filtered under reduced pressure with a microfilter having an average pore size of 0.25 μm to prepare an ink solution for cyan.

Phthalocyanine dye (Compound 1A) 0.5g
Phthalocyanine dye (compound 2B) 4.5 g
Phenylphosphonic acid (compound 4A) 0.1 g
Diethylene glycol 2g
Glycerin 12g
Diethylene glycol monobutyl ether 23g
2-pyrrolidone 8g
1.79 g of triethanolamine
Benzotriazole 0.006g
Surfynol TG 0.85g
PROXEL XL2 0.18g

(Examples 102 to 136, Comparative Examples 101 to 106)
Examples 102 to 136 were the same as the preparation of the ink liquid of Example 101, except that the type and addition amount of the dye and the type and addition amount of the organic monophosphonic acid were changed as shown in Tables 19 and 20 below. Ink liquids of Comparative Examples 101 to 106 were prepared.

<Image recording and evaluation>
The following evaluation was performed on the ink jet inks of the above Examples (Examples 101 to 136) and Comparative Examples (Comparative Examples 101 to 113). The results are shown in Tables 19 and 20.

(Discharge accuracy evaluation)
As the ink jet recording apparatus, an ink jet printer (trade name: PIXUS iP8600; manufactured by Canon Inc.) was used. A photo gloss film HG201 manufactured by Canon Inc. was used as a recording medium. The distance between the lines 5 cm from the droplet ejection start part of the print sample was measured with a dot analyzer EDA-6000 manufactured by Oji Scientific Instruments, its standard deviation was calculated, and the ejection direction accuracy was evaluated according to the following criteria.

<Evaluation criteria>
A: Standard deviation is less than 3 μm B: Standard deviation is 3 μm or more and less than 4 μm C ... Standard deviation is 4 μm or more and less than 5 μm D ... Standard deviation is 5 μm or more

(Image clarity evaluation)
As the ink jet recording apparatus, an ink jet printer (trade name: PIXUS iP8600; manufactured by Canon Inc.) was used. A photo glossy film HG201 manufactured by Canon Inc. was used as a recording medium to obtain an ink jet recorded product. Based on the test method defined in JIS H8866-2, the image clarity C value (%) of the ink jet recorded material was measured based on the test method defined in JIS H8866-2 using a image clarity measuring device ICM-1 (manufactured by Suga Test Instruments Co., Ltd.) Was measured. The image clarity C value (%) is calculated for each optical comb by the following formula a, and the sum of image clarity is obtained by adding the image clarity C value of each optical comb, according to the following evaluation criteria. evaluated.
Image clarity C value (%) = {(M−m) / (M + m)} × 100 Expression a
<Measurement conditions>
Measurement angle: 60 degrees Optical comb: 2.0 mm, 1.0 mm, 0.5 mm, 0.25 mm, 0.125 mm
<Evaluation criteria>
AA: Sum of image clarity is 100 or more A: Sum of image clarity is 70 or more and less than 100 B: Sum of image clarity is 40 or more and less than 70 C: Sum of image clarity is less than 40

Compound 4A: Phenylphosphonic acid Compound 4B: Ethylphosphonic acid Compound 4C: Phosphonic acid A having the following structure

  From the results shown in Tables 19 and 20, when the ink of the present invention was used for inkjet recording, it was superior in ejection accuracy and image clarity as compared with the comparative example.

Claims (21)

A coloring composition comprising a phthalocyanine dye represented by the following general formula (1) and a phthalocyanine dye represented by the following general formula (2),
Furthermore, the coloring composition containing the organic monophosphonic acid represented by a phosphonate compound or following General formula (3).

In general formula (1),
R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl 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, sulfonamide group, carbamoyl group, sulfamoyl 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, an acyl group or an ionic hydrophilic group. These groups may further have a substituent.
Z ₁ , Z ₂ , Z ₃ and Z 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. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent.
l, m, n, p, q ₁ , q ₂ , q ₃ and q ₄ each independently represent 1 or 2.
M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
General formula (2):

In general formula (2),
R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl 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, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group , Heterocyclic thio group, phosphoryl Represents an acyl group or an ionic hydrophilic group. These groups may further have a substituent.
Z ₅ , Z ₆ , Z ₇ and Z ₈ 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. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₅ , Z ₆ , Z ₇ , and Z ₈ has an ionic hydrophilic group as a substituent.
t, u, v, w, q ₅ , q ₆ , q ₇ and q ₈ each independently represent 1 or 2.
M ₂ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.

(In general formula (3), R represents a group selected from the following 1) or 2).
1) an unsubstituted alkyl group, or an alkyl group substituted with a hydroxyl group, amino group, nitro group or carboxyl group,
2) An unsubstituted phenyl group or a phenyl group substituted with an amino group, an alkyl group or a hydroxyl group. ) The coloring composition according to claim 1, wherein R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ in the phthalocyanine dye represented by the general formula (2) are hydrogen atoms. . Z ₅ , Z ₆ , Z ₇ and Z ₈ in the phthalocyanine dye represented by the general formula (2) are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. The colored composition according to claim 1 or 2, which represents a substituted heterocyclic group. In the phthalocyanine dye represented by the general formula (2), Z ₅ , Z ₆ , Z ₇ , and Z ₈ represent a substituted alkyl group, and at least one of the substituents of the alkyl group is a —SONHR group (where R is a substituted group). Or a substituted or unsubstituted phenyl group). The colored composition according to any one of claims 1 to 3.   The coloring composition according to any one of claims 1 to 4, wherein t, u, v and w in the phthalocyanine dye represented by the general formula (2) are 1. The colored composition according to claim 1, wherein q ₅ , q ₆ , q ₇ and q ₈ in the phthalocyanine dye represented by the general formula (2) are 2. The R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ in the phthalocyanine dye represented by the general formula (1) are hydrogen atoms. The coloring composition according to item. Z ₁ , Z ₂ , Z ₃ and Z ₄ in the phthalocyanine dye represented by the general formula (1) are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. The colored composition according to any one of claims 1 to 7, which represents a substituted heterocyclic group.   The coloring composition according to claim 1, wherein l, m, n, and p in the phthalocyanine dye represented by the general formula (1) are 1. The colored composition according to claim ₁ , wherein q ₁ , q ₂ , q ₃ and q ₄ in the phthalocyanine dye represented by the general formula (1) are 2.   The mass ratio of the phthalocyanine dye represented by the general formula (1) and the phthalocyanine dye represented by the general formula (2) is 50/50 to 10/90. Coloring composition.   The coloring composition according to any one of claims 1 to 11, wherein the content of the phthalocyanine dye represented by the general formula (1) is 0.1 to 10% by mass.   The phosphonate compound comprises a sodium salt of aminotri (methylene-phosphonic acid), a sodium salt of hydroxyethylidene diphosphonic acid, a sodium salt of diethylenetriaminepenta (methylenephosphonic acid), and a potassium salt of hexamethylenediaminetetra (methylenephosphonic acid). The coloring composition according to claim 1, which is at least one selected from the group consisting of:   The colored composition according to any one of claims 1 to 13, wherein a content of the phosphonate compound is 0.05% by mass or more and 0.8% by mass or less based on the total mass of the colored composition.   The coloring composition according to any one of claims 1 to 12, wherein, in the general formula (3), R is an alkyl group substituted with a carboxyl group, an unsubstituted alkyl group, or an unsubstituted phenyl group. object.   The coloring composition of any one of Claims 1-12 and 15 which contains 0.01-0.25 mass% of compounds represented by the said General formula (3) on the basis of coloring composition total mass. object.   The mass ratio of the total amount of the phthalocyanine dyes represented by the general formula (1) and the general formula (2) and the phosphonate compound or the compound represented by the general formula (3) is 500/1 to 25/4. The coloring composition of any one of Claims 1-16.   Ink for inkjet recording containing the coloring composition of any one of Claims 1-17.   An ink jet recording method using the ink for ink jet recording according to claim 18.   An ink cartridge filled with the ink jet recording ink according to claim 18.   An ink-jet recorded matter in which a colored image is formed on a recording material using the ink-jet recording ink according to claim 18.