JP2007277416A - New porphyrazine pigment, ink, ink set, inkjet recording method using this ink or ink set, colored article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a porphyrazine pigment which is suitable for inkjet recording having a good color tone as cyan ink, has good light resistance and ozone resistance, does not cause a bronze phenomenon. <P>SOLUTION: This porphyrazine pigment represented by formula (1) (A, B, C, D are each an aromatic six-membered ring; E is an alkylene; R<SB>1</SB>and R<SB>2</SB>are each a hydroxyalkyl or the like; X and Y are each a substituted anilino group or a substituted naphthyl group) and its salt. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a novel porphyrazine coloring matter, an ink, an ink set, an ink jet recording method using the ink or the ink set, and a colored body.

In recent years, a material for forming a color image has been mainly used as an image recording material. Specifically, an inkjet recording material, a thermal transfer type image recording material, a recording material using an electrophotographic system, a transfer type halogen, and the like. Silver halide photosensitive materials, printing inks, recording pens and the like are actively used. In addition, color filters are used in electronic parts such as LCDs (liquid crystal displays) and PDPs (plasma display panels) in displays and CCDs (imaging elements) in imaging equipment. In these color image recording materials and color filters, three primary colors (dyes and pigments) of the so-called additive color mixing method and subtractive color mixing method are used to reproduce or record a full color image. In fact, there is no dye having an absorption characteristic that can realize the above-mentioned characteristics and can withstand various use conditions, and improvement is strongly desired.

The ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording. Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. There are a method for discharging bubbles, a method for generating bubbles in ink by discharging heat, a method for discharging droplets, a method using ultrasonic waves, a method for sucking and discharging droplets by electrostatic force, and the like. Examples of inks suitable for inkjet recording include water-based inks, oil-based inks, and solid (melting type) inks.

For dyes used in inks suitable for such ink jet recording, the solvent has good solubility or dispersibility, high-density recording is possible, and both monochromatic and mixed colors have good hue. Being strong against light, heat, and active gases in the environment (SOx, etc. in addition to oxidizing gases such as NOx and ozone), having excellent durability against water and chemicals, and recording materials It is required that the toner has good fixability and is difficult to bleed, has excellent storability as an ink, has no toxicity, and can be obtained at low cost. In particular, it has a good cyan hue, is excellent in light resistance (durability against light), ozone resistance (durability against ozone gas) and moisture resistance (durability under high humidity), and is also called bronzing phenomenon (bronzing phenomenon) Cyan dyes that do not cause) are strongly desired. The bronze phenomenon refers to a phenomenon in which pigments aggregate on the surface of glossy paper or the like due to association or aggregation of pigments or poor absorption of ink in the medium, resulting in a metallic luster and glare. When this phenomenon occurs, the glossiness, print quality, and print density are all inferior.

Typical skeletons of water-soluble cyan dyes used in inks suitable for ink jet recording are phthalocyanine and triphenylmethane. Typical phthalocyanine dyes reported and used most widely include phthalocyanine derivatives classified as A to H below.

A: C.I. I. Direct Blue 86, C.I. I. Direct Blue 87, C.I. I. Direct Blue 199, C.I. I. Acid Blue 249 or C.I. I. Known phthalocyanine dyes such as Reactive Blue 71

B: phthalocyanine-based dyes described in Patent Documents 1 to 3 and the like [for _{example, Cu-Pc- (SO 3 Na} ) m (SO 2 NH 2) n: a mixture of m + n = 1 to 4]

C: phthalocyanine-based coloring matter described in Patent Literature 4 and the like [for _{example, Cu-Pc- (CO 2 H} ) m (CONR 1 R 2) n: m + n = 0~4 number]

D: phthalocyanine-based coloring matter described in Patent Literature 5 and the like [for _{example, Cu-Pc- (SO 3 H} ) m (SO 2 NR 1 R 2) n: m + n = 0~4 number, and, m ≠ 0]

E: phthalocyanine-based coloring matter described in Patent Literature 6 and the like [for _{example, Cu-Pc- (SO 3 H} ) l (SO 2 NH 2) m (SO 2 NR 1 R 2) n: l + m + n = 0~4 number]

F: phthalocyanine-based coloring matter described in Patent Literature 7 and the like [for _{example, Cu-Pc- (SO 2 NR} 1 R 2) n: n = number of 1 to 5]

G: phthalocyanine dyes described in Patent Documents 8, 9, 12, etc. [phthalocyanine compounds in which the substitution positions of substituents are controlled, phthalocyanine dyes having substituents introduced in the β-position]

H: Benzopyridoporphyrazine-based dye having a pyridine ring and a benzene ring described in Patent Documents 10, 13, 14, etc.

Currently widely used, C.I. I. Direct Blue 86 or C.I. I. A phthalocyanine dye represented by Direct Blue 199 has a feature that it is excellent in light resistance as compared with a generally known magenta dye or yellow dye. Phthalocyanine-based dyes have a greenish hue under acidic conditions, which is not preferable for cyan ink. Therefore, when these dyes are used as cyan ink, they are preferably used under neutral to alkaline conditions. However, even if the ink is neutral to alkaline, the hue of the printed matter may change greatly if the recording material used is acidic paper.

In addition, nitric oxide gas, ozone, and other oxidizing gases, which are often taken up as environmental problems in recent years, cause the green color to change and disappear, and at the same time, the print density decreases.

On the other hand, the triphenylmethane series has a good hue, but is very inferior in light resistance, ozone resistance and moisture resistance.

In the future, if the field of use expands and is widely used for exhibitions such as advertisements, it is often exposed to light and active gases in the environment, so it has particularly good hue, light resistance and There is a growing demand for pigments and inks that are excellent in resistance to active gases (NOx, oxidizing gases such as ozone, SOx, etc.), moisture resistance, and inexpensive. However, it is difficult to develop cyan dyes (for example, phthalocyanine dyes) and cyan inks that satisfy these requirements at a high level. So far, phthalocyanine dyes imparted with active gas resistance have been disclosed in Patent Documents 3, 8-12, 14 and the like, but all such as hue, light resistance, ozone resistance, moisture resistance and bronzing are not caused. However, a cyan dye and a cyan ink that satisfy the quality of the above and can be produced at low cost have not been obtained yet. Therefore, it has not yet fully satisfied the demands of the market.

JP 62-190273 A JP-A-7-138511 JP 2002-105349 A Japanese Patent Laid-Open No. 5-171085 Japanese Patent Laid-Open No. 10-140063 Special table hei 11-515048 JP 59-22967 JP 2000-30309 A JP 2002-249677 JP 2003-34758 A JP 2002-80762 A WO2004087815 WO2002034844 JP 2004-75986 A

The present invention provides a novel porphyrazine coloring matter that solves the above problems, has a good hue as a cyan ink, is excellent in light resistance, ozone resistance and moisture resistance, and does not cause bronzing. It is an object to provide an ink suitable for ink jet using the porphyrazine coloring matter and an ink jet recording method.

The present inventors have studied in detail porphyrazine dyes having a good hue, high light resistance and ozone resistance, and causing no bronzing phenomenon. As a result, specific porphyrazine dyes are used as ink dyes. As a result, it has been found that the above-mentioned problems can be solved, and the present invention has been completed. That is, the present invention
(1)
Porphyrazine dye represented by the following formula (1) or a salt thereof,

[In the formula (1), A, B, C and D independently represent a 6-membered ring having aromaticity, at least one is a benzene ring, and at least one contains a nitrogen-containing heteroaromatic ring. E represents alkylene, and R ₁ and R ₂ each independently represents an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group, a hydroxyalkoxyalkoxyalkyl group, or a hydrogen atom. However, the case where R ₁ and R ₂ are hydrogen atoms at the same time is excluded. X and Y are each independently an anilino group (sulfo group, carboxyl group, phosphono group, carbamoyl group, sulfamoyl group, ureido group, alkyl group, alkoxy group, allyloxy group, hydroxyl group, dialkylamino group, alkylamino group, arylamino group. Group, acetylamino group, cyano group, nitro group, halogen atom, or 0 to 4 substituents selected from two or more kinds selected from a heterocyclic group) or a naphthylamino group (sulfo group). , A carboxyl group, a ureido group, an alkyl group, an alkoxyl group, a hydroxyl group, a dialkylamino group, an alkylamino group, an arylamino group, an acetylamino group, a cyano group, a nitro group, a halogen atom, a heterocyclic group, or 0 to 4 substituents may be used.) Further, at least one of X and Y is a group having a sulfo group or a carboxyl group as a substituent. Also, b is 0 to 2.9, c is 0.1 to 3, and the sum of b and c is 1 to 3. ]
(2)
The porphyrazine coloring matter or salt thereof according to (1), wherein the nitrogen-containing heteroaromatic ring corresponding to A, B, C, D is a pyridine ring or a pyrazine ring,
(3)
(1) or (2) obtained by reacting a porphyrazine dye represented by the following formula (3) with an amine represented by the following formula (4) in the presence of an amine represented by the following formula (10) ) Porphyrazine coloring matter or a salt thereof,

[In Formula (3), A, B, C, D represents the same meaning as described in (1). N is 1 to 3. ]

[In Formula (4), E, X, and Y represent the same meaning as described in (1). ]

[In Formula (10), R ₁ and R ₂ represent the same meaning as described in (1). ]
(4)
The amine represented by the formula (4) described in (3) is used in an amount of 0.5 to 4 molar equivalents of (3) with respect to 1 molar equivalent of the porphyrazine dye represented by the formula (3) described in (3). Porphyrazine coloring matter or a salt thereof according to (3) obtained by reacting in the range of pH 6 to 10 in the reaction system in the presence of an amine represented by formula (10) according to
(5)
The number of pyridine rings or pyrazine rings corresponding to A, B, C and D is 1 to 3, E represents C2 to C4 alkylene, and X and Y are each independently an anilino group, a sulfo-substituted anilino group A carboxyl-substituted anilino group, a phosphono-substituted anilino group, a naphthylamino group, a sulfo-substituted naphthylamino group or a carboxy-substituted naphthylamino group, and the substituted anilino group and the substituted naphthylamino group are a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group. , An alkoxy group, a ureido group, an acetylamino group, a nitro group, and 0 to 2.9 substituents having one or more substituents selected from the group consisting of a chlorine atom and b may be from 0 to 2.9. The porphyrazine coloring matter or a salt thereof according to (2), wherein c is 0.1 to 3 and the sum of b and c is 1 to 3,
(6)
E represents ethylene or propylene, X and Y are each independently a sulfo-substituted anilino group, a carboxyl-substituted anilino group or a sulfo-substituted naphthylamino group, b is from 0 to 2.9, and c is 0.1 Or a porphyrazine dye or a salt thereof according to (4), wherein the sum of b and c is 1 to 3;
(7)
A is a pyridine ring condensed at the 2-position and 3-position or 3-position and 4-position or a pyrazine ring condensed at the 2-position and 3-position, and B is condensed at the 2-position and 3-position or 3-position and 4-position Pyridine ring or pyrazine ring or benzene ring condensed at the 2-position and 3-position, and C is condensed at the 2-position, 3-position, 3-position and 4-position, or pyridine ring or 2-position and 3-position A pyrazine ring or a benzene ring, D is a benzene ring, E is a C2-C4 alkylene, and X and Y are each independently a sulfo group, a carboxy group, a methoxy group, a nitro group, a chlorine atom, a hydroxy group. The anilino group or naphthylamino group having 1 to 3 substituents selected from the group consisting of: b is 0 to 2.9, and c is 0.1 to 3, Porphyrazine dye or a salt thereof,
(8)
The porphyrazine coloring matter or salt thereof according to (1) or (2) represented by the following formula (2):

[In Formula (2), Z ₁ to Z ₈ each independently represents a nitrogen atom or a carbon atom. However, at least one of the combinations of Z ₁ and Z ₂ , Z ₃ and Z ₄ , Z ₅ and Z ₆ , and Z ₇ and Z _{8 is} a combination of carbon atoms. E, X, Y, b and c have the same meaning as described in (1). ]
(9)
A porphyrazine dye represented by the following formula (5) and an amine represented by the formula (4) described in (3) are reacted in the presence of the amine represented by the formula (10) described in (3). Porphyrazine coloring matter or a salt thereof according to (8) obtained by

[In formula (5), Z ₈ from Z ₁ have the same meanings as those described in (7). N is 1 to 3. ]
(10)
0.5 mol to 4 mol equivalent of amine represented by formula (4) according to (3) with respect to 1 mol equivalent of porphyrazine dye represented by formula (5) according to (9) (3) Porphyrazine coloring matter or a salt thereof according to (9) obtained by reacting in the range of pH 6 to 10 in the reaction system in the presence of an amine represented by formula (10) according to
(11)
A is a pyridine ring condensed at the 2-position and 3-position, B is a pyridine ring or benzene ring condensed at the 2-position and 3-position, and C is a pyridine ring or benzene condensed at the 2-position and 3-position A ring, D is a benzene ring, E is a C2-C4 alkylene, R ₁ and R ₂ are each independently a hydrogen atom, a hydroxy C1-C4 alkyl group, a hydroxy C1-C4 alkyloxy C1-C4 alkyl group. Wherein X and Y are independently selected from the group consisting of a sulfo group and a carboxy group, except that R ₁ and R ₂ are simultaneously hydrogen atoms. A porphyrazine coloring matter or a salt thereof according to (1), which is an anilino group or a naphthylamino group having three substituents, b is 0 to 2.9, and c is 0.1 to 3;
(12)
(1) to a dye mixture containing the porphyrazine dye or the salt thereof according to any one of (11),
(13)
(1) to the porphyrazine coloring matter according to any one of (12) or a dye mixture of a salt thereof and a phthalocyanine coloring matter,
(14)
An ink comprising the porphyrazine dye or the dye mixture according to any one of (1) to (12) as a dye component;
(15)
The ink according to (14) containing an organic solvent,
(16)
(14) or the ink according to (15), which is for inkjet recording;
(17)
In an ink jet recording method in which ink droplets are ejected in accordance with a recording signal and recording is performed on a recording material, the ink according to any one of (14) to (16) or an ink set including the ink is used as ink. An ink jet recording method comprising:
(18)
The inkjet recording method according to (17), wherein the recording material is an information transmission sheet,
(19)
The inkjet recording method according to (18), wherein the information transmission sheet is a surface-treated sheet, and the sheet has an ink image-receiving layer containing white inorganic pigment particles on a support.
(20)
A container containing the ink according to any one of (14) to (16),
(21)
An inkjet printer having the container according to (20),
(22)
(14) to (16) a colored body colored with the ink according to any one of
(23)
a porphyrazine coloring matter or a salt thereof according to (4) containing a compound represented by formula (1) according to (1), wherein b is 0.1 to 2.5;
(24)
a porphyrazine coloring matter or a salt thereof according to (10), comprising a compound represented by formula (2) according to (8), wherein b is 0.1 to 2.5;
About.

The ink using the compound of the present invention has a good hue as a cyan ink and is excellent in light resistance, ozone resistance and moisture resistance. In addition, there is no crystal precipitation, physical property change, color change, etc. after long-term storage, and storage stability is good. Furthermore, when used together with other magenta ink and yellow ink, a color tone in a wide visible region can be produced. Therefore, the cyan ink using the porphyrazine coloring matter of the present invention is extremely useful as an ink for inkjet recording.

The present invention will be described in detail. An ink suitable for ink jet recording of the present invention contains the porphyrazine coloring matter of the formula (1). That is, tetrabenzoporphyrazine (usually called phthalocyanine) in which one to three benzo rings are replaced with nitrogen-containing heteroaromatic rings is used as a dye nucleus, and an alkyl group (hydroxyl group, alkoxy group). Ink using a substituted sulfamoyl group substituted by a group) and a porphyrazine dye introduced with a substituted sulfamoyl group having a triazine ring as a substituent is extremely resistant to ozone gas and exhibits a bronze phenomenon. It has been found that it is difficult to wake up. Furthermore, the porphyrazine coloring matter has high solubility in a water-soluble organic solvent, and the long-term storage stability of the ink is high.

In the formula (1), examples of the nitrogen-containing heteroaromatic ring corresponding to A, B, C, and D include a pyridine ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring. Of these, the pyridine ring is most preferred. 1 to 3 of A, B, C, and D are nitrogen-containing heteroaromatic rings, and the rest are benzene rings. As the number of nitrogen-containing heteroaromatic rings increases, ozone resistance improves, but bronzing tends to occur easily. The number of nitrogen-containing heteroaromatic rings is appropriately determined in consideration of ozone resistance and bronzing properties. Adjust and select a well-balanced ratio.

b is 0 to 2.9, c is 0.1 to 3, and the sum of b and c is 1 to 3. As c increases, solubility in water tends to increase, while ozone resistance tends to decrease. Taking into account ozone resistance and solubility, the number of b and c is adjusted as appropriate, and a balanced ratio is selected. Just do it. Preferred c is 0.1 to 2.5, and the remainder is b.

Examples of the alkylene in E include alkylene having 2 to 12 carbons, and more preferably alkylene having 2 to 6 carbons. Specific examples include ethylene, propylene, butylene, pentylene, hexylene, cyclopropylenediyl, 1,2- or 1,3-cyclopentylenediyl, 1,2-, 1,3- or 1,4- Examples include cyclohexylene. Preferred are ethylene, propylene and butylene.

R ₁ and R ₂ each independently represents an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group, a hydroxyalkoxyalkyl group, or a hydrogen atom. However, the case where R ₁ and R ₂ are hydrogen atoms at the same time is excluded.

As said alkyl group, a C1-C12 alkyl group is mention | raise | lifted, for example. More preferred are alkyl groups having 1 to 4 carbon atoms, specifically, methyl group, ethyl group, isopropyl group, isobutyl group, t-butyl group, sec-butyl group and the like.

Examples of the hydroxyalkyl group include alkyl groups having 1 to 12 carbon atoms. More preferred are hydroxy C1-C4 alkyl groups, specifically 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2,3-dihydroxypropyl group, 4-hydroxybutyl group, 2 -Hydroxybutyl group, 1-ethyl-2-hydroxyethyl group, bis (hydroxymethyl) methyl group, 1,1-bis (hydroxymethyl) propyl group, 6-hydroxyhexyl group, 3-methyl-4-hydroxybutyl group Etc.

As said alkoxyalkyl group, a C3-C12 alkoxyalkyl group is mention | raise | lifted, for example. More preferred are alkoxyalkyl groups having 3 to 8 carbon atoms, specifically 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 1-ethyl-2. -Methoxyethyl group, 2-n-propoxyethyl group, 3-n-propoxypropyl group and the like can be mentioned.

Examples of the alkoxyalkoxyalkyl group include alkoxyalkoxyalkyl groups having 6 to 12 carbon atoms. Specific examples include ethoxyethoxyethyl group.

Examples of the hydroxyalkoxyalkyl group include an alkoxyalkoxyalkyl group having 4 to 12 carbon atoms having a hydroxy group as a substituent, preferably a hydroxy C1 to C4 alkyloxy C1 to C4 alkoxy group. Specific examples include 2-hydroxyethoxyethyl group.

X and Y each independently represents an unsubstituted or substituted anilino group or an unsubstituted or substituted naphthylamino group. Examples of the substituent of the substituted anilino group include a sulfo group, a carboxyl group, a phosphono group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkyl group, an alkoxy group, an allyloxy group, a hydroxyl group, a dialkylamino group, an alkylamino group, an arylamino group, Examples thereof include an acetylamino group, a cyano group, a nitro group, a halogen atom, and a heterocyclic group, and 1 to 2 or more kinds of substituents may be included among these. Preferable substituents include a sulfo group, a carboxyl group, and a hydroxyl group. Specifically, for example, 2,5-disulfoanilino group, 2-sulfoanilino group, 3-sulfoanilino group, 4-sulfoanilino group, 2-carboxyanilino group, 4-carboxyanilino group, 4-ethoxy-2-sulfoanilino group 2-methyl-5-sulfoanilino group, 2-methoxy-4-nitro-5-sulfoanilino group, 2-chloro-5-sulfoanilino group, 3-carboxy-4-hydroxyanilino group, 3-carboxy-4-hydroxy -5-sulfoanilino group, 2-hydroxy-5-nitro-3-sulfoanilino group, 4-acetylamino-2-sulfoanilino group, 4-anilino-3-sulfoanilino group, 3,5-dichloro-4-sulfoanilino group, 3 -Phosphonoanilino group, 3,5-dicarboxyanilino group, 2-carboxy-4-sulfoani Amino group, such as 2-carboxy-5-sulfoanilino group. Examples of the substituent of the substituted naphthylamino group include sulfo group, carboxyl group, ureido group, alkyl group, alkoxyl group, hydroxyl group, dialkylamino group, alkylamino group, arylamino group, acetylamino group, cyano group, nitro group, halogen An atom and a heterocyclic group are mention | raise | lifted, You may have 1-4 substituents of 1 type, or 2 or more types from these. Preferred examples of the substituent include a sulfo group and a hydroxyl group. Specifically, for example, 5,7-disulfonaphthalen-2-ylamino group, 6,8-disulfonaphthalen-2-ylamino group, 3,6-disulfonaphthalen-1-ylamino group, 3,6,8 -Trisulfonaphthalen-1-ylamino group, 8-hydroxy-3,6-disulfonaphthalen-1-ylamino group, 4,8-disulfonaphthalen-2-ylamino group, 3,6,8-trisulfonaphthalene- 2-ylamino group, 4,6,8-trisulfonaphthalen-2-ylamino group, 8-chloro-3,6-disulfonaphthalen-1-ylamino group, 8-hydroxy-6-sulfonaphthalen-2-ylamino group And preferred are 5-hydroxy-7-sulfonaphthalen-2-ylamino group and the like.

The compound of the above formula (1) can form a salt by utilizing a sulfo group, a carboxyl group, a phosphono group and the like in the molecule. The salt of the compound of formula (1) is preferably an inorganic or organic cation salt. Examples of the salt include alkali metal salts, alkaline earth metal salts, and ammonium salts. Preferred alkali metal salts are lithium, sodium, and potassium salts.
Examples of the alkaline earth metal of the alkaline earth metal salt include calcium and magnesium. Examples of the organic amine include mono-, di- or di- or dialkylamines such as lower alkylamines having 1 to 3 carbon atoms such as methylamine and ethylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine. And tri (lower alkanol having 1 to 4 carbon atoms) amines. Preferred salts include alkali metal salts such as sodium salt, potassium salt and lithium salt, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and the like mono, di or tri (carbon number 1). To 4 lower alkanol) amine onium salts and ammonium salts.

Specific examples of A, B, C, D, E, R ₁ , R ₂ , X, Y, b, and c in the porphyrazine dye represented by the above formula (1) of the present invention are shown in Table 1. The porphyrazine coloring matter used in the invention is not limited to the following examples. In addition, when the nitrogen-containing heteroaromatic ring corresponding to A, B, C, and D is a pyridine ring, there are positional isomers of nitrogen atoms as described later, and a mixture of isomers is used during dye synthesis. can get. These isomers are difficult to isolate and are difficult to identify by analysis. For this reason, it is usually used as a mixture. However, even if it is a mixture of isomers, no particular problem occurs in the present invention, so these isomers will be described without distinction.

The manufacturing method of the compound of Formula (1) of this invention is demonstrated.
First, a copper porphyrazine coloring matter represented by the following formula (6) is synthesized. In order to synthesize a copper porphyrazine dye represented by the following formula (6), for example, by reacting an aromatic nitrogen-containing heteroaromatic dicarboxylic acid derivative with a phthalic acid derivative in the presence of a copper compound. can get. By changing the molar ratio of the reaction of the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative, it is possible to adjust the number of nitrogen-containing heteroaromatic rings of A, B, C and D and the number of benzene rings. Nitrogen-containing heteroaromatic dicarboxylic acid derivatives include quinolinic acid, 3,4-pyridinedicarboxylic acid, dicarboxylic acid compounds such as 2,3-pyrazinedicarboxylic acid, quinoline anhydride, 3,4-pyridinedicarboxylic acid anhydride, 2, Acid anhydride compounds such as 3-pyrazine dicarboxylic acid anhydride, dicarboxyamide compounds such as pyridine-2,3-dicarboxyamide, dicarboxylic acid monoamide compounds such as pyrazine-2,3-dicarboxylic acid monoamide, quinolinic acid imide, etc. And dicarbonitrile compounds such as pyridine-2,3-dicarbonitrile and pyrazine-2,3-dicarbonitrile. Examples of the phthalic acid derivative include phthalic acid, phthalic anhydride, phthalamide, phthalamic acid, phthalimide, phthalonitrile, 1,3-diiminoisoindoline, 2-cyanobenzamide and the like.

Methods for synthesizing copper porphyrazine dyes are generally called nitrile method and Weiler method, and reaction conditions and the like are different. The nitrile method is a method for synthesizing a porphyrazine dye using a dicarbonitrile compound such as pyridine-2,3-dicarbonitrile, pyrazine-2,3-dicarbonitrile, or phthalonitrile as a raw material. In contrast, the Weiler method includes dicarboxylic acid compounds such as phthalic acid, quinolinic acid, 3,4-pyridinedicarboxylic acid, and 2,3-pyrazinedicarboxylic acid, phthalic anhydride, quinolinic anhydride, and 3,4-pyridinedicarboxylic anhydride. Acid anhydride compounds such as 2,3-pyrazinedicarboxylic acid anhydride, dicarboxyamide compounds such as phthalamide and pyridine-2,3-dicarboxyamide, dicarboxylic acids such as phthalamic acid and pyrazine-2,3-dicarboxylic acid monoamide An acid imide compound such as an acid monoamide compound, phthalimide, or quinolinic acid imide is used as a raw material. In the Weiler method, addition of urea is essential, and the amount of urea used is 5 to 100 times the molar amount of the total of 1 mol of the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative.

[In the formula (6), A, B, C and D represent the same meaning as described above. ]

Usually, the reaction is carried out in the presence of a solvent. In the nitrile method, an organic solvent having a boiling point of 100 ° C. or higher, more preferably 130 ° C. or higher is used as the solvent. For example, n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 1-octanol, 2-ethylhexanol, N, N-dimethylaminoethanol, benzyl alcohol, ethylene glycol, Examples include propylene glycol, trichlorobenzene, chloronaphthalene, nitrobenzene, quinoline, sulfolane, and urea. In the Weiler method, an aprotic organic solvent having a boiling point of 150 ° C. or higher, more preferably 180 ° C. or higher is used as the solvent. For example, trichlorobenzene, chloronaphthalene, nitrobenzene, quinoline, sulfolane, urea and the like can be mentioned. The amount of the solvent used is 1 to 100 times the total amount of the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative.

As the catalyst, in the nitrile method, quinoline, 1,8-diazabicyclo [5,4,0] -7-undecene, tributylamine, ammonia, amines such as N, N-dimethylaminoethanol, sodium ethoxide, sodium methoxy Alkali metal alcoholates such as Examples of the Weiler method include ammonium molybdate and boric acid. The addition amount is 0.001 to 1 times the mol of the total of 1 mol of the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative.

Examples of copper compounds include metallic copper, copper halides, carboxylates, sulfates, nitrates, acetylacetonates, complexes, and the like. For example, copper chloride, copper bromide, copper acetate, copper acetylacetonate and the like can be mentioned. The usage-amount of a metal compound is 0.15-0.35 times mole with respect to 1 mol of total of a nitrogen-containing heteroaromatic dicarboxylic acid derivative and a phthalic acid derivative.

In the nitrile method, the reaction temperature is usually 100 to 200 ° C, preferably 130 to 170 ° C. On the other hand, in the Weiler method, the reaction temperature is 150 to 300 ° C, preferably 170 to 220 ° C. Moreover, although reaction time changes with reaction conditions, it is 1 to 40 hours normally. After completion of the reaction, a copper porphyrazine dye is obtained by filtration, washing and drying.

Taking as an example a compound (copper dibenzobis (2,3-pyrido) porphyrazine) in which two of A, B, C and D in the formula (6) are pyridine rings and the remaining two are benzene rings. This will be described in detail.

In sulfolane solvent, quinolinic acid (0.5 mol), phthalic anhydride (0.5 mol), copper (II) chloride (0.25 mol), ammonium phosphomolybdate (0.004 mol), urea (6 mol) ) At 200 ° C. for 5 hours, copper dibenzobis (2,3-pyrido) in which two of A, B, C and D in the formula (6) are pyridine rings and the remaining two are benzene rings. Porphyrazine is obtained. The reactivity varies depending on the type and amount of quinolinic acid, phthalic anhydride, metal compound, solvent, catalyst, etc., and is not limited to the above.

In addition, when synthesized by the above synthesis method, the main component is copper dibenzobis (2,3-pyrido) porphyrazine, which includes five isomers having different positions of the pyridine ring and the nitrogen atom of the pyridine ring [formula (7-A) to (7-E)] are generated. At the same time, copper tribenzo (2,3-pyrido) porphyrazine [formula (8)] in which one of A, B, C and D in the formula (6) is a pyridine ring and the remaining three are benzene rings. And copper benzotris (2,3-pyrido) porphyrazine in which three of A, B, C and D in the formula (6) are pyridine rings and the other one is a benzene ring, and these compounds In addition, there are positional isomers of the pyridine ring nitrogen atom [formulas (9-A) to (9-D)], resulting in a complicated mixture. In addition, copper tetrakis (2,3-pyrido) porphyrazine and copper phthalocyanine (copper tetrabenzoporphyrazine) are also produced in a small amount. Usually, it is difficult to isolate only the target product from these mixtures, and on average, two are pyridine rings and the other two are benzene rings, and this mixture is used as copper dibenzobis (2,3-pyrido) porphyrazine as it is. Most of them are used.

Next, the copper chlorosulfonylporphyrazine dye represented by the formula (3) is represented by the chlorosulfonated copper porphyrazine dye represented by the formula (6) in chlorosulfonic acid, or represented by the formula (6). The copper porphyrazine dye is sulfonated in sulfuric acid or fuming sulfuric acid and then converted into a chlorosulfone group with a chlorinating agent. The chlorosulfone group or sulfo group thus obtained is introduced onto the benzene ring when A, B, C, D in the formula (6) corresponds to the benzene ring, and A, B, C, D Is not introduced when it corresponds to a heteroaromatic ring group. As another synthesis example, a copper porphyrazine dye having a sulfo group represented by the following formula (11) was synthesized by condensing and ring-closing with sulfophthalic acid having a sulfo group and quinolinic acid in advance, and then the sulfo group was converted to chloro The target compound of formula (3) can also be obtained by conversion to a sulfone group.

The conditions for the chlorosulfonation reaction of the copper porphyrazine dye are usually chlorosulfonic acid as a solvent, and the amount used is 3 to 20 times by weight, preferably 5 to 10 times by weight of the porphyrazine dye. About reaction temperature, it is 100-150 degreeC normally, Preferably it is 120-150 degreeC. Although reaction time changes with reaction conditions, such as reaction temperature, it is 1 to 10 hours normally. In this case, the substituent of the copper porphyrazine dye obtained is a mixture of chlorosulfone groups and sulfo groups, and if the ratio of chlorosulfone groups is to be further improved, it can be achieved by adding a chlorinating agent to the reaction system. it can. Examples of the chlorinating agent include, but are not limited to, chlorosulfonic acid, thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like.

It can also be obtained by converting a sulfo group into a chlorosulfone group by allowing a chlorinating agent to act on a copper porphyrazine dye having a sulfo group represented by the following formula (11). Examples of the solvent used in the chlorination reaction include, but are not limited to, sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, benzene, toluene, nitrobenzene, chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide and the like. It is not a thing. Examples of the chlorinating agent include, but are not limited to, chlorosulfonic acid, thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like.

[In Formula (11), A, B, C, D represents the same meaning as the above, and p is 1-3. ]

Next, the corresponding copper chlorosulfonylporphyrazine dye, the amine represented by the following formula (4) and the amine represented by the above formula (10) are usually pH 6 to 10, preferably pH 6.5 in an aqueous solvent. The target compound is obtained by reacting at 9.5, more preferably pH 7-9, usually 5-70 ° C., usually 1-20 hours. The base used for pH adjustment during the reaction may be an amine represented by the formula (10), or may be an alkali metal hydroxide or an alkali metal carbonate.
Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Examples of the alkali metal carbonate include sodium carbonate and potassium carbonate. Reaction with a copper chlorosulfonyl porphyrazine pigment | dye, the amine represented by Formula (4), and the amine represented by Formula (10) is normally performed in an aqueous solvent.
When trying to obtain the above formula (1), if the pH in the reaction system is less than 6, the chlorosulfonyl compound is hydrolyzed to increase the ratio of the by-product sulfonic acid derivative, and the pH is higher than 10. When it becomes larger, hydrolysis of the chlorosulfonyl compound occurs, and when an excess of the amine of formula (10) is present in the reaction system, the amine of formula (10) preferentially reacts with the chlorosulfonyl compound, and the following formula There exists a tendency for the reaction rate of the compound of (4) and a chlorosulfonyl body to fall remarkably.
Therefore, the ratio of the compound of the above formula (10) and the following formula (4) and the ratio of adding the chlorosulfonyl compound should be appropriately set in consideration of these points.

[In the formula (4), E, X and Y represent the same meaning as described above. ]

In addition, the usage-amount of the amine represented by the said Formula (4) is 0.5 mol equivalent of a theoretical value normally with respect to 1 mol of copper chlorosulfonyl porphyrazine pigment | dyes, Preferably 4 mol equivalent Equivalent to 3.5 molar equivalents, more preferably 1 molar equivalent to 3 molar equivalents. However, it varies depending on the reactivity and reaction conditions of the organic amine, and is not limited thereto.

A method for producing the amine represented by the formula (4) will be described. For example, aniline or naphthylamine corresponding to X is usually 0.95 to 1.1 mol and 2,4,6-trichloro-S-triazine (cyanuric chloride) 1 mol in water, usually pH 3 to 7, usually 5 The primary condensate is obtained by reacting at -40 ° C, usually 2-12 hours. Next, a secondary condensate is obtained by reacting anilines or naphthylamines corresponding to Y, usually 0.95 to 1.1 mol, usually pH 4 to 10, usually 5 to 80 ° C., usually 0.5 to 12 hours. . Subsequently, the compound of the said Formula (4) is obtained by making 1-50 mol of alkylene diamines corresponding to E react normally pH 9-12, normally 5-90 degreeC, normally 0.5-8 hours. Examples of pH adjustment during condensation usually include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate. The order of condensation is appropriately determined according to the reactivity of various compounds, and is not limited to the above.

Further, the copper porphyrazine dye represented by the formulas (1) and (2) is obtained from the copper chlorosulfonylporphyrazine represented by the formula (3) and the amine represented by the formula (4). The chlorosulfonyl compound of formula (3) was partially converted to sulfonic acid by hydrolysis with water in the reaction system in the presence of an amine represented by It is conceivable that the compound is produced as a by-product and mixed into the target dyes of the formulas (1) and (2). Although this by-product can be detected by performing mass spectrometry or the like, in this specification, for the sake of convenience, all the chlorosulfonyl groups are considered to have reacted with the amines of formula (4) and formula (10) as the target compound. The compounds of formula (1) and formula (2) are indicated.

Furthermore, the copper porphyrazine dyes represented by the above formulas (1) and (2) are partially dimerized (for example, Pz-L-) with a copper porphyrazine ring (Pz) via a divalent linking group (L). Pz) or impurities forming a trimer may be by-produced and mixed into the reaction product.

Examples of the divalent linking group represented by _{L -SO 2 -, - SO 2} -NH-SO 2 - include, by-products of these two L are combined in the case of a trimer Sometimes it is formed.

The copper porphyrazine coloring matter of the present invention thus obtained can be separated by filtration or the like after aciding out or salting out. For example, salting out is preferably carried out in the range of acidic to alkaline, preferably pH 1-11. Although the temperature at the time of salting out is not specifically limited, It is preferable to salt out by adding salt etc. after heating to 40-80 degreeC normally, Preferably it is 50-70 degreeC.

The copper porphyrazine coloring matter represented by the above formulas (1) and (2) of the present invention synthesized by the above method can be obtained in the form of a free acid or a salt thereof. In order to obtain a free acid, for example, acid precipitation may be performed. In addition, in order to obtain a salt, when salting out or a desired salt cannot be obtained by salting out, for example, a normal salt exchange method in which a desired organic or inorganic base is added to a free acid is used. That's fine.

Next, the ink of the present invention will be described. The porphyrazine coloring matter of formula (1) and the salt thereof produced by the above method exhibit a clear cyan color. Therefore, ink containing these is also mainly used as cyan ink, but low dye density cyan ink (light cyan ink) used to reduce the smooth reproducibility of the gradation part of the image and the graininess of the light color area. Or a photocyan ink or the like).

The ink of the present invention is prepared using water as a medium, if, Cl included in the porphyrazine coloring matter and a salt thereof using this ink as an ink for inkjet recording ^- content and SO ₄ ^2-like anion preferably contains less, a measure of the content thereof, Cl in the porphyrazine coloring matter and in the salt ^- and SO ₄ 5 wt% or less as the total content of the ^2-, preferably 3 wt% or less, more preferably 1 wt% Or less than 1% by mass in the ink. Cl ^- and SO ₄ in the production of porphyrazine coloring matter or a salt thereof ^2- less present invention, alcohol porphyrazine coloring matter and dry product or a wet cake of the salt of the usual methods or the present invention using a reverse osmosis membrane for example And desalting by a method such as stirring in a mixed solvent of water, filtration, and drying. The alcohol to be used is a lower alcohol having 1 to 4 carbon atoms, preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol, ethanol or 2-propanol. Further, in the desalting treatment with alcohol, a method of heating to near the boiling point of the alcohol used and then cooling to desalinate can be employed. The content of Cl ^- and SO ₄ ^2- is measured, for example, by ion chromatography.

When the ink of the present invention is used as an ink for inkjet recording, it contains a heavy metal (ion) such as zinc and iron, an alkaline earth metal (ion) such as calcium and magnesium, silicon, etc. contained in the porphyrazine coloring matter and its salt It is preferable to use a material having a small amount (excluding copper contained in the porphyrazine skeleton as a central metal atom by an ionic bond or a coordinate bond). The standard of the content is, for example, about 500 ppm or less for each of refined and dried porphyrazine pigments and salts thereof, heavy metals (ions) such as zinc and iron, alkaline earth metals (ions) such as calcium and magnesium, and silicon. It is. The contents of heavy metals (ions) and metals (ions) are measured by ion chromatography, atomic absorption spectrometry or ICP (Inductively Coupled Plasma) emission analysis.

In the ink of the present invention, the porphyrazine coloring matter of formula (1) and a salt thereof are contained in an amount of 0.1 to 8% by mass, preferably 0.3 to 6% by mass. The ink of the present invention further contains a water-soluble organic solvent as necessary within a range that does not impair the effects of the present invention. Water-soluble organic solvents are used as dye solubilizers, drying inhibitors (wetting agents), viscosity modifiers, penetration enhancers, surface tension modifiers, antifoaming agents, and the like. Other ink preparation agents include, for example, antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventive agents, UV absorbers, viscosity adjusters, dye dissolving agents, antifading agents, emulsion stabilizers, surface tension adjusters, You may use additives, such as a foaming agent, a dispersing agent, a dispersion stabilizer. The content of the water-soluble organic solvent is 0 to 60% by mass, preferably 10 to 50% by mass, and the ink preparation agent is 0 to 20% by mass, preferably 0 to 15% by mass.

Examples of water-soluble organic solvents that can be used in the present invention include C1-C4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol, N, N-dimethyl. Carboxamide such as formamide or N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2- Heterocyclic ketones such as ON, ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one or cyclic ethers such as ketoalcohol, tetrahydrofuran, dioxane, ethylene glycol, 1,2- or 1,3 -Propylene glycol, 1,2-ma Has (C2-C6) alkylene units such as 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol, etc. Monomer, oligomer or polyalkylene glycol or thioglycol, polyol (triol) such as glycerin, hexane-1,2,6-triol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether or diethylene glycol Monobutyl ether or triethylene glycol monomethyl ether or trie Polyhydric alcohols (C1 -C4) monoalkyl ethers such as glycol monoethyl ether, gamma-butyrolactone or dimethyl sulfoxide and the like.

In the ink of the present invention, preferred as the water-soluble organic solvent are isopropanol, glycerin, mono-, di- or triethylene glycol, dipropylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, more preferably isopropanol, Glycerin, diethylene glycol and 2-pyrrolidone. These water-soluble organic solvents are used alone or in combination.

Examples of antiseptic / antifungal agents include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8- Oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, brominated indanone And compounds such as benzyl bromacetate and inorganic salts. Examples of the organic halogen compound include sodium pentachlorophenol, examples of the pyridine oxide compound include sodium 2-pyridinethiol-1-oxide, and examples of the inorganic salt compound include sodium acetate. Examples of the isothiazoline-based compound include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, and 5 -Chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Can be mentioned. Other antiseptic / antifungal agents include sodium sorbate sodium benzoate and the like. Specific examples of other antiseptic / antifungal agents include, for example, trade names Proxel GXL (S) and Proxel XL-2 (S) manufactured by Avecia.

As the pH adjuster, any substance can be used as long as it can control the pH of the ink within the range of 6.0 to 11.0 for the purpose of improving the storage stability of the ink. For example, alkanolamines such as diethanolamine and triethanolamine, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate. And carbonates.

Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate and the like. Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

Examples of the ultraviolet absorber include a compound that emits fluorescence by absorbing ultraviolet rays represented by benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, stilbene compounds, or benzoxazole compounds, so-called fluorescence. Brighteners can also be used.

Examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents, such as polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.

Examples of the dye solubilizer include urea, ε-caprolactam, ethylene carbonate, and the like.

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.

Examples of the surface tension adjusting agent include a surfactant, and examples thereof include an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant. Anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and their salts, N-acyl methyl taurates, alkyl sulfates polyoxyalkyl ether sulfates Salt, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkyl allyl sulfonate, diethyl sulfosuccinate , Diethylhexylsyl sulfosuccinate, dioctyl sulfosuccinate and the like. Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives. Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and other imidazoline derivatives. is there. Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Ethers such as alkyl ethers, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate Ester, such as polyoxyethylene stearate, 2,4,7,9-tetramethyl-5-decyne-4,7- Acetylene glycols such as all, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3ol (for example, Surfinol 104, 82, 465 manufactured by Nisshin Chemical Co., Ltd.) , Olfine STG, etc.).

As the antifoaming agent, a highly oxidized oil-based, glycerin fatty acid ester-based, fluorine-based, or silicone-based compound is used as necessary.

These ink preparation agents are used alone or in combination. The surface tension of the ink of the present invention is usually 25 to 70 mN / m, more preferably 25 to 60 mN / m. The viscosity of the ink of the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less.

In producing the ink of the present invention, there is no particular limitation on the order in which the respective drugs are dissolved. In preparing the ink, the water to be used is preferably one having few impurities such as ion exchange water or distilled water. Furthermore, if necessary, fine filtration may be performed using a membrane filter to remove impurities. When used as ink for an inkjet printer, it is preferable to perform fine filtration. The pore diameter of the filter for performing microfiltration is usually 1 to 0.1 microns, preferably 0.8 to 0.2 microns.

The ink of the present invention can be used not only for monochromatic image formation but also for full color image formation. In order to form a full-color image, it is also used as an ink set of three primary colors with magenta ink and yellow ink, and further as an ink set of four colors with black ink added thereto. Furthermore, in order to form a higher-definition image, the ink set is used in combination with light magenta ink, blue ink, green ink, orange ink, dark yellow ink, gray ink, and the like.

Various yellow ink pigments 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 type active methylene compounds as examples; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dyes Examples of the species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

Various types of magenta ink can be used. For example, aryl or heteroazo 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.

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.

Examples of applicable black pigments include disazo, trisazo, and tetraazo dyes, and carbon black dispersions.

  The ink of the present invention can be used in recording methods such as printing, copying, marking, writing, drafting, stamping and the like, and is particularly suitable for use in ink jet printing.

In the ink jet recording method of the present invention, energy is supplied to the ink prepared as described above, and a known image receiving material, that is, plain paper, resin-coated paper, ink jet exclusive paper, glossy paper, glossy film, electrophotographic co-paper, fiber Images are formed on fabrics (such as cellulose, nylon and wool), glass, metal, ceramics, and leather.

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 for applying the polymer latex to the recording material may be before, after, or simultaneously with the application of the colorant. Alternatively, it may be in an ink or may be used as a liquid material of a polymer latex alone.

The colored product of the present invention is colored with the porphyrazine coloring matter of the present invention and a salt thereof or an aqueous ink composition containing the same. Examples of materials that can be colored include information transmission sheets such as paper and film, fibers and cloth (cellulose, nylon, wool, etc.), leather, and base materials for color filters. The information transmission sheet is preferably a surface-treated sheet, specifically, a sheet such as paper, synthetic paper, or film provided with an ink receiving layer. In the ink receiving layer, inorganic fine particles capable of absorbing the pigment in the ink such as porous silica, alumina sol, and special ceramics are impregnated or coated with the cationic polymer on the base material, for example, polyvinyl alcohol or polyvinyl pyrrolidone. It is provided by coating on the surface of the substrate together with a hydrophilic polymer such as. Those provided with such an ink receiving layer are usually called ink jet dedicated paper (film), glossy paper (film) and the like. Among these, it is said that ozone gas and other gases having an oxidizing action in the air are easily affected by inorganic fine particles that can absorb pigments in inks such as porous silica, alumina sol and special ceramics. This type of inkjet paper is coated on the surface of the material. For example, typical commercial products include Pictorico (manufactured by Asahi Glass Co., Ltd.), professional photo paper, super photo paper, matte photo paper (all Also Canon Inc.), Photographic Paper Crispier <High Gloss>, Photographic Paper <Glossy>, Photo Matte Paper (both made by Seiko Epson Corporation), Advanced Photo Paper (Glossy) Premium Glossy Film, Photo Paper (all Also from Hewlett-Packard Japan), Photo-like QP (manufactured by Konica Corporation), Takashi Place coated paper, photo glossy paper (both Sony Co., Ltd.), and the like. Of course, plain paper can also be used.

  The colored body of the present invention is obtained by coloring a material to be colored with the ink using the ink jet printer. The colorant is not particularly limited as long as it is an article that can be colored by the recording material and other ink jet printers.

In order to record on the recording material by the ink jet recording method of the present invention, for example, a container containing the above-mentioned ink may be set at a predetermined position of the ink jet printer and recorded on the recording material by an ordinary method. Examples of the ink jet printer include a piezo printer using mechanical vibration and a bubble jet (registered trademark) printer using bubbles generated by heating.

The ink according to the present invention does not precipitate or separate during storage. Further, when the ink according to the present invention is used in ink jet printing, the ejector (ink head) is not blocked. The ink according to the present invention does not cause changes in physical properties even under constant recirculation for a relatively long time by a continuous ink jet printer or intermittent use by an on-demand ink jet printer.

The ink of the present invention has a clear cyan color, and is particularly excellent in ozone resistance and can provide a recorded matter excellent in light resistance and water resistance. By using it as a set of dark and light cyan inks, it can be used together with other yellow, magenta, and other inks such as green, red, orange, blue, etc. that are excellent in ozone resistance, light resistance, and water resistance. A color tone having a wide visible range can be obtained, and a recorded matter having excellent ozone resistance and light resistance and water resistance can be obtained.

Hereinafter, the present invention will be described more specifically with reference to examples. In the text, “parts” and “%” are based on mass unless otherwise specified.

The compounds of the above formula (1) synthesized in the examples are all mixtures, and unless otherwise specified, the positional isomer of the nitrogen-containing heteroaromatic ring described above, the positional isomer of the nitrogen atom of the nitrogen-containing heteroaromatic ring, And compounds having different ratios of benzo ring / nitrogen-containing heteroaromatic ring corresponding to A to D in formula (1) and α / β positional isomers of substituted or unsubstituted sulfamoyl groups in the benzo ring. As described above, it is extremely difficult to isolate a specific single compound from a mixture of these isomers and to determine the structure thereof. Therefore, in the present specification, for convenience, the nitrogen-containing heteroaromatic ring and the positional isomer of the nitrogen atom are described. Among the possible isomers, one example was given as a representative example, and the chemical structural formula was described.
Further, in the examples, what is described as “compound” is a mixture in principle, except for those obtained by elemental analysis.
In addition, about the compound obtained in the Example, it can analyze by the following two methods etc. as needed.
1. DI-MS (direct mass) measurement by mass spectrometry EI method. Measuring equipment and conditions are as follows.
Apparatus: SSQ-7000
Ion source temperature: 230 ° C
Degree of vacuum: about 8mT
2. ICP emission spectroscopy measurement of copper content for copper-containing compounds.
Apparatus: SPS3100 (manufactured by SII)
About 0.1 g of the sample was precisely weighed, dissolved in pure water, and then fixed in a 100 ml volumetric flask. 1 ml of this constant volume solution is weighed into a 50 ml volumetric flask with a whole pipette, a certain amount of Y (yttrium) is added as an internal standard substance, and the volume is adjusted to 50 ml with pure water, followed by quantification by ICP emission spectroscopy.

Example 1
(1) Mixture of copper tribenzo (2,3-pyrido) porphyrazine and copper dibenzobis (2,3-pyrido) porphyrazine (1.5 in A, B, C and D in the following formula (6) And a pyridine ring condensed at the 3-position with the remaining 2.5 being a benzene ring)

In a four-necked flask, 250 parts of sulfolane, 18.4 parts of phthalimide, 12.5 parts of quinolinic acid, 72.0 parts of urea, 8.8 parts of copper (II) chloride dihydrate (purity 97.0%) Then, 1.0 part of ammonium molybdate was added, the temperature was raised to 200 ° C., and the temperature was maintained for 5 hours. After completion of the reaction, the reaction mixture was cooled to 65 ° C., 200 parts of methanol was added, and the crystals were filtered. The obtained crystal was washed with 150 parts of methanol and subsequently with 200 parts of warm water and dried to obtain 72.2 parts of a wet cake. The total amount of the obtained wet cake was put into 500 parts of 5% hydrochloric acid, heated to 60 ° C., and held at that temperature for 1 hour. The crystals were filtered and washed with 200 parts of water. Next, the entire amount of the obtained wet cake was put into 500 parts of 10% ammonia water, and kept at 60 ° C. for 1 hour. The crystals were filtered, washed with 300 parts of water and 100 parts of methanol, and 33.6 parts of the wet cake were added. Obtained. The obtained wet cake was dried at 80 ° C. to obtain 19.8 parts of a mixture of copper tribenzo (2,3-pyrido) porphyrazine and copper dibenzobis (2,3-pyrido) porphyrazine as blue crystals.
λmax: 663.5 nm (in pyridine)

(2) A mixture of copper tribenzo (2,3-pyrido) porphyrazine trisulfonyl chloride and copper dibenzobis (2,3-pyrido) porphyrazine disulfonyl chloride (among A, B, C and D in the following formula (3)) 1.5 is a pyridine ring condensed at the 2-position and 3-position, the remaining 2.5 is a benzene ring, and n is 2.5.

Copper tribenzo (2,3-pyrido) porphyrazine and copper dibenzobis (2,3-pyrido) porphyrazine obtained in Example 1- (1) at 60 ° C. or lower with stirring in 46.2 parts of chlorosulfonic acid 5.8 parts of the above mixture was gradually added and reacted at 140 ° C. for 4 hours. Next, the reaction liquid was cooled to 70 ° C., 17.9 parts of thionyl chloride was added dropwise over 30 minutes, and the reaction was performed at 70 ° C. for 3 hours. The reaction solution is cooled to 30 ° C. or lower, slowly poured into 800 parts of ice water, the precipitated crystals are filtered, washed with 200 parts of cold water, and washed with copper tribenzo (2,3-pyrido) porphyrazine trisulfonyl chloride and copper. 40.0 parts of a wet cake of a mixture of dibenzobis (2,3-pyrido) porphyrazine disulfonyl chloride was obtained.

(3) Synthesis of the following formula (14) (compound in which X in formula (4) is 3,6,8-trisulfonaphthalen-1-ylamino group, Y is 4-carboxyanilino group, and E is ethylene)

18.4 parts of cyanuric chloride and 0.02 part of Leocol TD-90 (trade name, surfactant, manufactured by Lion Corporation) were added to 150 parts of ice water and stirred at 10 ° C. or lower for 30 minutes. Next, 51.6 parts of 8-aminonaphthalene-1,3,6-trisulfonic acid (purity 91.4%) was added and the pH was adjusted to 2.0 to 3.0 using a 10% aqueous sodium hydroxide solution. The reaction was carried out at 10 ° C for 1 hour 50 minutes and at 20-25 ° C for 1 hour 15 minutes. Next, 14.1 parts of 4-aminobenzoic acid was added to the reaction solution, and the reaction was performed at 20 ° C. for 2 hours and at 40 ° C. for 2 hours while adjusting the pH to 7.0 to 8.0 using a 10% aqueous sodium hydroxide solution. . The temperature was raised to 60 ° C., and 60 parts of ethylenediamine was added dropwise. Then, after stirring overnight, the pH was adjusted to 1.0 using concentrated hydrochloric acid. During this time, the temperature was raised to 20 ° C. while adding ice. At this time, the liquid volume was 1250 parts. To this reaction liquid, 250 parts of sodium chloride was added over 15 minutes and stirred for 15 minutes to precipitate crystals. The precipitated crystals were filtered to obtain 368.2 parts of a wet cake. The obtained wet cake was put into a beaker, 700 parts of water was added, and it was dissolved at pH 10.0 using a 10% aqueous sodium hydroxide solution. At this time, the liquid volume was 1000 parts. The reaction solution was adjusted to pH 1.0 using concentrated hydrochloric acid, 200 parts of sodium chloride was added over 20 minutes, and the mixture was stirred for 20 minutes to precipitate crystals. The precipitated crystals were filtered to obtain 236.2 parts of a wet cake. The obtained wet cake was added to 1250 parts of methanol and 125 parts of water and stirred at 50 ° C. for 1 hour, followed by filtration to obtain 196.5 parts of a wet cake. The obtained wet cake was dried to obtain 58.4 parts of a compound of the formula (14) as a white powder.

(4) The following formula (15) (mixture of No. 1, No. 2, and No. 3 in Table 1: 1.5 out of A, B, C, and D in the formula (1) is the second and third positions. And the remaining 2.5 is a benzene ring, R ₁ is a 2-hydroxyethyl group, R ₂ is a hydrogen atom, X is a 3,6,8-trisulfonaphthalen-1-ylamino group, Y Of 4-carboxyanilino group and E is ethylene)

Add 40.0 parts of the copper benzo (2,3-pyrido) porphyrazinesulfonyl chloride wet cake obtained in Example 1- (2) to 100 parts of ice and add water to adjust the liquid volume to 400 parts. The suspension was stirred and suspended at 5 ° C or lower. After 15 minutes, a solution obtained by dissolving 13.1 parts of the compound of the formula (14) obtained in Example 1- (3) in 65 parts of warm water and 4 parts of 70% monoethanolamine was added. After the addition, the pH was adjusted to 9.0 with a 10% monoethanolamine aqueous solution. While maintaining the same pH, the temperature was raised to 20 ° C. over 10 minutes and kept at the same temperature for 8 hours. The liquid volume at this time was 600 parts. The temperature of the reaction solution was raised to 50 ° C., 120 parts of sodium chloride was added and stirred for 10 minutes, and then adjusted to pH 0.7 with hydrochloric acid over 5 minutes, followed by filtration to obtain 70 parts of a wet cake. Water was added to 70 parts of the obtained wet cake to make the liquid amount 400 parts, the temperature was raised to 60 ° C., and the pH was adjusted to 9.5 with 25% sodium hydroxide solution to complete dissolution. After adding 80 parts of sodium chloride and stirring for 15 minutes, the pH was adjusted to 4.1 with hydrochloric acid over 5 minutes, followed by filtration to obtain 58.2 parts of a wet cake. 58.2 parts of the obtained wet cake was put into 400 parts of methanol, 40 parts of water was added and suspended and stirred at 50 ° C. for 1 hour, then filtered, washed with methanol, dried, and 8.6 parts of blue powder Got.
λmax: 599 nm (in aqueous solution)

Example 2
(1) The following formula (16) (a mixture of No. 5, No. 6, and No. 7 in Table 1: 1.5 out of A, B, C, and D in the formula (1) is 2nd and 3rd positions) And the remaining 2.5 are benzene rings, R ₁ and R ₂ are 2-hydroxyethyl groups, X is 3,6,8-trisulfonaphthalen-1-ylamino group, and Y is 4- Synthesis of carboxyanilino group, a compound in which E is ethylene)

Add 40.0 parts of the copper benzo (2,3-pyrido) porphyrazinesulfonyl chloride wet cake obtained in Example 1- (2) to 100 parts of ice and add water to adjust the liquid volume to 400 parts. The suspension was stirred and suspended at 5 ° C or lower. After 15 minutes, a solution obtained by dissolving 13.1 parts of the compound of the formula (14) obtained in Example 1- (3) in 65 parts of warm water and 4 parts of 80% diethanolamine was added. After the addition, the pH was adjusted to 9.0 with a 10% diethanolamine aqueous solution. While maintaining the same pH, the temperature was raised to 20 ° C. over 10 minutes and kept at the same temperature for 8 hours. The liquid volume at this time was 670 parts. The temperature of the reaction solution was raised to 50 ° C., 134 parts of sodium chloride was added and stirred for 10 minutes, and then adjusted to pH 0.6 with hydrochloric acid over 5 minutes, followed by filtration to obtain 116.2 parts of a wet cake. Water was added to 116.2 parts of the obtained wet cake to adjust the liquid volume to 450 parts, the temperature was raised to 60 ° C., and the pH was adjusted to 8.0 with a 25% sodium hydroxide solution to complete dissolution. After adding 90 parts of sodium chloride and stirring for 15 minutes, the pH was adjusted to 3.8 with hydrochloric acid over 5 minutes, followed by filtration to obtain 69.8 parts of a wet cake. 69.8 parts of the obtained wet cake was put into 400 parts of methanol, 40 parts of water was added and suspended and stirred at 50 ° C. for 1 hour, followed by filtration, washing with methanol, drying, and 9.5 parts of blue powder Got.
λmax: 612 nm (in aqueous solution)

Example 3
(1) The following formula (17) (a mixture of No. 9, No. 10, and No. 11 in Table 1: 1.5 out of A, B, C, and D in the above formula (1) is 2nd and 3rd positions) Of the pyridine ring condensed with benzene ring, R ₁ is 2- (2-hydroxyethoxy) ethyl group, R ₂ is hydrogen atom, X is 3,6,8-trisulfonaphthalene-1 -Ylamino group, compound in which Y is 4-carboxyanilino group and E is ethylene)

Add 40.0 parts of the copper benzo (2,3-pyrido) porphyrazinesulfonyl chloride wet cake obtained in Example 1- (2) to 100 parts of ice and add water to adjust the liquid volume to 400 parts. The suspension was stirred and suspended at 5 ° C or lower. After 15 minutes, a solution obtained by dissolving 13.1 parts of the compound of the formula (14) obtained in Example 1- (3) in 65 parts of hot water and 4 parts of 2-aminoethoxyethanol was added. After the addition, the pH was adjusted to 9.0 with a 10% 2-aminoethoxyethanol aqueous solution. While maintaining the same pH, the temperature was raised to 20 ° C. over 10 minutes and kept at the same temperature for 8 hours. The liquid volume at this time was 500 parts. The temperature of the reaction solution was raised to 50 ° C., 100 parts of sodium chloride was added and stirred for 10 minutes, and then adjusted to pH 0.9 with hydrochloric acid over 5 minutes, followed by filtration to obtain 59.2 parts of a wet cake. Water was added to 59.2 parts of the obtained wet cake to adjust the liquid volume to 450 parts, the temperature was raised to 60 ° C., and the pH was adjusted to 10.5 with a 25% sodium hydroxide solution to complete dissolution. After adding 90 parts of sodium chloride and stirring for 15 minutes, the pH was adjusted to 2.0 with hydrochloric acid over 5 minutes, followed by filtration to obtain 54.2 parts of a wet cake. 54.2 parts of the resulting wet cake was put into 570 parts of methanol, 57 parts of water was added and suspended and stirred at 50 ° C. for 1 hour, followed by filtration, washing with methanol and drying, 10.4 parts of blue powder Got.
λmax: 609 nm (in aqueous solution)

Example 4 (Ink evaluation)
(A) Preparation of ink Each component shown in Table 2 below was mixed and dissolved, and filtered through a 0.45 μm membrane filter (manufactured by Advantech) to obtain an ink. The water used was ion exchange water. Further, water and caustic soda (pH adjuster) were added so that the pH of the ink was pH = 8 to 10 and the total amount was 100 parts.

Table 2
Each porphyrazine dye mixture obtained in Example 3 5.0 parts water + caustic soda 75.9 parts glycerin 5.0 parts urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts IPA (isopropyl alcohol) 3.0 parts butyl carbitol 2.0 parts Surfinol 104PG50 (manufactured by Nissin Chemical) 0.1 part 100.0 parts in total

As a comparative example, C.I. I. Inkjet recording dye used as Direct Blue 199, product name: Projet Cyan 1 (manufactured by Avecia: Comparative Example 1) and a dye mixture synthesized and purified by the method described in Example 1 of Patent Document 8 ( Comparative Example 2) and the coloring compound synthesized and purified by the method described in Example 3 of Patent Document 12 (Comparative Example 3), when printed, have the same print density as the ink of Example 3 in Table 1. Was adjusted in the same manner. The ink using the product of Comparative Example 1 was C-A, the ink using the compound of Comparative Example 2 was C-B, and the ink using the product of Comparative Example 3 was C-C.
Structural formulas of the compounds of Comparative Example 2 (101) and Comparative Example 3 (102) are shown below.

For evaluation of mixed color parts, C.I. I. A yellow ink having the composition shown in Table 3 below was prepared using Direct Yellow 132.

Table 3
C. I. Direct Yellow 132 3.0 parts water + caustic soda 77.9 parts glycerin 5.0 parts urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts IPA (isopropyl alcohol) 3.0 parts butyl carbitol 2.0 Part Surfinol 104PG50 (manufactured by Nissin Chemical) 0.1 part total 100.0 parts

For the evaluation of the mixed color portion, a magenta ink having a composition shown in Table 4 below was prepared using the dye described in Example 3 of JP-A No. 2003-192930, that is, the following formula (103) as a magenta dye.

Table 4
Dye of formula (103) 5.0 parts water + caustic soda 75.9 parts glycerin 5.0 parts urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts IPA (isopropyl alcohol) 3.0 parts butyl carbitol 2.0 parts Surfinol 104PG50 (manufactured by Nissin Chemical) 0.1 parts total 100.0 parts

The structural formula of the dye described in Example 3 of JP-A-2003-192930 is represented by the following formula (103).

(B) Inkjet printing Using an inkjet printer (trade name: PIXUS ip3100 manufactured by Canon Inc.), glossy paper A (Advanced Photo Paper (Glossy) Q7871A manufactured by Hewlett-Packard Japan), glossy paper B (Epson Photographic Paper <Glossy> Inkjet recording was performed on two types of KA420PSK).
When printing, an image pattern is created so that six levels of gradation can be obtained with a cyan single color and a reflection density of 100%, 85%, 70%, 55%, 40%, 25%, and a halftone printed matter is obtained. It was. In the light resistance test and the ozone resistance test, the measurement was performed using the gradation portion having the reflection density D value of the printed material before the test closest to 1.0. Printing of the mixed color portion is a green pattern for the mixed color with the yellow color and a blue pattern for the mixed color with the magenta color, and the densities are 100%, 85%, 70%, 55%, 40%, and 25, respectively. An image pattern was created so that 6 gradations of% could be obtained.

(C) Evaluation of recorded image Hue evaluation of a single color portion The hue of the recorded image is a *, b * when the recording paper is color-measured using a colorimetry system (SpectroEye: manufactured by GretagMacbeth) and L * of the printed material is in the range of 40-80. The value was measured. The evaluation was performed in three stages, with a preferable a * value being defined as -60 to -20 and a b * value being defined as -60 to -20.
○: Both a * and b * values exist in a preferred region. Δ: Only one a * and b * value exist in a preferred region. ×: Both a * and b * values exist outside a preferred region.

2. Evaluation of Mixed Color Portion Using the above colorimetric system, the C * value was compared and evaluated for the mixed color portion of the cyan ink and yellow ink of the present invention or the cyan ink and magenta ink of the present invention. For the green color, that is, the hue (green), which is a color mixture with the yellow ink, the measurement is performed in the portion where the L * value of the printed material is in the range of 54 to 62, and the C * value there is used in the following three stages. evaluated. Similarly, for a blue color, that is, a hue (blue), which is a color mixture portion with magenta ink, measurement is performed in a portion where the L * value of the printed material is in the range of 37 to 43, and the following 3 depending on the C * value there. Rated by stage.
Hue (green)
○: C * value is 75 or more Δ: C * value is less than 75 and 70 or more x: C * value is less than 70 Hue (blue)
○: C * value is 63 or more Δ: C * value is less than 63 and 60 or more X: C * value is less than 60

3. The test piece of the light fastness test recorded image was irradiated with a xenon weather meter (Model Ci4000 manufactured by ATLAS) at 0.36 W / m2 illuminance for 50 hours under the conditions of a bath temperature of 24 ° C. and a humidity of 60% RH. After the test, the reflection density before and after the test was measured using a color measurement system in the range of the reflection density (D value) of 0.70 to 0.85. After the measurement, the dye residual ratio was calculated by (reflected density after test / reflected density before test) × 100 (%) and evaluated in three stages.
○: Residual rate of 70% or more Δ: Residual rate of less than 70, 50% or more ×: Residual rate of less than 50%

4). The test piece of the ozone resistance test record image was left for 8 hours at an ozone concentration of 12 ppm, a bath temperature of 24 ° C., and a humidity of 60% RH using an ozone weather meter (model OMS-H manufactured by Suga Test Instruments Co., Ltd.). After the test, the reflection density before and after the test was measured using a color measurement system in the range of the reflection density (D value) of 0.70 to 0.85. After the measurement, the dye residual ratio was calculated by (reflected density after test / reflected density before test) × 100 (%) and evaluated in four stages.
◎: Residual rate 85% or more ○: Residual rate less than 85%, 70% or more Δ: Residual rate less than 70%, 50% or more ×: Residual rate less than 50%

5). The specimen of the moisture resistance test recorded image was left for 3 days at a temperature of 50 ° C. and a humidity of 90% RH using a thermo-hygrostat (manufactured by Applied Giken Sangyo Co., Ltd.). After the test, the bleeding of the test piece was visually evaluated in three stages.
○: No blurring is observed Δ: Slight blurring is observed ×: Large blurring is observed

6). Bronze property evaluation Bronze property evaluation is performed at any level or higher with respect to six levels of print density of 100% density, 85% density, 70% density, 55% density, 40% density, and 25% density. This was evaluated visually. For the case where bronzing did not occur, OK, and for the case where bronzing occurred, the minimum density in the above six steps among the printing densities where bronzing occurred was described.

Table 5 (Glossy Paper A) and Table 6 (Glossy Paper) show the hue evaluation, light resistance test result, ozone resistance test result, moisture resistance test and bronze resistance evaluation result of the ink recorded image obtained in Example 4 above. B).

As is apparent from Tables 5 and 6, the cyan ink using the compound of the present invention showed a good hue regardless of whether it was a single color or a mixed color. In particular, in the hue (blue) that is a color mixture portion with magenta ink, when glossy paper A is used, the C * values of C-A, C-B, and C-C, which are the respective inks of the comparative examples, are C- A and C-C are less than 60 and C-B is less than 63 and 60 or more, whereas in Example 4 which is the ink of the present invention, the same is 63 or more, and when glossy paper B is used. The C * values of C-A, C-B, and C-C, which are the inks of the comparative examples, are C-A and C-B of less than 63 and 60 or more, respectively, whereas C-C is less than 60. Thus, in Example 4 which is the ink of the present invention, it is similarly 63 or more, and it can be seen that the saturation is higher than each ink of the comparative example.
Further, in any ozone resistance test using glossy papers A and B, the residual ratio of dyes before and after the test of C-A and C-B as comparative examples is less than 50%, and in C-C, less than 85% 70 On the other hand, Example 4 of the present invention has a dye residual ratio of 85% or more, and is excellent in ozone resistance.
As described above, the ink using the coloring matter of the present invention can broaden the color reproduction range of the printed matter as compared with the ink of the comparative example, and is excellent in light resistance, ozone resistance and moisture resistance, particularly It can be said that the ozone resistance is very excellent.

Claims (24)

Porphyrazine coloring matter represented by the following formula (1) or a salt thereof

[In the formula (1), A, B, C and D independently represent a 6-membered ring having aromaticity, at least one is a benzene ring, and at least one contains a nitrogen-containing heteroaromatic ring. E represents alkylene, and R ₁ and R ₂ each independently represents an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group, a hydroxyalkoxyalkoxyalkyl group, or a hydrogen atom. However, the case where R ₁ and R ₂ are hydrogen atoms at the same time is excluded. X and Y are each independently an anilino group (sulfo group, carboxyl group, phosphono group, carbamoyl group, sulfamoyl group, ureido group, alkyl group, alkoxy group, allyloxy group, hydroxyl group, dialkylamino group, alkylamino group, arylamino group. Group, acetylamino group, cyano group, nitro group, halogen atom, or 0 to 4 substituents selected from two or more kinds selected from a heterocyclic group) or a naphthylamino group (sulfo group). , A carboxyl group, a ureido group, an alkyl group, an alkoxyl group, a hydroxyl group, a dialkylamino group, an alkylamino group, an arylamino group, an acetylamino group, a cyano group, a nitro group, a halogen atom, a heterocyclic group, or 0 to 4 substituents may be used.) Further, at least one of X and Y is a group having a sulfo group or a carboxyl group as a substituent. Also, b is 0 to 2.9, c is 0.1 to 3, and the sum of b and c is 1 to 3. ] The porphyrazine coloring matter or a salt thereof according to claim 1, wherein the nitrogen-containing heteroaromatic ring corresponding to A, B, C, or D is a pyridine ring or a pyrazine ring. Claim 1 or 2 obtained by reacting a porphyrazine dye represented by the following formula (3) with an amine represented by the following formula (4) in the presence of an amine represented by the following formula (10). Porphyrazine coloring matter or salt thereof described

[In the formula (3), A, B, C and D represent the same meaning as in claim 1. N is 1 to 3. ]

[In Formula (4), E, X, and Y represent the same meaning as described in claim 1. ]

[In Formula (10), R < ₁ > and R < ₂ > represent the same meaning as described in claim 1. ] The amine represented by the formula (4) according to claim 3 and 0.5 to 4 molar equivalents of the amine represented by the formula (4) according to claim 3 with respect to 1 molar equivalent of the porphyrazine dye represented by the formula (3) according to claim 3. The porphyrazine coloring matter or a salt thereof according to claim 3, obtained by reacting in the reaction system at a pH in the range of 6 to 10 in the presence of the amine represented by formula (10) according to claim 4. The number of pyridine rings or pyrazine rings corresponding to A, B, C and D is 1 to 3, E represents C2 to C4 alkylene, and X and Y are each independently an anilino group, a sulfo-substituted anilino group A carboxyl-substituted anilino group, a phosphono-substituted anilino group, a naphthylamino group, a sulfo-substituted naphthylamino group or a carboxy-substituted naphthylamino group, and the substituted anilino group and the substituted naphthylamino group are a sulfo group, a carboxyl group, a phosphono group, and a hydroxyl group. , An alkoxy group, a ureido group, an acetylamino group, a nitro group, and 0 to 2.9 substituents having one or more substituents selected from the group consisting of a chlorine atom and b may be from 0 to 2.9. The porphyrazine coloring matter or a salt thereof according to claim 2, wherein c is 0.1 to 3, and the sum of b and c is 1 to 3. E represents ethylene or propylene, X and Y are each independently a sulfo-substituted anilino group, a carboxyl-substituted anilino group or a sulfo-substituted naphthylamino group, b is from 0 to 2.9, and c is 0.1 The porphyrazine coloring matter or a salt thereof according to claim 5, wherein the sum of b and c is 1 to 3. A is a pyridine ring condensed at the 2-position and 3-position or 3-position and 4-position or a pyrazine ring condensed at the 2-position and 3-position, and B is condensed at the 2-position and 3-position or 3-position and 4-position Pyridine ring or pyrazine ring or benzene ring condensed at the 2-position and 3-position, and C is condensed at the 2-position, 3-position, 3-position and 4-position, or pyridine ring or 2-position and 3-position A pyrazine ring or a benzene ring, D is a benzene ring, E is a C2-C4 alkylene, and X and Y are each independently a sulfo group, a carboxy group, a methoxy group, a nitro group, a chlorine atom, a hydroxy group. The anilino group or naphthylamino group having 1 to 3 substituents selected from the group consisting of: b is 0 to 2.9, and c is 0.1 to 3. Porphyrazine dye or its salt The porphyrazine coloring matter or salt thereof according to claim 1 or 2 represented by the following formula (2):

[In Formula (2), Z ₁ to Z ₈ each independently represents a nitrogen atom or a carbon atom. However, at least one of the combinations of Z ₁ and Z ₂ , Z ₃ and Z ₄ , Z ₅ and Z ₆ , and Z ₇ and Z _{8 is} a combination of carbon atoms. E, X, Y, b, and c have the same meaning as described in claim 1. ] A porphyrazine dye represented by the following formula (5) and an amine represented by the formula (4) according to claim 3 are reacted in the presence of the amine represented by the formula (10) according to claim 3. A porphyrazine coloring matter or a salt thereof according to claim 8, obtained by

[In the formula (5), Z ₁ to Z ₈ represent the same meaning as in claim 8. N is 1 to 3. ] The amine represented by the formula (4) according to claim 3 and 0.5 to 4 mole equivalent of the amine represented by the formula (4) according to claim 3 with respect to 1 molar equivalent of the porphyrazine dye represented by the formula (5) according to claim 9. The porphyrazine coloring matter or salt thereof according to claim 9, obtained by reacting in the reaction system in the range of pH 6 to 10 in the presence of the amine represented by formula (10) according to claim 10. A is a pyridine ring condensed at the 2-position and 3-position, B is a pyridine ring or benzene ring condensed at the 2-position and 3-position, and C is a pyridine ring or benzene condensed at the 2-position and 3-position A ring, D is a benzene ring, E is a C2-C4 alkylene, R ₁ and R ₂ are each independently a hydrogen atom, a hydroxy C1-C4 alkyl group, a hydroxy C1-C4 alkyloxy C1-C4 alkyl group. Wherein X and Y are independently selected from the group consisting of a sulfo group and a carboxy group, except that R ₁ and R ₂ are simultaneously hydrogen atoms. The porphyrazine coloring matter or a salt thereof according to claim 1, which is an anilino group or naphthylamino group having three substituents, b is 0 to 2.9, and c is 0.1 to 3. A dye mixture containing the porphyrazine dye or a salt thereof according to any one of claims 1 to 11. The porphyrazine coloring matter or the salt thereof and the phthalocyanine coloring matter mixture according to any one of claims 1 to 12. An ink comprising the porphyrazine dye or the dye mixture according to any one of claims 1 to 12 as a dye component. The ink according to claim 14 containing an organic solvent. The ink according to claim 14 or 15, which is for inkjet recording. In an ink jet recording method in which ink droplets are ejected according to a recording signal and recording is performed on a recording material, the ink according to any one of claims 14 to 16 or an ink set including the ink is used as ink. INK JET RECORDING METHOD The inkjet recording method according to claim 17, wherein the recording material is an information transmission sheet. 19. The ink jet recording method according to claim 18, wherein the information transmission sheet is a surface-treated sheet having an ink image-receiving layer containing white inorganic pigment particles on a support. A container containing the ink according to any one of claims 14 to 16. An ink jet printer having the container according to claim 20. Colored body colored with the ink according to any one of claims 14 to 16. The porphyrazine coloring matter or a salt thereof according to claim 4, comprising a compound represented by the formula (1) according to claim 1, wherein b is 0.1 to 2.5. The porphyrazine coloring matter or a salt thereof according to claim 10, comprising a compound represented by the formula (2) according to claim 8, wherein b is from 0.1 to 2.5.