JP2008013706A - Ink composition, inkjet recording method, method for preventing bronzing, and colored matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition having a good hue as cyan ink and being excellent in image solidity such as light resistance, ozone resistance, and moisture resistance while preventing bronzing, and to provide an inkjet recording method. <P>SOLUTION: The ink composition comprises a compound represented by formula (1) as a porphyrazine dye or a salt thereof and a water-soluble copper phthalocyanine dye having an alkylsulfonyl group as a substituent or a salt thereof. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an ink composition, a method for suppressing a bronze phenomenon using the ink composition, an ink jet recording method, and a colored body.

  A recording method using an ink jet printer, which is one of the representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.) for recording. Is what you do. This method has been spreading rapidly in recent years due to the fact that the recording head and the recording material do not contact each other and is quiet with little sound generation, and is easy to downsize and speed up. Expected. Conventionally, water-based inks in which water-soluble dyes are dissolved in an aqueous medium have been used as inks such as fountain pens, felt-tip pens, and ink-jet recording inks. In order to prevent clogging of ink, a water-soluble organic solvent is generally added. For this reason, these conventional inks provide a recording image with sufficient density, do not cause clogging of the pen tip and nozzles, have good drying properties on the recording material, and have little bleeding. It is required that a bronze phenomenon (also referred to as a bronzing phenomenon) does not easily occur on the material, and that storage stability is excellent. Further, the formed image is required to have image fastness such as water resistance, light resistance, ozone gas resistance and moisture resistance.

  The bronze phenomenon refers to a phenomenon in which the dye becomes a piece of metal on the surface of the recording material due to the association of the dye or poor absorption of the ink, and so on. When this phenomenon occurs, the glossiness, print quality, and print density are all inferior. Especially when a metal phthalocyanine dye is used as a pigment, it often appears as a red floating phenomenon in a portion printed at a high density, and the color balance becomes uneven as a whole image, resulting in a decrease in image quality. The improvement is desired. In recent years, glossy paper has been widely used as a recording medium with a texture close to that of a photographic tone, but due to the bronze phenomenon of specific colors, the glossiness on the surface of the printed matter varies, and the image Therefore, the improvement is strongly desired from the viewpoint of maintaining the glossiness of the entire image.

  Ozone gas resistance is usually called ozone resistance or gas resistance, but this means that ozone gas with an oxidizing action present in the air reacts with dyes in recording paper and discolors the printed image. It is resistance to the phenomenon. In addition to ozone gas, examples of the oxidizing gas having this kind of action include NOx, SOx, etc., but the reason why ozone gas promotes the color fading phenomenon of ink jet recording images more than these oxidizing gases. It is considered a substance. For this reason, ozone gas is used in the acceleration test to know the degree of ozone gas resistance. Such a discoloration and fading phenomenon caused by an oxidizing gas is characteristic of an ink jet image, so that improvement of ozone gas resistance has become a more important issue. In particular, the ink receiving layer provided on the surface of photographic image quality inkjet paper uses a porous material such as a white inorganic pigment to speed up ink drying and reduce bleeding at high image quality. In many cases, discoloration due to ozone gas is more noticeable on such recording paper.

  Typical skeletons of water-soluble cyan dyes used in ink jet recording inks are phthalocyanine and triphenylmethane. In recent years, phthalocyanine-based dyes have been reported most extensively for improving pigments from the viewpoint of improving image fastness and used as inks. However, the bronze phenomenon is particularly noticeable in cyan inks using phthalocyanine dyes that have improved ozone resistance, and there is a need for improvement.

  In the future, in order to expand the field of use of printing methods using ink, it is expected that the types of recording materials for ink-jet recording will increase. Therefore, ink that can be used in various applications and environments is required. ing. Among them, as a cyan ink, there is a high technical demand for suppressing the bronze phenomenon as much as possible while maintaining a high level of ozone resistance.

Patent Documents 1 to 4 disclose a technique of using a dye having good ozone resistance and suppressing the bronze phenomenon by adding an additive. However, any technique can be said to be sufficient when used alone. Not so effective.
Patent Documents 5 to 11 disclose cyan dyes having good ozone resistance. However, in inks using these, bronze phenomenon is observed depending on the type of recording material and printing density, and suppression of the bronze phenomenon. From this point of view, it does not meet the market requirements sufficiently.

JP 2003-31478 A JP 2004-91630 A JP 2004-91631 A JP 2004-263155 A Japanese Patent Laid-Open No. 2002-249677 JP 2002-275386 A JP 2002-294097 A JP 2002-302623 A JP 2002-327132 A JP 2003-003099 A JP 2003-213168 A

  An object of the present invention is to solve the above problems, and to provide an ink composition having a good hue as a cyan ink and excellent in image fastness such as light resistance, ozone resistance and moisture resistance while suppressing a bronze phenomenon. It is another object of the present invention to provide an ink jet recording method using the ink composition.

The inventors of the present invention have studied in detail the pigments having good hue, light resistance and ozone resistance, and the ink composition is prepared by mixing two kinds of a specific porphyrazine dye and a specific phthalocyanine dye. As a result of the preparation, it was found that the above problems can be solved, and the present invention has been completed. That is, the present invention
(1)
The following formula (1) as a porphyrazine coloring matter or a salt thereof (I)

[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 X and Y each independently represent 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) You may have 0-4 1 type (s) or 2 or more types of substituents selected from a group, an alkylamino group, an arylamino group, an acetylamino group, a cyano group, a nitro group, a halogen atom, and a heterocyclic group. ) And naphthylamino group (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 atom, heterocyclic ring 1 to 2 or more kinds of substituents selected from a group may be included.) . 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. ]
An ink composition comprising a compound represented by the formula: and a water-soluble copper phthalocyanine dye or a salt thereof (II) having an alkylsulfonyl group as a substituent,
(2)
The ink composition according to (1), wherein the nitrogen-containing heteroaromatic ring corresponding to A, B, C, and D in formula (1) is a pyridine ring or a pyrazine ring,
(3)
Porphyrazine dye or its salt (I) is represented by the following formula (3)

[In the formula (3), A, B, C and D represent the same meaning as in claim 1. N is 1 to 3. ]
And a compound represented by the following formula (4)

[In Formula (4), E, X, and Y represent the same meaning as described in claim 1. ]
The ink composition according to (1) or (2), which is a compound obtained by reacting an amine compound represented by:
(4)
The amount of the amine compound represented by formula (4) is 0.5 to 4 molar equivalents relative to 1 molar equivalent of the compound of general formula (3), and the pH in the reaction system is 7 in the presence of ammonia. The ink composition according to (3), which is reacted in the range of
(5)
The number of pyridine rings or pyrazine rings corresponding to A, B, C, and D in formula (1) is 1 to 3, E represents C2-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, wherein the substituted anilino group and the substituted naphthylamino group are a sulfo group and a carboxyl group , A phosphono group, a hydroxyl group, an alkoxy group, a ureido group, an acetylamino group, a nitro group and 0 to 3 substituents of one or more selected from the group consisting of chlorine atoms, The ink composition according to (2), wherein 0 to 2.9, c is 0.1 to 3, and the sum of b and c is 1 to 3.
(6)
E in formula (1) 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, the ink composition according to (5), wherein c is from 0.1 to 3, and the sum of b and c is from 1 to 3;
(7)
A in formula (1) 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 2-position, 3-position or 3-position and A pyridine ring condensed at the 4-position or a pyrazine ring or a benzene ring condensed at the 2-position and the 3-position, wherein the C-condensed pyridine ring at the 2-position, 3-position, 3-position and 4-position, or the 2-position and 3-position A pyrazine ring or a benzene ring condensed at the position, D is a benzene ring, E is C2-C4 alkylene, and X and Y are each independently a sulfo group, a carboxy group, a methoxy group, a nitro group, An anilino group or a naphthylamino group having 1 to 3 substituents selected from the group consisting of a chlorine atom and a hydroxy group, b is 0 to 2.9, and c is 0.1 to 3 ( The ink composition according to 1),
(8)
Porphyrazine dye or its salt (I) is 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. ]
The ink composition according to (1), which is a compound represented by:
(9)
The compound represented by the formula (3) is represented by the following formula (5).

[In formula (5), Z ₈ from Z ₁ has the same meaning as those described in (7). N is 1 to 3. ]
The ink composition according to (3), which is a compound represented by:
(10)
The amount of the amine compound represented by formula (4) is 0.5 to 4 molar equivalents relative to 1 molar equivalent of the compound of general formula (5), and the pH in the reaction system is 7 in the presence of ammonia. The ink composition according to (9), which is reacted in the range of
(11)
In Formula (1), 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 condensed at the 2-position and 3-position. A pyridine ring or a benzene ring, D is a benzene ring, E is C2-C4 alkylene, and X and Y are each independently 1 to 3 selected from the group consisting of a sulfo group and a carboxy group The ink composition according to (1), which is an anilino group or naphthylamino group having a substituent of: b is 0 to 2.9, and c is 0.1 to 3.
(12)
A water-soluble copper phthalocyanine dye or salt (II) having an alkylsulfonyl group as a substituent is represented by the following formula (6):

(Wherein R ₁ to R ₄ each independently represents a substituted or unsubstituted alkyl group, provided that at least one of R ₁ to R ₄ has an ionic hydrophilic group as a substituent.)
The ink composition according to any one of (1) to (11), which is a compound represented by:
(13)
In Formula (6), R ₁ to R ₄ are substituted (C1-C4) alkyl groups, and the substituent is a hydroxyl group, a carboxyl group, a sulfone group, an alkoxy group (a hydroxyl group, an alkoxy group, a carboxyl group, or a sulfo group). Further, a carbamoyl group (which may be further substituted with an alkyl group further substituted with a hydroxyl group, an alkoxy group, a carboxyl group or a sulfo group), a sulfamoyl group (a hydroxyl group, which may be substituted with a substituted alkoxy group) And may be substituted by an alkyl group further substituted with an alkoxy group, a carboxyl group or a sulfo group), and at least one of R ₁ to R ₄ contains a carboxyl group or a sulfo group (1) To the ink composition of any one of (12),
(14)
The mixing ratio of the porphyrazine dye or its salt (I) and the water-soluble copper phthalocyanine dye or its salt (II) having an alkylsulfonyl group as a substituent is 10:90 to 80:20 by mass ratio (1) To the ink composition according to any one of (13),
(15)
When the ratio of the porphyrazine dye or salt (I) and the water-soluble copper phthalocyanine dye or salt (II) having an alkylsulfonyl group as a substituent contained in the ink composition is 0.5 The ink composition according to any one of (1) to (13), which is 8 to 8% by mass and 0.1 to 2.5% in the case of a low concentration,
(16)
The ink composition according to any one of (1) to (15), wherein the maximum absorption wavelength in water of a porphyrazine dye or a salt thereof (I) in a visible light region is 595 nm to 610 nm,
(17)
The ink composition according to any one of (1) to (16), wherein the porphyrazine dye or a salt thereof (I) occupies 10 to 80% by mass in all the dyes in the ink composition,
(18)
An ink containing the ink composition according to any one of (1) to (17) for inkjet recording;
(19)
In an inkjet recording method for recording on a recording material by ejecting ink droplets according to a recording signal, the inkjet recording method comprising using the ink according to (18) or an ink set including the ink,
(20)
A bronze suppression method using the ink or ink set according to (19),
(21)
The inkjet recording method according to (19), wherein the recording material is an information transmission sheet,
(22)
The inkjet recording method according to (20), wherein the information transmission sheet is a surface-treated sheet and has an ink image-receiving layer containing white inorganic pigment particles on a support.
(23)
(1) to the ink composition according to any one of (18), or a colored product colored with the ink or ink set according to (19),
About.

The ink composition of the present invention has a good hue as a cyan ink, and is excellent in image fastness such as light resistance, ozone resistance and moisture resistance while suppressing the bronze phenomenon. In addition, there is no crystal precipitation, physical property change, color change, etc. after long-term storage, and storage stability is good. Furthermore, by using with other magenta ink and yellow ink, a color tone in a wide visible region can be obtained. Therefore, the ink composition of the present invention is extremely useful as an ink for inkjet recording.

The present invention will be described in detail. The ink suitable for inkjet recording of the present invention is an ink composition in which at least two kinds of dyes, that is, a porphyrazine dye or a salt thereof (I) and a phthalocyanine dye (II) are mixed, and one of them (I ) Is particularly represented by the formula (1) and (II), particularly by the formula (6).
In the present invention, a porphyrazine dye having a nitrogen-containing heteroaromatic ring represented by the formula (1) or a salt thereof and a copper phthalocyanine dye having an alkylsulfonyl group represented by the formula (6) or a salt thereof are mixed. It was found that the obtained ink composition is excellent in ozone resistance and suppression of bronzing phenomenon.

  An ink composition suitable for inkjet recording of the present invention comprises a porphyrazine dye of the above formula (1) and copper phthalocyanine having an alkylsulfonyl group represented by the above formula (6). That is, tetrabenzoporphyrazine (usually called phthalocyanine) in which one to three benzo rings are replaced with nitrogen-containing heteroaromatic rings is used as the dye mother nucleus, and an unsubstituted sulfamoyl group, substituted Ink containing a combination of a porphyrazine dye having a sulfamoyl group and a copper phthalocyanine dye having an alkylsulfonyl group having an ionic hydrophilic group is extremely resistant to ozone gas and hardly causes bronzing. Is found.

  First, the porphyrazine dye or its salt (I) will be described. 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, the ozone resistance improves, but tends to deviate from the normal cyan hue. The number of nitrogen-containing heteroaromatic rings may be appropriately adjusted in consideration of ozone resistance and hue, and a balanced ratio may be selected.

  b is 0 to 2.9, c is 0.1 to 3, and the sum of b and c is 1 to 3. As b increases, ozone resistance tends to improve, but bronzing tends to occur easily. Taking into account ozone resistance and bronzing, the number of b and c is adjusted as appropriate to achieve a balance. Select a good ratio. 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.

X and Y each independently represents an unsubstituted or substituted anilino group or an unsubstituted or substituted naphthylamino group.
As the substituent of the substituted 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, 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 5-hydroxy-7-sulfonaphthalen-2-ylamino group.

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.
Particularly preferred salts are lithium and sodium salts.

Specific examples of A, B, C, D, E, X and Y in the porphyrazine dye represented by the above formula (1) of the present invention are shown in Table 1, but the porphyrazine dye used in the present invention is as follows. It is not limited to the example.
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, the mixture is usually used as it is, but even if it is a mixture of isomers, no particular problem is caused in the present invention, so these isomers will be described without distinction.

Table 2 shows specific examples of the substituents R ₁ to R _{4 in} the water-soluble copper phthalocyanine dye or salt (II) having an alkylsulfonyl group as a substituent used in the ink composition of the present invention. In the table, carboxyl groups and sulfo groups that are ionic hydrophilic groups are described in the form of free acids.
Table 3 shows specific combinations of substituents in the copper phthalocyanine dye (II).

(Continued from Table 2)

Table 3
Compound No. R ₁ R ₂ R ₃ R ₄
201 2-1 2-1 2-1
202 2-1 2-1 2-1 2-5
203 2-1 2-1 2-5 2-5
204 2-1 2-1 2-1 2-6
205 2-1 2-1 2-1 2-7
206 2-1 2-1 2-1 2-8
207 2-1 2-1 2-1 2-9
208 2-1 2-1 2-1 2-10
209 2-1 2-1 2-1 2-11
210 2-1 2-1 2-1 2-12
211 2-1 2-1 2-1 2-13
212 2-1 2-1 2-1 2-14
213 2-1 2-1 2-1 2-15
214 2-1 2-1 2-15 2-15
215 2-1 2-15 2-15 2-15
216 2-1 2-1 2-1 2-16
217 2-1 2-1 2-16 2-16
218 2-1 2-16 2-16 2-16
219 2-1 2-1 2-1 2-17
220 2-1 2-1 2-17 2-17
221 2-1 2-17 2-17 2-17
222 2-1 2-1 2-1 2-18
223 2-1 2-1 2-18 2-18
224 2-1 2-18 2-18 2-18
225 2-1 2-1 2-1 2-21
226 2-1 2-1 2-21 2-21
227 2-1 2-1 2-1 2-22
228 2-1 2-1 2-22 2-22
229 2-1 2-1 2-1 2-23
230 2-1 2-1 2-1 2-24
231 2-2 2-2 2-2 2-2
232 2-2 2-2 2-2 2-14
233 2-2 2-2 2-14 2-14
234 2-2 2-2 2-2 2-19
235 2-2 2-2 2-2 2-20
236 2-3 2-3 2-3 2-3
237 2-4 2-4 2-4 2-4
238 2-6 2-6 2-6 2-6
239 2-7 2-7 2-7 2-7
240 2-11 2-11 2-11 2-11
241 2-12 2-12 2-12 2-12
242 2-13 2-13 2-13 2-13
243 2-14 2-14 2-14 2-14
244 2-18 2-18 2-18 2-18
245 2-20 2-20 2-20 2-20

  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 (7) is synthesized. The copper porphyrazine coloring matter represented by the following formula (7) can be obtained, for example, by reacting a nitrogen-containing heteroaromatic dicarboxylic acid derivative with a phthalic acid derivative in the presence of a catalyst and a copper compound. 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.
Examples of the nitrogen-containing heteroaromatic dicarboxylic acid derivative include dicarboxylic acid compounds such as quinolinic acid, 3,4-pyridinedicarboxylic acid, and 2,3-pyrazinedicarboxylic acid; quinolinic anhydride, 3,4-pyridinedicarboxylic anhydride, Acid anhydrides such as 3-pyrazine dicarboxylic acid anhydride; dicarboxyamide compounds such as pyridine-2,3-dicarboxamide; dicarboxylic acid monoamide compounds such as pyrazine-2,3-dicarboxylic acid monoamide; quinolinic acid imide and the like Acid imide compounds; 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 (7), 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, drying, and the like.

  In the above formula (7), a synthesis method of a compound in which two of A, B, C, and D are pyridine rings and the remaining two are benzene rings is taken as an example of copper dibenzobis (2,3-pyrido) porphyrazine. Further details will be described.

  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 (7) 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 [below Formulas (8-A) to (8-E)] are generated. At the same time, copper tribenzo (2,3-pyrido) porphyrazine represented by one of A, B, C and D in the formula (7) is a pyridine ring and the remaining three are benzene rings [the following formula (9) And copper benzotris (2,3-pyrido) porphyrazine, in which three of A, B, C and D in the formula (7) are pyridine rings and the remaining one is a benzene ring, are produced as by-products. The compound further contains positional isomers of the pyridine ring nitrogen atom [the following formulas (10-A) to (10-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. As an average value, two are pyridine rings and the other two are benzene rings, which are used directly as copper dibenzobis (2,3-pyrido) porphyrazine. In most cases.

  Next, the copper chlorosulfonylporphyrazine dye represented by the above formula (3) is obtained by chlorosulfonating the copper porphyrazine dye represented by the above formula (7) in chlorosulfonic acid, or the formula (7) Is obtained by converting a sulfo group to a chlorosulfone group with a chlorinating agent after sulfonation in sulfuric acid or fuming sulfuric acid. The chlorosulfone group or sulfo group thus obtained is introduced onto the benzene ring when A, B, C, D in the formula (7) 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, by reacting the corresponding copper chlorosulfonylporphyrazine dye, the amine compound represented by the following formula (4) and ammonia in an aqueous solvent, usually pH 8 to 10, usually 5 to 70 ° C., usually 1 to 20 hours. The target compound represented by the above formula (1) is obtained. Examples of ammonia or an ammonia generation source used in the reaction include, but are not limited to, ammonium salts such as ammonium chloride and ammonium sulfate, urea, aqueous ammonia, and ammonia gas. The reaction of the copper chlorosulfonylporphyrazine dye, the organic amine and the aminating agent is usually performed in an aqueous solvent.
For pH adjustment at the time of condensation, for example, 28% ammonia water available as a commercial product can be used directly or diluted with water as necessary. Further, for example, when it is desired to synthesize a compound in which b is 2 and c is 1 in the formula (1), the compound in which p is 3 in the above formula (11) is led to a chlorosulfonyl derivative, and then the chlorosulfonyl compound In the presence of at least 2 molar equivalents of ammonia, the pH in the reaction system is adjusted to alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or alkali metal carbonate such as sodium carbonate or potassium carbonate. It is also possible to obtain a compound of the above formula (1) wherein b is 2 and c is 1 by adjusting and reacting with the above.
About pH in a reaction system, it is good to carry out reaction in the range of 7-10 normally, Preferably it is 7.5-10, More preferably, it is 8-10, Most preferably, it is the range of 8-9.5. When trying to obtain the above formula (1), if the pH in the reaction system is less than 7, 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 excess ammonia is present in the reaction system, the ammonia preferentially reacts with the chlorosulfonyl compound, and the compound of the following formula (4), the chlorosulfonyl compound, The reaction rate tends to decrease remarkably.
Therefore, ammonia, the ratio of adding the compound of the following formula (4) and the chlorosulfonyl compound, and the pH in the reaction system 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 compound 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 it is 0.5 mol equivalent. Molar equivalent to 3.5 molar equivalent, more preferably 1 molar equivalent to 3 molar equivalent. However, it varies depending on the reactivity of the amine compound and the reaction conditions, and is not limited thereto.

  The manufacturing method of the amine compound represented by Formula (4) is demonstrated. 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 organic amine represented by the formula (4) in the presence of ammonia. As a result, a compound in which the chlorosulfonyl compound of the formula (3) is hydrolyzed by water partially mixed in the reaction system and converted into a sulfonic acid is produced as a by-product, and the target formula (1) And it is theoretically considered to be mixed in the dye of (2). However, it is difficult to distinguish an unsubstituted sulfamoyl group and a sulfonic acid group in mass spectrometry. In the present invention, the chlorosulfonyl group in the formula (3) other than the one reacted with the organic amine represented by the formula (4) is used. Are all expressed as having been converted to an unsubstituted sulfamoyl group.

  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.

  When λmax (maximum absorption wavelength) in an aqueous solution in the visible light region of the porphyrazine dye of the formula (1) of the present invention or a salt thereof obtained as described above is measured, it is usually 580 to 620 nm, preferably 590 to 590 nm. It shows 615 nm, particularly preferably 595 to 610 nm.

Next, a water-soluble copper phthalocyanine dye or a salt (II) thereof having an alkylsulfonyl group as a substituent will be described. The water-soluble copper phthalocyanine dye (II) having an alkylsulfonyl group as a substituent used in the ink composition of the present invention is represented by the general formula (6). In the general formula (6), R ₁ to R ₄ each independently represents a substituted or unsubstituted alkyl group. However, at least one of R ₁ to R ₄ has an ionic hydrophilic group as a substituent.
The carbon chain of the substituted or unsubstituted alkyl group may be linear or branched, and the number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 to 4.
Examples of the substituent in the substituted alkyl group include a hydroxyl group, a carboxyl group, a sulfone group, an alkoxy group (which may be further substituted by an alkoxy group further substituted with a hydroxyl group, an alkoxy group, a carboxyl group, or a sulfo group), a carbamoyl group ( Substituted with an alkyl group further substituted with a hydroxyl group, an alkoxy group, a carboxyl group or a sulfo group), a sulfamoyl group (substituted with an alkyl group further substituted with a hydroxyl group, an alkoxy group, a carboxyl group or a sulfo group) May be used). As the ionic hydrophilic group, a sulfo group or a carboxyl group is preferable, and a sulfo group is particularly preferable.

As a preferable group in R ₁ to R ₄ of the general formula (6), a group selected from a sulfo group, a hydroxyl group, a methoxy group, and a sulfonamide group which may have a substituent may be used as a substituent. Good n-propyl group or n-butyl group. Particularly preferred R ₁ to R ₄ are 3-sulfo-n-propyl group, 4-sulfo-n-butyl group, 2-hydroxy-3-sulfo-n-propyl group, 3-sulfo-n-butyl group, 3-[(1-carboxy-2-hydroxy) ethylamino] sulfonyl-n-propyl, 3-[(2-methyl-n-butyl) amino] sulfonyl-n-propyl, 3-[(2,3-dihydroxy -N-propyl) amino] sulfonyl-n-propyl, 3-[(2-hydroxy-n-propyl) amino] sulfonyl-n-propyl, 3-[(2-ethyl-n-hexyl) amino] sulfonyl-n -Propyl, 3-[(2-methoxy-n-propyl) amino] sulfonyl-n-propyl, 3-[(1-methyl-n-propyl) amino] sulfonyl-n-propyl.

The porphyrazine dye or its salt (I) and copper phthalocyanine dye (II) used in the ink composition of the present invention may be each independently a free acid or a salt, and each independently a free acid and a salt. Or a mixture of different salts, a mixture of a free acid and a different salt, or the like.
Examples of these salts include alkali metal salts, onium salts of organic amines, ammonium salts, and the like. Sodium salts, lithium salts, and ammonium salts are preferable, and sodium and lithium salts are particularly preferable.

  The porphyrazine coloring matter, its salt (I), and the copper phthalocyanine coloring matter (II) used in the ink composition of the present invention are separated from the reaction solution obtained by synthesis, respectively, after aciding out or salting out, by filtration or the like. I can do it. 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 porphyrazine dye (I) and the copper phthalocyanine dye (II) obtained by the above method are each 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.

  Details of the method for producing the copper phthalocyanine dye of general formula (6) or a salt thereof used in the ink composition of the present invention are described in Patent Document 5 or Patent Document 11.

The ink composition of the present invention is prepared using water as a medium. When this ink is used as an ink for inkjet recording, it is contained in a porphyrazine dye or a salt thereof (I) and a copper phthalocyanine dye or a salt thereof (II). The content of anions such as Cl ^- and SO ₄ ^2- is preferably small, and the standard of the content is 5% by mass as the total content of Cl ^- and SO ₄ ^2- in each dye or its salt. Hereinafter, it is preferably 3% by mass or less, more preferably 1% by mass or less, and 1% by mass or less in the ink. Cl ^- and SO ₄ in preparing ^2- less the respective dye or a salt thereof, for example the usual way, or respectively by the reverse osmosis membrane dye or alcohol and a mixed solvent of water of a dry product or a wet cake of the salt The solution may be desalted by stirring, filtering 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 composition of the present invention is used as an ink for inkjet recording, a heavy metal (ion) such as zinc or iron contained as an impurity in the porphyrazine dye or its salt (I) and the copper phthalocyanine dye or its salt (II) It is preferable to use an alkaline earth metal (ion) such as calcium, magnesium, or the like having a low content such as silicon (contained as a central metal atom in a porphyrazine skeleton and a phthalocyanine skeleton by an ionic bond or a coordinate bond) Except copper). The standard of the content is, for example, about 500 ppm or less for each of the refined and dried products of each pigment or salt thereof, for 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) or a salt thereof is 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.

  In the ink composition of the present invention, the porphyrazine dye or its salt (I) and the copper phthalocyanine dye or its salt (II) are usually 0.1 to 10% by mass, preferably 0.5 to 8% by mass. Contained. The ink having a low concentration usually contains 0.1 to 2.5% by mass of (I) and (II).

  Each ratio of the porphyrazine dye or its salt (I) and the copper phthalocyanine dye or its salt (II) is preferably in the range of (I) :( II) = 10: 90 to 80:20, (I ) :( II) = 30: 70 to 60:40 is more preferable. Particularly preferably, (I) :( II) = 45: 55 to 55:45.

  The ink composition of the present invention is prepared using water as a medium. If necessary, the ink composition of the present invention further contains a water-soluble organic solvent 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 solubilizers, antifading agents, emulsion stabilizers, surface tension adjusters, Well-known additives, such as an antifoamer, a dispersing agent, a dispersion stabilizer, are mentioned. 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, based on the entire ink. Is good. The remainder other than the above is water.

  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 Amides such as formamide or N, N-dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2-one Heterocyclic ketones such as; ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one or keto alcohols; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1, 2- or 1, 3 -Propylene glycol, 1,2- or 1 Monomers and oligomers having (C2 to C6) alkylene units such as 4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and thiodiglycol Or polyalkylene glycol or thioglycol; polyol (triol) such as glycerin, hexane-1,2,6-triol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Triethylene glycol monomethyl ether or triethylene glycol Polyhydric alcohols Roh ethyl ether (C1 -C4) monoalkyl 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. Other specific examples of 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 antifading agent, various organic and metal complex antifading 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 monoole Esters such as ate and polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7- Acetylene glycol (alcohol) series such as all, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3ol (for example, trade name Surfy manufactured by Nisshin Chemical Co., Ltd.) Nord 104, 82, 465, Orphine 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 order to produce the ink of the present invention, there is no particular limitation on the order of dissolving each agent such as an additive. 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, it is also used as an ink set used in combination with each ink such as light magenta, blue, green, orange, dark yellow, and gray.

  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 body of the present invention is an ink composition containing the pigments (I) and (II) or colored with an ink 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, a synthetic paper, a film or the like provided with an ink receiving layer. The ink receiving layer may be formed by impregnating or coating the base material with a cationic polymer, or inorganic fine particles capable of absorbing the pigment in the ink, such as porous silica, alumina sol, and special ceramics. It is provided by coating the surface of the substrate together with the hydrophilic polymer.
Those provided with such an ink receiving layer are usually called ink jet dedicated paper (film), glossy paper (film) and the like. Among them, the ink jet paper of the type provided with the ink receiving / feeding described above is considered to be easily affected by gas having an oxidizing action in the air such as ozone gas. For example, Pictorico (manufactured by Asahi Glass Co., Ltd.), professional photo paper, super photo paper, matte photo paper (all manufactured by Canon Inc.), photo paper Krispia (high gloss), photo paper (gloss), Photomat paper (both manufactured by Seiko Epson Corporation), advanced photo paper (glossy) premium gloss film, photo paper (both manufactured by Hewlett-Packard Japan), photolike QP (manufactured by Konica Corporation), There are high-quality coated paper and photographic glossy paper (both manufactured by Sony Corporation).
Of course, plain paper can also be used.

  The colored body of the present invention includes a colored material colored with the ink using the inkjet printer. The material to be colored 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 method include a piezo method 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 of the present invention is used for ink jet printing, the ejector (ink head) is not blocked. The ink according to the present invention does not change its physical properties even when used 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. Although it is generally known that a high-quality recorded image with less graininess can be obtained by using a dark and light cyan ink set, the ink composition of the present invention is further divided into dark cyan and light cyan, respectively. By using it, you can avoid the bronze phenomenon that tends to be a problem with dark cyan, and use it with other yellow, magenta, and other inks such as green, red, orange, blue, etc. It is possible to obtain a color tone, and to obtain a recorded matter that is excellent in ozone resistance and excellent in light resistance and water resistance.

  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, 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 a substituted or unsubstituted sulfamoyl group in the benzo ring are included. 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 the description of the examples, when “(20% to the liquid)” is used when salting out, the total amount of the dye solution or dye suspension to be salted out (mass basis). Represents that 20% by mass of sodium chloride was used.
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 (7) 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 sulfolane, 18.4 parts phthalimide, 12.5 parts quinolinic acid, 72.0 parts urea, 8.8 parts copper (II) chloride dihydrate (purity 97.0%), 1.0 part of ammonium molybdate was added, the temperature was raised to 200 ° C., and kept at the same temperature for 5 hours. After completion of the reaction, the 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% aqueous ammonia, 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 (12) (compound in which X in formula (4) is 3,6,8-trisulfonaphthalen-1-ylamino group, Y is 2-carboxyanilino group, and E is ethylene)

  18.4 parts of cyanuric chloride and 0.02 part of trade name Leocol TD-90 (surfactant, manufactured by Lion Corporation) were added to 150 parts of ice water, and the mixture was 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 maintained at 2.0 to 3.0 using a 10% aqueous sodium hydroxide solution. The reaction was carried out at 0 to 10 ° C for 1 hour and 50 minutes, and at 20 to 25 ° C for 1 hour and 15 minutes. Next, 14.1 parts of 2-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 maintaining pH 7.0 to 8.0 using a 10% aqueous sodium hydroxide solution. went. The temperature was raised to 60 ° C., 60 parts of ethylenediamine was added dropwise, and then stirred overnight. Concentrated hydrochloric acid was added to adjust the pH to 1.0 while adding ice and maintaining the temperature at 20 ° C. or lower. At this time, the liquid volume was 1500 parts. To this reaction solution, 300 parts of sodium chloride was added over 15 minutes and then stirred for 15 minutes. The precipitated crystals were filtered to obtain 138.2 parts of a wet cake. The obtained wet cake was added to 500 parts of water and dissolved at a pH of 10.0 using a 10% aqueous sodium hydroxide solution. At this time, the liquid volume was 700 parts. Concentrated hydrochloric acid was added to the reaction solution to adjust to pH 1.0, 140 parts of sodium chloride was added over 20 minutes, and then stirred for 20 minutes. The precipitated crystals were filtered to obtain 160.0 parts of a wet cake. The obtained wet cake was added to a mixed liquid of 1250 parts of methanol and 125 parts of water and stirred at 50 ° C. for 1 hour, followed by filtration and washing with methanol to obtain 104.8 parts of a wet cake. The obtained wet cake was dried to obtain 64.3 parts of a compound of formula (12) as a white powder.

  (4) The following formula (13) (a 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. A compound in which the remaining 2.5 is a benzene ring, X is 3,6,8-trisulfonaphthalen-1-ylamino group, Y is 2-carboxyanilino group, and E is ethylene) Synthesis of

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 prepared by dissolving 13.16 parts of the compound of the formula (12) obtained in Example 1- (3) with 65 parts of warm water and 6 parts of 28% aqueous ammonia was added. After the addition, the pH was adjusted to 9.0 with 28% aqueous ammonia. 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 800 parts. The temperature of the reaction solution was raised to 50 ° C., 160 parts of sodium chloride was added and stirred for 10 minutes, and then adjusted to pH 1.0 with concentrated hydrochloric acid over 5 minutes, followed by filtration to obtain 85.2 parts of a wet cake. . Water was added to 85.2 parts of the obtained wet cake to make a liquid volume of 520 parts, the temperature was raised to 50 ° C., and the pH was adjusted to 10.0 with a 25% sodium hydroxide solution to complete dissolution. 104 parts of sodium chloride was added, stirred for 15 minutes, adjusted to pH 1.2 with hydrochloric acid over 5 minutes, and filtered to obtain 68.0 parts of a wet cake. 68.0 parts of the obtained wet cake was put into 440 parts of methanol, 44 parts of water was added, and the mixture was suspended and stirred at 50 ° C. for 1 hour, followed by filtration, washing with methanol and drying, and 13.0 parts of blue powder. Got.
λmax: 607 nm (in aqueous solution)

Example 2
(1) Synthesis of the following formula (14) (compound in which X and Y in formula (4) are 3-sulfoanilino groups and E is ethylene)

  18.5 parts of cyanuric chloride and 0.02 part of trade name Leocol TD-90 (surfactant, manufactured by Lion Corporation) were added to 150 parts of ice water, and the mixture was stirred at 10 ° C. or lower for 30 minutes. Next, 34.8 parts of metanilic acid (purity 99.3%) was added and the mixture was stirred at 10 ° C. or lower for 1 hour while adjusting the pH to 3 to 4 using a 13% aqueous sodium hydroxide solution. After the liquid temperature was adjusted to 0 to 5 ° C., 60 parts of ethylenediamine was added all at once. After stirring overnight at room temperature, the pH was adjusted to 1 using concentrated hydrochloric acid. After stirring for a while, it was salted out with sodium chloride (20% to the liquid) and filtered to obtain 104 parts of a wet cake. The obtained wet cake was put in a beaker, 400 parts of water was added, and the pH was adjusted to 8 using a 13% aqueous sodium hydroxide solution. Subsequently, the solution was adjusted to pH 1 with concentrated hydrochloric acid, salted out with sodium chloride (20% to the liquid), and filtered to obtain 116 parts of a wet cake. The obtained wet cake was added to 300 parts of methanol and 30 parts of water, stirred at 50 ° C. for 1 hour, and then filtered to obtain 73 parts of a wet cake. The obtained wet cake was dried to obtain 45.7 parts of a compound of formula (14) as a white powder.

  (2) The following formula (15) (a mixture of No. 9, No. 10, and No. 11 in Table 1: 1.5 out of A, B, C, and D in the formula (1) is 2nd and 3rd) Of a pyridine ring condensed with a benzene ring, the remaining 2.5 being a benzene ring, X and Y being a 3-sulfoanilino group, and E being 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, 6.23 parts of the compound of the formula (14) obtained in Example 3- (1), 50 parts of water, and a solution dissolved in aqueous ammonia were added. After the addition, the pH was adjusted to 9.0 with 28% aqueous ammonia. While maintaining the same pH, the temperature was raised to 20 ° C. over 10 minutes and kept at the same temperature for 8 hours. Subsequently, the temperature was adjusted to 60 ° C., and then salted out with sodium chloride (20% to the liquid) to obtain 51.2 parts of a wet cake. The obtained wet cake was put into a beaker, 300 parts of water was added, and the solution was adjusted to pH 11 using a 13% aqueous sodium hydroxide solution. The solution was salted out with sodium chloride (20% to the liquid), adjusted to pH 1 with concentrated hydrochloric acid, and then filtered to obtain 48.4 parts of a wet cake. The obtained wet cake was put into 300 parts of methanol and 30 parts of water, stirred at 60 ° C. for 1 hour, filtered, washed with methanol, and dried to obtain 9.69 parts of blue powder.
λmax: 605 nm (in aqueous solution)

Example 3 (Ink evaluation)
(A) Preparation of Ink Each component shown in Table 4 or Table 5 below was mixed and dissolved to obtain the ink of the present invention. Subsequently, impurities were removed by filtering with a 0.45 μm membrane filter (manufactured by Advantech). The water used was ion exchange water. Further, the pH of the ink was adjusted with caustic soda (pH adjuster) so that the pH was 9 to 10, and water was added so that the total amount became 100 parts. As the porphyrazine dye or its salt (I), the dye obtained in Example 1 above is used, and as the water-soluble copper phthalocyanine dye or its salt (II) having an alkylsulfonyl group as a substituent, Patent Document 11 The dye of the specific compound example 154 (the coloring matter represented by the following formula (16) and the compound number 219 in Table 3) was used. The dye of the following formula (16) was synthesized according to the method described in Patent Document 11.
The ink having the composition shown in Table 4 was designated as C-1, and the ink having the composition shown in Table 5 was designated as C-2.

Table 4
Porphyrazine dye obtained in Example 1 3.5 parts Dye of formula (16) 3.5 parts Glycerin 8.0 parts Urea 8.0 parts N-methyl-2-pyrrolidone 7.0 parts IPA (isopropyl Alcohol) 5.0 parts Butyl carbitol 3.0 parts Product name Surfinol 104PG50 (manufactured by Nissin Chemical) 0.2 parts Water + NaOH for pH adjustment 61.8 parts Total 100.0 parts

Table 5
Porphyrazine dye obtained in Example 2 3.5 parts Dye of formula (16) 3.5 parts Glycerin 8.0 parts Urea 8.0 parts N-methyl-2-pyrrolidone 7.0 parts IPA (isopropyl Alcohol) 5.0 parts Butyl carbitol 3.0 parts Trade name Surfinol 104PG50 (manufactured by Nissin Chemical Co., Ltd.) 0.2 parts Water + NaOH for pH adjustment 61.8 parts
100.0 parts in total

  As Comparative Example 1, an ink was prepared with the same composition as in Table 4 except that 7.0 parts of the porphyrazine dye obtained in Example 1 and 0 parts of the dye of the formula (16) were used.

  As Comparative Example 2, an ink was prepared with the same composition as in Table 5 except that 7.0 parts of the porphyrazine dye obtained in Example 2 and 0 parts of the dye of the formula (16) were used.

  As Comparative Example 3, an ink was prepared with the same composition as in Table 4 except that 0 part of the porphyrazine dye obtained in Example 1 and 7.0 part of the dye of the formula (16) were used.

(B) Inkjet printing Using an inkjet printer (trade name: PIXUS ip4100 manufactured by Canon Inc.), exclusive film A (photo glossy film HG201 manufactured by Canon Inc.), exclusive film B (PICTORICA PRO Glossy Film PPF-A4 manufactured by Canon Inc.) Inkjet recording was performed on the seeds. The dedicated paper A and the dedicated paper B used in the test are recording media having an ink image receiving layer containing white inorganic pigment particles on a support.
At the time of printing, an image pattern was prepared so that gradations with several levels of reflection density were obtained, and a halftone printed matter was obtained. In the measurement of the light resistance test and the ozone resistance test, the measurement was performed by using the gradation portion where the reflection density D value of the printed material before the test was closest to 1.0. The bronze phenomenon was also evaluated using the same part.

(C) Evaluation of recorded image Hue Evaluation The hue of the recorded image is the a * and b * values when the color of the recording paper is measured using a colorimetric system (model name: SpectroEye: manufactured by GretagMacbeth) and the L * of the printed material is in the range of 40-80. Was measured. Evaluation was carried out in three stages, with preferable a * values defined as -60 to -20 and b * values 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. Light resistance test An air layer and a glass plate with a thickness of 2 mm are placed on a test piece of a recorded image, and a xenon weather meter (Model Ci4000 manufactured by ATLAS) is used, and the temperature in the bath is 24 ° C. and the humidity is 0.36 W / square meter. Irradiation was performed for 100 hours under the condition of 60% RH. After the test, the reflection density was measured using a color measurement system. 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 70% or more Δ: Residual rate 50-70%
×: Residual rate less than 50%

3. Ozone resistance test The test piece of the recorded image was allowed to stand for 3 hours at an ozone concentration of 40 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 was measured using the color measurement system. 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 70% or more, less than 85% △: Residual rate 40% or more, less than 70% ×: Residual rate less than 40%

4). Humidity resistance test The test piece of the 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

4). Evaluation of Bronze Phenomenon The test piece of the recorded image was measured for the glossiness of 60 ° light entering the company using a gloss meter (model PG-1M manufactured by Nippon Denshoku Co., Ltd.). The difference in gloss before printing and after printing was calculated and evaluated in three stages according to the following criteria.
○: Glossiness difference is less than 5 Δ: Glossiness difference is 5 or more and less than 15 ×: Glossiness difference is 15 or more

  The hue evaluation, the light resistance test result, the ozone resistance test result, and the moisture resistance test result of the ink (C-1) having the composition of Table 4 and the ink having the composition of Table 5 are shown in Table 6 (special film A) and This is shown in Table 7 (Special Film B).

Table 6
Ink evaluation result: Dedicated film A
Ink number Hue Light resistance Ozone resistance Moisture resistance Bronze phenomenon C-1 ○ ○ ◎ ○ △
C-2 ○ ○ ◎ ○ △
Comparative Example 1 ○ ○ ◎ ○ ×
Comparative Example 2 ○ ○ ◎ ○ ×
Comparative Example 3 ○ ○ ◎ ○ ×

Table 7
Ink evaluation result: Dedicated film B
Ink number Hue Light resistance Ozone resistance Moisture resistance Bronze phenomenon C-1 ○ ○ ◎ ○ ○
C-2 ○ ○ ◎ ○ ○
Comparative Example 1 ○ ○ ◎ ○ △
Comparative Example 2 ○ ○ ◎ ○ △
Comparative Example 3 ○ ○ ◎ ○ △

As is apparent from Tables 6 and 7, the ink composition of the present invention was excellent in hue, and showed lightness, ozone resistance, and moisture resistance as fast as those of conventional products. Further, regarding the bronze phenomenon, it was found that the gloss difference is smaller than that of the conventional product in both cases of the dedicated films A and B, and the bronze phenomenon is clearly improved.

Claims (23)

The following formula (1) as a porphyrazine coloring matter or a salt thereof (I)

[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 X and Y each independently represent 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) You may have 0-4 1 type (s) or 2 or more types of substituents selected from a group, an alkylamino group, an arylamino group, an acetylamino group, a cyano group, a nitro group, a halogen atom, and a heterocyclic group. ) And naphthylamino group (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 atom, heterocyclic ring 1 to 2 or more kinds of substituents selected from a group may be included.) . 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. ]
And a water-soluble copper phthalocyanine dye having an alkylsulfonyl group as a substituent or a salt thereof (II) The ink composition according to claim 1, wherein the nitrogen-containing heteroaromatic ring corresponding to A, B, C, and D in formula (1) is a pyridine ring or a pyrazine ring. Porphyrazine dye or its salt (I) is represented by the following formula (3)

[In the formula (3), A, B, C and D represent the same meaning as in claim 1. N is 1 to 3. ]
And a compound represented by the following formula (4)

[In Formula (4), E, X, and Y represent the same meaning as described in claim 1. ]
The ink composition according to claim 1, which is a compound obtained by reacting an amine compound represented by the formula: The amount of the amine compound represented by the general formula (4) is 0.5 to 4 molar equivalents relative to 1 molar equivalent of the compound of the general formula (3), and the pH in the reaction system is adjusted in the presence of ammonia. The ink composition according to claim 3, wherein the reaction is performed in a range of 7 to 10. The number of pyridine rings or pyrazine rings corresponding to A, B, C, and D in formula (1) is 1 to 3, E represents C2-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, wherein the substituted anilino group and the substituted naphthylamino group are a sulfo group and a carboxyl group , A phosphono group, a hydroxyl group, an alkoxy group, a ureido group, an acetylamino group, a nitro group and 0 to 3 substituents of one or more selected from the group consisting of chlorine atoms, The ink composition according to claim 2, wherein 0 to 2.9, c is 0.1 to 3, and the sum of b and c is 1 to 3. E in formula (1) 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, 6. The ink composition according to claim 5, wherein c is 0.1 to 3, and the sum of b and c is 1 to 3. A in formula (1) 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 2-position, 3-position or 3-position and A pyridine ring condensed at the 4-position or a pyrazine ring or a benzene ring condensed at the 2-position and the 3-position, wherein the C-condensed pyridine ring at the 2-position, 3-position, 3-position and 4-position, or the 2-position and 3-position A pyrazine ring or a benzene ring condensed at the position, D is a benzene ring, E is C2-C4 alkylene, and X and Y are each independently a sulfo group, a carboxy group, a methoxy group, a nitro group, An anilino group or a naphthylamino group having 1 to 3 substituents selected from the group consisting of a chlorine atom and a hydroxy group, b is 0 to 2.9, and c is 0.1 to 3 Item 2. The ink composition according to Item 1. Porphyrazine dye or its salt (I) is 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. ]
The ink composition according to claim 1, which is a compound represented by the formula: The compound represented by the formula (3) is represented by the following formula (5).

[In the formula (5), Z ₁ to Z ₈ represent the same meaning as described in claim 7. N is 1 to 3. ]
The ink composition according to claim 3, which is a compound represented by the formula: The amount of the amine compound represented by formula (4) is 0.5 to 4 molar equivalents relative to 1 molar equivalent of the compound of general formula (5), and the pH in the reaction system is 7 in the presence of ammonia. The ink composition according to claim 9, which is reacted in a range of from 10 to 10. In Formula (1), 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 condensed at the 2-position and 3-position. A pyridine ring or a benzene ring, D is a benzene ring, E is C2-C4 alkylene, and X and Y are each independently 1 to 3 selected from the group consisting of a sulfo group and a carboxy group The ink composition according to claim 1, which is an anilino group or naphthylamino group having the following substituents: b is 0 to 2.9, and c is 0.1 to 3. A water-soluble copper phthalocyanine dye or salt (II) having an alkylsulfonyl group as a substituent is represented by the following formula (6):

(Wherein R ₁ to R ₄ each independently represents a substituted or unsubstituted alkyl group, provided that at least one of R ₁ to R ₄ has an ionic hydrophilic group as a substituent.)
The ink composition according to claim 1, wherein the ink composition is represented by the formula: In Formula (6), R ₁ to R ₄ are substituted (C1-C4) alkyl groups, and the substituent is a hydroxyl group, a carboxyl group, a sulfone group, an alkoxy group (a hydroxyl group, an alkoxy group, a carboxyl group, or a sulfo group). Furthermore, a carbamoyl group (which may be further substituted with an alkyl group further substituted with a hydroxyl group, an alkoxy group, a carboxyl group or a sulfo group), a sulfamoyl group (a hydroxyl group, which may be substituted with a substituted alkoxy group) 2. It may be substituted by an alkyl group which is further substituted with an alkoxy group, a carboxyl group or a sulfo group, and at least one of R ₁ to R ₄ further contains a carboxyl group or a sulfo group. The ink composition according to any one of 1 to 12 2. The mixing ratio of the porphyrazine dye or its salt (I) and the water-soluble copper phthalocyanine dye or its salt (II) having an alkylsulfonyl group as a substituent is from 10:90 to 80:20 by mass ratio. 14. The ink composition according to any one of 1 to 13 When the ratio of the porphyrazine dye or salt (I) and the water-soluble copper phthalocyanine dye or salt (II) having an alkylsulfonyl group as a substituent contained in the ink composition is 0.5 The ink composition according to any one of claims 1 to 13, wherein the ink composition is 0.1 to 2.5% at a low concentration. The ink composition according to any one of claims 1 to 15, wherein a maximum absorption wavelength in water of a porphyrazine coloring matter or a salt thereof (I) in a visible light region is 595 nm to 610 nm. The ink composition according to any one of claims 1 to 16, wherein the porphyrazine dye or a salt thereof (I) accounts for 10 to 80% by mass in all the dyes in the ink composition. The ink containing the ink composition according to any one of claims 1 to 17, which is for inkjet recording. 19. An ink jet recording method for recording on a recording material by ejecting ink droplets according to a recording signal, wherein the ink according to claim 18 or an ink set containing the ink is used. A bronze suppression method using the ink or ink set according to claim 19. The ink jet recording method according to claim 19, wherein the recording material is an information transmission sheet. 21. The ink jet recording method according to claim 20, 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 colored body colored with the ink composition according to any one of claims 1 to 18, or the ink or ink set according to claim 19.