JP2010100739A - Porphyrazine dye, ink composition containing the same and colored matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a porphyrazine dye suitable for inkjet recording, having a good hue as cyan ink, with excellent various durabilities, especially in ozone resistance, and providing high print density, and an ink composition containing the same. <P>SOLUTION: The porphyrazine dye represented by formula (1) or a salt thereof is provided; wherein rings A through D are each independently a benzene ring or a nitrogen-containing heteroaromatic ring, the number of the nitrogen-containing heteroaromatic ring being more than 0.00 and 3.00 or less on average, the rest being the benzene ring, E is an alkylene, X is a sulfo-substituted napthylamino group or the like, b is 0.00 to less than 3.90 on average, and c is 0.10 or more on average. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

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

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

The performance required for the dyes used in inks suitable for such ink jet recording includes good solubility or dispersibility in solvents, high density recording, and good hue. , Strong against light, heat, and active gases in the environment (NOx, ozone and other oxidizing gases, SOx, etc.), excellent durability against water and chemicals, fixability to recording materials And good bleeding resistance, excellent storability as ink, no toxicity, and availability at low cost. In particular, printed matter having a good cyan hue and high print density can be obtained, and various resistances such as light resistance (durability to light), ozone resistance (durability to ozone gas) and moisture resistance (high There is a strong demand for cyan dyes having excellent durability under humidity.

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

A: C. such as Direct Blue 86, Direct Blue 87, Direct Blue 199, Acid Blue 249, or Reactive Blue 71 I. A known phthalocyanine dye having a (color index) number.

B: phthalocyanine dyes described in Patent Documents 1 to 3, etc.
[For _{example, Cu-Pc- (SO 3 Na} ) m (SO 2 NH 2) n; mixture of m + n = 1~4].

C: a phthalocyanine dye described in Patent Document 4 and the like,
[For _{example, Cu-Pc- (CO 2 H} ) m (CONR 1 R 2) n; m + n = 0~4 number.

D: a phthalocyanine dye described in Patent Document 5 and the like,
[For _{example, Cu-Pc- (SO 3 H} ) m (SO 2 NR 1 R 2) n; m + n = 0~4 number, and, m ≠ 0]

E: a phthalocyanine dye described in Patent Document 6 and the like,
[For _{example, Cu-Pc- (SO 3 H} ) l (SO 2 NH 2) m (SO 2 NR 1 R 2) n; l + m + n = 0~4 number.

F: a phthalocyanine dye described in Patent Document 7 and the like,
[For _{example, Cu-Pc- (SO 2 NR} 1 R 2) n; n = number of 1-5].

G: Phthalocyanine dyes described in Patent Documents 8, 9, and 12, etc.
[A phthalocyanine compound in which the substitution position of a substituent is controlled, a phthalocyanine dye having a substituent introduced at the β-position].

H: A benzopyridoporphyrazine-based dye having a pyridine ring and a benzene ring described in Patent Documents 10, 13, 14 to 16, and the like.

Phthalocyanine dyes typified by Direct Blue 86 or Direct Blue 199, which are currently widely used, are characterized by being excellent in light resistance compared to generally known magenta dyes and yellow dyes. Phthalocyanine-based dyes have a greenish hue under acidic conditions, which is not preferable for cyan ink. Therefore, when these dyes are used as cyan ink, they are preferably used under neutral to alkaline conditions. However, even if the ink is neutral to alkaline, if the recording material to be used is acidic paper, the hue of the printed matter may change greatly.

In addition, when phthalocyanine dyes are used as cyan ink, the hue of the printed matter changes to a green taste and is also decolored by oxidizing gases such as nitric oxide gas and ozone, which are often cited as environmental problems. Since this occurs, the print density also decreases at the same time.

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

In the future, when the field of use of inkjet recording expands and is widely used in exhibits such as advertisements, the dyes and inks used therein have good hues and are inexpensive, Since exposure to light and oxidizing gases in the environment increases, there is an increasing demand for particularly good hue and excellent light resistance, oxidizing gas resistance and moisture resistance. The oxidizing gas here means resistance to a phenomenon in which an oxidizing gas present in the air reacts with a dye (dye) of a recorded image on the recording paper or in the recording paper to cause the recorded image to discolor and fade. That is. Among oxidizing gases, ozone gas is considered to be a main causative substance that promotes the discoloration and fading phenomenon of ink jet recorded images. Since this discoloration phenomenon is characteristic of ink jet recorded images, improvement of ozone gas resistance is an important technical problem in this field. However, it is difficult to develop cyan dyes (for example, phthalocyanine dyes) and cyan inks that satisfy these requirements at a high level. So far, phthalocyanine dyes imparted with ozone gas resistance have been disclosed in Patent Documents 3, 8-12, 14-17, etc., but hue, print density, light resistance, ozone gas resistance, moisture resistance and bronzing phenomenon are disclosed. Cyan dyes and cyan inks that satisfy all the qualities, such as non-advancing, and can be manufactured at low cost have not been obtained yet. Therefore, it has not yet fully satisfied the demands of the market.

Japanese Patent Laid-Open No. 62-190273 JP-A-7-138511 JP 2002-105349 A Japanese Patent Laid-Open No. 5-171085 Japanese Patent Laid-Open No. 10-140063 Japanese National Patent Publication No. 11-515048 JP 59-22967 JP 2000-303009 A Japanese Patent Laid-Open No. 2002-249677 JP 2003-34758 A JP 2002-80762 A WO2004087815 WO2002034844 JP 2004-75986 A WO2007091631 WO2007116933 WO2008111635

The present invention provides a porphyrazine coloring matter suitable for ink jet recording having a good hue as a cyan ink, excellent in ozone resistance and moisture resistance, and capable of obtaining a high printing density, and an ink composition containing the same. This is the issue.

The present inventors have examined in detail a dye having a good hue, high light resistance and ozone resistance, and causing no bronze phenomenon. As a result, a specific porphyrazine represented by the following formula (1) is obtained. The present inventors have found that a dye can solve the above problems and have completed the present invention. That is, the present invention
1)
Porphyrazine dye represented by the following formula (1) or a salt thereof,

[In Formula (1),
Rings A to D each independently represent a benzene ring or a six-membered nitrogen-containing heteroaromatic ring condensed to a porphyrazine ring, and the average number of nitrogen-containing heteroaromatic rings exceeds 0.00. 00 or less, the rest are benzene rings,
E represents alkylene;
X is a naphthylamino group having at least one sulfo group, carboxy group or phosphate group as a substituent;
The naphthylamino group further includes a sulfo group, a carboxy group, a phosphate group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkoxy group, an amino group, a mono or dialkylamino group, a mono or diarylamino group, an acetylamino group, and a ureido group. May be substituted with one or more substituents selected from the group consisting of an alkyl group, a nitro group, a cyano group, a halogen atom, an alkylsulfonyl group and an alkylthio group,
b is an average value of 0.00 or more and less than 3.90,
c is an average value of 0.10 or more and less than 4.00,
The sum of b and c is an average value of 1.00 or more and less than 4.00. ],

2)
The porphyrazine dye or salt thereof according to 1) above, wherein the six-membered nitrogen-containing heteroaromatic ring represented by rings A to D is a pyridine ring or a pyrazine ring,
3)
The porphyrazine dye described in the above 1) or 2) obtained by reacting a porphyrazine compound represented by the following formula (3) with an organic amine represented by the following formula (4) in the presence of ammonia: Its salt,

[In Formula (3), Rings A to D represent the same meaning as described in Claim 1, and n is 1.00 or more and less than 4.00. ],

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

4)
E is C2-C4 alkylene,
X is a naphthylamino group having a sulfo group, a carboxy group or a phosphate group as a substituent,
The substituted naphthylamino group is one or more selected from the group consisting of a sulfo group, a carboxy group, a phosphate group, a hydroxy group, an alkoxy group, an acetylamino group, a ureido group, a nitro group, and a chlorine atom. The porphyrazine dye or salt thereof according to 1) or 2) above, which is a substituted naphthylamino group which may further have 0 to 3 groups,
5)
E is a linear C2-C4 alkylene,
X is a sulfo-substituted naphthylamino group or a carboxy-substituted naphthylamino group,
The substituted naphthylamino group may further have 0 to 2 one or more substituents selected from the group consisting of a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, a nitro group, and a chlorine atom. The porphyrazine dye or salt thereof according to 4) above, which is a good substituted naphthylamino group,
6)
The nitrogen-containing heteroaromatic rings in rings A to D are independently a pyridine ring condensed at the 2-position and the 3-position, or the 3-position and the 4-position, or a pyrazine ring condensed at the 2-position and the 3-position,
E is ethylene or propylene,
X is a sulfo-substituted naphthylamino group or a carboxy-substituted naphthylamino group,
The substituted naphthylamino group may further have one or two or more substituents selected from the group consisting of a sulfo group, a carboxy group, a hydroxy group, a methoxy group, a nitro group, and a chlorine atom. A substituted naphthylamino group,
Porphyrazine coloring matter or salt thereof according to 1) or 2) above,
7)
The nitrogen-containing heteroaromatic rings in rings A to D are pyridine rings condensed at the 2-position and 3-position, or at the 3-position and 4-position, respectively,
E is ethylene or propylene,
The porphyrazine dye or salt thereof according to 1) above, wherein X is a sulfo-substituted naphthylamino group, and further has 0 to 2 sulfo groups as substituents;
8)
An ink composition comprising the porphyrazine coloring matter according to any one of 1) to 7) or a salt thereof as a coloring matter;
9)
Furthermore, the ink composition as described in 8) above containing an organic solvent,
10)
The ink composition as described in 9) above, which is for inkjet recording,
11)
An ink jet recording method for recording on a recording material by using the ink composition according to any one of 8) to 10) as an ink, and discharging ink droplets of the ink according to a recording signal;
12)
The inkjet recording method according to 11) above, wherein the recording material is an information transmission sheet,
13)
The inkjet recording method according to 12), wherein the information transmission sheet is a surface-treated sheet, and the sheet has an ink receiving layer containing white inorganic pigment particles on a support.
14)
A container containing the ink composition according to any one of 8) to 10) above;
15)
An inkjet printer loaded with the container described in 14) above,
16)
The present invention relates to a colored body colored with the ink composition according to any one of 8) to 10).

The ink composition using the coloring matter of the present invention has a good hue as a cyan ink. The recorded image obtained by the ink composition of the present invention is excellent in various fastnesses such as light resistance, ozone resistance and moisture resistance, particularly ozone resistance. Moreover, there is no solid precipitation, physical property change, color change, etc. after long-term storage, and storage stability is good. Furthermore, when used together with other magenta ink and yellow ink, a color tone in a wide visible region can be produced. Moreover, since it has a high printing density, the dye density in the ink can be lowered, and it has an industrial advantage associated with cost reduction.
Therefore, the cyan ink using the porphyrazine coloring matter of the present invention is extremely useful as an ink for inkjet recording.

The present invention will be described in detail. An ink composition suitable for inkjet recording of the present invention is characterized by containing the porphyrazine coloring matter of the formula (1) or a salt thereof. In other words, tetrabenzoporphyrazine (usually referred to as phthalocyanine) in which the number of four benzo (benzene) rings is replaced with a nitrogen-containing heteroaromatic ring in excess of zero and three or less is used as a dye mother nucleus. An unsubstituted sulfamoyl group and a porphyrazine dye or a salt thereof into which a specific substituted sulfamoyl group is introduced are very suitable for an ink jet ink, and recorded matter with an ink using the dye or a salt thereof is extremely resistant to ozone gas. It has been found that it is excellent in resistance and hardly causes bronzing. In the present specification, in order to avoid complication, unless otherwise specified, hereinafter, it is simply described as “porphyrazine dye of the present invention” including both of “porphyrazine dye of the present invention or a salt thereof”. To do.

In the formula (1), examples of the nitrogen-containing heteroaromatic ring in the rings A to D (four rings A, B, C, and D) represented by broken lines include, for example, a pyridine ring, a pyrazine ring, a pyrimidine ring, and Examples thereof include nitrogen-containing heteroaromatic rings containing 1 to 2 nitrogen atoms such as pyridazine rings. Among these, a pyridine ring or a pyrazine ring is preferable, and a pyridine ring is more preferable. As the number of nitrogen-containing heteroaromatic rings increases, ozone resistance improves, but bronzing tends to occur easily. The number of nitrogen-containing heteroaromatic rings is appropriately determined in consideration of ozone resistance and bronzing properties. Adjust and select a well-balanced ratio. Although the number of nitrogen-containing heteroaromatic rings depends on the type of heterocycle, it cannot be generally stated, but is usually an average value of more than 0.00 to 3.00 or less, preferably 0.20 to 2.00, More preferably, it is 0.50 or more and 1.75 or less, More preferably, it is the range of 0.75 or more and 1.50 or less. The remaining rings A to D are benzene rings, and the benzene rings in the rings A to D are also generally average values of 1.00 or more and less than 4.00, preferably 2.00 or more and 3.80 or less. Preferably they are 2.25 or more and 3.50 or less, More preferably, they are 2.50 or more and 3.25 or less. The porphyrazine dye of the present invention is a dye mixture of a plurality of dyes as is apparent from the average value of the number of nitrogen-containing heterocycles of rings A to D. In the present specification, unless otherwise specified, the number of the nitrogen-containing heteroaromatic rings is rounded off to the second digit by rounding off the third digit after the decimal point.

In the formula (1), the alkylene in E includes, for example, C2-C12 linear, branched or cyclic alkylene, preferably C2-C6, more preferably C2-C4, and still more preferably C2-C3 alkylene. Is mentioned. Of the straight chain, the branched chain, and the ring, the straight chain or the ring is preferable, and the straight chain is more preferable.
Specific examples include ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, and the like; branched chains such as 2-methylethylene; cyclopropylene diyl, 1, Examples include cyclic ones represented by cyclohexylene such as 2- or 1,3-cyclopentylenediyl, 1,2-, 1,3- or 1,4-; Preferred is ethylene, propylene or butylene, more preferred is ethylene or propylene, and still more preferred is ethylene.

In the formula (1), X represents a naphthylamino group having at least one sulfo group, carboxy group or phosphate group as a substituent. A sulfo-substituted or carboxy-substituted naphthylamino group is preferred, and a sulfo-substituted naphthylamino group is more preferred.
The substituted naphthylamino group further includes a sulfo group, carboxy group, phosphate group, sulfamoyl group, carbamoyl group, hydroxy group, alkoxy group, amino group, mono- or dialkylamino group, mono- or diarylamino group, acetylamino group, ureido 1 type or 2 or more types selected from the group of 20 groups consisting of a group, an alkyl group, a nitro group, a cyano group, a halogen atom, an alkylsulfonyl group and an alkylthio group, preferably 1 to 3 types, more preferably 1 type Or you may substitute by 2 types, More preferably, 1 type of substituents. The number of substituents selected from the group of 20 groups is usually 0 to 3, preferably 0 to 2.

Examples of the alkoxy group in the substituent selected from the group of 20 groups include linear, branched or cyclic C1-C6, preferably C1-C4, and more preferably C1-C3 alkoxy groups. A straight chain or branched chain is preferable, and a straight chain is more preferable.
Specific examples include linear chains such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, and n-hexyloxy; branched chains such as isopropoxy, isobutoxy, t-butoxy, isopentoxy, and isohexyloxy; And cyclic groups such as cyclopropoxy, cyclopentoxy, cyclohexyloxy and the like.

Examples of the monoalkylamino group in the substituent selected from the group of 20 groups include linear or branched mono C1-C4, preferably mono C1-C3 alkylamino groups. Specific examples thereof include linear ones such as methylamino, ethylamino, n-propylamino and n-butylamino; branched ones such as isopropylamino, isobutylamino and t-butylamino;

Examples of the dialkylamino group in the substituent selected from the group of the 20 groups include a dialkylamino group having independently two alkyls exemplified in the monoalkylamino group. Specific examples include dimethylamino, diethylamino, methylethylamino and the like.

The monoarylamino group in the substituent selected from the group of the 20 groups includes a mono C6-C10 aromatic amino group, preferably a phenylamino group or a naphthylamino group, more preferably a phenylamino group.

Examples of the diarylamino group in the substituent selected from the group of 20 groups include diarylamino groups having two aryls independently mentioned as the monoarylamino group. Preferred are those having the same aryl, more preferably two phenyls, and a specific example is diphenylamino.

Examples of the alkyl group in the substituent selected from the group of 20 groups include linear, branched or cyclic C1-C6, preferably C1-C4, more preferably C1-C3 alkyl groups. A straight chain or branched chain is preferable, and a straight chain is more preferable. Specific examples include straight chain such as methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl; branched chain such as isopropyl, isobutyl, isopentyl and isohexyl; cyclopropyl, cyclopentyl, A cyclic group such as cyclohexyl; and the like.

Examples of the halogen atom in the substituent selected from the group of 20 groups include a fluorine atom, a chlorine atom and a bromine atom, preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom.

Examples of the alkylsulfonyl group in the substituent selected from the group of 20 groups include linear or branched C1-C6, preferably C1-C4, and more preferably C1-C3 alkylsulfonyl groups. A straight chain is preferred. Specific examples include straight chain such as methanesulfonyl, ethanesulfonyl and propanesulfonyl; branched chain such as isopropylsulfonyl; and the like.

Examples of the alkylthio group in the substituent selected from the group of 20 groups include linear or branched C1-C6, preferably C1-C4, more preferably C1-C3 alkylthio groups. A straight chain is preferred. Specific examples include straight chain such as methylthio, ethylthio, propylthio and butylthio; branched chain such as isopropylthio;

The substituent selected from the group of the 20 groups is preferably a sulfo group, a carboxy group, a phosphate group, a hydroxy group, an alkoxy group, an acetylamino group, a ureido group, a nitro group and a chlorine atom, and a sulfo group, a carboxy group. Hydroxy group, alkoxy group, nitro group and chlorine atom are more preferred, sulfo group, carboxy group, hydroxy group, methoxy group, nitro group and chlorine atom are more preferred, and sulfo group is particularly preferred.

Specific examples of the sulfo-substituted naphthylamino group in X include those having a sulfo group and a hydroxy group such as 3,6-disulfo-8-hydroxy-1-naphthylamino; 4,8-disulfo-4-nitro-2 -Those having a sulfo group and nitro group such as naphthylamino; Those having a methoxy group such as 6-sulfo-2-methoxy-1-naphthylamino; 3,6-disulfo-8-chloro-1-naphthylamino, etc. And those having a sulfo group and a chlorine atom.

X in the formula (1) is a sulfo-substituted naphthylamino group, and further preferably has 0 to 2 sulfo groups as substituents.
Specific examples include 6-sulfo-1-naphthylamino and the like having no sulfo group (and further having 0 sulfo group); 1,5-disulfo-2-naphthylamino, 3,6-disulfo-1 -Naphthylamino, 3,8-disulfo-1-naphthylamino, 4,8-disulfo-1-naphthylamino, 4,8-disulfo-2-naphthylamino, 5,7-disulfo-2-naphthylamino, 6, Those having one more sulfo group as a substituent, such as 8-disulfo-2-naphthylamino; 3,6,8-trisulfo-1-naphthylamino, 3,6,8-trisulfo-2-naphthylamino, 4 , 6,8-trisulfo-2-naphthylamino and the like, and further having two sulfo groups as substituents.

The sum of b, c and b and c in the formula (1) is an average value. b is 0.00 or more and less than 3.90, c is 0.10 or more and less than 4.00, and the sum of b and c is an average value of 1.00 or more and less than 4.00. At this time, the nitrogen-containing heteroaromatic rings in rings A to D have an average value exceeding 0.00 and not more than 3.00, and similarly the benzene rings are not less than 1.00 and less than 4.00.
Preferably, when the nitrogen-containing heteroaromatic ring in rings A to D is 0.20 or more and 2.00 or less, and the benzene ring is 2.00 or more and 3.80 or less, b is 0.00 or more and 3.20 or less, c is 0.60 or more and 2.00 or less, and the sum of b and c is 2.00 or more and 3.80 or less.
More preferably, when the nitrogen-containing heteroaromatic ring in rings A to D is 0.50 or more and 1.75 or less, and the benzene ring is 2.25 or more and 3.50 or less, b is 0.45 or more and 2.70 or less. , C is 0.80 or more and 1.80 or less, and the sum of b and c is 2.25 or more and 3.50 or less.
More preferably, when the nitrogen-containing heteroaromatic ring in rings A to D is 0.75 or more and 1.50 or less, and the benzene ring is 2.50 or more and 3.25 or less, b is 0.90 or more and 2.25 or less. , C is 1.00 or more and 1.60 or less, and the sum of b and c is 2.50 or more and 3.25 or less.
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.
Note that each of the unsubstituted sulfamoyl group and the substituted sulfamoyl group represented by b and c is a group that is substituted on the benzene ring when the rings A to D are benzene rings, When A to D are 6-membered nitrogen-containing heteroaromatic rings, they are not substituted.
In this specification, b, c, and the sum of b and c are all rounded off to the second digit by rounding off the third digit after the decimal point.

In the rings A to D, E, X, b, and c, a dye that combines preferred ones is more preferable, and a dye that combines more preferable ones is more preferable. The same applies to combinations of more preferable ones.

The dye represented by the above formula (1) can form a salt by utilizing sulfo, carboxy, phosphoric acid and the like in the molecule. When the salt is formed, the salt is an inorganic metal. It is preferable to form a salt with each cation of ammonium or organic base.
Inorganic metals include alkali metals and alkaline earth metals. Examples of the alkali metal include lithium, sodium, potassium and the like. Examples of the alkaline earth metal include calcium and magnesium.
Examples of the organic base include organic amines, for example, lower alkylamines having 1 to 3 carbon atoms such as methylamine and ethylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanol. Mono, di- or tri (C1-C4 alkanol) amines such as amines may be mentioned.
Among these, particularly preferable salts include alkali metal salts such as sodium, potassium and lithium, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and other mono, di or tri (carbon number). 1 to 4 lower alkanol) amine onium salts and ammonium salts.

Table 1 shows specific examples of rings A to D, E and X, and the numbers of b and c in the porphyrazine dye represented by the formula (1) of the present invention.
The following examples show typical dyes for specifically explaining the dyes of the present invention, and are not limited to the following examples.
Further, when the nitrogen-containing heteroaromatic rings of rings A to D are pyridine rings, there are positional isomers of nitrogen atoms as will be described later, and they are obtained as a mixture of isomers during dye synthesis. These isomers are difficult to isolate and are difficult to identify by analysis. For this reason, it is usually used as a mixture. The pigment | dye of this invention also contains such a mixture. In the present specification, when a structural formula is used without distinguishing these isomers, a typical structural formula is described for convenience. In addition, about the number of b and c in a table | surface, in order to avoid complexity, the 2nd digit after a decimal point was rounded off and it described to the 1st digit.

The porphyrazine coloring matter of the present invention can usually be used without blending other pigments. However, in some cases, the porphyrazine coloring matter may be blended with a known cyan coloring matter within a range not inhibiting the effects of the present invention.
When used in combination with known cyan dyes, phthalocyanine dyes are preferred as the dyes to be added.

The manufacturing method of the pigment | dye represented by the said Formula (1) is demonstrated.
The coloring matter represented by the formula (1) of the present invention comprises reacting the porphyrazine compound represented by the formula (3) with the organic amine represented by the formula (4) in the presence of ammonia. Can be obtained.
Any of the porphyrazine compounds represented by the formula (3) can be obtained by synthesizing a compound represented by the following formula (6) according to a known method or a similar method and then chlorosulfonylating the compound. it can.

That is, the compound represented by the following formula (6) can be synthesized according to a known method disclosed in, for example, WO2007 / 091631 and WO2007 / 116933. These known documents do not disclose a production method relating to a compound in which the number of nitrogen-containing heteroaromatic rings in rings A to D is less than 1. However, when synthesizing by a known nitrile method or Weiler method, the inclusion ratio in the rings A to D can be changed by changing the blending ratio of the nitrogen-containing heteroaromatic dicarboxylic acid derivative used as a reaction raw material and the phthalic acid derivative. A compound represented by the formula (6) in which the number of nitrogen heteroaromatic rings is less than 1 can also be synthesized. The obtained compound represented by the formula (6) is a mixture of positional isomers relating to the substitution positions of nitrogen-containing heteroaromatic rings in rings A to D and the substitution positions of nitrogen atoms in the nitrogen-containing heteroaromatic rings. This is also as described in the known literature.

[In Formula (6), Rings A to D represent the same meaning as described above. ].

The porphyrazine compound represented by the formula (3) can be obtained by chlorosulfonylating the compound represented by the formula (6) according to a known method disclosed in WO2007 / 091631 and WO2007 / 116933. it can. The chlorosulfonyl group in the formula (3) is introduced on the benzene ring in the rings A to D, and is not introduced when the rings A to D correspond to nitrogen-containing heteroaromatic ring groups. Since one chlorosulfonyl group is usually introduced on the benzene ring, the number of n in the formula (3) is within the number of benzene rings in the rings A to D. Therefore, the number “n” of chlorosulfonyl groups in the formula (3) is 1.00 or more and less than 4.00 depending on the number of benzene rings of the porphyrazine compound represented by the formula (3).
As another synthesis method of the porphyrazine compound represented by the formula (3), a sulfo group having a sulfo group can be obtained by condensation ring closure of a sulfophthalic acid having a sulfo group and a nitrogen-containing heteroaromatic dicarboxylic acid derivative such as quinolinic acid in advance. By synthesizing a porphyrazine compound and then converting the sulfo group in the compound to a chlorosulfonyl group with an appropriate chlorinating agent such as thionyl chloride, the desired porphyrazine compound represented by the formula (3) You can also get In this case, the sulfo group introduced on the porphyrazine compound represented by the formula (3) by selecting the substitution position of the sulfo group of sulfophthalic acid, which is a synthetic raw material, from the 3-position and 4-position. The replacement position of can be controlled. That is, when 3-sulfophthalic acid is used, a sulfo group can be selectively introduced at the “α” position in the following formula (10), and when 4-sulfophthalic acid is used, it can be similarly introduced at the “β” position. . In the present specification, unless otherwise specified, the term “α-position of a porphyrazine ring” or “β-position of a porphyrazine ring” means a corresponding position in the following formula (10).

On the other hand, the organic amine represented by the formula (4) can also be produced by a known method.
For example, 0.95 to 1.1 mol of naphthylamines corresponding to X and 1 mol of 2,4,6-trichloro-S-triazine (cyanuric chloride) in water at about pH 3 to 7, 5 to 40 ° C, The reaction is carried out for 2 to 12 hours to obtain a primary condensate.
Next, an alkali metal hydroxide such as sodium hydroxide is added to the reaction solution of the primary condensate and reacted under conditions of approximately pH 4 to 10, 5 to 80 ° C., and 0.5 to 12 hours. A subcondensate is obtained. Next, 1 mole of the obtained secondary condensate is reacted with 1 to 50 moles of alkylenediamine corresponding to E under conditions of approximately pH 9 to 12, 5 to 90 ° C., and 0.5 to 8 hours. Thus, an organic amine represented by the formula (4) is obtained. For pH adjustment during each condensation, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, etc. are usually used. The order of condensation is appropriately determined according to the reactivity of various compounds condensed with cyanuric chloride, and is not limited to the above order.

The reaction between the porphyrazine compound represented by the formula (3) and the organic amine represented by the formula (4) is approximately pH 8 to 10, 5 to 70 ° C., 1 to The reaction is carried out for 20 hours to obtain the target dye of the present invention represented by the formula (1). “Ammonia” used in the reaction usually means aqueous ammonia. However, any chemical substance that generates ammonia by neutralization or decomposition can be used. Examples of chemical substances that generate ammonia include those that generate ammonia by neutralization, such as ammonium salts such as ammonium chloride and ammonium sulfate; those that generate ammonia by thermal decomposition of urea and the like; However, it is not limited to these. As the “ammonia”, aqueous ammonia is preferable. Concentrated aqueous ammonia (usually commercially available as approximately 28% aqueous ammonia) or a solution diluted with water as necessary may be used. It ’s fine.

The amount of the organic amine represented by the formula (4) is usually the theoretical value [the dye represented by the desired formula (1) per 1 mol of the porphyrazine compound represented by the formula (3). The number of moles of the organic amine represented by the formula (4) necessary for obtaining the value of c in the formula] is 1 mole or more, but it depends on the reactivity of the organic amine used and the reaction conditions. It is not limited.
Usually, it is about 1 to 3 mol, preferably about 1 to 2 mol of the above theoretical value.

The dye of the present invention represented by the formula (1) is synthesized from the formula (3) and the compound represented by the formula (4) under reaction conditions that do not particularly require anhydrous conditions. . For this reason, a compound in which the chlorosulfonyl group in the formula (3) is partially hydrolyzed by water mixed in the reaction system and converted to sulfonic acid is produced as a by-product. It is theoretically considered to be mixed into the dye represented by the formula (1).
However, it is difficult to distinguish an unsubstituted sulfamoyl group and a sulfo 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) Are all described as being converted to unsubstituted sulfamoyl groups.

Furthermore, in the dye represented by the formula (1), a copper porphyrazine ring (Pz) is a dimer (for example, Pz-L-Pz) or a trimer via a divalent linking group (L). The formed impurities 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 - or the like it has, by-products of these two L are combined in the case of a trimer Sometimes it is formed.

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

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

Next, the ink composition of the present invention will be described. The dye of the present invention represented by the formula (1) produced by the above method exhibits a clear cyan color. Therefore, an ink composition containing these can also be used mainly as cyan ink. The ink is not only used as a high density cyan ink but also as a low dye density cyan ink (light cyan ink or photocyan) which is used to smoothly reproduce the gradation portion of an image or to reduce graininess in a light color area. May also be used as ink). Further, it may be used as a green ink by blending with a yellow pigment, or may be used as a violet or blue ink by blending with a magenta pigment. Furthermore, ink can be prepared by blending multiple colors and used as a dark yellow color, gray color or black color.

The ink composition of the present invention is prepared using water as a medium.
If this ink is the inkjet ink, the porphyrazine coloring matter of the present invention is contained therein, Cl ^- and the content of SO ₄ ^2-like anions preferably have less of the content guide is a dye In the total mass, the total content of Cl ^- and SO ₄ ^2- is 5% by mass or less, preferably 3% by mass or less, and more preferably 1% by mass or less. 1% by mass or less. The lower limit may be less than the detection limit of the detection device, that is, 0%.
Cl ^- and the production of porphyrazine coloring matter of the SO ₄ ^2-less invention, for example, conventional methods using a reverse osmosis membrane, or a dried product or a wet cake of the porphyrazine coloring matter of the present invention, stirring in a hydroalcoholic Desalting treatment may be performed by a method such as
In the latter case, the alcohol used is a C1-C4 alcohol, preferably a C1-C3 alcohol, more preferably methanol, ethanol, n-propanol or 2-propanol. A method may also be employed in which a hydrous alcohol containing a pigment to be desalted is heated to near its boiling point and then cooled to desalinate.
The porphyrazine coloring matter of the present invention, which has been desalted in hydrous alcohol, can also be obtained in a dry state by filtration separation and drying by a conventional method.
The content of Cl ^- and SO ₄ ^{2- in} the dye is measured by, for example, ion chromatography.

When using the ink composition of the present invention to an inkjet recording applications, the porphyrazine coloring matter of the present invention to be contained in the outer ink composition, the above Cl ^- and SO ₄ as ^non-2, zinc, heavy metals such as iron, calcium The content of impurities such as silica and impurities such as silica is preferably small.
However, since the porphyrazine of the present invention has a central metal and forms a copper complex by an ionic bond, a coordinate bond, or the like, this central metal is not included in impurities.
The standard of the impurity content is preferably about 500 ppm or less for each heavy metal such as zinc and iron, each ion such as calcium, and silica in the dried purified product of the porphyrazine pigment, and the lower limit is an analytical instrument. Or below 0 ppm, that is, 0 ppm.
The ion content of heavy metals and the like can be measured by ion chromatography, atomic absorption method or ICP (Inductively Coupled Plasma) emission analysis.

The ink composition of the present invention contains 0.1 to 8% by mass, preferably 0.3 to 6% by mass of the porphyrazine coloring matter represented by the formula (1).
This ink composition may further contain a water-soluble organic solvent as necessary within a range that does not impair the effects of the present invention. The water-soluble organic solvent may function as a dye solubilizer, a drying inhibitor (wetting agent), a viscosity modifier, a penetration accelerator, a surface tension modifier, an antifoaming agent, and the like, and the ink composition of the present invention. It is preferable to contain it inside.
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 add a foaming agent, a dispersing agent, a dispersion stabilizer, etc. as needed.
The water-soluble organic solvent is used in an amount of 0 to 60% by mass, preferably 10 to 50% by mass, and the ink preparation agent is used in an amount of 0 to 20% by mass, preferably 0 to 15% by mass, based on the total mass of the ink. good. The balance is water.

Examples of the water-soluble organic solvent include C1-C4 alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol; N, N-dimethylformamide or N, Carboxylic acid amides such as N-dimethylacetamide; complex such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2-one Cyclic ketones; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1,2- or 1,3-propylene glycol; 1,2- or 1,4-butylenegri 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol and other mono-, oligo- or polyalkylene glycols having C2-C6 alkylene units 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 (butyl carbitol) , Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether C1-C4 monoalkyl ethers of polyhydric alcohols such as Le; gamma-butyrolactone or dimethyl sulfoxide.

Preferred as the above 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, 2-pyrrolidone or butyl carbitol.
These may be used alone or in combination.

Examples of antiseptic / antifungal agents include organic sulfur, organic nitrogen sulfur, organic halogen, haloaryl sulfone, 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 isothiazoline compound include 1,2-benzisothiazoline. -3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one Examples thereof include magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, and 2-methyl-4-isothiazolin-3-one calcium chloride.
Examples of other antiseptic / antifungal agents include sodium sorbate, sodium benzoate, and sodium acetate, and 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, hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide (ammonia water), or lithium carbonate, sodium carbonate, potassium carbonate, etc. And alkali metal carbonates.

Examples of chelating reagents include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate, and the like. Examples of the rust inhibitor 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 typified by a benzophenone compound, a benzotriazole compound, a cinnamic acid compound, a triazine compound, a stilbene compound, or a benzoxazole compound, 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 surfactants, and examples thereof include anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants.
Anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, alkyl sulfate polyoxyalkyl ether sulfates Salt, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester salt, lauryl alcohol sulfate ester salt, alkylphenol type phosphate ester, alkyl type phosphate ester, alkyl aryl sulfonate, diethyl sulfosuccinate , Diethylhexylsylsulfosuccinate, dioctylsulfosuccinate and the like.
Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
Examples of 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 ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl -1-hexyne-3-acetylene alcohol such as ol (e.g., manufactured by Nissin Chemical Industry Co., Ltd. Surfynol 104,82,465, Olfine STG and the like) and the like.

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 composition of the present invention, there is no particular limitation on the order in which the respective drugs are dissolved. The water used for preparing the ink composition is preferably water with 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 ink jet printer, it is preferable to perform fine filtration. The pore size of the filter for performing microfiltration is usually 1 micron to 0.1 micron, preferably 0.8 micron to 0.1 micron.

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

Known dyes for the yellow ink include, for example, azo dyes having aryl and / or heteroaryl; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinones such as naphthoquinone dyes and anthraquinone dyes System pigments. Other examples include quinophthalone dyes; nitro / nitroso dyes; acridine dyes; acridinone dyes;

Examples of known dyes for the magenta ink include azo dyes having aryl and / or heteroaryl; azomethine dyes; methine dyes such as arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, oxonol dyes; And carbonium dyes such as diphenylmethane dye, triphenylmethane dye, and xanthene dye; quinone dyes such as naphthoquinone, anthraquinone, and anthrapyridone; condensed polycyclic dyes such as dioxazine dye; .

Examples of the known dyes for the black ink include azo dyes such as disazo, trisazo, and tetraazo; sulfur dyes; carbon black dispersions; and the like.

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

The ink jet recording method of the present invention uses the ink composition of the present invention as an ink, supplies energy to the ink in accordance with a recording signal, and ejects ink droplets of the ink, thereby known recording materials, Record images on plain paper, resin-coated paper, inkjet paper, glossy paper, glossy film, electrophotographic co-paper, fiber and cloth (cellulose, nylon, wool, etc.), glass, metal, ceramics, leather, etc. to form images To do.

In forming an image, a polymer fine particle dispersion (also referred to as polymer latex) may be used for the purpose of imparting glossiness or water resistance or improving weather resistance.
The timing of applying the polymer latex to the recording material may be before, after or at the same time as applying the colorant.
Therefore, the recording material containing the polymer latex may be recorded with the ink composition of the present invention, or the polymer latex may be contained in the ink composition. Alternatively, before or after recording on the recording material with the ink composition, the polymer latex may be applied to the recording material as a single liquid.

The colored body of the present invention means a substance colored with the porphyrazine coloring matter of the present invention or an aqueous ink composition containing the same. The substance to be colored is not particularly limited, and examples thereof include information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, and base materials for color filters. Sheets are preferred.
The information transmission sheet is preferably a surface-treated sheet, specifically, a sheet such as paper, synthetic paper, or film provided with an ink receiving layer. The ink receiving layer is formed by, for example, impregnating or coating the above-mentioned base material with a cationic polymer; inorganic fine particles capable of absorbing pigments in inks such as porous silica, alumina sol, and special ceramics are hydrophilic such as polyvinyl alcohol and polyvinylpyrrolidone. Coating on the surface of the base material together with the conductive polymer;
An information transmission sheet provided with such an ink receiving layer is usually called ink jet paper (film), glossy paper (film), or the like. Among these, it is said that it is easily affected by gases having an oxidizing action in the air, such as ozone gas, based on inorganic fine particles capable of absorbing pigments in inks such as porous silica, alumina sol and special ceramics. It is a type of inkjet paper that is coated on the surface of the material.
Typical examples of the above-mentioned special paper that can be obtained as a commercial product include Canon Inc., trade name: Professional Photo Paper, Glossy Gold, Glossy Professional; Seiko Epson Corporation, trade name: Photographic Paper Crispia (High Gloss) ), Photo paper (gloss), photo matte paper; manufactured by Nippon Hewlett-Packard Co., Ltd., trade name Advanced Photo Paper (gloss); manufactured by Brother Co., Ltd., trade name Premium Plus Glossy Photo Paper; Of course, plain paper can also be used. Specific examples include PB Paper GF500 manufactured by Canon Inc., trade name: Double-sided plain plain paper manufactured by Seiko Epson Corporation, etc. Absent.

  Any known method may be used as a coloring method for obtaining the colored product of the present invention. One of the preferable coloring methods is a method of coloring the above material with the ink of the present invention using an ink jet printer. The material to be colored may be the above-mentioned substance or other materials.

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

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

The ink composition of the present invention has a clear cyan color, and by using this as an ink, it is possible to obtain a recorded matter having high printing density, particularly excellent in ozone resistance, light resistance and water resistance. it can.
Use dark and light cyan inks, in addition to other yellow, magenta, and other inks such as green, red, orange, and blue as required. Thus, it is possible to express a color tone of a wider visible region.

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. Moreover, each operation, such as reaction and crystallization, was performed under stirring unless otherwise specified. Further, “trade name Leocol TD-90” used in the synthesis reaction is a surfactant manufactured by Lion Corporation.

In addition, all the pigment | dyes represented by the said Formula (1) synthesize | combined in the Example are mixtures containing an isomer etc. as mentioned above. Therefore, when a structural formula is described, unless otherwise specified, the chemical structural formula of the main component or one chemical structural formula therein is described. The yield also includes the isomers. Unless otherwise specified, the substitution positions of the unsubstituted and substituted sulfamoyl groups in the dye of the present invention are a mixture of those substituted at the α-position and β-position of the porphyrazine ring.

Example 1
(1) Synthesis of a compound in which 1.00 of the rings A to D in the following formula (6) is a pyridine ring condensed at the 2-position and 3-position, and the remaining 3.00 is a benzene ring

To a four-necked flask was added 375 parts of sulfolane, 33.29 parts of phthalic anhydride, 12.53 parts of quinolinic acid, 108 parts of urea, 10.1 parts of copper (II) chloride, 1.5 parts of ammonium molybdate, The temperature was raised to 0 ° C. and held at that temperature for 5 hours. After completion of the reaction, the reaction mixture was cooled to 65 ° C., 50 parts of DMF (N, N-dimethylformamide) was added, and the precipitated solid was separated by filtration. The obtained solid was washed with 50 parts of DMF to obtain 73.1 parts of a wet cake. The total amount of the obtained wet cake was added to 450 parts of DMF, the temperature was raised to 110 ° C., and kept at the same temperature for 1 hour. The precipitated solid was separated by filtration and washed with 200 parts of water. Next, the obtained wet cake was added to 450 parts of 5% hydrochloric acid, heated to 60 ° C., and stirred at the same temperature for 1 hour. The precipitated solid was separated by filtration and washed with 200 parts of water. Next, the total amount of the obtained wet cake was added to 450 parts of 5% aqueous ammonia, and the mixture was stirred at 60 ° C. for 1 hour. The precipitated solid was separated by filtration and washed with 200 parts of water to obtain 78.1 parts of a wet cake. . The obtained wet cake was dried at 80 ° C. to obtain 24.1 parts of the objective compound as a blue solid.

(2) Synthesis of a compound in which 1.00 of the rings A to D in the following formula (3) is a pyridine ring condensed at the 2-position and 3-position, the remaining 3.00 is a benzene ring, and n is 3.

Under room temperature, 5.8 parts of the compound obtained in Example 1 (1) was gradually charged into 46.2 parts of chlorosulfonic acid so as not to exceed 60 ° C., and reacted at 140 ° C. for 4 hours. . The obtained reaction liquid was cooled to 70 ° C., 17.9 parts of thionyl chloride was added dropwise over 30 minutes, and the reaction was further carried out at 70 ° C. for 3 hours. The reaction solution was cooled to 30 ° C. or lower, slowly poured into 800 parts of ice water, the precipitated solid was separated by filtration, and washed with 200 parts of cold water to obtain 42.4 parts of the target compound wet cake.

(3) Synthesis of an organic amine represented by the following formula (11) [an organic amine in which X in the above formula (4) is 3,6,8-trisulfo-1-naphthylamino and E is ethylene]

36.8 parts of cyanuric chloride and Leocol TD-90 (0.4 parts) were added to 150 parts of ice water, and the mixture was stirred at 10 ° C. or lower for 30 minutes. Next, 95.8 parts of 3,6,8-trisulfo-1-naphthylamine (use a commercial product of 91.0% purity) was added, and the pH was adjusted to 2.5 to 3.0 with a 10% aqueous sodium hydroxide solution. Reaction was performed at 20 ° C. for 1 hour 30 minutes at 20 ° C. The obtained reaction solution was reacted at 50 ° C. for 2 hours while adjusting the pH to 9.0 to 9.5 with a 10% aqueous sodium hydroxide solution. To the obtained reaction liquid, 250 parts of ice was added and cooled to 0 ° C., and 60 parts of ethylenediamine was added dropwise while maintaining the temperature at 5 ° C. or lower. Then, after stirring overnight at room temperature, the pH was adjusted to 2.0 with concentrated hydrochloric acid. During this time, ice was added to suppress heat generation, and the liquid temperature was maintained at 10 to 15 ° C. The obtained liquid was heated to 50 ° C. or lower, and 208 parts of hydrochloric acid was added while maintaining the same temperature to adjust the pH to 1.0. At this time, the liquid volume was 1000 parts. 200 parts of sodium chloride was added and stirred for 30 minutes to precipitate a solid. The precipitated solid was separated by filtration to obtain 161 parts of a wet cake. The obtained wet cake was put into a beaker, 500 parts of water was added, and the pH was 10.0 dissolved using a 10% aqueous sodium hydroxide solution. The solution was adjusted to pH 1.0 by adding 63 parts of hydrochloric acid. At this time, the liquid volume was 850 parts. 170 parts of sodium chloride was added and stirred for 30 minutes to precipitate a solid. The precipitated solid was separated by filtration to obtain 321 parts of a wet cake. The obtained wet cake was put into a beaker, 350 parts of methanol and 150 parts of water were added and stirred at 50 ° C. for 1 hour, and then the precipitated solid was separated by filtration to obtain 207.3 parts of a wet cake. The obtained wet cake was dried to obtain 116.3 parts of the target organic amine white powder.

(4) Dye of the present invention represented by the following formula (12) [of the rings A to D in the formula (1), 1.00 is a pyridine ring condensed at the 2-position and 3-position, and the remaining 3.00 is Synthesis of a benzene ring, a dye in which E is ethylene and X is 3,6,8-trisulfo-1-naphthylamino)

In 50 parts of ice water, 40.0 parts of the wet cake of the compound obtained in Example 1 (2) was added and suspended by stirring at 5 ° C. or lower. 10 minutes later, while maintaining 10 ° C. or less, 2 parts of 28% aqueous ammonia and 50 parts of water were added with 6.6 parts of the organic amine represented by formula (11) dissolved therein, and 28% aqueous ammonia The reaction was carried out while maintaining pH 9.0. While maintaining the same pH, the temperature was raised to 20 ° C. over 1 hour, and the reaction was further continued at the same temperature for 8 hours. The liquid volume at this time was 650 parts. The temperature of the reaction solution was raised to 50 ° C., 130 parts of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 1.0 with concentrated hydrochloric acid over 20 minutes. Washing with 100 parts gave 156.0 parts wet cake. The obtained wet cake was added to 550 parts of water and dissolved by adjusting the pH to 9.5 with a 25% sodium hydroxide solution. The liquid volume at this time was 700 parts. The solution was heated to 60 ° C., 140 parts of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 1.0 with concentrated hydrochloric acid over 20 minutes, and then the precipitated solid was separated by filtration, and 20% aqueous sodium chloride solution was obtained. Washing with 100 parts gave 91.2 parts of a wet cake. The obtained wet cake was added to a mixed solvent of 600 parts of methanol and 60 parts of water and stirred at 50 ° C. for 1 hour, and then the precipitated solid was separated by filtration to obtain 11.2 parts of a wet cake. The obtained wet cake was dried to obtain 9.5 parts of a free acid of the dye represented by the above formula (12) as a blue powder.
λmax: 601 nm (in aqueous solution)

Example 2
(1) Synthesis of an organic amine represented by the following formula (13) [an organic amine in which X in the above formula (4) is 4,8-disulfo-2-naphthylamino and E is ethylene]

18.4 parts of cyanuric chloride and trade name Leocol TD-90 (0.2 parts) were added to 150 parts of ice water, and the mixture was stirred at 10 ° C. or lower for 30 minutes. Next, 40.2 parts of 2-amino-4,8-disulfonaphthalene (use a commercial product having a purity of 77.0%) was added, and the pH was adjusted to 2.0 to 2.5 using a 10% aqueous sodium hydroxide solution. The reaction was carried out at 10 ° C for 1 hour 30 minutes and at 20-25 ° C for 3 hours. Subsequently, the reaction was performed at 50 ° C. for 3 hours while adjusting the pH to 9.0 to 9.5 with a 10% aqueous sodium hydroxide solution. At this time, the liquid volume was 500 parts. To this reaction liquid, 100 parts of sodium chloride was added and stirred for 30 minutes to precipitate a solid. The precipitated solid was separated by filtration to obtain 82.1 parts of a wet cake.
60 parts of ice was added to 60 parts of ethylenediamine, and 82.1 parts of the total amount of the wet cake obtained as described above were further added. During this time, ice was added to the reaction solution to suppress heat generation, and the reaction was continued at 10 ° C. or lower. The reaction solution was stirred overnight at room temperature and then adjusted to pH 1.0 using concentrated hydrochloric acid. Also at this time, ice was added to keep the liquid temperature at 10 to 15 ° C. At this time, the liquid volume was 700 parts. To the reaction solution, 140 parts of sodium chloride was added and stirred for 30 minutes to precipitate a solid. The precipitated solid was separated by filtration to obtain 51.2 parts of a wet cake. The obtained wet cake was put into a beaker, 220 parts of water was added, and the pH was adjusted to 9.5 with a 10% aqueous sodium hydroxide solution. At this time, the liquid volume was 500 parts. This solution was adjusted to pH 1.0 with concentrated hydrochloric acid, 100 parts of sodium chloride was added, and the mixture was stirred for 30 minutes to precipitate a solid. The precipitated solid was separated by filtration to obtain 57.8 parts of a wet cake. The obtained wet cake was put into a beaker, 210 parts of methanol and 90 parts of water were added and stirred at 50 ° C. for 1 hour, and then the precipitated solid was separated by filtration to obtain 41.2 parts of a wet cake. The obtained wet cake was dried to obtain 19.2 parts (HPLC purity: 89.3%) of the desired organic amine white powder.

(2) The dye of the present invention represented by the following formula (14): 1.00 of the rings A to D in the formula (1) is a pyridine ring, the remaining 3.00 is a benzene ring, E is ethylene, Of Dye wherein X is 4,8-disulfo-2-naphthylamino]

In 50 parts of ice water, 40.0 parts of a wet cake of the compound obtained in the same manner as in Example 1 (1) and (2) was added and suspended by stirring at 5 ° C. or lower. After 10 minutes, while maintaining the temperature at 10 ° C. or less, 2 parts of 28% aqueous ammonia and 50 parts of water in which 5.1 parts of the organic amine represented by the formula (13) were dissolved were added, and 28% aqueous ammonia was added. Was added while maintaining pH 9.0. While maintaining the same pH, the temperature was raised to 20 ° C. over 1 hour and further reacted at the same temperature for 8 hours. The liquid volume at this time was 250 parts. The temperature of the reaction solution was raised to 50 ° C., 37.5 parts of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 2.0 with concentrated hydrochloric acid over 20 minutes. This was washed with 100 parts of an aqueous sodium solution to obtain 92.1 parts of a wet cake. The obtained wet cake was added to 100 parts of water, adjusted to pH 9.0 with 25% sodium hydroxide solution and dissolved. The liquid volume at this time was 250 parts. The temperature of this solution was raised to 50 ° C., 37.5 parts of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 1.0 with concentrated hydrochloric acid over 20 minutes. The wet cake was washed with 100 parts of an aqueous sodium solution to obtain 62.1 parts of a wet cake. The obtained wet cake was added to a mixed solvent of 160 parts of ethanol and 40 parts of water and stirred at 50 ° C. for 1 hour, and then the precipitated solid was separated by filtration to obtain 44.0 parts of a wet cake. The obtained wet cake was dried to obtain 9.4 parts of a free acid of the dye of the present invention represented by the above formula (14) as a blue powder.
λmax: 605 nm (in aqueous solution)

Example 3
(1) Synthesis of an organic amine represented by the following formula (15) [an organic amine in which X is 4,8-disulfo-1-naphthylamino and E is ethylene in formula (4)]

18.4 parts of cyanuric chloride and trade name Leocol TD-90 (0.2 parts) were added to 150 parts of ice water, and the mixture was stirred at 10 ° C. or lower for 30 minutes. Next, 32.8 parts of 1-amino-4,8-disulfonaphthalene (use a commercial product with a purity of 95.0%) was added, and the pH was adjusted to 2.6 to 3.0 with a 10% aqueous sodium hydroxide solution. The reaction was carried out at 0 ° C. for 1 hour and at pH 3.0 to 3.5 for 1 hour at 0 to 5 ° C. for 1 hour at 25 to 30 ° C. Subsequently, the reaction was further performed at 50 ° C. for 3 hours while adjusting the pH to 9.0 to 9.5 with a 10% aqueous sodium hydroxide solution. To the reaction solution, 250 parts of ice was added, cooled to 0 ° C., and 60 parts of ethylenediamine was added dropwise while maintaining the temperature at 5 ° C. or lower. The reaction solution was further stirred overnight at room temperature, and then adjusted to pH 1.0 with concentrated hydrochloric acid. During this time, ice was added and heat generation was suppressed, and the temperature was maintained at 10 to 15 ° C. At this time, the liquid volume was 830 parts. 166 parts of sodium chloride was added to the reaction solution and stirred for 30 minutes to precipitate a solid. The precipitated solid was separated by filtration to obtain 59.3 parts of a wet cake. The obtained wet cake was put in a beaker, 280 parts of water was added, and the pH was adjusted to 9.0 with a 10% aqueous sodium hydroxide solution. At this time, the liquid volume was 400 parts. Concentrated hydrochloric acid was added to this solution to adjust to pH 1.0, and 80 parts of sodium chloride was further added and stirred for 30 minutes to precipitate a solid. The precipitated solid was separated by filtration to obtain 53.5 parts of a wet cake. The obtained wet cake was put into a beaker, a mixed solvent of 420 parts of methanol and 80 parts of water was added and stirred at 50 ° C. for 1 hour, and then the precipitated solid was separated by filtration to obtain 55.9 parts of a wet cake. The obtained wet cake was dried to obtain 18.9 parts (HPLC purity: 63%) of the target organic amine white powder.

(2) The dye of the present invention represented by the following formula (16) [of the rings A to D in the formula (1), 1.00 is a pyridine ring, the remaining 3.00 is a benzene ring, E is ethylene, and X is Of 4,8-disulfo-1-naphthylamino dye]

In 50 parts of ice water, 40.0 parts of a wet cake of the compound obtained in the same manner as in Example 1 (1) and (2) was added and suspended by stirring at 5 ° C or lower. After 10 minutes, while maintaining the temperature at 10 ° C. or lower, 2 parts of 28% ammonia water and 7.04 parts of organic amine represented by the formula (15) in 100 parts of water were added, and 28% ammonia water was added. Was added while maintaining pH 9.0. While maintaining the same pH, the temperature was raised to 20 ° C. over 1 hour, and the reaction was carried out at the same temperature for 8 hours. The liquid volume at this time was 275 parts. The temperature of the reaction solution was raised to 50 ° C., 55 parts of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 1.0 with concentrated hydrochloric acid over 20 minutes. Washing with 100 parts gave 94.7 parts of a wet cake. The obtained wet cake was added to 230 parts of water, and adjusted to pH 9.0 with 25% sodium hydroxide solution and dissolved. The liquid volume at this time was 350 parts. The temperature of this solution was raised to 50 ° C., 70 parts of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 1.0 with concentrated hydrochloric acid over 20 minutes. Washing with 100 parts gave 112.0 parts of a wet cake. The obtained wet cake was added to a mixed solvent of 800 parts of methanol and 200 parts of water and stirred at 50 ° C. for 1 hour, and then the precipitated solid was separated by filtration to obtain 46.3 parts of a wet cake. The obtained wet cake was dried to obtain 9.5 parts of a free acid of the dye represented by the above formula (16) of the present invention as a blue powder.
λmax: 601 nm (in aqueous solution)

Example 4
(1) Synthesis of a compound represented by the following formula (17)

To a four-necked flask, add 750 parts of sulfolane, 295.4 parts of 4-sulfophthalic acid (use a commercial product obtained as a 50% aqueous solution), 43.7 parts of 28% aqueous ammonia, and warm to 200 ° C. Reacted at temperature for 2 hours. Thereafter, it is cooled to 65 ° C., 33.4 parts of quinolinic acid, 288 parts of urea, 26.88 parts of copper (II) chloride and 4 parts of ammonium molybdate are added, the temperature is raised again to 200 ° C., and the reaction is carried out at the same temperature for 5 hours. did. After completion of the reaction, the reaction mixture was cooled to 65 ° C., 50 parts of methanol was added, and the precipitated solid was separated by filtration and washed with 200 parts of methanol to obtain 531 parts of a wet cake. The total amount of the obtained wet cake was added to 2800 parts of water, 400 parts of hydrochloric acid, and 720 parts of sodium chloride, heated to 60 ° C., and stirred at the same temperature for 1 hour. The precipitated solid was separated by filtration and washed with 400 parts of a 20% aqueous sodium chloride solution to obtain a wet cake. The obtained wet cake was added to 3000 parts of water, 80 parts of sulfuric acid and 600 parts of sodium chloride, heated to 60 ° C., and stirred at the same temperature for 1 hour. The precipitated solid was separated by filtration and washed with 400 parts of a 20% aqueous sodium chloride solution to obtain a wet cake. The obtained wet cake was added to a mixed solvent of 1500 parts of methanol, 200 parts of 28% aqueous ammonia and 100 parts of water, heated to 60 ° C., and stirred at the same temperature for 1 hour. The precipitated solid was separated by filtration and washed with 400 parts of 20% aqueous methanol to obtain 361 parts of a wet cake. The obtained wet cake was dried at 80 ° C. to obtain 144.2 parts of the target compound represented by the above formula (17) as a blue solid.
λmax = 603 nm (in aqueous solution)

(2) A compound represented by the following formula (18) [of the rings A to D in the above formula (3), 1.00 is a pyridine ring condensed at the 2nd and 3rd positions, the remaining 3.00 is a benzene ring, Compound in which n is 3.00 and the substitution position of the chlorosulfonyl group is the β-position of the porphyrazine ring]

To 52.1 parts of chlorosulfonic acid, 8.68 parts of the compound represented by the formula (17) obtained in Example 4 (1) were gradually added so as not to exceed 60 ° C., and the temperature was raised to 140 ° C. The reaction was performed for 4 hours. The reaction solution was cooled to 70 ° C., 17.9 parts of thionyl chloride was added dropwise over 30 minutes, and the reaction was performed at 80 ° C. for 3 hours. The reaction solution was cooled to 30 ° C. or lower, slowly poured into 1000 parts of ice water, the precipitated solid was separated by filtration, and washed with 100 parts of cold water to obtain 94.4 parts of the desired compound wet cake.

(4) The dye of the present invention represented by the following formula (19) [of the rings A to D in the formula (1), 1.00 is a pyridine ring condensed at the 2-position and 3-position, and the remaining 3.00 is A dye having a benzene ring, E being ethylene, X being 3,6,8-trisulfo-1-naphthylamino, and the substitution positions of the unsubstituted sulfamoyl group and the substituted sulfamoyl group are both β-positions of the porphyrazine ring] Synthesis of

In 50 parts of ice water, 94.4 parts of a wet cake of the compound represented by the formula (18) obtained in Example 4 (2) was added and suspended by stirring at 5 ° C. or lower. After 10 minutes, while maintaining the temperature at 10 ° C. or lower, a solution in which 2 parts of 28% aqueous ammonia and 13.2 parts of the organic amine represented by the formula (11) were dissolved in 50 parts of water was added, and 28% aqueous ammonia was added. The reaction was carried out while maintaining pH 9.0. While maintaining the same pH, the temperature was raised to 20 ° C. over 1 hour, and the reaction was further continued at the same temperature for 8 hours. The liquid volume at this time was 260 parts. The temperature of the reaction solution was raised to 50 ° C., 39 parts of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 1.0 with concentrated hydrochloric acid over 20 minutes. Washing with 100 parts gave 226.0 parts of a wet cake. The obtained wet cake was added to 800 parts of water, adjusted to pH 9.0 with 25% sodium hydroxide solution and dissolved. The liquid volume at this time was 1250 parts. The resulting solution was heated to 60 ° C., 125 parts of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 1.5 with concentrated hydrochloric acid over 20 minutes. The wet cake was washed with 400 parts of an aqueous sodium solution to obtain 85.2 parts of a wet cake. The obtained wet cake was added to a mixed solvent of 600 parts of methanol and 60 parts of water and stirred at 50 ° C. for 1 hour, and then the precipitated solid was separated by filtration to obtain 31.5 parts of a wet cake. The obtained wet cake was dried to obtain 8.7 parts of a free acid of the dye of the present invention represented by the above formula (19) as a blue powder.
λmax: 598 nm (in aqueous solution)

Synthesis of Comparative Dye A method for synthesizing a comparative dye is described below.

Synthesis example 1
(1) Synthesis of comparative organic amine represented by the following formula (20)

Cyanuric chloride (18.4 parts) and trade name Leocol TD-90 (0.2 parts) were added to 330 parts of ice water and stirred at 10 ° C. or lower for 30 minutes. Next, 17.4 parts of 4-sulfoaniline (use a commercial product having a purity of 99.3%) was added, and the pH was adjusted to 2.6-3.0 with a 10% aqueous sodium hydroxide solution, at 0-5 ° C. for 1 hour, pH 3. The reaction was carried out at 0 to 5 ° C. for 1 hour and at 25 to 30 ° C. for 1 hour while adjusting to 0 to 3.5. Next, 12.6 parts of 2-sulfoethylamine was added to the reaction solution, and the reaction was carried out at 25 ° C. for 2 hours while adjusting the pH to 7.0 to 8.0 with a 10% aqueous sodium hydroxide solution. To the reaction solution, 250 parts of ice was added, cooled to 0 ° C, and 60 parts of ethylenediamine was added dropwise while maintaining the temperature at 5 ° C or lower. Then, after stirring overnight at room temperature, the pH was adjusted to 1.0 using concentrated hydrochloric acid. During this time, ice was added to suppress heat generation, and the temperature was maintained at 10 to 15 ° C. At this time, the liquid volume was 980 parts. To this reaction liquid, 190 parts of sodium chloride was added and stirred for 30 minutes to precipitate a solid. The precipitated solid was separated by filtration to obtain 70.6 parts of a wet cake. The obtained wet cake was put in a beaker, 280 parts of water was added, and the pH was adjusted to 9.0 with a 10% aqueous sodium hydroxide solution. At this time, the liquid volume was 400 parts. The solution was adjusted to pH 1.0 with concentrated hydrochloric acid, 80 parts of sodium chloride was added, and the mixture was stirred for 30 minutes to precipitate a solid. The precipitated solid was separated by filtration to obtain 110.1 parts of a wet cake. The obtained wet cake was added to a mixed solvent of 260 parts of methanol and 26 parts of water and stirred at 50 ° C. for 1 hour, and then the precipitated solid was separated by filtration to obtain 89.1 parts of a wet cake. The obtained wet cake was dried to obtain a white powder of 49.3 parts of a comparative organic amine represented by the target formula (20).

(2) Synthesis of a comparative dye represented by the following formula (21) [of the rings A to D in the formula (21), 1.00 is a pyridine ring condensed at the 2-position and 3-position, and the remaining 3.00 is Benzene ring. ].

In 50 parts of ice water, 40.1 parts of a wet cake of the compound represented by the above formula (3) obtained in the same manner as in Examples 1 (1) and (2) was added and suspended by stirring at 5 ° C. or lower. . After 10 minutes, while maintaining the temperature at 10 ° C. or less, 2 parts of 28% aqueous ammonia and 60 parts of water in which 3.0 parts of a comparative organic amine represented by the formula (20) were dissolved were added, and 28% The reaction was carried out while maintaining pH 9.0 with aqueous ammonia. While maintaining the same pH, the temperature was raised to 20 ° C. over 1 hour and further reacted at the same temperature for 8 hours. The liquid volume at this time was 620 parts. The temperature of the reaction solution was raised to 50 ° C., 93 parts of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 2.0 with concentrated hydrochloric acid over 20 minutes. Washing with 100 parts gave 42.1 parts of a wet cake. The obtained wet cake was added to 360 parts of water and adjusted to pH 9.0 with 25% sodium hydroxide solution to obtain a solution. The liquid volume at this time was 400 parts. The temperature of the resulting solution was raised to 50 ° C., 60 parts of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 1.0 with concentrated hydrochloric acid over 20 minutes. This was washed with 100 parts of an aqueous sodium solution to obtain 41.2 parts of a wet cake. The obtained wet cake was added to a mixed solvent of 255 parts of methanol and 45 parts of water and stirred at 50 ° C. for 1 hour, and then the precipitated solid was separated by filtration to obtain 21.2 parts of a wet cake. The obtained wet cake was dried to obtain 10.1 parts of a free acid of a comparative dye represented by the target formula (21) as a blue powder. The amount of copper as the central metal of this dye and the amount of sulfur atoms in the unsubstituted and substituted sulfamoyl groups were quantified, and the average molecular weight was calculated to be 1082.8. From this result, the number of unsubstituted and substituted sulfamoyl groups in formula (21) was calculated.
λmax: 602.7 nm (in aqueous solution)

Synthesis example 2
(1) Synthesis of comparative organic amine represented by the following formula (22)

Cyanuric chloride (18.4 parts) and Leocol TD-90 (0.2 parts) were added to 330 parts of ice water and stirred at 10 ° C. or lower for 30 minutes. Next, 32.5 parts of 4,8-disulfo-1-naphthylamine (use a commercial product with a purity of 96.0%) was added and the pH was adjusted to 2.6 to 3.0 with a 10% aqueous sodium hydroxide solution at 0 to 5 ° C. The reaction was carried out for 1 hour at 0 to 5 ° C for 1 hour and at 25 to 30 ° C for 1 hour while adjusting the pH to 3.0 to 3.5. 10.8 parts of diethanolamine was added to the resulting reaction solution, and the reaction was carried out at 30 ° C. for 2 hours while adjusting the pH to 6.0 to 7.0 with a 10% aqueous sodium hydroxide solution. To the resulting reaction solution, 250 parts of ice was added, cooled to 0 ° C., and 60 parts of ethylenediamine was added dropwise while maintaining a reaction temperature of 5 ° C. or less. The reaction solution was stirred overnight at room temperature and then adjusted to pH 1.0 with concentrated hydrochloric acid. During this time, ice was added to suppress heat generation, and the temperature was maintained at 10 to 15 ° C. At this time, the liquid volume was 700 parts. To the obtained liquid, 140 parts of sodium chloride was added and stirred for 30 minutes to precipitate a solid. The precipitated solid was separated by filtration to obtain 105 parts of a wet cake. The obtained wet cake was put into a beaker, 400 parts of water was added, and the solution was adjusted to pH 9.0 with a 10% aqueous sodium hydroxide solution. At this time, the liquid volume was 600 parts. This solution was adjusted to pH 1.0 with concentrated hydrochloric acid, 160 parts of sodium chloride was added, and the mixture was stirred for 30 minutes to precipitate a solid. The precipitated solid was separated by filtration to obtain 115 parts of a wet cake. The obtained wet cake was added to a mixed solvent of 800 parts of methanol and 200 parts of water and stirred at 50 ° C. for 1 hour, and then the precipitated solid was separated by filtration to obtain 54.3 parts of a wet cake. The obtained wet cake was dried to obtain 33.8 parts of a white powder of a comparative organic amine represented by the target formula (22).

(2) Synthesis of a comparative dye represented by the following formula (23)

In 50 parts of ice water, 40.1 parts of a wet cake of the compound represented by the above formula (3) obtained in the same manner as in Examples 1 (1) and (2) was added and suspended by stirring at 5 ° C. or lower. . After 10 minutes, while maintaining the temperature at 10 ° C. or lower, 2 parts of 28% ammonia water and 30 parts of water with 5.4 parts of the organic amine represented by formula (22) dissolved therein were added, and 28% ammonia water was added. At pH 9.0 and reacted. While maintaining the same pH, the temperature was raised to 20 ° C. over 1 hour and further reacted at the same temperature for 8 hours. The liquid volume at this time was 225 parts. The temperature of the reaction solution was raised to 50 ° C., 45 parts of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 1.0 with concentrated hydrochloric acid over 20 minutes. The wet cake was washed with 100 parts to obtain 82.0 parts of a wet cake. The obtained wet cake was added to 200 parts of water and adjusted to pH 9.0 with a 25% sodium hydroxide solution to obtain a solution. The liquid volume at this time was 300 parts. The temperature of the resulting solution was raised to 50 ° C., 60 parts of sodium chloride was added and stirred for 30 minutes, and then adjusted to pH 1.0 with concentrated hydrochloric acid over 20 minutes. The wet cake was washed with 100 parts of an aqueous sodium solution to obtain 72.1 parts of a wet cake. The obtained wet cake was added to a mixed solvent of 255 parts of methanol and 45 parts of water and stirred at 50 ° C. for 1 hour, and then the precipitated solid was separated by filtration to obtain 37.5 parts of a wet cake. The obtained wet cake was dried to obtain 9.3 parts of a free acid of a comparative dye represented by the target formula (23) as a blue powder.
λmax: 601 nm (in aqueous solution)

(A) Preparation of ink Each component described in Table 2 below was mixed and dissolved, and filtered through a 0.45 μm membrane filter (manufactured by Advantech) to prepare an ink for an evaluation test. Ion exchange water was used as “water” in the preparation of the ink. Further, water and sodium hydroxide (pH adjusting agent) were added so that the pH of the ink was 8 to 10 and the total amount was 100 parts. Preparation of ink using the dye obtained in Example 1 is referred to as Example 5, and similarly, preparation of ink using the dye obtained in Examples 2 to 4 is referred to as Examples 6 to 8, respectively. In addition, comparative inks were prepared in the same manner as in Examples 5 to 8, except that the comparative dye obtained in Synthesis Example 1 or 2 was used instead of the dye obtained in the Examples. The inks were prepared as Comparative Examples 1 (using the comparative pigment obtained in Synthesis Example 1) and 2 (using the comparative pigment obtained in Synthesis Example 2), respectively.

Table 2
Dye obtained in each of the above Examples 5.0 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Taurine 0.3 Part Disodium ethylenediaminetetraacetate 0.1 part Surfactant [manufactured by Nissin Chemical Co., Ltd., trade name Surfinol 104PG50]
0.1 part water + aqueous sodium hydroxide solution 75.5 parts total 100.0 parts

(B) Inkjet recording Using an inkjet printer (Canon, trade name: PIXUS ip4100), glossy paper A is photographic paper Krispia (high gloss) made by Seiko Epson, and glossy paper B is photographic paper premium plus gloss. Inkjet recording was carried out on shi photo paper.
In inkjet recording, an image pattern is created so that six levels of gradation of 100%, 85%, 70%, 55%, 40%, and 25% density can be obtained, and a halftone recorded matter is obtained. Was used as a test piece. In the ozone resistance test, measurement was performed at the gradation portions of 55% and 40%, and the dye residual ratio was determined.
The reflection density was measured using a color measurement system (SpectroEye, manufactured by GretagMacbeth). Colorimetry was performed under the conditions of DIN, a viewing angle of 2 °, and a light source D65 as a density standard.
Various test methods for recorded images and evaluation methods for test results are described below.

(C) Evaluation of recorded image Ozone resistance test (A)
The test piece was allowed to stand for 8 hours at an ozone concentration of 40 ppm, an internal 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, measurement was performed at 55% gradation, and the dye residual ratio was calculated by (reflected density after test / reflected density before test) × 100 (%) and evaluated in four stages. The average reflection density of each test piece before the test was 1.09.
A: Residual rate of 80% or more O: Residual rate of less than 80%, 70% or more Δ: Residual rate of less than 70%, 60% or more X: Residual rate of less than 60% The higher the numerical value, the better. The results are shown in Table 3 below.

2. Ozone resistance test (B)
The test piece was allowed to stand for 8 hours at an ozone concentration of 40 ppm, an internal 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, measurement was performed at a gradation part of 40%, and the residual ratio of the dye was calculated by (reflected density after test / reflected density before test) × 100 (%) and evaluated in four stages. The average reflection density of each test piece before the test was 0.57.
A: Residual rate of 80% or more O: Residual rate of less than 80%, 70% or more Δ: Residual rate of less than 70%, 60% or more X: Residual rate of less than 60% The higher the numerical value, the better. The results are shown in Table 4 below.

3. Dc value of test piece The reflection density Dc value of cyan was measured using the above colorimetric system for 100% of the gradation part of the test piece. This was evaluated in four stages.
◎: Dc value is 2.45 or more ○: Dc value is 2.30 or more and less than 2.45 Δ: Dc value is 2.20 or more and less than 2.30 ×: Dc value is less than 2.20 Dc value is a large numerical value This means that the print density is higher (darker) and is superior. The results are shown in Table 5 below.

Table 3
Ozone test results (A)
Glossy paper A Glossy paper B
Example 5
Example 6 ○ ○
Example 7 ○ ○
Example 8
Comparative Example 1
Comparative Example 2

Table 4
Ozone test results (B)
Glossy paper A Glossy paper B
Example 5
Example 6 ○ ○
Example 7
Example 8 ○ ○
Comparative Example 1
Comparative Example 2

Table 5
Evaluation result of Dc value
Glossy paper A Glossy paper B
Example 5
Example 6 ○ ◎
Example 7 ○ ◎
Example 8
Comparative Example 1 × △
Comparative Example 2 × ○

As is apparent from Tables 3 and 4, the cyan ink of each example using the compound of the present invention has better ozone resistance than the ink of the comparative example. Specifically, both high and low density portions of the printed matter showed high ozone resistance.
Further, as apparent from Table 5, the reflection density of the recorded matter obtained with the ink of each example is extremely high, and it is clear that it is superior to any of the comparative examples. It is remarkable.

As described above, it is clear that the recorded image obtained by the porphyrazine coloring matter of the present invention and the ink composition containing the same can be obtained with high ozone resistance and high printing density. Very useful for applications.

Claims (16)

Porphyrazine dye represented by the following formula (1) or a salt thereof,

[In Formula (1),
Rings A to D each independently represent a benzene ring or a six-membered nitrogen-containing heteroaromatic ring condensed to a porphyrazine ring, and the average number of nitrogen-containing heteroaromatic rings exceeds 0.00. 00 or less, the rest are benzene rings,
E represents alkylene;
X is a naphthylamino group having at least one sulfo group, carboxy group or phosphate group as a substituent;
The naphthylamino group further includes a sulfo group, a carboxy group, a phosphate group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkoxy group, an amino group, a mono or dialkylamino group, a mono or diarylamino group, an acetylamino group, and a ureido group. May be substituted with one or more substituents selected from the group consisting of an alkyl group, a nitro group, a cyano group, a halogen atom, an alkylsulfonyl group and an alkylthio group,
b is an average value of 0.00 or more and less than 3.90,
c is an average value of 0.10 or more and less than 4.00,
The sum of b and c is an average value of 1.00 or more and less than 4.00. ]. The porphyrazine coloring matter or a salt thereof according to claim 1, wherein the six-membered nitrogen-containing heteroaromatic ring represented by rings A to D is a pyridine ring or a pyrazine ring. The porphyrazine coloring matter according to claim 1 or 2, which is obtained by reacting a porphyrazine compound represented by the following formula (3) with an organic amine represented by the following formula (4) in the presence of ammonia. salt,

[In Formula (3), Rings A to D represent the same meaning as described in Claim 1, and n is 1.00 or more and less than 4.00. ],

[In formula (4), E and X represent the same meaning as in claim 1. ]. E is C2-C4 alkylene,
X is a naphthylamino group having a sulfo group, a carboxy group or a phosphate group as a substituent,
The substituted naphthylamino group is one or more selected from the group consisting of a sulfo group, a carboxy group, a phosphate group, a hydroxy group, an alkoxy group, an acetylamino group, a ureido group, a nitro group, and a chlorine atom. The porphyrazine coloring matter or a salt thereof according to claim 1 or 2, which is a substituted naphthylamino group which may further have 0 to 3 groups. E is a linear C2-C4 alkylene,
X is a sulfo-substituted naphthylamino group or a carboxy-substituted naphthylamino group,
The substituted naphthylamino group may further have 0 to 2 one or more substituents selected from the group consisting of a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, a nitro group, and a chlorine atom. The porphyrazine coloring matter or a salt thereof according to claim 4, which is a good substituted naphthylamino group. The nitrogen-containing heteroaromatic rings in rings A to D are independently a pyridine ring condensed at the 2-position and the 3-position, or the 3-position and the 4-position, or a pyrazine ring condensed at the 2-position and the 3-position,
E is ethylene or propylene,
X is a sulfo-substituted naphthylamino group or a carboxy-substituted naphthylamino group,
The substituted naphthylamino group may further have one or two or more substituents selected from the group consisting of a sulfo group, a carboxy group, a hydroxy group, a methoxy group, a nitro group, and a chlorine atom. A substituted naphthylamino group,
The porphyrazine coloring matter or salt thereof according to claim 1 or 2. The nitrogen-containing heteroaromatic rings in rings A to D are pyridine rings condensed at the 2-position and 3-position, or at the 3-position and 4-position, respectively,
E is ethylene or propylene,
The porphyrazine dye or a salt thereof according to claim 1, wherein X is a sulfo-substituted naphthylamino group, and further has 0 to 2 sulfo groups as substituents. An ink composition comprising the porphyrazine coloring matter or a salt thereof according to any one of claims 1 to 7 as a coloring matter. The ink composition according to claim 8, further comprising an organic solvent. The ink composition according to claim 9, which is for ink jet recording. 11. An ink jet recording method in which recording is performed on a recording material by using the ink composition according to any one of claims 8 to 10 as ink, and ejecting ink droplets of the ink according to a recording signal. The inkjet recording method according to claim 11, wherein the recording material is an information transmission sheet. 13. The inkjet recording method according to claim 12, wherein the information transmission sheet is a surface-treated sheet, and the sheet has an ink receiving layer containing white inorganic pigment particles on a support. A container containing the ink composition according to any one of claims 8 to 10. An inkjet printer loaded with the container according to claim 14. A colored body colored with the ink composition according to any one of claims 8 to 10.